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Journal of Power Sources 274 (2015) 56e64

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Journal of Power Sources


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Degradation characteristics of air cathode in zinc air fuel cells


Ze Ma a, Pucheng Pei a, *, Keliang Wang a, Xizhong Wang a, Huachi Xu a, Yongfeng Liu b,
Guanlin peng c
a
State Key Lab. of Automotive Safety and Energy, Tsinghua University, Beijing 100084, China
b
School of Mechanical-electronic and Automobile Engineering, Beijing University of Civil Engineering and Architecture, Beijing 100044, China
c
School of Aerospace Engineering, Tsinghua University, Beijing 100084, China

h i g h l i g h t s

 The peak power density of the 25 cm2 ZAFC can be as high as 454 mW cm2.
 The EIS of ZAFCs were measured to study the performance of air cathode.
 The degradation was due to the micropores clogging and catalysts losing.
 Degradation mechanisms and mitigation strategies of air cathode were studied.

a r t i c l e i n f o a b s t r a c t

Article history: The zinc air fuel cell (ZAFC) is a promising candidate for electrical energy storage and electric vehicle
Received 5 May 2014 propulsion. However, its limited durability has become a major obstacle for its successful commercial-
Received in revised form ization. In this study, 2-cell stacks, 25 cm2 cells and three-electrode half-cells are constructed to
5 September 2014
experimentally investigate the degradation characteristics of the air cathode. The results of electro-
Accepted 6 October 2014
Available online 15 October 2014
chemical tests reveal that the peak power density for the 25 cm2 cell with a new air cathode is
454 mW cm2, which is twice as the value of the used air cathode. The electrochemical impedance
analysis shows that both the charge transfer resistance and the mass transfer resistance of the used air
Keywords:
Zinc air fuel cell
cathodes have increased, suggesting that the catalyst surface area and gas diffusion coefficient have
Air cathode decreased significantly. Additionally, the microstructure and morphology of the catalytic layer (CL) and
Degradation characteristics gas diffusion layer (GDL) are characterized by scanning electron microscopes (SEM). SEM results confirm
Electrochemical impedance analysis that the micropores in CL and GDL of the used air cathode are seriously clogged, and many catalyst
particles are lost. Therefore, the performance degradation is mainly due to the clogging of micropores
and loss of catalyst particles. Furthermore, hypotheses of degradation mechanism and mitigation stra-
tegies for GDL and CL are discussed briefly.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction 2DS. However, both the worldwide demand for electricity and ve-
hicles are estimated to more than double by 2050 [2,3], producing a
To achieve greenhouse-gas emission targets for limiting global great challenge for this goal. All things considered, generating
warming to 2  C Scenario (2DS) [1], the energy-related CO2 emis- electricity from renewable sources and developing electric vehicles
sions must be reduced by more than 64% by 2050 (compared with (EVs) are necessary and promising solutions [4,5].
2009), and a continued falling must be maintained thereafter [2]. Solar and wind are not constant and reliable sources of power,
Two industrial sectors produced nearly two-thirds of global CO2 which will cause significant challenges for the electric grid opera-
emissions in 2010: 41% is accounted by electricity and heat gener- tors [6]. Electrical energy storage (EES) can smooth out the inter-
ation and 22% from transportation [3], therefore the reduction of mittency of renewable energy production and balance the supply
CO2 emissions from these two sectors are the key to achieving the and demand of electricity (electricity generation, distribution, and
usage requirement). Therefore, EES has been considered to be a key
enabler for the smart grid or future grid [6e8]. Several different
* Corresponding author. Tel./fax: þ86 10 62788558.
types of energy storage can be used for large-scale stationary ap-
E-mail address: pchpei@tsinghua.edu.cn (P. Pei). plications, including mechanical, electrical, chemical, and

http://dx.doi.org/10.1016/j.jpowsour.2014.10.030
0378-7753/© 2014 Elsevier B.V. All rights reserved.
Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64 57

electrochemical. Electrochemical energy storage is a strong candi- 2. Experimental


date solution due to its high energy density, flexibility, and scal-
ability [9e14]. Meanwhile, to achieve the 2DS, International Energy 2.1. Air cathode
Agency (IEA) analysis shows that 70% of global car sales will need to
be of advanced vehicles (hybrid, plug-in hybrid, and batteries) by The air cathode was constructed of three layers (as shown in
2035, and more than 90% of new light-duty vehicles will need to be Fig. 1): (1) a catalytic layer (CL), (2) a current collection layer (CCL),
propelled by an electric motor by 2050 [3]. Overall, advanced bat- and (3) a gas diffusion layer (GDL). The CL was produced from a
teries are essential for EES and EVs propulsion. mixture of active carbon powder with manganese oxide catalyst
Several battery technologies, such as lead-acid, nickel- powder and PTFE binder. The CCL was a woven nickel mesh. The
ecadmium, nickel-metal hydride, and Li-ion batteries, have been GDL was a porous Teflon film. All of the air cathodes tested in this
in use in many fields, but all of the present batteries suffer from work were cut from a large air cathode sheet. The used air cathodes
low energy density and a short lifetime. Recently, zinc air fuel cell had been used in ZAFCs and seriously degraded. To study the per-
(ZAFC) [15e22] and electrical rechargeable zinc air batteries formance degradation of the air cathode, the polarization charac-
[23e26] were considered highly promising because of their high teristics and electrochemical impedance spectroscopy (EIS) were
energy densities (the theory energy density of zinc air system is tested. It should be noted that the used air cathodes in this work
1.35 kWh kg1) and unique characteristics of zinc [15,16,27e32]. were first tested in the 2-cell stack, and then cut into pieces with
In our recent work [21], a ZAFC stack with inexpensive MnO2 as different sizes for the 25 cm2 cells, three-electrode half-cells and
the catalyst was designed, in which the circulation flowing 40 wt.% SEM tests.
potassium hydroxide (KOH) electrolyte carried the reaction
product away, while acting as a coolant in the process. The power 2.2. ZAFC and three-electrode half-cell
density could be as high as 435 mW cm2 and the dynamic
response time was in the order of several milliseconds, indicating At first, a 2-cell ZAFC stack was assembled with a configuration
that the ZAFC can be excellently applied to EES and EVs propul- of a bipolar plate [21], which is similar to the proton exchange
sion. However, the unsatisfactory lifetime of ZAFC, which is one of membrane fuel cell stack. Each cell had anode chamber of type Y
the most serious obstacles to its commercialization, was not fully [21], and the active surface area was 21.5 cm  10 cm. The upper slit
investigated. According to the basic principle of ZAFC (shown in of the cuneiform trough of type Y was 4.0 mm and the lower slit
Fig. 1), air cathode is commonly considered as the heart of the fuel was 2 mm in width. Zinc pellets were fed into the anode chamber to
cell system. The degradation of the air cathode is a key factor form a pellets bed, and a mesh layer at the bottom of the anode
affecting the durability of the fuel cells. Up till now, most studies chamber can allow electrolyte and extremely small particles to fall
were focused on catalysts with higher activation for oxygen out of the pellets bed. A separator was adhered to the air cathode to
reduction reaction, while the degradation mechanism of the air prevent zinc pellets contacting with the air cathode. Second, a
cathode, especially in relation to the cell system, has not been 25 cm2 single cell was designed, in which the anode current col-
provided. Therefore, a more comprehensive knowledge of the lector was a nickel mesh and the cathode plate was a stainless steel
degradation mechanism of the air cathode is essential to attain plate. The 25 cm2 cell had a cuboid anode chamber, 5 cm in length,
desirable lifetime requirements for ZAFC applications. Only after 5 cm in height and 3 mm in width. Since the GDL was insulated, the
the degradation is characterized and correctly quantified can we electrons could only be transported from the air cathode margins
develop mitigation strategies. In this work, 2-cell stacks, 25 cm2 into the CCL and the CL. In order to electrically connect the circuit
single cells and three-electrode half-cells were constructed with between the air cathode and cathode plate of both the 2-cell stacks
new air cathodes and used air cathodes, respectively. Electro- and 25 cm2 cells, nickel foils (0.08 mm thick) were used to edge-
chemical tests were carried out to comparatively study the per- clad the air cathode sheets [21]. To minimize the ohmic resis-
formance of air cathodes and investigate the reasons behind the tance, the CL in the edge-clad regions were cleared so that the
performance degradation. The microstructure and morphology of nickel foils could contact the CCL directly. The zinc fuels used in
the catalytic layer (CL) and gas diffusion layer (GDL) of new air these tests were zinc pellets with an average size of 0.8 mm. The
cathode and used air cathode were characterized by scanning electrolyte, which was pumped into the cells, was free to flow
electron microscope (SEM). through the zinc pellet bed under gravity, and the excessive

Fig. 1. Basic principle of ZAFC.


58 Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64

electrolyte could overflow via an overflow channel. The flow rates pressure drop; m, the viscosity of fluid; L, the length over which the
of the electrolyte that flowed through the anode chambers were pressure drop is taking place), the permeability of the air cathode
900 mL min1 and 96 mL min1 for 2-cell stack and 25 cm2 cell, can be determined by the pressure drop (DP) when air flows
respectively. The ambient air was fed by an electric fan. Meanwhile, through the GDL to the CL. The pressure drop (DP) when the air flux
the electrochemical characterization of the air cathodes was carried (Q/A) was 4 sccm cm2, 8 sccm cm2 and 12 sccm cm2 were
out in a three-electrode half-cell in 40 wt.% KOH with a Hg/HgO measured in the tests.
reference electrode and a nickel plate counter electrode. The air
cathode was pressed onto a copper plate which was acted as the 3. Results and discussion
current collect plate and had a round hole, 20 mm in diameter. Thus
the geometrical area of the air cathode was 3.14 cm2. 3.1. Electrochemical characterization of 2-cell stack

2.3. Electrochemical test and morphology examination Two 2-cell stacks were tested: one was assembled with two new
air cathodes, and the other was assembled with two used air
For the 2-cell stack and the 25 cm2 cell, the polarization char- cathodes. In the 2-cell stacks, the cell located close to the positive
acteristics of each cell were tested with an electronic load (Hoecherl electrode of the stack was numbered #1, and the other cell was
& Hackl GmbH ZLSV1502). A NI PXI-1033 data acquisition instru- numbered #2. The polarization characteristics of each cell in the 2-
ment was used to measure each cell voltage. To investigate the cell stacks are plotted in Fig. 2. The performances of cell #2 are
reasons for air cathode degradation over time, the electrochemical better than cell #1 in both of the stacks, and these differences may
impedance spectroscopy (EIS) measurements of ZAFCs were carried be caused by the non-uniform air distribution for different cells
out in the galvanostatic mode using a TrueData-EIS Impedance with non-optimized air supplying [21]. As shown in Table 1, the
Spectroscopy Analyzer. The impedance spectra were recorded by peak power density of cell #2 with a new air cathode is
sweeping frequencies over the range of 20 kHze100 mHz. 435 mW cm2, which is almost twice as the value of the cell with a
Note that the concentration of the hydroxide in the electrolyte used air cathode. This suggests an obvious degradation of the used
decreases with discharge Ah (Ampere Hour). The electrolyte con- air cathode. Meanwhile, it can be found that concentration polari-
ductivity would decrease and result in an increased cell resistance. zation occurs at relatively low current conditions in the cells with a
Measuring an EIS spectrum takes time, and the change of the used air cathode. This suggests that the degraded performance of
electrolyte concentration should be avoided throughout the mea- the cells for a used air cathode may be largely due to limited gas
surement. Each cell in the 2-cell stack had an active surface area of diffusion.
215 cm2, and the discharge current could be higher than 100 A. Fig. 3 presents the impedance spectra of the cell #1 in 2-cell
Thus, the EIS spectra of the 2-cell stacks were only measured at stacks with new and used cathodes. The high-frequency intercept
open circuit. For the 25 cm2 cell, which has a quite low discharge of the single impedance arc on the real axis, RU, represents the total
current, the change of electrolyte concentration was negligible as ohmic resistance of the cell, which can be expressed as the sum of
long as the amount of electrolyte was not too little. Therefore, the the contributions from contact resistances between components
EIS spectra of the 25 cm2 cells were measured at a discharge current and ohmic resistances of the cell components, such as the elec-
of 0 A, 1 A, 2 A and 3 A. The electrochemical characterizations of the trolyte, air cathode, zinc anode and polar plates. As seen in Fig. 3,
air cathodes were then studied in a three-electrode half-cell using a both the resistance values RU for the cell with a new air cathode and
CHI660D electrochemical workstation (CH Instruments Inc.). For a used air cathode are approximately 0.78 U cm2, which suggests
the chronopotentiometry with linear current scanning, the current that the two stacks were assembled in the same condition, such as
was linearly increased from 0 A to 0.24 A with a scan rate of assembly pressure, electrolyte flow condition and zinc pellets
2 mA s1. Impedance measurements were conducted at polarized filling state. However, the impedance spectra of the two are quite
conditions at 0 V, 0.1 V, 0.2 V and 0.3 V versus Hg/HgO by different. For the new air cathode, the impedance arc appears as a
sweeping frequencies over the range of 20 kHze10 mHz with a straight line with a slope of almost 1. The Nyquist spectrum of the
sinusoidal perturbation of 5 mV amplitude. The performance of the used cathode shows an additional semicircle in the high frequency
air cathode would degrade continuously when the fuel cells were (HF) range, and a big impedance loop is observed in low frequency
discharging. Since the EIS tests takes a long time, each air cathode range. The appearance of this HF semicircle is likely related to
was used only once to measure an EIS spectrum in the 25 cm2 cell electrode geometry changing [33].
tests and half-cell tests. The used air cathodes tested in the 25 cm2
cells were cut from the used air cathode, which had been tested in
2-cell stack. It is worth noticing that the air cathode, zinc pellets,
and KOH electrolyte were replaced with fresh ones before every
test.
To further quantify and identify the geometric structure changes
of the air cathode before and after fuel cell operation, the micro-
structure and morphology of the catalytic layer (CL) and gas
diffusion layer (GDL) were characterized by scanning electron mi-
croscopes (SEM) (Tescan MIRA 3 and JSM7401). Before the SEM
observation, the used air cathodes were soaked in deionized water
for 24 h and then dried at room temperature. Since the GDL was
insulated, the surfaces of GDL for the samples were Au-sputtered in
vacuum before the SEM examination.
Additionally, in order to characterize the changes of cathode
permeability over long-term operation, gas diffusion coefficients of
new and used air cathodes were measured. According to the Darcy
law (Q ¼ kA/mLDP; Q, the total discharge;k, the intrinsic perme- Fig. 2. Polarization characteristics of ZAFCs with the new air cathodes and used air
ability of the medium; A, the cross-sectional area; DP, the total cathodes.
Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64 59

Table 1
Polarization characteristics of the zinc air fuel cell.

Fuel cell OCV (V) Peak power (mW cm2) EPa (V) iPb (mA cm2)

2-cell stack with new air cathode (215 cm2)


cell#1 1.453 330 0.888 372
cell#2 1.446 436 0.853 512
2-cell stack with used air cathode (215 cm2)
cell#1 1.463 224 0.716 313
cell#2 1.455 227 0.726 313
2
25 cm single cell
New air cathode 1.455 454 0.733 620
Used air cathode 1.465 202 0.775 260
a
EP is the cell voltage at the peak power point.
b
iP is the discharge current density at the peak power point.

3.2. Electrochemical characterization of 25 cm2 single cell


Fig. 4. Polarization characteristics of 25 cm2 ZAFC with a new air cathode and a used
The polarization characteristics of 25 cm2 single cells, one with air cathode.
new air cathode and the other a used air cathode are given in Fig. 4.
These results were consistent with the 2-cell stacks tests. The cell
with a new air cathode produced a peak power density of
454 mW cm2, and the cell with a used air cathode produced a
maximum power density of 201 mW cm2, as shown in Table 1.
Since the electrons could only be transported from the air
cathode margins into the CCL and the CL [21], the average distance
for the electron transport in the air cathode increases with the size
of air cathode, which will lead to a larger ohmic resistance.
Therefore, the peak power density of the 25 cm2 cell with a new air
cathode is higher than the cell #2 in 2-cell stack. In contrast, in the
case of a used air cathode, the peak power density of the 25 cm2 cell
is slightly lower than the 2-cell stack. It is noteworthy that the used
air cathode in the 25 cm2 cell was cut from the used air cathode,
which had been tested in the 2-cell stack. This performance dif-
ferences may result from the fact that a small amount of catalyst
particles at the surface of CL was peeled off by the separator during
the 2-cell stack dismantling in the work.
Fig. 5. Nyquist plots of EIS spectra for 25 cm2 ZAFC with a new air cathode.
Figs. 5 and 6 present the EIS spectra of 25 cm2 cells with new air
cathodes and used air cathodes at different currents. There are
three impedance loops in the Nyquist plot from high frequency to constant. For all of the 25 cm2 cells with new cathodes and used
low frequency, which can be described as high, medium, and low cathodes, the high-frequency intercept of the single impedance arc
frequency loops, respectively. As shown in Fig. 5, in the case of new on the real axis are consistent and smaller than those obtained in 2-
air cathodes, as current increases from 0 A to 3 A, the medium cell stacks. Both the values of RU are approximately 0.5 U cm2.
frequency loop (MFL) becomes larger, while the high frequency Fischer et al. [34] have explained that the internal ohmic resis-
loop (HFL) and low frequency loop (LFL) show little variance. While tance and the contact capacitance in the granular electrode struc-
for the used air cathodes, in Fig. 6, with increasing current, the LFL ture might be the responsible for the high frequency loop. In our
becomes larger, the HFL grows slightly and the MFL remain almost study, the diameter of the HFL in the cell with a new cathode is

Fig. 3. Nyquist plots of EIS spectra for cell #1 in ZAFCs with a new air cathode and a
used air cathode. Fig. 6. Nyquist plots of EIS spectra for 25 cm2 ZAFC with a used air cathode.
60 Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64

much smaller than that in the cell with a used cathode. Therefore, Table 2
these results imply that the HFL is related to air cathode geometry Calculated parameters of the equivalent circuit for 25 cm2 zinc air fuel cell.

rather than zinc anode. The medium frequency loop (MFL) becomes Fuel cell Re Ri Rk Rm
smaller as the current increases in the case of a new air cathode, as (U cm2)
seen in Fig. 5. As the overpotential increases with the increasing
25 cm2 cell with a new air cathode
current, and larger overpotential would enhance the kinetic driving
0A 0.535 0.177 0.243 0.093
force and decrease the charge transfer resistance [35e37], it can be 1A 0.532 0.158 0.153 0.076
concluded that the MFL is related to the kinetic behavior of the air 2A 0.535 0.143 0.098 0.073
cathode. However, there is no appreciable increase in the MFL for 3A 0.533 0.140 0.083 0.082
25 cm2 cell with a used air cathode
the cell with a used air cathode, which implies that the electro-
0A 0.556 1.134 0.469 0.455
catalytic activity of the used air cathode has degraded greatly. 1A 0.562 1.130 0.577 0.544
Furthermore, the low frequency loop (LFL) becomes larger with the 2A 0.567 1.115 0.765 1.201
increasing current for the cell with a used air cathode, as seen in 3A 0.568 1.105 0.903 3.234
Fig. 6. This behavior is indicative of mass transfer limitation,
because the mass transfer effect always becomes more significant
with the increasing current [35e37]. Interestingly, the LFL in the
cell with a new cathode does not vary much with increasing cur- also noteworthy that the Rk and Rm for the used air cathode are
rent. Therefore, it can be concluded that the LFL is related to the gas much larger than the new air cathode. The larger Rk implies that the
diffusion in GDL. The much smaller LFL in the cell with a new air catalyst surface area was smaller, or electrocatalytic activity was
cathode suggests that the gas diffusion coefficient of the new air lower, and the much larger Rm confirms that the gas diffusion co-
cathode is much higher. Therefore, these results may explain the efficient decreased seriously.
difference in the polarization behavior of the new air cathode and
used air cathode, and also prove that the degradation of the used air 3.3. Electrochemical characterization of air cathode in three-
cathode is mainly due to the decrease of electrocatalytic activity of electrode half-cell
CL and the gas diffusion coefficient of GDL.
To simulate the experimental data and evaluate the associated In order to make a clear comparison, the electrochemical char-
parameters, an equivalent circuit model for zinc air fuel cell is acterizations of the new air cathodes and the used air cathodes
proposed based on the above discussions, as shown in Fig. 7. This were investigated in a three-electrode half-cell. Fig. 8 gives the
model includes an external ohmic resistance, Re, which is the sum results of the chronopotentiometry with linear current scanning of
of uncompensated electrolyte resistance (between the working and air cathodes. This result was consistent with the 2-cell stack and
the reference electrodes), electronic resistance of cell components, 25 cm2 cell tests, suggesting that the used air cathode had degraded
and any contact resistances. The internal ohmic resistance, Ri, is the significantly.
sum of the electrolyte resistance within the electrode, the elec- Figs. 9 and 10 present the EIS spectra of half-cell with new air
tronic resistance of the electrode material, and the contact resis- cathodes and used air cathodes. There are two impedance loops in
tance between the electrode components. The faradaic impedance, the Nyquist plot of the new cathode, but a knot is observed, possibly
Zf, is further divided into a kinetic resistance, Rk, and a mass- caused by serious overlapping of the two loops. And the imaginary
transfer impedance, Zm. In this model, Zm is represented by a par- part of the high frequency impedance is positive, as shown in Fig. 9.
allel combination of overall mass-transport resistance, Rm, and While for the Nyquist plot of the used cathodes, as clearly seen in
capacitance, Cm [38]. The double-layer capacitance is distributed, Fig. 10, there is clear distinction between the loops and the imag-
according to the difference in the magnitude of the time constant, inary part of the high frequency impedance is negative. There is no
between the ohmic and faradaic processes and represented by Cd1 appreciable increase in the HF loop with the increasing over-
and Cd2, respectively. A quantitative analysis was performed to potential for both of the two cathodes, which indicates that this
estimate ohmic, kinetic, and mass-transfer resistances and double- portion of the impedance is related to the air cathode geometry
layer capacitance by fitting the impedance spectra with the model. [33,39]. In contrast, the diameters of the low frequency loop (LFL)
The values of the equivalent-circuit components are shown in for both air cathodes decrease with the increasing overpotential.
Table 2.
For the 25 cm2 cell with a new air cathode, the Re and Rm remain
almost constant, and the Ri and Rk decrease with the increasing
discharge current. However, the values of Rk and Rm increase
significantly for the 25 cm2 cell in the case of used air cathode. It is

Fig. 7. Schematic representation of the equivalent circuit for the EIS of the zinc air fuel
cell. Fig. 8. Polarization characteristics of the new air cathode and used air cathode.
Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64 61

Table 3
Calculated parameters of the equivalent circuit for three-electrode half-cell (vs. Hg/
HgO).

Half-cell Re Ri Rk

(U cm2)

Three-electrode half-cell with a new air cathode


0V 2.259 24.650 3349
0.1 V 2.243 1.632 4.814
0.2 V 2.236 0.450 0.238
0.3 V 2.286 0.360 0.090
Three-electrode half-cell with a used air cathode
0V 0.573 6.622 248.9
0.1 V 0.637 6.778 53.71
0.2 V 0.647 5.451 3.503
0.3 V 0.630 5.511 2.767

Fig. 9. Nyquist plots of EIS spectra for the new air cathodes.
3.4. Microstructure and morphology of CL and GDL and air
permeability
The size of the LFL, which is expected for kinetic impedance of ORR
[39], decreases with the increasing overpotential. The LFLs in Representative SEM images of CL and GDL are given in Figs. 11
Nyquist plots at 0 V and 0.1 V present the start of an incomplete and 12, which show marked differences between these two air
semicircle with a large diameter, which is related to the small value cathodes. As illustrated in Fig. 11A and C, there are many macro-
of exchange current density for ORR. Therefore, the larger LFL for pores and crevices at the CL surface of the new air cathode, while
used air cathodes suggests that electrocatalytic activity has these pores and crevices have been clogged seriously for the used
degraded seriously. Furthermore, the high-frequency intercepts of air cathode. The clogging may result from the KOH and potassium
the used cathodes are smaller. This may be explained by the lower zincate (K2ZnO2) precipitation in the residual electrolyte after the
ohmic resistance between the current collector layer (CCL) and cell was dismantled and soaked in deionized water. Fortunately, the
copper plate, since the thickness of the catalytic layer in the used air solid KOH and K2ZnO2 would be dissolved into the flowing alkaline
cathodes was decreased due to catalyst particles loss. electrolyte in the cell's operation. As shown in Fig. 11B and D, the CL
Similar to the ZAFC, the EIS data of the half-cell can also be of the used air cathode presents a more compact and less porous
simulated by the equivalent circuit model shown in Fig. 7 to eval- structure, and the roughness has decreased significantly compared
uate the associated parameters. However, the mass limitations with the new one, and the height of the salient portions and the
caused by shortage of air was not observed in the three-electrode depth of the pores decreases. Part of the problem may result from
half-cell, so the faradaic impedance, Zf, in the equivalent circuit the loss of surface catalyst particles in the cell's operation and in the
model can be simplified to a kinetic resistance, Rk. The values of the process of dismantling, which would lead to a decrease of catalyst
equivalent-circuit components are shown in Table 3. The Ri and Rk surface area. Similarly, the microstructure and morphology of the
decrease with the increasing overpotential. Smaller Re for the GDL has also changed greatly, as shown in Fig. 12. There are a large
three-electrode half-cell with a used air cathode suggests that the number of micropores in the new cathode's GDL (Fig. 12A and B),
thickness of the catalytic layer has decreased. Moreover, the Re of but most of them have been clogged in the used air cathode
the three-electrode half-cell is larger than that of the 25 cm2 cell, (Fig. 12C and D). The clogging of the micropores in the air cathode
which is due to the fact that the CL in the edge-clad regions of the results in a higher gas diffusion resistance.
air cathodes used in the 25 cm2 cells were cleared to minimize the Air permeability of the new air cathode and used air cathode
ohmic resistance. The much larger Rk for the used air cathode were quietly different. Fig. 13 shows the pressure drop (DP) when
suggests the catalyst surface area was smaller or electrocatalytic compressed air flowed through the air cathodes. For a certain air
activity was lower. The Ri of the used air cathodes increased flux, the pressure drop (DP) of the used air cathode was almost
dramatically, and this may be a result of the change of air cathode three times higher than that of the new air cathode, indicating that
geometry. the intrinsic permeability (k) of the used air cathode has decreased
by 70%. This was likely due to the clogging of pores, and it was
consistent with the increase of diffusion resistances in EIS tests as
discussed above.

4. Hypothesis of degradation mechanism and mitigation


strategies

According to the electrochemical analyses and SEM observation,


the performance degradation is mainly due to the degradation of
catalytic layer (CL) and gas diffusion layer (GDL).

4.1. Catalytic layer

During the fuel cell operation, the CL components tend to


experience subtle changes and function losses. Catalytic layer
degradation can mainly be classified into two categories: me-
chanical, and chemical/electrochemical. First, the exposed particles
Fig. 10. Nyquist plots of EIS spectra for the used air cathodes. in CL would be washed-out by the flowing KOH electrolyte,
62 Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64

Fig. 11. SEM pictures of the catalytic layer of air cathode: A and B show the new air cathode, C and D show the used air cathode.

especially at the electrolyte inlet and outlet. Second, during the by phase transition between KOH solution and crystal will cause
standby condition, the KOH electrolyte would precipitate in the uneven mechanical stress for different components, and resulting
porous of CL. Thus, after numerous precipitate/dissolve cycles be- in interfacial delaminations and damages. Third, carbon would be
tween fuel cell operation and parking periods, a shear force induced oxidized by O2, especially at high potentials and high temperatures

Fig. 12. SEM pictures of the gas diffusion layer of air cathode: A and B show the new air cathode, C and D show the used air cathode.
Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64 63

changes of the porous geometry. All these effects will lead not only
to blocking of the diffusion paths but also to destruction of the
layers mechanically, resulting in apparent gas diffusion coefficient
decrease in the GDL during long-term operation.
In order to enhance the lifetime of air cathode, carbon dioxide
and air particles must be removed from the feed air. One possible
way is scrubbing of the air by chemical absorption including soda
lime, LiOH, Ca(OH)2, to lower the CO2 concentration to a tolerable
level [43,44]. A high efficiency particulate air filter can also be used
to eliminate the particle matters (PM). Additionally, if the air
cathode has been clogged seriously by particle matters, compressed
air (the gauge pressure is about 50 mbar) can be supplied inter-
mittently to flush the air cathode, and the clogging particle matters
can be pushed through the cathode and carried out by electrolyte.
Therefore, the porosity can be regenerated to a certain extent. With
respect to the degradation of PTFE, making the distribution of the
Fig. 13. Pressure drop (DP) between the two sides of air cathode. micropores in GDL more uniformly can alleviate the negative in-
fluence of the porous geometry changing.

[40]. Carbon oxidation weakens the attachment of catalyst particles


5. Conclusions
to the carbon surface, eventually leading to structural collapse and
the detachment of catalyst particles from the carbon support,
In this study, 2-cell stacks, 25 cm2 cells and three-electrode half-
resulting in declines of the catalyst active surface area and fuel cell
cells were constructed with new air cathodes and used air cath-
performance. Fourth, the changes in the MnO2 oxidation state and
odes,with inexpensive manganese dioxide (MnO2) as the catalyst.
crystallographic features during extensive operation of the cell
The peak power density for fuel cells with new air cathodes was
would decrease the activity of the catalyst [41]. Fifth, the plastic
almost twice the value of used air cathodes. The degradation
binder (even PTFE) is attacked by the hot caustic electrolyte [42].
characteristics of the used air cathodes have been experimentally
The electrolyte contains peroxides, which are produced during
investigated by different means. The results of the electrochemical
incomplete oxygen reduction. These peroxides can induce radical
impedance analysis show that both the charge transfer resistance
chain destruction. Destruction of the polymers the CL lowers their
and the mass transfer resistance of the used air cathodes are
mechanical stability and hydrophobicity.
dramatically increased. Additionally, the SEM images confirm that a
Several strategies can be employed to enhance catalytic layer
small amount of catalyst particles in CL are lost, and the pores in CL
durability for long-term operation. First of all, the electrolyte
and GDL of the used air cathode are clogged seriously. The
scouring can be suppressed by redesigning the air cathode. For
permeability of the used air cathode has decreased by 70%
example, bonding an additional composite membrane with CL at
compared with the new cathode. Therefore, the performance
the electrolyte side can successfully prevent electrolyte scouring,
degradation of the used air cathodes may be mainly due to the
and can also act as the insulated separator. Meanwhile, the flow
considerable decrease of the catalyst active surface area of the
field structure must be carefully designed to avoid local high speed
catalytic layer (CL) and the gas diffusion coefficient of the gas
flowing and high temperature of the air cathode. With respect to
diffusion layer (GDL).
precipitate/dissolve issues, one possible mitigation strategy is to
Furthermore, hypothesis of degradation mechanisms and miti-
keep the CL marinated in electrolyte during the parking period. The
gation strategies for CL and GDL were discussed briefly. Material
negative influence of carbon oxidation on fuel cell performance can
oxidation, catalyst particles loss, carbonate precipitation, particle
be alleviated by using more stable materials as catalyst supports.
matters in the feed air, and numerous precipitate/dissolve cycles of
Recently, carbon nanotubes or carbon nanofibers have been pro-
electrolyte between fuel cell operation and parking periods all
posed as promising support materials for fuel cell catalysts due to
would decrease the catalyst active surface area of CL and the gas
their unique characteristics [32,40]. Furthermore, it is necessary to
diffusion coefficient of GDL. In order to mitigate the degradation,
prevent the fuel cells from operating at high potentials such as OCV
further studies in materials, air cathode structure, and fuel cell
and idle conditions. The problem of plastic binder corrosion can be
structure and operation conditions are needed.
alleviated by introducing radical collectors into the chains (e.g.
styrenes) or using improved catalysts with lower peroxide forma-
tion [42]. Acknowledgments

4.1.1. Gas diffusion layer The National Basic Research Program of China (973 Program)
Direct reasons for GDL degradation include: (1) electrolyte (2012CB215500), the National Natural Science Foundation of China
leakage and carbonate precipitation, (2) particle matters clogging, (No. 21376138), 863 Programs (2012AA110601, 2012AA053402) are
and (3) degradation of PTFE. In typical operation, the electrolyte gratefully acknowledged for funding this work.
and gas fill pores inside the active layer side by side, and no elec-
trolyte goes inside the GDL because of its high hydrophobicity. References
However, the electrolyte would leak throughout the GDL for some
€fer, Energy Policy
[1] W. Krewitt, S. Simon, W. Graus, S. Teske, A. Zervos, O. Scha
reasons, for example electrocapillary migration. Irreversible car-
35 (2007) 4969e4980.
bonate precipitation will occur inside the electrolyte-filled pores of [2] World Energy Outlook 2012, International Energy Agency, Paris, 2012.
GDL as the feed air contains carbon dioxide (CO2). Moreover, there [3] Energy Technology Perspectives 2012, International Energy Agency, Paris,
are lots of particle matters (PM) in the feed air, such as PM2.5, 2012.
[4] E.K. Hart, M.Z. Jacobson, Energy Environ. Sci. 5 (2012) 6592e6601.
which would also clog the macropores in GDL. Last but not least, [5] E.V. Global, Outlook: Understanding the Electric Vehicle Landscape to 2020,
the PTFE may be degraded by caustic electrolyte, resulting in International Energy Agency, Paris, 2013.
64 Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64

[6] C.J. Barnhart, M. Dale, A.R. Brandt, S.M. Benson, Energy Environ. Sci. 6 (2013) [26] R. Cao, J.-S. Lee, M. Liu, J. Cho, Adv. Energy Mater. 2 (2012) 816e829.
2804e2810. [27] X.G. Zhang, Corrosion and Electrochemistry of Zinc, Plenum Publisher, 1996.
[7] J. Rugolo, M.J. Aziz, Energy Environ. Sci. 5 (2012) 715e7160. [28] D. Linden, D.B. Reddy, Handbook of Batteries, third ed., McGraw Hill, New
[8] B. Müller, W. Arlt, P. Wasserscheid, Energy Environ. Sci. 4 (2011) 4322e4331. York, NY, 2002.
[9] M.C. Toroker, E.A. Carter, J. Mater. Chem. A 1 (2013) 2474e2484. [29] C.W. Lee, K. Sathiyanarayanan, S.W. Eom, H.S. Kim, M.S. Yun, J. Power Sources
[10] T.J. Kucharski, Y. Tian, S. Akbulatov, R. Boulatov, Energy Environ. Sci. 4 (2011) 160 (2006) 161e164.
4449e4472. [30] X.G. Zhang, ECS Trans. 16 (2009) 47e59.
[11] Z. Yang, J. Zhang, M.C.W. Kintner-Meyer, X. Lu, D. Choi, J.P. Lemmon, J. Liu, [31] M.A. Rahman, X. Wang, C. Wen, J. Electrochem. Soc. 160 (2013) 1759e1771.
Chem. Rev. 111 (2011) 3577e3613. [32] J.-S. Lee, S.T. Kim, R. Cao, N.-S. Choi, M. Liu, K.T. Lee, J. Cho, Adv. Energy Mater.
[12] G.L. Soloveichik, Annu. Rev. Chem. Biomol. Eng. 2 (2011) 503e527. 1 (2011) 34e50.
[13] Q. Li, R. Cao, J. Cho, G. Wu, Adv. Energy Mater. 4 (2014) 1301415. [33] F. Zhang, D. Pant, B.E. Logan, Biosens. Bioelectron. 30 (2011) 49e55.
[14] J.W.D. Ng, Y. Gorlin, T. Hatsukade, T.F. Jaramillo, Adv. Energy Mater. 3 (2013) [34] A. Fischer, J. Jindra, H. Wendt, J. Appl. Electrochem. 28 (1988) 277e282.
1545e1550. [35] E. Barsoukov, J.R. Macdonald, Impedance Spectroscopy Theory, Experiment,
[15] F. Cheng, J. Chen, Chem. Soc. Rev. 41 (2012) 2172e2192. and Applications, John Wiley & Sons, Inc., Hoboken, NJ, 2005.
[16] H. Kim, G. Jeong, Y.-U. Kim, J.-H. Kim, C.-M. Park, H.-J. Sohn, Chem. Soc. Rev. 42 [36] X. Yuan, H. Wang, J.C. Sun, J. Zhang, Int. J. Hydrogen Energy 32 (2007)
(2013) 9011e9034. 4365e4380.
[17] J. Goldstein, I. Brown, B. Koretz, J. Power Sources 80 (1999) 171e179. [37] X. Yuan, J.C. Sun, M. Blanco, H. Wang, J. Zhang, D.P. Wilkinson, J. Power
[18] P. Sapkota, H. Kim, J. Ind. Eng. Chem. 15 (2009) 445e450. Sources 161 (2006) 920e928.
[19] V. Neburchilov, H. Wang, J.J. Martin, W. Qu, J. Power Sources 195 (2010) [38] R. Holze, W. Vielstich, J. Electrochem. Soc. 131 (1984) 2298e2303.
1271e1291. [39] H. Huang, W. Zhang, M. Li, Y. Gan, J. Chen, Y. Kuang, J. Colloid Interface Sci. 284
[20] S.I. Smedley, X.G. Zhang, J. Power Sources 165 (2007) 897e904. (2005) 593e599.
[21] P. Pei, Z. Ma, K. Wang, X. Wang, M. Song, H. Xu, J. Power Sources 249 (2014) [40] S. Zhang, X.-Z. Yuan, J.N. Cheng Hin, H. Wang, K.A. Friedrich, M. Schulze,
13e20. J. Power Sources 194 (2009) 588e600.
[22] J. F. Cooper, D. Fleming, D. Hargrove, R. Koopman, K. Peterman, SAE papers [41] P.H. Benhangi, A. Alfantazi, E. Gyenge, Electrochim. Acta 123 (2014) 42e50.
951948. [42] M. Cifrain, K.V. Kordesch, J. Power Sources 127 (2004) 234e242.
[23] G. Du, X. Liu, Y. Zong, T.S.A. Hor, A. Yu, Z. Liu, Nanoscale 5 (2013) 4657e4661. [43] J.-F. Drillet, F. Holzer, T. Kallis, S. Müller, V.M. Schmidt, Phys. Chem. Chem.
[24] S. Yang, X. Feng, X. Wang, K. Müllen, Angew. Chem. Int. Ed. 50 (2011) Phys. 3 (2001) 368e371.
5339e5343. [44] H.-H. Cheng, C.-S. Tan, J. Power Sources 162 (2006) 1431e1436.
[25] M. Prabu, K. Ketpang, S. Shanmugam, Nanoscale 6 (2014) 3173e3181.