Coupling Anion-Capturer with Polymer Chains in Fireproof Gel Polymer Electrolyte Enables Dendrite-Free Sodium Metal Batteries

Abstract

Sodium metal batteries (SMBs) using gel polymer electrolytes (GPEs) with high theoretical capacity and low production cost are regarded as a promising candidate for high energy-density batteries. However, the inherent flammability of GPEs and uncontrolled Na dendrite caused by inferior mechanical properties and interfacial stability hinder their practical applications. Herein, an anion-trapping fireproof composite gel electrolyte (AT-FCGE) is designed through a chemical grafting–coupling strategy, where functionalized boron nitride nanosheets (M-BNNs) used as both nanosized crosslinker and anion capturer are coupled with poly(ethylene glycol)diacrylate in poly(vinylidene fluoride-co-hexafluoropropylene) matrix, to expedite Na+ transport and suppress dendrite growth. Experimental and calculation studies suggest that the anion-trapping effect of M-BNNs with abundant Lewis-acid sites can promote the dissociation of salts, thus remarkably improving the ionic conductivity and Na+ transference number. Meanwhile, the formation of highly crosslinked semi-interpenetrating network can effectively in situ encapsulate non-flammable phosphate without sacrificing the mechanical properties. Consequently, the resulting AT-FCGE shows significantly enhanced Na+ conductivity, mechanical properties, and excellent interfacial stability. The AT-FCGE enables a long-cycle stability dendrite-free Na/Na symmetric cell, and prominent electrochemical performance is demonstrated in solid-state SMBs. The approach provides a broader promise for the great potential of fire-retardant gel electrolytes in high-performance SMBs and the beyond.