粘合剂反应放热在锂离子电池热失控中的作用
收稿日期: 2025-08-10
修回日期: 2025-11-10
录用日期: 2025-12-03
网络出版日期: 2025-12-03
Deciphering the Role of Binder Reaction Exothermicity in Thermal Runaway of Lithium-Ion Cells
Received date: 2025-08-10
Revised date: 2025-11-10
Accepted date: 2025-12-03
Online published: 2025-12-03
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。
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, 2026 , 32(3) : 2508112 . DOI: 10.61558/2993-074X.3598
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.
| [1] | Tang Y Y. Review on the application status and development of lithium-ion batteries in electric vehicles[J]. Environ. Technol., 2023, 41(7): 94-100. https://doi.org/10.3969/j.issn.1004-7204.2023.07.020. |
| [2] | Ouyang C Z, Liang B, Liu Y P, Lai Y Q, Liu Y X. Progress of thermal safety characteristics of high power lithium-ion batteries[J]. CJPS, 2014, 38(2): 382-385. https://doi.org/10.3969/j.issn.1002-087X.2014.02.058. |
| [3] | Li Q, Yu J S, Liu S Z, Zhu G Q. Review on the characteristics and hazards of lithium-ion battery thermal runaway under various conditions[J]. Fire Sci. Technol., 2023, 42(11): 1482-1487. https://doi.org/10.3969/j.issn.1009-0029.2023.11.006. |
| [4] | He X M, Feng X N, Ouyang M G. On the safety issues of lithium ion battery[J]. ?Sci. Technol. Rev., 2016, 34(6): 32-38. https://doi.org/10.3981/j.issn.1000-7857.2016.06.003. |
| [5] | Niu H C, Wu J Y, Li Z, Li L, Jiang S H, Ji D. Thermal runaway and combustion characteristics of NCM ternary lithium-ion batteries under different induced conditions[J]. Equip. Environ. Eng., 2022, 19(7): 83-92. https://doi.org/10.7643/issn.1672-9242.2022.07.011. |
| [6] | Kong D P, Lv H P, Ping P, Wang G Q. A review of early warning methods of thermal runaway of lithium ion batteries[J]. J. Energy Storage, 2023, 64: 107073. https://doi.org/10.1016/j.est.2023.107073. |
| [7] | Hatchard T D, MacNeil D D, Basu A, Dahn J R. Thermal model of cylindrical and prismatic lithium-ion cells[J]. J. Electrochem. Soc., 2001, 148(7): A755-A761. https://doi.org/10.1149/1.1377592. |
| [8] | Abraham D P, Roth E P, Kostecki R, McCarthy K, MacLaren S, Doughty D H. Diagnostic examination of thermally abused high-power lithium-ion cells[J]. J. Power Sources, 2006, 161(1): 648-657. https://doi.org/10.1016/j.jpowsour.2006.04.088. |
| [9] | Lisbona D, Snee T. A review of hazards associated with primary lithium and lithium-ion batteries[J]. Process Saf. Environ., 2011, 89(6): 434-442. https://doi.org/10.1016/j.psep.2011.06.022. |
| [10] | Peng P, Sun Y Q, Jiang F M. Thermal analyses of LiCoO2 lithium-ion battery during oven tests[J]. Heat Mass Transfer, 2014, 50(10): 1405-1416. https://doi.org/10.1007/s00231-014-1353-x. |
| [11] | Yang H, Bang H, Amine K, Prakash J. Investigations of the exothermic eractions of natural graphite anode for Li-ion batteries during thermal runaway[J]. J. Electrochem. Soc., 2005, 152(1): A73-A79. https://doi.org/10.1149/1.1836126. |
| [12] | Chiu K C, Lin C H, Yeh S F, Lin Y H, Chen K C. An electrochemical modeling of lithium-ion battery nail penetration[J]. J. Power Sources, 2014, 251: 254-263. https://doi.org/10.1016/j.jpowsour.2013.11.069. |
| [13] | Aurbach D, Zaban A, Ein-Eli Y, Weissman I, Chusid O, Markovsky B, Levi M, Levi E, Schechter A, Granot E. Recent studies on the correlation between surface chemistry, morphology, three-dimensional structures and performance of Li and Li-C intercalation anodes in several important electrolyte systems[J]. J. Power Sources, 1997, 68(1): 91-98. https://doi.org/10.1016/s0378-7753(97)02575-5. |
| [14] | Shin J S, Han C H, Jung U H, Lee S I, Kim H J, Kim K. Effect of Li2CO3 additive on gas generation in lithium-ion batteries[J]. J. Power Sources, 2002, 109(1): 47-52. https://doi.org/10.1016/s0378-7753(02)00039-3. |
| [15] | Spotnitz R, Franklin J. Abuse behavior of high-power, lithium-ion cells[J]. J. Power Sources, 2003, 113(1): 81-100. https://doi.org/10.1016/s0378-7753(02)00488-3. |
| [16] | Onuki M, Kinoshita S, Sakata Y, Yanagidate M, Otake Y, Ue M, Deguchi M. Identification of the source of evolved gas in Li-ion batteries using 13C-labeled solvents[J]. J. Electrochem. Soc., 2008, 155(11): A794-A797. https://doi.org/10.1149/1.2969947. |
| [17] | Gachot G, Ribiere P, Mathiron D, Grugeon S, Armand M, Leriche J B, Pilard S, Laruelle S. Gas chromatography/mass spectrometry as a suitable tool for the Li-ion battery electrolyte degradation mechanisms study[J]. Anal. Chem., 2011, 83(2): 478-485. https://doi.org/10.1021/ac101948u. |
| [18] | Gachot G, Grugeon S, Eshetu G G, Mathiron D, Ribière P, Armand M, Laruelle S. Thermal behaviour of the lithiated-graphite/electrolyte interface through GC/MS analysis[J]. Electrochim. Acta, 2012, 83: 402-409. https://doi.org/10.1016/j.electacta.2012.08.016. |
| [19] | MacNeil D D, Dahn J R. The reaction of charged cathodes with nonaqueous solvents and electrolytes: I. Li0.5CoO2[J]. J. Electrochem. Soc., 2001, 148(11): A1205-A1210. https://doi.org/10.1149/1.1407245. |
| [20] | Arai H, Tsuda M, Saito K, Hayashi M, Sakurai Y. Thermal reactions between delithiated lithium nickelate and electrolyte solutions[J]. J. Electrochem. Soc., 2002, 149(4): A401-A406. https://doi.org/10.1149/1.1452114. |
| [21] | Wang Q S, Ping P, Zhao X J, Chu G Q, Sun J H, Chen C H. Thermal runaway caused fire and explosion of lithium ion battery[J]. J. Power Sources, 2012, 208: 210-224. https://doi.org/10.1016/j.jpowsour.2012.02.038. |
| [22] | Moshkovich M, Cojocaru M, Gottlieb H E, Aurbach D. The study of the anodic stability of alkyl carbonate solutions by in situ FTIR spectroscopy, EQCM, NMR and MS[J]. J. Electroanal. Chem., 2001, 497(1-2): 84-96. https://doi.org/10.1016/s0022-0728(00)00457-5. |
| [23] | Kawamura T, Kimura A, Egashira M, Okada S, Yamaki J I. Thermal stability of alkyl carbonate mixed-solvent electrolytes for lithium ion cells[J]. J. Power Sources, 2002, 104(2): 260-264. https://doi.org/10.1016/s0378-7753(01)00960-0. |
| [24] | Gnanaraj J S, Zinigrad E, Asraf L, Gottlieb H E, Sprecher M, Aurbach D, Schmidt M. The use of accelerating rate calorimetry (ARC) for the study of the thermal reactions of Li-ion battery electrolyte solutions[J]. J. Power Sources, 2003, 119-121: 794-798. https://doi.org/10.1016/s0378-7753(03)00255-6. |
| [25] | Wang Q S, Sun J H, Yao X L, Chen C H. Thermal stability of LiPF6/EC+DEC electrolyte with charged electrodes for lithium ion batteries[J]. Thermochim. Acta, 2005, 437(1-2): 12-16. https://doi.org/10.1016/j.tca.2005.06.010. |
| [26] | Yang H, Shen X D. Dynamic TGA-FTIR studies on the thermal stability of lithium/graphite with electrolyte in lithium-ion cell[J]. J. Power Sources, 2007, 167(2): 515-519. https://doi.org/10.1016/j.jpowsour.2007.02.029. |
| [27] | Anon. Japanese scientists develop new technology to solve the biggest problem of lithium batteries: maintaining 95% capacity after 1,700 charge-discharge cycle[J]. Electr. Appl., 2021, (3): 6-7. |
| [28] | Markevich E, Salitra G, Aurbach D. Influence of the PVdF binder on the stability of LiCoO2 electrodes[J]. Electrochem. Commun., 2005, 7(12): 1298-1304. https://doi.org/10.1016/j.elecom.2005.09.010. |
| [29] | Wang G Q, Kong D P, Ping P, Lv H P. Thermal runaway modeling of lithium-ion batteries: A review[J]. CJEE, 2022, 17(4): 61-71. https://doi.org/10.11985/2022.04.008. |
| [30] | Kwon K H, Shin C B, Kang T H, Kim C S. A two-dimensional modeling of a lithium-polymer battery[J]. J. Power Sources, 2006, 163(1): 151-157. https://doi.org/10.1016/j.jpowsour.2006.03.012. |
| [31] | Baba N, Yoshida H, Nagaoka M, Okuda C, Kawauchi S. Numerical simulation of thermal behavior of lithium-ion secondary batteries using the enhanced single particle model[J]. J. Power Sources, 2014, 252: 214-228. https://doi.org/10.1016/j.jpowsour.2013.11.111. |
| [32] | Melcher A, Ziebert C, Rohde M, Seifert H. Modeling and simulation of the thermal runaway behavior of cylindrical Li-ion cells—computing of critical parameters[J]. Energies, 2016, 9(4): 292-310. https://doi.org/10.3390/en9040292. |
| [33] | Coman P T, Darcy E C, Veje C T, White R E. Modelling Li-ion cell thermal runaway triggered by an internal short circuit device using an efficiency factor and arrhenius formulations[J]. J. Electrochem. Soc., 2017, 164(4): A587-A593. https://doi.org/10.1149/2.0341704jes. |
| [34] | He T F, Zhang T, Gadkari S, Wang Z R, Mao N, Cai Q. An investigation on thermal runaway behaviour of a cylindrical lithium-ion battery under different states of charge based on thermal tests and a three-dimensional thermal runaway model[J]. J. Clean Prod., 2023, 388: 135980. https://doi.org/10.1016/j.jclepro.2023.135980. |
| [35] | Azuaje-Berbecí B J, Ertan H B. A model for the prediction of thermal runaway in lithium-ion batteries[J]. J. Energy Storage, 2024, 90: 111831. https://doi.org/10.1016/j.est.2024.111831. |
| [36] | Yang M H, Yue L H. Thermal runaway simulation and prevention and control of lithium-ion batteries based on COMSOL[J]. Adv. New Renewable En., 2022, 10(4): 375-382. https://doi.org/10.3969/j.issn.2095-560X.2022.04.011. |
| [37] | Yao Y H. Study and simulation on thermal runaway of NCM ternary lithium-ion traction battery[D]. Chang’an University, 2018. |
| [38] | Ouyang D X, Huang J, Zheng Y Y, Wang Z R. Numerical simulation and analysis of the effect of charging and discharging on the thermal runaway of lithium-ion batteries under external heating conditions[J]. Appl. Therm. Eng., 2025, 274: 126616. https://doi.org/10.1016/j.applthermaleng.2025.126616. |
| [39] | Fu H, Wang J L, Li L, Gong J H, Wang X. Numerical study of mini-channel liquid cooling for suppressing thermal runaway propagation in a lithium-ion battery pack[J]. Appl. Therm. Eng., 2023, 234: 121349. https://doi.org/10.1016/j.applthermaleng.2023.121349. |
| [40] | Gong J H, Liu B, Lian H C, Liu J Y, Fu H, Miao Y X, Liu J L. Numerical investigation of suppressing thermal runaway propagation in a lithium-ion battery pack using thermal insulators[J]. Process Saf. Environ., 2023, 176: 1063-1075. https://doi.org/10.1016/j.psep.2023.06.092. |
| [41] | Zhang T, Qiu X Y, Li M M, Yin Y X, Jia L Z, Dai Z Q, Guo X X, Wei T. Thermal runaway propagation characteristics and preventing strategies under dynamic thermal transfer conditions for lithium-ion battery modules[J]. J. Energy Storage, 2023, 58: 106463. https://doi.org/10.1016/j.est.2022.106463. |
| [42] | Abhilash K, Jadhav A, Kalamkar V R, Jilte R D. Numerical study on thermal runaway in a cell and battery pack at critical heating conditions with variation in heating powers[J]. J. Energy Storage, 2024, 90: 111813. https://doi.org/10.1016/j.est.2024.111813. |
| [43] | Zhang P F, Lu J J, Yang K B, Chen H P, Huang Y Q. A 3D simulation model of thermal runaway in Li-ion batteries coupled particles ejection and jet flow[J]. J. Power Sources, 2023, 580: 233357. https://doi.org/10.1016/j.jpowsour.2023.233357. |
| [44] | Ding Y, Lu L, Zhang H W. Simulation of lithium-ion battery thermal runaway considering active material volume fraction effect[J]. Int. J. Therm. Sci., 2024, 206: 109336. https://doi.org/10.1016/j.ijthermalsci.2024.109336. |
| [45] | Kim G H, Pesaran A, Spotnitz R. A three-dimensional thermal abuse model for lithium-ion cells[J]. J. Power Sources, 2007, 170(2): 476-489. https://doi.org/10.1016/j.jpowsour.2007.04.018. |
| [46] | Kong D P, Wang G Q, Ping P, Wen J. Numerical investigation of thermal runaway behavior of lithium-ion batteries with different battery materials and heating conditions[J]. Appl. Therm. Eng., 2021, 189: 116661. https://doi.org/10.1016/j.applthermaleng.2021.116661. |
| [47] | MacNeil D D, Hatchard T D, Dahn J R. A comparison between the high temperature electrode/electrolyte reactions of LixCoO2 and LixMn2O4[J]. J. Electrochem. Soc., 2001, 148(7): A663-A667. https://doi.org/10.1149/1.1375798. |
| [48] | Li Y. Simulation research on thermal runaway problem of ternary lithium battery based on COMSOL[D]. Harbin University of Science and Technology, 2022. |
| [49] | Newman J S, Tobias C W. Theoretical analysis of current distribution in porous electrodes[J]. J. Electrochem. Soc., 1962, 109(12): 1183-1191. https://doi.org/10.1149/1.2425269. |
| [50] | Xu Y, Chen Y Q, Zhou J H, Sui Z J, Zhou X G. Numerical simulation of lithium-ion battery with LiFePO4 effect of particle size[J]. CIESE J., 2020, 71(2): 821-830. https://doi.org/10.11949/0438-1157.20191199. |
| [51] | Lakienko G P, Bobyleva Z V, Korneeva E Y, Babkin A V, Drozhzhin O A, Yashina L V, Antipov E V. Effect of binder on the electrochemical, mechanical, and thermal properties of hard carbon anodes in Na-ion batteries[J]. Next Energy, 2025, 9: 100373. https://doi.org/10.1016/j.nxener.2025.100373. |
| [52] | Wang G Q, Ping P, Zhang Y, Zhao H L, Lv H P, Gao X Z, Gao W, Kong D P. Modeling thermal runaway propagation of lithium-ion batteries under impacts of ceiling jet fire[J]. Process Saf. Environ., 2023, 175: 524-540. https://doi.org/10.1016/j.psep.2023.05.047. |
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