Research progress in the electrolyte additives in silicon-based anode for lithium-ion batteries： Challenges and prospects

doi:10.19799/j.cnki.2095-4239.2023.0594

Abstract

Abstract:

As the application of new energy and power systems becomes increasingly mature, lithium-ion batteries (LIBs) could play an increasingly crucial role in the future. High-specific-energy batteries could become a research hotspot, constantly introducing greater performance requirements. Silicon-based materials with ultra-high theoretical energy density are the new generation of anode materials that can alleviate the anxiety in the electric vehicle industry. The next few years are anticipated as the golden period for the industrial application and commercialization of silicon-based anode LIBs. However, silicon undergoes repeated shrinkage and expansion during the lithium removal/insertion process (with a volume change rate of approximately 300%), causing the anode material to powder, fall off, and subsequently lose the electrical contact and material deactivation. Moreover, the continuous volume change during the cycle causes damage to the solid electrolyte interphase (SEI) on their surface, making it difficult to form a stable SEI, which leads to the consumption of enormous active lithium and electrolyte and ultimately results in rapid capacity decay. This review aims to analyze the challenges faced by electrolyte additives in SEI formation and modification, Lewis base neutralization, solvation regulation, and other mechanisms of action and highlight the latest achievements of silicon-based electrolyte additives. In addition, through an in-depth discussion and comparison of functional group structures, such as fluorine, silane, amide, cyanate ester, etc., this review delves into the design of electrolyte additives to inspire the readers to generate new ideas and help them in identifying/designing and synthesizing electrolyte additives suitable for silicon-based anode, thereby paving the way for the development of high-specific-energy batteries.

Key words: silicon-based anode, electrolyte additive, solid-electrolyte interphase film

CLC Number:

TM 911

Shanshan CHEN, Xiang ZHENG, Ruo WANG, Mingman YUAN, Wei PENG, Boming LU, Guangzhao ZHANG, Chaoyang WANG, Jun WANG, Yonghong DENG. Research progress in the electrolyte additives in silicon-based anode for lithium-ion batteries： Challenges and prospects[J]. Energy Storage Science and Technology, 2024, 13(1): 279-292.

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添加剂体系	分子结构	电极	倍率；截止电压	循环性能; 库仑效率
3.5 mol/L LiFSI/FEC-TFEC	TFEC ^[45]	SiNPs \|\| LiFePO₄	0.5 C; 3.8 V	80.8% after 300 cycles; 99.8%
2% HFPN-1 mol/L LiPF₆ in EC∶EMC (3∶7, 质量比)	HFPN ^[46]	SiO _x /C \|\| NCM523	0.5 C; 4.3 V	70% after 412 cycles； 80.9%±≤0.1%
2% EtPFPN-1 mol/L LiPF₆ in EC∶EMC (3∶7, 质量比)	EtPFPN ^[46]	SiO _x /C \|\| NCM523	0.5 C; 4.3 V	70% after 395 cycles; 80.7%±≤0.1%
10% DFEC-1 mol/L LiPF₆ in EC∶DMC∶DEC (1∶1∶1, 体积比)	DFEC ^[47]	Li \|\| SiO _x @C	0.5 C; 1.5 V	70.3% after 200 cycles; 99.8%
3% FEC-1.2 mol/L LiPF₆ in EC∶EMC (3∶7, 质量比)	FEC ^[48]	SiO _x /C \|\| NCM622	0.1C; 4.1 V	82% after 308 cycles; >99.9%

添加剂体系	分子结构	电极	倍率；截止电压	循环性能; 库仑效率
1% DMDOS in 1 mol/L LiPF₆-5% (质量分数) FEC-EC∶DEC∶DMC=3∶2∶5	DMDOS^[49]	Si@C \|\| LiNi_0.8Co_0.15Al_0.05O₂	0.2 C; 4.2 V	85.5% after 100 cycles; 99.62%
5% (质量分数) TEOSCN in 1 mol/L LiPF₆-EC∶DEC (1∶1, 质量比)	TEOSCN^[50]	Si-Alloy \|\| NMC622, (45 ℃)	1 C; 4.2 V	58.29% after 417 cycles; 100%
5% (质量分数) VTMS in 1 mol/L LiPF₆-EC∶DEC (3∶7, 质量比)	VTMS^[51]	Li \|\| Si/C	0.1 C; 1.5 V	91.8% after 50 cycles; 99%
2% NACA in 1 mol/L LiPF₆-EC∶DEC (3∶7, 质量比)	NACA^[35]	Li \|\| SiO _x /C	0.5 C; 1.5 V	58% after 150 cycles; 99%
3% [PIVM][TFSA] in 1 mol/L LiPF₆ in EC∶DMC∶EMC (1∶1∶1, 质量比)	[PIVM][TFSA]^[52]	Li \|\| Si/C	0.1 C; 1.5 V	94.7% after 50 cycles; 84.8 %（ICE）
2% (质量分数) CPI in 1 mol/L LiPF₆-EC∶EMC (3∶7, 质量比)	CPI^[55]	Li \|\| Si/G	0.5 C; 1.5 V	87.5% after 100 cycles;
1% IEM in 1 mol/L LiPF₆-9%FEC-EC∶ DEC∶DMC (1∶1∶1, 质量比)	IEM^[56]	Li \|\| Si/G	0.1 C; 1.5 V	58% after 100 cycles; 91.25% (ICE)
0.5% (质量分数) APS in 1 mol/L LiPF₆-EC∶DEC (3∶7, 质量比)	APS^[58]	SiO _x /C \|\| NCM90	1 C; 4.3 V	83.1% after 200 cycles; 71% (ICE)

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