The polymer-ceramic composite electrolyte is considered as one of promising electrolytes for solid-state battery.However,in previous research,ceramic particles are usually dispersed in polymer matrix and could not form continuous Li+conductive channels.The agglomeration of ceramic particles could also lead to low ionic conductivity and poor interfacial electrode/electrolyte contact.In this paper,self-supported porous Li6.4La3Zr1.4Tao.6O12(LLZTO)electrolyte is synthesized by gelcasting process,which possesses three-dimensional(3D)interconnected pore channels and relatively high strength.The 1,3-diox-olane(DOL)could penetrate into the porous LLZTO framework for its excellent fluidity.The subsequent in situ polymerization process by thermal treatment could com-pletely fill the internal pores and improve the interfacial contact with electrode.The resulting 3D composite elec-trolyte with dual continuous Li+transport channels in ceramic and polymer components exhibits high ionic conductivity of 2.8×104 S·cm-1 at room temperature and low Li/electrolyte interfacial resistance of 94 Ω·cm2 at 40℃.The corresponding Li/Li symmetric cell delivers stable voltage profiles for over 600 h under 0.1 and 0.2 mA·cm-2.The solid-state Li/LiFePO4 battery shows superior rate and cycling performance under 0.1C and 0.2C.This work guides the preparation of composite electrolyte with dual continuous Li+conductive paths as well as high ceramic ratio and interface modification strategy for solid-state Li metal battery.

State Key Lab of New Ceramics and Fine Processing,School of Materials Science and Engineering,Tsinghua University,Beijing 100084,China;College of Materials Science and Technology,Nanjing University of Aeronautics and Astronautics,Nanjing 210016,China;School of Materials Science and Engineering,Zhengzhou University,Zhengzhou 450001,China

[1]Lin-Hui Chen;Ze-Ya Huang;Shi-Le Chen;Rong-Ao Tong;Hai-Long Wang;Gang Shao;Chang-An Wang-.In situ polymerization of 1,3-dioxolane infiltrating 3D garnet framework with high ionic conductivity and excellent interfacial stability for integrated solid-state Li metal battery)[J].稀有金属（英文版）,2022(11):3694-3705

Li+conductive,4Tao,olane

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