Advances in intrinsically self-healing solid polymer electrolytes for lithiumion batteries. Review article.

Abstract The demand for high safety and long cycle life of lithium-ion batteries has driven in-depth research on solid polymer electrolytes (SPEs), but the problem of mechanical damage has severely limited their practical applications. Intrinsic self-healing SPEs provide innovative solutions for healing micro cracks and inhibiting dendrite growth, enabling dynamic network reconfiguration capabilities. In this paper, we systematically review the design strategies and research progress of self-healing SPEs: SPEs based on supramolecular interactions (e.g., quadruple hydrogen bonds achieving >95% healing efficiency within 1–60 min at room temperature); SPEs based on dynamic covalent bonds (e.g., imine bonds enabling ionic conductivities up to 7.48 × 10 –4 S cm –1 ); and synergistic design strategies combining dynamic covalent bonds with supra-molecular interactions. Critical limitations persist, including low intrinsic ionic conductivity (10 –4 S cm –1 without plasticizers) impeding fast charging, unresolved trade-offs between mechanical strength (>10 MPa) and healing efficiency (>95%), along with unverified scalable manufacturing and long-term stability under extreme conditions such as high voltage or bending. Future research should prioritize cross-scale co-design of dynamic networks, develop intelligent sensing and adaptive healing systems, and advance engineering manufacturing processes. These developments will facilitate the transformation of self-healing SPEs from fundamental research to practical high-safety, long-lifespan energy storage devices.