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August, 2006
CASE WESTERN RESERVE UNIVERSITY
Bushan K Purushothaman
______________________________________________________
________________________________________________
________________________________________________
06/26/06
(date) _______________________
*We also certify that written approval has been obtained for any
proprietary material contained therein.
I dedicate the dissertation to my family members for their love and steadfast
support to me at all times. I am grateful for their many sacrifices to make my life
successful.
iii
TABLE OF CONTENTS
Page
Number
List of Tables x
List of Figures xiii
Acknowledgements xxvi
List of Symbols xxvii
Abstract xxviii
1.0 Introduction 1
1.1 Background of Networked Neuroprosthetic System 1
1.2 Existing Rechargeable Battery Technologies 2
1.3 Overview of High Pressure Nickel-Hydrogen Batteries 4
1.3.1 Introduction 4
1.3.2 Cell Components and Electrochemistry involved 5
1.3.3 Nickel-Hydrogen Cell Construction 8
1.4 Proposed Research 12
1.5 Prior Work 12
1.6 Objective and Overview of this work 12
1.6.1 Primary Objective 13
1.3.3 Secondary Objective 14
Works Cited 14
2.0 Cycle Life Tests on Lithium Ion Batteries for Implantable Applications 16
2.1 Overview of Lithium Ion Batteries 16
2.2 Description of Li Ion Cell 17
2.3 Implantable Li Ion Batteries 18
2.4 Objective 19
2.5 Charging Protocol for Lithium Ion Batteries 19
2.6 Experimental Design 21
iv
2.6.1 Effect of Charge Rate on Cycle life Performance 23
2.6.2 Effect of Discharge Rate on Cycle Life Performance 32
2.6.3 Effect of Charge Voltage Cutoff on Cycle Life 36
Performance
2.6.4 Effect of DOD on Cycle Life Performance 37
2.6.4.1 Sony Lithium Ion Cells at 100 and 80% DOD 37
2.6.4.2 Wilson Greatbatch Lithium Ion Cells at 80 and 40
60% DOD
2.6.5 Effect of Temperature on Cycle Life Performance 41
2.6.6 Comparison of Sony, Wilson Greatbatch and Quallion 43
2.6.7 Comparison of Sony and WG at 80% DOD 48
2.7 Comparison of Implantable battery technologies 49
2.7.1 Cycle life of Quallion and WG at 60% DOD 49
2.7.2 Cycle Life of WG and Quallion at 100% DOD 52
2.6.3 Long term tests on WG and Quallion 52
2.8 Comparison of Charge Times for New and Used Quallion cells 54
2.9 Conclusions 61
Works Cited 62
v
3.3.2 Conditioning of ESNS Electrodes with Cyclic 78
Voltammetry
3.3.3 Effect of Rest 81
3.3.4 Effect of soaking in KOH for days 82
3.4 Testing of Current Collectors 83
3.5 Testing of Separators 85
3.6 Conclusions 85
Works Cited 87
vi
5.4.1 Overview of Reactions in the Nickel Hydroxide 110
Electrode
5.4.2 Overview of Electrochemical Voltage Spectroscopy 111
5.4.3 Mechanism of Formation 112
5.4.4 Effect of Incomplete Formation 117
5.4.5 Effect of Different Rates of Formation 121
5.4.6 Effect of Overcharging during Formation 123
5.4.6.1 No Overcharge during Formation 123
5.4.6.2 50% Overcharge during Formation 124
5.4.6.3 Comparison of No Overcharge and 50% 125
Overcharge
5.5 Characterization of Nickel Hydroxide Electrode 129
5.5.1 Effect of PVDF Content on Electrode Performance 129
5.5.2 Effect of Loading Density 135
5.5.3 Effect of Fine Ni 139
5.5.3.1 Electronic Conductivity Studies 139
5.5.3.2 Comparison of electrodes Containing 0% and 142
8.8% Ni
5.5.3.3 Comparison of Electrodes Containing 5.2% 147
and 8.7% PVDF in the Presence of Fine Ni
5.5.4 Effect of Pressing the Electrode 148
5.6 Other Methods of Fabrication 148
5.6.1 Mechanical Impregnation Using Spatula 148
5.6.2 Mechanical Impregnation Using Hot Press 150
5.7 Conclusions 151
Works Cited 152
6.0 Assembly and Testing of Low Pressure Nickel Hydrogen Battery 155
6.1 Description of Experimental Setup 155
6.2 Performance of the Ni-H2 Cell in Comparison to the Liquid Cell 157
6.3 Columetric Efficiency of the Ni-H2 Cell 162
vii
6.3.1 Effect of Depth of Charge on Columetric Efficiency 162
6.3.2 Effect of Rest Period on Columetric Efficiency – Self- 165
discharge
6.4 Pressure Data Analysis 169
6.4.1 Pressure Variations During Charge 171
6.4.2 Pressure Variations During the Rest Period 174
6.4.3 Self Discharge at Different Depths of Charge 177
6.4.4 Recombination in the Ni-H2 Cell During Charge and 178
Rest Period
6.4.5 Pressure Contributions – Self discharge and 180
Recombination
6.4.6 Efficiency Loss – Self Discharge and Recombination 180
6.5 Comparison of Efficiency Based on Charge Data and Pressure 183
Data
6.6 Ni-H2 Cell Tests – Below Atmospheric Pressure 183
6.7 Cycle Life Tests 185
6.8 Conclusions 190
viii
7.5.3 Pressure Variations During Charge 207
7.5.4 Pressure Variations During Rest after Discharge 208
7.5.5 Pressure Variations During Rest after Charge 210
7.5.6 Correlation of Pressure Variations During Discharge to 212
Pressure Composition Isotherm – Fuel Gauging
7.5.7 Correlation of Pressure Variations During Charge to 216
Pressure Composition Isotherm – Fuel Gauging
7.5.8 Self discharge at Different Depth of Charge 218
7.5.9 Recombination During Charge and Rest 218
7.5.10 Prediction of State of Charge 219
7.6 Problems associated with Ni-H2 Battery 219
7.7 Conclusions 224
Works Cited 225
ix
LIST OF TABLES
Page
Number
Table 2.1: Comparison of Quallion and Wilson Greatbatch lithium ion cells. 19
Table 2.2: Description of Sony lithium ion cells subjected to different test 24
conditions.
Table 2.5: Linear fit parameters and their error estimations of the end of 52
discharge voltage data. Wilson Greatbatch and Quallion lithium ion cells were
charged and discharged at C rate to 60% DOD.
Table 2.6: Linear fit parameters and their error estimations of the end of 54
discharge voltage data. Wilson Greatbatch and Quallion lithium ion cells were
charged and discharged at C/5 and C/4 rate, respectively.
x
Table 3.3: Estimated parameters for fresh electrodes based on the linear fit 77
applied to the CV data.
Table 3.4: Estimated parameters for fresh electrodes based on the linear fit 81
applied to the CV data.
Table 5.2: Utilization of electrode containing about 10% PVDF and 90% 122
Ni(OH)2 charged at different during formation.
Table 5.4: Peak potentials for different electrochemical reactions of electrodes 133
containing different amounts of PVDF.
Table 6.1: Parameters associated with the ESNS platinum electrode. 162
Table 6.2: Parameters associated with the nickel hydroxide electrode. 162
Table 6.3: Parameters associated with the complete Ni-H2 cell. 162
Table 6.4: Columetric efficiency of the Ni-H2 cell as a function of depth of 165
charge cycled at C/5 rate.
Table 6.5: Pressure loss contributions of recombination and self discharge for 180
6h rest period.
xi
Table 7.1: Change in various parameters following the desorption curve of the 215
pressure composition isotherm for discharge.
Table 7.2: Change in various parameters following the adsorption curve of the 217
pressure composition isotherm for charge.
Table 7.3: Change in various parameters following the desorption curve of the 217
pressure composition isotherm for charge.
Table 7.4: Self discharge rate for different depths of charge. 218
xii
LIST OF FIGURES
Page
Number
Figure 1.1.1: Schematic picture of the networked neuroprosthetic system. The 2
complete system in the body is shown in the left side of the figure. A
magnified view of the access port, the network cables and the modules is
shown in right side of the figure.
Figure 1.3.3: Exploded view showing the components of an Air Force cell in 10
stacking arrangement7.
Figure 2.6.1: Discharge capacity as a function of cycle index for Sony Li ion 24
cell 1. The cell loses discharge capacity with cycles. The cell was charged and
discharged at C rate. The scattered points in the cycle number range 1-100 is
due to instrumentation error and does not reflect the battery’s discharge
capacity.
xiii
Figure 2.6.2: Discharge capacity as a function of cycle index for Sony lithium 25
ion cell 1 fitted to a straight line. The linear fit is poor for discharge capacity in
the cycle number range 1-200. The capacity loss is 1.5x10-4 Ah/cycle. The cell
was charged and discharged at C rate.
Figure 2.6.3: Discharge capacity as a function of cycle index for Sony Li ion 26
cell 1 fitted to a straight line for the first 200 cycles. The estimated capacity
loss per cycle is 4x10-4 Ah. The cell was charged and discharged at C rate.
Figure 2.6.4: Discharge capacity as a function of cycles for Sony Li ion cell 1 28
fitted to a non-linear curve. The parameters k1 and k2 are 1.47 Ah and 8x10-
3
Ah / cycle . The cell was charged and discharged at C rate.
Figure 2.6.5: Discharge capacity as a function of cycles for Sony Li ion cell 2 28
fitted to a non-linear curve. The parameters k1 and k2 are 1.47 Ah and 7.2x10-
3
Ah / cycle . The cell was charged and discharged at C rate.
Figure 2.6.6: Discharge capacity as a function of cycles for Sony Li ion cell 3 29
fitted to a non-linear curve. The parameters k1 and k2 are 1.48 Ah and 8.1x10-
3
Ah / cycle . The cell was charged and discharged at C rate.
Figure 2.6.7: Discharge capacity as a function of cycles for Sony Li ion cell 4 29
fitted to a non-linear curve. The parameters k1 and k2 are 1.5 Ah and 5.2x10-
3
Ah / cycle . The cell was charged at C/5 rate and discharged at C rate.
Figure 2.6.10: Discharge capacity as a function of cycles for Sony Li ion cell 34
cycled at C charge rate and C/5 discharge rate fitted to a non-linear curve. The
parameters k1 and k2 are 1.38 Ah and 1.1x10-2 Ah / cycle .
Figure 2.6.11: Discharge capacity as a function of cycles for Sony Li ion cell 34
cycled at C charge rate and 2W discharge rate fitted to a non-linear curve. The
parameters k1 and k2 are 1.38 Ah and 1.36x10-2 Ah / cycle .
xiv
Figure 2.6.12: Discharge capacity as a function of cycles comparing lithium 35
ion cells cycled at different discharge rates. The degradation constant, k2, is
larger for the lithium ion cell with C/5 discharge in comparison to the lithium
ion cell with C discharge.
Figure 2.6.14: Discharge capacity as a function of cycles for Sony Li ion cell 37
cycled at C charge rate with 4.2 voltage cut off and 2W discharge rate. The
parameters k1 and k2 are 1.66 Ah and 1.25x10-2 Ah / cycle for the first 350
cycles.
Figure 2.6.15: Total number of cycles obtained for Sony lithium ion cells 39
cycled to different states of depth of discharge.
Figure 2.6.16: Total number of ampere-hours obtained for Sony lithium ion 39
cells cycled to different states of depth of discharge.
Figure 2.6.17: Total number of cycles obtained for Wilson Greatbatch lithium 40
ion cells cycled to 80 and 60% of depth of discharge.
Figure 2.6.19: End of discharge voltage in the cycle number range 0-175 42
comparing Sony Li ion cell cycled at room temperature and 37o C. The cells
were charged and discharged at C rate to 80% DOD.
Figure 2.6.22: Number of cycles obtained at 10% capacity loss for different 46
lithium ion cell manufacturers Sony, Wilson Greatbatch and Quallion. The
cells were cycled at C/5 charge rate and C discharge rate to 100% DOD.
xv
Figure 2.6.23: Number of cycles obtained at 10, 20 and 30% capacity loss for 47
Wilson Greatbatch and Quallion lithium ion cells. The cells were cycled at C/5
charge rate and C discharge rate to 100% DOD at 37o C.
Figure 2.6.24: The degradation constant, k2, for different lithium ion cell 47
manufacturers Sony, Wilson Greatbatch and Quallion. The normalized rate
constants were obtained by ratioing the rate constant to the cell’s nominal
capacity. The cells were cycled at C/5 charge rate and C discharge rate to
100% DOD.
Figure 2.6.25: Total number of cycles obtained for Sony and Wilson 48
Greatbatch lithium ion cells cycled to 80 % of depth of discharge at C rate
charge/ C rate discharge.
Figure 2.8.1: Total charge time as a function of different charging rates for 58
new and used Quallion cells.
Figure 2.8.2: Percentage of constant current and constant voltage charge times 58
as a function of different charging rates for new Quallion cells. The cells
during charging spend more time in the constant current phase rather than in
the constant voltage phase.
Figure 2.8.3: Percentage of constant current and constant voltage charge times 59
as a function of different charging rates for used Quallion cells.
xvi
Figure 2.8.5: Watt-hour efficiency of the used and the new Quallion cell at 60
different charging rates.
Figure 2.8.6: Percentage increase in charge time of the used Quallion cell in 60
comparison to the charge time of the new Quallion cell. The percentage charge
time is maximum for the 1C charge rate.
Figure 3.2.2: Impedance spectra of the ESNS electrode in the potential range - 71
8 to -154 mV. The charge transfer resistance decreases with increase in the bias
potential.
Figure 3.2.4: Potentiodynamic scan of the ESNS electrode at a scan rate of 0.1 74
mV/s. Two different regimes are indicated in the figure.
Figure 3.2.5: Linear fit of the potentiodynamic scan in the potential range -6 to 74
-16 mV. The scan rate is 0.1 mV/s. The parameter ‘B’ is the inverse of the
charge transfer resistance.
Figure 3.4.1: The high frequency resistance of the cell using nickel chromium 84
mesh current collectors and nickel mesh current collectors is compared.
xvii
Figure 3.4.2: The high frequency resistance of the cell, one using nickel 84
chromium mesh as current collectors and other using nickel mesh as current
collectors is compared for two different conditions fresh and used.
Figure 4.3.1: Voltage profile during the charge-discharge of the Ni-H2 cell 95
using the D cell nickel hydroxide electrode for cycles 1 and 5. There is no
discharge cut-off voltage. The cell was cycled at C/3 rate to 80% capacity with
no voltage cutoff.
Figure 4.3.2: Impedance spectra of the Ni-H2 cell using the D cell nickel 95
hydroxide electrode measured at the end of charge of cycles 1 and 5. The cell
was cycled at C/3 rate to 100% capacity.
Figure 4.3.3: Voltage profile during the charge-discharge of the Ni-H2 cell 96
using the D cell nickel hydroxide electrode for 5 cycles. The discharge cut off
voltage is 1.0 V The cell was cycled at C/3 rate to 80% capacity.
Figure 4.3.4: Voltage profile during the charge-discharge of the Ni-H2 cell 96
using the D cell nickel hydroxide electrode comparing overcharge with no
overcharge. The cell was cycled at C/6 rate with no voltage cutoff.
Figure 4.4.2: Variations in the open circuit voltage of series cell with different 99
bipolar plates. The cell is purged first with nitrogen and then with hydrogen.
Figure 4.4.3: Voltage profile during the charge-discharge of the series cell. The 100
discharge cut off voltage is 2.0 V The cell was cycled at C/3 rate to 80%
capacity.
Figure 4.4.4: Impedance spectra of the series cell measured at the end of 100
discharge of cycles 1, 5 and 10. The cell was cycled at C/3 rate to 80%
capacity.
xviii
Figure 4.4.5: Voltage profile at the end of charge for cycles 4, 7 and 10 of the 101
series cell. The discharge cut off voltage is 2.0 V The cell was cycled at C/3
rate to 80% capacity.
Figure 4.4.6: Voltage profile for the 12th charge of the series cell. The 101
discharge cut off voltage is 2.0 V The cell was cycled at C/3 rate to 80%
capacity.
Figure 5.3.1: SEM image of INCO nickel foam of thickness 1.6 mm and cell 107
size 550-700 µm.
Figure 5.4.1: Schematic diagram of the cell setup used for the formation of the 110
nickel hydroxide electrode.
Figure 5.4.2: Schematic diagram for interconversion of active material phases 111
in the nickel hydroxide electrode44.
Figure 5.4.3: Variations in voltage during charge and discharge of cycles 1 and 114
2. The electrode composition is 10% PVDF and 90% Ni(OH)2 by weight.
Figure 5.4.4: Voltage variation in the time period 0 to 0.5h during the first 114
charge. The electrode composition is 10% PVDF and 90% Ni(OH)2 by weight.
Figure 5.4.5: Impedance data of 10% PVDF containing electrode: (A) Before 115
formation, (B) End of discharge after cycles 1 and 2.
Figure 5.4.6: Voltage profile during charge and discharge of cycles 1 and 2 for 116
15% PVDF containing nickel hydroxide electrode.
Figure 5.4.7: Impedance data of 15% PVDF containing electrode measured at 117
the end of discharge after cycles 1, 2 and 3.
Figure 5.4.8: Comparison of EVS scans for completely and incompletely 119
formed nickel electrode containing 16% PVDF and 84% Ni(OH)2.
Figure 5.4.10: SEM image of nickel hydroxide electrodes: (A) Fresh 16% 121
PVDF electrode, (B) Used 12.7% PVDF electrode incompletely formed.
xix
Figure 5.4.11: Comparison of EVS scans for two different electrodes, one 123
charged at C/10 and another at C/20 rate with 50% overcharge. The electrode
composition is 10% PVDF and 90% Ni(OH)2 by weight.
Figure 5.4.12: Impedance spectra of the electrode measured at the end of 126
discharge (A) and charge (B) without overcharge at C/10 rate for the first 5
cycles.
Figure 5.4.14: Utilization as a function of cycles for electrodes formed with 128
0% and 50% overcharge.
Figure 5.4.15: Impedance spectra measured after discharge for electrodes 128
formed with 0% and 50% overcharge.
Figure 5.5.2: Impedance spectra measured at the end of discharge (A) and 132
charge (B) for electrodes containing different PVDF content. The electrodes
were formed at C/10 rate with 50% overcharge.
Figure 5.5.3: EVS scans for electrodes containing different PVDF content 133
formed at C/10 rate with 50% overcharge.
Figure 5.5.5: Utilization of 10% PVDF electrodes with different capacities 136
(different loading levels). The electrodes were cycled at C/10 rate with 50%
overcharge.
Figure 5.5.6: Utilization of 15% PVDF electrodes with different capacities 136
(different loading levels). The electrodes were cycled at C/10 rate with 50%
overcharge.
Figure 5.5.7: Impedance spectra measured at the end of discharge (A) and 137
charge (B) for electrodes containing 10% PVDF with different capacities. The
electrodes were formed at C/10 rate with 50% overcharge.
xx
Figure 5.5.8: Impedance spectra measured at the end of discharge (A) and 138
charge (B) for electrodes containing 15% PVDF with different capacities. The
electrodes were formed at C/10 rate with 50% overcharge.
Figure 5.5.9: Four-point conductivity ceramic base used for AC impedance 140
spectroscopy.
Figure 5.5.10: Electronic conductivity of the paste containing nickel hydroxide 141
particles (Kansai) as a function of nickel Wt. %.
Figure 5.5.11: Electronic conductivity of the paste containing nickel hydroxide 141
particles (OMG) as a function of nickel Wt. %.
Figure 5.5.12: Comparison of the voltage profile in the first formation cycle 143
for electrodes with and without nickel.
Figure 5.5.13: Impedance spectra measured at the end of discharge (A) and 144
charge (B) for electrodes containing 0% and 8.8% Ni. The electrodes were
formed at C/10 rate with 50% overcharge.
Figure 5.5.14: Utilization of electrodes with and without nickel. The electrodes 145
were cycled at C/10 rate with 50% overcharge. The electrodes containing
nickel show higher utilization.
Figure 5.5.15: Top view of SEM image of the nickel hydroxide electrode. The 145
spherical structures are the nickel hydroxide particles and the filamentary
structures are the nickel 210.
Figure 5.5.16: EVS scans for electrodes containing 0% and 8.8% nickel. The 146
electrodes were formed at C/10 rate with 50% overcharge.
Figure 5.6.1: Theoretical capacity of electrodes containing 8.8 % Nickel and 149
8.7% PVDF (dry active mass) fabricated by screen printing and pressing using
flat spatula. The electrodes were formed at C/10 rate with 50% overcharge.
Figure 5.6.2: Utilization of electrodes containing 8.8 % Nickel and 8.7% 150
PVDF (dry active mass) fabricated by screen printing and pressing using flat
spatula. The electrodes were formed at C/10 rate with 50% overcharge.
xxi
Figure 6.1.2: Schematic picture of the experimental set up. 156
Figure 6.2.1: Voltage profile of the nickel hydroxide electrode during charge 158
and discharge in the liquid cell and in the nickel-hydrogen cell configuration.
Figure 6.2.2: Impedance spectra measured at the end of discharge (A) and 161
charge (B) for electrodes cycled at C/5 rate in liquid cell and nickel-hydrogen
cell configuration.
Figure 6.3.3: Columetric efficiency of the Ni-H2 cell as a function of the rest 167
period at 50% DOC, cycled at C/5 rate.
Figure 6.3.4: Columetric efficiency of the Ni-H2 cell as a function of the rest 167
period at 70% DOC, cycled at C/5 rate.
Figure 6.3.5: Columetric efficiency of the Ni-H2 cell as a function of the rest 168
period at 70% DOC, cycled at C/5 rate.
Figure 6.3.6: Columetric efficiency of the Ni-H2 cell cycled at C/5 rate as a 169
function of the depth of charge for different rest periods.
Figure 6.4.1: Voltage variation during charge, rest and discharge periods of a 170
cycle. The cell was cycled at C/5 rate to 90% depth of charge. The rest period
is 6h.
Figure 6.4.2: Changes in pressure during the charge, the rest and the discharge 171
periods of a cycle. The cell was cycled at C/5 rate to 90% depth of charge. The
rest period is 6h.
Figure 6.4.3: Changes in pressure during the charge. The cell was cycled at 173
C/5 rate to 90% depth of charge.
Figure 6.4.5: Pressure changes during the rest period. The cell was cycled at 175
C/5 rate to 90% depth of charge. A straight line is fit to the pressure data in the
3 to 6h rest period and extrapolated back to time 0.
xxii
Figure 6.4.6: Pressure changes due to recombination reaction during the rest 177
period. The cell was cycled at C/5 rate to 90% depth of charge. An exponential
decay line is fit to the pressure data.
Figure 6.4.7: Self discharge rate estimated as a function of depth of charge for 178
Dataset 1 and 2.
Figure 6.4.8: Pressure drop due to the recombination reaction as a function of 179
depth of charge during the charge and the rest period.
Figure 6.5.1: Comparison of efficiency calculated based on the charge data and 184
pressure data at different depth of charge for data set 1.
Figure 6.5.2: Comparison of efficiency calculated based on the charge data and 184
pressure data at different depth of charge for data set 2.
Figure 6.7.1: Discharge capacity as a function of cycle index for a nickel- 187
hydrogen cell with a capacity of 41 mAh.
Figure 6.7.2: Discharge capacity as a function of cycle index for a nickel- 187
hydrogen cell with a capacity of 62.5 mAh.
Figure 6.7.3: Voltage profiles during charge and discharge for cycles 1, 4 and 188
12. The capacity of the cell was 62.5 mAh.
Figure 6.7.4: Voltage profiles during charge and discharge for cycles 15, 18 188
and 21. The capacity of the cell was 62.5 mAh.
Figure 6.7.5: End of charge voltage as a function of cycle index. The capacity 189
of the cell was 62.5 mAh.
Figure 6.7.6: Pressure measured at the end of every cycle. The capacity of the 189
cell was 62.5 mAh.
Figure 6.7.7: Picture of the failed nickel-hydrogen cell at the end of 190
experiment.
xxiii
Figure 7.3.1: Effect of air exposure on the first hydrogen absorption of 199
palladium treated LaNi4.7Al0.3 for periods greater than 2 years. This figure is
taken from reference 36.
Figure 7.4.1: Effect of soaking in KOH solution on the hydrogen absorption of 200
palladium treated LaNi4.7Al0.3. The hydrogen pressure at the end of absorption
is about 1.1 atm pressure.
Figure 7.5.1: Schematic picture of the Ni-H2 cell with metal hydride. 201
Figure 7.5.2: Schematic picture of the Ni-H2 cell with metal hydride. 202
Figure 7.5.3: Pressure variation inside the nickel hydrogen cell during venting 203
and subsequent hydrogen gas equilibration with the metal hydride.
Figure 7.5.6: Columetric efficiency of the Ni-H2 cell cycled at C/5 rate as a 205
function of the depth of charge for different rest periods.
Figure 7.5.7: Changes in pressure during the charge, the rest and the discharge 207
periods of two successive cycles. The cell was cycled at C/5 rate to 70% depth
of charge. The rest period for the 1st cycle and the 2nd cycle is 5 min and 6h,
respectively.
Figure 7.5.8: Changes in pressure during charge. The cell was cycled at C/5 208
rate to 70% depth of charge with 5 min rest period.
Figure 7.5.9: Changes in pressure during the rest period at the end of the 2nd 210
cycle shown in Fig. 7.5.7. The cell was cycled at C/5 rate to 70% depth of
charge.
Figure 7.5.10: Pressure changes during the 6h rest period after 2nd charge. The 211
cell was cycled at C/5 rate to 70% depth of charge. A straight line is fit to the
pressure data in the 4 to 6h rest period.
Figure 7.5.11: Pressure changes due to recombination reaction and hydrogen 212
equilibration with the metal hydride during the rest period after 2nd charge. The
cell was cycled at C/5 rate to 70% depth of charge. An exponential decay line
is fit to the pressure data.
xxiv
Figure 7.5.12: Changes in pressure during the rest period after charge, the 215
discharge period and the subsequent rest period of the 2nd cycle. The cell was
cycled at C/5 rate to 70% depth of charge.
Figure 7.6.2: Comparison of impedance spectra for two different cases (i) no 222
oxygen leak and (ii) oxygen leak measured at the end of charge (A) and
discharge (B). The cell was cycled at C/5 rate to 50% depth of charge.
Figure 7.6.3: Changes in pressure during the rest period at the end of discharge 223
for the case ‘oxygen leak’. The cell was cycled at C/5 rate to 50% depth of
charge.
Figure 7.6.4: Change in pressure inside the nickel hydrogen cell by increasing 223
the pressure suddenly to 31.8 psi for the case ‘oxygen leak’. The cell was
cycled at C/5 rate to 50% depth of charge. The pressure variation shows
hydrogen gas equilibration with the metal hydride.
xxv
Acknowledgements
I acknowledge and greatly appreciate Prof. Jesse S. Wainright for his constant
support and feedbacks during my Ph.D. I thank NIH (NINDS R01-NS41809) for
supporting this work financially. I also acknowledge the Bio-research group members
Brian Smith, Jim Buckett, Tim Crish, George Blomgren and Prof. Payer for useful
I acknowledge Prof. Landau for his support and guidance in all my work. I
acknowledge Prof. Mark DeGuire and Prof. Savinell for giving intellectual insights and
I thank my friends who had supported me in all times. Finally, I thank my family
especially my parents and my grandparents for their love and belief in me.
xxvi
List of Symbols
Greek letters
α anodic transfer coefficient
β cathodic transfer coefficient
ηa activation overpotential (volt)
Ω ohmic
xxvii
Development of Batteries for Implantable Applications
Abstract
By
implantable power sources with exceptional cycle life, safety, and sufficient energy and
power density. Of the rechargeable battery technologies, lithium ion batteries have the
highest energy density; however, they have limited cycle life of about 1000 cycles.
long cycle life (40,000) and low maintenance; however they utilize high hydrogen
pressures (60 atm) making them unsuitable for implantable applications. The present
work involves design and development of low pressure nickel-hydrogen batteries (1 atm)
by utilizing a metal hydride (MH) to store hydrogen, rather than as a negative electrode in
electrode using cyclic voltammetry was developed. A nickel mesh was chosen as the
current collector because of its low resistance and stability in alkaline solutions. The
tested separators, zirconium oxide and polypropylene, were not significantly different
xxviii
A pasted type nickel hydroxide electrode was fabricated by two means: screen
printing and spatula pressing. The mechanism of electrode formation, the effect of
different formation rates with and without overcharge and the effect of binder and nickel
Charge and pressure data were analyzed to study the oxygen evolution, the recombination
reaction and the self discharge of the cell. Oxygen evolution increases with the depth of
charge; however the evolved oxygen recombines completely – 70% during charging and
the remainder during the first hour of the rest period. About 40-45% hydrogen from the
metal hydride was used as fuel during cycling. The pressure composition isotherm was
used to estimate the state of charge and to fuel gauge the cell. The MH is deactivated
Of the tested implantable lithium ion cells, Quallion outperformed the Wilson
Greatbatch cells in cycle life. The conditions for maximum cycle life were determined.
xxix
1. Introduction
enhancing the functions of patients such as paraplegics, quadriplegics, people with spinal
cord injury and people suffering from other daily activities like standing, steeping,
reaching and grasping. Two common methods of stimulation are surface stimulation
(stimulation outside the body) and percutaneous stimulation (stimulation inside the
body). The neuroprosthetic system being developed at Case Western Reserve University
is completely implantable and can be employed for different clinical applications because
cosmetics and flexibility. Instead of using a single large implantable module, a network
based system consisting of smaller modules distributed throughout the body is proposed
The three main components of the implantable system are the centralized power
system, backbone network cables and the modules. The centralized power system is the
access port which holds the power source and provides power to the entire network. The
network cables connect the power system to the modules. The main function of the
modules is to sense and actuate the muscles. This system will have a life of about 30 to
40 yrs and therefore will be typically used in patients in their twenties. The power source
in the access port will be charged inductively across the skin. This system requires a
1
Figure 1.1.1: Schematic of the networked neuroprosthetic system. The complete system
in the body is shown on the left side of the figure. A magnified view of the access port,
the network cables and the modules is shown in right side of the figure.
Large and renewable power (about 500 mW) required for the networked neural
battery was chosen as the power source. The three major requirements of the power
source are long cycle life, safety and high energy density. The NNPS has a life about 30
years and therefore the battery cycle life should be comparable, say about 10 to 20 yrs. A
power source that is reliable and safe is an important criterion for the patients.
2
The energy densities of existing battery technologies1 are compared in Fig.1.1.2.
The lithium ion batteries have the highest energy densities both in terms of weight and
volume, excluding lithium metal batteries which are unsafe. Because of the high energy
density and the ease of minimizing battery size, they are ideal for portable equipments
like laptop computers, digital video cameras, cellular phones and other hand held devices.
Companies like Quallion and Greatbatch manufacturer implantable grade lithium ion
batteries and are described in detail in Chapter 2. However these are limited by cycle life
of about 1000 cycles at complete charge and discharge. Assuming that the battery is
cycled once a day, the lithium ion battery will last 3 years necessitating surgery after that.
lithium ion batteries; however they have an order of magnitude higher cycle life of about
40,000-60,000 cycles at 40% DOD 2 and therefore could be expected to meet or exceed
the design goal of 20-30 yr life time.. They are also referred to as low maintenance
batteries because over-charging and over-discharging the system does not affect the cycle
life significantly in comparison to the lithium ion batteries. However, the main
disadvantage is that they utilize hydrogen at high pressures of about 60 atm and therefore
are unsafe for implantable applications. They are currently used in aerospace
applications2.
A low pressure nickel-hydrogen battery that is safe is proposed in section 1.4 and
3
Volumetric
Ni-H2
Gravimetric
Figure 1.2.1: Comparison of the different battery technologies in terms of volumetric and
gravimetric energy density 1. The energy density of the nickel-hydrogen batteries was
added to the figure.
1.3.1. Introduction
technologies. The nickel hydroxide positive electrode is similar to that used in battery
platinum negative electrode is similar to that used in alkaline fuel cells. The remarkable
features of the battery, as discussed earlier, are the long cycle life compared to other
battery systems and their tolerance towards overcharge and reversal (over-discharge)
leading to inherent safety. The state of charge is determined easily by measuring the
hydrogen pressure. All these characteristics have resulted in their use in satellites both
4
geosynchronous earth-orbit (GEO) and low earth-orbit (LEO) applications for many
years 2, 3.
The different components in the nickel-hydrogen cell are the positive nickel
electrode, the negative platinum electrode and the separator which is filled with
Positive Electrode
the sintered type electrode that consists of a sintered porous nickel plaque impregnated
with nickel hydroxide active material 2, 4. The properties of this electrode are high
porosity, large surface area, high electrical conductivity and good mechanical strength.
Other fabrication methods of the nickel hydroxide electrode are discussed in Chapter 5.
Negative Electrode
The negative electrode (also called the hydrogen electrode) is made based on
techniques developed for gas electrodes in alkaline fuel cells. They typically consist of
Teflon bonded with platinum particles on a nickel substrate and are described in detail in
chapter 3.
Separator
The main function of the separator is to serve as reservoirs for the electrolyte
through which ionic conduction occurs. It should also be dimensionally stable on long-
5
term storage and cycling. The separators typically used in the high pressure Ni-H2 cells
are (1) asbestos and (2) Zircar 7, 8. Most of the first nickel-hydrogen cells used asbestos
separators and they were replaced by Zircar because of asbestos’s toxic nature. Zircar is
the trade name for woven zirconium oxide fibers stabilized with yttria.
Electrolyte
The electrolyte used is 26 wt% KOH solution in comparison to the 31 wt% KOH
solution typically used in nickel-cadmium batteries. The use of 26% KOH solution has
significantly increased cycle life of the Ni-H2 batteries by reducing electrode swelling7, 8.
Reactions Involved
electrode according to equation [1.1]. The reverse of the reaction occurs during
discharge.
ch arg e
ZZZZZX NiOOH + H 2O + e −
Ni (OH )2 + OH − YZZZZZ [1.1]
disch arg e
charge and the hydrogen gas is oxidized during discharge according to equation [1.2].
ch arg e
ZZZZZX 12 H 2 + OH −
H 2O + e − YZZZZZ [1.2]
disch arg e
The net reaction in the cell during charge and discharge is:
ch arg e
ZZZZZX NiOOH + 12 H 2
Ni (OH )2 YZZZZZ [1.3]
disch arg e
Therefore the net effect is the change in the oxidation state of nickel and the formation or
the depletion of hydrogen gas depending on charge or discharge. The hydroxyl ion and
6
Overcharge
When the cell is overcharged, oxygen is evolved at the nickel hydroxide positive
electrode (equation [1.4]) whereas there is no change in reaction at the platinum negative
electrode (equation [1.5]). The evolved oxygen recombines with hydrogen at the
+ ve ,electrode 1
2OH − ⎯⎯⎯⎯⎯ → O2 + H 2O + 2e − [1.4]
2
− ve ,electrode
2 H 2O + 2e − ⎯⎯⎯⎯⎯ → H 2 + 2OH − [1.5]
1
H 2 + O2 ⇒ H 2O + heat [1.6]
2
Over-discharge
(equation [1.7]) and is consumed at the negative platinum electrode (equation [1.8]),
without any change in pressure in the nickel-hydrogen cell 2. The net amount of KOH and
water in the cell does not change on over-discharge. Therefore these batteries are called
+ ve ,electrode
H 2O + e − ⎯⎯⎯⎯⎯ → 12 H 2 + OH − [1.7]
− ve ,electrode
1
2 H 2 + OH − ⎯⎯⎯⎯⎯ → H 2O + e − [1.8]
7
Figure 1.3.1: The components of COMSAT nickel-hydrogen cell in stacking
arrangement2.
of Inconel alloy 718 to withstand high pressures of hydrogen formed during charging,
typically 80 atm pressure. The most common type of these pressure vessels are referred
to as individual pressure vessels (IPV) because each individual cell is contained within its
own pressure vessel. The electrodes in the cell are stacked together as shown in Figs.
1.3.1 and 1.3.3 and are connected in parallel. Therefore the nominal voltage of these
8
individual pressure vessels (Fig. 1.3.2) is only 1.25 V. The IPV cells are then arranged in
series to get the desired voltage. Two commonly used constructions based on the IPV
1.3.2. The electrodes are stacked together in a back to back design as shown in Fig. 1.3.1.
The two nickel hydroxide electrodes are placed back to back. A separator soaked in KOH
solution separates the nickel hydroxide and the negative platinum electrodes. A gas
diffusion screen is positioned on the back of the negative electrodes to facilitate gas
diffusion. A complete stack of electrodes arranged in parallel are shown in Fig. 1.3.2. It is
noted that the bus bars for the positive and the negative electrodes are located along the
outside of the electrode stack. The oxygen evolved during overcharge at the nickel
hydroxide electrode diffuses out at the back of these electrodes and then recombines at
9
Air Force Ni-H2 Cell
The first Air Force nickel-hydrogen cells were based on recirculating electrode
stack design. In these cells, the recombination is carried out in a separate module
containing the hydrogen electrode placed at the end of the stack. The water is then
recirculated back to the electrodes using a wall wick made of zirconium oxide. The newer
Air Force cells utilize the back to back design employed in Comsat cells. The electrode
components in the stack are shaped like a pineapple slice7 as shown in Fig. 1.3.3. A
polysufone central core is used to assemble the cell components. The electrodes are
Figure 1.3.3: Exploded view showing the components of an Air Force cell in stacking
arrangement7.
10
Advanced Cell Configurations
Other advanced battery designs developed to improve the gravimetric and volumetric
energy densities in comparison to the individual pressure vessel cells are (i) common
In the common pressure vessel Ni-H2 battery, the individual cells are connected in
series and are contained within one common pressure vessel. This design results in higher
volumetric energy density and lower manufacturing cost. These batteries were designed
and developed by Comsat and Johnson Controls, Inc. In bipolar Ni-H2 battery, a bipolar
plate contacts two cells in series and were designed and developed at NASA Lewis
companies Wilson Greatbatch and Quallion were investigated as near-term solution for
powering the NNPS. Initial tests were conducted on Sony rechargeable batteries to
establish the conditions for performance testing. The Wilson Greatbatch and Quallion
In order to meet the goal of long cycle life, a low pressure nickel-hydrogen
battery were designed and developed. The metal hydride, palladium treated LaNi4.3Al0.7,
developed by Prof. Payer and his co-workers 9-11, Material Science Department, Case
Western Reserve University will be used as a hydrogen storage module thereby allowing
11
the battery to operate at near atmospheric pressures. The cycle life performance of the
high pressure nickel-hydrogen batteries will be duplicated in our low pressure batteries.
The metal hydride is used only as hydrogen storage device and not as an electrode as in
the case of the nickel-metal hydride batteries. This prevents metal hydride corrosion that
limits the performance of the Ni-MH batteries and is discussed in detail in Chapter 7. The
battery developed will operate at atmospheric pressures with long cycle life.
battery was conceptualized and patented by Dunlop, Martin and Van Ommering12 of
of nickel-metal hydride batteries which uses metal hydride as the negative electrode
However the cycle life of Ni-MH batteries is lower than that of the Ni-H2 batteries
because of the oxide layer formation on the metal hydride and particle pulverization
Recently, Ergenics Inc (HERA USA Inc.) have been developing a low pressure
the assembly as well as the performance of the low pressure nickel-hydrogen battery.
Additionally, the estimation of the state of charge is no longer straightforward for the low
pressure Ni-H2 battery because the pressure change is non-linear in comparison to the
high pressure Ni-H2 battery. The mechanisms like oxygen evolution and the
recombination reaction are critical issues that determine the cycle life of the nickel-
12
hydrogen battery. It is noted that there is no literature available on these aspects for the
The primary objective of this research is to design and develop a low pressure
nickel-hydrogen battery that is safe and has long cycle life. The important goals under
a. The performance and the activation of the platinum electrode from E-tek,
Inc. are discussed in chapter 3. The different current collectors and the
b. Nickel hydroxide electrode from a D size Ni-MH battery was used a guide
electrode components like the binder and the conductive filler content on
2. Assembling single cells and testing them for cycle life. Pressure data were
analyzed to understand the oxygen evolution, the recombination reaction and the
self discharge mechanism of the cell. The coulometric efficiency and the state of
charge of the Ni-H2 cell was predicted by fuel gauging (chapter 6).
3. Incorporating the metal hydride to store hydrogen gas resulting in a low pressure
13
metal hydride deactivation on the cell performance. The hydrogen fuel was
gauged based on the pressure composition isotherm of the metal hydride and was
The development of the nickel-hydrogen cell was the long term solution to powering the
The secondary objective of my dissertation was to maximize the cycle life of the
implantable lithium ion cells – Quallion and Wilson Greatbatch and to choose one of
them as short term solution for powering the NNPS. The performance of these
implantable cells is compared to the Sony lithium ion cells (not implantable grade). The
effect of various factors like depth of discharge, charge cut off voltage, temperature,
charge rate and discharge rate on cycle life were investigated. All of these parameters are
References
14
7. L. H. Thaller and A. H. Zimmerman, Nickel-hydrogen life cycle testing: review
and analysis, Aerospace Press, El Segundo, California, (2003).
15
2. Cycle Life Tests on Lithium Ion Batteries for
Implantable Applications
graphitic carbons as negative electrodes to intercalate the lithium, replacing lithium metal
and overcoming the problems encountered when lithium metal was present. Lithium
deposition 2, shorting and reaction of the electrolyte with metallic lithium resulting in
thermal runaway 3.
The amount of electrical energy, expressed either per unit weight (Wh/kg) or per
unit volume (Wh/l), that a battery is able to deliver is a function of the cell voltage (V)
and capacity (Ah/kg). The volumetric and gravimetric energy densities of different
battery technologies are compared in Fig. 1.2.1. Lithium ion batteries have high cell
voltage (~ 3.5V) and excellent negative electrode capacity (∼ 372 Ah/kg of graphite
mass). Therefore the lithium ion batteries have large gravimetric energy density (~150
Wh/kg) and large volumetric energy density (~300 Wh/l) making it lighter and smaller
compared to other battery technologies. Because of their high energy density and the ease
of minimizing battery size, they are ideal for portable equipment like laptop computers,
digital video cameras, cellular phones and other hand held devices. Li-based batteries
currently account for about 63% of worldwide sales values in portable batteries. Lithium
ion batteries are now being tested for use in aerospace, bio-implantable, and hybrid
16
2.2. Description of Li Ion Cell
A schematic representation of the lithium ion cell is shown in Fig. 2.2.1. The
negative electrode consists of porous graphite connected to a copper current collector and
the positive electrode consists of cobalt oxide or manganese oxide in contact with an
solution containing lithium ions or a polymer electrolyte separates the electrodes. During
Simultaneously, the lithium ions are electrochemically reduced and intercalated into the
Li x − y C 6 + yLi + + ye − → Li x C 6 [2.2]
During the first charging cycle, solution species next to the graphite electrode are reduced
at about 1.5 V versus Li/Li+ to form a film, the “solid electrolyte interface” (SEI) 4, 5,
allowing only lithium ion migration while preventing insertion of electrolyte into the
graphite 6-9. The stability of the SEI film 5 is very important to passivation as it prevents
exfoliation and dendritic growth of lithium. The thickness of this solid electrolyte
interphase film 5 is limited by the tunneling range of the electrons to about 300 nm. The
capacity fade of these batteries upon cycling is due to the impedance buildup of this film
17
Charger
electrons current
SEI
e- Li Li e-
Cu current Al current
collector Li collector
Li
Li
Li e-
e- Li
Figure 2.2.1: Schematic representation of a lithium ion battery during charging. The
separator is impregnated with liquid electrolyte.
Sony, Sanyo, Panasonic and Matsushita. The potential use of lithium ion batteries for
automotive applications has been explored and these batteries are developed by
specialized manufacturers (e.g. Johnson Controls Inc.) for hybrid electric vehicle
applications.
Quallion and Wilson Greatbatch are manufacturers of lithium ion batteries for
were tested and compared in this chapter. The Wilson Greatbatch Cells, (WG) R10398
are prismatic cells and are hermetically sealed in a stainless steel case. The nominal
capacity of the Wilson Greatbatch Cells is 1.4Ah. The Quallion cells, model QL0200I-A,
are also hermetically sealed in a titanium case. Some of the tests were started by Mike
Haugh10 and were continued by the author. Though the Quallion cells were rated at
18
nominal capacity of 200 mAh, Haugh had tested them based on a capacity of 225 mAh.
Therefore the test results for Quallion are based on a capacity of 225 mAh. Table 2.1
compares the weight, volume and capacity of Quallion and Wilson Greatbatch cells. The
gravimetric capacity density of Quallion is twice that of the Wilson Greatbatch indicating
less weight for the same capacity. However, the volumetric capacity density is the same
Table 2.1: Comparison of Quallion and Wilson Greatbatch lithium ion cells
Manufacturer Nominal Weight Volume Capacity Capacity
type capacity (Ah) (g) (cc) density (Ah/kg) density (Ah/cc)
Wilson
1.4 60 22.6 23.33 6.2 x 10-2
Greatbatch
Quallion 0.2 8 3.3 50 6.1 x 10-2
2.4. Objective
1. To identify conditions for increased cycle life. The parameters considered are
the charge rate, the discharge rate, the charge voltage cut-off and the depth of
discharge.
3. To predict the cycle life of the cells based on fitting the experimental data.
The lithium ion battery charging occurs in two stages as shown in Fig. 2.5.1. The
battery is charged first at constant current until the cell voltage reaches the upper limit of
19
4.1 or 4.2 volts, followed by constant voltage charging until the current drops to the
prescribed value provided by the manufacturer. The constant current charging time (stage
1) and constant voltage charging time (stage 2) depend on the charge rate. For typical 1C
rate of charging, the charge time for stage 1 (constant current charging) is about 0.85 h,
by which time about 85 % of the battery is charged. The 2nd stage (constant voltage
charging) takes about 1 h or less and extends the charging time of the batteries. The total
charge time and the choice of constant voltage in stage 2 depend on the chemistry used in
STAGE 1 STAGE 2
Current (A)
1.4
(A)
0
0 tT Time (h)
Cell Voltage (V)
4.2
3.5 (B)
0 tT Time (h)
Capacity (%)
100
85
(C)
0
0 tT Time (h)
Figure 2.5.1: Schematic of DC charge characteristics. During the initial stage (stage 1),
charging is done at a constant current, 1.4 A for Sony cell 18650 (Capacity – 1.4 Ah, 1 C
charge rate) (A) and the voltage is rising (B). tT designates the time at which the voltage
reaches a value of about 4.2 V and the charging mode switches from constant current to
stage 2, where charging continues at constant voltage while the current is continuously
decreasing. About 85 % of the capacity is charged in stage 1 and the rest, 15 %, is
charged in stage 2.
20
2.6. Experimental Design
Lithium ion batteries from three different manufactures Sony, Wilson Greatbatch
LTD., and Quallion were tested. The implantable lithium ion cells Quallion and Wilson
Greatbatch are compared to the standard Sony cell 18650, which is 18 mm in diameter
and 65 mm tall. This cell was used as a reference as it is the most commonly used cell.
The Sony 18650 cells were obtained from Sony NP-F550 battery packs designed for use
in digital cameras. The cells were labeled as 1.5 Ah capacities though in the course of
this research it has been found that the nominal capacity is closer to 1.4Ah. This is fairly
common as the labeled capacities of the cell are typically rated for very slow discharge
currents (around 1/5 of the labeled battery capacity or slower). In this research most of
the discharge currents are much higher than this so the batteries were never able to
The lithium ion cells were tested using an Arbin BT2000 test station. It is a
general purpose testing equipment for battery testing, life cycling, and material research.
The Arbin test station has 20 channels. Each channel is a fully functional
potentiostat/galvanostat and covers very wide current, voltage and power ranges. A
sequence of steps can be written in a program, which is called a schedule, to test the
battery. Current and voltage of the battery is monitored throughout the test.
The implantable batteries, Quallion and Wilson Greatbatch were tested at 37o C to
simulate the human body temperature. A heated bath with silicon oil was used to
maintain the required temperature of the batteries. All the Sony cells were tested at room
temperature except one which was tested at 37o C (in the oil bath) to determine the effect
21
The lithium ion cells were cycled at different charge and discharge conditions and
other variables were held constant. The effect of various variables on cycle life was
studied:
battery’s capacity used during the discharge phase. The DOD is based on the nominal
capacity of the cells and is given in percentages (for example 80% DOD of 1.4Ah cell is
1.12Ah). In addition to the above variables, the effect of temperature (37o C) on the cycle
life of the lithium ion cell was analyzed. The capacity fade data was then fitted to a model
to predict cycle life of the lithium ion cells under a given set of conditions. The Quallion
b. Charge at constant voltage, 4.1V, until the current drops below 4% of the
22
4. Discharge at constant current. The discharge is terminated based on a depth of
The effect of different charge rates on the capacity fade (capacity degradation) of
Sony lithium ion 18650 cells with cycling was monitored and studied. Three Sony
lithium ion cells (denoted as Cells 1, 2, 3) were cycled at C charge and C discharge rate
and one Sony lithium ion cell was cycled at C/5 charge and C discharge rate (denoted as
Cell 4) as listed in Table 2.2. All other parameters were held constant (Table 2.2).
of cycle number is shown in Fig. 2.6.1. The discharge capacity of this cell averaged over
the first 5 cycles is 1.44 Ah and is in agreement with the manufacture’s rated capacity of
1.5 Ah. The discharge capacity of the lithium ion cell decreases with cycling and this
phenomenon is commonly referred as the capacity fade. The capacity fade is rapid for the
first 180 cycles and then slows down considerably. It is noted that the data points are
scattered in the cycle number range of 1-100. These scattered points were caused by
instrumentation error and are due to a mis-configured setting in the Arbin unit causing
cross talk between the channels. This cross talk occasionally caused early termination of
tests. Therefore a charge or a discharge step was stopped before completion leading to
either a higher or a lower value recording of discharge capacity. Data point for every
cycle is shown in Fig.2.6.1. In all the following figures, only one data point for every 10
23
Table 2.2: Description of Sony lithium ion cells subjected to different test conditions.
Cell No. Charge Discharge Charge voltage Temperature Depth of
rate rate cutoff, V discharge, %
Cell 1 C C 4.1 RT 100
Cell 2 C C 4.1 RT 100
Cell 3 C C 4.1 RT 100
Cell 4 C/5 C 4.1 RT 100
Cell 5 C C/5 4.1 RT 100
Cell 6 C 2W 4.1 RT 100
Cell 7 C 2W 4.2 RT 100
Cell 8 C C 4.1 RT 80
Cell 9 C C 4.1 37o C 80
1.6
Discharge capacity (Ah)
1.5
1.4
1.3
1.2
1.1
1.0
0 500 1000 1500 2000
Cycle index
Figure 2.6.1: Discharge capacity as a function of cycle index for Sony Li ion cell 1. The
cell loses discharge capacity with cycles. The cell was charged and discharged at C rate.
The scattered points in the cycle number range 1-100 is due to instrumentation error and
does not reflect the battery’s discharge capacity.
24
1.5
1.3
1.2
1.1
1.0
0 500 1000 1500 2000
Cycle index
Figure 2.6.2: Discharge capacity as a function of cycle index for Sony lithium ion cell 1
fitted to a straight line. The linear fit is poor for discharge capacity in the cycle number
range 1-200. The capacity loss is 1.5x10-4 Ah/cycle. The cell was charged and discharged
at C rate.
In order to compare the test results of the lithium ion cells subjected to different
previous work at Case Western Reserve University by Haugh 10, linear fits were used to
model the capacity fade data. A linear fit to the discharge capacity data following
Haugh’s work is shown in Fig.2.6.2. The equation of the straight line fitted is
parameter ‘a’ is the estimated initial discharge capacity and parameter ‘b’ is the estimated
capacity loss per cycle. It is evident from Fig. 2.6.2 that the fit is poor for cycle numbers
in the range 1 to 200 where the capacity fade rate is high. Additionally the initial
discharge capacity, ‘a’ estimated by the linear fit is 1.38 mAh and is less than the nominal
capacity of the lithium ion cell. The capacity loss per cycle, ‘b’ is 1.5x10-4 Ah/cycle.
25
A linear fit of the capacity data over the first 200 cycles is shown in Fig. 2.6.3.
The estimated capacity loss per cycle is 4x10-4 Ah and is 2.7 times larger than that
predicted by the linear fit over the entire cycle number range. Based on the capacity loss
estimated, the linear fit model predicts the cell will reach 80% of its capacity (1.12 Ah) in
about 775 cycles. In comparison, the experimental data (Fig. 2.6.1) shows that the cell
reaches 80% of its capacity (1.12 Ah) in 1735 cycles. This suggests that a linear fit does
not predict the cycle life of the lithium ion cells accurately.
1.6
Discharge capacity (Ah)
1.4
1.3
1.2
Figure 2.6.3: Discharge capacity as a function of cycle index for Sony Li ion cell 1 fitted
to a straight line for the first 200 cycles. The estimated capacity loss per cycle is 4x10-4
Ah. The cell was charged and discharged at C rate.
The capacity fade of lithium ion batteries has been studied by numerous
researchers11-39. Most of the studies were focused on estimating cycle life of these
batteries. Spotnitz 12 has reviewed the different experimental studies on cycle life. The
capacity fade and the ageing of these batteries have also been modeled12-14, 23, 28, 33.
26
The capacity fade with cycles is non-linear and a model to explain the non-linear
behavior was proposed by Broussely et al19. They attributed the capacity loss to the
growth of solid electrolyte interphase film (SEI) on the electrodes. The model shows that
the capacity loss varies with the square root of float time (idle or shelf time). This
capacity loss relates to the calendar life of the battery, i.e., degradation of battery in
storage. Inoue et al.25 showed that the capacity loss due to cycling is linear. However, no
attempt is made to separate the capacity losses due to the cycle life and the calendar life.
A nonlinear equation which describes the discharge capacity variation with the square
root of cycle number was fit to the experimental data as shown in Fig. 2.6.4. The equation
degradation constant. The equation fits the experimental data well with R2 (correlation
coefficient) value of 0.95. The estimated initial capacity, k1 is about 1.47 Ah and the
of k1 and k2 are small and are listed in Table 2.3. The capacity fade data for cells 2 and 3
(C charge and C discharge) with their non-linear fits are shown in Figs. 2.6.5 and 2.6.6.
The fitted parameters k1 and k2 are listed in Table 2.3. The estimated discharge capacity,
k1, and the degradation constant, k2 are similar for the cells 1, 2 and 3 that were tested in
the same conditions. The degradation constant, k2, for the cells are within 3% of the
average value.
27
1.5
1.3
1.2
1.1
1.0
0 500 1000 1500 2000
Cycle index
Figure 2.6.4: Discharge capacity as a function of cycles for Sony Li ion cell 1 fitted to a
non-linear curve. The parameters k1 and k2 are 1.47 Ah and 8x10-3 Ah / cycle . The cell
was charged and discharged at C rate.
Discharge capacity (Ah)
1.5
-3 0.5
Cd = 1.47 -7.22x10 (cycle)
1.4
1.3
1.2
1.1
Figure 2.6.5: Discharge capacity as a function of cycles for Sony Li ion cell 2 fitted to a
non-linear curve. The parameters k1 and k2 are 1.47 Ah and 7.2x10-3 Ah / cycle . The cell
was charged and discharged at C rate.
28
1.5
1.2
1.1
Figure 2.6.6: Discharge capacity as a function of cycles for Sony Li ion cell 3 fitted to a
non-linear curve. The parameters k1 and k2 are 1.48 Ah and 8.1x10-3 Ah / cycle . The cell
was charged and discharged at C rate.
Discharge Capacity (Ah)
1.50 -3 0.5
Cd = 1.5 -5.21x10 (cycle)
1.45
1.40
1.35
1.30
1.25
Figure 2.6.7: Discharge capacity as a function of cycles for Sony Li ion cell 4 fitted to a
non-linear curve. The parameters k1 and k2 are 1.5 Ah and 5.2x10-3 Ah / cycle . The cell
was charged at C/5 rate and discharged at C rate.
29
Table 2.3: Comparison of parameters and errors estimated by fitting the discharge
capacity as a function of cycle life to equation Cd = k1 + k2 cycle for C and C/5 rate
of charging.
Cell No. Charge rate k1, Ah Error in k1 k2 Ah / cycle Error in k2 R2
Cell 1 C 1.47 1.30x10-3 -8.02x10-3 4x10-5 0.95
Cell 2 C 1.47 1.28x10-3 -7.22x10-3 4x10-5 0.94
Cell 3 C 1.48 1.41x10-3 -8.13x10-3 5x10-5 0.94
Cell 4 C/5 1.50 0.97x10-4 -5.21x10-3 5x10-5 0.94
The discharge capacity degradation of the lithium ion cell charged at C/5 rate and
discharged at C rate (cell 4) with cycling is shown in Fig. 2.6.7. The data was fitted using
the non-linear equation Cd = k1 + k2 N 0.5 and the fitted parameters are listed in Table 2.3.
The degradation constant k2 for this cell (charged at C/5 rate) is 5.21x10-3 and is smaller
in comparison to that obtained for the cells 1, 2 and 3 charged at C rate indicating that the
capacity fade is smaller when charged at C/5 rate. The discharge capacity of Cell 1 (C
charge rate) and Cell 4 (C/5 charge rate) with cycling are compared in Fig. 2.6.8. At 1500
cycles, the lithium ion cell cycled at C charge has lost about 17.9% of its capacity and the
lithium ion cell cycled at C/5 charge has lost only about 7.6% of its capacity. This clearly
shows that the cycle life of lithium ion cell charged at C/5 rate is longer than that
charged at C rate.
The energy efficiency of cell 1 (charged at C rate) and cell 4 (charged at C/5 rate)
are compared in Fig. 2.6.9. The energy efficiency is defined as the ratio of the discharge
energy to the charge energy. It is evident from the figure that the efficiency for the C/5
rate is larger than that of the C rate for all cycles. The difference in the energy efficiency
increases with cycling. In the first few cycles the difference primarily results from the C
rate charging (1.4 A) of cell 1 which results in large energy consumption and C/5 rate
charging (0.28 A) of cell 4 which results in small energy consumption. This results in
30
lower energy efficiency for the cell 1. However as the cells are cycled, the capacity fade
of the cells are different. The capacity fade is larger for the C rate ‘cell 1’ and smaller for
the C/5 rate ‘cell 4’ as discussed earlier. This explains the increase in the difference of the
1.5
Discharge capacity (Ah)
C
C/5
1.4 -3
Cd = 1.5 -5.21x10 (cycle)
0.5
1.3
1.2
-3 0.5
Cd = 1.47 -8.02x10 (cycle)
1.1
Figure 2.6.8: Discharge capacity as a function of cycles comparing Sony Li ion cells 1
and 4. The capacity fade data is fitted to a non-linear curve. Cell 1 was charged at C rate
and Cell 4 was charged at C/5 rate. The degradation constant is smaller for the lithium
ion cell with C/5 charge in comparison to the lithium ion cell with C charge.
31
100
Energy efficiency, %
C
95 C/5
90
85
80
75
0 500 1000 1500 2000
Cycle Index
Figure 2.6.9: Energy efficiency as a function of cycles comparing Sony Li ion cells 1
and 4. Cell 1 was charged at C rate and Cell 4 was charged at C/5 rate. The energy
efficiency of Cell 1 is always smaller than that of the Cell 4.
Three Sony lithium ion cells cycled at C rate charge and C discharge (cells 1, 2
and 3) discussed in the previous section will be compared with Sony lithium ion cells
cycled at C/5 (cell 5) and 2W (cell 6) discharge rates. The 2W discharge is roughly
equivalent to C/2.53 discharge rate. The other relevant parameters were fixed and are
Lithium ion cells cycled at C rate charge and C rate discharge were fitted using a
non-linear equation and two fit parameters were estimated (section 2.6.1). The parameters
k1 and k2 averaged over the three lithium ion cell tests are 1.47 Ah and 7.8x10-3 Ah cycle-
0.5
respectively. The lithium ion cells cycled at C/5 and 2W discharge are shown in Figs.
2.6.10 and 2.6.11, respectively. These cells were tested by Michael Haugh and were
stopped after about 300 cycles. The initial discharge capacity of the cells tested at C/5
and 2W discharge rate (over the first few cycles) was about 1.34 Ah and 1.37 Ah
32
respectively. In comparison the initial discharge capacity of cells tested at C rate
discharge (cells 1, 2 and 3) was about 1.44 Ah. This drastic decrease in the initial
capacity before cycling is related to the calendar life of the cells. The lithium ion cells
tested at C rate discharge were fresh and hence their capacity fade (before cycling) is low.
However, the lithium ion cells tested at C/5 and 2W discharge rates were old and hence
their capacity fade (before cycling) was significant. This clearly illustrates the calendar
life issues of Sony 18650 batteries. It is noted here that the exact floating time (idle time)
of these batteries is not known and therefore only qualitative comparisons can be made.
The differences in these lithium ion cells are clearly illustrated in Fig.2.6.12.
The discharge capacity data of the cells cycled at C/5 and 2W discharge rates was
fitted to a non-linear equation Cd = k1 + k2 N 0.5 (Figs. 2.6.10 and 2.6.11). The fitted
parameter k2 for lithium ion cells discharged at C/5 and 2W rate is 1.1x10-2 and 1.36 x10-
2
Ah / cycle , respectively and is larger that that of the C rate discharge (7.8x10-3
Ah / cycle ). This indicates that the cells with long idle time undergo larger capacity
degradation during cycling and illustrates the effect of calendar life on the capacity fade
The energy efficiency of lithium ion cells discharged at C and C/5 rate is
compared in Fig. 2.6.13. The energy efficiency of the cell discharged at C rate is higher
compared to the cell discharged at the C/5 rate for the first 50 cycles and is due to
calendar life effect on these cells. However, in spite of poor calendar life, the cell cycled
at C/5 discharge rate has better energy efficiency in the range from 50 to 350 cycles. This
indicates that cycling at C/5 discharge rate results in higher energy efficiency than
33
1.40
1.30
1.25
1.20
1.15
0 100 200 300 400
Cycle index
Figure 2.6.10: Discharge capacity as a function of cycles for Sony Li ion cell cycled at C
charge rate and C/5 discharge rate fitted to a non-linear curve. The parameters k1 and k2
are 1.38 Ah and 1.1x10-2 Ah / cycle .
1.40
Discharge capacity (Ah)
-2 0.5
1.35 Cd,Ah = 1.4 - 1.36x10 (cycle)
1.30
1.25
1.20
1.15
1.10
0 100 200 300 400
Cycle index
Figure 2.6.11: Discharge capacity as a function of cycles for Sony Li ion cell cycled at C
charge rate and 2W discharge rate fitted to a non-linear curve. The parameters k1 and k2
are 1.38 Ah and 1.36x10-2 Ah / cycle .
34
1.5
1.3
1.2
1.1
0 100 200 300 400
Cycle index
Figure 2.6.12: Discharge capacity as a function of cycles comparing lithium ion cells
cycled at different discharge rates. The degradation constant, k2, is larger for the lithium
ion cell with C/5 discharge in comparison to the lithium ion cell with C discharge.
91
C
Wh efficiency (%)
90 C/5
89
88
87
86
0 100 200 300 400
Cycle index
Figure 2.6.13: Energy efficiency as a function of cycles comparing lithium ion cells
subjected to C and C/5 rate of discharge.
35
2.6.3. Effect of Charge Voltage Cutoff on Cycle Life Performance
In this section, two lithium ion cells cycled at C rate charge and 2W discharge are
considered. The depth of discharge was 100%. The cells were tested at room temperature
(25o C). One lithium ion cell was charged at 4.1V (Cell 6, Table 2.2) and the other
lithium ion cell was charged at 4.2 V (Cell 7, Table 2.2) following the constant current
charge phase. The objective of these two tests was to study the effect of different charge
The discharge capacity of the lithium ion cell with 4.1 voltage cut off is shown in
Fig. 2.6.11 and was discussed in detail in the previous section. The conclusion was that
the lithium ion cell tested was an old cell with capacity loss due to idling. The fitted
The discharge capacity of the cell with 4.2 voltage cutoff is shown in Fig. 2.6.14.
The discharge capacity of this cell (4.2 voltage cutoff) for cycle 1 is 1.63 Ah and in
comparison the discharge capacity of fresh cells (Cells 1, 2 and 3) charged at 4.1 voltage
cutoff is 1.44 Ah. This indicates that the constant voltage charging at 4.2 V after the
constant current charging results in higher charge and discharge capacity, although the
charging is stopped when current drops below 4% of the rated current at C rate similar to
other lithium ion cell tests. The discharge capacity profile (Fig. 2.6.14) shows two
different fades, one in the cycle number range 1-350 and the other in cycle number range
500 to 1200. The capacity fade in the cycle number range 1-350 was fit using the non-
linear equation Cd = k1 + k2 N 0.5 as shown in Fig. 2.6.14. This indicates that the capacity
fade decays to the square root of cycle number and supports the mechanism of SEI
growth as the main contributor to capacity fade. The discharge capacity decreases rapidly
36
from 1.37 Ah at 400 cycles to 0.33 Ah at 1700 cycles. The average capacity loss in this
This test illustrates that charging the Sony lithium ion cell with 4.2V charge cutoff
(C rate charge, 2W ≈ C/2.5 rate discharge) causes rapid capacity fade after 400 cycles. In
comparison, Sony lithium ion cells with 4.1 V cutoff (C rate charge, C rate discharge)
results in long cycle life (1.08 Ah at 1923 cycles). This shows that the charge voltage
cutoff should be 4.1 V rather than 4.2 V for good cycle life performance.
-2 0.5
Cd,Ah = 1.66 - 1.25x10 (cycle)
Discharge capacity (Ah)
1.6
1.2
0.8
0.4
0.0
0 200 400 600 800 1000 1200
Cycle index
Figure 2.6.14: Discharge capacity as a function of cycles for Sony Li ion cell cycled at C
charge rate with 4.2 voltage cut off and 2W discharge rate. The parameters k1 and k2 are
1.66 Ah and 1.25x10-2 Ah / cycle for the first 350 cycles.
Three Sony lithium ion cells (Cell 1, Cell 2 and Cell 3) cycled to 100% DOD and
two lithium ion cells (Cell 8, Cell 9) cycled to 80% DOD as listed in Table 2.2 are
37
compared in this section. Cell 9 was cycled at 37o C and other cells were cycled at room
In order to make a fair comparison of the different DOD tests, the cycle life of the
lithium ion cells cycled to 100% DOD was determined when the discharge capacity
dropped to 80% of the nominal capacity. For the 80% DOD lithium ion cells, the cycle
life was determined when the end of discharge voltage reached 2.75 V. The cycle life of
the cells cycled to different depths of discharge is shown in Fig. 2.6.15. The lithium ion
cell cycled to 80% DOD (Cell 8) has a longer cycle life than that of the lithium ion cells
cycled at 100% DOD. The cell cycled at room temperature (Cell 8) has a longer cycle life
than the cell cycled at 37o C. This result is discussed in more detail in the subsequent
section.
DOD and 80% DOD on the basis of cycle life. For the same number of cycles and same
charge and discharge rates, the total hours discharged by the 100% DOD lithium ion cell,
is more than that of the total hours discharged by the 80% DOD lithium ion cell. Taking
this into consideration, the total ampere hours discharged by the cells was calculated and
is shown in Fig. 2.6.16. The total ampere-hours for the 80% DOD is larger than that of
the 100% DOD. This shows that discharging the cell to 80% of its capacity (80% DOD)
not only enhances cycle life but also increases the total ampere-hours obtained in
comparison to discharging the cell to 100% of its capacity (100% DOD). It is also
evident that the total ampere-hours obtained for the cell cycled at 37o C is less than that
38
3500
3000
2500
Cycles
2000
1500
1000
500
0
100%, Cell 1 100%, Cell 2 100%, Cell 3 80%, Cell 8 80% Cell 9,
37 C
Depth of discharge (%)
Figure 2.6.15: Total number of cycles obtained for Sony lithium ion cells cycled to
different states of depth of discharge.
4000
3500
Total ampere-hours
3000
2500
2000
1500
1000
500
0
100%, Cell 1 100%, Cell 2 100%, Cell 3 80%, Cell 8 80% Cell 9,
37 C
Depth of discharge (%)
Figure 2.6.16: Total number of ampere-hours obtained for Sony lithium ion cells cycled
to different states of depth of discharge.
39
2.6.4.2. Wilson Greatbatch Lithium Ion Cells at 80 and 60% DOD
Wilson Greatbatch cells cycled to 80% and 60% DOD are compared here. The
cells were charged and discharged at C rate. The voltage cutoff during charge and
discharge was 4.1 and 2.75 V respectively. All the Wilson Greatbatch cells were tested at
37o C.
Cycle life of three cells tested to 80% DOD and one cell tested to 60% DOD is
shown in Fig. 2.6.17. The total number of cycles was determined when the end of
discharge voltage reached 2.75 V. The 60% DOD lithium ion cells have an order of
magnitude higher cycle life than the 80% DOD lithium ion cells.
These tests show that cycle life can be significantly increased by discharging the
1600
1400
1200
Total cycles
1000
800
600
400
200
0
80%, Cell 1 80%, Cell 2 80%, Cell 3 60%, Cell 1
Figure 2.6.17: Total number of cycles obtained for Wilson Greatbatch lithium ion cells
cycled to 80 and 60% of depth of discharge.
40
2.6.5. Effect of Temperature on Cycle Life Performance
Sony lithium ion cells were cycled at two different temperatures, one cell (Cell 8)
at room temperature and another cell (Cell 9) at 37o C. These cells were charged and
discharged at C rate with 4.1 V charge cutoff and 2.75 V discharge cutoff. They were
discharged to 80% of their nominal capacity (80% DOD) every cycle. Figs. 2.6.15 and
2.6.16 show that the total cycles and the total-ampere hours obtained at 37o C is less than
is shown in Fig. 2.6.18. The cycle life at 37o C is smaller than that at the room
temperature. The data for different temperatures was fitted linearly as shown in Fig.
2.6.18. The slope of the lines fitted to data at the room temperature and 37o C are 2.4x10-4
and 2.6x10-4, respectively. These values are not significantly different. The end of
discharge voltage for the first 175 cycles is shown in Fig.2.6.19. The end of discharge
voltage decreased rapidly in the first 50 cycles for the cell tested at 37o C and in
comparison the end of discharge voltage decreases linearly for the cell tested at room
temperature.
The data points for the cell tested at RT is scattered and therefore a much cleaner
data set would be required to compare the two cells based on their linear fits.
41
3.6
RT
Linear fit (RT)
37 C
3.4 Linear fit (37 C)
-4
EODV = 3.55 -2.4x10 N
EODV (V)
3.2
3.0
-4
EODV = 3.49 -2.6x10 N
2.8
2.6
0 1000 2000 3000
Cycle index, N
Figure 2.6.18: End of discharge voltage as a function of cycles comparing Sony Li ion
cell cycled at room temperature and 37o C. The cells were charged and discharged at C
rate to 80% DOD. The data was fitted to a straight line.
3.54
RT
3.52 37 C
3.50
EODV (V)
3.48
3.46
3.44
3.42
0 50 100 150 200
Cycle index
Figure 2.6.19: End of discharge voltage in the cycle number range 0-175 comparing
Sony Li ion cell cycled at room temperature and 37o C. The cells were charged and
discharged at C rate to 80% DOD.
42
2.6.6. Comparison of Sony, Wilson Greatbatch and Quallion
Quallion were investigated at C/5 charge rate and C discharge rate. The charge and
discharge voltage cutoff are 4.1 and 2.75 V, respectively. The Sony lithium ion cell was
cycled at room temperature, however, the Wilson Greatbatch and Quallion cells were
cycled 37o C simulating human body temperature. The cells were discharged completely
(100% DOD). The discharge capacity of all the cells was fitted to the non-linear
equation Cd = k1 + k2 N 0.5 .
The discharge capacity fade as a function of cycle index for the Sony lithium ion
cell (cell 4) was discussed in section 2.6.1 and is shown in Fig. 2.6.7. The initial
discharge capacity of the cell is about 1.46 Ah. The non-linear fit parameters are listed in
Table 2.4. The discharge capacity degradation of the Wilson Greatbatch cell is shown in
Fig. 2.6.20. The discharge capacity of cycle 1 is 1.37 Ah. The discharge capacity data in
the cycle number range 1-500 was fit to the non-linear equation. The fit parameters (k1,
k2) are listed in Table 2.4. This fit reinforces the SEI growth mechanism as the primary
factor contributing to capacity loss with cycling. The error in the fit parameters k1 and k2
is small. The discharge capacity drops rapidly after 500 cycles and only 47% capacity
remains at 600 cycles. This suggests a different mechanism for capacity loss after 500
The capacity fade of the Quallion cell on cycling is shown in Fig. 2.6.21. The
discharge capacity for the 1st cycle is 0.197 Ah. The capacity fade was fitted to the non-
linear equation for all cycles and the fit parameters are listed in Table 2.4. The correlation
fits the data well and the error in the fit parameters is small.
43
The number of cycles obtained for the lithium ion cells of different manufacturers
at 10% capacity loss was determined and is shown in Fig. 2.6.22. The total capacity loss
for the Sony cell was only 10% over the 1600 cycles tested and therefore the 10%
capacity loss was used as the criteria to compare cells of different manufacturers. For the
Sony and Wilson Greatbatch battery a 10% capacity loss corresponds to 0.14 Ah and for
the Quallion battery a 10% capacity loss corresponds to 22.5 mAh. The cycles obtained
from the Sony cell (2122 cycles) were an order of magnitude higher than that obtained
from the Wilson Greatbatch (28 cycles) and Quallion cells (99 cycles).
The number of cycles obtained for Wilson Greatbatch and Quallion cells at 10, 20
and 30% losses in capacity are compared in Fig.2.6.23. It is evident that the Quallion
cells provide more cycles than that of Wilson Greatbatch cells at different losses in
capacity. The difference in the cycles provided by Quallion and Wilson Greatbatch cells
The performance of these different cells is described by the fit parameter, k2. This
degradation constant, k2, for different lithium ion cell manufacturers is shown in Fig.
2.6.24 and is listed in Table 2.4. It is evident that the degradation constant is an order of
magnitude smaller for Sony and Quallion than that of Wilson Greatbatch. However the fit
parameters are based on different nominal capacities of the lithium ion cell. The nominal
capacity of the Quallion cell is 0.225 Ah and is smaller than that of the Sony and Wilson
Greatbatch (1.4 Ah). Hence, the degradation constant, k2, was normalized by dividing
with the nominal capacity of the lithium ion cells. The normalized degradation constant is
the smallest for Sony, followed by the Quallion and the Wilson Greatbatch as shown in
44
Fig.2.6.24. This agrees well with the cycle life prediction: Sony > Quallion > Wilson
Greatbatch.
1.4
Discharge capacity (Ah)
-2 0.5
EODV = 1.4 - 2.7x10 (cycle)
1.2
1.0
0.8
0.6
0 100 200 300 400 500 600 700
Cycle index
Figure 2.6.20: Discharge capacity as a function of cycles for Wilson Greatbatch Li ion
cell 4 fitted to a non-linear curve. The parameters k1 and k2 are 1.4 Ah and 2.7x10-
2
Ah / cycle for a fit to the first 500 cycles. The cell was charged at C/5 rate and
discharged at C rate.
Discharge Capacity (Ah)
0.20
-3 0.5
EODV = 0.2 - 1.5x10 (cycle)
0.18
0.16
0.14
0.12
Figure 2.6.21: Discharge capacity as a function of cycles for Quallion Li ion cell 4 fitted
to a non-linear curve. The parameters k1 and k2 are 0.2 Ah and 2.7x10-3 Ah / cycle . The
cell was charged at C/5 rate and discharged at C rate.
45
Table 2.4: Comparison of parameters and errors estimated by fitting the discharge
capacity as a function of cycle life to equation Cd = k1 + k2 cycle for lithium ion cells
of different manufacturers charged at C/5 rate and discharged at C rate.
Manufacturer k1, Ah Error in k1 k2 Ah / cycle Error in k2 R2
Sony 1.5 9.7x10-4 -5.2x10-3 3x10-5 0.94
Wilson Greatbatch 1.4 1.5x10-3 -2.7x10-2 9x10-5 0.99
Quallion 0.2 1.0x10-4 -1.5x10-3 2.7x10-6 0.99
2500
10% Capacity Loss
2000
1500
Cycles
1000
500
0
Sony WG Quallion
Manufacturer type
Figure 2.6.22: Number of cycles obtained at 10% capacity loss for different lithium ion
cell manufacturers Sony, Wilson Greatbatch and Quallion. The cells were cycled at C/5
charge rate and C discharge rate to 100% DOD.
46
1800
WG
Quallion
1500
1200
Cycles
900
600
300
0
10 20 30
Loss in capacity (%)
Figure 2.6.23: Number of cycles obtained at 10, 20 and 30% capacity loss for Wilson
Greatbatch and Quallion lithium ion cells. The cells were cycled at C/5 charge rate and C
discharge rate to 100% DOD at 37o C.
3.0E-02
Rate constant
Normalized rate constant
2.5E-02
-0.5
2.0E-02
k2 (cycle)
1.5E-02
1.0E-02
5.0E-03
0.0E+00
Sony WG Quallion
Manufacturer type
Figure 2.6.24: The degradation constant, k2, for different lithium ion cell manufacturers
Sony, Wilson Greatbatch and Quallion. The normalized rate constants were obtained by
ratioing the rate constant to the cell’s nominal capacity. The cells were cycled at C/5
charge rate and C discharge rate to 100% DOD.
47
2.6.7. Comparison of Sony and WG at 80% DOD
Two Sony lithium ion cells and three Wilson Greatbatch cells were charged and
discharged at C rates to 80% of their capacity (80% DOD) and are compared in this
section. The charge and discharge cutoff voltages were 4.1 and 2.75 V respectively. Of
the two lithium ion cells, one was cycled at room temperature and the other at 37o C. Fig.
2.6.25 compares the total number of cycles obtained from the Sony and Wilson
Greatbatch cells before the end of discharge voltage reached the cutoff value of 2.75 V.
3500
80% DOD
3000
2500
Total cycles
2000
1500
1000
500
0
Sony cell 1 Sony cell 2, WG cell 1 WG Cell 2 WG Cell 3
37 C
Manufacturer type
Figure 2.6.25: Total number of cycles obtained for Sony and Wilson Greatbatch lithium
ion cells cycled to 80 % of depth of discharge at C rate charge/ C rate discharge.
48
2.7. Comparison of Implantable battery technologies
In this section, the cycle life performances of the WG and Quallion batteries are
compared.
A WG cell and a Quallion cell were cycled at C rate charge and C rate discharge.
The voltage cutoff during charge and discharge were 4.1 and 2.75 V respectively. The
cells were cycled to 60% DOD and were tested at 37o C, simulating body temperature.
The end of discharge voltage of the WG cell with cycling is shown in Fig.2.7.1.
The end of discharge voltage decreases with cycles linearly up to 1200 cycles and then
drops sharply. The linear part of the data was fitted to a straight line, EODV = Vo + mN ,
where EODV and N are the end of discharge voltage and cycle number, respectively. Vo
is the end of discharge voltage when N is zero and ‘m’ is the voltage drop per cycle. For
the WG cell, the voltage drop per cycle, m, is 3.6x10-3 V/cycle and Vo is 3.56 V.
In comparison, the end of discharge voltage of the Quallion cell cycled in the
same conditions is shown in Fig. 2.7.2. Two linear trends in the end of discharge voltage,
one in the cycle number range 1-3500 and another in the cycle number range 4000-6000
cycles are observed. These two linear trends were fitted to straight lines and the fitted
parameters are listed in Table 2.12. According to the linear fit in the cycle number range
1-3500, the voltage drop per cycle, m, is 6x10-5 V/cycle and Vo is 3.32 V (Table 2.5). For
the linear fit in the cycle number range 4000-6000, the voltage drop per cycle is 1.6x10-4
V/cycle and Vo is 3.75 V. The voltage drop per cycle in the cycle number range 4000-
6000 is an order of magnitude higher than the voltage drop per cycle in the cycle number
49
range 1-3500. This indicates that the voltage drop shifts to a higher rate after a large
number of cycles. In comparison, the voltage drop per cycle of the WG cell is two orders
of magnitude higher when compared with the voltage drop per cycle of the Quallion cell
in the same cycle number range (Table 2.5). This clearly indicates the superior
performance of the Quallion cell at 60% DOD. The cycle life of the Quallion cell is about
four times that of the Wilson Greatbatch cell at 60% DOD (Table 2.5).
The fit parameter, Vo, for the WG and Quallion lithium ion cell is 3.55 and 3.32
V. The difference of this value is 0.23 V. The high frequency resistance (solution
resistance) of the WG cell is about 0.12 ohms, whereas the high frequency resistance of
the Quallion cell is about 1 ohm. Therefore at C rate, the ohmic voltage drop of the WG
cell is 1.4 A x 0.12 Ω = 0.168 V and the ohmic voltage drop of the Quallion cell is 0.225
0.057 V which is considerably smaller than the difference in the Vo value of the two cells
and does not explain the difference in the end of discharge voltage. This suggests that the
value Vo of the two cells is related to the chemistry of the different lithium ion cells.
50
3.6 EODV = 3.56 -3.6x10 N
-3
3.4
EODV (V)
3.2
3.0
2.8
0 300 600 900 1200 1500
Cycle index
Figure 2.7.1: End of discharge voltage as a function of cycles for WG Li ion cell tested
at 37o C. The cells were charged and discharged at C rate to 60% DOD. The data was
fitted to a straight line over cycles 1 to 1200.
-5
EODV = 3.32 - 6x10 N
3.4
EODV (V)
3.2
3.0
-4
2.8 EODV = 3.75 - 1.6x10 N
Figure 2.7.2: End of discharge voltage as a function of cycles for Quallion Li ion cell
tested at 37o C. The cells were charged and discharged at C rate to 60% DOD. The data
was fitted to two straight lines.
51
Table 2.5: Linear fit parameters and their error estimations of the end of discharge
voltage data. Wilson Greatbatch and Quallion lithium ion cells were charged and
discharged at C rate to 60% DOD.
Total cycles
Manufacturer Vo, V Error in Vo m, V/s Error in m R2 to EODV = 2.8V
Wilson Greatbatch 3.56 5.4x10-3 -3.6x10-3 7.8x10-7 0.99 ~1500
Quallion, 1-3500 cycles 3.32 3.9x10-4 -6x10-5 1.9x10-7 0.96
~6000
Quallion, 4000-6000 cycles 3.75 2.8x10-3 -1.6x10-4 5.6x10-7 0.97
The cycle life of Wilson Greatbatch and Quallion lithium ion cell at 100% DOD
was tested using the Arbin test stand. The cells were cycled at C/5 charge and C
discharge rates. The results of these two cells was analyzed and discussed in section
2.6.6. It was shown that the cycle life of Quallion cell was longer than that of the WG cell
In this section, implantable lithium ion cells cycled at low charge and discharge
rates (C/4, C/5) are compared and its effect on cycle life is analyzed. Two Wilson
Greatbatch cells were cycled at C/5 charge and discharge rate to 60% depth of discharge.
One Quallion cell was cycled at C/4 charge and discharge rate to 80% depth of discharge.
The charge and discharge cutoff voltage was set at 4.1 and 2.75 V respectively. All the
The end of discharge voltage for the WG cell is shown in Fig. 2.7.3. The data was
fitted to the equation EODV = Vo + mN . The voltage drop per cycle, m, is 8x10-5 V/cycle.
The voltage drop for another WG cell tested at the same conditions is 7x10-5 V/cycle and
is listed in Table 2.6. The Vo values for these two WG cells are 3.71 and 3.72 V
respectively.
52
The end of discharge voltage variation for a Quallion cell charged and discharged
at C/4 rate to 80% DOD is shown in Fig. 2.7.4. The data was fitted the equation
EODV = Vo + mN and the voltage drop per cycle, m, is 9x10-5 V/cycle (Table 2.6). This
voltage drop per cycle for the Quallion cell at C/4 rate to 80% DOD is about the same as
the voltage drop per cycle for the WG cell at C/5 rate to 60% DOD. Although the
Quallion cell was discharged deeper and at a higher rate than that of the WG cell the
voltage loss per cycle is the same. This again reinforces the superior performance of the
Quallion cells.
3.8
-5
EODV = 3.71 - 8x10 (cycle)
3.7
EODV (V)
3.6
3.5
3.4
0 500 1000 1500 2000 2500 3000
Cycle index
Figure 2.7.3: End of discharge voltage as a function of cycles for WG Li ion cell tested
at 37o C. The cells were charged and discharged at C/5 rate to 60% DOD. The data was
fitted to a straight line.
53
3.40
-5
EODV (V) EODV = 3.39 - 9x10 (cycle)
3.35
3.30
3.25
0 300 600 900 1200
Cycle index
Figure 2.7.4: End of discharge voltage as a function of cycles for Quallion Li ion cell
tested at 37o C. The cells were charged and discharged at C/4 rate to 80% DOD. The data
was fitted to a straight line.
Table 2.6: Linear fit parameters and their error estimations of the end of discharge
voltage data. Wilson Greatbatch and Quallion lithium ion cells were charged and
discharged at C/5 and C/4 rate, respectively.
Manufacturer Vo, V Error in Vo m, V/s Error in m R2
Wilson Greatbatch, Cell 1, C/5, 60% DOD 3.71 6.1x10-4 -8x10-5 3.9x10-7 0.94
-4 -5
Wilson Greatbatch, Cell 2, C/5, 60% DOD 3.72 3.4x10 -7x10 2.2x10-7 0.98
Quallion, C/4, 80% DOD 3.39 2.8x10-4 -9x10-5 3.8x10-7 0.98
2.8. Comparison of Charge Times for New and Used Quallion cells
The discussions of the previous section concluded that the Quallion cells are
superior to the Wilson Greatbatch cells. In this section, the charge times of new Quallion
cells to used Quallion cells are compared. A substantial increase in the charge time can be
considered as a mode of failure. Therefore it is essential that the charging time of these
The cells (both used and new) were charged and discharged at different rates, C/5,
C/4, C/3, C/2, 3C/5, 3C/4 and C to 80% depth of discharge. The cells were first charged
54
at a constant current followed by a constant voltage charging at 4.1 V. This was followed
by a 5 minute rest period. Subsequently the cells were discharged at constant current. The
test results were analyzed and are discussed in this section. It is noted that the data values
reported in this section were averaged over 5 cycles. The new Quallion cell was
represented by a cell that was cycled 200 times at C rate charge and discharge to 60%
depth of discharge. The used Quallion cell was represented by a cell that was cycled 6000
times at C rate charge and discharge to 60% DOD prior to the charge time tests.
The charge times of new and used Quallion cells at different charge rates are
compared in Fig. 2.8.1. It is evident that the total charge time decreases with increase in
charge rate (increase in charge current) as expected. For the slowest charging rate, C/5,
the total charge time of the cells is less than 5 hours because the cell is only discharged to
80% of its capacity. For rapid charging rate, 1C, the total charge time is about 1.14h for
the new cell and 1.45h for the used cell. It is evident that the total charge time of the used
cells is always larger than that of the new cells for any given charge rate.
The total charge time is comprised of the constant current charging phase and
constant voltage charging phase. It is therefore relevant to look at the constant current
charge time and constant voltage charge time to understand the increase in the total
The percentage of charge time for the constant current phase and the constant
voltage phase during charging for the new Quallion cell is shown in Fig. 2.8.2. The cell
spends most of the charging time in the constant current phase for all charging rates
except at the C rate. For C/5 rate of charging, the constant current charge time is about
85% and the constant voltage charge time is about 15%. For C rate of charging, the
55
constant current and the constant voltage charge times are nearly equal. At higher
charging rates the overpotentials are larger; the cell reaches 4.1 V sooner, and spends
The percentage charge time spent in the constant current and the constant voltage
charging phase for the used Quallion cell is shown in Fig. 2.8.3. As discussed in the
previous paragraph, similar to the new cell results, the constant current charge time
percentage decreases and the constant voltage charge time percentage increases with the
charging rate for the used cell. However for the 3C/5 charging rate, the constant current
charging time is equal to the constant voltage charging time. For all charging rates greater
than the 3C/5, the constant voltage charge time is greater than the constant current charge
time. Comparing Figs. 2.8.2 and 2.8.3 for new and used cells, it is evident that the used
cells spend more time in the constant voltage charging mode thereby increasing the total
charging time. For example, at 1C charge rate, the new cell spends only 49% of the total
charge time in the constant voltage mode, whereas the used cell spends about 73% of the
This behavior can be attributed to the increase in the cell impedance on use. The
increase in the cell impedance causes the used cells to reach 4.1V earlier in comparison to
the new cells and therefore the used cells spend more time in the constant voltage
charging phase.
The end of discharge voltage as a function of charge rate for the used and the new
cells is shown in Fig.2.8.4. There are two major differences between the used and the
new cells. The first difference is that the end of discharge voltage is lower for the used
cell in comparison to the new Quallion cell. This suggests increased cell impedance upon
56
cycling. The second major difference is the slope of the linear fit to the data for the used
cell is 278 mV per unit charge rate and in comparison the slope for the new cell is small
and is about 22 mV per unit charge rate. Assuming the concentration overpotentials in the
electrolyte to be the same in both the used and new cells, the difference in slope can be
attributed to the increase in the ohmic and charge transfer resistance due to the increase in
The Wh efficiency of the used and the new cells for different rates of charging is
shown in Fig. 2.8.5. It is evident that the Wh efficiency is less than 100% even for the
new cell and is due to the various overpotentials which increase the energy consumption
during charge and decreases the energy released during discharge. For the new cell, the
Wh efficiency decreases linearly with charge rate. The Wh efficiency of the used cells is
lower than that of the new cells again indicating that the cell impedance has increased
The percentage increase in the total charge time for the used cells in comparison
to the new cells at different charging rates is shown in Fig.2.8.6. The first conclusion is
that even at large charging rate (1C) the percentage increase in the charging time is only
30% (low). The percentage increase in the charge time increases with the charging rate.
At C/5 rate of charging (0.2C) the increase in total charge time is only about 9.2%. It
should be noted that calculations show that at the C/5 rate the energy consumed for
The conclusions that can be drawn from this section are that the cell impedance
increases with cycling, decreasing the Wh efficiency obtained and increasing the total
charge time of the Quallion cells. By charging at low rates, the percentage increase in
57
charge time is lowered and a small gain of 3.5% energy is obtained. This is significant
because it is important to efficiently deliver the energy from the RF frequency generator
to the access port (which holds the battery) implanted in the body.
5
New cell
Old cell
4
Total charge time (h)
0
0 0.2 0.4 0.6 0.8 1 1.2
Charge rate (C)
Figure 2.8.1: Total charge time as a function of different charging rates for new and used
Quallion cells.
100
CC time, %
CV time, %
80
Charge time (%)
60
40
20
0
0 0.2 0.4 0.6 0.8 1 1.2
Figure 2.8.2: Percentage of constant current and constant voltage charge times as a
function of different charging rates for new Quallion cells. The cells during charging
spend more time in the constant current phase rather than in the constant voltage phase.
58
80
60
Charge time (%)
CC time, %
CV time, %
40
20
0
0 0.2 0.4 0.6 0.8 1 1.2
Figure 2.8.3: Percentage of constant current and constant voltage charge times as a
function of different charging rates for used Quallion cells.
3.5
y = -0.0215x + 3.3307
End of discharge voltage (V)
3.3
3.1
New Cell
Old Cell
2.9
y = -0.2783x + 3.0113
2.7
2.5
0 0.2 0.4 0.6 0.8 1 1.2
Charge rate (C)
Figure 2.8.4: End of discharge voltage as a function of different charge rates for new and
used Quallion cells. A straight line is fit to the data.
59
96
94
Watthr efficiency (%)
92
90 New Cell
Old Cell
88
86
84
82
0 0.2 0.4 0.6 0.8 1 1.2
Figure 2.8.5: Watt-hour efficiency of the used and the new Quallion cell at different
charging rates.
30
Charge time increase (%)
25
20
15
10
0
0 0.2 0.4 0.6 0.8 1 1.2
Figure 2.8.6: Percentage increase in charge time of the used Quallion cell in comparison
to the charge time of the new Quallion cell. The percentage charge time is maximum for
the 1C charge rate.
60
2.9. Conclusions
Lithium ion cells from the manufacturers Sony, Wilson Greatbatch and Quallion
were investigated. The Wilson Greatbatch and Quallion are implantable batteries. The
effect of different operating conditions on the cycle life of Sony Li ion cell was studied.
Factors favoring increased cycle life were identified. The cycle life can be enhanced by
(i) charging at C/5 rather than C rates, (ii) using 4.1V cutoff rather than 4.2V cutoff, (iii)
low depth of discharge. The effect of discharge rate on the cycle life of the Sony lithium
ion cell is unclear due to the ageing of the tested lithium ion cells. The cycle life of the
Sony Li ion cell was diminished when cycling at 37o C in comparison to cycling at room
temperature. The cycle life of the lithium ion cells was fitted considering a non-linear
model rather than a linear fit used in the previous work10 at Case. The non-linear model
accounts for SEI film growth due to cycling and can then be used to predict the cycle life
of these batteries. The fit parameters were estimated accurately (very small errors) and
The cycle life of lithium ion cells from different manufacturers was compared.
The performance of the Sony cells is superior in comparison to the Wilson Greatbatch
and Quallion cells. Of the implantable battery technologies, the Quallion cells show
longer cycle life in comparison to the Wilson Greatbatch cells and therefore the Quallion
cells will be the choice for our implantable power source. The Quallion cells can last
about 6000 cycles at 60% DOD, C rate charge, C rate discharge, 4.1V charge cutoff and
37o C. The cycle life of the Wilson Greatbatch cells can be significantly increased by
cycling the cells at 60% depth of discharge, however, it is still less than that of the
Quallion cells.
61
The charge time of the new and used Quallion cells was studied. The charge time
of the used cells increases by about 30% and 9% at C rate and C/5 rate, respectively. It is
concluded that charging at low rates results in more efficient energy transfer to the
batteries.
References
1. T. Nagaura and K. Tozawa, Progress in Batteries & Solar Cells, 9, 209 (1990).
10. M. J. Haugh, M.S. thesis, Dept. of Electrical Engineering and Computer Science,
Case Western Reserve University, Cleveland, Ohio., 2003.
11. P. Arora, R. E. White, and M. Doyle, Journal of the Electrochemical Society, 145,
3647 (1998).
62
14. P. Arora, M. Doyle, and R. E. White, Journal of the Electrochemical Society, 146,
3543 (1999).
22. M. Broussely and G. Archdale, Journal of Power Sources, 136, 386 (2004).
23. G. Ning and B. N. Popov, Journal of the Electrochemical Society, 151, A1584
(2004).
26. T. Kishi, H. Ohta, and Y. Satoh, Electrochemistry (Tokyo, Japan), 71, 1090
(2003).
63
30. P. Ramadass, B. Haran, R. White, and B. N. Popov, Journal of Power Sources,
112, 614 (2002).
64
3. Platinum Negative Electrode – Testing and
Activation
In this chapter, three major components of the low pressure nickel-hydrogen cell
– the negative electrode, the current collector and the separator are analyzed.
The negative electrode used in the development of our low pressure nickel-
charged, hydrogen is evolved at the negative electrode and when the cell is used
the negative electrode is to facilitate the hydrogen evolution and the hydrogen oxidation
(depending on charge or discharge) with fast kinetics. The overpotentials for these
Platinum with other platinum group metals either as single, binary or ternary
combinations 1-12 has been the preferred option for the hydrogen oxidation reaction in
alkaline fuel cells. The overpotential of these electrodes is about only 20 mV for current
densities less than 400 mA/cm2. Other catalysts like nickel boride, Raney nickel and
sintered nickel 9-13 have been investigated for oxidation of hydrogen. However the
catalytic activity and the stability of these catalysts are limited. Kiros and Schwartz 14
have shown that the Pt/Pd bimetallic combination catalyst is more stable than the Raney
Ni catalyst at long oxidation times. The main objective of this work is to develop a
battery with long cycle life and therefore the Pt catalyst, which is more stable, was
65
chosen as the negative electrode. Platinum electrodes are also the negative electrodes in
The platinum electrodes used in the high pressure nickel-hydrogen cells and in
our low pressure nickel-hydrogen cells are based on electrode designs developed for the
gas diffusion (GDE) electrodes used in the alkaline fuel cells. Typically the platinum
particles are supported on carbon (Vulcan XC-72) are mixed in the form of liquid slurry
along with polytetrafluoroethylene (PTFE) particles and are then blended together with
an emulsifying agent like Triton X100. They are then filtered to the required size and
thickness and pressed onto a nickel screen, followed by sintering to hold the PTFE
particles together. The electrode structures are typically 50% porous and only one half of
the pores are wetted by the electrolyte. The other half of the electrode is hydrophobic and
facilitates hydrogen diffusion in and out of the electrode filled with a thin layer of
electrolyte.
were used in the electrodes. In our cells, a platinum loading of 0.6 mg/cm2 was used and
the results discussed in this chapter shows that the loading levels are sufficient.
The negative electrode used in our nickel-hydrogen batteries is the A-2 silver-
plated nickel screen electrode (ESNS) from E-tek. The support is 80 mesh silver plated
nickel screen and the thickness of the finished electrode is about 0.4 mm. 10% Pt on
Vulcan XC-72 is used as the catalyst and is loaded on one side only. Catalyst containing
10% Pt has a platinum area of about 141 m2/gm (technical information available from E-
tek). Hence, the ESNS electrode with 0.6 mg/cm2 has a platinum area of 846 cm2 per cm2
of electrode.
66
In this chapter, the performance of the E-tek electrode used in the development of
the low pressure nickel-hydrogen battery is presented. The negative platinum electrode
was studied and analyzed in the liquid cell (section 3.2) and bolt nut cell configuration
(section 3.3) simulating the nickel-hydrogen battery conditions. The activation of the
platinum electrode required to increase the exchange current density is also discussed. In
section 3.4, the effect of two different current collectors, nickel chromium and nickel, on
the high frequency resistance will be discussed. In section 3.5, the performance of two
briefly.
reversible hydrogen electrode as the reference electrode and a platinum gauze as the
counter electrode was set up in the BASi electrochemical cell (Fig. 3.2.1). The electrolyte
was 26 wt% potassium hydroxide solution. The cell was purged with nitrogen overnight
and cycled at 25 mV/s in the voltage range -0.1 to 0.75 V to remove dissolved oxygen in
the electrolyte.
ESNS
Reference H2 electrode
electrode Pt mesh
N2 N2
Inlet Outlet
26 wt. % KOH
Figure 3.2.1: Schematic representation of the experimental setup.
67
3.2.1. Hydrogen Evolution Reaction Kinetics
⎛ ⎛ α nFηa ⎞ ⎛ β nFηa ⎞ ⎞
i = io ⎜ exp ⎜ ⎟ − exp ⎜ − RT ⎟ ⎟ [3.1]
⎝ ⎝ RT ⎠ ⎝ ⎠⎠
where i is the current density and ηa is the activation overpotential for the faradaic
reaction. α and β are the anodic and cathodic transfer coefficients respectively. n is the
The current –potential relation can be separated into two regimes for convenience.
For small activation overpotentials,ηa << RT/nF , the kinetics are considered linear and
for large activation overpotentials, ηa >> RT/nF , the anodic part in the Butler-Volmer
equation (first part) can be neglected for the hydrogen evolution reaction (cathodic
RT i
give ηa = . The equation indicates that the activation overpotential increases
nF io
RT ⎛ i ⎞
ηa = ln ⎜ ⎟ . The equation indicates that the activation overpotential increases with
β nF ⎝ io ⎠
the current density, however, with a slower rate in comparison to the linear regime.
68
∂η a
The charge transfer resistance is defined as Rct = . For linear regime, the
∂i
RT
charge transfer resistance is given as: Rct = . It is evident from the equation that the
nFio
charge transfer resistance is independent of the applied current density. The charge
RT
transfer resistance in the Tafel regime is given as: Rct = . The equation indicates
β nFi
that the charge transfer resistance decreases with increase in the current density.
It is evident from these discussions that the charge transfer resistance measured
and could be either in the Tafel or linear regime. This will be discussed in detail in the
The open circuit voltage (OCV) of the negative ESNS electrode in de-aerated
electrolyte was 0.56 V. The ESNS electrode was biased at various negative DC potentials
(reduction reaction), between 0 to -0.5V and the impedance spectra was measured as a
The potential at which the impedance spectra were measured was then corrected
for the ohmic potential drop and is labeled as IR corrected potential. Table 3.1 shows that
the IR corrected potential range is -0.008 to -0.154 V and covers both the linear and Tafel
regimes of the polarization curve. The impedance spectra of the ESNS electrode obtained
at different biased potentials is shown in Fig. 3.2.2 in the form of a Nyquist plot. The
diameter of the semicircle gives the charge transfer resistance. The solution resistance,
69
Rs, charge transfer resistance, Rct, and the double layer capacitance, Cdl, were estimated
based on the impedance spectra (Fig. 3.2.2) and are listed in Table 3.1.
As expected, the solution resistance does not change significantly through the
entire potential range. The charge transfer resistance decreases as function of the
potential indicating that the cell is in Tafel regime (the charge transfer resistance is
constant in the linear regime). It is noted that the only data point in the linear regime is -
0.008V. The other data points are scattered over the intermediate and Tafel regimes. It is
also evident from Table 3.1 that the solution resistance is larger than the charge transfer
resistance and is due to the fact that the reference hydrogen electrode was placed far from
the working electrode (negative ESNS electrode). The capacitance decreases with
70
-0.50
-0.25
Decrease in Rct
Z''
0
-8 mV
-29 mV
-41 mV
0.25 -52 mV
-102 mV
-125 mV
-154 mV
0.50
1.00 1.25 1.50 1.75 2.00
Z'
Figure 3.2.2: Impedance spectra of the ESNS electrode in the potential range -8 to -154
mV. The charge transfer resistance decreases with increase in the bias potential.
The negative ESNS electrode will typically be in the linear regime when used in
the nickel-hydrogen cell because of the low charge and discharge currents required by the
Impedance spectra at different bias potentials in the linear regime were measured
and are shown in Fig. 3.2.3. The bias potentials were IR corrected and are listed in Table
3.2. The solution resistance, charge transfer resistance and the double layer capacitance
were calculated. It is evident that the charge transfer resistance is constant in the potential
range 0 to -15mV and hence, the measurements are in the linear regime. The average
71
value of the charge transfer resistance in this regime is about 1.6 ohm cm2. The double
layer capacitance in the linear regime is also constant as shown in Table 3.2.
The impedance data analysis shows linear polarization in the potential range, 0 to
-20 mV. In the next section, the potentiodynamic data measured in the linear polarization
range will be used to calculate the charge transfer resistance and the exchange current
-1.0
-0.5 -8 mV
-11 mV
-15 mV
Z''
0.5
1.0
0.5 1.0 1.5 2.0 2.5
Z'
Figure 3.2.3: Impedance spectra of the ESNS electrode in the linear polarization regime.
The potential range is -8 to -15 mV. The charge transfer resistance does not change with
the bias potential.
72
3.2.3. Potentiodynamics
A potentiodynamic scan was also used to estimate the kinetic parameters of the
ESNS electrode. The potentiodynamic scan was performed in the potential range 0 to -
0.15V at a slow scan rate, 0.1 mV/s, and is shown in Fig. 3.2.4. It is assumed that the
electrode is in equilibrium at such slow scan rates. It is evident from the figure that the
current increase is linear in the potential range, 0 to -25 mV, corresponding to linear
The data in the range, -6 to -16 mV (Fig. 3.2.5) was fitted linearly using Origin
and the error in the parameter estimations is small. The charge transfer resistance is the
reciprocal of the estimated slope and is 1.25 Ω cm2 and is about the same value, 1.6 Ω
cm2, estimated using the impedance spectroscopy. The exchange current density
comparison, Alcaide et al.16 calculated the exchange current density as 2.03 mA/cm2 for
an E-tek electrode containing 0.5 mg/cm2 of platinum loading, five times smaller than the
73
Potentiodynamic scan 0.1mV/s
Non-linear Linear
-0.1 Regime
I (Amps/cm2)
-0.2
-0.3
-0.4
-0.20 -0.15 -0.10 -0.05 0 0.05
E (Volts)
Figure 3.2.4: Potentiodynamic scan of the ESNS electrode at a scan rate of 0.1 mV/s.
Two different regimes are indicated in the figure.
0
y = A + B*x
R^2 = 0.99742
-2 A 0.004 ± 0.00011
B 0.8 ± 0.00986
2
-4
i mA/cm
-6
-8
-10
Figure 3.2.5: Linear fit of the potentiodynamic scan in the potential range -6 to -16 mV.
The scan rate is 0.1 mV/s. The parameter ‘B’ is the inverse of the charge transfer
resistance.
74
3.2.4. Conclusions
The exchange current density and the charge transfer resistance were calculated
current density is 10.3 mA/cm2 and is larger than that calculated in the work by Alcaide
et al16 for a similar E-tek electrode. The charge transfer resistance is in the range 1.3-1.6
ohm cm2.
The Pt surface area in the given electrode area is 846 cm2 /cm2. Based on this
value and our estimated exchange current density for the electrode (10.3 mA/cm2), the
exchange current density per unit Pt area is ~ 0.012 mA/cm2 Pt. This is an order of
density, in the range 0.1-0.5 mA/cm2, for pure platinum4, 17. A slightly lower value than
that of pure platinum is expected because not all the platinum in the electrode is exposed
to the electrolyte. However, the calculated exchange current density corresponds to only
Our nickel-hydrogen cells will be operated at about 3 mA/cm2 (C/5 rate) and the
Configuration
The ESNS electrodes were tested in a bolt nut cell configuration as shown
schematically in Figure 3.3.1. The main objective, here, is to study the performance of
the negative electrode in a cell setup which will be used for the Ni-H2 cell testing. It is
noted that the main limitation of the negative electrode studies in the liquid cell (previous
section 3.2) is that the results were based only on the hydrogen evolution reaction. Using
75
the bolt nut cell configuration, the oxidation of hydrogen and the evolution of hydrogen
at the two electrodes can be studied, simultaneously. Hydrogen is formed during charge
soaked in 26 wt. % KOH solution were assembled in a stainless steel compartment filled
with H2 gas (Fig. 3.3.1). In this setup, one of the ESNS electrodes is the working
electrode and the other is the counter and reference electrode. Nickel chromium mesh
was used both as current collector and gas diffusion layer. Electrochemical impedance
Insulator
ESNS/Pt ESNS/Pt
H2
Nut
Bolt
A set of fresh ESNS electrodes and a fresh separator were soaked in KOH
overnight and then assembled in the double negative cell configuration. Impedance
76
spectra were measured at open circuit voltage (~ 0V) with an AC amplitude of 10 mV.
The charge transfer resistance and the double layer capacitance were estimated based on
the impedance data and the values for one electrode are listed in Table 3.3.
The charge transfer resistance, 6.8 Ω cm2, for the fresh electrode is larger than
that of the measurement in the liquid cell, 1.3-1.5 Ω cm2. The double layer capacitance, 7
mF/cm2, is almost two orders of magnitude lower than the corresponding measurement in
There are significant differences between the liquid cell test and the bolt nut cell
test. In the liquid cell the electrode is flooded with the electrolyte and in comparison the
bolt nut cell has electrolyte primarily in the separator. This difference is amplified by the
fact that the ESNS electrode as made is hydrophobic so as to facilitate three phase (solid
liquid gas) reactions. This affects the wetting of the electrode. The other significant
difference is in the liquid cell the charge transfer resistance was measured based on the
hydrogen evolution. However, in the bolt nut cell configuration, charge transfer
resistance includes both hydrogen evolution at one electrode and hydrogen oxidation at
the other electrode. It is noted that the hydrogen oxidation depends on the distribution of
Table 3.3: Estimated parameters for fresh electrodes based on the linear fit applied
to the CV data.
Electrode Parameter Calculated Value
Charge transfer resistance (ohm cm2) 6.8
Double layer capacitance (mF cm-2) 7
77
3.3.2. Conditioning of ESNS Electrodes with Cyclic Voltammetry
The fresh ESNS electrodes were then conditioned by cyclic voltammetry (CV) in
the potential range -0.5 to 0.5 V at scan rates of 5 mV/s to decrease the charge transfer
resistance. The impedance spectra were measured after every set of the cyclic
voltammograms. The calculated charge transfer resistance and the double layer
The charge transfer resistance decreases significantly with cycling (Fig. 3.3.2)
from 7 Ω cm2 to 1.75 Ω cm2 and is due to the increase in the wetting of the ESNS
electrode by the electrolyte. This assumption is supported by the fact that the double layer
capacitance increases from 7 to 27 mF/cm2 on cycling (Fig. 3.3.2). It is noted that for the
ESNS electrode most of the capacitance contribution is due to carbon (carbon 5-6
mg/cm2, Pt 0.6 mg/cm2). However, it is assumed that the increase in the wetting of
electrode. This indicates that cycling results in the activation of the platinum electrodes.
The charge transfer resistance and the double capacitance as shown in Fig. 3.2.2
does not change for the last two sets of cyclic voltammograms indicating that no
significant changes in the wetting of the electrode. It is noted that the charge transfer
resistance at the end of cycling is 1.75 Ω cm2 is about the same value measured in the
The first set of cyclic voltammograms (used for electrode conditioning) recorded
in the voltage range -0.5 to 0.5 V were IR corrected and are shown in Fig. 3.3.3. Two
distinct regions, linear and Tafel regimes as discussed in the previous section 3.2 are
identified. It is assumed that the overpotential due to mass transport is negligible in the
78
voltage range -0.2 to 0.2 V. It is noted that the voltage measured is the sum of activation
overpotential contributions due to the two electrodes (after IR correction). Therefore the
data fit range -2 to -22 mV can be approximated as -1 to -11 mV for one ESNS electrode,
assuming that the two electrodes are identical. The linear polarization region corresponds
to the voltage range of -22 to 22 mV. The cathodic and anodic Tafel polarization regions
are in the voltage range of -0.15 to -0.2V and 0.15 to 0.2V, respectively. It is evident that
the current density of the electrode increases with cycling indicating decrease in the
8 32
Resistance, ohm cm2
Rct Cdl
Capacitance, mF cm-2
6 24
4 16
2 8
0 0
Before 5 mV/s, 5 mV/s, 5 mV/s, 5 mV/s, 5 mV/s, 5 mV/s, 5 mV/s,
scans 3 cy 5 cy 3 cy 5 cy 10 cy 25 cy 10 cy
Electrode condition
Figure 3.3.2: Charge transfer resistance and double layer capacitance as a function of
electrode condition based on impedance measurements before and after every set of
cyclic voltammograms. ‘Cy’ in the x-axis text indicates cycles.
79
30
Increase in
20 Current
10 Linear
i (mA/cm2)
Tafel
0
Tafel
-10
-20
-30
-0.3 -0.2 -0.1 0 0.1 0.2 0.3
E (Volts)
Figure 3.3.3: First set of cyclic voltammogramms (3 cycles) at a scan rate of 5 mV/s.
Fig.3.3.4 shows a linear fit to the cyclic voltammogram data in the potential
range, -2 to -22 mV, taken at 5 mV/s (cathodic region, cycle 1) without any electrode
conditioning. The calculated charge transfer resistance is 7.1 Ω cm2 and is about the same
measured using the impedance spectroscopy. The exchange current density is 1.8
mA/cm2 about an order of magnitude lower than that measured in the liquid cell. The
charge transfer resistance and the exchange current density for every cycle were
determined similarly.
The exchange current density and the charge transfer resistance calculated based
on the first and last scan of electrode conditioning are listed in Table 3.4. The charge
density increased on cycling (other data not shown, Table 3.4). This is similar to the
decrease in charge transfer resistance observed for the impedance data (Fig. 3.3.2). The
80
exchange current density for the last set of scans did not change significantly and is about
5.6 mA/cm2. This shows that cycling is beneficial by increasing the exchange current
3
Rct
RpFit Result
2 Data Range: -2 to -22 mV
Rct (Ohms/cm2)= 7.2
io (mA/cm2)= 1.8
1
i (mA/cm2)
-1
-2
-3
-25 -20 -15 -10 -5 0 5 10 15 20 25
E (mV)
Figure 3.3.4: IR corrected cyclic voltammogramms showing the linear regime at a scan
rate of 5 mV/s. The data in the voltage range, -2 to -22mV, was linearly fit.
Table 3.4: Estimated parameters for fresh electrodes based on the linear fit applied
to the CV data.
Electrode condition Exchange current Charge transfer
density, io (mA/cm2) resistance (ohm cm2)
Beginning of cycling 1.8 7.2
End of cycling 5.6 2.3
The ESNS electrodes used in the previous experiments were soaked in 26 wt%
KOH solution overnight. Then the cell with the two ESNS electrodes was assembled and
subjected to rest. The impedance spectra were evaluated at different rest periods. The
81
calculated charge transfer resistances and the double layer capacitance do not change
significantly when the cells are rested (Fig. 3.3.5). This in principle shows that the
conditioned electrode is stable and does not change drastically with the rest periods.
4 37
Rct Cdl
Capacitance, mF cm-2
2
Resistance, ohm cm
3 36
2 35
1 34
0 33
Just assembled after 16h rest after 22h rest
Electrode condition
Figure 3.3.5: Charge transfer resistance and double layer capacitance as a function of
electrode condition based on impedance measurements before and after different rest
periods.
The activated ESNS electrodes were soaked in liquid KOH for 6 days. The charge
transfer resistance and the double layer capacitance calculated using the impedance
82
3.4. Testing of Current Collectors
Two types of current collectors, nickel chromium mesh and nickel mesh, were
tested using the negative electrodes in the bolt nut cell configuration. The high frequency
resistance of the cell was estimated based on the impedance spectra. The high frequency
resistance includes contributions from all the contact resistances in the cell, as well as the
Fig. 3.4.1 compares the high frequency resistance of two cells one using nickel
chromium mesh current collectors and the other using nickel mesh current collectors. It is
evident that the high frequency resistance of the cell using nickel mesh current collectors
is about 2 times smaller than the cell using nickel chromium mesh current collectors.
The degradation of the current collectors when used in the bolt nut cell is
compared in Fig. 3.4.2. It is evident that the high frequency resistance of the cell with
nickel mesh current collector does not degrade significantly when used. However, the
high frequency resistance of the cell using nickel-chromium current collector increases
by a factor of 5. The increase in the high frequency resistance of the Ni-Cr mesh is due to
the corrosion (formation of oxide layer) when two different meals are in contact with
KOH solution. This concludes that the nickel mesh current collectors are better suited to
83
3
2.5
Resistance, Ω cm2
2
1.5
0.5
0
Nickel chromium Nickel
Figure 3.4.1: The high frequency resistance of the cell using nickel chromium mesh
current collectors and nickel mesh current collectors is compared.
20
Ni
Ni-Cr
Resistance, Ω cm2
16
12
0
Fresh Used
Figure 3.4.2: The high frequency resistance of the cell, one using nickel chromium mesh
as current collectors and other using nickel mesh as current collectors is compared for
two different conditions fresh and used.
84
3.5. Testing of Separators
Two separators (a) Zircar ZYK-15 and (b) Celgard 3400 were tested in the double
negative cell configuration. Zircar is the trade name of zirconium oxide stabilized with
hydrophilicity and excellent solution retention property. The other separator, Celgard
wetting agent and is used in aqueous battery systems. The high frequency resistance of
the cell was not significantly different for the two separators.
The ohmic overpotential of the cell including the current collector resistance and
3.6. Conclusions
A platinum electrode, called as ESNS electrode, from E-tek Inc. was tested in the
liquid cell configuration and in the double negative cell configuration. The platinum
loading in the electrode is 0.6 mg/cm2. The electrodes were analyzed by electrochemical
In the liquid cell the evolution of hydrogen on the platinum electrode was studied.
Based on the impedance and the potentiodynamic data, the charge transfer resistance was
estimated in the range 1.2 to 1.6 Ω cm2. The estimated exchange current density for the
hydrogen evolution reaction is 10.3 mA/cm2 electrode area and is five times larger than
that calculated by Alcaide et al.16 The calculated exchange current density based on
platinum area is 0.018-0.026 mA/cm2 and is small. However, the results also show that
85
operation of our nickel-hydrogen cells), is about 20 mV. This amount of overpotential is
small and therefore the ESNS electrodes are satisfactory for our application.
our nickel-hydrogen battery. Both hydrogen evolution reaction and hydrogen oxidation
spectroscopy and cyclic voltammetry initially shows a large charge transfer resistance of
7.2 Ω cm2. It is shown that cycling the electrodes in the voltage range -0.5 to 0.5 V
Correspondingly the exchange current density increases from 1.8 mA/cm2 before cycling
to 5.6 mA/cm2 after cycling. This increase in exchange current density is attributed to
better wetting of the electrolyte. Once the electrode is activated by cycling, the charge
transfer resistance does not change significantly with further cycling and/or rest periods.
Two different current collectors nickel chromium and nickel were studied.
Analysis shows that the nickel chromium current collectors are easily oxidized and the
high frequency resistance of the cell increases dramatically to 15-20 Ω cm2. However
resistance of 2 Ω cm2. On the other hand, the high frequency resistance of clean nickel
current collectors is about 1.2 Ω cm2 and is lower than the nickel chromium current
collector. The solution resistance of the nickel current collectors also did not significantly
change with time. These results clearly indicate that the nickel current collectors are
better than the nickel chromium current collectors. Two separators, Zirconium oxide
86
stabilized with yttria and polypropylene membrane were tested and no significant
References
12. E. Gulzow, M. Schulze, and G. Steinhilber, Journal of Power Sources, 106, 126
(2002).
13. J. Shim and H. K. Lee, Materials Chemistry and Physics, 69, 72 (2001).
14. Y. Kiros and S. Schwartz, Journal of Power Sources, 87, 101 (2000).
87
16. F. Alcaide, E. Brillas, and P.-L. Cabot, Journal of the Electrochemical Society,
152, E319 (2005).
88
4. Testing of ‘D Cell’ Nickel Hydroxide Electrode
A ‘D size’ nickel metal hydride cell was cut open to separate the nickel hydroxide
electrode from other battery components. The characteristics of this nickel hydroxide
electrode: specific capacity, coulometric efficiency, cycle life and impedance were
analyzed in the liquid cell and in the nickel-hydrogen cell configuration. The
performance of the electrode in two cells in series was tested and analyzed. The study of
this electrode served as a guide in the development of the pasted nickel hydroxide
electrode (Chapter 5) and the design of the nickel-hydrogen cell (Chapter 6).
Based on the charge-discharge tests, the capacity of the nickel metal hydride cell
was estimated as 6.8 Ah. The D cell was opened and the nickel hydroxide electrode was
removed. The total area of the double sided nickel hydroxide electrode is 465.6 cm2.
liquid cell filled with 26 wt. % KOH solution. A three electrode system, consisting of
working counter and reference electrode was used, similar to the setup used for testing
the platinum electrode (Fig. 3.2.1). The D cell nickel hydroxide electrode was used as the
working electrode. Platinum wire gauze was used as the counter electrode. A reversible
89
hydrogen electrode was used as the reference electrode. The electrochemical cell was
The D cell nickel hydroxide electrode was soaked in 26 wt% KOH overnight. The
electrode was cycled at C/3 rate in the liquid cell. A rest period of 1h was applied
between the charge and the discharge period. The voltage profiles during charge and
discharge of the electrode is shown in Fig. 4.2.1. It is evident that the charge voltage was
larger and the discharge voltage was smaller for the 1st cycle in comparison to other
cycles, indicating larger power consumption during the charge and smaller power output
during discharge. However, the charge voltage decreased and the discharge voltage
increased with cycles as shown in Fig. 4.2.1. For cycles 11 to 25, the voltage profiles
remained the same and no significant changes are observed (Figure not shown). This
indicates good cyclability of the electrode. The coulometric efficiency of the nickel
hydroxide electrode for 26 cycles is shown in Fig. 4.2.3. It is evident that the efficiency is
about 99% and does not change significantly with cycles. The inset in the figure shows
small changes in the efficiency of the nickel hydroxide electrode with cycling.
(SOC) was measured and is shown in Fig.4.2.3. At 100% SOC, most of the active
material is nickel oxyhydroxide and at 0% SOC the active material is nickel hydroxide
(chapter 1). It is noted that nickel oxyhydroxide is a good electronic conductor whereas
electrode is enhanced typically by the addition of cobalt and zinc and will be discussed in
90
detail in Chapter 5. It is evident that the charge transfer resistance of the electrode is
about the same for 100% and 67% SOC. This resistance increases for 33% and 0% SOC
and is attributed to the poor electronic conductivity of the nickel hydroxide, formed
electrode was not characterized for materials composition and therefore the variation in
1.5
1.3
E (Volts)
1 charge
1.2 1 discharge
2 charge
2 discharge
Increase in discharge
1.1 3 charge voltage with cycling
3 discharge
4 charge
1.0 4 discharge
5 charge
5 discharge
0.9
0 1 2 3
Time (Hours)
Figure 4.2.1: Voltage profile during charge-discharge of the D cell nickel hydroxide
electrode for cycles 1 to 5. The cell was cycled at C/3 rate to 100% capacity.
91
120
Columetric Efficiency, %
100
80
100.5
60 100.0
99.5
40 99.0
98.5
20 0 10 20 30
0
0 5 10 15 20 25 30
Cycle Number
Figure 4.2.2: Coulometric efficiency of the D cell nickel hydroxide electrode as a
function of cycles. The inset shows the small variations in the coulometric efficiency.
The cell was cycled at C/3 rate to 100% capacity.
-1.0
100 % Charge
67 % Charge
33 % Charge
0 % Charge
-0.5
0%
Z'' (ohm cm2)
0
100 %
0.5
1.0
0 0.5 1.0 1.5 2.0
2
Z' (ohm cm )
Figure 4.2.3: Impedance spectra of the D cell nickel hydroxide electrode as a function of
state of charge. The cell was cycled at C/3 rate.
92
4.3. Performance of the D cell Electrode in Nickel-Hydrogen Cell
The D cell nickel hydroxide electrode was assembled in the bolt-nut type cell
described in Chapter 3 as shown in Fig. 3.3.1. The D cell nickel hydroxide is the positive
electrode and the platinum electrode (discussed in chapter 3) is the negative electrode.
The separator is a polypropylene membrane soaked in 26 Wt. % KOH. In this section the
significance of fixing the end of discharge voltage and the effect of overcharging will be
discussed.
cycle 5 in Fig. 4.3.1. The cell was cycled at C/3 rate to 80% of the nickel hydroxide
electrode capacity. No discharge cutoff voltage was used. During charging, a fraction of
the charge passed to the cell results in oxygen evolution. Therefore when the cell is
discharged to 3h, the cell is discharged to a lower state of charge than the state it
originally started with. Therefore the end of discharge voltage decreases from cycle 1 to
cycle 5 as shown in the Fig. 4.3.1 and the coulometric efficiency is 100%. It is evident
from the figure that the end of charge voltage also increases from cycle 1 to cycle 5,
contrary to the expectation that the charge voltage will decrease. This is due to the
increase in the charge transfer resistance of the nickel hydroxide and the platinum
It is noted here that the large charge transfer resistance in Fig. 4.3.2 corresponds
to that of the used platinum electrode. The charge transfer resistance is significantly
reduced for fresh platinum electrodes as discussed in chapter 3 and chapter 6. The
pertinence of the two semi-circles to the charge transfer reactions at the different
93
In contrast the voltage profile during charge-discharge of the electrode with a
discharge cut-off voltage of 1V for 5 cycles is shown in Fig. 4.3.3. No significant change
in voltage profile is observed. By choosing an end of discharge voltage close to the knee,
The effect of overcharging the cell at C/6 rate is shown in Fig. 4.3.4. Voltage
profiles during two different cycles, one overcharged by 50% and another with no
overcharge are compared. The SOC of the cell before the beginning of charge is different
for the two cycles and the end of discharge voltage is not fixed. Therefore the
coulometric efficiency is 100% for both cycles. It is evident that when the cell is
overcharged, the voltage fluctuates at the end of charge as a result of oxygen evolution
and in comparison is absent for the cell with no overcharge. The rise in voltage is due to
the oxygen bubble formation at the electrode, which cannot diffuse out at a sufficient
rate. Finally the bubble breaks out or recombines at the platinum electrode with a large
pop, resulting in the fall in voltage1. The voltage fluctuation is also present during the
initial discharge of the overcharged cell indicating that the oxygen formed during
discharge is still recombining at the platinum electrode. In comparison, for the cycle with
no overcharge no voltage fluctuations are observed during the discharge. The charge and
the discharge voltage are higher for the overcharged cell in comparison to the cell with no
overcharge because the overcharged cell is in a higher state of charge. The consequence
94
1.5
5
1.4 1 charge
E (Volts)
1.3
1 discharge
1.2
5
1.1
0 1 2 3
Time (Hours)
Figure 4.3.1: Voltage profile during the charge-discharge of the Ni-H2 cell using the D
cell nickel hydroxide electrode for cycles 1 and 5. There is no discharge cut-off voltage.
The cell was cycled at C/3 rate to 80% capacity with no voltage cutoff.
-10.0
1
5
-7.5
-5.0
Z''
-2.5
2.5
2.5 5.0 7.5 10.0 12.5 15.0
Z'
Figure 4.3.2: Impedance spectra of the Ni-H2 cell using the D cell nickel hydroxide
electrode measured at the end of charge of cycles 1 and 5. The cell was cycled at C/3 rate
to 100% capacity.
95
1.5
1.4
1.3
E (Volts)
1.2
1.1
1.0
0.9
0 1 2 3
Time (Hours)
Figure 4.3.3: Voltage profile during the charge-discharge of the Ni-H2 cell using the D
cell nickel hydroxide electrode for 5 cycles. The discharge cut off voltage is 1.0 V The
cell was cycled at C/3 rate to 80% capacity.
O2 evolution
1.5
50% Overcharge
1.4 No overcharge
E (Volts)
1.2 No overcharge
1.1
0 1 2 3 4 5 6
Time (Hours)
Figure 4.3.4: Voltage profile during the charge-discharge of the Ni-H2 cell using the D
cell nickel hydroxide electrode comparing overcharge with no overcharge. The cell was
cycled at C/6 rate with no voltage cutoff.
96
4.4. Performance of the D cell Electrode in Series Cell
Two cells in series were assembled in the bolt-nut cell setup using the ‘D cell’
nickel hydroxide electrode and the platinum electrode as shown in Fig. 4.4.1. A bipolar
plate is used to provide electrical connection between the cells. The requirements of a
bipolar plate are (a) good electronic conductivity (b) good gas permeability and (c) no
KOH migration. Three different materials, nickel chromium mesh, carbon cloth,
spectracarb 2050-A (porous carbon paper) were considered as bipolar plates. The
variation of open circuit voltage during the cell assembly for different bipolar plates is
shown in Fig. 4.4.2. The series cells are first purged in nitrogen gas, when the OCV is
about 0.25-0.4 V for different bipolar plates in the time period 0 to 0.1h. The cell voltage
increases rapidly when purged with hydrogen gas. This voltage rises to about 2.52 V for
the series cells using carbon cloth and Ni-Cr mesh. The cell voltage corresponds to
voltage of two cells in series. However for the spectracarb 2050-A, the cell voltage rises
to only about 1.36V, which is more than a single cell voltage in discharged state and less
than ‘two cells in series’ voltage indicating that the spectracarb was shorting the two cells
by KOH migration. It is noted that the D cell nickel hydroxide electrode is double-sided
and results in formation of an opposite cell when there is KOH in the current collector.
The series cell utilizing carbon cloth as the bipolar plate was stopped after one
cycle because of poor charging and discharging. The voltage profile during charge is
similar to that shown in Fig. 4.4.6. The series cell with Ni-Cr mesh as current collector
performed better at C/3 rate to 80% capacity. The voltage profile during charge-discharge
for cycles 1, 5 and 10 is shown in Fig. 4.4.2. The discharge cut-off voltage is 2V. The
97
coulometric efficiency is about 100% for cycle 1. However, the discharge time
(coulometric efficiency) decreases with cycling. The charge voltage increases and the
cycling. This is evident in the impedance data measured at the end of discharge for cycle
1, 5 and 10, as shown in Fig. 4.4.4. The voltage profile for the 10th cycle (Fig. 4.4.5)
shows voltage fluctuations at the end of charge indicating significant oxygen evolution in
the cell.
The voltage fluctuations at the end of charge for cycles 4, 7 and 10 are shown in
Fig. 4.4.5. It is evident that the fluctuations increase on cycling indicating that the oxygen
evolution increases with cycles. This results in poor cell performance as shown by the
The double-sided nickel hydroxide electrode causes uneven charging and results
in overcharging of one of the electrodes. By this, the state of charge of one nickel
hydroxide electrode at the end of discharge is not actually 0% but higher. On further
cycling, the SOC of one electrode increases in comparison to the other resulting in more
and more oxygen evolution for the overcharged electrode at the end of charge. This
98
Positive Negative
electrode electrode Current
Ni(OH)2 Platinum collector
Separator
Cell 1 Cell 2
Bipolar plate
Ni-Cr mesh
2 Spectracarb 2050
Carbon cloth
E (Volts)
0
0 0.25 0.50 0.75
Time (Hours)
Figure 4.4.2: Variations in the open circuit voltage of series cell with different bipolar
plates. The cell is purged first with nitrogen and then with hydrogen.
99
3.2
10
3.0
5
1
2.8
E (Volts)
2.6
2.4
1
2.2
10 5
2.0
0 1 2 3
Time (Hours)
Figure 4.4.3: Voltage profile during the charge-discharge of the series cell. The discharge
cut off voltage is 2.0 V The cell was cycled at C/3 rate to 80% capacity.
-40
1
5
10
-30
Z''
-20
-10
0
0 10 20 30 40
Z'
Figure 4.4.4: Impedance spectra of the series cell measured at the end of discharge of
cycles 1, 5 and 10. The cell was cycled at C/3 rate to 80% capacity.
100
3.05
10
3.00
7
E (Volts)
4
2.95
2.90
1.5 2.0 2.5 3.0
Time (Hours)
Figure 4.4.5: Voltage profile at the end of charge for cycles 4, 7 and 10 of the series cell.
The discharge cut off voltage is 2.0 V The cell was cycled at C/3 rate to 80% capacity.
3.1
3.0
E (Volts)
2.9
2.8
0 1 2 3
Time (Hours)
Figure 4.4.6: Voltage profile for the 12th charge of the series cell. The discharge cut off
voltage is 2.0 V The cell was cycled at C/3 rate to 80% capacity.
101
4.5. Conclusions
The ‘D cell’ nickel hydroxide was tested in liquid and nickel-hydrogen cell
configurations. The importance of fixing the discharge cut-off voltage was studied.
Overcharging the electrode results in voltage fluctuations at the end of discharge due to
The performance of the electrode in two cells in series was studied. The nickel
hydroxide electrode contains active material on both sides which results in shorting of the
cell because the potassium hydroxide solution seeps into the current collector. Therefore
it is necessary to fabricate a nickel hydroxide electrode with active material on one side
References
102
5. Fabrication and Formation of Nickel
Hydroxide Electrode
5.1. Introduction
size nickel metal hydride battery was discussed in detail. The D cell electrodes are loaded
with nickel hydroxide on both sides and as a consequence cannot be used as electrodes in
a series cell configuration because they form opposite cells with the platinum electrode in
the front and the platinum electrode in the back due to KOH seepage. This results in the
drop in voltage of the series cells. A nickel hydroxide electrode with active material on
In this chapter, the fabrication of the nickel hydroxide electrode and its
components on the electrode performance was studied. The main objective was to
develop a nickel hydroxide electrode that can be used in the development of the low
chemistries like the nickel-cadmium batteries, the nickel-zinc batteries, the nickel-metal
hydride batteries and the nickel-hydrogen batteries. The common methods of adding the
nickel hydroxide active material to the substrate are (i) mechanical impregnation1, 2 and
103
In the mechanical impregnation method, the active material is blended with a
binder solution. Cobalt and zinc are added to increase the conductivity of the paste and
the overvoltage for oxygen evolution. The paste is extruded or rolled or pasted into the
substrate. The two major types of electrode fabricated by mechanical means are (i) pasted
type nickel electrode1, 2 and (ii) plastic bonded electrode8. Of the two methods, the pasted
chemically or electrochemically precipitated into the substrate3-7. The substrate used for
this method has to be sintered and therefore they are called as sintered electrodes. This
a porous nickel substrate. The substrate can be non-woven nickel fiber or a variety of
materials. Recently, the nickel foam has been used as the substrate. The main advantage
of the pasted type electrode is the simplicity of the fabrication method. The nickel foam is
remove the base polyurethane. The foam so obtained is light in weight and is about 95%
porous.
The plastic bonded electrode was primarily developed for nickel-zinc batteries. In
this method, the active material - nickel hydroxide, and the additives are blended together
with polytetrafluoroethylene (PTFE) binder and then roll-bonded into a porous three-
104
dimensional structure by fibrillating with binder. The fibrillated PTFE locks the active
material firmly into the structure. This eliminates shedding of the active material which is
a problem with the pasted nickel electrode. The base structure is graphite eliminating
metallic nickel thereby saving cost and reducing weight. This method is complex in
manufacturing steps and consequently require significant capital investment. The sintered
substrate is obtained by pasting nickel filamentary fiber onto a perforated foil. These
impregnation techniques. The main advantage of these electrodes is high rate and power
capability; however, they contain a relatively low ratio of active materials to inactive
5.3.1. Substrate
Nickel foam was used as the substrate because of its large porosity (95%).
Precision sized, high purity and uniform nickel foam from INCO was used. The thickness
of the nickel foam is about 1.6 mm and the density is about 420 g/m2. The number of
105
pores per inch is 110. A scanning electron microscope image of the nickel foam is shown
in Fig. 5.3.1.
Nickel hydroxide powder from Kansai Catalyst Corporation LTD was used as the
active material. The composition of this nickel hydroxide formulation as obtained is 54%
Ni, 3.2% Co and 4.5% Zn. According to the product information, 4.5% Zn and 0.7% Co
were mixed as a solid solution with nickel hydroxide. These particles were then coated
with 2.5% Co. The cobalt coating is a mixture of cobalt hydroxide and cobalt
performance of the electrodes and has been studied by many researchers1, 9-25. The two
major beneficial effects of adding cobalt are (i) increase in electrode conductivity1, 9-12
and (ii) increase in the oxygen overvoltage 13-15. This results in increased electrode
capacity. The other beneficial effects are (i) lowering of the β-nickel oxyhydroxide peak
potential16, 17, (ii) minimization of the γ-nickel oxyhydroxide growth18, (iii) increase in
electrode mechanical resistance19, 20, and (iv) increase in proton diffusion17. Addition of
zinc increases the long term stability of the electrodes and delays the formation of γ-
nickel oxyhydroxide phase12, 26. The average size of the nickel hydroxide particles is
about 12 µm. The active material was blended with a binder and a solvent using a
homogenizer. The binder was polyvinylidene fluoride (PVDF, Kynar 2800) and the
solvent was N-methyl pyrrolidone. The binder provides adhesion of particles to one
106
Filamentary nickel powder (Novamet, INCO type 210, 0.5-1 µm) was used as a
filler to enhance the conductivity of the paste. The addition of nickel powder to the
electrode increases the utilization27, 28 and will be discussed in detail in section 5.5.3.
Figure 5.3.1: SEM image of INCO nickel foam of thickness 1.6 mm and cell size 550-
700 µm.
Screen printing was used to mechanically press the formulated paste into the
nickel foam substrate. Screen printing is one of the several thick film printing
technologies used for selective coating of flat surfaces. The technology was originally
developed for the production of miniature, robust, and cheap electronic circuits with high
reliability and versatility 29. In the last decade, thick film printing has been studied to
fabricate batteries 30-32 and fuel cells 33-43. The screen printing technique reproduces the
image from the image carrier to the substrate. A mesh or screen is used as the image
carrier. The paste is then pressed through the pores in the screen using a squeegee on to
107
the substrate as shown in Fig. 5.3.2. For the fabrication of nickel hydroxide electrode, the
nickel foam was used as the substrate. For good performance of the nickel hydroxide
electrode, it is desired that all the paste is pushed into the foam as shown in Fig. 5.3.2
rather than forming a thick film on top. This is achieved by adjusting the several process
parameters including the squeegee pressure, the screen height from the substrate and
squeegee height from the screen. Other parameters like the viscosity of the paste and the
screen pore size are critical for efficient impregnation of the paste into the substrate. The
squeegee is cycled as many times as needed to get the desired loading level into the
substrate.
The nickel foam electrode with the paste is then dried in vacuum at 100o C
overnight. This completes the fabrication of the nickel hydroxide electrode. The results
discussed in this chapter were based on electrodes fabricated by screen printing unless
otherwise specified.
Squeegee Frame
Paste Mesh
Ni Foam
108
5.4. Formation of the Nickel hydroxide Electrode
The next step is the formation of the nickel hydroxide electrode. The electrode
obtained at the end of the fabrication process contains nickel hydroxide particles held
together by the binder PVDF. The nickel hydroxide particles themselves have relatively
low electronic conductivity and are coated with cobalt oxide to enhance the conductivity.
During formation the electrodes are charged and discharged successively. The cobalt
oxide is oxidized to cobalt oxyhydroxide forming highly conductive films during this
process1, 2. This decreases the electronic resistance between the nickel hydroxide
The Ni foam containing the nickel hydroxide paste was soaked in 26 wt% KOH
overnight. The binder PVDF is hydrophobic; however upon soaking overnight the pores
of the nickel foam are filled with KOH due to capillary effects. The soaked electrode
was then formed in a BAS liquid cell shown schematically in Fig. 5.4.1. The nickel
hydroxide electrode was the working electrode. A platinum mesh was used as the counter
electrode. A reversible hydrogen electrode was used as the reference electrode. The cell
The steps involved in the formation of the nickel hydroxide electrode are:
1. The electrode was first charged at C/10 or C/20 rate (with or without
3. Then the electrode was discharged at C/10 or C/20 rate with a discharge
109
The electrode is cycled continuously by repeating steps 1 to 4 until the electrode
was formed.
Ni Foam based
electrode
Reference H2
electrode Pt mesh
N2 N2
Inlet Outlet
26 wt. % KOH
Figure 5.4.1: Schematic diagram of the cell setup used for the formation of the nickel
hydroxide electrode.
The electrochemical reactions occurring during charge and discharge and the
reaction pathways under different conditions are represented in Fig. 5.4.2. It is well
understood that during charging the β-Ni(OH)2 phase is converted β-NiOOH phase44.
This is the principal reaction in the nickel hydroxide electrode and is given as:
ch arg e
⎯⎯⎯⎯
Ni (OH )2 + OH − ←⎯⎯⎯ → NiOOH + H 2O + e −
⎯ [5.1]
disch arg e
the beta form of nickel oxyhydroxide is converted to the γ-NiOOH as shown in the Fig.
5.4.2. The discharge of the γ-NiOOH phase results in α-Ni(OH)2 phase without the
formation of the β-Ni(OH)2 phase. The α-Ni(OH)2 thermally restructures to the beta form
of nickel hydroxide. The potential for these reactions depends on the electrolyte
110
potential in the traditional sense because the electrode always operates at a mixed
with the formation of both the β and γ-NiOOH phases and is given as:
4OH − → 2 H 2O + O2 + 4e − [5.2]
Charge
β-Ni(OH)2 β-NiOOH
Discharge
Thermal Overcharge
rearrangement
Charge
α-Ni(OH)2 γ-NiOOH
Discharge
Figure 5.4.2: Schematic diagram for interconversion of active material phases in the
nickel hydroxide electrode44.
study the effect of cycling conditions like temperature, electrolyte concentration, number
of cycles, and recharge ratio on the usable capacity of the electrodes and the efficiency of
the charging reaction. In this work, electrochemical voltage spectroscopy was used to
study the effect of incomplete formation, the binder content and the nickel content on the
111
Electrochemical voltage spectroscopy is a form of cyclic voltammetry. A slow
scan rate of 2 µV/s was used for charging and discharging the electrode, in the voltage
range 1.2 to 1.48 V. It is assumed that the electrode kinetics is in equilibrium at such slow
scan rates. The charge and discharge peaks observed were used to compare the
The voltage variations during the charge period, the rest period and the discharge
period were monitored. Impedance data was measured at the end of the charge and
discharge periods. The voltage profiles during charge and discharge for the first two
cycles of an electrode containing 10% PVDF and 90% Ni(OH)2 by weight basis are
shown in Fig. 5.4.3. The electrode was charged at C/10 rate with 50% overcharge (15 h)
and discharged at C/10 with a voltage cutoff of 1.2 V. During charging the active
It is evident from the figure that the voltage during the 2nd charge is lower than
that of the 1st charge. The high voltage during the first charge cycle is due to the poor
addition to the oxidation of nickel hydroxide reaction, the cobalt oxide present is oxidized
active mass within the nickel foam electrode1. This results in a lower charge voltage in
the 2nd cycle. A change in slope is observed in the time period 10-15 h (overcharge) and
this corresponds to the evolution of oxygen after the completion of the nickel
oxyhydroxide reaction.
112
Utilization is defined as the ratio of the discharge capacity obtained to the
theoretical capacity of the electrode. The utilization of the 10% PVDF containing
The voltage profile in the beginning of the 1st charge in the time period 0 to 30
min is shown in Fig. 5.4.4. It is evident that the voltage rises initially and then falls
during the first 3 minutes. At the start of charging, the poor conductivity of the particles
causes the potential to rise steeply, however the formation of cobalt oxyhydroxide on
The impedance data of the 10% PVDF containing nickel hydroxide electrode
measured before forming is shown in Fig. 5.4.5. It is evident that the impedance profile
indicates capacitive behavior within the frequency range used (20,000 to 0.2 Hz) because
of the large charge transfer resistance, which is due to the poor conductivity of the paste
impregnated into the nickel foam and substantiates the observations noted for the voltage
profile during charging. The impedance of the electrode measured after discharge at the
end of cycles 1 and 2 is shown in Fig. 5.4.6. The data shows a semi-circle corresponding
to the charge transfer resistance for the nickel hydroxide to nickel oxyhydroxide reaction
and the impedance is smaller in comparison to that measured before forming. It is also
evident from the figure that the charge resistance (semi-circle) decreases with cycling.
113
Change of slope
1.5
1 charge
1.3
1 discharge
2 discharge
1.2
Discharge
voltage cutoff
1.1
0 5 10 15
Time (Hours)
Figure 5.4.3: Variations in voltage during charge and discharge of cycles 1 and 2. The
electrode composition is 10% PVDF and 90% Ni(OH)2 by weight.
1.45
1 charge
1.44
E (Volts)
1.42
0 0.1 0.2 0.3 0.4 0.5
Time (Hours)
Figure 5.4.4: Voltage variation in the time period 0 to 0.5h during the first charge. The
electrode composition is 10% PVDF and 90% Ni(OH)2 by weight.
114
-3000
Before forming
-2000
Z''
-1000
(A)
1000
0 1000 2000 3000 4000
Z'
-10
After cycle 1
After cycle 2
-5
Z''
(B)
0
5
0 5 10 15
Z'
Figure 5.4.5: Impedance data of 10% PVDF containing electrode: (A) Before formation,
(B) End of discharge after cycles 1 and 2.
115
The voltage variations during charge and discharge for a nickel hydroxide
electrode containing 15% PVDF and 85% Ni(OH)2 by weight basis is shown in Fig.
5.4.6. It is evident that the voltage profiles do not change significantly from cycle 2 to
cycle 3. The utilizations for cycle 2 and cycle 3 are 85.2 and 85.1, respectively. The
impedance data measured at the end of discharge for cycles 1, 2 and 3 is shown in Fig.
5.4.7. It is evident from the figure that the impedance profile does not change
significantly for cycles 2 and 3. Figs. 5.4.6 and 5.4.7 clearly show that the electrode
1.5
2, 3 charge
1.4
E (Volts)
1.3 2, 3 discharge
1.2
1.1
0 5 10 15
Time (Hours)
Figure 5.4.6: Voltage profile during charge and discharge of cycles 1 and 2 for 15%
PVDF containing nickel hydroxide electrode.
116
-15
-10
Z''
-5 End of 1 discharge
2
3
0
5
0 5 10 15 20
Z'
Figure 5.4.7: Impedance data of 15% PVDF containing electrode measured at the end of
discharge after cycles 1, 2 and 3.
Some of the nickel hydroxide electrodes were charged to only 60% of their
theoretical capacity during formation. The effect of such incomplete formation was
studied using electrochemical voltage spectroscopy (EVS). It is noted that this mode of
formation.
hydroxide electrode containing 16% PVDF and 84% Ni(OH)2 (weight basis) are
compared in Fig. 5.4.8. The voltage is IR corrected for the solution resistance. It is noted
that the completely formed electrode was charged to its theoretical capacity (no
117
overcharge) and the incompletely formed electrode was charged to only 60% of its
theoretical capacity. The current measured in the EVS scan is normalized with the
theoretical electrode capacity and the units are h-1. The positive and negative current
corresponds to the charge and the discharge of the electrode. The completely formed
nickel hydroxide electrode shows peaks only for the β-NiOOH phase and β-Ni(OH)2
phase. However, the incompletely formed electrode shows peaks for both forms, β and γ-
NiOOH phases, and the α-Ni(OH)2 phase. The β-Ni(OH)2 peak is absent due to the
5.4.1.
The peak potentials for the different reactions are listed in Table 5.1. It is evident
from the table that the β-NiOOH peak potential is the same for the both the electrodes.
However the discharge potential peaks are different because of the different phases
formed electrode than the completely formed electrode and this results in lower watt-hour
capacity. It is also evident from the Figure 5.4.8 that the oxygen evolution rate is larger
and the oxygen evolution potential is lower for the incompletely formed electrode.
Oshitani et al.1, 2 was extended to this case. When the electrode is charged incompletely,
only the cobalt oxide on the nickel hydroxide particles close to the nickel foam fiber is
oxidized and that further away is not oxidized forming a poorly conductive network of
the nickel hydroxide particles as shown schematically in Fig. 5.4.9. This results in
charging (β-NiOOH phase) and then overcharging of the particles (γ-NiOOH) close to the
118
nickel fiber. These discussions clearly suggest the importance of charging the nickel
The SEM image of a fresh 16% PVDF electrode is shown in Fig. 5.4.10A. The
nickel foam and the nickel hydroxide particles are evident. In contrast the SEM image of
an incompletely formed 12.7% PVDF electrode taken after the EVS scan is shown in Fig.
5.4.10B. It is evident that nickel hydroxide particles are structurally damaged because of
poor formation.
0.6
Incomplete formation
Complete formation O2
0.4
Current/Capacity (h-1)
γ-NiOOH
0.2 β-NiOOH
-0.2 β-Ni(OH)2
α-Ni(OH)2
-0.4
1.2 1.3 1.4 1.5
E (Volts)
Figure 5.4.8: Comparison of EVS scans for completely and incompletely formed nickel
electrode containing 16% PVDF and 84% Ni(OH)2.
119
Table 5.1: Peak potentials for different electrochemical reactions.
Type of β-NiOOH (V) γ-NiOOH (V) β-Ni(OH)2 (V) α-Ni(OH)2 (V)
Formation
Complete 1.419 - 1.308 -
Incomplete 1.418 1.459 - 1.217
Ni Foam CoOH
Charging
Ni(OH)2 PVDF
Incomplete
Figure 5.4.9: Schematic representation of complete and incomplete charging of the nickel
hydroxide electrode.
120
(A)
(B)
Figure 5.4.10: SEM image of nickel hydroxide electrodes: (A) Fresh 16% PVDF
electrode, (B) Used 12.7% PVDF electrode incompletely formed.
performance was studied and is discussed in this section. The charging rates considered
121
Two electrodes, one containing 10% PVDF and the other containing 10.7%
PVDF were cycled at C/10 and C/20 rate with 50% overcharge, respectively. Utilization
is defined as the ratio of the discharge capacity obtained to the theoretical capacity of the
electrode. The utilization during the first two cycles as a function of charge rate is listed
in Table 5.2. It is evident that the utilization is about the same for the two charging rates.
difference was observed in the impedance spectra measured at the end of discharge for
the electrodes cycled at different rates. However, the impedance spectra measured at the
end of charge showed a smaller charge transfer resistance for the C/20 rate in comparison
and the scans are compared in Fig. 5.4.11. It is evident that the peak potentials for the β-
NiOOH and the β-Ni(OH)2 are about the same for electrodes charged at different rates.
However for the electrode formed at C/20 rate, the γ-NiOOH peak is also evident. In
either case, there is no clear separation of the NiOOH peak from the oxygen evolution
peaks, suggesting that at the end of charging the oxygen evolution is significant.
Table 5.2: Utilization of electrode containing about 10% PVDF and 90% Ni(OH)2
charged at different during formation.
Charge rate Utilization
Cycle 1 Cycle 2
C/10 82.1 83.1
C/20 81.0 83.1
122
0.2
C/10
C/20
0.1
Current/Capacity (h-1)
-0.1
-0.2
-0.3
1.2 1.3 1.4 1.5
E (Volts)
Figure 5.4.11: Comparison of EVS scans for two different electrodes, one charged at
C/10 and another at C/20 rate with 50% overcharge. The electrode composition is 10%
PVDF and 90% Ni(OH)2 by weight.
section.
An electrode containing 15% PVDF and 85% Ni(OH)2 was charged and
discharged at C/10 rate without overcharge. The impedance data measured at the end of
discharge for cycles 1 to 5 is shown in Fig. 5.4.12A. It is evident that the charge transfer
resistance decreases with increasing cycles and does not change significantly for cycles 4
and 5 which indicates that the electrode is completely formed. The decrease in charge
hydroxide particles due to the formation of the highly conductive cobalt oxyhydroxide
123
from cobalt oxide. When all the conversion is complete, the charge transfer resistance
does not change significantly as in cycles 4 and 5. The impedance data measured at the
end of charge for cycles 1 to 5 is shown in Fig. 5.4.12B. The charge transfer resistance
cycle 3 to 5.
Another electrode containing 15% PVDF and 85% Ni(OH)2 was charged at C/10
rate with 50% overcharge for the first two cycles. It was established in section 5.4.3 that
the electrode formation is complete by two cycles. For cycle 3, the electrode was not
overcharged. Impedance data measured at the end of discharge and charge are shown in
Figs. 5.4.13A and 5.4.13B, respectively. It is evident that the charge transfer resistance at
the end of discharge decreases from cycle 1 to cycle 2 as expected due to the
cycle 3 the charge transfer resistance increases slightly when the electrode is not
overcharged. The charge transfer resistance measured at the end of charge (Fig. 5.4.13B)
is about the same for cycle 1 and 2. For cycle 3, when the electrode is not overcharged
the charge transfer resistance is significantly larger. This is because when the electrode is
although with more oxygen evolution) in comparison to the case without overcharge. It is
noted that nickel oxyhydroxide is a good electronic conductor whereas nickel hydroxide
oxyhydroxide when the electrode is overcharged (cycles 1 and 2) results in lower charge
transfer resistance.
124
5.4.6.3. Comparison of No Overcharge and 50% Overcharge
The utilization of the two electrodes, one charged with 50% excess and the other
without overcharge is compared in Fig. 5.4.14. For the electrode cycled without
overcharge, the utilization is about 59.9% for cycle 1 and increases to 81.1% for cycle 2.
The utilization at the end of cycle 5 is about 81.6%. For the electrode cycled with 50%
overcharge, the utilization is about 85.6% for the first cycle and increases to 88.3% for
the second cycle. The utilization of cycle 3, which is without overcharge, is about 81%
and is same as the utilization obtained for the electrode formed without any overcharge.
The impedance data measured at the end of the formation for electrodes, one with
overcharge and the other without overcharge is compared in Fig. 5.4.15. It is evident that
the charge transfer resistance is the same for both the electrodes. Thus, there is no
significant difference between charging with 50% overcharge and charging without any
overcharge.
125
-20
Cycle 1
Cycle 2
Cycle 3
Cycle 4
Cycle 5
-10
(A)
Z''
10
0 10 20 30
Z'
-1.5
1
2
3
-1.0 4
5
Z''
-0.5
(B)
0
0.5
0 0.5 1.0 1.5 2.0
Z'
Figure 5.4.12: Impedance spectra of the electrode measured at the end of discharge (A)
and charge (B) without overcharge at C/10 rate for the first 5 cycles.
126
-20
1
2
3
-10
(A)
Z''
10
0 10 20 30
Z'
-2
After charge 1 - 50% overcharge
After charge 2 - 50% overcharge
After charge 3 - No overcharge
-1
Z''
(B)
0
1
0 1 2 3
Z'
Figure 5.4.13: Impedance spectra of an electrode measured at the end of discharge (A)
and charge (B) at C/10 rate with 50% overcharge for the first two cycles.
127
No overcharging 50% overcharging
100
80
Utilization, %
60
40
20
0
0 1 2 3 4 5 6
Cycle No.
Figure 5.4.14: Utilization as a function of cycles for electrodes formed with 0% and 50%
overcharge.
-20
No overcharge
50% overcharge
-10
Z''
10
0 10 20 30
Z'
Figure 5.4.15: Impedance spectra measured after discharge for electrodes formed with
0% and 50% overcharge.
128
5.5. Characterization of Nickel Hydroxide Electrode
The effect of PVDF content on the electrode performance was investigated and
the results are discussed in this section. Electrodes containing 5, 10 and 15% PVDF were
formed at C/10 rate with 50% overcharge and the utilization of these electrodes for the
first two cycles is shown in Fig. 5.5.1. The theoretical capacity of these electrodes is
similar and is listed in Table 5.3. It is evident from the Fig. 5.5.1 that the utilization
increases with increase in the PVDF content by about 9% from 5% PVDF to 15% PVDF
for the 2nd cycle. This indicates that the electrode with higher PVDF content gives better
performance. It is also evident from the figure that the utilization increases on cycling for
the 10 and 15% PVDF electrodes and decreases with cycling for the 5% PVDF electrode.
It was noted that the 5% PVDF electrode was shedding particles on cycling and this is
Impedance data measured at the end of end of discharge and charge for electrodes
containing different amounts of PVDF is shown in Fig. 5.5.2. It is evident that the charge
transfer resistance measured at the end of discharge decreases with increasing PVDF
content in the electrodes. This result reinforces the observation that the electrodes with
higher PVDF content yields higher utilization. The charge transfer resistance measured at
the end of charge decreases from 5% to 10% PVDF. However it increases for the 15%
PVDF and this behavior is possibly related to the slightly different capacities of the
electrodes.
The EVS scans of electrodes containing different amounts of PVDF are compared
in Fig. 5.5.3. The peaks for the β-NiOOH phase and the β-Ni(OH)2 phase are evident for
129
all the electrodes. The peak potentials for the β-NiOOH phase and the β-Ni(OH)2 phase
shifts towards lower values with increase in the PVDF content and are listed in Table 5.4.
The peak for the γ-NiOOH phase is absent in the 5% PVDF electrode. However, they are
present in the 10 and 15% PVDF electrode and the peak potentials decrease with increase
in the PVDF content (Table 5.4). This suggests that the electrodes containing larger
amounts of PVDF are overcharged in some regions resulting in the formation of the γ-
NiOOH phase. The cobalt oxyhydroxide formed does not provide a sufficiently
conductive network resulting in the overcharging of the 10 and 15% PVDF electrodes.
The α-Ni(OH)2 peak is present in all the electrodes and is small, indicating that the γ-
NiOOH phase formed at the end of charging is also small. The peak currents for the β-
NiOOH phase and the β-Ni(OH)2 phase increase with PVDF content. Due to the different
loading levels (difficult to precisely control during fabrication), it is noted that the
theoretical capacity of these electrodes decreases with increase in the PVDF content. The
increase in peak currents is possibly related to the normalization of the current with the
electrode capacity.
130
90
5% PVDF
88 10% PVDF
15% PVDF
86
Utilization, %
84
82
80
78
76
74
1 2
Cycle No.
131
-10
5% PVDF
10% PVDF
15% PVDF
-5
(A)
Z''
5
0 5 10 15
Z'
-0.25
(B)
5%
Z''
10 %
15 %
0.25
0.50
0.25 0.50 0.75 1.00
Z'
Figure 5.5.2: Impedance spectra measured at the end of discharge (A) and charge (B) for
electrodes containing different PVDF content. The electrodes were formed at C/10 rate
with 50% overcharge.
132
0.2
5% PVDF
10% PVDF
15% PVDF
0.1
Current/Capacity (h-1)
-0.1
-0.2
-0.3
1.2 1.3 1.4 1.5
E (Volts)
Figure 5.5.3: EVS scans for electrodes containing different PVDF content formed at C/10
rate with 50% overcharge.
133
The effect of PVDF content on the electrode performance was also studied for a
set of electrodes with low theoretical capacities. The utilization of 10% and 15% PVDF
containing electrodes for cycles 1 and 2 is shown in Fig. 5.5.4. The theoretical capacity of
these electrodes was similar and is listed in Table 5.5. It is evident from the figure that
the utilization increases with PVDF content and with cycles and is similar to the results
89.0
88.0
Cycle 1
Cycle 2
87.0
Utilization,%
86.0
85.0
84.0
83.0
82.0
81.0
10% PVDF 15% PVDF
134
5.5.2. Effect of Loading Density
The loading levels of the active material can be varied depending on the number
of times the squeegee is cycled during screen printing. In this section, the effect of
Figs. 5.5.5 and 5.5.6 show the utilization of 10% PVDF and 15% PVDF
loading levels. It is evident that the electrodes with lower theoretical capacity (lower
loading level) have higher utilization. The impedance data measured at the end of charge
and discharge for 10% PVDF and 15% PVDF electrodes is shown in Figs. 5.5.7 and 5.5.8
respectively. It is evident that the charge transfer resistance measured at the end of charge
and discharge is smaller for the electrodes with the higher loading level. Higher loading
levels correspond to electrodes with larger active area (higher active material) which
means lower charge transfer resistance. It is noted that the charge transfer resistance is
the dominant impedance at the end of discharge than at the end of charge and therefore
this effect is magnified for the impedance measured at the end of discharge as shown in
135
85.5
85.0
84.5
Utilization, %
84.0
83.5
83.0
82.5
82.0
6.51 13.95
Figure 5.5.5: Utilization of 10% PVDF electrodes with different capacities (different
loading levels). The electrodes were cycled at C/10 rate with 50% overcharge.
89.0
88.0
Utilization, %
87.0
86.0
85.0
84.0
83.0
7.1 12.8
136
-20
6.5
14
-10
(A)
Z''
10
0 10 20 30
Z'
-0.50
6.5
14
-0.25
(B)
Z''
0.25
0.50
0.50 0.75 1.00 1.25 1.50
Z'
Figure 5.5.7: Impedance spectra measured at the end of discharge (A) and charge (B) for
electrodes containing 10% PVDF with different capacities. The electrodes were formed at
C/10 rate with 50% overcharge.
137
-20
7.1
12.8
-10
(A)
Z''
10
0 10 20 30
Z'
-0.50
7.1
12.8
-0.25
(B)
Z''
0.25
0.50
0.25 0.50 0.75 1.00 1.25
Z'
Figure 5.5.8: Impedance spectra measured at the end of discharge (A) and charge (B) for
electrodes containing 15% PVDF with different capacities. The electrodes were formed at
C/10 rate with 50% overcharge.
138
5.5.3. Effect of Fine Ni
The utilization of the nickel electrodes without nickel is about 80 to 86%. The
main objective is to enhance the utilization of the electrodes by adding filamentary nickel
(INCO 210). In this section, the effect of nickel on the electrode performance will be
discussed.
The nickel hydroxide powder from Kansai Catalyst, as described in section 5.3.2,
was mixed homogenously with nickel 210 using PVDF binder and NMP solvent. The
conductivity of the paste was studied using electrochemical impedance spectroscopy. The
paste was printed on a 4 point conductivity base as shown in Fig. 5.5.9. The thickness of
the printed paste was estimated using a laser profilometer. The electronic resistance of the
paste is given by the high frequency resistance measured. The electronic conductivity of
the paste as a function of the nickel weight percent is shown in Fig. 5.5.10 for two hand
mixed samples and one homogenized sample. The conductivity of the homogenized
sample is always higher than the conductivity of the hand mixed samples. The
conductivity of the paste with 0% Ni is about 10-4 Ω-1 cm-1 and increases to 0.94 Ω-1 cm-1
for 8.4% Ni. Therefore the critical weight percent for conductivity is about 8.4. More data
points are needed to clearly estimate the critical weight fraction. It is evident that the
electronic conductivity of the paste increases with nickel weight up to 12.2%. For nickel
observed.
Nickel hydroxide powder with no cobalt and zinc, from OMG, was mixed
homogeneously with nickel 210 powder. The electrical conductivity of the paste was
139
monitored using impedance spectroscopy and is compared with the nickel hydroxide
powder from Kansai Catalyst. The electrical conductivity of the nickel hydroxide powder
from OMG with the addition of nickel is shown in Fig. 5.5.11. It is evident that the
paste increases to about 0.1 to 1 Ω-1 cm-1 at 30 wt. % nickel. This shows that the critical
weight fraction is in the range 20 to 30% Ni. Comparing Figs. 5.5.10 and 5.5.11, it is
observed that the electrical conductivity of the Kansai powder is always higher than that
of the OMG powder. This indicates that the cobalt oxide coated on the nickel hydroxide
particles (Kansai) does play a role in enhancing the conductivity of the paste, even before
Figure 5.5.9: Four-point conductivity ceramic base used for AC impedance spectroscopy.
140
100
Handmixed 1
0.1
0.01
1E-3
1E-4
1E-5
0 5 10 15 20 25
Nickel, Wt %
Figure 5.5.10: Electronic conductivity of the paste containing nickel hydroxide particles
(Kansai) as a function of nickel Wt. %.
1
-1
Sample 1
Conductivity, ohm cm
Sample 2
0.1
-1
0.01
1E-3
1E-4
1E-5
0 5 10 15 20 25 30 35
Nickel, Wt %
Figure 5.5.11: Electronic conductivity of the paste containing nickel hydroxide particles
(OMG) as a function of nickel Wt. %.
141
5.5.3.2. Comparison of Electrodes Containing 0% and 8.8% Ni
In this section, a set of nickel electrodes containing 10% PVDF and 0% nickel
will be compared to another set of nickel electrodes containing 8.7% PVDF and 8.8%
nickel. The first formation cycle of two such electrodes is compared in Fig. 5.5.12. The
charge voltage for the electrode containing nickel is lower in comparison to the other
electrode. The voltage rise and fall in the 0-0.5h charge period in the electrode without
nickel (Fig. 5.4.4) is absent in the electrode containing nickel. It is also evident that the
discharge time for the electrode containing nickel is longer indicating better utilization of
the active material. The impedance spectra obtained at the end of discharge and charge
for the formed electrodes is shown in Figs. 5.5.13A and 5.5.13B respectively. The
impedance at the end of discharge (Fig. 5.5.13A) of the electrode containing nickel is
nickel. This is supported by the fact that the electrodes containing nickel charges at lower
voltage. The impedance at the end of charge for the electrode containing 8.8% Ni shows
only a small decrease in the charge transfer resistance in comparison to the electrode
without Ni. This is because the nickel oxyhydroxide formed at the end of charging is
conductive and the addition of nickel makes little difference to conductivity of the
electrode paste.
The utilization of electrodes with and without nickel is shown in Fig. 5.5.14. It is
evident that the utilization for the electrodes containing nickel is about 10% higher than
the utilization obtained in electrodes without nickel. A model based on three level
conductive networks in the pasted electrode was proposed to explain the effect of
addition of nickel by Yang et al27. The same model can be used to explain our results.
142
The nickel foam substrate forms the primary network or first level network via its nickel
strands with a cell size of about 400 to 700 µm as shown in Fig. 5.3.1. The filamentary
nickel powder (INCO nickel 210) provides the secondary network by spreading among
the nickel hydroxide particles of size 10 µm as shown in Fig. 5.5.15. The cobalt
oxyhydroxide formed on the surface of nickel hydroxide forms the tertiary network and
enhances the conductivity among the nickel hydroxide particles. Therefore, when 8.8
Wt% Ni is added, the utilization of the electrode is increased as shown in Fig. 5.5.14. It is
noted that the effect of cobalt enhancing the conductivity of the nickel hydroxide powder
along with nickel was not taken into account in the work done by Yang et al.27
1.5
0% Ni
8.8% Ni
1.4
E (Volts)
1.3
1.2 0% Ni 8.8% Ni
1.1
0 5 10 15
Time (Hours)
Figure 5.5.12: Comparison of the voltage profile in the first formation cycle for
electrodes with and without nickel.
143
-20
0% Ni
8.8% Ni
-10
Z''
(A)
0
10
0 10 20 30
Z'
-0.5
0% Ni
8.8% Ni
0
Z''
(B)
0.5
1.0
0 0.5 1.0 1.5
Z'
Figure 5.5.13: Impedance spectra measured at the end of discharge (A) and charge (B)
for electrodes containing 0% and 8.8% Ni. The electrodes were formed at C/10 rate with
50% overcharge.
144
100
90
80
70
Utilization, %
60
50
40
30
20
10
0
0% Ni - 1 0% Ni - 2 0% Ni - 3 8.8% Ni - 1 8.8% Ni - 2
Figure 5.5.14: Utilization of electrodes with and without nickel. The electrodes were
cycled at C/10 rate with 50% overcharge. The electrodes containing nickel show higher
utilization.
Figure 5.5.15: Top view of SEM image of the nickel hydroxide electrode. The spherical
structures are the nickel hydroxide particles and the filamentary structures are the nickel
210.
145
The EVS scans of electrode with and without nickel are compared in Fig. 5.5.16.
The electrodes without nickel and with nickel were fabricated by screen printing and
spatula pressing, respectively. The β-NiOOH and β-Ni(OH)2 peaks are present for both
the electrodes and they shift towards lower potentials for the electrode containing nickel.
The γ-Ni(OH)2 phase is present for electrode without nickel and is absent for electrode
with nickel. This indicates that the addition of nickel enhances the conductivity of the
The other benefit of adding nickel is the separation of the β-NiOOH peak from the
oxygen evolution as shown in Fig. 5.5.16. This clearly suggests that addition of nickel
enhances the conductivity of the electrode and decreases the side reaction – oxygen
evolution.
0.2
0% Ni, 10% PVDF
8.8% Ni, 8.7% PVDF
0.1
Current/Capacity (h-1)
-0.1
-0.2
-0.3
1.2 1.3 1.4 1.5
E (Volts)
Figure 5.5.16: EVS scans for electrodes containing 0% and 8.8% nickel. The electrodes
were formed at C/10 rate with 50% overcharge.
146
5.5.3.3.Comparison of Electrodes Containing 5.2% and 8.7% PVDF in the
Presence of Fine Ni
In section 5.5.1, it was shown that the utilization increases with increase in PVDF
content. The effect of PVDF in the presence of fine nickel is discussed here. One set of
electrodes containing 5.2% PVDF and the other set of electrodes containing 8.7% PVDF
were formed at C/10 rate with 50% overcharge. The nickel content in these electrodes is
about 8.5-8.7% Nickel. The utilization of these electrodes is shown in Fig. 5.5.17. The
utilization for electrodes containing 5.2% PVDF is less than the electrodes containing
8.7% PVDF. This result agrees with the previous conclusion in section 5.5.1 that the
Cycle 1 Cycle 2
100
90
Utilization, %
80
70
60
50
40
5.2% PVDF 5.2% PVDF 5.2% PVDF 5.2% PVDF 8.7% PVDF 8.7% PVDF
1 2 3 4 1 2
147
5.5.4. Effect of Pressing the Electrode
Electrodes containing 8.5% Ni and 5.2% PVDF were reduced in thickness using a
hot press before the electrodes were formed. Two electrodes were reduced to 50 and 75%
of their original thickness. The electrodes were then characterized using impedance
observed. The utilization of these electrodes also did not change significantly. By
reducing the thickness of the electrodes, volumetric energy density of the battery can be
increased.
When thick inks are used the solvent drying during screen printing results in poor
penetration of the paste into the foam and formation of a thin layer of paste on top of the
foam. This causes particle shedding from the surface of the nickel foam during cycling.
When thin inks are used, they flow through the nickel foam because of the squeegee
pressure resulting in low electrode capacities. These problems are associated with the
screen printed nickel hydroxide electrodes. By impregnating the paste using a spatula
(section 5.6.1) or hot press (section 5.6.2) these problems can be alleviated.
A spatula was used to mechanically press the paste into the nickel foam. This
method is simpler than screen printing and is advantageous when thin inks that flow
easily are used. The composition of the paste in dry active mass was 8.8% PVDF, 8.7%
nickel and the rest nickel hydroxide. The capacities of the electrodes fabricated by screen
printing and by pressing using the spatula are shown in Fig.5.6.1. The theoretical capacity
148
of the electrodes fabricated by spatula was in the range 16-20 mAh/cm2 and was twice
The utilization of the electrodes fabricated using screen printing and spatula is
compared in Fig.5.6.2. The average value of the utilization of the electrodes made by
spatula pressing is larger than that of electrodes made by screen printing. This is in spite
of the fact that the theoretical capacity of the electrodes made by pressing using spatula
being large (Fig. 5.6.1). It is noted that the nickel hydroxide electrodes tested in the low
20
Theoretical Capacity, mAh cm2
16
12
0
Screen Screen Pressed by Pressed by Pressed by Pressed by Pressed by
printing, printing, spatula, spatula, spatula, spatula, spatula,
Sample 1 Sample 2 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5
Figure 5.6.1: Theoretical capacity of electrodes containing 8.8 % Nickel and 8.7% PVDF
(dry active mass) fabricated by screen printing and pressing using flat spatula. The
electrodes were formed at C/10 rate with 50% overcharge.
149
100
Utilization, % 96
92
88
84
80
Screen Screen Pressed by Pressed by Pressed by Pressed by Pressed by
printing, printing, spatula, spatula, spatula, spatula, spatula,
Sample 1 Sample 2 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5
Figure 5.6.2: Utilization of electrodes containing 8.8 % Nickel and 8.7% PVDF (dry
active mass) fabricated by screen printing and pressing using flat spatula. The electrodes
were formed at C/10 rate with 50% overcharge.
The existing fabrication methodology for pasted electrodes involves two steps, (a)
mechanical impregnation of the paste and (b) reducing the electrode thickness by
compression. By using a hot press both the steps can be accomplished in a single stroke.
By adjusting the load of the press and the paste composition, the desired electrode
thickness and electrode capacity can be obtained. The hot press was operated at room
92% was obtained. The existing hot press in the lab operates at heavy loads and is
difficult to press the paste without crushing the nickel foam. The main disadvantage of
this technique is the formation of a thick electrode layer on top or bottom of the nickel
foam due to excess paste and load. These problems can be solved by trial and error
method.
150
5.7. Conclusions
nickel hydroxide electrode. Nickel foam from INCO was used as the substrate. The paste
was the pressed into the foam by two different techniques: (a) screen printing and (b)
using spatula. Electrodes with higher capacity were obtained by mechanical impregnation
The parameters for the electrode formation were varied and their effect on
utilization, impedance spectra and electrochemical voltage spectroscopy data when the
electrode was formed at C/10 or C/20 rate. The electrode is completely formed in two
cycles when overcharged by 50% and in 5 cycles without any overcharge. However, no
differences in utilization, impedance or EVS data are evident with or without overcharge
during formation.
formation, the PVDF content and the nickel content on the electrode performance. In the
overcharging in some regions of the electrode and is evident by the γ-NiOOH phase
formation.
The utilization of the electrodes increases with the PVDF content in the
electrodes, however higher PVDF content also results in the formation of the γ-NiOOH
phase. The electronic conductivity of the Kansai and OMG nickel hydroxide powder was
enhanced by the addition of INCO nickel 210. The electrode paste made from Kansai
151
(with Co and Zn) and OMG nickel hydroxide powder were conductive at 8.4 and 30 wt.
% nickel respectively. The utilization of the electrodes containing fine nickel was
increased by 10% to about 95%. The peak potentials of the β-NiOOH and β-Ni(OH)2
phase decreased with the addition of nickel. The peak of the γ-NiOOH is completely
absent indicating that the overcharging of the electrode is prevented by addition of nickel.
The other beneficial effect is the increase in the separation between the β-NiOOH peak
and the oxygen evolution rise. These clearly show the advantages of the adding of fine
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38. R. N. Basu, S. K. Pratihar, M. Saha, and H. S. Maiti, Materials Letters, 32, 217
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40. L. J. Hobson, Y. Nakano, H. Ozu, and S. Hayase, Journal of Power Sources, 104,
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41. Y. Matsuzaki and I. Yasuda, Solid State Ionics, 152-153, 463 (2002).
42. A. C. Muller, D. Herbstritt, and E. Ivers-Tiffee, Solid State Ionics, 152-153, 537
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(2002).
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154
6. Assembly and Testing of Low Pressure Nickel
Hydrogen Battery
The main objective in this chapter was to assemble and test a low pressure nickel
hydrogen cell. The cell components studied and developed independently were put
together. The factors that affect the cell performance, (a) self discharge, (b) oxygen
A schematic picture of the nickel hydrogen battery is shown in Fig. 6.1.1. The
formed nickel hydroxide electrode and the platinum electrode (from E-tek) separated by a
polypropylene membrane (Celgard 3400) filled with 26 wt. % KOH were assembled in a
bolt-nut cell. The nickel mesh serves as both current collector and gas diffusion layer.
Two chlorinated polyvinyl chloride discs, 3.2 cm in diameter, at the ends of the cell are
for insulation. A nylon bolt, 1/8″ diameter, was used to assemble the cell (Fig. 6.1.1). The
bolt-nut cell is hosted in a stainless steel cylinder filled with hydrogen gas. The inlet and
outlet valves are used for purging and filling the cell to the required hydrogen pressure.
potentiostat/galvanostat as shown in Fig. 6.1.2. The pressure inside the cell is monitored
using a pressure gauge, which is a strain meter from Omega Corporation and is connected
to the outlet of the Ni-H2 cell. The accuracy of the pressure gauge according to
155
was used to convert the analog pressure signal to digital and the data is then logged into a
Positive Negative
electrode electrode
Ni(OH)2 Platinum Insulator
H2
3.2 cm Outlet
Nut valve
Bolt
Outlet
Inlet
Valve
Valve
Pressure
Ni H2 Cell Gauge
+ -
Potentiostat/
Galvanostat
156
6.2. Performance of the Ni-H2 Cell in Comparison to the Liquid Cell
the liquid cell (described in detail in chapter 5). The electrode contained 8.7% PVDF,
8.8% nickel and the rest Ni(OH)2 in dry weight basis. The utilization of these electrodes
efficiency of this electrode when charged completely at C/5 rate without overcharge was
charged to a capacity of 14.3 mAh/cm2 due to the decrease in the oxygen evolution at the
end of charging. The experimental capacity of the electrode was therefore taken as 14.3
mAh/cm2. The performance of this electrode in the Ni-H2 cell will be discussed in this
The voltage profiles during charge and discharge of the nickel hydroxide
electrode at C/5 rate in the liquid cell and in the nickel-hydrogen cell configuration are
compared in Fig. 6.2.1. It is noted that the nickel hydroxide electrode in the nickel-
hydrogen cell was charged to only 90% of the experimental capacity (14.3 mAh/cm2). It
is evident that the charge voltage is larger and the discharge voltage smaller for the
nickel-hydrogen cell in comparison to the liquid cell measurement. This indicates larger
overpotentials for the nickel-hydrogen cell than observed in the liquid cell. It is noted that
the voltage measured in the liquid cell includes only the overpotentials for the solution iR
loss and the nickel hydroxide electrode. However for the Ni-H2 cell, in addition to the
above overpotentials, the voltage measured also includes the overpotential for the
157
The coulometric efficiency of the nickel-hydrogen cell was about 90.9-91.2 %
(charged to 90% experimental capacity) and is lower than the coulometric efficiency of
the nickel hydroxide electrode in the liquid cell, 93.2-96.3% (charged to 100%
experimental capacity). Fig. 6.2.1 shows a change in slope at the end of charging both in
the liquid cell and nickel-hydrogen cell tests suggesting that the oxygen evolution is the
reason for the decrease in coulometric efficiency. This will be discussed in more detail in
1.5
Ni-H2 cell
1.4
Ni(OH)2 electrode
E (Volts)
1.3
Ni-H2 cell
1.2
1.1
0 1 2 3 4 5
Time (Hours)
Figure 6.2.1: Voltage profile of the nickel hydroxide electrode during charge and
discharge in the liquid cell and in the nickel-hydrogen cell configuration.
Impedance spectra measured in the frequency range 20000 to 0.2 Hz, at the end of
discharge and charge in the liquid cell and nickel-hydrogen cell configuration are
compared in Figs. 6.2.2A and 6.2.2B. It is evident from the figures, that the impedance at
the end of charge and discharge is larger for the nickel hydrogen cell in comparison to the
158
liquid cell. This explains the higher charge voltage and the lower discharge voltage
observed in Fig. 6.2.1. The major difference between the two measurements is that the
impedance measured in the case of the nickel-hydrogen cell configuration includes the
impedance of both the nickel hydroxide and the platinum electrode (two electrode cell).
However, in the case of the liquid cell measurements a reference electrode is used and the
The impedance spectra measured at the end of charge and discharge in the nickel-
hydrogen cell configuration show two semi-circles, whereas only one semi-circle is
evident in the liquid cell configuration. The two semi-circles present in the impedance
spectra are related to the charge transfer resistances associated with the nickel hydroxide
electrode and the ESNS platinum electrode. This was confirmed by comparing time
configurations.
The electrochemical parameters and the time constant associated with the charge
transfer reaction (hydrogen evolution, hydrogen oxidation) and double layer charging of
the ESNS platinum electrode are listed in Table 6.1. The time constant is estimated as the
product of charge transfer resistance and double layer capacitance, which are measured
by a semi-circle fit to the impedance data. The time constant for the platinum electrode
measured in the liquid cell and in the nickel hydrogen cell configuration (two negative
electrodes in bolt nut cell as described in detail in Chapter 3) are in the same range, 160-
The time constant for the nickel hydroxide electrode relevant to the charge
transfer reaction and double layer capacitance in the liquid cell configuration is listed in
159
Table 6.2. The resistance and the capacitance measured are different for the electrode in
the charged and in the discharged states, however, the time constant is about 10 ms, an
order of magnitude lower in comparison to the time constant measured for the platinum
The time constants of the two semicircles evident in the impedance spectra
measured in the nickel-hydrogen cell configuration (Fig. 6.2.2) were calculated and are
listed in Table 6.3. It is extremely difficult to calculate the charge transfer resistance and
the double layer capacitance of the 2nd semi-circle accurately using the data available.
The frequency corresponding to the last data point of the 2nd semi-circle is 0.2 Hz and the
relevant frequency of the semi-circle is less than 0.2 Hz. The frequency of first semi-
circle is 14-28 Hz, about the same as that measured for the nickel hydroxide electrode in
the liquid cell configuration (Table 6.2). The frequency of the 2nd semi-circle is about 0.2
Hz and is close to the frequency estimated for the platinum electrode (Table 6.1). This
strongly suggests that the negative electrode is the main contributor to the large
for the platinum electrode, about 2.6 Ω cm2, has been obtained. The solution resistance is
about 0.6 Ω cm2. The corresponding overpotentials including the solution and the charge
transfer resistances are small (about 10 mV). Unused platinum electrodes have low
charge transfer resistance resulting in low charge voltage and high discharge voltage.
However, the charge transfer resistance of the platinum electrode is always larger than
160
-10
Liquid cell
Ni-H2 cell
-5
(A)
Z''
5
0 5 10 15
Z'
-5
Liquid cell at 100% DOC
Ni-H2 cell at 90% DOC
-4
-3
(B)
Z''
-2
-1
1
0 1 2 3 4 5 6
Z'
Figure 6.2.2: Impedance spectra measured at the end of discharge (A) and charge (B) for
electrodes cycled at C/5 rate in liquid cell and nickel-hydrogen cell configuration.
161
Table 6.1: Parameters associated with the ESNS platinum electrode.
Mode of cell test Rct, Cdl, Time constant, Frequency,
Ω cm2 F/cm2 mS Hz
Liquid cell 0.88 0.4 350 0.45
Ni-H2 cell, Best condition 0.74 0.222 160 0.97
Ni-H2 cell, Used condition 3.5 0.058 200 0.78
especially for the nickel hydrogen cells that evolve oxygen as a side reaction at the end of
charging.
of charge is analogous to the depth of discharge typically used in lithium ion batteries.
Depth of charge is defined as the charge applied to the cell from a state of complete
discharge. This parameter is more relevant to the nickel hydrogen cells, whose efficiency
and cycle life, as will be shown in this chapter, is highly dependent on the depth of
162
The voltage profile during charge and discharge of the nickel-hydrogen cell
cycled at C/5 rate to different depth of charge is shown in Fig. 6.3.1. The charge cut off is
based on the depth for charge, e.g. for 50% DOC the cell is charged for 2.5 h (at C/5
rate). The end of discharge is based on the cut-off voltage of 1.15 V, which is determined
by the knee at the end of the discharge profile. It is evident from Fig. 6.3.1 that the cell
cycles well at different depth of charges. For 90% DOC, a change in slope at the end of
charging due to oxygen evolution is observed. The coulometric efficiency decreases with
increase in the different depth of charge as listed in Table 6.4. This supports the
discussions in chapter 5 that the side reaction, oxygen evolution, increases at higher
charge potentials (which translates to longer charging times, here) leading to a decrease
in efficiency.
163
1.5
Charge
1.4
E (Volts)
1.3 End of
discharge
(A)
cutoff
Discharge
1.2
1.1
0 1 2 3
Time (Hours)
1.5
1.4
E (Volts)
1.3 (B)
1.2
1.1
0 1 2 3 4
Time (Hours)
1.5
1.4 O2
Evolution
E (Volts)
1.3 (C)
1.2
1.1
0 1 2 3 4 5
Time (Hours)
Figure 6.3.1: Charge-discharge voltage profiles of the nickel-hydrogen cell cycled at C/5
rate to different depth of charge: (A) 50% DOC, (B) 70% DOC and (C) 90% DOC.
164
Table 6.4: Coulometric efficiency of the Ni-H2 cell as a function of depth of charge
cycled at C/5 rate.
Depth of charge, % Efficiency
50 95.5
70 94.2
90 91.2
It is well known that the nickel hydrogen cells suffer from self discharge due to
and KOH electrolyte. The self discharge rate is directly proportional to the hydrogen gas
pressure inside the cell. Monitoring and understanding the self discharge is therefore
The self discharge in our low pressure nickel hydrogen battery should be lower
than in the high pressure nickel hydrogen batteries used in space applications. The self
discharge phenomenon was studied by introducing a rest period between charge and
discharge. The rest period was varied and the coulometric efficiency was estimated. The
voltage profiles during charge and discharge of the nickel-hydrogen cell with different
rest periods, 5 min, 1h and 6h are shown in Fig. 6.3.2. It is evident that the discharge time
decreases with increase in the rest period. This indicates that the low pressure nickel
165
1.5
1.4
Discharge
E (Volts)
time
1.3 decreases
5 min
1.2 1h
6h
1.1
0 1 2 3 4 5
Time (Hours)
Figure 6.3.2: Charge-discharge voltage profiles of the nickel-hydrogen cell cycled at C/5
rate to 90% DOC with different rest periods, 5 min, 1h and 6h.
Coulometric efficiency of the cell was determined for different rest periods at 50,
70 and 90% depth of charge and is shown in Figures 6.3.3, 6.3.4 and 6.3.5 respectively.
The coulometric efficiency decreases with rest period for all depths of charge and
indicates self discharge of the battery. A straight line was used to fit the coulometric
efficiency as a function of the rest period. The slope of the linear fit (Figs. 6.3.3, 6.3.4,
and 6.3.5) shows that the rate of self discharge is about 1% per hour. This indicates that
the battery will discharge completely in about 100 hours. No definite difference in the
166
96
Figure 6.3.3: Coulometric efficiency of the Ni-H2 cell as a function of the rest period at
50% DOC, cycled at C/5 rate.
Equation: y = A + B*x
94
Columetric efficiency (%)
R^2 = 0.996
A 93.67 ±0.29
B -1.29 ±0.08
92
90
88
86
0 1 2 3 4 5 6
Rest period after charge, h
Figure 6.3.4: Coulometric efficiency of the Ni-H2 cell as a function of the rest period at
70% DOC, cycled at C/5 rate.
167
92
Equation: y = A + B*x
88
86
84
0 1 2 3 4 5 6
Rest period after charge, h
Figure 6.3.5: Coulometric efficiency of the Ni-H2 cell as a function of the rest period at
70% DOC, cycled at C/5 rate.
The coulometric efficiency of the cell for different depth of discharges and
different rest periods was compiled and is shown in the Fig. 6.3.6. The efficiency
decreases with increasing depth of charge because of the oxygen evolution reaction at the
(EVS) study of the nickel hydroxide electrodes. The efficiency at 90% depth of charge is
dramatically lower than that at 50 and 70% depth of discharge for 5 min and 1h rest
periods when the efficiency is primarily determined by the amount of oxygen evolution
during charge. This result will be substantiated by analyzing the pressure variations at the
For a given depth of discharge, the efficiency decreases with increase in the rest
period and is due to the self discharge of the battery. This will be verified below by
analyzing the pressure variations during the rest period. The decrease in efficiency from 5
168
min rest period to 6h rest period is about the same for all depths of charge, indicating that
96
0.083h
1h
Columetric efficiency
94 6h
92
90
88
86
50 60 70 80 90
Depth of charge (%)
Figure 6.3.6: Coulometric efficiency of the Ni-H2 cell cycled at C/5 rate as a function of
the depth of charge for different rest periods.
The voltage variations during the charge, the rest, and the discharge period of the
cell cycled at C/5 rate to 90% depth of charge are shown in Fig. 6.4.1. The rest period in
this case is about 6h. It is evident from the figure that the voltage increases during charge,
followed by relaxation of the voltage during the rest period. Subsequently, during
discharge the voltage drops until the cut-off voltage of 1.15V is reached followed by
relaxation of the voltage during the rest period for 6h. The change in slope at the end of
The cell pressure was measured simultaneously during the charge-discharge cycle
and is shown in Fig. 6.4.2. The pressure inside the cell increases during charge due to the
formation of hydrogen at the platinum electrode. The rate of pressure increase is linear
169
and corresponds to the current applied to the cell. Based on the pressure change and
charge passed, the gaseous volume inside the cell was estimated as 40 cc. During the rest
period, the pressure is not constant as one would expect; instead a decrease in the
hydrogen pressure is seen. This decrease in pressure can be accounted for by two
decrease. In reality, the pressure decrease is a combination of the above two mechanisms
and will discussed in detail, below. The pressure decreases linearly during discharge
because of the hydrogen oxidation at the platinum electrode. During the rest period after
1.5
Discharge
1.4
Rest
E (Volts)
Charge Rest
1.3
1.2
1.1
0 5 10 15 20
Time (Hours)
Figure 6.4.1: Voltage variation during charge, rest and discharge periods of a cycle. The
cell was cycled at C/5 rate to 90% depth of charge. The rest period is 6h.
170
36
Absolute Pressure, psi
34
32
30
28
Rest
26 Charge Rest
Discharge
24
0.0 4.0 8.0 12.0 16.0 20.0
Time, h
Figure 6.4.2: Changes in pressure during the charge, the rest and the discharge periods of
a cycle. The cell was cycled at C/5 rate to 90% depth of charge. The rest period is 6h.
The pressure inside the cell as a function of the charge time is shown in the Fig.
6.4.3. The pressure variation during the initial charging time (0 to 1h) was fitted to a
straight line. The slope of the linear fit (parameter B), 2.52 psi/h, in Fig. 6.4.3
towards the end of the charging phase is non-linear when compared to the straight line fit.
shown in Fig. 6.4.4. At initial charge times, it is assumed there is no significant oxygen
evolution and that all current goes to the main reaction which is oxidation of nickel
171
corresponding to the rate of hydrogen formation as shown by a straight line marked as
‘No O2’ in Fig. 6.4.4, which assumes that there is no oxygen evolution.
In reality, as evident in the voltage profile change at the end of charging (Fig.
6.4.1) part of the current to the nickel hydroxide electrode goes to oxygen evolution,
electrode, there is also oxygen evolution in the nickel hydroxide electrode causing a steep
rise in pressure as shown by the curve marked as ‘Yes O2 Poor recombination’ in Fig.
6.4.4. It is assumed here that the recombination of oxygen with hydrogen is poor and
rapidly with the hydrogen evolved at the platinum electrode a decrease in the pressure
rate will be evident as shown by the curve marked as ‘Yes O2 Good recombination’ in
Fig. 6.4.4. It is evident by comparing Figs. 6.4.3 and 6.4.4 that the evolved oxygen does
recombine with hydrogen during charging. This is evident from the difference in the
predicted pressure based on the linear fit and the measured pressure at the end of 4.5 h,
which is about -0.84 psi. This indicates that the measured pressure at the end of the
charge period (4.5 h) is mostly hydrogen plus a small amount of the oxygen that has not
recombined.
172
36 0.84
y = A + B*x
34
A 25.42
Pressure, psia
32 B 2.52
30
Non-linear
28
26
Figure 6.4.3: Changes in pressure during the charge. The cell was cycled at C/5 rate to
90% depth of charge.
Yes O2
Poor recombination
No O2
Pressure
Yes O2
Good recombination
Charge time
Figure 6.4.4: Schematic representation of different pressure variations due to different
possible mechanisms during charging.
173
6.4.2. Pressure Variations During the Rest Period
The pressure in the cell decreases monotonously during the rest period is shown
in Fig. 6.4.5. This pressure drop when no charge or discharge current is applied to the cell
is due to (a) the recombination of oxygen with hydrogen gas and (b) the self discharge of
the cell. The leftover oxygen gas that was not recombined during the charge period
recombines at the Pt electrode. The self discharge occurs due to the oxidation of the
hydrogen gas at the nickel electrode and reduction of nickel oxyhydroxide to nickel
hydroxide. Both these processes results in the decrease of hydrogen pressure in the cell. It
is noted that the noise in the pressure data is due to 60 Hz electrical noise introduced
The self discharge rate is assumed constant at a given state of charge of the
battery. Therefore the hydrogen pressure in the cell will decrease linearly with rest time
as a result of self discharge. It is also evident from the Fig. 6.4.5 that the pressure change
is linear in the rest period from 3 to 6h and therefore it is assumed that all oxygen
recombination is complete in the first 3h of the rest period. A linear fit to the pressure
data in the time period, 3 to 6h is shown in Fig. 6.4.5. The error calculated for the linear
fit is very small. The slope of the line or the rate of the pressure change is 0.108 psi/h.
This self discharge rate is about 23 times slower than the charge rate (C/5). At this rate,
the cell will discharge completely in about 117h and the self discharge rate can be
expressed as C/117. In principle, the self discharge rate is not constant and decreases with
decrease in state of charge of the cell and therefore the cell will last significantly longer
than 117h. It is noted that the linear fit based on the coulometric efficiency data estimated
the self discharge rate as C/100 (section 6.3.2). This agrees well with the result based on
174
the pressure data analysis. Based on the self discharge rate, the drop in pressure due to
self discharge is about 0.648 psi. The effect of state of charge of the nickel-hydrogen cell
36.0
Equation: y = A + B*x
R^2 = 0.90743
35.8 A 35.45 ±0.002
-4
Pressure, psia
B -0.108 ±3.4x10
35.6
35.4
35.2
35.0
34.8
34.6
0.0 1.4 2.8 4.2 5.6 6.9
Rest period, h
Figure 6.4.5: Pressure changes during the rest period. The cell was cycled at C/5 rate to
90% depth of charge. A straight line is fit to the pressure data in the 3 to 6h rest period
and extrapolated back to time 0.
The pressure contribution due to the self discharge of the cell during the rest
period based on the linear fit was subtracted from the total pressure data and the
difference, the pressure contribution due to the recombination reaction, is plotted in Fig.
6.4.6. The pressure variation due to the recombination reaction follows an exponential
decay and the pressure changes are nearly complete in 2h. The recombination of oxygen
with hydrogen gas is considered to be a first order reaction in oxygen and zero order in
175
hydrogen due to hydrogen excess in the cell. The rate equation for the recombination
reaction is:
dP
= − kP
dt
P = P0 exp( − kt )
where P0 is the initial pressure of oxygen. The above solution is in the form of an
exponential decay. Therefore the pressure drop due to the recombination reaction was
fitted to an exponential decay equation as shown in Fig. 6.4.6. An excellent fit with low
error values is obtained. The parameter P0 represents the total pressure drop due to the
recombination reaction during the rest period and is 0.445 psi. The pressure drop due to
the self discharge (0.648 psi) and that due to the recombination are of the same order and
therefore neither one can be neglected. The time constant t1 represents the total time it
takes to for all oxygen to recombine completely and is 1.02 h. In comparison, the time
constant for the recombination reaction obtained for just the platinum electrode in a
separate experiment, is about 15 min. This difference in time indicates that the
recombination process is limited by the diffusion of oxygen from the nickel hydroxide
electrode to the platinum electrode. The reciprocal of time constant t1 gives the rate
176
0.5
Equation: P = P0exp(-t/t1)
0.4 R^2 = 0.93
P0 0.445 ±0.001
Pressure, psia
-3
0.3 t1 1.02 ±4.4x10
0.2
0.1
0.0
Figure 6.4.6: Pressure changes due to recombination reaction during the rest period. The
cell was cycled at C/5 rate to 90% depth of charge. An exponential decay line is fit to the
pressure data.
The self discharge rate determined by the linear fit described in section 6.4.2 is
plotted as a function of depth of charge for two datasets from the same cell in Fig. 6.4.7.
It is evident from the figures that the self discharge rate is lower for 50% depth of charge
in comparison to the 70% and 90% DOC. The self discharge rate at 50% DOC is 0.068
psi/h and corresponds to a rate of C/180. Dataset 1 shows that the self discharge rate
increases with depth of charge; however no definite trend is noted for dataset 2. For the
70% and 90% DOC, the self discharge rate varies between 0.11 and 0.14 psi/h. This
corresponds to rates of C/117 and C/90. The decrease in hydrogen pressure in the rest
period due to self discharge can be calculated by multiplying the self discharge rate with
177
0.16
Data set 1
Self discharge rate, psi/h Data set 2
0.12
0.08
0.04
0.00
50 70 90
Depth of charge, %
Figure 6.4.7: Self discharge rate estimated as a function of depth of charge for Dataset 1
and 2.
6.4.4. Recombination in the Ni-H2 Cell During Charge and Rest Period
The difference in the predicted pressure based on the linear fit and the measured
pressure at the end of the charge as described in section 6.4.1 was calculated for different
depth of charge. This decrease in pressure is due to the recombination of hydrogen gas
with oxygen gas and will be referred to as the pressure drop due to recombination
(∆P(H2/02)) during the charge period. It is noted here that only a fraction of oxygen
formed is recombined during the charging period and the rest recombines during the rest
period. The pressure drop due to the recombination reaction in the rest period was
the charge and the rest period is shown in Fig. 6.4.8. The pressure drop due to the
178
recombination increases with increase in the depth of charge. Assuming that the
recombination rate is the same at all depth of charges, the figure indicates that the oxygen
evolution increases and therefore the recombination increases with the depth of charge.
This increase in oxygen evolution agrees well with the coulometric efficiency results,
(section 6.3.1) which show a decrease in efficiency with increase in depth of charge.
Comparing the pressure drops in the charge and the rest period, it is evident that
about 70% of the recombination is complete during the charge period for the 70 and 90%
DOC and about 50% of the recombination is complete for the 50% DOC. This clearly
The rate constant obtained for the recombination reaction is about the same, 0.94
h-1, for all depths of charge. This indicates that all the recombination is complete during
1.0 Charge
Rest
∆P( H2 / O2), psi
0.8
0.6
0.4
0.2
0.0
50 70 90
Depth of charge, %
Figure 6.4.8: Pressure drop due to the recombination reaction as a function of depth of
charge during the charge and the rest period.
179
6.4.5. Pressure Contributions – Self discharge and Recombination
The pressure loss contribution due to self discharge and recombination at different
depths of charge for the nickel-hydrogen cell is listed in Table 6.5. The rest period
between the charge and the discharge is 6h. It is evident that the pressure loss due to the
total recombination (including charge and rest) and self discharge increases with the
depth of charge. In terms of percentage loss, the self discharge contribution decreases
with depth of charge. This indicates that the oxygen evolution is the major mechanism for
pressure loss at deep depth of charges and the self discharge is the major mechanism for
For the 5 min and 1h rest periods, oxygen evolution is the predominant factor for
Table 6.5: Pressure loss contributions of recombination and self discharge for 6h
rest period.
Pressure drop 50% DOC 70% DOC 90% DOC
Recombination, psi 0.22 0.62 1.48
Self discharge, psi 0.41 0.68 0.77
Recombination, % 34.6 47.9 65.7
Self discharge, % 65.4 52.1 34.3
nickel-hydrogen cell for different depth of charge was calculated based on the pressure
data analysis and are shown in the Figs. 6.4.9 (A), (B) and (C). The rest period between
The coulometric efficiency for the 50% depth of charge is 89.9%. The efficiency
loss is due to self discharge and oxygen evolution. The efficiency loss due to self
180
discharge is higher than the loss due to the O2 evolution. As expected, the coulometric
efficiency drops to 84.9% and 83% for 70% and 90% depth of charge. For the 70% depth
of charge, the efficiency loss due to self discharge and oxygen evolution are about the
same. At 90% depth of charge, the efficiency loss due oxygen evolution is two times that
In comparing the Figs 6.4.9(A), (B) and (C), it is evident that the efficiency loss
due to O2 evolution increases with increase in the depth of charge (as observed in the
pressure data measurements) from 3.5% for the 50% depth of charge to 11.3% for the
90% depth of charge. This indicates that the oxygen evolution is the main contributor to
efficiency loss at high depth of charge. The efficiency loss due to self discharge for 50,
For the 5 min and 1h rest periods, the efficiency loss is mainly due to the oxygen
181
Efficiency
89.9%
O2 evolution (A)
3.5%
Self discharge
6.6%
Efficiency
84.9%
O2 evolution
7.2% (B)
Self discharge
7.9%
Efficiency
83%
O2 evolution
11.3% (C)
Self discharge
5.7%
Figure 6.4.9: Contributions of different processes at different depth of charge: (A) 50%
(B) 70% and (C) 90%. The rest period is 6h.
182
6.5. Comparison of Efficiency Based on Charge Data and Pressure Data
data analysis for two different data sets in Figs. 6.5.1 and 6.5.2. The estimated efficiency
based on the pressure data matches the efficiency based on the charge data for the 50%
depth of charge very well. However, small differences of about 2% are observed for the
70 and 90% depth of charge. The pressure data analysis under predicts the actual
coulometric efficiency observed. For a practical cell, under prediction would be preferred
These two figures clearly show that the efficiencies obtained from pressure data
analysis are correct and supports the analysis of extracting the contributions of different
mechanisms during charge and discharge of the nickel hydrogen cell. With the clear
understanding of the pressure variations during charge and discharge, it is possible to use
the pressure data, in addition to other methods, to reliably estimate the state of charge of
the nickel-hydrogen cells. In fact, the pressure data will be more reliable as it directly
accounts for the self discharge and the oxygen evolution occurring in the cell.
The performance of the nickel-hydrogen cell was also studied in the pressure
range 0.4-1 atm. The cell was cycled to different depth of charge with different rest
periods between charge and discharge. The pressure data and the charge-discharge data
were analyzed. The results obtained regarding the different mechanisms – self-discharge,
oxygen evolution and recombination were the same as discussed earlier for the nickel
183
Data set 1
Charge data
Efficiency, % 90 Pressure data
80
20
10
0
50 70 90
Depth of charge, %
Figure 6.5.1: Comparison of efficiency calculated based on the charge data and pressure
data at different depth of charge for data set 1.
Data set 2
100
Charge data
Pressure data
90
Efficiency, %
80
20
10
0
40 50 60 70 80 90 100
Depth of charge, %
Figure 6.5.2: Comparison of efficiency calculated based on the charge data and pressure
data at different depth of charge for data set 2.
184
6.7. Cycle Life Tests
The cycle life of the nickel-hydrogen cells were investigated using the Arbin test
station. Two cells of different experimental capacities, one 41 mAh and another 62.5
mAh were cycled at C/5 rate to 90% of their capacity. The discharge capacity as a
function of cycles for the two nickel-hydrogen cells is shown in Figs. 6.7.1 and 6.7.2. The
41 mAh cell (Fig.6.7.1) degrades with cycling and loses about 50% of its capacity by 40
cycles. The 62.5 mAh cell (Fig. 6.7.2) provides constant discharge capacity for 10 cycles
and then degrades significantly losing 50% of its capacity by 20 cycles. The failure of the
The voltage profiles during the charge-discharge of cycles 1, 4 and 12 are shown
in Fig. 6.7.3. It is evident that the discharge time increases from cycle 1 to 4 and then
decreases to cycle 12. The voltage profile for the 12th charge shows a larger voltage at
the end of charging in comparison to 1st and 2nd charge. The voltage profiles of cycles 15,
18 and 21 are shown in Fig. 6.7.4. The discharge time (coulometric efficiency) of the
nickel-hydrogen cell decreases rapidly from cycle 15 to 21. The voltage profile during
charge for cycles 15, 18 and 21 shows a large change in voltage at the end of the
charging. This change to higher voltage corresponds to oxygen evolution during charge.
The timing of this transition to larger voltage decreases with cycles. This clearly shows
large amounts of oxygen evolution in the cell, which results in the decrease in
The end of charge voltage as a function of cycle number is shown in Fig. 6.7.5. It
is evident that the voltage increases at a slow rate below 11 cycles and then increases
rapidly from cycle 12 to 22. This corresponds well with cycle life data shown in
185
Fig.6.7.2. The pressure inside the cell at the end of every cycle is shown in Fig.6.7.6. The
pressure increases with cycles suggesting that the oxygen evolved does not recombine
completely during the rest period or during the subsequent discharge. The pressure
increases at a slow rate until cycle 14, and then increases rapidly. This again agrees with
the fact that the discharge capacity is constant up to 10 cycles and then decreases rapidly
Based on the results, the failure of the battery can be explained as follows:
• If the oxygen recombines with hydrogen at the platinum electrode, the total
water content in the cell does not change and should not affect the cell
evolution. This creates a loop resulting in more and more oxygen evolution
The picture of the failed cell is shown in Fig. 6.7.7. It is noted that nickel
hydroxide material is extruded out of the nickel foam and can be seen as a lump in the
picture. This is the typical mode of failure of these nickel hydrogen cells.
The cycle life performance of the cell needs to be improved by facilitating easy
recombination at the negative electrode and preventing material extrusion from the nickel
186
hydroxide electrode. These two modes of failure need to studied in detail to enhance the
cycle life.
35
Discharge capacity, mAh
30
25
20
15
10
0
0 10 20 30 40 50
Cycle Index
Figure 6.7.1: Discharge capacity as a function of cycle index for a nickel-hydrogen cell
with a capacity of 41 mAh. The cell was charged at C/5 rate to 90% depth of charge.
60
Discharge capacity, mAh
50
40
30
20
10
0
0 5 10 15 20 25
Cycle index
Figure 6.7.2: Discharge capacity as a function of cycle index for a nickel-hydrogen cell
with a capacity of 62.5 mAh. The cell was charged at C/5 rate to 90% depth of charge.
187
1.55
1.5 12
4
1.45 1
1.4
Voltage(V)
1.35
1.3
1.25
1.2 12 4
1
1.15
1.1
0 2000 4000 6000 8000 10000 12000 14000 16000 18000
Time (s)
Figure 6.7.3: Voltage profiles during charge and discharge for cycles 1, 4 and 12. The
capacity of the cell was 62.5 mAh.
1.55 21
18
1.5
15
1.45
1.4
Voltage (V)
1.35
1.3
1.25
1.2
21 15
1.15
18
1.1
0 2000 4000 6000 8000 10000 12000 14000 16000 18000
Time (s)
Figure 6.7.4: Voltage profiles during charge and discharge for cycles 15, 18 and 21. The
capacity of the cell was 62.5 mAh.
188
1.54
1.5
1.48
1.46
1.44
0 5 10 15 20 25
Cycle Index
Figure 6.7.5: End of charge voltage as a function of cycle index. The capacity of the cell
was 62.5 mAh.
20
16
Pressure (psi)
12
0
0 5 10 15 20 25
Cycle index
Figure 6.7.6: Pressure measured at the end of every cycle. The capacity of the cell was
62.5 mAh.
189
Figure 6.7.7: Picture of the failed nickel-hydrogen cell at the end of experiment.
6.8. Conclusions
A low pressure nickel hydrogen battery of 2-3 atm. pressure was successfully
performance of the individual electrodes in the liquid cell configuration. It was shown
that the increase in charge voltage and the decrease in the discharge voltage of the Ni-H2
cell in comparison to the liquid cell are due to the large charge transfer resistance of
platinum electrode. It is noted that the charge transfer resistance is significantly reduced
for fresh negative electrodes and the total overpotential drop in these cells is small, about
10 to 20 mV.
oxygen evolution increases with depth of charge. The efficiency also decreases with
increase in the rest period after charge indicating self-discharge of the nickel-hydrogen
cell.
190
The pressure data measured simultaneously during charge and discharge were
analyzed. The results and discussions show that the oxygen evolution is observed at the
end of charging and increases with depth of charge supporting the charge data
measurement. The evolved oxygen recombines with the hydrogen gas and about 70% of
recombination occurs during the charge period. The rest of the recombination (30%) is
complete in the first 1h of the rest period. The recombination time constant is 1h in the
nickel-hydrogen cell in comparison to 15 min measured for a cell containing only the
platinum electrode. The time constant is large because the oxygen formed at the nickel
hydroxide electrode has to diffuse to the platinum electrode. The self discharge rate was
measured and is about C/117 at 90% DOC indicating that battery will discharge
completely in 117h.
Coulometric efficiency was estimated based on the pressure data analysis and
compares well with coulometric efficiency calculated based on the charge-discharge data.
SOC of the Ni-H2 cell can be estimated by monitoring the cell pressure in addition to the
The cycle life of the Ni-H2 cells was limited by the large amount of oxygen
evolution and poor recombination. More studies need to be done to enhance the cycle life
191
7. Low Pressure Nickel-Hydrogen Battery with
Metal Hydride
In this chapter, the performance of the nickel-hydrogen cell using a metal hydride
for hydrogen storage will be discussed. The aspects of fuel gauging and state of charge
estimation and the problems associated with the nickel-hydrogen battery will be
introduced. The metal hydride technology for hydrogen storage will be briefly reviewed.
The differences between the nickel-metal hydride battery and our low pressure nickel-
Metal hydride technology was developed in the 1970’s for hydrogen storage
The nickel metal hydride cell has higher gravimetric and volumetric energy densities than
the conventional nickel cadmium cell by approximately 30-40% for cells of the same
size. They are also environmentally benign in comparison to the toxic cadmium present
hydride forming element (A) and one weak hydride forming element (B). Commonly
used hydrogen storage alloys are (1) a wide set of alloys composed of rare earth elements
with nickel (AB5 type systems) and (2) alloys of zirconium, vanadium, magnesium and/or
titanium with nickel (A2B, AB or AB2 type systems). Various hydrogen storage alloy
192
systems used as metal hydride negative electrodes are reviewed by Klepris et al.12 and
Feng et al13.
The performance of the metal hydride electrodes are measured in terms of their
capacity, cycle life and power density. These capabilities are determined by the kinetics
of the processes occurring at the electrode/electrolyte interface and the rate of hydrogen
diffusion in the bulk of the alloy. For good cycle life, the metal hydride electrodes should
exhibit good oxidation resistance in alkaline electrolyte and when exposed to oxygen gas.
The nickel metal hydride battery operates in a strongly oxidizing environment containing
highly concentrated alkaline electrolyte. Therefore, the chemical elements often react to
form oxides (e.g. Lanthanum oxide13-16, Magnesium oxide17, 18) and fail to store hydrogen
reversibly. In some metal hydride systems, the metal (aluminum) dissolves19 and
migrates to the positive electrode. The oxidation of the chemical elements and dissolution
of aluminum in the metal hydrides can be minimized by adding Pd to the metal hydride17,
18, 20-34
. Palladium is added to the metal hydride by either electroless coating20-23, ball
milling along with the hydrogen storage alloy18 and electrodeposition17. High resolution
have shown that the addition of Pd minimizes the formation of Mg(OH)2 and La(OH)218.
These studies show that addition of Pd by coating or by bulk mixing (ball milling) to
The other factor that increases the corrosion of the metal hydrides is commonly
193
electrode which has high storage capacity and large molar volume of hydrogen in the
hydride phase will undergo large volume changes upon cycling and pulverize rapidly.
This results in increased particle to particle contact resistance and polarization resistance
formulate electrodes with low molar volume of hydrogen or with a narrow plateau region
from Pd-coated alloy has much less ohmic resistance (particle to particle contact
resistance and current collector to electrode pellet contact resistance) when compared to
bare alloy. Researchers have also shown that the addition of palladium also enhances the
spectroscopy and linear polarization have shown that the polarization resistance for the
hydrogen desorption/adsorption reaction is smaller when the metal hydride is coated with
Pd. Other studies show that the addition of Ce to the AB5 alloy37 retards corrosion
a protective oxide film on the metal surface37. These studies indicate that the cycle life of
The two factors discussed above, (a) surface passivation due to the presence of
surface oxide or hydroxide and (b) pulverization due to the large molar volume of
hydrogen in the hydride phase, primarily determine the cycle life of the battery. No other
194
7.1.3. Comparison of Metal Hydride in Ni-MH and Low Pressure Ni-H2 Cell
The low pressure nickel hydrogen battery developed in this work uses a metal
hydride to store the hydrogen gas. The major difference between the low pressure nickel
hydrogen battery and the Ni-MH battery is that the metal hydride in the Ni-H2 cell is no
longer an electrode but just a hydrogen storage alloy. The metal hydride is physically and
electrically separated from the electrodes and the highly concentrated electrolyte in the
Ni-H2 cell. This should significantly reduce the oxidation of the chemical elements in the
metal hydride and enhance the cycle life of the metal hydride. The metal hydride used in
our Ni-H2 cell is LaAl0.3Ni4.7 surface modified by Pd and was developed in Prof. Payer’s
lab34, 36, 38 (Material Science dept.). Test results showed that the metal hydride does not
metal hydride is used as a negative electrode (in a Ni-MH cell) or as a hydrogen storage
alloy (in a low pressure Ni-H2 cell). The consequence of pulverization of particles is
electrical isolation. In the case of Ni-MH cells, pulverization leads to increased particle to
particle contact resistance, metal hydride to current collector resistance and polarization
The increase in the polarization resistance is due to the decrease in the electrochemically
active area of metal hydride as a result of increased particle to particle contact resistance.
All these factors contribute to the decrease in the capacity and cycle life of the metal
as follows:
M + xH 2O + xe − U MH x + OH − [7.1]
195
where M is the hydrogen storage alloy that forms metal hydride MHx. The water in the
In comparison, the pulverization of the metal hydride particles in the low pressure
Ni-H2 cell does not affect the capacity or cycle life of the metal hydride. The broken
reaction which occurs through the interaction of hydrogen gas with the hydrogen storage
material M as follows:
1
M (s) + xH 2 ( g ) U MH x ( s ) [7.2]
2
Therefore the contact resistance and the polarization resistance for the electrochemical
mechanism in the case of the Ni-MH cell becomes irrelevant for the low pressure Ni-H2
cell. The pulverization phenomenon will not affect the cycle life of the Ni-H2 cell. In
addition, the metal hydride, LaAl0.3Ni4.7 surface modified by Pd, used in our low pressure
Ni-H2 cell has a fairly narrow plateau width, ∆x = 0.62 approximately. This compares
well with the plateau width, ∆x = 0.54 of the stable metal hydride La0.7Sm0.3Ni4.0Fe1.035.
The narrow plateau width also significantly reduces the decrepitation phenomena of the
metal hydride.
minimizing the formation of metallic oxides and the pulverization of the particles. This is
pressure nickel hydrogen batteries. However, the cycle life of the metal hydride in the
low pressure Ni-H2 cell is enhanced (in comparison to Ni-MH cell) due to two reasons.
1. In the low pressure nickel hydrogen cells, the formation of oxide is significantly
lower because the metal hydride is physically separated from the electrolyte.
196
2. The pulverization phenomena does not decrease the capacity of the metal hydride
LaNi4.7Al0.3 with palladium developed by Shan et al (Prof. Payers Lab, Material Science
Dept., Case Western Reserve University) was used in our nickel hydrogen cell setup. The
isotherm (PCI) of the surface modified alloy is shown in Fig. 7.2.1. The hydrogen
concentration in the alloy is expressed in terms of the atom ratio of hydrogen to metal,
H/M. The equilibrium pressure, pounds per square inch, at different hydrogen
compositions in the alloy is shown in the figure. As the hydrogen pressure is increased
during absorption, the hydrogen concentration increases in the alloy. It is noted that one
atm. pressure corresponds to 14.7 psia and most of the absorption is below 1 atm.
pressure. The pressure composition curve is lower during the desorption indicating
hysteresis.
The pressure composition curves for adsorption and desorption were fitted using a
polynomial to predict the hydrogen concentration for a given pressure. For adsorption,
197
[7.4]
18
16 LaNi4.7Al0.3 with 10wt% Pd
14
Pressure, psia
12
10
Absorption
8
6
4 Desorption
2
0
0 0.2 0.4 0.6 0.8 1
H/M
The effect of air exposure on the hydrogen absorption of the metal hydride was
studied by Shan et al. 36 and is shown in Fig. 7.3.1. It is evident that the no significant
degradation is observed for 110 weeks (2 years) of exposure. A small decrease in the
initial reaction rate and a small increase in the time constant for absorption are evident for
the hydrogen absorption for 60 and 110 weeks, however these changes are negligible
198
This indicates that the metal hydride, Pd treated LaNi4.7Al0.3, is suitable for the
0.8
LaNi4.7Al0.3 treated with 10wt% Pd
0.7
Hydrogen Concetration, H/M
0.6
0.5
0.3
Freshly ground
5 weeks
0.2
11 weeks
60 weeks
0.1
110 weeks
0.0
0 5 10 15 20 25 30
Time, min
Figure 7.3.1: Effect of air exposure on the first hydrogen absorption of palladium treated
LaNi4.7Al0.3 for periods greater than 2 years. This figure is taken from reference 36.
The effect of potassium hydroxide solution on the metal hydride pasted in nickel
foam was studied by soaking the metal hydride in KOH solution for a day. The hydrogen
absorption, in moles, before and after soaking in KOH solution is shown in Fig. 7.4.1.
The time constant of the hydrogen absorption reaction before soaking in KOH solution is
about 5 min, similar to that shown in Fig. 7.3.1. It is evident that the rate of hydrogen
199
absorption is slower for the metal hydride soaked in KOH in comparison to that of the
fresh metal hydride. The soaked metal hydride absorbs only about 50% of its original
capacity at the end of 2.5h. This indicates that the metal hydride is deactivated, probably
necessary to physically isolate the metal hydride from the KOH solution in the nickel-
hydrogen cell. It is known that the metal hydride can be activated again by raising the
pressure.
-4
2.0x10
Fresh
H2 abosrbed,moles
-4
1.5x10
-4
1.0x10
-5 1 day
5.0x10
0.0
0 30 60 90 120 150
Time, min
Figure 7.4.1: Effect of soaking in KOH solution on the hydrogen absorption of palladium
treated LaNi4.7Al0.3. The hydrogen pressure at the end of absorption is about 1.1 atm
pressure.
A nickel-hydrogen cell with metal hydride for hydrogen storage was assembled as
shown schematically in Fig. 7.5.1. It is a bolt nut cell as described in section 6.1. Nickel
200
foam pasted with the metal hydride, Pd treated LaNi4.7Al0.3, was placed at the end of the
bolt nut cell and was physically separated from the platinum electrode by a chlorinated
polyvinyl chloride disc. This minimizes contact of the KOH solution with the metal
hydride. The metal hydride was placed close to the platinum electrode to facilitate easy
hydrogen oxidation during discharge. The hydrogen absorption of the metal hydride was
tested in a Sievert’s Apparatus38 before use in the cell. The stainless steel compartment
was first purged with N2. This was followed by purging with hydrogen gas, and the metal
section 7.2. The final pressure of the cell at the end of purging was about 1-2 atm
pressure.
Positive Negative
Metal
electrode electrode
Hydride Insulator
Ni(OH)2 Platinum
H2
3.2 cm Outlet
Nut valve
Bolt
Figure 7.5.1: Schematic picture of the Ni-H2 cell with metal hydride.
201
The nickel-hydrogen cell was reduced to lower pressure as shown schematically
in Fig. 7.5.2 by opening the cell to an evacuated chamber. This method eliminates the use
of a vacuum pump which affects the potassium hydroxide electrolyte during pumping.
The corresponding pressure change measured during venting is shown in Fig. 7.5.3. The
time constant for the hydrogen gas to equilibrate with the metal hydride in the nickel
hydrogen cell setup is about 0.1 to 0.2h and is about the same time as that measured for
the metal hydride separately (Fig. 7.3.1) indicating that there is no problem associated
mAh/cm2 (positive electrode) will be discussed in the section. The experimental capacity
was determined in a liquid cell for coulometric efficiency greater than 90%. The absolute
capacity of the positive electrode is 72 mAh. The capacity of the metal hydride used is
121 mAh (1 atm pressure). The capacity of the gaseous volume (excluding the cell
volume) at 1 atm pressure is 86 mAh. Therefore the total capacity of the negative
electrode for hydrogen oxidation (including the gas capacity and metal hydride capacity)
is 207 mAh. This shows that the capacity of the positive electrode is limiting in
Inlet Evacuated
Valve Ni-H2 Cell chamber
Outlet
Valve
Figure 7.5.2: Schematic picture of the Ni-H2 cell with metal hydride.
202
Venting of H2
12
10 Pressure
Equilibration
Equlibration time
8
0.00 0.25 0.50 0.75 1.00
Time, h
Figure 7.5.3: Pressure variation inside the nickel hydrogen cell during venting and
subsequent hydrogen gas equilibration with the metal hydride.
The coulometric efficiency of the cell containing the metal hydride was
investigated at different depths of charge and different rest periods to evaluate oxygen
evolution during charge and the self discharge mechanism during rest period of the cell.
The cell was cycled at C/5 rate to different depths of charge, 50, 70 and 90%. The voltage
variations during charge and discharge are shown in Fig. 7.5.4. The discharge cut-off
voltage is 1.15 V. The rest period between charge and discharge was about 5 min. The
voltage profile during the charge is about the same for different depths of charge
The rest period between the charge and the discharge was varied from 5 min to 1h
to 6h. The voltage profile during charge-discharge of the cell for different rest periods is
203
shown in Fig. 7.5.5. The depth of charge is 50%. It is evident that the time of discharge
decreases with increase in the rest period indicating self discharge. The voltage plateau
during the discharge also decreases with increase in the rest period because the state of
charge of the cell at the end of rest period is lower with increase in the rest period.
The coulometric efficiency of the cell was calculated for different depths of
charge and different rest periods and is shown in Fig. 7.5.6. It is evident that the
coulometric efficiency decreases with increasing depth of charge for all rest periods
indicating that the oxygen evolution increases with depth of charge, similar to the results
obtained for the nickel-hydrogen cell without metal hydride. The coulometric efficiency
also decreases with increase in the rest period for different depths of charge indicating
that self discharge is occurring in the nickel-hydrogen cell. Self discharge in the nickel
hydrogen cell with metal hydride will be compared to the cell without metal hydride in
section 7.5.8.
1.5
1.4
E (Volts)
1.3
1.2
Figure 7.5.4: Charge-discharge voltage profiles of the nickel-hydrogen cell cycled at C/5
rate to different depth of charge.
204
1.5
1.4
E (Volts)
1.3
1.2
5 min
6h 1h
1.1
0 1 2 3
Time (Hours)
Figure 7.5.5: Charge-discharge voltage profiles of the nickel-hydrogen cell cycled at C/5
rate to 50% DOC with different rest periods, 5 min, 1h and 6h.
96
0.083h
Columetric efficiency, %
1h
94 6h
92
90
88
86
50 60 70 80 90
Depth of charge (%)
Figure 7.5.6: Coulometric efficiency of the Ni-H2 cell cycled at C/5 rate as a function of
the depth of charge for different rest periods.
205
7.5.2. Pressure Variations During the Charge-Discharge Cycle
The pressure inside the nickel hydrogen cell was monitored using a pressure
gauge as described in section 6.4. The pressure variation during two successive cycles of
the nickel-hydrogen cell with metal hydride is shown in Fig. 7.5.7. The cell was cycled at
C/5 rate to 70% depth of charge. The rest period for the first cycle and the second cycle is
5 min and 6h, respectively. The pressure variation during charge and discharge is similar
to that observed for the nickel-hydrogen cell without the metal hydride discussed in
chapter 6. The pressure increases during the charge due to hydrogen evolution and the
pressure decreases during discharge due to hydrogen oxidation at the platinum electrode.
However, three major differences are observed in the cell with metal hydride in
comparison to the cell without metal hydride. The first difference is the net drop in
pressure measured at the end of the first cycle with 5 min rest period as shown in Fig.
7.5.7. For the cell without metal hydride no such drop in pressure was observed. The
second difference is the pressure rise during the 6h rest period after the 2nd discharge. The
pressure at the end of two cycles is equal to the pressure measured at the beginning of the
two cycles. This suggests that the 6h rest periods results in good hydrogen equilibration
with the metal hydride. No pressure rise was observed during the rest period after
discharge of the cell without metal hydride (Fig. 6.4.2). It is noted that the pressure
variation during discharge is non-linear in comparison to the linear variation observed for
the cell without metal hydride (third difference). The non-linear pressure variation during
the charge and the discharge are related to hydrogen gas equilibration with the metal
hydride and will be discussed in detail in section 7.5.3. The pressure drop evident during
the 6h rest period after charge is related to the recombination reaction, the hydrogen
206
equilibration with the MH and the self discharge of the cell and will be discussed in
section 7.5.5.
10
∆P ∆P
6
0 4 8 12 16 20 24
Time, h
Figure 7.5.7: Changes in pressure during the charge, the rest and the discharge periods of
two successive cycles. The cell was cycled at C/5 rate to 70% depth of charge. The rest
period for the 1st cycle and the 2nd cycle is 5 min and 6h, respectively.
The change in pressure during the charge corresponding to the cycle with 5 min
rest period is shown in Fig. 7.5.8. The capacity of the nickel hydrogen cell is 72 mAh
(13.24 mAh/cm2). The volume of the cell is about 40 cc. For C/5 charge rate, the rate of
calculated based on Faraday’s law and ideal gas law is 2.33 psi/h (when there is no MH).
However, part of the hydrogen formed is absorbed into the metal hydride and therefore
the rate of pressure change should be lower than 2.33 psi/h. Two different slopes
corresponding to two rates of pressure rise are shown in Fig. 7.5.8. The pressure rate in
207
the time period, 0 to 0.5h is 1.73 psi/h and that in the 1 to 2h is 1.51 psi/h. As expected
they are lower than the pressure rate of 2.33 psi/h. This indicates that the hydrogen
formed is absorbed into the MH. The two different slopes are related to the pressure
plateau and the pressure rise observed in the pressure composition isotherm.
12
11
Pressure, psia
1.51 psi/h
10
8 1.73 psi/h
6
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Time, h
Figure 7.5.8: Changes in pressure during charge. The cell was cycled at C/5 rate to 70%
depth of charge with 5 min rest period.
The pressure during the 6h rest period at the end of the 2nd cycle rises to a higher
value as shown in Fig. 7.5.9. It is noted that there is no oxygen evolution and therefore no
section 7.4 that the time constant for metal hydride equilibration increases (metal hydride
is deactivated) when soaked in KOH solution. Therefore it is likely that this pressure rise
during the rest period is related to slow hydrogen equilibration (slow hydrogen
desorption/absorption) with the metal hydride. This is also supported by the fact that the
208
pressure measured at the end of the rest period, after the pressure rise, is equal to the
pressure measured at the beginning of the 1st charge (Fig. 7.5.7). The slow hydrogen
desorption was also observed when the cell pressure was lowered by venting the
The time constant for the hydrogen to equilibrate with the metal hydride was
estimated using an exponential fit as shown in Fig. 7.5.8. Oh et al. 39 have developed a
model for the hydrogen absorption based on different rate controlling steps: (a)
dissociative chemisorption of the hydrogen molecule (b) diffusion of the hydrogen atoms
through the metal hydride and (c) chemical reaction of the hydrogen atom with the
hydride. Here we do not analyze which of them is a rate determining step and instead
focus our attention on estimating the time constant for hydrogen absorption. Shan et al. 36
have briefly reviewed the literature on the kinetics of hydrogen adsorption in metal
hydride. The exponential fit to the pressure data is good and estimates the time constant
as 1.37h. In comparison, it is noted that the time constant of a fresh metal hydride to
equilibrate with hydrogen gas is 0.1-0.2h. The increase in time constant is attributed to
the formation of oxide layer on the metal hydride particles. The oxide layer is formed due
KOH solution seeping into the metal hydride probably through the bolt hole in the cell.
The increase in pressure during the rest period, given by parameter ‘A1’ is 0.59 psi.
209
6.8
6.4
Equation: y = A1*exp(-x/t1) + y0
R^2 = 0.99
-4
y0 6.6 ±2.4x10
6.2 -4
A1 -0.59 ±4.5x10
-3
t1 1.37 ±2.5x10
6.0
5.8
0 1 2 3 4 5 6
Rest period, h
Figure 7.5.9: Changes in pressure during the rest period at the end of the 2nd cycle shown
in Fig. 7.5.7. The cell was cycled at C/5 rate to 70% depth of charge.
The change in pressure during the rest period after the 2nd charge (Fig. 7.5.7) is
shown in Fig. 7.5.10. As discussed in chapter 6, the pressure decrease during the rest
period after charge is due to the recombination of oxygen with hydrogen and self
discharge of the nickel hydroxide electrode consuming hydrogen gas. The self discharge
occurs throughout the rest period. However, it was shown that the recombination reaction
is complete in the first 1h of the rest period. In addition to the self discharge and the
recombination reaction during the rest period, there is also the hydrogen equilibration
with the metal hydride as discussed in the previous section. The time constant for the
hydrogen equilibration is about 1.4h. Therefore any changes in pressure observed for rest
periods longer than 1.5h correspond to the self discharge of the cell.
210
A straight line was fit to the pressure data in the time period of 4 to 6h as shown
in Fig. 7.5.10. The straight line fit corresponds to the self discharge of the battery. The
error for the fit is small. The self discharge rate given by the slope of line or parameter
‘B’ of the fit is 0.063 psi/h. This self discharge rate is about 37 times slower than the C/5
rate. That is, the battery will discharge completely in about 185h at this rate and the self
discharge rate is expressed as C/185. The effect of state of charge on the discharge rate
11.4
11.2
11.0
10.8
0 1 2 3 4 5 6 7
Rest period, h
Figure 7.5.10: Pressure changes during the 6h rest period after 2nd charge. The cell was
cycled at C/5 rate to 70% depth of charge. A straight line is fit to the pressure data in the
4 to 6h rest period.
The pressure drop due to the self discharge mechanism was subtracted out of the
pressured data based on the linear fit parameters and the difference, the pressure
contributions due to the recombination reaction and the hydrogen equilibration with the
MH is plotted in Fig. 7.5.11. An exponential decay equation was fit to the pressured data
as shown in the figure. The estimated time constant is about 1.29h. It is noted that the
211
time constant for the recombination reaction (chapter 6) and that of the hydrogen
equilibration with the metal hydride are about 1h (section 7.5.4) and therefore it is
difficult to separate the pressure contributions due to these two mechanisms. However, it
is noted that in the pressure range during the rest period, 11.8 -11 psi, the hydrogen
(Fig.7.2.1). Therefore the pressure variation shown in Fig. 7.5.11 is mostly due to the
0.5
Equation: y = A1*exp(-x/t1) + y0
R^2 = 0.99
0.4 -4
Pressure, psia
y0 -0.009 ±1.9x10
-4
A1 0.47 ±3.9x10
-3
0.3 t1 1.29 ±2.4x10
0.2
0.1
0.0
0 1 2 3 4 5 6 7
Rest period, h
The change in pressure during the rest period after 2nd charge, the subsequent
discharge and the following rest period is shown in Fig. 7.5.12. As discussed earlier, it is
212
noted that the decrease in pressure during the discharge is due to hydrogen oxidation at
the platinum electrode. Though the hydrogen oxidizes at a constant rate (pressure change
should be linear), the pressure measured during discharge is non-linear because the
hydrogen equilibration with the metal hydride is non-linear as shown in the pressure
composition isotherm (Fig. 7.2.1). The pressure variation and other parameters as a
function of the state of charge (SOC) of the cell were calculated from the pressure
composition isotherm and are listed in Table 7.1. It is noted that the state of charge of cell
discharge during the rest period after charge (coulometric efficiency for this cycle is
86.4%).
The pressure at the start of discharge is 10.93 psi as shown in Fig. 7.5.12 and
listed in Table 7.1. As the pressure decreases during discharge, hydrogen from the
gaseous phase and from the metal hydride is oxidized at the platinum electrode. For
example, when the cell is discharged from the 60.5% SOC to 31.4% SOC (Table 7.1), the
contribution of hydrogen atom from the gaseous phase is 6.2x10-4 moles and that from
the metal hydride is 1.6x10-4 moles. The method to calculate these contributions is
discussed below.
The contribution of the hydrogen from the gaseous phase is based on ideal gas
law: n = ∆PV RT , where ∆P is the pressure drop, V is the volume gaseous space in the
cell, R is the gas constant and T is the temperature. From 60.5% to 31.4% SOC, the
pressure drop is (10.93-8.12) = 2.81 psi. The volume of the gaseous space is 40 cc. The
213
The number of moles of hydrogen atom = 2 × 3.1 × 10−4 = 6.2 × 10−4
The contribution of the hydrogen from metal hydride phase is obtained from the
pressure composition isotherm. For 8.12 psia, the polynomial fit given by equation [7.5]
was used to estimate the H/M ratio as 0.735. The number of hydrogen atoms consumed
n = ∆ ( H M ) × N MH × 6
where M/H is the number of hydrogen atoms per metal atom, NMH is the number moles of
the metal hydride, 9.64x10-4, and 6 represents that there are 6 metal atoms per mole of
metal hydride. When the cell discharges from 60.5% to 31.4% SOC, the change in the
M/H ratio is (0.762-0.735) = 0.027. The moles of hydrogen atom oxidized from the metal
The rate of pressure change in the 0-1 h discharge (16.85-17.85h,) is 1.94 psi/h as
shown in the Fig. 7.5.12. For this period, 0-1 h, the corresponding pressure change is
10.93 to 9 psia. It is noted for this pressure range, there is no significant change in the
H/M ratio and as listed in Table 7.1 all the hydrogen consumed is from the gaseous phase
rather than from the metal hydride. This is explains the fact that the actual pressure rate
measured, 1.94 psi/h, is close to that of 2.33 psi/h (without MH). It is evident from the
figure that the rate of pressure change decreases towards the end of discharge agreeing
with the fact that the hydrogen oxidized is both from gaseous and the metal hydride phase
as listed in Table 7.1. It is noted that at the end of discharge, about 41% of hydrogen
oxidized at the platinum electrode is from the metal hydride and the rest, 59%, is from the
gaseous phase.
214
It can be seen in Table 7.1 that the pressure estimated at 0% SOC is 6.62 psi. This
agrees well with the pressure measured at the end of the rest period after discharge, 6.58
psi. This clearly indicates that the pressure inside the nickel hydrogen cell during
discharge follows the desorption curve of the pressure composition isotherm as expected
and can be used to gauge the fuel (hydrogen available) in the metal hydride.
12
11 10.93
Discharge
Pressure, psia
10 Rest
1.94 psi/h
8
Rest
7
6.58
5.94
6
12 14 16 18 20 22 24 26
Time, h
Figure 7.5.12: Changes in pressure during the rest period after charge, the discharge
period and the subsequent rest period of the 2nd cycle. The cell was cycled at C/5 rate to
70% depth of charge.
Table 7.1: Change in various parameters following the desorption curve of the
pressure composition isotherm for discharge.
Pressure, H moles, M/H ratio H moles, Total H SOC,%
psia from air from MH moles
10.93 0 0.762 0 0 60.5
10.06 1.9E-04 0.756 3.6E-05 2.3E-04 52.0
9.67 2.8E-04 0.753 5.4E-05 3.3E-04 48.1
8.89 4.5E-04 0.745 9.9E-05 5.5E-04 40.0
8.12 6.2E-04 0.735 1.6E-04 7.8E-04 31.4
7.35 8.0E-04 0.701 3.6E-04 1.2E-03 17.6
6.96 8.8E-04 0.675 5.1E-04 1.4E-03 8.8
6.62 9.6E-04 0.647 6.7E-04 1.6E-03 0.0
215
7.5.7. Correlation of Pressure Variations During Charge to Pressure
The change in pressure in the nickel-hydrogen cell during charging was estimated
using the adsorption curve of the pressure composition isotherm and is listed in Table 7.2
7.5.6. It is noted that the coulometric efficiency to 70% depth of charge is 92.9%, based
on the 5 min rest cycle. Therefore the SOC of the cell is actually 65.1% at the end of
charge instead of 70%. Based on the pressure composition isotherm, the pressure at the
end of discharge is estimated as 9.63 psi (Table 7.2). The pressure measured at the end of
2nd charge and at the end of the subsequent rest period is about 11.81 and 10.93 psi,
respectively as shown in Fig. 7.5.7. It is evident that the estimated pressure based on the
adsorption curve of the isotherm does not agree and is smaller than the pressure measured
at the end of charge or that measured at the end of the subsequent rest period.
The pressure variation for different states of charge during charging was then
estimated based on the desorption curve of the pressure composition isotherm and is
listed in Table 7.3. The pressure estimated by the PCI at 65.1% SOC (end of charge) is
11.49 psi and is below the pressure measured at the end of charge, 11.81 psi, and is above
the pressure measured at the end of the rest period, 10.93 psi. This suggests that the
pressure change during charge follows the desorption curve rather than the adsorption
curve of the pressure composition isotherm. It should be noted that the desorption curve
of the pressure composition isotherm as shown in Fig. 7.2.1 starts from complete
desorption and in our experiments the metal hydride is not desorbed completely before
216
The pressure analysis during charge and discharge (sections 7.5.6 and 7.5.7)
shows that the desorption curve can be used to gauge the fuel (hydrogen available) of the
nickel-hydrogen cell. As discussed in page 11, the positive electrode capacity is about 2.9
times smaller than the hydrogen capacity in the tested cell. In the case of the hydrogen
capacity being limiting, the pressure variations will be significant and can be followed
using the desorption curve. In either case, a voltage cutoff should be used terminate the
the positive electrode and hydrogen evolution at the negative electrode resulting in
Table 7.2: Change in various parameters following the adsorption curve of the
pressure composition isotherm for charge.
Pressure, H moles, M/H ratio H moles, Total H SOC,%
psia from air from MH moles
6.67 0 0.366 0 0 0.0
6.96 6.5E-05 0.386 1.2E-04 1.8E-04 6.8
7.35 1.5E-04 0.413 2.7E-04 4.2E-04 15.7
7.73 2.4E-04 0.439 4.2E-04 6.6E-04 24.6
8.12 3.2E-04 0.464 5.7E-04 8.9E-04 33.2
8.51 4.1E-04 0.489 7.1E-04 1.1E-03 41.7
8.89 5.0E-04 0.512 8.5E-04 1.3E-03 50.1
9.28 5.8E-04 0.535 9.8E-04 1.6E-03 58.1
9.63 6.6E-04 0.555 1.1E-03 1.8E-03 65.2
Table 7.3: Change in various parameters following the desorption curve of the
pressure composition isotherm for charge.
Pressure, H moles, M/H ratio H moles, Total H SOC,%
psia from air from MH moles
6.65 0 0.650 0 0 0.0
6.96 6.9E-05 0.675 1.5E-04 2.1E-04 8.0
7.35 1.5E-04 0.701 3.0E-04 4.5E-04 16.8
7.73 2.4E-04 0.721 4.1E-04 6.5E-04 24.3
8.12 3.3E-04 0.735 4.9E-04 8.2E-04 30.6
8.89 5.0E-04 0.745 5.5E-04 1.1E-03 39.2
9.67 6.7E-04 0.753 6.0E-04 1.3E-03 47.3
10.44 8.4E-04 0.759 6.3E-04 1.5E-03 55.0
11.49 1.1E-03 0.766 6.7E-04 1.7E-03 65.1
217
7.5.8. Self discharge at Different Depth of Charge
The self discharge rate was estimated based on the linear fit on the pressure data
in the 4 to 6h rest period after charge as discussed in section 7.5.5 and is listed in Table
7.4. It is evident that the self discharges rate at 70 and 90% depth of charge are the same
and are greater than that at the 50% depth of charge. The self discharge rate of cell with
MH is C/185 at 90% DOC. In comparison, the self discharge rate of the nickel hydrogen
cell without the MH is C/117 indicating that the self discharge rate is lower for the cell
with MH. However, it is noted that these tests were based on two different experiments
during the charge period and the rest period are difficult to estimate from the pressure
data for this cell with the metal hydride because of the slow equilibration of hydrogen
with the MH. However, in the case of a fresh metal hydride, the kinetics of hydrogen
absorption/desorption are fast, and the amount of oxygen evolution can be estimated
deactivation of the metal hydride which makes it difficult to estimate the pressure drop
218
7.5.10. Prediction of State of Charge
As discussed in section 7.5.4, the time constant for the hydrogen equilibration
with the metal hydride is about 1.37h and indicates deactivation of the metal hydride.
This slow equilibration causes difficulty in the estimation of oxygen evolution and the
coulometric efficiency. Therefore the state of charge of the nickel hydrogen cells cannot
be predicted accurately based on pressure data analysis. However for the fresh metal
The main requirement of the low pressure nickel-hydrogen cell is that it should be
hermetically sealed to prevent oxygen diffusion into the cell and hydrogen loss out of the
cell. Loss of hydrogen results in low fuel and will affect the cell performance. The effect
of oxygen diffusion into the cell is discussed in this section. The diffused oxygen
recombines with hydrogen at the platinum electrode to form water. Excess oxygen
diffusion leads to flooding at the platinum electrode due to excess water formation. This
results in poor hydrogen distribution to the platinum electrode. The voltage profile during
charge and discharge of a nickel hydrogen cell with and without any oxygen leak is
shown in Fig. 7.6.1. The cell was cycled at C/5 rate to 50% depth of charge. It is evident
from the figure that the voltage profile during charge is the same for the two cases
because hydrogen is formed as a result of charging and there are no diffusion limitations.
However, the voltage profile during discharge is lower for the case with oxygen leak
because of poor hydrogen diffusion to the platinum electrode. The impedance measured
at the end of charge and discharge for the two cases is shown in Fig.7.6.2. It is evident
219
that the charge transfer loop corresponding to the platinum electrode (2nd loop) is larger
for the case of oxygen leak in comparison to the case with no oxygen leak. This supports
The pressure variation during the rest period after discharge for the case ‘oxygen
leak’ is shown in Fig. 7.6.3. It is evident that pressure rises during the rest period and
could be due to (a) poor hydrogen equilibration with the metal hydride as discussed in
section 7.5.4 or (b) poor hydrogen diffusion in the platinum electrode. An exponential fit
to the pressure data measured during the rest period shows that the time constant is 1.85h.
The time constant for hydrogen equilibration with the metal hydride was
determined by increasing the pressure inside the cell from about 6.34 psi to about 31.8 psi
as shown in Fig. 7.6.4. During this time the no current was applied to the cell. The time
constant estimated from the exponential fit as shown in the figure is about 0.29h (17.4
min) and corresponds to the time constant for a fresh metal hydride. This indicates that
Therefore the time constant measured at the end of discharge (Fig. 7.6.3)
corresponds to poor hydrogen diffusion in the platinum electrode. This analysis illustrates
the importance of hermetically sealing the cell to prevent oxygen leaking or otherwise
The other main problem is the deactivation of the metal hydride when exposed to
the potassium hydroxide solution as discussed earlier in the chapter. This deactivation
oxygen evolution. It is necessary to utilize a metal hydride that does not deactivate on
220
1.50
1.25
E (Volts)
No oxygen leak
1.00
Oxygen leak
0.75
0 1 2 3
Time (Hours)
Figure 7.6.1: Charge-discharge voltage profiles of the nickel-hydrogen cell cycled at C/5
rate to 50% depth of charge for the case with and without oxygen leak.
221
-4
Flooding
Oxygen leak
-3
-2 No flooding
No Oxygen (A)
Z''
-1
1
0 1 2 3 4 5
Z'
-7.5
Oxygen
Flooding
-5.0 leak
No flooding
oxygen
Z''
-2.5
(B)
2.5
0 2.5 5.0 7.5 10.0
Z'
Figure 7.6.2: Comparison of impedance spectra for two different cases (i) no oxygen leak
and (ii) oxygen leak measured at the end of charge (A) and discharge (B). The cell was
cycled at C/5 rate to 50% depth of charge.
222
6.4
6.3
Pressure, psia
6.2
Equation: y = A1*exp(-x/t1) + y0
6.1 R^2 = 0.97
-4
y0 6.34 ±3.3x10
-4
A1 -0.42 ±5x10
6.0 -3
t1 1.85 ±5.7x10
5.9
5.8
0 1 2 3 4 5 6
Rest period, h
Figure 7.6.3: Changes in pressure during the rest period at the end of discharge for the
case ‘oxygen leak’. The cell was cycled at C/5 rate to 50% depth of charge.
32
Equation: y = A1*exp(-x/t1) + y0
30 R^2 = 0.97
-3
y0 19.70 ±3.6x10
Pressure, psia
-2
28 A1 8.20 ±1.8x10
-3
t1 0.29 ±1x10
26
24
22
20
18
Figure 7.6.4: Change in pressure inside the nickel hydrogen cell by increasing the
pressure suddenly to 31.8 psi for the case ‘oxygen leak’. The cell was cycled at C/5 rate
to 50% depth of charge. The pressure variation shows hydrogen gas equilibration with the
metal hydride.
223
7.7. Conclusions
A nickel-hydrogen cell with metal hydride for hydrogen storage was assembled
and tested successfully. The coulometric efficiency of the cell was studied for different
depth of charge and different rest periods. The coulometric efficiency decreases with
increase in depth of charge because of oxygen evolution as side reaction. The coulometric
efficiency also decreases with increasing rest period because of self discharge of the cell.
These results are similar to the observations in the cell without the metal hydride.
to the variables: oxygen evolution, recombination reaction and self discharge for the cell,
the use of metal hydride for hydrogen storage introduces another variable the
equilibration of hydrogen with the metal hydride. It was shown that metal hydride is
deactivated when soaked in potassium hydroxide solution for one day. For the nickel
hydrogen cell discussed in detail, it was shown that the hydrogen equilibration with the
metal hydride is slow based on the exponential fit for the pressure data in the rest period
after discharge. The time constant for the slow equilibration and for the recombination
reaction (chapter 6) is about one hour making it difficult to separate the pressure
contributions due to these mechanisms. The self discharge rate, however, was obtained
It was shown that the discharge of the battery follows the desorption part of the
pressure composition isotherm very well. However, the pressure variation during charge
does not follow the adsorption part of the pressure composition isotherm and in fact
follows the desorption part of the isotherm. About 40-45 % hydrogen from the metal
224
hydride was used as fuel for cycling the battery. Based on the pressure composition
For a well behaved metal hydride (fast hydrogen equilibration) and with the
knowledge of the pressure composition isotherm, the oxygen evolution and the
coulometric efficiency can be estimated based on the pressure data analysis, similar to
The problems associated with nickel hydrogen battery as constructed were briefly
discussed. It was shown that oxygen diffusion into the cell caused flooding at the
negative electrode leading to poor hydrogen access at the platinum electrode. The cell
should be hermetically sealed to prevent oxygen diffusion into the cell. The other
problem, the deactivation of metal hydride has to be eliminated either by improving the
metal hydride or by preventing the seeping of potassium hydroxide solution into the
metal hydride.
References
225
8. C. Iwakura and M. Matsuoka, Progress in Batteries & Solar Cells, 10, 81 (1991).
14. Z. Zhou, J. Yan, Y. Li, D. Song, and Y. Zhang, Journal of Power Sources, 72,
236 (1998).
15. P. Ruetschi, F. Meli, and J. Desilvestro, Journal of Power Sources, 57, 85 (1995).
17. H. J. Park, N. H. Goo, and K. S. Lee, Journal of the Electrochemical Society, 150,
A1328 (2003).
18. T. Ma, Y. Hatano, T. Abe, and K. Watanabe, Journal of Alloys and Compounds,
391, 313 (2005).
20. R. C. Ambrosio and E. A. Ticianelli, Surface and Coatings Technology, 197, 215
(2005).
24. J.-W. Lee and S.-I. Pyun, Electrochimica Acta, 50, 1777 (2005).
25. T. Ma, Y. Hatano, T. Abe, and K. Watanabe, Toyama Daigaku Suiso Doitai
Kagaku Kenkyu Senta Kenkyu Hokoku, 22, 35 (2002).
226
26. T. Ma, Y. Hatano, T. Abe, and K. Watanabe, Journal of Alloys and Compounds,
372, 251 (2004).
27. V. Badri and A. M. Hermann, International Journal of Hydrogen Energy, 25, 249
(1999).
28. D. B. Willey, I. R. Harris, and A. S. Pratt, Journal of Alloys and Compounds, 293-
295, 613 (1999).
38. X. Shan, Ph.D. dissertation, Material Science Dept., Case Western Reserve
University, Cleveland, Ohio., 2004.
227
8. Conclusions and Recommendations for Future
Work
8.1. Conclusions
The main objective of this work was to develop batteries with long cycle life and
safety for implantable applications. Lithium ion batteries, although limited by cycle life,
were chosen as the short term option for powering networked neuroprosthetic system
(NNPS). The potential of the low pressure nickel-hydrogen batteries using metal hydride
for hydrogen storage was identified as having an order higher magnitude cycle life in
Implantable grade lithium ion cells from Quallion and Wilson Greatbatch (WG)
were tested and compared to Sony Li ion cells (chapter 2). The conditions for
maximizing cycle life were determined: lower charge and discharge rates, lower charge
voltage cutoff, lower depth of discharge and lower temperature. The ‘discharge capacity’
and the ‘end of discharge voltage’ data were modeled to predict the cycle life and to
compare the different lithium ion cells. Based on the fit parameters, it was concluded that
the cycle life of Sony cells was better than that of the Quallion and WG cells. Of the
implantable batteries, the Quallion cells outperformed the WG cells and were chosen as
the short term powering option for NNPS. The cycle life of the Quallion cells is about
6000 cycles at C rate charge, C rate discharge and 60% depth of discharge.
A low pressure nickel-hydrogen battery was designed and developed in this work
(chapters 3, 4, 5, 6 and 7). The main components of this battery are the positive nickel
hydroxide electrode, the negative platinum electrode, the separator, the current collector
228
and the metal hydride. A platinum catalyzed electrode from E-tek Inc. was used as the
negative electrode. The charge transfer resistance of this electrode was decreased using
cyclic voltammetry (chapter 3). Nickel mesh was chosen as the current collector because
of its low resistance and stability in alkaline solutions (chapter 3). Two separators,
zirconium oxide stabilized by yttria and polypropylene were tested and no significant
was tested in liquid and nickel-hydrogen cell configurations. The electrode contained
active material on both sides. The problems associated with using it in a series cell were
discussed in chapter 4. This electrode served as a guide in the development of the pasted
nickel hydroxide electrode (chapter 5) and the design of the nickel-hydrogen cell.
using either screen printing or spatula pressing (chapter 5). Higher capacity and higher
that of screen printing. The mechanism of nickel hydroxide electrode formation was
studied and discussed in detail in chapter 5. The effect of different formation rates with
and without overcharge and the effect of PVDF and nickel content on the electrode
spectroscopy. The electrode utilization increases with PVDF content. The electrode
performance was enhanced by the addition of nickel, which increases the utilization by
successfully and the results are discussed in chapter 6. The decrease in the coulometric
229
efficiency due to oxygen evolution and self discharge was investigated. The
recombination of the evolved oxygen with hydrogen was studied. Pressure data analysis
shows that 70% of the recombination is complete during the charge and the remaining
during the 1st h of the rest period following the charge. Pressure variations due to oxygen
evolution, the recombination reaction and self discharge were completely understood.
Coulometric efficiency calculated based on the pressure data analysis agreed well with
the measured coulometric efficiency. It was shown that the state of charge of the cell can
be estimated by monitoring the cell pressure. The cycle life of the nickel-hydrogen cells
was limited because of significant oxygen evolution and material extrusion from the
successfully developed (chapter 7). The metal hydride, palladium treated LaNi4.7Al0.3,
was stable in humid air. However, it deactivates on soaking in KOH solution and
therefore was physically separated from the electrodes. In spite of this separation, the
metal hydride deactivated with time resulting in increased hydrogen equilibration time
with the MH. The time constant for this equilibration increased from 0.1h to about 1h. It
was shown that the pressure variation during charge and discharge of the cell followed
the desorption curve of the pressure composition isotherm. The pressure variation can be
used to estimate the state of charge and to fuel gauge the cell after accounting for
contributions due to oxygen evolution, recombination, and self discharge. About 40-45%
hydrogen from the metal hydride was used as fuel during the cycling of the cell.
230
8.2. Recommendations for Future Work
In the future, there are three major issues that need to be investigated:
1. The cycle life of the nickel-hydrogen cells needs to be improved. This can be
2. The metal hydride, though physically separated from the KOH solution, was
deactivated due to KOH solution seeping along the nylon bolt used to
3. After solving the cycle life issues, a series cell can be developed using a
active material on only one side and can be used in the series cell
development.
231
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