Construction and characteristic analysis of key parameters in a gas-thermal model for thermal runaway in lithium-ion battery based on overcharge

doi:10.19799/j.cnki.2095-4239.2025.0262

Abstract

Abstract:

Overcharging has been identified as a primary contributor to thermal runaway (TR) in lithium-ion batteries (LIBs), where TR modeling plays a pivotal role in understanding coupled heat-gas generation mechanisms for safety enhancement. This study develops an integrated gas-thermal TR model incorporating side reaction-driven gas generation and internal pressure dynamics to characterize overcharge-induced failure. Systematic analysis reveals that charging rate (C-rate) and electrolyte decomposition potential critically govern TR progression, with parametric studies demonstrating that reducing C-rate from 2 C to 1 C combined with elevating electrolyte decomposition potential from 4.3 V to 4.7 V delays TR initiation by 22% in state-of-charge (SOC) while postponing safety valve activation by 15% SOC. The C-rate predominantly regulates temperature evolution during early overcharging (SOC<110%), whereas electrolyte decomposition potential dominates reaction kinetics in later stages (SOC>130%). Notably, increased C-rate substantially weakens the TR-suppressing effect of elevated decomposition potential (22% SOC reduction in suppression efficacy at 3 C vs 1 C), while safety valve activation exhibits stronger dependence on electrolyte stability with merely 3% SOC variation across 1—3 C rates. These findings establish quantitative correlations between material properties and failure thresholds, providing actionable insights for optimizing LIB thermal safety through coordinated charging protocol design and electrolyte stabilization strategies.

Key words: lithium-ion battery, overcharge, thermal runaway, gas-thermal model, characteristic analysis

CLC Number:

TM 912

Ziming MO, Zongxin RAO, Jianfei YANG, Menghao YANG, Liming CAI. Construction and characteristic analysis of key parameters in a gas-thermal model for thermal runaway in lithium-ion battery based on overcharge[J]. Energy Storage Science and Technology, 2025, 14(5): 1784-1796.

Figures/Tables 13

Fig. 1

Fig. 2

Table 1

Thermal parameter of each part of LIB"

组件名称

密度

ρ / (k g / m 3)

定压比热容

c p / [J / (k g ⋅ K)]

热导率

$λ / [W / (m ⋅ K)]$

参考文献

电芯

2000

840

λ x = λ z = 37

，

λ y = 1.1

[13]

正极柱

2700

900

240

[13]

负极柱

8900

385

400

[13]

Table 1

Table 2

The main values of parameters corresponding to each side reactions"

副反应类别	化学反应焓 $H x / (J / K g)$	密度 $W x / (K g / m 3)$	指前因子 $A x / s - 1$	活化能 $E a, x / (J / m o l)$	参考文献
锰分解	$1.40 × 104$	$8.55 × 102$	$5.15 × 105$	$6.84 × 104$	[13]
锂沉积	$5.85 × 105$	$6.10 × 102$	$4.40 × 1016$	$1.40 × 105$	[13]
电解液分解	$5.20 × 105$	$5.17 × 102$	$1.20 × 103$	$6.11 × 104$	[11]
SEI膜分解	$2.57 × 105$	$5.17 × 102$	$1.69 × 1015$	$1.37 × 105$	[13, 28]
负极-电解液反应	$1.74 × 106$	$2.23 × 102$	$2.50 × 1013$	$1.35 × 105$	[28, 32]
正极分解	$7.70 × 104$	$8.55 × 102$	$6.90 × 1013$	$1.15 × 105$	[27]
正极黏结剂分解	$4.52 × 105$	$8.55 × 102$	$6.54 × 1013$	$1.78 × 105$	[33]
负极黏结剂分解	$1.08 × 105$	$2.23 × 102$	$4.97 × 1015$	$1.95 × 105$	[33]

Table 2

Table 3

The main values of parameters corresponding to each gas generation chemical reaction"

反应化学方程式	所属反应	指前因子 $A x / s - 1$	活化能 $E a, x / (J / m o l)$	反应物浓度 $c x /$ (mol $/ m 3)$	修正式 $g x$	参考文献
$C H 2 O C O 2 L i 2 → L i 2 C O 3 + C 2 H 4 + C O 2 + 12 O 2$	SEI膜分解反应	$7.88 × 1036$	$2.81 × 105$	$2.40 × 103$	1	[28, 36]

$2 L i + C 3 H 4 O 3 E C → L i 2 C O 3 + C 2 H 4$	锂沉积反应	$1.95 × 1020$	$2.00 × 105$	$2.44 × 103$	1	[36]

$C 5 H 10 O 3 D E C + 4 L i + + 4 e - + 32 O 2 → 2 L i 2 C O 3 + C H 4 + C 2 H 6$	负极-电解液反应	$2.50 × 1013$	$1.35 × 105$	$1.80 × 103$	$e x p - c S E I t c S E I, 0$	[28]
$2 C O 2 + 2 L i + + 2 e - → L i 2 C O 3 + C O$	负极-电解液反应	$2.50 × 1013$	$1.35 × 105$	$8.00 × 103$	$e x p - c S E I t c S E I, 0$	[28]

$52 O 2 + C 3 H 4 O 3 E C → 3 C O 2 + 3 H 2 O$	电解液分解反应	$1.20 × 103$	$6.11 × 104$	$2.44 × 103$	1 (热分解) $e x p γ e l e F V c a + I r c a - V e l e R T$ (氧化分解)	[11]
$3 O 2 + C 3 H 6 O 3 D M C → 3 C O 2 + 2 H 2 O$		$1.20 × 103$	$6.11 × 104$	$1.96 × 103$
$6 O 2 + C 5 H 10 O 3 D E C → 5 C O 2 + 5 H 2 O$		$1.20 × 103$	$6.11 × 104$	$1.80 × 103$

Table 3

Fig. 3

Fig. 4

Fig. 5

Fig. 6

Fig. 7

Fig. 8

Fig. 9

Fig. 10

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