粘合剂反应放热在锂离子电池热失控中的作用

doi:10.61558/2993-074X.3598

摘要/Abstract

摘要：

锂离子电池作为动力电池应用中的热安全问题始终是行业关注的重点。全面了解电池内部副反应对电池温升的影响规律，对准确分析热失控过程和预测锂离子电池的热安全性至关重要。虽然在之前的研究中，已有多种副反应已被确定为热源，如固体电解质界面膜分解、负极与电解液反应、正极与电解液反应以及电解液分解反应，但这些反应的量化仍然不够标准化。尤其是高温下粘合剂分解（最常见的是聚偏二氟乙烯）产生的热量对锂离子电池热失控过程的影响知之甚少。因此，本文针对18650型锂离子电池构建了一个电热耦合数值模型，系统分析了高温条件下这五种主要副反应导致热失控的协同作用，特别聚焦于精确量化热失控过程中粘合剂反应热的贡献。结果表明，一旦环境温度超过引发链式放热副反应所需的阈值，模型中包含或排除粘合剂反应不会影响锂离子电池热失控的评估结果。然而，在该条件下，粘合剂反应对总热量释放的热量贡献显著增加，因此成为热失控传播过程中温度升高的主要热源之一。相反，如果环境温度未达到阈值，则粘合剂分解的热量贡献可以忽略不计。此外，改进的电热耦合模型可作为一种有效的模拟工具，用于设计具有增强安全保证的电池系统，选择合适的粘合剂材料以减轻热失控的不利影响，并优化电池开发过程中的热管理，可大大缩短了研发周期。本文的研究结果为不同精度要求的电热模型建立了热源选择标准，同时为锂离子电池设计中的模型简化和高保真度优化提供了理论基础。

关键词: 电化学, 锂离子电池, 数学模拟, 热失控, 粘合剂反应

Abstract:

Thermal safety associated with lithium-ion cells as power sources remains a critical industry concern. A comprehensive understanding of how internal exothermic side reactions contribute to temperature rise is fundamental for accurately analyzing thermal runaway processes and predicting the thermal safety of lithium-ion cells. While various side-reactions, such as decomposition of solid electrolyte interphase layer, reaction between anode materials and electrolyte, reaction between cathode materials and electrolyte, and electrolyte decomposition, have been identified as heat generation sources in previous studies, the quantification of these reactions remains insufficiently standardized. Particularly, the impact of heat generation from binder decomposition (most commonly polyvinylidene difluoride) at elevated temperatures on the thermal runaway process of lithium-ion cells has not been fully elucidated. Therefore, in this study, an electro-thermal coupled numerical model was developed for 18650-type lithium-ion cells to systematically investigate the synergistic effects of these five major side-reactions under high-temperature conditions leading to thermal runaway. Special emphasis was placed on precisely quantifying the contribution from binder decomposition heat during the thermal runaway process. The results demonstrate that once the ambient temperature exceeds the threshold required to initiate cascading exothermic side reactions, the inclusion or exclusion of the binder reaction in the model does not affect the overall assessment results of thermal runaway for lithium-ion cells. However, under these conditions, the heat contribution from binder decomposition to the total heat release increases significantly and therefore becomes one of the dominant heat sources for temperature rise during the thermal runaway propagation. Conversely, when ambient temperatures do not reach the threshold, the heat contribution from binder decomposition is negligible. Additionally, the improved electro-thermal coupling model serves as an effective simulation tool for designing battery systems with enhanced safety, selecting appropriate binder materials to mitigate the adverse effects of thermal runaway, and optimizing thermal management during battery development. This approach significantly reduces the research and development cycle. These findings establish appropriate heat source selection criteria for electro-thermal models under varying precision requirements and provide a theoretical foundation for both model simplification and high-fidelity optimization in lithium-ion battery design.

Key words: Electrochemistry, Lithium-ion battery, Mathematical modeling, Thermal runaway, Binder decomposition

闻文, 周静红, 鲁浩天, 周兴贵. 粘合剂反应放热在锂离子电池热失控中的作用[J]. 电化学（中英文）, 2026, 32(3): 2508112.

Wen Wen, Jing-Hong Zhou, Hao-Tian Lu, Xing-Gui Zhou. Deciphering the Role of Binder Reaction Exothermicity in Thermal Runaway of Lithium-Ion Cells[J]. Journal of Electrochemistry, 2026, 32(3): 2508112.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3598

https://electrochem.xmu.edu.cn/CN/Y2026/V32/I3/2508112

图/表 19

参考文献 52

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Parameter	Anode current collector	Anode	Separator	Cathode	Cathode current collector
Density, kg·m^-3	8960	1347.44	1008.98	2328.5	2700
specific heat Capacity, J/(kg·K)	385	1437.4	1978.16	1269.21	900
thermal Conductivity, W/(m·K)	400	1.04	0.344	3.6	238
Thickness, μm	10	200	30	200	10

Parameter	Anode current collector	Anode	Separator	Cathode	Cathode current collector
Maximum Li⁺ Capacity, mol/m³	/	31507	/	29000	/
Particle Radius, μm	/	2	/	2	/
Porosity	/	0.38	0.6	0.52	/
Electrolyte Concentrationmol, 1/m³	/	1200	1200	1200	/
Electrical Conductivity, S/m	5.998e7	100	/	100	3.774e7
Charge Transfer Coefficient	/	0.5, 0.5	/	0.5, 0.5	/
Solid-State Li Diffusion Coefficient, m²/s	/	1.4523e-13	/	1e-14	/

	ELE	SEI	NEG	POS	PVDF
A, 1·s^-1	5.14e25	1.667e15	2.5e13	6.66e13	1.91e25
E_a, J·mol^-1	2.74e5	1.3508e5	1.35e5	1.396e5	2.86e5
H, J·g^-1	155	257	1714	314	1500
M, g·m^-3	4.069e5	1.947e5	6.104e5	1.293e6	8.14e4

Temperature	ELE	SEI	POS	NEG	PVDF
t = 150 ℃	0.0%	1.6%	69.8%	28.6%	0.0%
t = 155 ℃	7.8%	0.9%	48.4%	33.8%	8.9%
t = 157 ℃	7.1%	0.8%	43.6%	34.8%	13.7%
t = 160 ℃	7.0%	0.8%	43.4%	35.1%	13.6%

E_a, J·mol^-1	2.63e5	2.74e5	2.86e5	2.98e5	3.09e5
t_max, ℃	348	347	342	318	315
time, min	32.2	32.3	32.3	32.4	32.4