Decoupling‐Gliding Ion Transport in Polymer Electrolytes via Ferroelectric Order‐Structuring: Toward High‐Voltage and High‐Rate Solid‐State Batteries

ABSTRACT Polymer‐based electrolytes offer processability and interfacial compliance but suffer from low ionic conductivity, narrow electrochemical windows, and uncontrolled Li + transport, limiting their viability for high‐voltage cathodes. Herein, we design an order‐engineered ferroelectric solid electrolyte (OE‐FSE) by integrating a relaxor ferroelectric terpolymer, P(VDF‐TrFE‐CTFE‐FA) (PVTCF), with ambient Curie temperature and double‐bond defects, into a covalently cross‐linked triazine‐based gel network. The spontaneously aligned ferroelectric dipoles within the electrolyte create an internal electric field that promotes lithium‐salt dissociation and facilitates rapid, decoupled, and directional Li‐ion transport. The optimized OE‐FSE exhibits exceptional electrochemical stability up to 5.2 V and liquid‐like ionic conductivity of 5.39 mS cm −1 at room temperature. Consequently, LRMO||Li coin cell shows a capacity of up to 160.4 mAh/g at a high rate of 10 C with a capacity retention of 81.3% after 280 cycles. LRMO||graphite solid‐state pouch cells achieve a long cycle life of up to 700 cycles and exhibit significantly reduced voltage decay, while LRMO||Li metal pouch cells with an energy density of 502 Wh kg −1 retain 80% of capacity after 70 cycles. This work establishes molecular‐scale ferroelectric ordering as a powerful paradigm for regulating bulk ion transport and interfacial electrochemistry, paving the way for next‐generation, high‐energy solid‐state batteries.