Chemically and Physically Cross-Linked Inorganic–Polymer Hybrid Solvent-Free Electrolytes

Safe, self-standing, all-solid-state batteries with improved solid electrolytes that have adequate mechanical strength, ionic conductivity, and electrochemical stability are strongly desired. Hybrid electrolytes comprising flexible polymers and highly conductive inorganic electrolytes must be compatible with soft thin films with high ionic conductivity. Herein, we propose a new type of solid electrolyte hybrid comprising a glass–ceramic inorganic electrolyte powder (Li1+x+yAlxTi2−xSiyP3−yO12; LICGC) in a poly(ethylene)oxide (PEO)-based polymer electrolyte that prevents decreases in ionic conductivity caused by grain boundary resistance. We investigated the cross-linking processes taking place in hybrid electrolytes. We also prepared chemically cross-linked PEO/LICGC and physically cross-linked poly(norbornene)/LICGC electrolytes, and evaluated them using thermal and electrochemical analyses, respectively. All of the obtained electrolyte systems were provided with homogenous, white, flexible, and self-standing thin films. The main ionic conductive phase changed from the polymer to the inorganic electrolyte at low temperatures (close to the glass transition temperature) as the LICGC concentration increased, and the Li+ ion transport number also improved. Cyclic voltammetry using [Li metal|Ni] cells revealed that Li was reversibly deposited/dissolved in the prepared hybrid electrolytes, which are expected to be used as new Li+-conductive solid electrolyte systems.