Energy Conversion and Management 180 (2019) 724–732

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

An improved calorimetric method for characterizations of the specific heat T

and the heat generation rate in a prismatic lithium ion battery cell
⁎ ⁎
Lei Shenga, Lin Sua, , Hengyun Zhangb, , Yidong Fanga, Haifeng Xua, Wen Yec
a
School of Energy and Power Engineering, University of Shanghai for Science and Technology, Shanghai 200093, PR China
b
Automotive Engineering College, Shanghai University of Engineering Science, Shanghai 201620, PR China
c
Shanghai Technical Center, Shenzhen BAK Power Battery Co., Ltd, Shanghai 201800, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: The specific heat and the heat generation rate are the key thermal properties for lithium ion battery cells.
Lithium ion battery cells Nonetheless, there exists large scattering in data of thermal properties due to factors such as battery temperature
Specific heat nonuniformity during experimental measurement. In this work, a novel calorimetric method for measuring
Heat generation rate thermal properties of a lithium ion battery cell is proposed by introducing a temperature even out process to
Improved calorimetric method
minimize the effect of the temperature difference across the battery. Through this method, the specific heat and
Heat loss calibration
the heat generation rate can be characterized for the electrochemical batteries. Thermal parameters of a pris-
matic lithium iron phosphate battery cell are determined for the wide temperature range at varying operating
currents. It is found that the specific heat of the lithium ion battery cell has a linear relationship with the
operating temperature, whereas the heat generation rate has a quadratic relationship with the operating current.
The measured heat generation rate shows a good agreement with calculated results as per Bernardi's heat
generation model. This new method allows one to obtain thermal properties of lithium ion battery cells at a
lower cost and in a shorter time.

1. Introduction vacuum environment. This method, based on the Neumann boundary

With the advantages of the high power density, the long cycle life
and the convenient energy storage and conversion, lithium ion batteries
(LIBs) have been widely applied in consumer electronic systems and
passenger vehicles [1]. However, as the energy density increases, LIBs
generate more and more heat during operation and can result in the
thermal runaway if the heat is not dissipated in a timely manner [2].
The rise of the battery temperature depends highly on its specific heat
and heat generation rate [3]. Therefore, it is important to understand
and grasp these thermal properties of LIBs.
Specific heat is a significant thermal parameter of a LIB and in-
dicates the temperature rise rate of the LIB to contain heat, and for an
object is usually defined by the amount of heat absorbed or released
when 1 °C changed per unit mass [4]. Recently, the LIB's thermal
properties are becoming the research focus due to the increasing im-
portance of the thermal safety of the LIB. Many methods about the LIB's
specific heat have been developed currently. Drake et al. [5] applied
constant heat flux in the LIB's surface to obtain the specific heat in a
condition of the heat transfer, measures thermal properties of objects by
the quasi-steady state principle. Bazinsky and Wang [6] and Onda et al.
[7] put LIBs in a constant temperature environment and gave them a
certain amount of heat. They used calorimeter to measure the LIB's
specific heat and found that the LIBs' specific heat was almost not af-
fected with the state of charge (SOC), but affected obviously by the
operating temperature. Maleki et al. [8] obtained the LIB's specific heat
by Xenon Flash Technology (XFT) and the steady state principle. Their
technique was somewhat tedious and the test equipment was expensive.
Herzmann et al. [9] and Chen et al. [10] integrated a large amount of
data to obtain the specific heat and specific gravity of each material
constituting LIBs. Villano et al. [11] measured specific heat of each
component of a LIB by differential scanning calorimetry (DSC) and
calculated the specific heat for the LIB. The last two methods for the
LIB's specific heat required extensive time and efforts during the testing.
The LIB's heat generation rate is generally expressed as the heat
generation of per unit volume of a cell per unit of time [12]. Since the
LIB's temperature is affected by the specific heat and heat generation

⁎
Corresponding authors at: School of Energy and Power Engineering, University of Shanghai for Science and Technology, 516 Jungong Road, Yangpu District,
Shanghai 200093, PR China (L. Su). Automotive Engineering College, Shanghai University of Engineering Science, 333 Longteng Road, Songjiang District, Shanghai
201620, PR China (H. Zhang).
E-mail addresses: linsu@usst.edu.cn (L. Su), zhanghengyun@sues.edu.cn (H. Zhang).

https://doi.org/10.1016/j.enconman.2018.11.030
Received 22 August 2018; Received in revised form 11 November 2018; Accepted 13 November 2018
Available online 19 November 2018
0196-8904/ © 2018 Published by Elsevier Ltd.
L. Sheng et al. Energy Conversion and Management 180 (2019) 724–732

Nomenclature SOC state of charge (%)

P input power (W)
ρ battery density (kg·m−3) T battery cell temperature (°C)
c battery cell specific heat (J·kg−1 °C−1) Tloss temperature drop in battery due to the heat loss (°C)
m battery cell mass (kg) T'loss temperature of the heat loss calibration period from 0 to t
qb battery cell heat generation rate (W·m−3) (s)
qavg battery cell's average heat generation rate (W·m−3) Tc thermostatic chamber temperature (°C)
t time (s) T0 initial temperature (°C)
t' a moment of the heat loss calibration period from 0 to t (s) T1 battery temperature of the first heating period from 0 to t1
t1 first heating period for the battery cell (s) (°C)
t'1 a moment of the first heating period from 0 to t1 (s) T2 battery temperature of the second period from t1 to t2 (°C)
t2 time period for the battery cell cooling (s) ΔT1-loss temperature drop in battery caused by heat loss when it is
R internal resistance in battery cell (Ω) heated up (°C)
I battery cell operating current (A) ΔT2-loss temperature drop in battery caused by heat loss when it is
UOCV open circuit voltage in battery cell (V) cooled (°C)

rate, it is of great significance to precisely grasp LIB's heat generation derived based on the obtained specific heat and characterized through
characteristics for the design and development of electric vehicles' experimental measurement. The theoretical analysis and experimental
battery thermal management systems [13]. Hong et al. [14] and Ko- measurement are presented in detail in this paper. This proposed
bayashi et al. [15] measured cylindrical 18,650 cells’ heat generation method provides an easy-to-use approach for researchers to measure
rate by an accelerating rate calorimetry (ARC) and an isothermal heat the thermal properties such as the specific heat and the heat generation
conduction calorimetry (IHC) respectively under different operating rate of LIBs.
conditions. They found that the operating temperature and the oper-
ating current were the main influencing factors for the LIB's heat gen- 2. Experimental
eration. Chen et al. [16] designed a special setup for testing LIB's heat
generation rate. They considered the operating cell as a time-varying This study primarily focuses on investigating the specific heat and
heat generation object, which was wrapped by a high-density poly- heat generation rate in a lithium iron-phosphate (LiFePO4, LFP) battery
ethylene (HDPE) board, and its heat generation rate by the temperature cell as a function of its temperature and SOC. Hence, the commercial
variation of the HDPE board could be obtained from an abstract com- LFP cells serving as the specimens were procured from the manu-
putational model. facturer of Shanghai Aerospace Power Technology Co., Ltd. and all of
Drake et al. [17] calculated the heat generation rate of LIBs by these samples were produced from the same batch. This commercially
testing the internal/external temperatures and the heat flux of cell's available battery core consists of a graphite coated anode and the LFP
surface during an operating period and the experiment results were in cathode with the organic separator, which is encased in an aluminum-
good agreement with the theoretical calculation results [18]. Currently alloy 3003 container. The size of battery is 17 × 79 × 124 mm3.
widely applied heat generation rate calculation method for LIBs is the According to the product specifications, the nameplate capacity is 8Ah,
heat generation model proposed by Bernardi, which mainly includes the weight is 328 g, and the upper charge limit is 3.65 V whereas the
irreversible heat and reversible heat after simplification [19]. Zhang lower discharge limit is 2.0 V.
et al. [12] summarized the intermittent current method, voltage-current
characteristics method, and energy method for the measurement of the 2.1. Test setup
LIB's irreversible heat, and potentiometer method and calorimetric
method for the measurement of the LIB's reversible heat. In addition, Fig. 1 shows the schematic diagram of the test system. The system
the microscopic models of the heat generation rate of LIBs, such as the consists of the sample setup (No. 1), a thermostatic chamber (No. 2), DC
electro-thermal coupling model (ETCM), the electrochemical thermal power supply (No. 3), Agilent 34972A temperature data collection (No.
coupling model (ECTCM) are also reported [20]. These models are able 4), computer (No. 5), and battery cycler 60V100A (No. 6). Fig. 2(a)
to predict the heat generation at the electrode level but difficult to
forecast the heat generation at the cell level. For example, The ECTCM
generally assumes that LIB's current density is uniformly distributed,
which may result in acceptable accuracy for small-format cells but a
significant error for large-format cells [20].
In summary, the specific heat and heat generation rate of a LIB were
mainly obtained by dedicated equipment such as ARC at high cost, or
by the Bernardi's method which is time consuming and may under-
estimates the power consumption for large-format LIBs. In addition, the
conventional calorimetric methods generally ignore the temperature
non-uniformity of the tested cell [21], which might cause insufficient
accuracy in the thermal characterization of batteries.
In this paper, an improved calorimetric method for measuring LIB's
thermal properties is proposed. The battery temperature ramps up first
by subjected to a short heating process and then drops down after the
heating is stopped. To reduce the uncertainty in the average battery
temperature measurement, an extra period of time is introduced for the
battery temperature to even out. The specific heat can be obtained
based on the heating energy, and battery temperature rises with a ca-
libration of the heat loss. In addition, the LIB's heat generation rate was Fig. 1. Schematic diagram of test system.

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L. Sheng et al. Energy Conversion and Management 180 (2019) 724–732

Cell 300 + 45
-3
Aerogel 25
EPE 1

300
5

124
5 2

z z z
4 x 4 y
y X 17
79

Fig. 2. Test sample setup (Unit: mm) (a) Setup visualization; (b) Thermocouples layout.

shows the detail of the test sample setup for the LIB cell. The cell is first of time from 0 to t2 in Fig. 3(a), the governing equation as per energy
wrapped with 20 mm thick aerogel blanket, and then in a solid thermal conservation for the cell can be denoted as:
insulation box of the expandable polyethylene (EPE) material to avoid
P·T1 = cm (T2 − T0) + cmΔT1 − loss + cmΔT2 − loss (1)
the stripping of the aerogel. Fig. 2(b) shows arrangements of T-type
thermocouples (TC) in the LIB cell surface and the surface area covered where P is the input power (W), c is the specific heat in battery cell
by the flexible Kapton heater with 150 × 124 mm and thickness of (J·kg−1 °C−1), m is the battery cell mass (kg), T0 is the initial tem-
0.2 mm, which covered three sides of the cell surface, including one of perature (°C) of the battery cell, ΔT1−loss and ΔT2−loss are the overall
the lateral side and two larger surfaces. Five thermocouples were cell temperature drop due to the heat loss during the first and second
mounted to the battery for purpose of characterizing the battery cell's periods, respectively.
specific heat and heat generation rate. Among them, TC1 and TC2 were Therefore, the specific heat in cell can be denoted as:
located at one of the larger surface, TC4 and TC5 were located at the P·t1
lateral side, as indicated in Fig. 2(b). TC3 was placed on the cell's ne- c=
m (T2 − T0 + ΔT1 − loss + ΔT2 − loss) (2)
gative tab, which could better reflect the internal cell temperature due
to the excellent thermal conductivity of the cathode made of copper. The heat loss is related to the battery temperature to the ambient
temperature difference, which is obtained based on the temperature-
drop curve as shown in Fig. 3(b). Under the same temperature differ-
2.2. Theoretical fundamental ence, the heat loss rate is same, therefore, dT1−loss/dť1 = dT'loss/dť can
be obtained. The magnitude of temperature-drop ΔT1−loss caused by the
Consider the prismatic battery wrapped around with thermally heat loss during the first period from 0 to t1 can be denoted as:
adiabatic materials located in a thermostat environment. During the '
t1 dT1 − loss t1 dTloss
first period from 0 to t1, the battery cell temperature starts to ramp up ΔT1 − loss = ∫0 dt1′
dt = ∫0 dt ′
dt
(3)
when it is heated by the heater at its surface. Once the heater is power-
off at t1, the cell temperature drops down during the second period from where t1′ is the moment in the first heating period from 0 to t1 in
t1 to t2 due to the inevitable heat loss. Fig. 3(a) shows the battery Fig. 3(a), T'loss and t' are respectively the cell temperature and a moment
surface temperature curve during the heating and cooling processes. At of the heat loss calibration period from 0 to t in Fig. 3(b).
the end of heating, the cell temperature reaches its maximum Tmax. In Fig. 3(a), from the energy conservation law, the magnitude of
After the heating is stopped, the cell temperature T2 drops with time. temperature decrease is the temperature drop ΔT2−loss in the cell during
Furthermore, Fig. 3(b) shows the dropping of the cell temperature Tloss the second period from t1 to t2, which can be denoted as:
in the heat loss calibration process.
ΔT2 − loss = Tloss − T2 (4)
It is not appropriate to calculate the cell specific heat based on the
temperature difference T2 − T0 during the heating period since the cell Therefore, the cell specific heat can be calculated when substitute
temperature is not uniform under the condition of surface heating. ΔT1−loss and ΔT2−loss into Eq. (2).
Therefore, the temperature uniformization is required in the second To obtain the heat generation rate of the cell, one can assume the
period to even-out the temperature non-uniformity. During the period heat generation is uniform, and the heat generation can be given by the

Tloss
Temperature, ºC

(a) (b)
Tmax
ΔT2-loss
Temperature, ºC

T2
T'loss dT'loss /dĢ
T1

dT1-loss /dĢ1
T0 T0
0 Ģ1 t1 t2 0 Ģ t
Time, s Time, s

Fig. 3. Temperature variation of the cell (a) Battery temperature ramps up and ramps down during the heating and cooling periods respectively; (b) Without heating,
battery temperature ramps down since it is higher than the ambient temperature.

726
L. Sheng et al.
following equation:
dT dT
P = cm + cm loss
dt dT (5)
From Eq. (5), divided by the volume of the cell, the heat generation
rate per unit volume of the cell can be denoted as:
dT dT
db = cρ ⎛ + loss ⎞
⎝ dt dt ⎠ (6)
−3
where qb is the heat generation rate of the battery cell (W·m ), and ρ is
the mass density of the battery (kg·m−3), T is the temperature (°C) of
the battery cell, Tloss is the cell temperature (°C) due to the heat loss, dT/
dt and dTloss/dt are the temperature rise rate and temperature drop rate
of the cell due to the heat loss, respectively.
2.3. Experimental procedures
To verify the test method, an austenitic 304 stainless steel block
with the same size as the LIB cell was used. The steel block was covered
by the heater in the same way as that in the cell shown in Fig. 2(c), and
then was placed in a thermostatic chamber. A regulated heating power
was supplied with a stabilized voltage supply and the FLUKE multi-
purpose meter (with ± 0.09% accuracy) was connected in series to
measure the current accurately. As the chamber temperature varied
from −20 °C to 70 °C, the heater power increased by 2.5% which was
negligible for the end results. During the experiment, the actual output
power from the DC power supply was found to be less than 1.7% than
the preset power. In the data processing, the former power was used in
the calculation of the specific heat.
2.3.1. Calibration of the heat loss for the test setup
Even though an insulation material with an excellent insulation
property was employed to insulate the test sample cell as shown in
Fig. 2(a), there will always be a certain amount of the heat loss during
the test. To enhance the accuracy of the test, calibrations for the setup's
heat loss was carried out.
The calibration procedure for the heat loss for the test setup is de-
fined as following steps: (a) Prepared the sample setup as shown in
Fig. 2 and set the battery cell's SOC as 0.5, (b) placed the sample setup
into the thermostatic chamber as shown in Fig. 1 and adjusted the
chamber temperature to a test required value Tc, (c) allowed 15 min for
the thermostatic chamber and the cell to reach to an equilibrium tem-
perature Tc, turned on the power of the heater and started to record the
cell temperature thermal couples, (d) as the average cell temperature
increased to Tc + 45 °C, turned off the power of the heater, (e) as the
average cell temperature dropped below Tc + 5 °C, ended the test and
stopped the recording.
To calibrate the heat loss for the test setup, above test procedure
was repeated for three Tc conditions, namely, −26 °C, 9 °C and 54 °C.
After the test, the average temperature of the cell T was calculated from
TC1-TC5 for each Tc conditions. Fig. 4 shows the data after stopping
heating of the temperature difference (T − Tc) between the sample
overall cell temperature T and the chamber temperature Tc. Notice the
three lines are aligned in the time axis to have the time 0 for the point of
(T − Tc) of 40 °C for an easy comparison.
In Fig. 4, it is found that the difference among all three data lines is
less than 1.2 °C for these three Tc conditions and all three lines are with
the same trend; therefore, the chamber temperature has little effect on
the heat loss of the test setup. The average data for all three lines from
time 0 to 19500 s is best fitted by a polynomial curve. Fig. 5 shows the
curvilinear relationship between the cell temperature drop rate dTloss/dt
and the temperature difference (T − Tc), which the functional re-
lationship can be expressed by:
dTloss / dt = −1.27 × 10−4 (T − Tc ) + 2.18 × 10−4 (7)
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Energy Conversion and Management 180 (2019) 724–732
2.3.2. Measurement procedures for the specific heat of the lithium ion
battery cell
Testing process of the LIB's specific heat includes two periods.
During the first period from the time of 0 to t1, the cell is heated. The
heat source is turned off at time of t1 and the cell is allowed to cool
down slowly during the second period from the time of t1 to t2. In this
work, it was found that using the heating power of 24 W for a period of
200 s allowed the cell's temperature rise over 10 °C which would pro-
vide good data for the specific heat. With a test cell of SOC of 0.5 at the
chamber temperature of T0. The second period needed only 600 s.
Fig. 6 shows temperatures in various TC positions during battery
heating and temperature even-out processes at 9 °C oven temperature,
where the first period was 200 s, the power input was 24 W, and the
second period was 600 s. During the first period, the cell's temperature
rose sharply. The TC2 showed the highest temperature among TC1-TC5
since the TC2 was placed on the heater's surface. The cell's temperature
dropped down rapidly from 200 s to 300 s after heating source was
turned off since the cell surface heat was dissipated by the whole cell
volume. Notice that the cell's temperature gradually converged after
300 s and the temperature difference among TC1 to TC5 was lower than
0.6 °C.
The average battery temperature rise above the oven temperature
can be obtained in Fig. 6 for both the first period and the second period.
The temperature rise can be used to calculate the temperature drop for
each period, namely, ΔT1−loss and ΔT2−loss. Thus the nominator in the
right hand of Eq. (2) can be obtained so that the specific heat can be
determined. Furthermore, the calculation process for the cell specific
heat can be showed in Fig. 7.
2.3.3. Measurement procedures for the heat generation rate of the lithium
ion battery cell
Initial temperatures of the cell, the test setup and the thermostatic
chamber was set at a prescribed temperature Ti (chamber temperature
Tc = Ti). The cell's temperature changing with time was logged while it
was discharging in a given C-rate. The testing was stopped when the
cell's voltage dropped to 2.0 V. As per above, Fig. 8 shows temperature
ramp-up curve under the conditions of 10 °C and discharging rate of 1C.
In Fig. 8, the relationship between the average cell temperature and
time T = T(t) can be derived. By taking the derivative with respect to
time, the term dT/dt in Eq. (6) can be obtained. Similar approach can be
applied in Fig. 6 for the cell temperature change rate during the first
period as the cell is heated up to determine the cell temperature change
rate caused by the setup heat loss. Therefore, the term dTloss/dt in Eq.
(6) can be obtained. As a result, the cell temperature change rate with
respect to time become available. Then, the time can be divided into 10
equal parts from 0 to 3500 s corresponding to the SOC values of 1.0,
0.9, 0.8,…,0, and the cell's heat generation rate at each SOC can be
obtained.
40
T - Tc at Tc =54 ºC
T - Tc at Tc = 9 ºC
30
Temperature, ºC
T - Tc at Tc = -26 ºC
average of (T - Tc)
20
10
5 ºC
0
0 6500 13000 19500
Time, s
Fig. 4. Data of calibration for test setup heat loss.
L. Sheng et al. Energy Conversion and Management 180 (2019) 724–732

0 24
TC1 TC2
Temp. drop rate, ºC·s -1

-0.001

C
TC3 TC4
19 TC5 Tc

Temperature,
-0.002 Tavg

-0.003
14
dTloss/dt
-0.004 10 C
Linear fit (R2 = 0.998)

-0.005 9
5 12 19 26 33 40 0 700 1400 2100 2800 3500
T - Tc , ºC Time, s
Fig. 5. Relationship between temperature drop rate and temperature differ- Fig. 8. Temperature ramp-up curves.
ence.

1300
28 W/ calibration

Specific heat, J·kg-1 C-1

First
period Second period W/o calibration
23 1200
Temperature, ºC

18 TC1
TC3
TC5
13 Tc
9 ºC
8 0
0 200 400 600
Time, s
Fig. 6. Temperatures in various TC positions.
3. Results and discussions
In accordance with the experimental procedures as described in
Subsection 2.3 above, in this section, a study is carried out for the
curvilinear relationship between the cell's specific heat and operating
temperature, and the curvilinear relationship between the cell's heat
generation rate and operating temperature, SOC. Moreover, a suitable
stainless-steel block and the extensively used Bernardi's model are re-
spectively employed to verify the accuracy of the achieved specific heat
and heat generation rate of the cell.
3.1. Specific heat of the lithium ion battery cell
Based on Section 2.3, the cell's specific heat can be calculated when
the heat loss has been calibrated. Fig. 9 shows the calculation of the
cell's specific heat with and without heat loss calibration during the
second period of the time 200–800 s. The measured specific heat cor-
responded to an average cell of 15 °C during the second period of
400–800 s, as shown in Fig. 6.
At the beginning of the second period starting from t = 200 s, the
calculated specific heat with heat loss calibration increases with time.
The cell's specific heat reaches the constant level at t = 400 s and be-
yond deviations of the test results between 400 s and 800 s are almost
the same (lower than 1.5%). Compared with the t = 200 s at the end of
heating, the value of specific heat at the time t = 300 s has increased by
about 11.51% and at the time 400 s, about 13.16%. In Fig. 9, the
TC2
TC4
1100
Tavg
1000
200 400 600 800
800 Time, s
Fig. 9. Calculated cell specific heat.
specific heat without heat loss calibration keeps increasing with time,
which overestimated the specific heat significantly. Therefore, it is
crucial to calibrate the heat loss for the test setup appropriately, as has
demonstrated in Subsection 2.3.1.
To obtain the specific heat at a different cell temperature, the above
test process can be repeated by varying the oven temperature. Fig. 10
shows the specific heat of the cell under different cell temperature from
−20 to 60 °C, and the deviation of the specific heat at the time 800 s
relative to the time 400 s are also shown in this figure.
The data at t = 400 s are shown for all the cell operating tempera-
ture conditions due to the negligibly small deviation as shown for the
15 °C case. It is showed in Fig. 10 that from −20 °C to 60 °C, the cell's
specific heat increases by 17.2%, increasing almost linearly with cell
operating temperatures. Similar trends can be found in previous work
such as Bazinsky and Wang [6] and Onda et al. [7]. In Ref. [6], an
isothermal calorimeter was employed to measure the specific heat of a
pouch cell and the specific heat increased by 38% from −5°C to 55 °C.
In Ref. [7], a dual calorimeter was selected to measure the cell's specific
heat for a cylindrical battery cell, and the cell's specific heat increased
by 9% from 20 °C to 90 °C. However, it should be pointed out the ca-
libration of the heat loss was not well reported in their works [6,7]. The
specific heats of cylindrical 26,650 and 18,650 LiFePO4 cells were
measured under vacuum environment by Drake et al. [5], in which the
test results were 1605 J·kg−1 °C−1 and 1720 J·kg−1 °C−1 respectively.
These data were relatively high in literature, partially due to the lack of
heat loss calibration. Even though the cells' specific heat varies with
cells' constituent materials and different production processes, the heat

Fig. 7. Calculation process for the cell spe-

cific heat.

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L. Sheng et al. Energy Conversion and Management 180 (2019) 724–732

1300
Specific heat, J·Kg-1ºC-1
Specific heat
Linear fit
1175
c = 2.35T + 1108
R² = 0.9945
1050
-20 0 20 40
Battery cell temperature, ºC
Fig. 10. Cell's specific heat vs. operating temperatures.
loss calibration introduced in the present work provides an accurate
determination of the specific heat without resorting to expensive
equipment. Compared with the measurement method of battery cell's
specific heat by conventional calorimeter [6,7], this method seems
promisingly more accurate since the heat loss is carefully calibrated
during heating and even-out processes. Compared with the XFT and
DSC methods [8,11], this method is easy-to-use in a short timeframe
without resorting to expensive equipment. Additionally, the computa-
tional method by dissecting the battery to get the detailed dimensions
and specific heat of each constituents is a tedious procedure to de-
termine the specific heat. In comparison, the present method is able to
obtain the specific heat without damaging the battery with a fast yet
inexpensive manner, which is easy to implement in practice.
during either heating up and or natural cooling processes so that the
specific heat and heat generation could be obtained accurately. In ad-
dition, this method can save the test time significantly while comparing
with the simplified Bernardi's heat generation model [19], in which the
HPPC (Hybrid Pulse Power Characteristic) method [22] is usually em-
ployed to determine the cell's internal resistance. It would take over
12 h to conduct a test every 10% SOC from 100% to zero SOC under a
prescribed temperature condition. In addition, the determination of the
cell's entropy coefficient also takes a long time [24]. In the present
method, it took no more than 1 h to determine the cell's heat generation
rate under a prescribed test condition, thus a lot of time is saved.
60
3.3. Verification of results
In this work, the accuracy of the proposed method for determining
the cell specific heat and heat generation rate were verified respectively
through an austenitic 304 stainless steel block and a broadly used
Bernardi's battery heat generation model.
3.3.1. Verification of the lithium ion battery cell's specific heat
The austenitic 304 stainless steel block has a similar thermal dif-
fusivity with the sample cell. An object with the same size as the cell
was used for the test feasibility of the test method in this paper.
Following the test method of the cell's specific heat in the Section
2.3.2, the steel block is tested to be 493.31 J·kg−1 °C−1 at the object
temperature of 31 °C. As per Ref. [4], the retrieved real specific heat of
the steel block is 479.23 J·kg−1 °C−1 at 31 °C. The test error is only
2.9%. It shows that this method is effective for the LIB's specific heat.

3.3.2. Comparison of tested results of the lithium ion battery cell's heat
3.2. Heat generation rate of the lithium ion battery cell generation rate
The simplified Bernardi heat generation model [12] is employed to
Based on the described methods in Section 2.3.3, the cell's heat calculate the cell's average heat generation rate in this paper, and the
generation rate can be measured under different discharge rates and experimental procedures and calculation methods are shown in Ap-
temperatures. The heat generation rate at 1C rate for discharging under pendix A. Fig. 12 shows a comparison between tested results by the
the chamber temperature of −20, −10, 0, 20, and 30 °C is shown in proposed method and Bernardi's model.
Fig. 11(a), and that at high C-rates for discharging under ambient In Fig. 12, tested results of the cell heat generation rate by the
temperature of 30 °C is shown in Fig. 11(b). current method show a good agreement with the results tested by the
Notice, in the test of the battery cell's heat generation, the cell was traditional theoretical model. It is found that the cell's heat generation
first charged to the upper-limited voltage of 3.65 V at 1C charge rate
under the normal temperature 25 °C. After rest for over an hour, the 56 10
battery was then discharged to the cut-off voltage of 2.0 V under the (a)
30 ºC, 1C 20 ºC, 1C
8
Heat rate, KW·m-³

prescribed experimental conditions. 42 10 ºC, 1C 0 ºC, 1C

In Fig. 11, the cell's heat generation rates were found to turn upward -10 ºC, 1C -20 ºC, 1C

Power, W
obviously during the end of discharging period (at low SOC) under all 6
28
the operating conditions. This phenomenon was mainly caused by the
4
increased cell's internal resistance at the end of discharging [13]. In
Fig. 11(a), the cell's heat generation rate increased with the decreasing 14
2
cell's temperature, which was caused by the cell's larger internal re-
sistance as the ambient temperature was lower [12]. In Fig. 11(b), the 0 0
cell's heat generation rate increased as the operating current increased 0.0 0.2 0.4 0.6 0.8 1.0
under the same chamber temperature of 30 °C. Chen [16] got a similar SOC
trend and the cell's heat generation rate is proportional to the operating
230 40
current. It is found that the past test approaches of cell's heat generation (b) 30 ºC, 3C
rate generally used expensive calorimeters and complicated test setups 184 30 ºC, 5C 32
Heat rate, KW·m-³

[14–17]. Some used intermittent current method, voltage-current 30 ºC, 7C

Power, W

characteristics method and energy method to test cell's irreversible 138 30 ºC, 9C 24
heat, in addition, the cell's reversible heat was usually measured by the
potentiometer method, calorimetric method and so on [12]. The above 92 16
problems can be avoided by the proposed method in this work. The test
setup and theoretical calculations of this method are easy to under- 46 8

stand, which can be effectively applied to harsh conditions such as low-

0 0
temperature environment and high C-rate operation for cells. Compared 0.0 0.2 0.4 0.6 0.8 1.0
with the conventional calorimetric method for the battery cell's heat SOC
generation rate by ARC equipment [15] and complicated setup [16,17],
this method presents an instantaneous calibration of the heat loss Fig. 11. Heat generation rate.

729
L. Sheng et al. Energy Conversion and Management 180 (2019) 724–732

28 5 4. Experimental uncertainty analysis

(a) Current method
Bernardi model 4
Heat rate, KW·m-³

21 In this work, T-type thermocouples give rise to approximately 2%

Quatradic fit (Current.)
uncertainty due to they are accurate to 0.2 °C. In addition, experimental

Power, W
Quatradic fit (Bernardi.) 3
equipment DC power supply, Agilent 34972A, battery cycler, and
14
2
FLUKE multi-purpose meter will give rise to approximately 1%, 0.3%,
0.1%, and 0.18% uncertainty respectively. From Section 2.3, it was
7 observed that output power of the flexible heater was affected by
1
temperature by less than 2.5% as the chamber temperature varied from
0 0 −20 °C to 70 °C. As a result, it introduced additional uncertainty of
-20 -10 0 10 20 30 around 0.4% when the cell's specific heat c was tested under chamber
Temperature, ºC temperature of 9 °C.
140 25 According to the proposed uncertainty analysis from Moffat [23],
(b) the final result's uncertainty propagation is determined by the root
112 Current method 20 mean square of independent variables. For the specific heat and heat
Heat rate, KW·m-³

Bernardi model generation rate of the battery cell, the uncertainty can be estimated by
Quatradic fit (Current.)

Power, W
84 Quatradic fit (Bernardi.) 15 the following equation.
2 2 2
56 10 Δc ΔP 2 Δm 2 ⎛ ΔT2 ⎞ ΔT ΔT2 − loss ⎞
= ⎛ ⎞ +⎛ ⎞ + + ⎛ 1 − loss ⎞ + ⎛
⎜ ⎟ ⎜ ⎟ ⎜ ⎟

c ⎝ P ⎠ ⎝ m ⎠ ⎝ T2 ⎠ ⎝ T1 − loss ⎠ ⎝ max − T2 ⎠
T (8)
28 5
2 2
Δqb Δc 2 Δρ ΔT 2 ⎛ ΔTloss ⎞
0 0 = ⎛ ⎞ + ⎜⎛ ⎟⎞ + ⎛ ⎞ + ⎜ ⎟

1 3 5 7
Operating current, C
Fig. 12. Comparison of the average heat generation rate (a) 1C discharging rate
with various cell temperatures; (b) High C-rate for discharging at 30 °C.
rate has a quadratic nonlinear relationship with operating temperature
and operating current respectively. In comparison with tested results of
the cell heat generation rate by traditional theoretical model, deviations
are −12.4% and 14.3% at 10 °C and 30 °C conditions for 1C discharging
rate respectively; however, deviations are less than 10% under other
operating temperature conditions. This shows that the current method
for the cell's heat generation rate is effective. Other deviations may still
exist, such as that of errors in the acquisition of data by thermocouples
(TCs), the heat loss produced by TC wires and battery tab connectors,
the accuracy and human factors of test equipment, and so on.
9 qb ⎝ c ⎠ ⎝ ρ ⎠ ⎝ T ⎠ ⎝ T−loss ⎠ (9)
The uncertainty of the specific heat c and heat generation rate qb of
the cell is approximately 3.64% and 4.62% under chamber temperature
of 9 °C and 10 °C respectively from above analysis. For other conditions,
the measurement uncertainty of the cell's specific heat and heat gen-
eration rate is less than 4.0% and 5.0% respectively.
5. Conclusions
An improved calorimetric method for measuring the specific heat
and heat generation rate of LIBs is developed in this work. Under a
nearly adiabatic environment, the battery was heated up and then
cooled naturally to obtain the uniformed temperature rise. The cell
specific heat is determined via the energy conservation law with the
instantaneous heat loss compensation. For determining the battery cell's

110
(a) -20 ºC -10 ºC
Internal resistance, mȍ

0 ºC 10 ºC
88
20 ºC 30 ºC
40 ºC
66

44

22

0
0.0 0.2 0.4 0.6 0.8 1.0
SOC
18
(b)
Internal resistance, mȍ

3C 5C
14
7C 9C

10

2
0.0 0.2 0.4 0.6 0.8 1.0
SOC
Fig. A1. Cell's internal resistance. (a) 1C discharging rate with various temperatures; (b) High discharging C-rate at 30 °C.

730
L. Sheng et al. Energy Conversion and Management 180 (2019) 724–732

0.3

Entropy coefficient, mV·ºC-1

0.1
40 ºC ~ 30 ºC
-0.1 30 ºC ~ 20 ºC
20 ºC ~ 10 ºC
10 ºC ~ 0 ºC
-0.3 0 ºC ~ -10 ºC
-10 ºC ~ -20 ºC
avg(40 ºC ~ -20 ºC)
-0.5
0.0 0.2 0.4 0.6 0.8 1.0
SOC

Fig. A2. Entropy coefficient.

heat generation rate, the cell's temperature rise rate was measured
during the operating period, thus the heat generation rate was char-
acterized via the obtained specific heat. The present method was de-
monstrated for the characterization of the thermal properties of the
prismatic LiFePO4 cell. This method is easy to implement, and provide a
new clue in characterizing the battery thermal properties within a short
time without resorting to expensive equipment such as DSC and ARC.
The conclusions can be summarized as follows:
(1) The theoretical analysis of the present method is presented for both
heating up and temperature even-out processes, and the accurate
representation of the uniformed battery temperature is obtained
with the help of heat loss compensation.
(2) The LIB's specific heat ranges from 1081 J·kg−1 °C−1 to
1267 J·kg−1 °C−1 for the temperature ranges from −20 °C to 60 °C,
increasing almost linearly with the increase of operating tempera-
ture.
(3) The LIB's heat generation rate increases with the increase of oper-
ating current and the decrease of operating temperature, and it
appears a quadratic nonlinear relationship with the operating
temperature and the operating current respectively.
(4) Tested results of the LIB's heat generation rate by the proposed
method show a good agreement with calculated results by the
commonly used Bernardi's model for the heat generation.
Nonetheless, the test time can be greatly reduced in comparison
with the Bernardi's heat generation method.
Acknowledgements
This work was supported by the Shanghai municipal key discipline
(No. S30503), NSFC (51876113) and STCSM (14520501100) projects.
Helpful discussions with Ms. Huan Zhang, and other junior classmates
are grateful.

Appendix A. . Calculation of the lithium ion battery cell's heat generation rate by Bernardi's heat generation model

The tested results of LIB's heat generation rate are displayed in this appendix as per Bernaidi's heat generation model. The simplified Bernardi
heat generation model [12] is
1 ⎛ 2 dU
qb = I R − IT OCV ⎞
Vb ⎝ dT ⎠ (A.1)
−3 3
where qb is heat generation rate (W·m ), Vb, R and I are the sample cell's volume (m ), internal resistance (Ω), and operating current (A) re-
spectively. T and UOCV are the cell's operating temperature (K) and open circuit voltage (V). dUOCV/dT is entropy coefficient (V·K−1).
From Eq. (A.1), the cell's internal resistance and the entropy coefficient were measured by the intermittent current method and potentiometric
method respectively. Results are showed in Figs. A.1 and A.2.
In Fig. A.1, the cell's internal resistance increases as SOC and operating temperature decrease, and decreases as operating current increases. In
Fig. A.2, the cell's entropy coefficient is almost independent of the operating temperature and only relevant to the SOC. dUOCV/dT approaches to 0
when cell's SOC is 0.4 and dUOCV/dT is greater than 0 when SOC is between 1.0 and 0.4, and the entropy heats up as endothermic in this stage.
dUOCV/dT is less than 0 when SOC is between 0.4 and 0, and the entropy heats up as exothermic in this stage. References [12,24] showed a similar
trend.
From Figs. A.1, A.2 and Eq. (A.1), the functional equation between the cell's heat generation rate and SOC can be obtained, and its average heat
generation rate can be calculated by Eq. (A.2), which calculates the definite integral in SOC from 0 to 1.0.

qavg = ∫SOC qb (SOC ) dSOC (A.2)

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