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Progress in Chemistry 2023, Vol. 35 Issue (4): 620-642 DOI: 10.7536/PC220935 Previous Articles   Next Articles

• Review •

Review on Mechanism and Model of Heat Release and Safety Modification Technology of Lithium-Ion Batteries

Shuyang Yu1, Wenlei Luo3, Jingying Xie2(), Ya Mao2(), Chao Xu1()   

  1. 1. North China Electric Power University,Beijing 102206, China
    2. State Key Laboratory of Space Power Source Technology, Shanghai Institute of Space Power-sources,Shanghai 200245, China
    3. National Innovation Institute of Defense Technology, Academic of Military Science,Beijing 100071, China
  • Received: Revised: Online: Published:
  • Contact: *e-mail: jyxie@hit.edu.cn(Jingying Xie); maoya0106@163.com(Ya Mao); mechxu@ncepu.edu.cn(Chao Xu)
  • Supported by:
    National Project(2209KW0014)
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Lithium-ion batteries are widely used in mobile electronic products, electric vehicles, energy storage systems, aerospace and other fields due to their high energy and power density, long life and no memory effect. However, in recent years, the frequent safety accidents of electric vehicles and energy storage systems related to battery thermal runaway have attracted high attention. The high safety of high energy density batteries is the primary guarantee to promote the large-scale application of batteries, and the research on the characteristics of battery heat generation, thermal runaway mechanism, protection and suppression methods has become a hot topic in the field of battery thermal safety research in recent years. Therefore, the core issues in the field of battery thermal safety are comprehensively reviewed in this paper. Firstly, the thermal generation characteristics of the battery under normal conditions, the thermal runaway chain exothermic reaction and the failure mechanism of the battery under three kinds of abuse conditions are discussed; Secondly, the mechanistic equation, construction, application and evolution of the electrochemical-thermal coupling model and thermal runaway model are described; and then, the research progress of anode and cathode materials, separator, electrolyte and current collector safety modification technology are introduced; finally, this paper makes a prospect for the research trend in this field to provide ideas and directions for improving the intrinsic safety of lithium-ion batteries and preventing thermal runaway.

Key words: thermal stability, thermal runaway, failure mechanism, mechanism model, modification technology
Fig.1 Schematic diagram of lithium-ion battery
Table 1 Battery safety accidents in recent years
时间 事故回放 事故原因
2020.04 深圳一家充电站内电动汽车起火,多辆电动汽车烧毁 过充导致热量积累,触发热失控链式反应
2020.10.27 一辆威马 EX5 在北京市中国科学研究院力学研究所内发生起火事故,后发生剧烈爆燃 电芯供应商在生产过程中混入了杂质,导致动力电池产生异常析锂,极端情况下可能导致电芯短路,引发动力电池热失控
2021.04.06 韩国忠清南道洪城光伏+储能系统起火爆炸,爆炸摧毁 0.5 MW储能电池 电池过流过压保护不足、运行环境及安装工艺有待改进,智能储能系统 ESS 经验不足
2021.04.16 北京市丰台区福威斯油气技术有限公司光储充一体化项目发生火灾爆炸事故,造成 1 人遇难,两名消防员牺牲。 磷酸铁锂电池单体发生内短路故障,引发电池模组热失控扩散起火
2021.07.18 浙江省杭州市父女骑电动车在玉皇山路行驶的过程中,电动车突然起火爆燃,车上父女被严重烧伤 初步判断“7·18”电动车起火原因与其锂电池故障有关
2021.07.30 位于澳大利亚维多利亚州的“维多利亚大电池”(VBB)项目所装载的特斯拉 Megapack 储能系统在施工建设期间发生起火事故 冷却液泄露导致锂电池热管理失控,在风力作用下引发相邻的另外一个储能系统燃烧
2021.09.04 加利福尼亚州 Vistra Energy 旗下莫斯兰丁锂离子储能站一期项目,7000 个电池组融化,占全部的 7% 热管理系统在极低的烟雾水平下错误启动,系统中部分柔性软管和管道上的少数接头发生故障引发系统喷水降温,造成电池损坏出现过热现象
2022.02.08 上海普陀区宜川四村住宅发生一起火灾造成 3 人死亡 住户将电动自行车锂离子蓄电池放在卧室内,电池故障引发火灾,引发火灾的锂电池输出电压超过 60 伏,属于典型的超标电池
Fig.2 Some battery safety accidents in recent years
Fig.3 Trigger factors of battery thermal runaway
Fig.4 Schematic diagram of thermal runaway chain reaction of lithium-ion battery[13]
Fig.5 “Three stages” of thermal runaway[14]
Fig.6 Characteristic temperature of battery thermal runaway
Fig.7 Thermal runaway triggered by chemical crosstalk between the cathode and anode[47]: (a) time-resolved XRD patterns of charged cathode material; (b) in situ heat generation and oxygen release at different temperatures of charged cathode materials; (c) at 100~500℃, the mixture of cathode and anode releases virtually no oxygen but has sharp heat generation enhancement; (d) cathode and anode cross chemical reaction process
Fig.8 Two endogenous pathways of oxygen involved in thermal runaway strong exothermic reactions[50]: (a) peak fitting of DSC curve of Ca+An+Ely_31%EC sample; (b) peak fitting of DSC curve of Ca+An+Ely_0%EC sample; (c) mechanism and pathway of oxygen release from cathode; (d) thermal runaway temperature rise rate of NMC811/Gr battery with EC-free-electrolyte (0%EC) compared with the control set (31%EC)
Fig.9 Thermal runaway is triggered by LiH-induced exothermic reaction at anode side and H2 migration to cathode side[57]. (a) ARC temperature rise curve and gas generation composition of 100%SOC anode/electrolyte; (b) DSC curves of dual electrolyte and LiH/dual electrolyte under N2 atmosphere; (c) thermal runaway route map for fully charged NCM523/Gr battery
Fig.10 Multi-step thermal runaway route map for SEs and metallic Li[60]
Fig.11 Schematic diagram of 1D electrochemical-3D thermal coupling model: (a) computational domain of 1D electrochemical model; (b) 3D geometric model
Fig.12 Model-based thermal runaway prediction of lithium-ion batteries from kinetics analysis of cell components[96]
Fig.13 High safety composite separators: (a) electrospun core-shell microfiber separator[127]; (b) new separator coated with electrolyte-insoluble flame retardants[128]
Fig.14 (a) DSC curves of components and their mixtures of NCM811/Gr battery using concentrated LiFSI/DMC electrolyte; (b) DSC curves of components and their mixtures of NCM523/Gr battery using concentrated LiFSI/DMC electrolyte; (c) comparison of thermal runaway features of NCM/Gr batteries with concentrated LiFSI/DMC and conventional 1 M LiPF6/EC:EMC electrolyte[136]
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