Viscoelastic and Nonflammable Interface Design–Enabled Dendrite‐Free and Safe Solid Lithium Metal Batteries

Abstract Herein, a composite polymer electrolyte with a viscoelastic and nonflammable interface is designed to handle the contact issue and preclude Li dendrite formation. The composite polymer electrolyte (cellulose acetate/polyethylene glycol/Li 1.4 Al 0.4 Ti 1.6 P 3 O 12 ) exhibits a wide electrochemical window of 5 V (vs Li + /Li), a high Li + transference number of 0.61, and an excellent ionic conductivity of above 10 −4 S cm −1 at 60 °C. In particular, the intimate contact, low interfacial impedance, and fast ion‐transport process between the electrodes and solid electrolytes can be simultaneously achieved by the viscoelastic and nonflammable layer. Benefiting from this novel design, solid lithium metal batteries with either LiFePO 4 or LiCoO 2 as cathode exhibit superior cyclability and rate capability, such as a discharge capacity of 157 mA h g −1 after 100 cycles at C/2 and 97 mA h g −1 at 5C for LiFePO 4 cathode. Moreover, the smooth and uniform Li surface after long‐term cycling confirms the successful suppression of dendrite formation. The viscoelastic and nonflammable interface modification of solid electrolytes provides a promising and general strategy to handle the interfacial issues and improves the operative safety of solid lithium metal batteries.