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Heat Generation in High Power Prismatic Li-

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DOI: 10.1002/er.3156

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 INTERNATIONAL JOURNAL OF ENERGY RESEARCH
Int. J. Energy Res. 2014; 38:14241437
Published online 10 February 2014 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/er.3156

Heat generation in high power prismatic Li-ion battery

cell with LiMnNiCoO2 cathode material
Yasir Abdul-Quadir1,*,, Tomi Laurila1, Juha Karppinen1, Kirsi Jalkanen2, Kai Vuorilehto2,
Lasse Skogstrm1 and Mervi Paulasto-Krckel1
1
Department of Electronics, Aalto University, School of Electrical Engineering, Otakaari 7, 02150 Espoo, Finland
2
Department of Chemistry, Aalto University, School of Chemical Technology, Kemistintie 1, PO Box 6100, FI-00076 Espoo, Finland

SUMMARY
While in use, battery modules and battery packs generate large amounts of heat, which needs to be accounted for. The main
challenge in battery thermal management is the correct estimation of heat generation in the battery cell during charging/
discharging. In this paper, a method to calculate accurate heat generation in one individual cell is provided. The heat
generation is calculated by measuring the overpotential resistances with four different methods and entropic heat generation
in the cell. The effect and contribution of entropic heat generation towards the total heat generation in the cell are also
calculated and measured. Finally, calorimeter tests are carried out to compare the calculated and measured heat generation.
The results indicate that except for direct current resistance measured by impedance spectroscopy, all the overpotential
resistances are very close to each other. Copyright 2014 John Wiley & Sons, Ltd.
KEY WORDS
Li-ion battery; heat generation; overpotential resistance; entropy change; calorimeter

Correspondence
*Yasir Abdul-Quadir, Aalto University, School of Electrical Engineering, Department of Electronics, Otakaari 7, 02150 Espoo, Finland.

E-mail: Yasir.abdul.quadir@aalto.

Received 8 May 2012; Revised 16 December 2013; Accepted 18 December 2013

1. INTRODUCTION mixing enthalpies and phase changes. Rao and Newman

The lithium-ion battery (Li-ion battery) is the preferred
power source for hybrid electric vehicles (HEVs) and
electric vehicles (EVs) because of its high specic energy,
high voltage and low self-discharge rate. To provide
affordable HEVs and EVs with satisfactory performance,
there are still major technical challenges to improve the
characteristics of Li-ion batteries such as low cost, high
power density, long service life and proven safety. Because
safety is one of the major challenges for the Li-ion battery
in HEV and EV applications, the thermal management of
Li-ion batteries is especially important. The main concern
in the thermal management of Li-ion battery is the
signicant temperature increase that can occur especially
during high power extraction in HEV and EV applications,
which may cause battery degradation and thermal runaway.
Thermal modelling can play a key role in controlling the
operating temperature and temperature uniformity of Li-ion
batteries within a suitable range [13].
There have been many previous studies on thermal
modelling of Li-ion batteries [417]. Bernardi et al. [4]
developed a general energy balance for battery systems
including the contributions from electrochemical reactions,
[5] presented a method of calculating the heat generation
rate based on the general energy balance and the enthalpy
potential method for a Li-ion battery system. Chen and
Evans [68] developed two-dimensional and three-
dimensional models to study the thermal behaviour of
lithium polymer batteries (Li-polymer batteries) and Li-
ion batteries. They assumed that the heat generation rate
is uniform throughout the cell. Pals and Newman presented
a one-dimensional model for predicting the thermal
behaviour of Li-polymer batteries for a single cell [9] and
a cell stack [10]. Baker and Verbugge [11] modelled the
three-dimensional current and temperature distributions in
Li-polymer battery modules. Botte et al. [12] studied the
inuence of design variables on the thermal behaviour of
Li-ion batteries based on one-dimensional model. Song
and Evans [13] developed an electrochemicalthermal model
of Li-polymer batteries by coupling a two-dimensional
thermal model with one-dimensional electrochemical
model. Gu and Wang [14] and Srinivasan and Wang [15]
developed a two-dimensional thermal and electrochemical
coupled model to analyse the electrochemical and thermal
behaviour of Li-ion battery cells. Chen et al. [16]
developed a three-dimensional model of Li-ion batteries

1424 Copyright 2014 John Wiley & Sons, Ltd.

Heat generation in high power prismatic Li-ion battery cell
considering the location-dependent convection and radia-
tion at the boundaries to reect the different heat
dissipation performances on all of the surfaces. Onda
et al. [17,18] proposed a simplied formula for total heat
generation in a battery cell, which included overpotential
and entropic heat. They went on to measure different
resistances related with overpotential heat. Karimi and
Li [19] implemented various cooling strategies to examine
the relationship between battery thermal behaviour and
thermal management design system. They reasoned that
the equivalent internal resistance for the at type batteries
used in the EV is proprietary and not available in the open
literature. They used the internal resistance, which has
been measured for the commercially available small size
Li-ion batteries, which is structurally very similar to those
of at batteries.
Bandhauer et al. [20] critically reviewed the available
literature on major thermal issues for Li-ion batteries. They
concluded that majority of the experimental work that
measure heat produced by the Li-ion battery has been
carried out on coin cells and at low to moderate charge/
discharge rates (<1C). They also commented that entropic
heat is nearly the same order of magnitude as the
irreversible heat for the 1C discharge rate, thus having a
non-negligible impact on the heat generation and perfor-
mance of a cell.
Hence, it is a fact that most of the heat generation exper-
imental work on Li-ion battery has been performed on
coin cells or cells with lower capacity. This work will
concentrate on the heat generation in a high power
prismatic cell, look at the signicance of entropic heat
generation for large capacity cells and the assumption that
heat generation in a cell is uniform. Calorimeter tests are
carried out to obtain necessary parameters for the heat
generation calculations and to validate the obtained results.
2. THEORY AND EXPERIMENTS
The most common equation describing heat generation in a
battery cell during an electrochemical process (charge or
discharge) is given by [4,19]:
dV o
q I V o  V  IT (1)
dT
where q is the heat generation in the battery cell, VO is the
open circuit voltage, V is the cell voltage, I is the applied
current and T is the temperature of the cell.
The rst term in Eqn (1) is the overpotential due to
ohmic losses in the cell, charge transfer overpotentials at
the interface and mass transfer limitations. The second
term is the entropic heat, and the potential derivative with
respect to temperature is often referred to as the entropic
heat coefcient [19].
When a current ows in a battery, the cell voltage V
deviates from the open circuit voltage VO because of
electrochemical polarization. The resulting energy loss is
Int. J. Energy Res. 2014; 38:14241437 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Y. Abdul-Quadir et al.
converted into heat. This heat generation can be expressed
as overpotential heat QP:
QP I V o  V I 2 R (2)
QP represents heat generation during both charging and
discharging. Expressing the difference between V and VO
by IR, QP can be related to the overpotential resistance R.
The entropic heat generation QS caused by the entropy
change S is expressed as follows:
   
I G E emf
Qs TS nFT (3)
nF T cell T
where n is the number of moles of electrons exchanged in the
reaction, F is the Faradays constant (9.648456 104C/mol)
and Eemf is the cell potential.
In this paper, a Li-ion battery cell is also discharged in
an adiabatic calorimeter to validate the overpotential and
entropic heat measurements. The following equation has
been used to compare the test results:

dT cell
C cell Cliquid Calorimeter Constant q (4)
dt
where q is the same as calculated in Eqn (1). The specic
heat capacity of the cell is measured separately as well as
the calorimeter constant. C is heat capacity of the material
in J/K and can be calculated by multiplying specic heat of
the material with its mass.
In order to obtain the total heat generation in the battery
cell, the overpotential resistance and entropic heat
generation within the cell have to be measured. Once these
parameters are obtained, Eqn (1) can be used to calculate
the total heat generation. This is then validated by charging
or discharging the cell inside a calorimeter and using
Eqn (4) to compare the measured heat generation with the
one calculated with Eqn (1). Some extra parameters used
in Eqn (4) are also measured here, namely, the specic heat
of the battery cell and the calorimeter constant.
The cell tested here is a high capacity commercially
available (Kokam SLPB100216216H [21]) Li-ion cell with
rated capacity of 40 Ah as shown Figure 2. The specica-
tions of the cell are listed in Table I.
States of charge (SOCs) were set at 100% and 0%,
respectively, at the end of the rated charge and discharge
cycles. The rated current is dened as the current to
discharge the rated capacity of 40 Ah in 1 h.
The following heat generation components were
measured:
2.1. Characterization of battery cell
Chargedischarge and capacity tests were performed on
the cell to make sure that the battery is in good working
condition. The charging prole was as follows:
At constant current until the voltage reaches 4.2 V.
At constant voltage until the current reaches 2 A.
1425
Y. Abdul-Quadir et al. Heat generation in high power prismatic Li-ion battery cell

Table I. Specications of the Li-ion battery cell used. this assumption, temperature during discharge at differ-
Size 220 215 10.7 mm
ent C-rates were measured on seven different points on
Anode material Graphite
the surface of the cell. This is illustrated in Figure 2.
Cathode material Lithium cobalt manganese The cell was placed on few plastic threads on one side
nickel oxide (LiMnNiCoO2) so as to mimic the hanging in air condition. This was
Electrolyte Solution of lithium done to ensure that all the sides were exposed to natural
hexauorophosphate (LiPF6) convection. Figure 3 shows the result of the temperature
Nominal voltage 3.7 V measured on battery during 1C, 2C and 4C discharge.
Cut-off voltage 2.7 V The gure clearly shows that temperature on the surface
Operating temperature Charge: 0 C to +40 C of the cell is relatively uniform, with the hottest point
Discharge: 20 C to +60 C being in the middle of the cell, which is position 7 in
Capacity 40 Ah Figure 2. While the temperature difference increases
Maximum charge current 80 A (2C) between the highest and the lowest point of the curves
Maximum discharge current 400 A (10C) with increasing C-rate, it is not signicant, and for all
practical purposes, the battery could be assumed to be
at a uniform temperature. Thus, even with relatively
The discharge was carried out at constant current until large temperature change, the surface temperature
the cell reached a voltage of 2.7 V. remains essentially evenly distributed. The result implies
Figure 1a shows the discharge curve at different rates.
Figure 1b shows the charge and discharge curve at 0.5C
with respect to the rated capacity of the cell.

2.2. Uniformity of heat generation in a

battery cell

Equation (1) is based on the assumption that there is a

uniform heat generation in a Li-ion battery cell. To validate

Figure 2. Location of thermocouples for heat generation

uniformity test.

Figure 1. (a) Discharge curves at different C-rates and (b) capacity Figure 3. Temperature change on cell surface for 1C, 2C and
of the cell at 1C charge and discharge. 4C discharge.

1426 Int. J. Energy Res. 2014; 38:14241437 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Heat generation in high power prismatic Li-ion battery cell Y. Abdul-Quadir et al.

that for thermal simulation, a uniform heat source could

be applied to the battery model.
The core temperature of the battery cell is very dif-
cult to measure, especially for a commercial battery
cell. Lee et al. [22] manufactured a voltage and
temperature sensor by microelectromechanical systems
process to monitor the temperature of the core. They
also monitored the temperature of the battery cell
surface using a thermocouple. They showed that while
the core temperature of the battery is higher than the
surface temperature, they both follow the same pattern
during charge or discharge. Similar result was shown
by Lin et al. [23]. Taheri and Bahrami [24] also
obtained similar temperature curves for a prismatic cell
for 10 A (0.5C), 20 A (1C), 40 A (2C), 60 A (3C) and
100 A (5C) discharge.
Overpotential resistance of the cell was measured with
four different techniques as follows.

2.3. Resistance by V  I characteristics

Charging (from 0.5C to 2C) and discharging (0.3C to 2C)

tests were carried out at room temperature for various
C-rates. The obtained data (cell voltage and charge
discharge current) from constant current chargedischarge
tests were plotted as V  I characteristic as function of
SOC. The V  I characteristics for charging and discharging
at ambient temperature are shown in Figure 4. The V  I
characteristics are generally linear. The overpotential
resistance is calculated from the slope of the V  I curve.
The slope of the curves is determined by the least squares
approximation assuming that the V  I characteristic is, on
the whole, a straight line. The R2 values for the t were on
average 0.98.
2.4. Resistance by open circuit voltage (VO)
and cell voltage (V)
Cell voltage (V) during chargedischarge cycle is differ-
ent to open circuit voltage (VO). Overpotential resis-
tance can be measured by dividing the difference
between V and VO by the charging or discharging
current. In our study, the cell was charged or
discharged to the desired SOC level with 1C current.
Once the desired SOC level was achieved, the cell
was left to stabilize. The stabilization time was chosen
on the basis of the moment when the battery reaches
a constant open circuit voltage and has started to self-
discharge. This period is necessary for active material
diffusion to enable the open circuit potential to be
reached (or at least approached). The cell voltage after
the chosen stabilization period was taken as open circuit
voltage (VO). The experiments showed that this stabili-
zation time increases as SOC decreases, with the cell
taking as long as 21 h to stabilize at 20% SOC, whereas
it took only 4 h to stabilize at 80% SOC.
Figure 4. Voltagecurrent characteristics during charging
and discharging.
2.5. Resistance by intermittent discharge
The overpotential cell resistance can also be measured by in-
termittent discharge. In this method, the cell is discharged
(with a known C-rate) to a known SOC and then kept at that
SOC for 10 min. This cycle is repeated until the cell voltage
limit is reached (2.7 V, 0% SOC). The drop in voltage in
60 s, after the commencement of discharge, is then divided
by the current to calculate the overpotential resistance corre-
sponding to the particular SOC.
2.6. Resistance obtained by alternating
current impedance method
Alternating current (AC) impedance measurements of the
cell at several SOC values were carried out by an electro-
chemical impedance analyzer (Autolab potentiostat
(PGSTAT302N), Frequency Response Analyzer (version
4.9)). The cell was charged to 100% SOC (4.15 V) at
which the rst electrical impedance spectroscopy (EIS)
measurements were carried out. It was then incrementally
discharged by 10% SOC until the voltage reached 2.7 V
(0% SOC). Discharge current was 20 A, and AC imped-
ance was measured at each of 10% SOC increments.
Impedance measurements were done in the frequency
range of 0.154000 Hz using galvanostatic mode and 0.5
perturbation amplitude.

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Y. Abdul-Quadir et al.
2.7. Measurement of entropy change
The following method was used to measure the entropy
change of the cell for 1C discharge.
a. Cell kept at open circuit voltage for about 2123 h at
room temperature.
b. Temperature was changed by 10 C after every 2.5 h.
c. VO was measured at temperatures 25, 35, 45 and 55 C.
d. The steps were repeated for different SOCs. The cell
was discharged to a desired SOC level at 1C.
Figure 5a shows the test procedure as explained in the
aforementioned steps for the cell at 100% SOC.
It can be seen from Figure 5a that once the cell is
fully charged, there is a steep decrease in the voltage
(for about 2 h), which is later followed by self-discharge
of the cell. After the cell has been stabilized for about
20 h, temperature is changed from 25 to 35 C. This
results in a sharp decline in the voltage, which later
stabilizes (as the self-discharge takes over). This sharp
Figure 5. (a) dVo/dT measurement steps at 100% state of charge, including the stabilization time and (b) dVo/dT at 60% state
of charge.
1428
Heat generation in high power prismatic Li-ion battery cell
decline is only observed for about 30 min, and the
open circuit voltage stabilizes with the temperature.
The graph also shows that the decline of open circuit
voltage (both due to change of temperature and self-
discharge) is higher at higher temperature. Bandhauer
et al. [19] mentioned that self-discharge can be an
important factor while determining an accurate value
of open circuit voltage at higher SOC and that many
researchers have had problems maintaining stable
voltages. Same phenomenon is observed in this study.
While it was difcult to maintain a stable open circuit
voltage at 100% SOC, shown in Figure 5a, it was
much easier at 60% SOC, which is shown in Figure 5b
(the stabilization time has been omitted from the graph
to show the effect of temperature on open circuit
voltage).
The self-discharge was accounted for in the calcula-
tions. The self-discharge of the battery at respective
temperatures was measured for 5 d. From these data, the
rate of self-discharge was calculated and accordingly used
in calculating dVO/dT.
Int. J. Energy Res. 2014; 38:14241437 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Heat generation in high power prismatic Li-ion battery cell Y. Abdul-Quadir et al.

2.8. Measurement of specic heat capacity cell cables and thermocouples are carefully sealed to avoid
of the battery any heat transfer to the ambient. Seven thermocouples
were attached inside the test area of the calorimeter. Six
To calculate the heat generation of the cell using Eqn (4), thermocouples measured the water temperature, and one
specic heat of the cell is required. To obtain this thermocouple (TC7) was attached to the centre of the
information, the following experiments were carried out. battery cell. As shown in previous section, the hottest
The rst step in this procedure was to heat up a known part in the cell is right in the middle, where the thermocouple
material (in our case, an aluminium plate, which has same is attached.
conguration as the cell) to a certain temperature (50 C in The stirrer mechanism used in the current calorimeter,
our case) and then cool it down at ambient temperature. as shown in Figure 6, uses an electric motor. The voltage
We measure the temperature decrease of this block in free applied to the motor can be controlled to obtain an
convection condition to ambient temperature. Block optimum speed for the stirrers. The speed of the stirrers
temperature T with a known capacity can be given by the was optimized to make sure that the stirring mechanism
following heat balance equation: in itself did not heat up the liquid.
Before determining the actual heat generation of the
dT Ah Ah cell, we had to calculate the heat capacity of the calorime-
 T  T room  T  T room (5)
dt C cp v ter (including the cell holder, cables and thermocouples).
This was achieved by cooling a known metal block (inside
where C is the heat capacity of the block (calculated from the calorimeter) after heating it up to a certain temperature.
its density , specic heat capacity cp and volume v) and A The following heat balance equation was used to calculate
and T are the surface area and the temperature, the heat capacity of the calorimeter (calorimeter constant):
respectively. The specic heat used here for the Al block

is 900 J/kgK. mmetal cps dT mliquid cpl calorimeter constant dT (6)
Similarly, we measure the temperature decrease of the
cell. where mmetal is the mass of the metal block, cps is the
specic heat capacity of the metal block (aluminium) and
2.9. Calorimeter test to measure the total dT in the left hand of Eqn (6) is the temperature drop in
heat generation in the battery cell the metal block. Similarly, mliquid is the mass of the water
used in the calorimeter (which can be calculated from
To measure the total heat generation of the battery cell
density and volume), and dT on the right-hand side of
during discharge, an adiabatic calorimeter was built using
Eqn (6) is the increase in water temperature. On the basis
Styrofoam material. The test section was constructed
of Eqn (6), the calorimeter constant was calculated to be
using insulation foam material [25]. Table II provides the
approximately 1000 J/K (calculation for this process is
properties of insulation foam used. Figure 6 shows a
shown in Appendix A).
schematic of the calorimeter and the actual calorimeter
used in this work. The corners and the terminals of the cell
are carefully sealed to avoid any penetration of the water
through the cell. The water level in the calorimeter is up
3. RESULTS
to the current collectors and not touching the cables
3.1. Overpotential resistance measurement
attached to them. The stirrer on the top of the calorimeter
lid is motorized and any openings mainly due to the battery Figure 7 shows the overpotential resistances for
discharging obtained by the R(V  I), R(VO  V) and R
Table II. Properties of insulation foam. (60s) methods. The graph shows a steady increase in resis-
Properties
tance after about 50% SOC and steep increase after 10%
SOC. All the resistances are in very good agreement with
Cell structure Over 90% sealed cells each other.
Thermal conductivity 0.023 W/mK Results obtained by Onda et al. [18] show that for a
3
Density 3238 kg/m higher capacity cell, resistance by intermittent discharge
Water absorption 1.5 vol. % was around half of R(V  I) and R(VO  V). This could be
12
Water vapour permeability 0.11.2 10 kg/msPa due to only 60 s of waiting time before each discharge in
Compression strength 100 kPa their work, while in our case, the waiting time is 10 min.
Tensile strength 230 kPa
5
Coefcient of 58 10 / C
3.2. Electrical impedance spectroscopy
thermal expansion
results
Heat resistance 40 to +100 C, momentary
+250 C Figure 8 shows the Nyquist plot for the cell impedance at
Normal products Over +400 C, ame approx. different SOCs. As described elsewhere [26], the Nyquist
Flashpoint +300 C
plot of a Li-ion cell is mainly comprised of an inductive tail

Int. J. Energy Res. 2014; 38:14241437 2014 John Wiley & Sons, Ltd. 1429
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Y. Abdul-Quadir et al. Heat generation in high power prismatic Li-ion battery cell

Figure 6. Schematic of the calorimeter used in this work.

Figure 7. Overpotential resistance measured using voltagecurrent characteristic curve.

(which has been neglected here) at high frequency frequencies. Our data only showed one semi-circle. Similar
followed by two semicircles at the medium and low results were also obtained by Onda et al. [18].

1430 Int. J. Energy Res. 2014; 38:14241437 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Heat generation in high power prismatic Li-ion battery cell Y. Abdul-Quadir et al.

Figure 8. Nyquist plot at different states of charge.

Rodrigues et al. [26] evaluated the impedance parameters
of a Li-ion cell at different SOCs using an equivalent circuit
shown in Figure 9a. L is the inductance taken in parallel to a
resistance RL corresponding to the high frequency inductive
tail in impedance spectra; R represents the ohmic resistance
of the battery; Q1 and Q2 are constant phase elements, which
are taken in parallel to the respective resistances, R1 and R2,
corresponding to the medium and low frequency semicircles,
respectively. In this work, as can be observed from Figure 8,
R1 is not present, and L and RL have been shown to be just
tting parameters. Thus, the circuit in Figure 9a can be
simplied to the Randles circuit shown in Figure 9b. In this
circuit, R represents the ohmic resistance of the battery,
Rct is charge transfer resistance, W is Warburg element and
Cdl is double layer capacitance. By adding the ohmic
resistance and the charge transfer resistance, one should be
able to obtain the DC resistance of the cell. Table III shows
the value of the tting parameters for the circuit shown in
Figure 9b. The DC resistance in Table III is obtained by
adding R and Rct.
Figure 7 shows the overpotential resistance measured
by the four different methods. The graph clearly shows that

Figure 9. (a) Circuit used by other researchers [22,23] and (b) Randles circuit.

Table III. Impedance parameters obtained in this work.

4
SOC (%) R()/m C(dl)/F R(ct)/m W/10 DC resistance/m

0 0.6 34.13 0.6 0.12 1.2

10 0.5 30.65 0.4 0.45 0.9
20 0.5 30.95 0.3 0.69 0.9
30 0.5 38.62 0.3 0.96 0.8
40 0.5 43.48 0.3 0.99 0.8
50 0.5 47.53 0.2 0.99 0.8
60 0.6 62.57 0.2 0.90 0.8
70 0.6 65.87 0.2 0.63 0.7
80 0.6 70.22 0.2 0.77 0.7
90 0.6 73.33 0.2 0.89 0.7
100 0.6 83.69 0.2 1.02 0.8
SOC, state of charge.

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Y. Abdul-Quadir et al.
the overpotential resistance measured by AC impedance
method is less than half of the resistances measured by
other three methods. Similar results were obtained by
Onda et al. [18]. It is most likely that this is because the
impedance measurements are carried out at a very low
current (0.5 A in this study, which is equivalent to
0.0125C), while the three other resistance measurement
methods use much higher currents (1280 A). The general
trend shown in all four resistances is similar, with the
resistance increasing with decreasing SOC. This is
expected as during discharge Li-ions are transferred
from anode to cathode and associated concentration
gradients increase in magnitude. At the end of discharge
cycle, Li-ions get depleted from anode, and more energy
is needed to transfer the Li-ions from anode to cathode.
3.3. Entropy change measurement
Table IV shows the values of entropic coefcient dVo/dT
for various SOCs at 1C discharge.
The values are generally small except at 0% SOC. The
increasing trend of dVO/dT values at higher temperatures
is also evident.
Hallaj et al. [27] provided values of dVO/dT between
0.43 and 0.72 mVK1 for Panasonic (CGR 18650H)
and the A&T (18 650) cells. The cathode in the cells
they studied was made of LiCoO2 material. Chen and
Evans [6] reported dVO/dT values of 0.414 mVK1,
averaged over a range of SOCs. In this work, the values
for dVO/dT are shown to be comparatively smaller
(except for at 0% SOC) than the aforementioned values
reported by other researchers. Lu et al. [28] performed
dVO/dT tests for Li1+x[Ni1/3Co1/3Mn1/3]1  xO2 half cells.
They calculated the values for dVO/dT to be between
0.06 and 0.12 mVK1. According to them, small
entropy coefcient values mean that the particular cathode
material is thermally more stable than other Ni-based layer
oxides, LiNiO2, LiNi1  xCoxO2 and LiNi1  xCoyAlO2. In
the current work, while we do see the entropy coefcient
turning positive at around 70% SOC, the values are very
small.
Figure 10a shows the entropy change, S calculated
from Eqn (3), at different SOCs for 1C discharge for
temperature difference of 25 to 35 C.
The graph shows that QS (entropic heat) is exothermic
until 80% SOC during discharge and endothermic between
Table IV. dVo/dT values obtained for three different temperature changes.
Temperature change/C 100% 80%
dVo/dT (mVK )
2535 0.13 0.03
3545 0.20 0.05
4555 0.38 0.08
SOC, state of charge.
1432
Heat generation in high power prismatic Li-ion battery cell
6040% SOC, becoming exothermic again at 20% SOC
and below. It is to be noted that the curve in Figure 10a
is the result of phenomena taking place both at the anode
and at the cathode.
The negative to positive change in entropy indicates a
stage structure change in the graphite anode or phase
transition in the cathode. When the change in the congu-
rational entropy is negative, ordering of the structure
typically takes place, whereas the opposite is true for the
positive change. It is to be noted that this is somewhat of
an oversimplication as the entropy is in fact composed
of a congurational part (arrangement of species in the
system) and a thermal part (energy distribution over the
energy states in the system).
Saito et al. [29] reported that cells using a LiNiCo
complex oxide cathode or a LiMn2O4 cathode have a
special feature in which the dVO/dT is positive or nearly
zero in the half range of high SOCs and negative in the half
range of low SOCs. They also mentioned that entropy
change in cells with the aforementioned cathode is very
small. Similar results are obtained in the current work.
Hallaj et al. [27] also reported that change in dVO/dT from
negative to positive occurs because of a phase change in
the cathode and a structural change in the anode material.
Thomas and Newman [30] reported entropy change in
LiNi0.8Co0.2O2 cathode material. Their investigation
suggests that there is no phase change in the cathode
during deintercalation of Li. To investigate the possibility
of structural changes with the present cathode material,
the open circuit voltage with respect to Li concentration
(y) in LiyMnNiCoO2 was plotted. As can be seen from
Figure 10b, no plateaus corresponding to two-phase
equilibrium are observed. This suggests that no phase
change (rst order transformation) should occur in the
cathode material of the cell under investigation.
Hallaj et al. [31] reported that the dVO/dT changes from
negative to positive for a coin cell with graphite anode and
LiCoO2 cathode at 77% SOC. The same phenomenon is
observed in the current work as illustrated in Figure 10a.
Hallaj [31] suggested that endothermic heat effects
noted for the Panasonic cell during discharge near 4.0 V
(77% SOC) are in part due to the endothermic heat effect
of Li deintercalation from the graphite anode, in conjunc-
tion with the endothermic heat effect of the simultaneous
order/disorder phase transition (from hexagonal to
monoclinic) that takes place in the cathode during that
SOC
60% 40% 20% 0%
1
0.06 0.02 0.07 0.44
0.15 0.14 0.08 0.47
0.14 0.15 0.09 0.48
Int. J. Energy Res. 2014; 38:14241437 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Heat generation in high power prismatic Li-ion battery cell
Figure 10. (a) Entropy change at different states of charge
(SOCs) when the temperature changes from 25 C to 35 C
and (b) dVo/dT versus state of charge. Graph shows the change
of entropy becoming endothermic at 60% and 40% SOC.
period only. They concluded that the cell discharge causes
structural transformations in the graphite anode, as Li is
deintercalated from graphite. These transformations,
characterized by an entropy increase and an endothermic
reversible heat effect, reinforce the endothermic spike due
to the monoclinic to hexagonal phase change following
the initial exothermic spike due to the hexagonal to
monoclinic phase change during discharge, as the SOC
approaches 77%. The dVO/dT values provided by Hallaj
et al. [31] are much higher at lower SOCs (around 0.5
mVK1) than in the current work, which implies structural
changes in cathode taking place during discharge. Our
situation is somewhat different in comparison with that of
Hallaj et al. [31], as there is no evidence of structural
transformation at the cathode side, as evidenced by very
low values of dVO/dT (Figure (10a) and Table IV).
If one considers just the congurational part of the
entropy, concentrates solely on the anode side and takes
a look at Figure(10a), the negative entropy change at
high SOC values could be taken to represent the
growing Li-Li repulsion in the LixC as the Li mole
fraction in graphite increases. The positive value
observed in the midrange of SOCs in Figure 10a can
correspond to the start of the population of a new empty
graphene-graphene layer (intercalation) or layers during
Int. J. Energy Res. 2014; 38:14241437 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Y. Abdul-Quadir et al.
charging as well as deintercalation during discharging.
In that case, the change in mixing entropy (congura-
tional part) should be relatively high. It is to be noted
that there is in fact a balance between three types of
interactions in the intercalated graphite. As the graphite
planes are held together by van der Waals (vdW) type
interactions, from this point of view, the planes should be
kept free of Li in order to maximize the attractive vdW
forces between the adjacent layers. On the other hand, there
is also an attractive Li-C interaction that tends to promote
intercalation of Li. Finally, as discussed earlier, there are also
the repulsive Li-Li interactions, which try to keep Li
cations as far away from each other as possible. The
accessibility of a new graphene-graphene layer during
charging, for instance, depends on the delicate balance
between these different interactions.
The cathode also plays a role in the entropy change, and
its effect must be considered as to be superimposed on the
anode side as discussed earlier. When one takes a look at
Figure 10b, it is noted that there are no sharp discontinuous
changes in the entropy, thus ruling out the possibility of
rst order transitions in our system. The smooth variation
in entropy is a characteristic of a second order transition,
thus heavily indicating that we are dealing here with or-
der/disorder transitions, both at the cathode and at the an-
ode side. This is also supported by the relatively small
values associated with the entropy changes. Lu et al. [28]
mentioned that the phase transition in the nickel-based lay-
ered oxide is suppressed because of the stabilizing effect of
Co and Al doping.
The entropy change (S) from Figure 10a indicates that
for this particular chemistry, its magnitude is small.
However, the heat generated by entropy change can be
signicant (in comparison with overpotential heat) and
should not be neglected while calculating the total heat
generation in the cell. The effect of entropic heat can be
clearly seen in Figure 3, where the temperature of the cell
at 1C discharge is measured. There exists a plateau in the
middle part of Figure 3. This plateau roughly corresponds
to the same SOC values where the entropy change is
positive. When a chemical reaction is endothermic, it
requires inow of heat to the system to drive the reaction
(positive enthalpy and entropy changes). Within this
region, the temperature, despite the continuous discharge,
remains almost constant, until it starts to rise again
(entropy becomes exothermic).
3.4. Specic heat of the battery cell
The method to calculate specic heat of the battery cell has
been explained earlier, where the cell and the Al block are
cooled down after heating them to a certain temperature.
Cooling of the Al block and the cell (Figure 11) is
compared and tted using Eqn (5). The same is also
simulated using the computational uid dynamics method
(Flotherm software [32]).
The tting procedure using Eqn (5) provides a specic
heat value of 670 J/kgK for the battery cell.
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Y. Abdul-Quadir et al. Heat generation in high power prismatic Li-ion battery cell

Figure 11. Cooling of battery cell to calculate its heat capacity.

3.5. Calorimeter tests to validate heat
generation in a battery cell
The cell was next discharged at 2C (80 A) and 3C (120 A)
inside the calorimeter. Figure 12 shows the increase in cell
temperature and the average water temperature during the
discharge process. The graph shows that for 3C discharge,
the rise in water temperature is about 3 C, while for 2C
discharge it is only 2 C. While the rise in water tempera-
ture is almost equal to the rise in cell temperature, at the
end of the discharge period (for both 2C and 3C), the rise
in cell temperature is too fast for the water to catch up. This
is due to a sudden increase in internal resistance of the cell
as it approaches 0% SOC (see EIS results for explanation).
This is also shown in our resistance measurements. The
results indicate that almost all of the heat released by
the cell is taken by the water and that the design of the
calorimeter is good.
The reason that we only see a small increase in the
temperature of water is mainly due to the high thermal
mass of the calorimeter. Because of the size of the cell, it
was not possible to build a calorimeter with a lower
thermal mass. While a higher discharge rate could have
been used to measure a higher change in temperature, the
time of discharge would have been very small. This time
would not have been enough for the water temperature to
stabilize. We see a similar trend at the end of the discharge
for both 2C and 3C, where the cell temperature rise is
higher compared with the water temperature.
The temperature rise shown in Figure 12 is calculated
using Eqn (4) for 2C and 3C discharge. A sample calcula-
tion for the rise in temperature of the cell (or water) when
the cell is discharged from 100% SOC to 80% SOC is
shown in Appendix A. Figure 12 also compares the experi-
mental rise in temperature with the calculated rise in temper-
ature using R(V  I) and R(60s) overpotential resistances.
We can now compare the overpotential and entopic heat
for 1C and 2C discharge by using Eqn (1). Figure 13
shows the total heat generated during 1C and 2C discharge,
along with the overpotential and entropic heat. The graph
clearly shows that the overpotential heat is much higher
than the entropic heat, especially between 100% and 20%
SOC. However, after 20% SOC, the entropic heat becomes
a higher percentage of the total heat. At 0% SOC (at the

Figure 12. Temperature change during calorimeter tests compared with calculated using two different overpotential resistances for
2C and 3C discharge.

1434 Int. J. Energy Res. 2014; 38:14241437 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Heat generation in high power prismatic Li-ion battery cell
Figure 13. Total heat during 2C and 1C discharge compared with overpotential and entropic heat.
Table V. Summary of measurements done in this work.
Parameter obtained
1 Uniformity of heat distribution in a battery cell
2 Overpotential resistance R(V  I)
3 Overpotential resistance R(VO  V)
4 Overpotential resistance R(60s)
5 Entropy coefcient (dVO/dT)
6 Specic heat capacity of the battery
7 Total heat generation of battery cell using calorimeter
SOCs, states of charge.
end of discharge), the entropic heat is almost equal to the
overpotential heat for 1C discharge, which implies that it
cannot be neglected. This effect is not seen in the
calorimeter results mainly because of high heat transfer
rate between the water surface and the cell and also
because of relatively small entropy effect between 20%
and 100% SOC levels.
4. CONCLUSIONS
A large capacity, commercially available Li-ion cell, is
used to quantify the heat generation in the cell. The total
heat generation is divided into two parts: overpotential heat
and entropic heat. Overpotential heat is calculated by
measuring four different resistances: resistance by V  I
characteristics during charge and discharge, resistance by
difference between open circuit voltage and cell voltage,
Int. J. Energy Res. 2014; 38:14241437 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Y. Abdul-Quadir et al.
Explanation
Measured the battery surface
temperature at 1C discharge.
Obtained the resistance value by
V  I characteristics at different C-rates.
Obtained the resistance value by measuring
the open circuit voltage at different SOCs.
Measured the resistance value by intermittent
discharge (with holding time of 10 min)
Obtained the value by measuring the open
circuit voltage at different temperatures.
Measured by tting the parameters in Eqn (5).
Measured by discharging the battery at
2C and 3C and obtaining the temperature
increase of the calorimeter.
resistance by intermittent discharge and by the AC
impedance measurement. The rst three resistances are
very close to each other, implying that any of the three
methods can be used to calculate the overpotential heat
generated in a battery cell. However, the resistance
measured by AC impedance method is much smaller
compared with other resistances.
Heat generation due to the entropy change is mea-
sured by measuring dVO/dT (entropy coefcient) at
different SOCs and temperatures. Although small in
magnitude, the entropy effect cannot be neglected in
total heat dissipation, which was shown in temperature
prole of the cell at 1C discharge. The entropy coef-
cient is also shown to change from exothermic to
endothermic, which is mainly due to ordering changes
at the anode. The results obtained here are mainly consis-
tent with the information available about small low
power Li-ion batteries.
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Y. Abdul-Quadir et al. Heat generation in high power prismatic Li-ion battery cell

Table V summarizes the measurements carried out in Calorimeter constant = 1005 J/K
this work.
b. Calculating temperature rise of the calorimeter system
during 2C discharge
NOMENCLATURE
A sample calculation for the rise in temperature of the
A = area (m2)
battery cell (or water) when the cell is discharged from
C = heat capacity (J/K)
100% SOC to 80% SOC is shown in Appendix A.
Cdl = double layer capacitance (F)
Figure 12 compares the experimental rise in temperature
cp = specic heat (J/kgK)
with the calculated rise in water temperature using R(V  I)
Eemf = cell potential (V)
and R(60s) overpotential resistance.
F = Faradays constant (9.648456 104C/mol)
G = Gibbs free energy (J) Specic heat capacity of the cell = 670 J/kgK
h = heat transfer coefcient (W/m2K) Mass of the cell = 0.99 kg
I = charge or discharge current (A) Volume of the water = 3.43 dm3
m = mass (kg) Heat capacity of water = 4180 J/kgK
n = number of moles of electrons exchanged in Density of water = 1000 kg/m3
the reaction
Heat capacity of calorimeter = 1000 J/K
q = total heat generated in battery cell (W)
Time to discharge from 100% SOC to 80% SOC at
QP = overpotential heat (W)
2C = approx. 180 s
QS = entropic heat (W)
Current = 80 A
Rct = charge transfer resistance ()
Qp = 80 80 0.0019 = 12.16 W (based on R(V  I)
R = overpotential resistance ()
resistance at 80% SOC)
R = ohmic resistance ()
Qs = [(80 300 (0.03)]/1000 = 0.7 W
S = entropy (J/K)
Total heat = Qp  Qs = 12.86 W
SOC = state of charge
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