h i g h l i g h t s
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a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 January 2015
Received in revised form
28 April 2015
Accepted 22 May 2015
Available online 31 May 2015
A thermal-runaway model of lithium-ion battery is developed by devising a resistive heating that includes short circuit current and integrating it with existing electrochemical and exothermic reaction
model of lithium-ion battery. With the developed model, a guideline for designing lithium-ion battery is
suggested to delay onset of thermal-runaway. First and foremost, the simulation result obtained from
developed mathematical model conrms that thermal-runaway is retarded when the area of heat
transfer is augmented in the cells of same volume and capacity. Next, it is also demonstrated that, under
the simulation condition in which the loading level of active materials is set as a design variable, if short
circuit resistance is same, thermal-runaway occurs in a lithium-ion battery with high loading level
whereas thermal-runaway do not occur when the loading level is low. Assuming the same area of
electrical short, thermal-runaway occurs when cathode active material of 619 [J/g] is used, but thermalrunaway does not occur with the cathode active material of 429 [J/g]. If short circuit resistance is same, a
cell of which the internal resistance equals 0.025 [U] drives itself into thermal-runaway, while cells with
higher internal resistance, i.e. 0.03 [U], do not.
2015 Elsevier B.V. All rights reserved.
Keywords:
Thermal-runaway
Lithium-ion battery
Exothermic reaction model
Design variable
1. Introduction
Along with the growing demands from customers, recent
lithium-ion batteries have more capacity and power than any other
cells before. As it is widely known, safety issue comes to the fore
when the capacity and power increases in lithium-ion batteries,
which, in turn, calls for necessity of securing safety in design stage
when developing a high-capacity, high-powered lithium-ion battery [1e8]. Safety refers to a multi-physical phenomenon in which
electrochemical and exothermic reactions happen simultaneously,
and thus is especially difcult to predict its quantitative data using
a single mathematical model in design stage of lithium-ion battery.
* Corresponding author.
E-mail address: chanho75.lee@samsung.com (C.H. Lee).
http://dx.doi.org/10.1016/j.jpowsour.2015.05.095
0378-7753/ 2015 Elsevier B.V. All rights reserved.
Fig. 1. Validation of electrochemical model: (a) 3.43 Ah polymer cell, (b) 2.43 Ah prismatic cell and (c) 2.5 Ah cylindrical cell.
499
500
Table 1
Cell design and electrochemical model parameter of 3.43 Ah polymer cell.
Positive
Negative
114
8.25
0.551
3.8
167
15
1150
0.118864
1.00E-13
2.00E-11
1.87E-11
126
10
0.608
100
360
Positive
Negative
129
8.25
0.466
3.8
165
14
1150
0.068482
9.00E-13
4.00E-11
1.99E-11
140
9
0.533
100
365
Positive
Negative
92
6
0.431
3.8
185
18
1150
0.10335
5.80E-13
5.00E-11
5.90E-11
101
7.5
0.518
100
390
3.90E-14
1.60E-12
Table 2
Cell design and electrochemical model parameter of 2.43 Ah prismatic cell.
3.00E-13
3.20E-12
Table 3
Cell design and electrochemical model parameter of 2.5 Ah cylindrical cell.
5.10E-13
5.00E-11
Table 4
Heat generation and onset point of reactions e 3.43 Ah polymer cell.
O2 generation
()
side
Core
AVG
On set point ( C)
Calorie (J/g)
205
196
201
235
223
229
288
277
283
626
611
618
Intercalated Li ion e binder reaction
SEI decomposition
()
Side
Core
AVG
On set point ( C)
Calorie (J/g)
On set point ( C)
Calorie (J/g)
108
151
130
39
24
31
251
255
253
268
452
360
application of its result [26e30]. Kim et al. [26] performed simulation of thermal exposure test, whereas Chen et al. [28] focused on
nail penetration test. Moreover, a guideline for designing commercial cells to delay or retard onset of thermal-runaway by verifying the effect of design variables has not been suggested from any
other research yet. Reecting the circumstance, a methodology
suggested in this paper combining an additional short circuit model
501
Table 5
Heat generation and onset point of reactions e 2.43 Ah prismatic cell.
O2 generation
()
side
Core
AVG
On set point ( C)
Calorie (J/g)
204
206
205
233
249
241
285
292
289
752
847
799
Intercalated Li ion e binder reaction
SEI decomposition
()
Side
Core
AVG
On set point ( C)
Calorie (J/g)
On set point ( C)
Calorie (J/g)
151
152
152
64
78
71
228
223
226
264
775
520
Table 6
Heat generation and onset point of reactions e 2.5 Ah cylindrical cell.
O2 generation
()
side
Core
AVG
On set point ( C)
Calorie (J/g)
181
177
179
209
206
208
264
261
263
274
252
263
SEI decomposition 1
()
Side
Core
AVG
SEI decomposition 2
On set point ( C)
Calorie (J/g)
On set point ( C)
Calorie (J/g)
On set point ( C)
Calorie (J/g)
69
73
71
78
22
50
123
122
123
31
93
62
183
227
205
643
571
607
Fig. 2. Raw data of ARC measurement: temperature vs. time of 3.43 A h polymer cell, 2.43 Ah prismatic cell & 2.5 Ah cylindrical cell.
502
Fig. 3. Raw data of ARC measurement: temperature rate vs. temperature of 3.43 Ah polymer cell, 2.43 Ah prismatic cell & 2.5 Ah cylindrical cell.
vC
v
vC
i Di
ajn;i 1 t
i
vt
vx
vx
(1)
where, C is concentration of salt in electrolyte, i is porosity of region i, Di is diffusion coefcient of Li in region i, jn,i is particle
surface ux in region i, a is specic interfacial area and t is
transference number.
The total current density is conserved as follows
Itotal i1 i2
(2)
i1 si
v41
vx
(3)
where, f1 is electric potential of solid phase. The variation of potential in the electrolyte is governed by modied Ohm's law as
follows.
1 vC
v4
2k RT
1 t
i2 ki 2 i
F
C vx
vx
(4)
vcs
1 v
vcs
Ds r 2
2
vt
vr
r vr
(5)
vcs 0; t
0
vr
(6)
Ds
vcs Rs ; t
ajn
vr
(7)
jn
i0;k
aa;k F
ac;k F
exp
hs;k exp
hs;k
F
RT
RT
(8)
i0;k F ka;k
ac;k
kc;k
hs;k 41 42 Uk
aa;k
Csmax;k Cs;k
ac;k
Cs;k
aa;k
(9)
(10)
503
Itotal
41
Rexternal short
(11)
Qohm seff
v41
vx
2
keff
v42
vx
2
2keff RT
0 1 vc v42
1 t
c vx vx
F
(15)
rCp
dT
v2 T
l 2 Qrxn Qrev Qohm
dt
vx
(12)
Qrxn FaJ41 42 U
Qrev FaJT
vU
vT
(13)
(14)
The additional heat source in short-circuit region of the lithiumion batteries as follows.
(16)
504
reaction onset time is lowest among the three exothermic reactions. Therefore, SEI decomposition is very important because the
onset temperature of exothermic reaction can be determined when
comparing thermal safety about different kinds of LIB. Because the
rate of each reaction differs from one to another, respective
Arrhenius-type reaction equation applies as below.
Decomposition of SEI layer:
vxf
E1
A1 $exp
$xf
vt
kB $T
(17)
vxi
E2
z
A2 $exp
$xi $exp
z0
vt
kB $T
(18)
vz
E2
z
A2 $exp
$xi $exp
vt
z0
kB $T
(19)
505
vu
E3
A3 $exp
$1 u$b u
vt
kB $T
(20)
Table 8
ARC simulation model parameter of 2.43 Ah prismatic
cell.
Params
G1LH
Params
PJ7A
h_1_C [J/g]
h_2_C [J/g]
h_3_C [J/g]
A1 [1/min]
E1 [eV]
x_f0 [e]
A2 [1/min]
E2 [eV]
x_i0 [e]
k_B
z_0 [e]
A3 [1/min]
E3 [eV]
Beta [e]
T_0 [ C]
31
360
618
4.20.E06
0.63
0.15
9.00.E13
1.32
0.75
0.0000862
0.033
1.67.E07
0.88
0.03
60
h_1_C [J/g]
h_2_C [J/g]
h_3_C [J/g]
A1 [1/min]
E1 [eV]
x_f0 [e]
A2 [1/min]
E2 [eV]
x_i0 [e]
k_B
z_0 [e]
A3 [1/min]
E3 [eV]
Beta [e]
T_0 [ C]
71
519
799
2.85.E05
0.56
0.15
4.55.E03
0.62
0.75
0.0000862
0.033
6.50.E04
0.73
0.08
51
506
25R
h_1_C [J/g]
h_2_C [J/g]
h_3_C [J/g]
A1 [1/min]
E1 [eV]
x_f0 [e]
A2 [1/min]
E2 [eV]
x_i0 [e]
k_B
z_0 [e]
A3 [1/min]
E3 [eV]
Beta [e]
T_0 [ C]
112
607
263
4.00.E 04
0.53
0.15
3.80.E 14
1.42
0.75
0.0000862
0.033
2.20.E 15
1.65
0.08
55
Table 10
Relationship of heat transfer area and thermal-runaway e simulation case.
Case
Case
Case
Case
1
2
3
4
Volume [mm3]
Surface/volume ratio
15,850
15,720
19,030
24,180
33,190
0.992
1.200
1.526
2.094
vT h1
E1
h
z
E2
2 A2 $xi $exp
$exp
A1 $xf $exp
vt
z0
Cp
kB $T
Cp
kB $T
h
E3
3 A3 $1 u$b u$exp
Cp
kB $T
(21)
where, h is specic energy of each exothermic reaction.
3. Thermal-runaway model parameter characterization
Fig. 8. Oven test experimental results under external temperature 130e170 [ C].
Fig. 7. Oven test simulation results under external temperature 130e170 [ C].
507
DSC analysis and ARC measurement are required for the three
cells mentioned above to quantify heat generation and
exothermic reaction rate during thermal-runaway process. For
DSC analysis, Q1000 of TA Instrument is utilized. The samples for
heat generation analysis are made in such a way that three
different kinds of cells cited in Tables 1e3 are disassembled after
being fully charged, and then each end of both electrodes is
sealed hermetically while punched in a circle with diameter of
3 mm. Heat generation is measured based on the weight of active
material in sample excluding metal substance from the sample.
In DSC analysis, temperature is tracked from 40[ C] to 400[ C],
while monotonically increased at the rate of 10[ C/min] under
dry air condition. Tables 4e6 summarize heat generation and
onset point of reaction of each sample. For ARC measurement, on
the other hand, ES ARC of THT co. ltd. is utilized. The analysis of
exothermic reaction rate employs the following conditions for
measurement: initial temperature of 50[ C], terminal temperature of 350 [ C], temperature increment of 5 [ C], temperature
508
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Nomenclature
eff: effective
ohm: ohmic heat generation
rev: reversible heat generation
rxn: reaction heat generation