Rationally Coordinating Polymer Enabling Effective Li-ion Percolation Network in Composite Electrolyte for Solid-state Li-metal Batteries

The sluggish lithium-ion mobility and inferior electrolyte/electrode interfacial compatibility of composite solid electrolytes greatly hinder the practical application of solid-state lithium-metal batteries. Here, a novel composite polymer electrolyte (CPE) with effective Li+ percolation network is synthesized based on single-ion conductive polymer lithiated polyvinyl formal (LiPVFM) and garnet Li6.4La3Zr2Ga0.2O12 (LLZGO) nanoparticles. The supramolecular interaction between the branched hydroxyl in LiPVFM and the lattice oxygen in LLZGO fillers endows CPE with a continuous percolation structure and improved toughness. Meanwhile, the rational O-Li+ coordination in the LiPVFM random polymer significantly enhances Li+ transfer within the percolation network. Therefore, this as-prepared CPE presents a lithium-ion transference number of 0.75 and an ionic conductivity of 0.527 mS cm−1 at 30°C, alongside an electrochemical stability window of 4.6 V and a substantial suppression of Li dendrite growth. In addition, ultra-stable interfaces between this CPE and high-voltage LiNi0.6Mn0.2Co0.2O2 (NMC) cathode during cycling can be determined by in-situ electrochemical impedance spectroscopy and in-situ differential electrochemical mass spectrometry characterization. This work is a new exploration for the structural design of CPEs and highlights the importance of "rational coordination" of alkali cation in solid batteries.