A Gel Polymer Electrolyte with High Uniform Na+ Flux and its Constructed Hybrid Interface Synergistically to Facilitate High‐Performance Sodium Batteries

Abstract Sodium metal batteries (SMBs) can be developed on a large scale to achieve low‐cost and high‐capacity energy storage systems. Gel polymer electrolyte (GPE) can relieve volatilization of liquid electrolyte, adapt to volume changes in electrodes, and better satisfy the requirements of long‐term SMBs. Herein, a dense polyurethane‐based GPE modified with polyacrylonitrile is synthesized by rapidly swelling two‐component polyurethane/polyacrylonitrile electrospun fiber film. Compared to traditional porous GPEs obtained by swelling porous matrixes, the fiber film provides uniform high Na + flux inside GPE due to its partial solubility property and ability to dissociate salts. Therefore, it can reduce the polarization effect and induce uniform metal deposition under high current in conjunction with its constructed hybrid N/F‐containing solid electrolyte interface (SEI) that possesses low ionic diffusion barrier. The study demonstrates that GPE has an ionic conductivity of 1.816 mS cm −1 at 20 °C and an ion transference number of 0.53. The full battery (NVP/GPE/Na) assembled with this GPE and Na 3 V 2 (PO 4 ) 3 (NVP) cathode shows 90.8% capacity retention rate after 1000 cycles at 10 C. Considering the convenient preparation and outstanding electrochemical performances of the obtained GPE, it can also be matched with other electrodes in the future to expand the application of sodium‐based batteries.