Li2ZrF6-based electrolytes for durable lithium metal batteries

• 成果类型: Article
• 署名作者: Xu, Qingshuai; Li, Tan; Ju, Zhijin; Chen, Guangxu; Ye, Daiqi; Waterhouse, Geoffrey I. N.; Lu, Yingying; Lai, Xuejun; Zhou, Guangmin; Guo, Lin; Yan, Keyou; Tao, Xinyong; Li, Hong; Qiu, Yongcai
• 署名单位: South China University of Technology; Wenzhou University; University of Auckland; Zhejiang University; Tsinghua University; Beihang University; Zhejiang University of Technology; Chinese Academy of Sciences
• 刊物名称: Nature
• ISSN/ISSBN: 0028-3249
• DOI: 10.1038/s41586-024-08294-z
• 发表日期: 2025-01-09
• 页码: 339-+
• 关键词: pouch cells; interphase; anode; morphology; fluoride; layer; oxide; LIFE

摘要

Lithium (Li) metal batteries (LMBs) are promising for high-energy-density rechargeable batteries(1-3). However, Li dendrites formed by the reaction between highly active Li and non-aqueous electrolytes lead to safety concerns and rapid capacity decay(4-7). Developing a reliable solid-electrolyte interphase is critical for realizing high-rate and long-life LMBs, but remains technically challenging(4,8). Here we demonstrate that adding excess m-Li2ZrF6 (monoclinic) nanoparticles to a commercial LiPF6-containing carbonate electrolyte of LMBs facilitates the release of abundant ZrF62- ions into the electrolyte driven by the applied voltage, converting to t-Li2ZrF6 (trigonal) and creating a stable solid-electrolyte interphase in situ with high Li-ion conductivity. Computational and cryogenic transmission electron microscopy studies revealed that the in situ formation of the t-Li2ZrF6-rich solid-electrolyte interphase markedly enhanced Li-ion transfer and suppressed the growth of Li dendrites. As a result, LMBs assembled with LiFePO4 cathodes (areal loading, 1.8/2.2 mAh cm(-2)), three-dimensional Li-carbon anodes (50-mu m-thick Li) and Li2ZrF6-based electrolyte displayed greatly improved cycling stability with high capacity retention (>80.0%) after 3,000 cycles (1C/2C rate). This achievement represents leading performance and, thus, delivers a reliable Li2ZrF6-based electrolyte for durable LMBs under practical high-rate conditions.