Oxide electrolyte-driven interphase reconfiguration enables durable solid-liquid hybrid lithium batteries

Lithium batteries with Ni-rich cathodes promise high energy density, yet deep delithiation triggers coupled chemo-mechanical degradation, including interfacial reactions, phase reconstruction, and crack propagation. Conventional coatings mainly passivate the outermost surface, leaving lattice instability unresolved. Here we introduce a solid electrolyte-driven interphase reconfiguration strategy by conformally coating LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) with a nanolayer of Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP). Beyond serving as a Li⁺-conductive, chemically stable surface, LATP releases Al³⁺ into NCM811 to form an endogenous interphase and a chemo-mechanically reinforced lattice. Al-O multicenter bonding and band hybridization stabilize the lattice-oxygen framework, dynamically buffering oxygen over-oxidation and enabling suppressed oxygen release without structural collapse. Nonmagnetic Al³⁺ further suppresses Li/Ni cation disorder, improving Li⁺ transport homogeneity and Ni³⁺/Ni⁴⁺ redox reversibility. Advanced single-particle 3D nano-tomography (TXM nano-CT coupled with spatially resolved XANES) reconstructs particles to correlate valence evolution with morphology, showing suppressed valence heterogeneity and crack-initiating strain localization. Consequently, the interphase-reconfigured NCM811 delivers 402 Wh kg^–1 in Li pouch cells and sustains 1200 cycles in 8.7 Ah pouch cells paired with Si-C anodes at a lean electrolyte level of 2.0 g Ah⁻¹. This work elevates interface engineering from passivation to an ionically active route for tuning redox-mechanics coupling in Ni-rich cathodes for high-energy-density batteries.