Physical and Chemical Properties of Silicone Electrolyte Materials Evaluated by Nuclear Magnetic Resonance Technology

doi:10.11938/cjmr20212888

Abstract

Abstract:

Organosilicon compounds are one of the hot topics in research on electrolyte materials, with their physical and chemical properties standing as important parameters for measuring battery performance. In this paper, the structure of CN(CH₂)₂SiCH₃(OCH₂CH₂OCH₃)₂(BNS), solvation effect, diffusion coefficient and thermal stability of LiPF₆/BNS were analyzed and evaluated by various nuclear magnetic resonance (NMR) methods (i.e., ¹H NMR, ¹³C NMR, DOSY, ⁷Li NMR and ¹⁹F NMR). It was observed that there was a solvation effect between BNS and LiPF₆. Cyano (CN) and ether bond (-O-) groups in BNS may help to form complexes with Li⁺, and the coordination ability of CN is better than that of -O-. The formation of complex bond accelerated dissociation and diffusion of LiPF₆, and also improved the thermal stability of electrolyte (LiPF₆/BNS). It was proved that decomposition of LiPF₆ at high temperature was the main cause of electrolyte failure. The results of this study provided a theoretical basis for the development of new electrolyte compounds and improvement of their performance.

Key words: silicone, electrolyte materials, ¹H NMR, ¹³C NMR, DOSY

CLC Number:

O482.53

Xiao-li CHEN,Tian-qiao YONG,Cheng CHEN,Juan FU,Jia-mei MO,Qiu-cheng SU. Physical and Chemical Properties of Silicone Electrolyte Materials Evaluated by Nuclear Magnetic Resonance Technology[J]. Chinese Journal of Magnetic Resonance, 2021, 38(3): 291-300.

Figures/Tables 10

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Table 1

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Table 2

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LiPF₆/BNS (mol/L)	δ_C
LiPF₆/BNS (mol/L)	-CN	-CH₂O-	-SiOCH₂-	CH₃O-	NCCH₂-	-SiCH₂-	-SiCH₃
0	121.27	73.78	62.24	58.37	10.71	10.54	-5.04
0.25	121.46	73.74	62.23	58.38	10.61	10.51	-5.08
0.50	121.60	73.67	62.19	58.38	10.47	10.47	-5.12
0.75	121.68	73.61	62.15	58.36	10.41	10.36	-5.19
1.00	121.81	73.55	62.12	58.37	10.37	10.22	-5.26

LiPF₆/BNS (mol/L)	D/(×10^-12 m²/s)
LiPF₆/BNS (mol/L)	BNS	Li⁺	PF₆^-
0	7.30	/	/
0.5	5.35	2.25	2.47
1.0	4.79	2.50	2.88

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