Localized high concentration polymer electrolyte enabling room temperature solid-state lithium metal batteries with stable LiF-rich interphases

Polyvinylidene fluoride hexafluoropropylene (PVDF-HFP) based polymer electrolyte shows mechanical flexibility, soft and intimidate physical contact and good electrochemical stability, however, low ionic conductivity at room temperature and unstable interphases against Li metal hinder its application. In this article, we propose a universal strategy to prepare localized high concentration polymer electrolytes (LHCPE) in which high concentration lithium salt (LiTFSI) dissolved in tiny residual solvent (DMF) and the PVDF-HFP serves as solid dilution. The LHCPE regulates the solvation structure of lithium ions with anions instead of DMF solvent, allowing more anions to coordinate with Li+ and forming amount contact ion pairs (CIPs) and aggregates (AGGs). As a result, high ionic conductivity (5.9 × 10−4 S cm−1) and low activation energy (0.10 eV) achieved. The LHCPE also induces the decomposition of anions-derived LiF-rich interphases, that is ionic conducive and mechanical robust, thereby greatly improving the charge transfer kinetics and stability towards Li metal anodes. Consequently, at 0.5 mA cm−2 and 0.25 mAh cm−2, stable and long-term cycling over 2000 h obtained under room temperature in Li//Li symmetric cells achieved. The full solid-state LFP//LHCPE//Li cells further exhibit excellent capacity retention of 82.83 % even after 1200 cycles at room temperature and a high rate of 8 C (1C=170 mA·g−1). Our work shed light on the design of high-performance polymer-based composite electrolytes by manipulating the Li solvation structure.