Interfacial self-healing polymer electrolytes for Long-Cycle silicon anodes in High-Performance solid-state lithium batteries.

An in-situ integrated electrode/self-healable polymer electrolyte for ultra-long cycling life in all-solid-state Si-based lithium batteries, driven by the incorporation of multiple dynamic bonds. [Display omitted] • Integration of Si anode/self-healing polymer electrolyte by in situ polymerization. • The Li+ environment was studied by experimental and theoretical calculation. • The electrolyte has high ionic conductivity and wide electrochemical window. • The Si-SHDSE|SHDSE|LCO-SHDSE pouch cells prototype with ultra-long cycling life. For all-solid-state lithium-ion batteries (ASSLIBs), silicon (Si) stands out as an appealing anodes material due to its high energy density and improved safety compared to lithium metal. However, the substantial volume changes during cycling result in poor solid-state physical contact and electrolyte–electrode interface issues, leading to unsatisfactory electrochemical performance. In this study, we employed in-situ polymerization to construct an integrated Si anodes/self-healing polymer electrolyte for ASSLIBs. The polymer chain reorganization stems from numerous dynamic bonds in the constructed self-healing dynamic supermolecular elastomer electrolyte (SHDSE) molecular structure. Notably, SHDSE also serves as a Si anodes binder with enhanced adhesive capability. As a result, the well-structured Li|SHDSE|Si-SHDSE cell generates subtle electrolyte–electrode interface contacts at the molecular level, which can offer a continuous and stable Li+ transport pathway, reduce Si particle displacement, and mitigate electrode volume expansion. This further enhances cyclic stability (>500 cycles with 68.1 % capacity retention and >99.8 % Coulombic efficiency). More practically, the 2.0 Ah wave-shaped Si||LiCoO 2 soft-pack battery with in-situ cured SHDSE exhibits strongly stabilized electrochemical performance (1.68 Ah after 700 cycles, 86.2 % capacity retention) in spite of a high operating temperatures up to 100 °C and in various bending tests. This represents a groundbreaking report in flexible solid-state soft-pack batteries containing Si anodes. [ABSTRACT FROM AUTHOR]