锂金属电池用高浓度电解液体系研究进展

doi:10.3866/PKU.WHXB202008044

Abstract

Abstract:

Improvement in the energy density of conventional lithium-ion batteries (LIBs), based on the intercalation-extraction chemistry of graphite and transition metal layered oxides, has apparently lagged behind the advances in consumer electronics and electric vehicles. Secondary Li-metal batteries (LMBs), utilizing metallic Li as the anode material, have incomparable advantages in terms of energy density due to their high specific capacity (3860 mAh·g^-1) and low redox potential (-3.04 V vs. standard hydrogen electrode) of Li metal. Irrespective of whether Li anodes are coupled with intercalation-type cathodes (e.g. LiFePO₄, LiCoO₂, LiNi_xCo_yMn_zO₂, etc.) or conversion-type cathodes (S, O₂), the energy density of LMBs is much higher than that of traditional LIBs, which should solve the range concern of electric vehicles. However, the intrinsically high reactivity between metallic Li and organic electrolytes could induce the formation of a solid electrolyte interface (SEI). The heterogeneous SEI, consisting of a flexible organic outer layer and a brittle inorganic inner layer, suffers from repeated rupture and regeneration due to infinite volume expansions associated with Li deposition and dissolution reactions. Meanwhile, Li is preferentially deposited on the "hot sites" and is stripped from the root of sediments, resulting in uncontrolled dendrite growth during charging and formation of electrochemically isolated Li ("dead" Li) during discharging. Thus, the Columbic efficiency of Li metal full cells is greatly limited by interfacial side effects and continuous loss of active Li, especially in conventional carbonate-based electrolyte, viz. 1 mol·L^-1 LiPF₆-EC/DEC (ethylene carbonate/diethyl carbonate), which impedes the large-scale employment of Li metal batteries. Recently, novel electrolytes with high or localized-high salt concentrations have attracted considerable attention because of their unique physiochemical properties and excellent electrochemical performance. In high-concentration electrolytes, the reduction in the population of free solvent molecules inhibits irreversible electrolyte decomposition at the electrode-electrolyte interface. In localized-high-concentration electrolytes, the introduction of a dilute reagent retains the desired solvation structure, while improving the physicochemical properties (conductivity and viscosity) of the electrolyte. Herein, we systemically review the latest progress in high-concentration and localized-high-concentration electrolytes for use in Li metal batteries. The solvation chemistry structure, physicochemical properties, and interfacial-stabilizing mechanisms are analyzed in detail, and special attention is devoted to their superior interfacial compatibility with Li metal anodes. Finally, we briefly clarify the current problems associated with the research of high-concentration and localized-high-concentration electrolytes from the viewpoints of basic scientific research and practical applications, and some possible solutions are provided to further pave the way to practical Li metal batteries.

Key words: Li metal battery, High concentration electrolyte, Localized high concentration electrolyte, Electrolyte solvation structure, Interfacial property

Chen Wu, Ying Zhou, Xiaolong Zhu, Minzhi Zhan, Hanxi Yang, Jiangfeng Qian. Research Progress on High Concentration Electrolytes for Li Metal Batteries[J].Acta Phys. -Chim. Sin., 2021, 37(2): 2008044.

Figures/Tables 9

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Classification	Electrolyte	Li metal batteries	Cycling Performance	Ref.
ether-based HCE	7 mol·L^-1 LiTFSI /DOL-DME	Li//S	74% @ 100^th	30
	4 mol·L^-1 LiFSI-DME	Li//Cu	CE = 99.2% for 1000 cycles	31
	3 mol·L^-1 LiFNFSI-DOL/DME	Li//LiFePO₄	98.5% @ 200^th	37
	2 mol·L^-1 LiDFOB + 2 mol·L^-1 LiTFSI -DME	Li//NCM333	80% @ 500^th	38
	3 mol·L^-1 LiTFSI-DME	Li//O₂	cycle life of 40^th	39
ester-based HCE	10 mol·L^-1 LiFSI-EC/DMC	Li//NCM622	86% @ 100^th	41
	7 mol·kg-1 LiFSI-FEC	Li//LiNi_0.5Mn_1.5O₄	94.26% @ 150^th	42
	4 mol·L^-1 LiTFSI+0.5 mol·L^-1 LiDFOB-FEC/DMC	Li//LiNi_0.5Mn_1.5O₄	88.5% @ 500^th	43
sulfone-based HCE	LiFSI-SL = 1: 2.5	Li//Cu	CE = 99.2% for 400 cycles	45
	4 mol·L^-1 LiNO₃-DMSO	Li//Cu	CE > 80% for 90 cycles	46
	LiTFSI-DMSO = 1 : 3	Li//O₂	cycle life of 90^th	47
nitrile-based HCE	LiTFSI-AN = 1 : 2	Li//Se	86% @ 200^th	48
phosphate-based HCE	LiFSI-TEP = 1 : 1.5	Li//Cu	CE > 80% for 90 cycles	49
ionic liquid-based HCE	5 mol·L^-1 LiFSI + 0.16 mol·L^-1 NaTFSI-[EMIm]FSI	Li//LiCoO₂	81% @ 1200^th	50

Dilute	Electrolyte	Li metal battery	Cycling Performance	Ref.
HFE	LiTFSI-G4/HFE(1 : 1 : 4)	Li//S	85% @ 100^th	51
	1 mol·L^-1 LiPF₆ FEC/FEMC/HFE	Li//NMC811	90% @ 400^th	56
	1 mol·L^-1 LiPF₆ FEC/FEMC/HFE	Li// LiCoPO₄	93% @ 1000^th	56
	1 mol·L^-1 LiPF₆ FEC/FEMC/HFE + 2% LiDFOB	Li//LiNiO₂	80% @ 400^th	57
	1 mol·L^-1 LiPF₆ + 0.02 mol·L^-1 LiDFOB-FEC/FDEC/HFE	Li //LiCoMnO₄	80% @ 1000^th	58
	1.2 mol·L^-1 LiPF₆ FEC/DMC/HFE + 0.15 mol·L^-1 LiDFOB	Li//LiCoO₂	84% @ 300^th	59
	1.28 mol·L^-1 LiFSI-FEC/FEMC/HFE	Li //NCA	90% @4 50^th (-20 ℃)	60
BTFE	1.2 mol·L^-1 LiFSI-DMC/BTFE	Li//NCM333	80% @ 700^th	52
	1.2 mol·L^-1 LiFSI-TEP/BTFE	Li//NCM622	97% @ 600^th	53
TTE	LiFSI-1.2 DME/3TTE	Li//NCM811	90% @ 250^th	61
	LiFSI-3TMS/3TTE	Li//NCM111	80% @ 150^th	55
OFE	1 mol·L^-1 LiFSI-95OFE/5DME	Li//S	60% @ 150^th	62
1, 2-dfBen	2 mol·L^-1 LiFSI-DMC/1, 2-dfBen	Li//NCM523	82% @ 140^th	63

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Research Progress on High Concentration Electrolytes for Li Metal Batteries

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