Non-Faradaic Li⁺ Migration and Chemical Coordination across Solid-State Battery Interfaces

Efficient and reversible charge transfer is essential to realizing high-performance solid-state batteries. Efforts to enhance charge transfer at critical electrode-electrolyte interfaces have proven successful, yet interfacial chemistry and its impact on cell function remains poorly understood. Using X-ray photoelectron spectroscopy combined with electrochemical techniques, we elucidate chemical coordination near the LiCoO₂-LIPON interface, providing experimental validation of space-charge separation. Space-charge layers, defined by local enrichment and depletion of charges, have previously been theorized and modeled, but the unique chemistry of solid-state battery interfaces is now revealed. Here we highlight the non-Faradaic migration of Li⁺ ions from the electrode to the electrolyte, which reduces reversible cathodic capacity by ∼15%. Inserting a thin, ion-conducting LiNbO₃ interlayer between the electrode and electrolyte, however, can reduce space-charge separation, mitigate the loss of Li⁺ from LiCoO₂, and return cathodic capacity to its theoretical value. This work illustrates the importance of interfacial chemistry in understanding and improving solid-state batteries.