Bridging Li7La3Zr2O12 Nanofibers with Poly(ethylene oxide) by Coordination Bonds to Enhance the Cycling Stability of All-Solid-State Lithium Metal Batteries

A solid-state composite polymer electrolyte comprising Li7La3Zr2O12 nanofibers (LLZO NFs) as fillers has the advantages of flexibility, ease of processing, and being low cost, thus being considered to be a promising electrolyte material for use in the next generation of highly safe lithium metal batteries. However, poor compatibility of organic parts and inorganic materials leads to quick capacity decay after long-term charge/discharging running because of inorganic/organic interface deterioration and thus, the related ineffective lithium-ion (Li+) conduction. Herein, a “Boston ivy-style” method is proposed to prepare a solid ceramic/polymer hybrid electrolyte that exhibits a dense interface structure. After grafting on Dynasylan IMEO (DI), the modified LLZO NFs are used as ligands to bond with coordinatively unsaturated metal centers of Ca2+. Furthermore, these Ca2+ bridge the modified LLZO NFs with poly­(ethylene oxide) (PEO) via the ether oxygen atoms they possess. The bridges built between the two phases, PEO and LLZO NFs, are effective to interface strengthening and guarantee rapid Li+ conduction even after 900 cycles. The PEO/LLZO NFs–DI–Ca2+/LiTFSI electrolyte shows a high Li+ transference number of 0.72 (60 °C). The Li||LiFePO4 cell delivers excellent cycling stability (capacity retention of 70.8% after 900 cycles, 0.5 C) and rate performance. The bridge strategy is proved to be effective and probably a promotion to the application of ceramic polymer-based solid-state electrolytes.