Piezoelectric Polymer Solid Electrolyte Integrating Electromechanical Coupling and Ferroelectric Polarization Effects

Abstract The unsatisfactory lithium‐ion conductivity ( σ ) and limited mechanical strength of polymer solid electrolytes hinder their wide applications in solid‐state lithium metal batteries (SSLMBs). Here, a thin piezoelectric polymer solid electrolyte integrating electromechanical coupling and ferroelectric polarization effects has been designed and prepared to achieve long‐term stable cycling of SSLMBs. The ferroelectric Bi 4 Ti 3 O 12 nanoparticle (BIT NPs) loaded poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) piezoelectric nanofibers (B‐P NFs) membranes are introduced into the poly(ethylene oxide) (PEO) matrix, endowing the composite electrolyte with unique polarization and piezoelectric effects. The piezoelectric nanofiber membrane with a 3D network structure not only promotes the dissociation of lithium (Li) salts through the polarization effect but also cleverly utilizes the coupling effect of a mechanical stress‐local electric field to achieve dynamic regulation of the Li electroplating process. Through the corresponding experimental tests and density functional theory calculations, the intrinsic mechanism of piezoelectric electrolytes improving σ and suppressing Li dendrites is fully revealed. The obtained piezoelectric electrolyte has achieved stable cycling of LiFePO 4 batteries over 2000 cycles and has also shown good practical application potential in flexible pouch batteries.