High-Performance Solid-State Lithium Batteries via Dipole-Matching: Enabling Compact Polymer Microstructure and Stable Interfaces

Abstract

Solid polymer electrolytes (SPEs) show great promise for solid-state lithium metal batteries but face challenges due to inherently slow ion transport and interfacial instability. In this work, we propose a dipole-matching strategy to engineer an SPE with a compact microstructure and stabilized interfaces. Through combined theoretical and experimental studies, we identify a molecular additive, such as 3,5-bis(trifluoromethyl)benzoic acid (N-CFF), that promotes rapid and uniform nucleation and directs phase alignment via dipole interactions with polymer chains, resulting in a compact microstructure conducive to rapid lithium-ion transport and homogeneous deposition. Simultaneously, the dipole-matched N-CFF creates an electron-rich environment that facilitates the formation of a LiF-rich solid electrolyte interphase, effectively suppressing lithium dendrite growth. Employing this strategy, we fabricate Li||LiFePO₄ solid-state batteries that deliver ultra-long cycle life (90% capacity retention after 3000 cycles), exceptional low-temperature and rate performance, as well as improved thermal safety. This work offers a comprehensive interface and microstructure co-design approach to promote the development and application of high-performance solid-state batteries.

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