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Flame-retardant electrolyte with boosted interfacial stability for practical Li metal batteries

具有增强界面稳定性的阻燃型电解液用于实际锂金属电池

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Abstract

Developing Li metal batteries (LMBs) with high-voltage cathodes is crucial for realizing high energy storage systems. Thus, advanced electrolytes that can derive stable interphases for both Li anode and high-voltage cathodes are highly desired. LiNO3 has been widely used as an efficient additive for solid electrolyte interphases in ether-based electrolytes, but its poor solubility in carbonate-based electrolytes limits its application in high-voltage LMBs. Herein, trimethyl phosphate was proposed as co-solvent in ethyl methyl carbonate/fluoroethylene carbonate electrolyte to endow the electrolyte with high LiNO3 solubility and flame-retardant properties. Additionally, lithium bis(oxalato) borate was added to improve the interfacial stability at both the anode and the cathode sides. As a result, the obtained electrolyte exhibited high compatibility towards both Li metal anode and high-voltage layered cathodes. After cycled between 2.8–4.3 V at a current density of 1.2 mA cm−2 for 300 times, Li∣LiCoO2 and Li∣LiNi0.8Co0.1Mn0.1O2 (NCM811) full cells delivered high capacity retention of 80.2% and 84.2%, respectively. More amazingly, the Li∥NCM811 cell with a negative-to-positive capacity ratio of 3.33 still remained a capacity retention of ∼80% after 150 cycles under the same charge/discharge conditions. The understanding of this fire-retardant, high-voltage electrolyte enriched with LiNO3 inspires the development of safe and high energy LMBs through interphases regulation.

摘要

开发匹配高电压正极的锂金属电池是实现高能量存储系统的关键. 因此, 研发可以同时为锂金属负极和高电压正极产生稳定界面相的先进电解液非常必要. LiNO3作为高效的固体电解质界面相添加剂被广泛应用于醚基电解液中, 然而其在碳酸脂类电解液中的低溶解性严重限制了其在高压锂金属电池中的应用. 本文利用磷酸三甲酯助溶剂提高LiNO3在碳酸乙基甲酯/氟代碳酸乙烯酯电解液中的溶解度, 并赋予电解液阻燃性能. 此外, 通过添加双草酸硼酸锂(LiBOB)进一步提高正负极的界面稳定性. 结果表明, 该电解液对锂金属负极和高电压层状氧化物正极均具有较高的兼容性. 在2.8–4.3 V电压范围内, Li∣LiCoO2和Li∣LiNi0.8Co0.1Mn0.1O2 (NCM811)电池在1.2 mA cm−2电流密度下循环300周后的容量保持率分别为80.2%和84.2%. 更令人惊喜的是, 负/正极容量比为3.33的Li∣NCM811电池在相同的充放电条件下循环150周后的容量保持率仍高达∼80%. 本论文对富含LiNO3的阻燃型高压电解液的研究将为通过界面相调控研发安全的高比能锂金属电池提供理论指导.

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Acknowledgements

This work was support by GuangDong Basic and Applied Basic Research Foundation (2021A1515111008).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Materials Science and Engineering & Research Institute of Interdisciplinary Science, Dongguan University of Technology, Dongguan, 523808, China

    Jiaolong Zhang  (张娇龙)

  2. School of Civil and Environmental Engineering, Harbin Institute of Technology, Shenzhen, Shenzhen, 518055, China

    Xiaohang Kou  (寇骁航), Chaolin Li  (李朝林) & Wenhui Wang  (王文辉)

  3. School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou, 310023, China

    Tingting Ruan  (阮挺婷)

  4. ZJU-Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou, 311215, China

    Ruhong Li  (李如宏)

Authors
  1. Xiaohang Kou  (寇骁航)
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  3. Chaolin Li  (李朝林)
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  6. Wenhui Wang  (王文辉)
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Contributions

Author contributions Kou X and Zhang J designed and performed the experiments, analyzed the data as well as wrote the original draft. Zhang J acquired the funding. Li C helped analyze the data. Li R conducted the theoretical calculations. Ruan T and Wang W validated the data analysis, supervised the project and revised the original draft. Wang W conceived the idea.

Corresponding authors

Correspondence to Tingting Ruan  (阮挺婷) or Wenhui Wang  (王文辉).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Wenhui Wang is an associate professor at Harbin Institute of Technology, Shenzhen. He received his Bachelor and PhD degrees from Harbin Institute of Technology and The Chinese University of Hong Kong, respectively. His research interests include Li/Na-ion batteries, seawater desalination, seawater Li mining, and advanced oxidation processes for wastewater treatment. He has published more than 60 peer review papers as (co-)first/corresponding author in Appl Catal B: Environ, Energy Storage Mater, Water Res, Sci China Mater, etc. He is the recipient of the Eco-environment Youth Science and Technology Award of Guangdong Environmental Science Society, Guangdong Environmental Protection Science and Technology Award, Shenzhen Science and Technology Progress Award, Nanoscale 2024 Emerging Investigators, etc.

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40843_2023_2745_MOESM1_ESM.pdf

Supporting Information for Flame-retardant electrolyte with boosted interfacial stability for practical Li metal batteries

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Kou, X., Zhang, J., Li, C. et al. Flame-retardant electrolyte with boosted interfacial stability for practical Li metal batteries. Sci. China Mater. 67, 804–815 (2024). https://doi.org/10.1007/s40843-023-2745-x

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  • DOI: https://doi.org/10.1007/s40843-023-2745-x

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