energies

Article
An Experimental Analysis of Entropic Coefficient of a
Lithium Titanate Oxide Battery
Seyed Saeed Madani * , Erik Schaltz and Søren Knudsen Kær
Department of Energy Technology, Aalborg University, DK-9220 Aalborg, Denmark
* Correspondence: ssm@et.aau.dk




Received: 21 June 2019; Accepted: 11 July 2019; Published: 12 July 2019


Abstract: In order to understand the thermal behaviour of a lithium-ion battery, the heat generation
within the cell should be determined. The entropic heat coefficient is necessary to determine for the
heat generation calculation. The entropic heat coefficient is one of the most important factors, which
affects the magnitude of the reversible heat. The purpose of this research is to analyze and investigate
the effect of different parameters on the entropic coefficient of lithium titanate oxide batteries. In this
research, a lithium ion pouch cell was examined in both charging and discharging situations. The
state of charge levels range was considered from 10% to 90%, and vice versa, in 10% increments. The
temperature levels vary from 5 ◦ C to 55 ◦ C and the voltage levels vary from 1.5 V to 2.8 V. The effect
of different parameters such as initial temperature, state of charge, thermal cycle, time duration for
thermal cycles, and procedure prior to the thermal cycle on the entropic coefficient of lithium titanate
oxide batteries were investigated. It was concluded that there is a strong influence of the battery cell
state of charge on the entropic heat coefficient compared with other parameters.

Keywords: entropic heat coefficient; lithium titanate oxide batteries

1. Introduction
A battery is an energy storage device. Energy-storing electrochemical batteries are the most
important components for mobile and stationary applications. The most prevalent battery on the
market for automotive usages is the lithium ion battery. A conventional lithium ion battery cell
comprises of an electrolyte, a separator, and a pair of electrodes with current collectors.
Lithium-ion batteries are extensively used for various applications such as laptops, cameras,
mobile phones, automotive, and telecommunication. Low self-discharge rate, long cycle life, high
open circuit voltage, high specific energy, and no memory effect are some of the advantages of
lithium-ion batteries.
Owing to several sustainability concerns such as exhausting greenhouse gases and fossil fuels,
there has been raised attentiveness to hybrid electrical vehicles (HEV) and electrical vehicles (EV).
Currently, batteries are considered to be the most favourable energy storage system (ESS). Among these,
lithium-based batteries have demonstrated high specific power. Consequently, they are considered as
main energy storage for the HEV and EVs [1].
Lithium-ion batteries have been extensively employed in many electric appliances, but derisive
accidents have happened occasionally. Therefore, it is necessary to understand their heat generation
and thermal behaviour. The computation of the heat generation from experimental measurements
of the entropic heat coefficient (EHC) and internal resistance can be applied to the thermal models.
Consequently, accurate estimation of EHC will contribute to determining a more precise thermal model,
which improves the thermal management systems’ (TMS) design process [2].
The potentiometric method is one of the main techniques, which is employed to determine the
reversible heat, which is generated in a cell. The changes in open circuit voltage (OCV) of a cell divided

Energies 2019, 12, 2685; doi:10.3390/en12142685 www.mdpi.com/journal/energies

Energies 2019, 12, 2685 2 of 10

into the change in its temperature could be related to the entropy change. In this method, by changing
the temperature of the environmental chamber while the SOC is constant in each step, the reversible
heat can be estimated. This procedure can be done in an opposite approach by retaining the chamber
temperature constant while altering the SOC level of the cell [3].
Temperature and SOC have an intense influence on entropic heat irrespective of the format or
specific chemistry of the lithium-ion cell. Unfortunately, cell producers hardly ever provide any details
on the amount of this influence on battery behaviour.
The entropic heat coefficient of a lithium-ion battery after and before each cycle was determined
by employing the electrochemical thermodynamics measurements tool [4]. Entropic heat coefficient
was attributed to the particular electrodes for the battery cell. Lithium intercalation number in
positive and negative electrode was compared and determined for the battery after and before each
cycle, correspondingly. Outcomes demonstrated that the tendency of entropic heat coefficient with
Li-intercalated state after and before each cycle is fundamentally stable, except for the maximum and
initial state [4].
Potentiometric measurements of the enthalpy of reaction and entropy as a function of state of
charge for different lithium-ion batteries were investigated [5]. Calorimetric measurements were
compared to potentiometric measurements of entropy. It was concluded that the potentiometric
procedure is most precise for thermally thin cells, whereas calorimetric procedures need big cells to
modify the signal-to-noise ratio [5].
A lumped-parameter thermal model for a cylindrical lithium-ion battery was designed [6]. Heat
capacity and heat transfer coefficients were determined from simultaneous measurements of the
internal temperature and the surface temperature of the battery cell. Heat transfer coefficients outside
and inside the battery cell were determined from thermal steady state temperature measurements,
while the heat capacity was determined from the transient part. The precision of the model was
validated through estimation of internal temperature from surface temperature measurements [6].
A series of experiments were accomplished on a lithium-ion battery under various conditions and
the parameters for reaction heat and Joule heat were analyzed and determined [7]. In addition, the
influence of current, aging, temperature, and state of charge was considered. The accuracy of heat
generation rate was validated using a lumped battery heat transfer model [7].
Heat loss measurement of lithium titanate oxide batteries under fast charging conditions was
investigated by using isothermal calorimeter [8]. Thermal and electrochemical behaviour of lithium
-ion cells were analysed to achieve a better comprehension of the thermal behaviour of lithium-ion
cells [9]. A two dimensional thermal-electrochemical modeling method was used, and the electrical
and thermal energy were estimated by simulations [9].
Temperature increase analysis and optimal heat transfer coefficient were determined for a
polymer lithium-ion battery under bus-driving cycle’s condition [10]. This investigation studied
the heat problems, which arise during the working of power batteries, especially high temperature
environments. Moreover, a lumped parameter thermal model was constructed to investigate the
thermal behaviour of the battery system. The outcomes demonstrated that the heat transfer coefficient
is the third power subordinate of the ambient temperature [10].
A battery thermal management system was investigated based on a thermoelectric effect [11].
In addition, an uncomplicated heat generation model for a cooling model and single battery
cell were developed. It was concluded that the thermoelectric cooling combined with liquid cooling
structure demonstrated better performance [11].
Several publications have appeared in recent years documenting the amount of entropic heat
coefficient to analyze and determine thermal behavior and thermal modeling of batteries. A summary
of these investigations was described [12,13]. However, most of the previous studies did not take
into account different influential parameters on entropic heat coefficient such as state of charge (SOC),
charge or discharge process before the thermal cycle, time duration, and thermal cycle. The electrical
modeling of this battery was determined [14]. In addition, different thermal behavior and modeling
Energies 2019, 12, 2685 3 of 10

Energies 2018, 11, x FOR PEER REVIEW 3 of 10

investigations were accomplished for this battery [15–19]. To analyze the thermal behavior of the
battery cell
battery in different
cell in different way,
way, aa comprehensive
comprehensive investigation
investigation was
was accomplished
accomplished on
on the
the entropic
entropic heat
heat
coefficient of
coefficient of the
the battery.
battery.

2. Open Circuit Potential Experiment

With the intention of determining the heat generation within the battery cell, the entropic heat
coefficient couldbe
coefficient could bespecified.
specified.There
Therearearedifferent
different methods
methods to estimate
to estimate the the entropic
entropic heatheat coefficient.
coefficient. The
The electrochemical
electrochemical thermodynamics
thermodynamics measurement
measurement tool istool
one is
of one of the methods,
the methods, which
which was was
used used to
to analyze
analyze
the the capacity
capacity fade of fade of a lithium-ion
a lithium-ion batterybattery [4]. Potentiometry
[4]. Potentiometry is the ismost
the most accepted
accepted procedure
procedure [20].
[20].
In thisIninvestigation,
this investigation, open circuit
open circuit potential
potential (OCP), (OCP),
which haswhich
the has the greatest
greatest influenceinfluence on the
on the entropic
entropic
heat heat coefficient,
coefficient, was determined
was determined as a of
as a function function
time and of time and theheat
the entropic entropic heat coefficient
coefficient was
was analyzed
analyzed using open circuit potential experiments. Entropic heat coefficient
using open circuit potential experiments. Entropic heat coefficient can be calculated from thecan be calculated from
the following
following equation:
equation:
dUOCV,avg
EHC = dUOCV ,avg , (1)
EHC = dT , (1)
dT
where
where
EHC: entropic heat coefficient
EHC: entropic heat coefficient
T: absolute temperature
T: absolute temperature
UOCV : open circuit potential
UOCV: open circuit potential
It is clear from the above-mentioned equation that voltage has a great influence on entropic heat
coefficient.
coefficient. Therefore,
Therefore,totoanalyze
analyze thethe
entropic heat heat
entropic coefficient, it is important
coefficient, to investigate
it is important the variation
to investigate the
of open circuit
variation potential.
of open circuit With the intention
potential. With theofintention
approximation, the entropicthe
of approximation, heat coefficient
entropic heata coefficient
procedure
was used. Awas
a procedure least-squares fitting in Matlab
used. A least-squares fitting was employed.
in Matlab The gradient
was employed. of the generated
The gradient surface
of the generated
demonstrates the entropic
surface demonstrates theheat coefficient
entropic heatatcoefficient
a designated at state of charge. Following
a designated designation
state of charge. of the
Following
surface fitting for every state of charge, the entropic heat coefficient was conveniently
designation of the surface fitting for every state of charge, the entropic heat coefficient was quantified by the
gradient of the
conveniently surface. by the gradient of the surface.
quantified

3. The Investigated
3. The Investigated Lithium-Ion
Lithium-Ion Battery
Battery
A 13 Ah
A 13 Ah lithium
lithiumtitanate
titanateoxide
oxidebattery
batterycell
cellwas
wasusedusedinin this
this investigation.
investigation. Li (Ni
Li (Ni xMn x yMn Co2zwas
Coyz)O )O2
was
usedused as cathode
as cathode ofbattery
of the the battery cell. Lithium
cell. Lithium titanate
titanate oxideoxide nanocrystals
nanocrystals were were
used usedon theonanode
the anode
side,
side, which is referred as Li
which is referred as Li4Ti5O124. The Ti O lithium titanate oxide-based battery has a 13 Ah nominal nominal
5 12 . The lithium titanate oxide-based battery has a 13 Ah capacity
capacity
and 2.26and 2.26 V nominal
V nominal voltage. voltage.
Maximum Maximum
chargingcharging and discharging
and discharging voltage
voltage are are2.82.8
V Vand and1.5
1.5V,V,
respectively.
respectively. Maximum
Maximumcharge chargeand anddischarge
discharge current
current areare
130130
A. Calendar life of
A. Calendar theofbattery
life is 25 years.
the battery is 25
There is a limitation for storage and operating temperature, which is between −40 ◦ C to +55 ◦ C. These
years. There is a limitation for storage and operating temperature, which is between −40 °C to +55 °C.
limits
These are based
limits are on manufacturer-imposed
based on manufacturer-imposed restrictions. The lithium-ion
restrictions. battery battery
The lithium-ion cell, whichcell,was used
which in
was
this research, is illustrated in Figure 1.
used in this research, is illustrated in Figure 1.

Figure 1. The lithium-ion battery cell.

Energies 2018, 11, x FOR PEER REVIEW 4 of 10

4. Experimental
Energies 2019, 12,Setup
2685 and Procedure 4 of 10

The Maccor automated test system was used for cycling the battery. The studied battery cell was
4. on
wired Experimental Setup
a test fixture andthen
and Procedure
was located inside the temperature chamber of the Maccor. The
experimental setup, which
The Maccor automated was test
used in thiswas
system experiment, is shown
used for cycling in Figure
the battery. The2. studied battery cell
Because
was wiredofonsafety issues and
a test fixture andthen
in order to provide
was located easytemperature
inside the connections for the
chamber of voltage
the Maccor.andThepower
cables, the lithium
experimental titanate
setup, which oxide battery
was used wasexperiment,
in this cycled in the battery
is shown laboratory
in Figure 2. by placing the battery
cell on a Because
fixture. of safety
This issueswill
fixture and prevent
in order tovariations
provide easy in connections
the batteryfor thevolume
cell voltage and
as apower cables, of
consequence
the lithium titanate oxide battery
working with high temperatures and high C-rates. was cycled in the battery laboratory by placing the battery cell on a
fixture.
PreliminaryThis fixture will preventwhich
measurements, variations in theof
consist battery cell volume as
a precondition a consequence
experiment andof aworking
relaxation
with high temperatures and high C-rates.
experiment, were applied to the battery cell. The intention of fulfilling a precondition experiment was
Preliminary measurements, which consist of a precondition experiment and a relaxation
to take out any achievable passivisation to which the battery cell was exposed to, among the
experiment, were applied to the battery cell. The intention of fulfilling a precondition experiment was
preliminary
to take outexperiments
any achievableand the manufacturing
passivisation time.cell
to which the battery Furthermore,
was exposed to, another
among theobjective of this
preliminary
experiment
experimentswas to andscrutinize if the battery
the manufacturing time.voltage, capacity,
Furthermore, andobjective
another temperatureof thisare stable. was to
experiment
After a short rest period, the battery was charged with
scrutinize if the battery voltage, capacity, and temperature are stable. 3.25 A current rate with voltage limitation
equal to 2.8 V and
After a shortend type
rest condition
period, for the
the battery was current, which
charged with 3.25was equal rate
A current to 0.52
withA.voltage
After limitation
a 15-min rest
period,
equalthetobattery
2.8 V and cellend
was discharged
type condition for withtheacurrent,
currentwhich
rate equal 3.25 to
was equal A0.52
andA. with
Aftervoltage
a 15-minlimitation
rest
less than 1.5 V. This cycle was applied to the battery in order to determine the real capacityless
period, the battery cell was discharged with a current rate equal 3.25 A and with voltage limitation of the
thanThis
battery. 1.5 V. This cycle
capacity waswas applied
used to the battery inof
for determination order to determine
the current pulses’the step
real capacity of the battery.
time duration. Then, the
Thiscell
battery capacity was used
was fully chargedfor determination
with voltageoflimitation
the currentequal
pulses’ tostep
2.8 time
V and duration.
end type Then, the battery
condition for the
cell was fully charged with voltage limitation equal to 2.8 V and end type condition for the current,
current, which was equal to 0.52 A. After 15-min rest period, discharge current pulses with ten
which was equal to 0.52 A. After 15-min rest period, discharge current pulses with ten percent state of
percent state of charge time duration were applied to the battery. For instance, for the first cycle, the
charge time duration were applied to the battery. For instance, for the first cycle, the cell’s state of
cell’scharge
state of charge was decreased by means of a discharging procedure from 100% to 90%, and then
was decreased by means of a discharging procedure from 100% to 90%, and then the thermal
the thermal
process wasprocess was accomplished.
accomplished. The mentioned The thermal
mentioned thermal
process process
is described in is
thedescribed
following in the following
sections and
sections and determines
determines the entropic theheat
entropic heatamount
coefficient coefficient amount
for this for this last-mentioned
last-mentioned state of charge. Thisstateprocess
of charge.
This was
process
redonewas redone
until until cell
the battery the was
battery cell was
completely completely
discharged discharged
for state of charges forofstate
80%, of charges
70%, of 80%,
60%, 50%,
70%,40%,
60%,30%,50%,20%,40%, and30%,
10%.20%, and 10%.

(a) (b)
Figure 2. (a)
Figure Experimental
2. (a) Experimentalsetup;
setup; (b) batteryinside
(b) battery insidechamber.
chamber.

5. Results and Discussion

In order to determine the heat generation, the relationship between SOC and OCV is needed. To
analyze the entropic coefficient of the lithium titanate oxide battery, five different cases were
considered for the experiments, which are described in the following parts. The nominal capacity and
specific energy of the cell are 13.4 Ah and 74 Wh/kg, respectively.
Energies 2019, 12, 2685 5 of 10

5. Results and Discussion

In order to determine the heat generation, the relationship between SOC and OCV is needed. To
analyze the entropic coefficient of the lithium titanate oxide battery, five different cases were considered
for the experiments, which are described in the following parts. The nominal capacity and specific
energy of the cell are 13.4 Ah and 74 Wh/kg, respectively.
For determining the entropy of reaction by using the potentiometry procedure, the authors in [5]
demonstrated that it is more advantageous to adjust the battery cell temperature for a specific state of
charge with the purpose of decreasing the fault from self-discharge.
Thermal modeling of the lithium titanate oxide battery during discharge was investigated [21]. A
detailed determination of entropic heat coefficient of the lithium titanate oxide battery was described.
It was seen that entropic heat coefficient could play an important role in determination of a precise
thermal modeling [21].

5.1. Case A
In order to determine the effect of thermal cycle duration on the entropic heat coefficient of the
lithium titanate oxide battery, an experiment was accomplished with equal durations for each thermal
cycle. In each experiment, the 13 Ah lithium-ion battery cell was charged or discharged to a specific
state of charge. For a rest period, it was permitted to relax. After that, a thermal cycle was applied to
the battery. The thermal process consist of four hours at 26 ◦ C, four hours at 4 ◦ C, four hours at 14 ◦ C,
four hours at 41 ◦ C, four hours at 55 ◦ C, and four hours at 23 ◦ C. This method was repeated for various
amounts of state of charge.

5.2. Case B
In order to determine both the effect of thermal cycle and the time duration on the entropic heat
coefficient of the lithium titanate oxide battery, case B experiment was repeated by implementing a
distinctive thermal cycle (three hours at 27 ◦ C, three hours at 15 ◦ C, three hours at 5 ◦ C, three hours at
20 ◦ C, three hours at 40 ◦ C, and three hours at 15 ◦ C). To assure the results, another distinctive thermal
cycle was considered for the lithium titanate oxide battery.

5.3. Case C
In case C experiment, the 13 Ah lithium-ion battery cell was discharged or charged to a specific
state of charge. A relaxation process was applied to the battery. The relaxation period was accompanied
by a thermal cycle. The thermal process consist of three hours at 26 ◦ C, three hours at 4 ◦ C, three hours
at 14 ◦ C, three hours at 41 ◦ C, three hours at 55 ◦ C, and three hours at 23 ◦ C. This method was repeated
for various amounts of state of charge. The temperature scope in the thermal procedure was selected
according to the temperature range in which the battery cell works safely, as attested by battery cell
specification sheets. In this investigation, ten percent state of charge was considered for the current
pulse step time duration.

5.4. Case D
In case D experiment, the thermal procedure consists of two hours at 5 ◦ C, two hours at 24 ◦ C, two
hours at 10 ◦ C, two hours at 5 ◦ C, two hours at 15 ◦ C, and two hours at 25 ◦ C. A small discrepancy was
seen in the results with different thermal cycles (cases A, B, C, and D). Thus, the complete independency
of the outcomes with the thermal cycle was not confirmed. Such behavior was expected. Thermal
profiles, which were applied to the battery, are shown in Table 1. Figure 3 shows the voltage variations
during different SOC levels and experiments for the lithium titanate oxide battery.
Energies 2019, 12, 2685 6 of 10
Energies 2018, 11, x FOR PEER REVIEW 6 of 10

Case A
2.48 Case B 2.39
Case C
Case D

2.478 2.388

2.386
2.476 Case A
Case B
2.384 Case C
2.474 Case D
SOC:90 %
SOC:80 %
2.382
500 1000 1500 2000 2500 3000 500 1000 1500 2000 2500 3000
Time (s) Time (s)

2.265
2.318
2.264

2.263
2.316
2.262

Case A 2.261
2.314 Case B Case A
Case C 2.26 Case B
Case D Case C
SOC:70 % 2.259 SOC:60 % Case D
2.312
2.258
500 1000 1500 2000 2500 3000 500 1000 1500 2000 2500 3000
Time (s) Time (s)

2.2
2.228
2.195

2.226 2.19

2.185
2.224 Case A Case A
Case B 2.18 Case B
Case C Case C
2.222 SOC:50 % Case D Case D
2.175
SOC:40 %

500 1000 1500 2000 2500 3000 500 1000 1500 2000 2500 3000
Time (s) Time (s)

2.182 2.158

2.18 2.156

2.178 2.154

2.176 2.152

2.174 2.15
Case A Case A
Case B Case B
2.172 Case C 2.148
Case C
Case D SOC:20 %
SOC:30 % Case D
2.17 2.146

500 1000 1500 2000 2500 3000 500 1000 1500 2000 2500 3000
Time (s) Time (s)
Voltage (V)

Figure 3. Voltage variations during four cases at various state of charge (SOC).
Figure 3. Voltage variations during four cases at various state of charge (SOC).

5.5. Case E
Energies 2019, 12, 2685 7 of 10

Table 1. Thermal profiles that were applied to the battery.

Duration
4h 3h 2h
Case A Case B Case C Case E Case D
26 ◦ C 27 ◦ C 26 ◦ C 26 ◦ C 5 ◦C
4 ◦C 15 ◦ C 4 ◦C 4 ◦C 24 ◦ C
14 ◦ C 5 ◦C 14 ◦ C 14 ◦ C 10 ◦ C
41 ◦ C 20 ◦ C 41 ◦ C 41 ◦ C 5 ◦C
55 ◦ C 40 ◦ C 55 ◦ C 55 ◦ C 15 ◦ C
23 ◦ C 15 ◦ C 23 ◦ C 23 ◦ C 25 ◦ C

5.5. Case E
In order to determine the effect of the process before the thermal cycle on the entropic heat
coefficient of the lithium titanate oxide battery, experiments were accomplished by both a fully charged
and discharged battery cell. After a short rest period, the battery was discharged with 3.25 A current
rate with voltage limitation equal and less than to 1.5 V. After a 15-min rest period, the battery cell was
charged with 3.25 A current rate with voltage limitation equal to 2.8 V and end type condition for the
current, which was equal to 0.52 A. Then, the battery cell was fully discharged with voltage limitation
equal and less than to 15 V. After a 15-min rest period, charge current pulses with ten percent state of
charge time duration were applied to the battery. For instance, for the first cycle, the cell’s state of
charge was increased by means of a charging procedure from 10% to 20% and then the thermal process
was accomplished, which determined the entropic heat coefficient amount for this last-mentioned state
of charge. This process was redone until the battery cell was completely charged for state of charges of
30%, 40%, 50%, 60%, 70%, 80%, 90%, and 100%.
The thermal process for case E consist of three hours at 26 ◦ C, three hours at 4 ◦ C, three hours at
14 C, three hours at 41 ◦ C, three hours at 55 ◦ C, and three hours at 23 ◦ C.
◦

Outcomes demonstrated that prior cycling, which consists of charging or discharging cycles,
could influence the value of entropic heat coefficient almost the same amount as different thermal cycle.
Voltage variations for case E during different SOC levels and experiments are illustrated in Figure 4.
It can be seen from the figure that voltage variation for 10% SOC is different compared with others.
Entropic heat coefficient at different SOC and cases is shown in Table 2. Entropic heat coefficient of the
lithium titanate oxide battery cell as a function of SOC is illustrated in Figure 5. As can be seen from
the figure, entropic heat coefficient of the battery demonstrates a similar variation for different cases; in
another word, there is a decreasing pattern, which is followed by a decreasing trend for all of them.
It is crystal clear from the figure that case E, which is corresponds to the process before the thermal
cycle, is much different compared with other cases. Another striking feature for all cases is the great
influence of SOC to entropic heat coefficient.

Table 2. Entropic heat coefficient (EHC) (mV/◦ C) at different state of charge (SOC) and cases.

SOC (%) Case A Case B Case C Case D Case E Average EHC

10 −0.1115 −0.1098 −0.107 −0.1045 −0.1199 −0.11054
20 −0.0814 −0.0802 −0.0766 −0.0745 −0.0899 −0.08052
30 −0.0562 −0.055 −0.0522 −0.0493 −0.0648 −0.0555
40 −0.0362 −0.0348 −0.0322 −0.0295 −0.0449 −0.03552
50 −0.0234 −0.0217 −0.018 −0.0164 −0.0319 −0.02228
60 −0.0166 −0.0151 −0.0127 −0.0095 −0.0248 −0.01574
70 −0.0184 −0.017 −0.0142 −0.0113 −0.0269 −0.01756
80 −0.0212 −0.0198 −0.016 −0.0145 −0.0298 −0.02026
90 −0.0413 −0.0402 −0.0376 −0.0345 −0.0499 −0.0407
 coefficient of the lithium titanate oxide battery cell as a function of SOC is illustrated in Figure 5. As
can be seen from the figure, entropic heat coefficient of the battery demonstrates a similar variation
for different cases; in another word, there is a decreasing pattern, which is followed by a decreasing
trend for all of them. It is crystal clear from the figure that case E, which is corresponds to the process
before the thermal cycle, is much different compared with other cases. Another striking feature for
Energies 2019, 12, 2685 8 of 10
all cases is the great influence of SOC to entropic heat coefficient.

2.166 Case E
Case E
2.133
SOC: 10 % 2.165
Charge
2.132
2.164

2.131 2.163

2.162
2.13 SOC:20 %
Charge
2.161
2.129

500 1000 1500 2000 3000 3500 4000 4500

Time (s) Time (s)

2.188 Case E
2.21

2.2095
Case E
2.187
2.209

2.2085
2.186
2.208

2.185 2.2075
SOC:30 %
Charge 2.207
SOC:40 %
Charge
2.184 2.2065
Energies 2018, 11, x FOR PEER REVIEW 8 of 10
5500 6000 6500 7000 8000 8500 9000 9500
Time (s) Time (s)

2.237
Case E
2.21

2.2095
Case E 2.236
2.209

2.2085 2.235
2.208

2.2075 2.234
SOC:40 % SOC:50 %
2.207 Charge
Charge
2.2065 2.233

8000 8500 9000 9500 1.05 1.1 1.15 1.2

Time (s) Time (s) 104

Case E Case E
2.274
2.328

2.273 2.327

2.272 2.326

2.325
2.271
SOC:60 % SOC:70 %
Charge 2.324
Charge
2.27
2.323
1.3 1.35 1.4 1.45 1.55 1.6 1.65 1.7
Time (s) 104 Time (s) 104

Case E
2.4 Case E
2.486
2.399

2.398 2.484

2.397
2.482
2.396
2.48
2.395 SOC:80 % SOC:90 %
Charge Charge
2.394 2.478

1.8 1.85 1.9 1.95 2.05 2.1 2.15 2.2

Time (s) 104 Time (s) 104

Figure
Figure 4. 4.Voltage
Voltage variations
variations during
during case
case E at
E at various
various SOC.
SOC.

Table 2. Entropic heat coefficient (EHC) (mV/°C) at different state of charge (SOC) and cases.

SOC (%) Case A Case B Case C Case D Case E Average EHC

10 −0.1115 −0.1098 −0.107 −0.1045 −0.1199 −0.11054
20 −0.0814 −0.0802 −0.0766 −0.0745 −0.0899 −0.08052
30 −0.0562 −0.055 −0.0522 −0.0493 −0.0648 −0.0555
40 −0.0362 −0.0348 −0.0322 −0.0295 −0.0449 −0.03552
50 −0.0234 −0.0217 −0.018 −0.0164 −0.0319 −0.02228
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Energies 2018, 11, x FOR PEER REVIEW 9 of 10

Figure 5. Entropic heat coefficient (EHC) (mV/◦ C) of the battery as a function of state of charge.
Figure 5. Entropic heat coefficient (EHC) (mV/°C) of the battery as a function of state of charge.

6. Conclusions and Future

6. Conclusions Research
and Future Research
Heat generation insideinside
Heat generation lithium
lithiumtitanate
titanate oxide batteries
oxide batteries is aiscomplicated
a complicatedprocedureprocedure
that needsthat needs
comprehending
comprehending of how of the
how rates
the ratesofofelectrochemical
electrochemical reaction vary with
reaction varytemperature and time. Forand
with temperature the time. For
researchers, a comprehensive understanding of entropic heat coefficient is essential to construct a
the researchers, a comprehensive understanding of entropic heat coefficient is essential to construct a
precise and practical thermal model. The objective of this research was to analysis entropic coefficient
precise andof apractical
lithium ionthermal model.
battery during The objective
charging of this
and discharging by research
employingwas to analysis entropic
the potentiometric technique. coefficient
of a lithium ionconcluded
It was battery that
during
amongcharging and discharging
different influential parameters, bySOC
employing the potentiometric
and the process before the thermal technique.
cycle havethat
It was concluded the greatest
amonginfluence
different on the entropic coefficient.
influential parameters, The thermal
SOC and cyclethe
andprocess
time duration havethe thermal
before
the lowest influence on entropic coefficient of the battery correspondingly. Thus, the dependence of
cycle have the greatest influence on the entropic coefficient. The thermal cycle and time duration have
entropic heat coefficient of the battery cell on the state of charge, thermal cycle, time duration for
the lowestthermal
influence
cycles,on
andentropic
procedure coefficient of thewas
prior to the thermal battery correspondingly.
confirmed. Thus,
The collected data will the dependence
be mapped
of entropic heat curve-fitting
through coefficienttoofyield
thethe battery
essentialcell on the
equations forstate
futureof charge,
work. In orderthermal
to relatecycle, time duration
the entropic
for thermalcoefficient
cycles,toandthe procedure
voltage, temperature,
prior tothermal cycle, and
the thermal wasstate of charge during
confirmed. charging and
The collected data will be
discharging, a function will be determined by analyzing the obtained experimental data.
mapped through curve-fitting to yield the essential equations for future work. In order to relate the
Author Contributions: S.S.M. proposed the idea of the paper; S.S.M. wrote the paper; E.S. provided suggestions
entropic coefficient to the voltage, temperature, thermal cycle, and state of charge during charging and
on the content and structure of the paper; S.K.K. and E.S. has been reviewing the draft manuscripts.
discharging, a function will be determined by analyzing the obtained experimental data.
Funding: This research received no external funding.

Conflicts of Interest:
Author Contributions: S.S.M.Theproposed
authors declare no conflict
the idea of the of paper;
interest. S.S.M. wrote the paper; E.S. provided suggestions
on the content and structure of the paper; S.K.K. and E.S. has been reviewing the draft manuscripts.
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