磷酸三甲酯-混盐阻燃电解液性能研究

doi:10.19964/j.issn.1006-4990.2024-0593

Abstract

Abstract:

The electrolyte is crucial to the energy density and stability of lithium-ion batteries.However，the lithium salt commonly used in commercial electrolytes，lithium hexafluorophosphate（LiPF₆），is prone to decomposition at temperatures above 60 ℃，which increases the risk of combustion or explosion of the battery under extreme high temperatures.A series of novel flame-retardant electrolyte systems were developed，which used lithium hexafluorophosphate（LiPF₆） and lithium difluorophosphate（LiPO₂F₂） as lithium salts，with ethylene carbonate（EC） and diethyl carbonate（DEC） as mixed solvents，and trimethyl phosphate（TMP） as a flame-retardant additive.The flame-retardant performance was evaluated by self-extinguishing time and infrared spectroscopy analysis，the thermal stability was analyzed by differential scanning calorimetry-thermogravimetric（DSC-TG） experiments，and the electrochemical performance was assessed through electrochemical charge-discharge testing，cycle performance testing，and impedance testing.The results showed that the electrolyte with 3% TMP added did not spread when burned，demonstrating excellent flame-retardant properties.The addition of the lithium salt LiPO₂F₂ to the electrolyte had improved the thermal stability of the electrolyte.The results indicated that the electrolyte（LiPF₆+LiPO₂F₂）+（EC+DEC）+3%TMP in a LiCoO₂/Li battery achieved a first discharge specific capacity of 132.9 mA·h/g and a coulombic efficiency of 99.63% at 25 ℃ and 0.5C rate.After 100 cycles at 80 ℃ and 1.0C rate，the discharge specific capacity was 110.8 mA·h/g，with a capacity retention rate of 92.49%.

Key words: lithium-ion batteries, electrolyte, flame retardant additive, synergistic effect, high temperature

CLC Number:

TQ126.3

WANG Yiren, DUO Xinghong. Study on trimethyl phosphate-mixed salt flame retardant electrolytes performance[J]. Inorganic Chemicals Industry, 2025, 57(6): 85-92.

Figures/Tables 12

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电解液样品	棉花球质量/g	燃烧前棉花球的质量/g	燃烧后棉花球的质量/g	燃烧样品质量/g	燃烧时间/s
A	0.17	1.45	0.49	0.96	159.9
B	0.18	1.62	0.74	0.88	141.3
C	0.15	1.51	0.72	0.79	102.9
D	0.16	1.65	1.04	0.61	97.8
E	0.18	1.83	1.42	0.41	20.1

电解液样品	T₀/℃			T_p/℃			残液率/%
电解液样品	1段	2段	3段	1段	2段	3段	残液率/%
A	39	70	129	36	48	114	0.37
B	—	115	192	—	74	180	0.79
C	53	78	170	48	56	135	2.02
D	—	119	191	—	73	176	3.07
E	106	—	219	59	—	169	3.19

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Inorganic Acid-Base-Salt Committee of CIESC

Study on trimethyl phosphate-mixed salt flame retardant electrolytes performance

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