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Research Article

Wide-temperature range and high safety electrolytes for high-voltage Li-metal batteries

Anran Pan1,2,§, Zhicheng Wang1,§, Fengrui Zhang1, Lei Wang1,2, Jingjing Xu1( ), Jieyun Zheng3( ), Jianchen Hu4, Chenglong Zhao5, Xiaodong Wu1( )
i-lab, Suzhou Institute of Nano-Tech and Nano-Bionics (SINANO), Chinese Academy of Sciences, Suzhou 215123, China
Nano Science and Technology Institute, University of Science and Technology of China, Hefei 230026, China
Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
College of Textile and Clothing Engineering, Soochow University, Suzhou 215123, China
Phylion battery Co., Ltd., Suzhou 215123, China

§ Anran Pan and Zhicheng Wang contributed equally to this work.

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Graphical Abstract

A non-flammable, wide-temperature, and localized highly concentrated electrolyte (LHCE) containing lithium difluoro(oxalato)borate (LiDFOB), triethyl phosphate (TEP), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (HFE) is reported. In the LHCE, Li+ is highly coordinated with TEP and DFOB−, which can effectively inhibit TEP decomposition on Li anode, and can also induce anion-derived SEI layer. Therefore, this LHCE exhibits excellent performance in 4.5 V high-voltage Li-metal batteries from −40 to 70 °C.

Abstract

Along with the keeping growing demand for high-energy-density energy storage system, high-voltage Li-metal batteries (LMBs) have attracted many attentions. In view of many defects of the commercial electrolytes, such as flammability, limited operation temperature range, and severe Li dendrite growth, non-flammable phosphate-based localized highly concentrated electrolytes (LHCE) have been explored as one of the safe electrolytes for LMBs. But until now there is rare report on wide-temperature range LMBs using phosphate-based electrolytes. Here, we prepare a wide-temperature LHCE, which is composed of lithium difluoro(oxalato)borate (LiDFOB), triethyl phosphate (TEP), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (HFE), and explore the applicability in wide-temperature LMBs from −40 to 70 °C. In the LHCE, both TEP and HFE are non-flammable, and Li+ is highly coordinated with TEP and DFOB−, which can effectively inhibit the TEP decomposition on anode, and facilitate the preferential reduction of DFOB−, thus obtain a robust solid electrolyte interphase (SEI) to suppress Li dendrite growth and side reactions. Therefore, this LHCE can not only endow Li/Cu and Li/Li cells with high Coulombic efficiency (CE) and long cycling lifespan, but also be applied to LiFePO4 (LFP)/Li and LiNi0.5Co0.2Mn0.3O2 (NCM523)/Li LMBs. Most importantly, the NCM523/Li LMBs with LHCE can deliver stable cycling performance at 4.5 V high-voltage and high-temperature (70 °C), as well as excellent low-temperature capacity retention even though both charging and discharging process were carried out at −40 °C.

Keywords

safe electrolyteswide-temperaturenon-flammablehigh-voltage batteries

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Nano Research
Volume 16 Issue 6,
June 2023
Pages 8260-8268
DOI: 10.1007/s12274-022-4655-1
Cite this article:
Pan A, Wang Z, Zhang F, et al. Wide-temperature range and high safety electrolytes for high-voltage Li-metal batteries. Nano Research, 2023, 16(6): 8260-8268. https://doi.org/10.1007/s12274-022-4655-1
Topics:
Lithium batteries
Part of a topical collection:
Conversion Reaction Lithium Metal Batteries

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Received: 18 April 2022
Revised: 23 May 2022
Accepted: 10 June 2022
Published: 08 July 2022
© Tsinghua University Press 2022
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