In Situ Curing Technology for Dual Ceramic Composed by Organic–Inorganic Functional Polymer Gel Electrolyte for Dendritic‐Free and Robust Lithium–Metal Batteries

Abstract Lithium–metal batteries (LiMBs) are promising energy storage devices due to the high capacity and minimum negative electrochemical potential. Nevertheless, their concrete applications remain disturbed by unbalanced electrolyte–electrode interfaces, limited electrochemical window, and high risk. Herein, a novel strategy to obtain dual ceramic‐based electrolytes that possesses a great potential in energy storages and higher level of energy densities in LiMBs. Dual‐ceramic (lithium aluminum titanium phosphate ‐lithium lanthanum titanium oxide (LATP‐LLTO)) gel polymer electrolyte (DCGPE) film developed via the curable system aims to prepare flexible Li + interpenetrating network film to integrate the two ceramic structures with polyethylene oxide (PEO) to yield the free‐standing electrolytes film for better battery safety and desired interfacial stability. The DCGPEs films present a satisfactory electrochemical performance, including good ionic conductivity, large transference number, and wide electrochemical stability window at room temperature. Most importantly, the fundamental function of LATP and LLTO is to support building a stable solid‐electrolyte‐interphase and limits the growth of dendrites. Thus, prepared dual ceramic‐based electrolytes effectively render to inhibit lithium dendrite growth in a symmetrical cell Li//PEO + 10% LATP + 15% LLTO//Li test during charge/discharge at a current density of 2 and 0.25 mA cm −2 above 2400 h without short‐circuiting occurrence at room temperature. Besides, the battery assembled of LiFePO 4 /PEO + 10% LATP + 20% LLTO/Li exhibits superior cyclic stability with high Coulombic efficiency. This study recommends that the binary network structures of Li‐ion conductor help to design a prime solution of promising electrolyte for high‐performance LiMBs applications.