In Situ Cross-linked 3D Composite Polymer Electrolytes Utilizing Ferroelectric Nanoparticle-Incorporated Nanowebs for Advanced Solid-State Lithium Batteries

All-solid-state lithium-metal batteries (ASSLBs) employing solid polymer electrolytes offer high energy density and intrinsic safety; however, their practical deployment is severely hindered by low room-temperature ionic conductivity, narrow electrochemical windows, and uncontrolled lithium dendrite growth. To address these fundamental macromolecular and interfacial limitations, this study presents a scalable structural design strategy. We synthesize 3D composite solid polymer electrolytes (3DCSPEs) by embedding electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) 3D nanowebs—functionalized with ferroelectric nanoparticles—into a poly(ethylene oxide) (PEO)-based matrix via in situ crosslinking polymerization.
From a macromolecular perspective, the in situ crosslinked network effectively suppresses polymer crystallization and macro-phase separation, thereby promoting amorphous chain segment mobility to accelerate ion transport kinetics. Concurrently, the nanoparticle-functionalized 3D nanoweb serves as a mechanically robust framework that establishes continuous, low-resistance pathways for Li⁺ flux. Notably, the spontaneous polarization induced by the embedded ferroelectric nanoparticles effectively regulates the local electric field within the polymer matrix, mitigating space-charge layer formation and enhancing charge-transfer kinetics at the electrolyte–electrode interface. This synergistic architectural modulation promotes uniform lithium deposition and significantly reduces interfacial overpotential. Consequently, this work highlights the critical role of in situ crosslinked, ferroelectric-reinforced 3D polymer networks in enhancing both bulk transport kinetics and interfacial stability, offering a promising paradigm for advanced lithium polymer batteries.