In Situ Construction Channels of Lithium‐Ion Fast Transport and Uniform Deposition to Ensure Safe High‐Performance Solid Batteries

Abstract Solid‐state lithium‐ion batteries (SLIBs) are the promising development direction for future power sources because of their high energy density and reliable safety. To optimize the ionic conductivity at room temperature (RT) and charge/discharge performance to obtain reusable polymer electrolytes (PEs), polyvinylidene fluoride (PVDF), and poly(vinylidene fluoride‐hexafluoro propylene) (P(VDF‐HFP)) copolymer combined with polymerized methyl methacrylate (MMA) monomers are used as substrates to prepare PE (LiTFSI/OMMT/PVDF/P(VDF‐HFP)/PMMA [LOPPM]). LOPPM has interconnected lithium‐ion 3D network channels. The organic‐modified montmorillonite (OMMT) is rich in the Lewis acid centers, which promoted lithium salt dissociation. LOPPM PE possessed high ionic conductivity of 1.1 × 10 −3 S cm −1 and a lithium‐ion transference number of 0.54. The capacity retention of the battery remained 100% after 100 cycles at RT and 0.5 C. The initial capacity of one with the second‐recycled LOPPM PE is 123.9 mAh g −1 . This work offered a feasible pathway for developing high‐performance and reusable LIBs.