Glassy/ceramic Li${}_2$TiO${}_3$/Li${}_x$B${}_y$O${}_z$ analogous 'solid electrolyte interphase' to boost 4.5 V LiCoO${}_2$ in sulfide-based all-solid-state batteries

Sulfide-based all-solid-state lithium-ion batteries (ASSLIBs) are the widely recognized approach toward high safety owing to excellent ionic conductivity and nonflammable nature of solid-state electrolytes (SSEs). However, narrow potential window of SSEs brings about serious interfacial parasitic reactions, resulting in fast degradation of the battery. Herein, a glassy/ceramic analogous solid electrolyte interface (SEI) is constructed on LiCoO${}_2$ (LCO) to enhance interfacial stability between LCO and the Li${}_{10}$GeP${}_2$S${}_{12}$ (LGPS) SSEs. In which, ceramic Li${}_2$TiO${}_3$ guarantees good mechanical toughness of analogous SEI, while glassy LixByOz reinforces the coverage to avoid parasitic reactions. Analogous SEI endows ASSLIBs with excellent cycling and rate performance under an upper charge voltage of 4.3 V with 82.3% capacity retention after 300 cycles at 0.2 C. When pushing charge voltage to 4.5 V, analogous SEI also enables desirable performance with an initial capacity of 172.7 mAh g${}^{-1}$ and long lifespan of 200 cycles at 0.2 C. Both experiments and theoretical computation reveal excellent stability between analogous SEI and LGPS, which endows ASSLIBs with small polarization and improved performance. This work provides an insight on glassy/ceramic analogous SEI strategy to boost the interfacial stability of ASSLIBs. (© 2023 Wiley‐VCH GmbH)