不同价态磷基阻燃剂对锂离子电池性能影响试验

doi:10.16265/j.cnki.issn1003-3033.2026.05.0316

中国安全科学学报 ›› 2026, Vol. 36 ›› Issue (5): 73-82.doi: 10.16265/j.cnki.issn1003-3033.2026.05.0316

不同价态磷基阻燃剂对锂离子电池性能影响试验

郗朋¹^,²(), 孙凤玲¹, 范小萍¹^,^**(), 唐潇宇¹, 卓启明³, 纪红兵¹

¹ 应急管理大学化工安全学院, 河北廊坊 065201
² 南京工业大学安全科学与工程学院, 江苏南京 211816
³ 中国矿业大学(北京) 化学与环境工程学院, 北京 100083

收稿日期:2025-12-10 修回日期:2026-03-05 出版日期:2026-05-28
通信作者:
^** 范小萍(1992—),女,山西临汾人,博士,讲师,主要从事锂离子电池正极材料及回收利用技术等方面的研究。E-mail: fanxp6566203@ncist.edu.cn。

作者简介:

郗朋 (1990—),男,安徽淮北人,博士,教授,主要从事危险化学品本质安全控制技术、化工安全和危化品安全监管课程教学方法及人才培养模式等方面的研究。E-mail: pengxi@ncist.edu.cn。

卓启明副教授。

纪红兵教授。

基金资助:
中央高校基本科研业务经费资助(3142021001); 河北省高等学校科学技术研究项目青年拔尖人才项目(BJK2023063); 动力机械与工程教育部重点实验室开放课题(H20230035); 廊坊市科学技术研究与发展计划自筹项目(2022011047)

Experimental study on effect of phosphorus-based flame retardants with different valence states on lithium-ion batteries performance

Xi Peng¹^,²(), Sun Fengling¹, Fan Xiaoping¹^,^**(), Tang Xiaoyu¹, Zhuo Qiming³, Ji Hongbing¹

¹ School of Chemical Safety, University of Emergency Management, Langfang Hebei 065201, China
² College of Safety Science and Engineering, Nanjing Technology University, Nanjing Jiangsu 211816, China
³ School of Chemical and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China

Received:2025-12-10 Revised:2026-03-05 Published:2026-05-28

摘要/Abstract

摘要：

为从本质上提升锂离子电池的安全性,向电解液中添加磷基阻燃剂,研究不同价态的磷基阻燃剂结构对其安全性能、电化学性能的影响。采用自熄灭时间(SET)和差示扫描量热对比研究磷基阻燃剂对电解液热稳定性的影响,采用线性扫描伏安分析磷基阻燃剂对电解液基本性质的影响,进一步通过循环伏安测试、循环性能测试、倍率性能测试和电化学阻抗谱测试探索不同体积比的磷基阻燃剂对LiFePO₄|Li半电池电化学性能的影响。结果表明:添加体积分数为5%的磷酸三甲酯(TMP)和亚磷酸三甲酯(TMPi)的电解液SET均显著降低,且前者提升了电解液电化学窗口,添加5%体积分数为TMP的LiFePO₄|Li半电池的氧化峰和还原峰的峰值电位电势差减小,电池极化减小,循环300圈后的放电比容量较大、容量保持率高达99.6%,而添加5%TMPi导致放电比容量衰减。磷酸甲酯类阻燃剂分子活性弱于亚磷酸甲酯类,负面作用较弱。在不减弱电化学性能前提下,添加5%的TMP更利于提升锂离子电池安全性。

关键词: 磷基阻燃剂, 锂离子电池, 电化学性能, 自熄灭时间(SET), 前线轨道能量

Abstract:

To fundamentally enhance the safety of lithium-ion batteries, phosphorus-based flame retardants were added to the electrolyte, and the effects of different valence states of phosphorus-based flame retardants on safety performance and electrochemical performance were studied. The impact of phosphorus-based flame retardants on the thermal stability of the electrolyte was compared using self-extinguishing time and differential scanning calorimetry. The influence of phosphorus-based flame retardants on the basic properties of the electrolyte was analyzed through linear sweep voltammetry. Further, cyclic voltammetry tests, cycling performance tests, rate capability tests, and electrochemical impedance spectroscopy were conducted to explore the effects of varying volume ratios of phosphorus-based flame retardants on the electrochemical performance of LiFePO₄|Li half-cells. The results show that electrolytes containing 5% trimethyl phosphate (TMP) and trimethyl phosphite (TMPi) exhibit significantly reduced self-extinguishing times, with the former also expanding the electrochemical window of the electrolyte. The LiFePO₄|Li half-cell with 5% TMP demonstrates a smaller potential difference between the oxidation and reduction peaks, reduced battery polarization, and maintains a higher discharge capacity after 300 cycles, with a capacity retention rate of 99.6%. In contrast, the addition of 5% TMPi leads to a decline in discharge capacity. Methyl phosphate flame retardants exhibit weaker molecular activity and less adverse effects compared to methyl phosphite flame retardants. Under the premise of not compromising electrochemical performance, adding 5% trimethyl phosphate is more effective in improving the safety of lithium-ion batteries.

Key words: phosphorus-based flame retardants, lithium-ion batteries, electrochemical properties, self-extinguishing time (SET), frontal orbital energy

中图分类号:

X932爆炸安全与防火、防爆

郗朋, 孙凤玲, 范小萍, 唐潇宇, 卓启明, 纪红兵. 不同价态磷基阻燃剂对锂离子电池性能影响试验[J]. 中国安全科学学报, 2026, 36(5): 73-82.

Xi Peng, Sun Fengling, Fan Xiaoping, Tang Xiaoyu, Zhuo Qiming, Ji Hongbing. Experimental study on effect of phosphorus-based flame retardants with different valence states on lithium-ion batteries performance[J]. China Safety Science Journal, 2026, 36(5): 73-82.

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编号	基础电解液组成	阻燃剂体积分数/%
BE(TMP0/ TMPi0)	LiPF₆物质的量浓度:1.0 mol/L EC∶DMC∶EMC质量比=1∶1∶1	0
TMP5	LiPF₆物质的量浓度:1.0 mol/L EC∶DMC∶EMC质量比=1∶1∶1	5
TMP8	LiPF₆物质的量浓度:1.0 mol/L EC∶DMC∶EMC质量比=1∶1∶1	8
TMP10	LiPF₆物质的量浓度:1.0 mol/L EC∶DMC∶EMC质量比=1∶1∶1	10
TMP15	LiPF₆物质的量浓度:1.0 mol/L EC∶DMC∶EMC质量比=1∶1∶1	15
TMPi5	LiPF₆物质的量浓度:1.0 mol/L EC∶DMC∶EMC质量比=1∶1∶1	5
TMPi8	LiPF₆物质的量浓度:1.0 mol/L EC∶DMC∶EMC质量比=1∶1∶1	8
TMPi10	LiPF₆物质的量浓度:1.0 mol/L EC∶DMC∶EMC质量比=1∶1∶1	10
TMPi15	LiPF₆物质的量浓度:1.0 mol/L EC∶DMC∶EMC质量比=1∶1∶1	15

模型	交互关联函数	截断能/eV	能量/eV
EC-Li⁺	GGA-PBE	200	-2 024.000
DMC-Li⁺	GGA-PBE	200	-2 055.933
EMC-Li⁺	GGA-PBE	200	-2 243.243
TMP	GGA-PBE	200	-2 497.629
TMPi	GGA-PBE	200	-2 078.930

样品	0.1 C切换前放电比容量/ (mA·h/g)	0.1 C切换后放电比容量/ (mA·h/g)	容量保持率/%	容量保持率均值/%
BE	191.5	188.6	98.49	98.47
	191.6	188.5	98.38
	191.0	188.6	98.74
	191.4	188.5	98.48
	191.3	188.0	98.27
TMP5	206.3	199.0	96.46	96.90
	205.5	198.3	96.50
	204.8	198.5	96.92
	204.1	198.2	97.11
	203.1	198.0	97.49
TMPi5	188.6	186.5	98.89	98.79
	188.2	186.1	98.88
	188.5	185.8	98.57
	188.7	186.3	98.73
	188.4	186.3	98.89

样品	第1圈循环			第300圈循环
样品	Rs	R_C	R_t	Rs	R_C	R_t
BE	8.92	47.26	232.4	9.62	132.30	38.9
TMP5	8.51	63.80	186.1	8.68	99.53	38.5
TMPi5	8.19	66.36	117.3	11.0	707.73	51.0

模型	前线轨道能量/a.u.		前线轨道能量差/a.u.
	前线轨道能量/a.u.		TMP		TMPi
	最高占据分子轨道	最低未占据分子轨道	ΔE₁	ΔE₂	ΔE₁	ΔE₂
EC-Li⁺	-0.032 268	-0.022 999	0.228 101	0.039 068	0.191 601	0.026 268
DMC-Li⁺	-0.044 349	-0.039 973	0.211 127	0.051 149	0.174 627	0.038 349
EMC-Li⁺	-0.043 434	-0.040 791	0.210 309	0.050 234	0.173 809	0.037 434
TMP	-0.251 100	0.006 800	—	—	—	—
TMPi	-0.214 600	-0.006 000	—	—	—	—

不同价态磷基阻燃剂对锂离子电池性能影响试验

Experimental study on effect of phosphorus-based flame retardants with different valence states on lithium-ion batteries performance

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