微量量热法分析锂离子电池热失控过程

doi:10.6023/A23110498

摘要/Abstract

动力锂离子电池(LIB)的安全问题, 尤其是热失控这一频发的安全事件严重影响乘车人员的安全以及新能源汽车的推广. 本工作使用C80微量量热仪准确测量了商用锂离子电池的内在产热, 通过研究分析不同质量比例的负极-电解液产热及不同质量比例的正极-负极产热, 明确了LIB在热失控阶段的主要反应分为负极与电解液反应放热(130~200 ℃), 三元镍钴锰酸锂(NCM)正极释氧与负极反应放热(200~240 ℃)和磷酸铁锂(LFP)正极释氧与负极反应放热(240~300 ℃)等. 通过使用去卷积数学方法对不同质量比例的负极-电解液及不同质量比例的正极-负极产热分析研究表明, 在商用锂电池注液系数条件下, 电解液会优先与负极反应且被全部消耗, 剩余嵌锂负极会进一步与正极反应放热, 且反应热与正极材料特性密切相关. 残余正极物质虽然结构坍塌仍会释氧, 但由于缺少与之反应的负极或电解液, 热量不会再明显增加. 通过对不同荷电状态(SOC)及不同类型的锂电池主材进行产热测试, 能更好地指导电极材料的改性和电池组装的开发设计, 从而提高LIB整体热稳定性和安全性, 最终获得整包和新能源车的安全提高.

关键词: 锂离子电池, 微量量热仪, 产热, 镍钴锰酸锂, 磷酸铁锂

With the vigorous development and large-scale applications of the global new energy vehicles, lithium ion battery (LIB) as the key components of electric vehicles has attracted extensive attention and research. While many urgent problems such as increasing energy density of LIB to alleviate range anxiety, developing fast charging strategy to shorten the driver's waiting time and prolonging LIB cycle life are to be solved. Especially the frequent thermal runaway incidents of LIB electric vehicles seriously affect the safety of passengers and the promotion of new energy vehicles. In order to understand the complex thermal reactions during thermal runaway occurrence, scanning calorimeter (C80 microcalorimeter) has been proposed to analyze the thermal behavior of different full cell systems, including positive electrodes, negative electrodes, separator and electrolyte of LiFePO₄ (LFP), Li[NiCoMn]O₂ (NCM) and LFP/NCM hybrid LIB. A deconvolution method is used to calculate heat generation based on specific electrode according to the deconvoluted data. Anode-electrolyte biphasic system at different state of charge (SOC), anode single-phase system, cathode-electrolyte biphasic system and LFP/NCM hybrid full cells without electrolyte are also studied to reveal detailed steps and specific heat generation during thermal runaway mechanism. According to the analysis, thermal runaway reactions of LIB full cells are comprised by the anode-electrolyte (130~200 ℃), anode-NCM (200~240 ℃) and anode-LFP (240~300 ℃). Additionally, in the case of injection co-efficient of commercial LIB, electrolyte will be used up during anode-electrolyte reaction. Then the leftover Li in anode subsequently react with cathode and the remaining decomposition of cathode will stop producing heat. Although the residual positive electrode material may still release oxygen due to structural collapse, the heat will not increase significantly due to the lack of negative electrodes or electrolytes that react with it. These results are crucial to reveal the internal mechanism of thermal reactions in LIB, providing the foundation of different battery systems applying to electric car.

Key words: lithium-ion battery, microcalorimeter, heat production, Li[NiCoMn]O₂, LiFePO₄

引用此文

顾晓瑜, 李进, 孙千, 王朝阳. 微量量热法分析锂离子电池热失控过程[J]. 化学学报, 2024, 82(2): 146-151.

Xiaoyu Gu, Jin Li, Qian Sun, Chaoyang Wang. Microcalorimetry Analysis of Thermal Runaway Process in Lithium-ion Batteries[J]. Acta Chimica Sinica, 2024, 82(2): 146-151.

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图/表 7

图1. (a) NCM、LFP及LFP/NCM混合全电池体系产热对比图; (b) NCM, (c) LFP及(d) LFP/NCM混合全电池原始及去卷积热流曲线

Figure 1. (a) Heat flow curves of NCM, LFP and LFP/NCM hybrid full cells; Original and deconvoluted curve of (b) NCM, (c) LFP and (d) LFP/NCM hybrid full cell

LFP/NCM	起始温度/℃	峰值温度/℃	反应热/J	基于电极产热/(J•g^-1)
peak 1	130	180	84	1408
peak 2	174	205	299	1408
peak 3	213	228	140	2293
peak 4	231	236	267
peak 5	241	245	29
peak 6	280	287	21	152
NCM	起始温度/℃	峰值温度/℃	反应热/J	基于电极产热/(J•g^-1)
peak 1	154	180	66	1632
peak 2	185	208	378	1632
peak 3	211	224	294	1285
peak 4	232	235	109
peak 5	226	236	249
peak 6	—	—	—
LFP	起始温度/℃	峰值温度/℃	反应热/J	基于电极产热/(J•g^-1)
peak 1	160	168	8	448
peak 2	180	209	65
peak 3	197	219	33
peak 4	198	231	16
peak 5	—	—	—
peak 6	222	294	122	240

表1. LFP/NCM混合、NCM及LFP全电池体系去卷积分峰产热参数

Table 1. The heat generation of deconvoluted peaks of different full cells

图2. (a) LFP/NCM混合全电池及无电解液体系产热对比图; (b) LFP/NCM混合无电解液体系原始及去卷积热流曲线

Figure 2. (a) Heat flow curves of LFP/NCM hybrid full cells and without electrolyte; (b) Original and deconvoluted curve of LFP/NCM without electrolyte

LFP/NCM无电解液	起始温度/℃	峰值温度/℃	反应热/J	基于电极产热/(J•g^-1)
peak 1	138	194	161	592
peak 2	193	221	211	4057
peak 3	218	222	53
peak 4	215	228	197
peak 5	229	239	259
peak 6	248	256	27	125
Peak7	270	275	14

表2. LFP/NCM无电解液体系去卷积分峰产热参数

Table 2. The heat generation of deconvoluted peaks of LFP/NCM without electrolyte

图3. (a)不同SOC状态负极片与电解液两相体系产热对比图; (b) 4.1V-SOC 90%负极-电解液, (c) 3.9V-SOC 70%负极-电解液及(d) 3.6V-SOC 30%负极-电解液的原始及去卷积热流曲线

Figure 3. (a) Heat flow curves of biphasic anode-electrolyte system with different state of charge; Original and deconvoluted curve of (b) 4.1V-SOC 90%, (c) 3.9V-SOC 70% and (d) 3.6V-SOC 30% anode-electrolyte biphasic system

4.1V-SOC-90%	起始温度/℃	峰值温度/℃	反应热/J	基于负极产热/(J•g^-1)
peak 1	160	218	845	1721
peak 2	—	—	—
peak 3	226	229	271
peak 4	229	232	418
peak 5	234	243	187
3.9V-SOC-70%	起始温度/℃	峰值温度/℃	反应热/J	基于负极产热/(J•g^-1)
peak 1	130	185	567	1765
peak 2	180	217	622	1765
peak 3	225	230	30
peak 4	235	238	413
peak 5	237	239	133
3.6V-SOC-30%	起始温度/℃	峰值温度/℃	反应热/J	基于负极产热/(J•g^-1)
peak 1	110	190	571	992
peak 2	170	214	336
peak 3	220	227	16
peak 4	232	234	69
peak 5	—	—	—

表3. 4.1V-SOC 90%负极-电解液、3.9V-SOC 70%负极-电解液及3.6V-SOC 30%负极-电解液去卷积分峰产热参数

Table 3. The heat generation of deconvoluted peaks of 4.1V-SOC 90%, 3.9V-SOC 70% and 3.6V-SOC 30% anode-electrolyte

样品	NCM全电池体系(mg)	LFP全电池体系(mg)	混合全电池体系(mg)	负极+电解液体系(mg)
负极极片	272	272	272	450
正极极片	507	507	507	—
隔膜	50	50	50	—
电解液	150	150	150	240
m(负极)∶m(电解液)	1.81	1.81	1.81	1.87

表4. NCM、LFP及LFP/NCM混合全电池体系及不同SOC状态的负极-电解液两相体系的各组分质量

Table 4. The mass of each component of NCM, LFP, LFP/NCM hybrid full cell and anode-electrolyte system with different state of charge

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