Designing weakly and strongly solvating polymer electrolytes: Systematically boosting high-voltage lithium metal batteries

Abstract

Practical high-voltage lithium metal batteries hold promise for high energy density applications, but face stability challenges in electrolytes for both 4 V-class cathodes and lithium anode. To address this, we delve into the positive impacts of two crucial moieties in electrolyte chemistry: fluorine atom (-F) and cyano group (-CN) on the electrochemical performance of polyether electrolytes and lithium metal batteries. Cyano-bearing polyether electrolytes possess strong solvation, accelerating Li⁺ desolvation with minimal SEI impact. Fluorinated polyether electrolytes possess weak solvation, and stabilize the lithium anode via preferential decomposition of F-segment, exhibiting nearly 6000-h stable cycling of lithium symmetric cell. Furthermore, the electron-withdrawing properties of -F and -CN groups significantly bolster the high-voltage tolerance of copolymer electrolyte, extending its operational range up to 5 V. This advancement enables the development of 4 V-class lithium metal batteries compatible with various cathodes, including 4.45 V LiCoO₂, 4.5 V LiNi_0.8Co_0.1Mn_0.1O₂, and 4.2 V LiNi_0.5Co_0.2Mn_0.3O₂. These findings provide insights into design principles centered around polymer components for high-performance polymer electrolytes.

Keywords

cyano-bearing copolymer electrolyte / fluorinated copolymer electrolyte / high-voltage lithium metal battery / in situ polymerization / solvation

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2024 The Author(s). SusMat published by Sichuan University and John Wiley & Sons Australia, Ltd.