How Metallic Protection Layers Extend the Lifetime of NASICON-Based Solid-State Lithium Batteries

The use of solid-state electrolytes (SSEs) within batteries is a promising strategy to safely access the high capacity of lithium metal anodes. However, most SSEs with practical ionic conductivity are chemically unstable in contact with lithium metal, which is detrimental to battery performance. Lithium aluminum germanium phosphate (LAGP) is an SSE with high ionic conductivity (10⁻⁴-10⁻³ S cm⁻¹) and good environmental stability, but it forms an amorphous interphase region that continuously grows in contact with Li, leading to chemo-mechanical failure within solid-state batteries. Here, we find that thin (∼30 nm) chromium interlayers deposited between the lithium electrode and LAGP extend cycle life to over 1000 h at moderate current densities (0.1–0.2 mA cm⁻²), compared to ∼30 h without protection. This significantly improved stability occurs because the metallic interlayer alters the trajectory of interphase formation and the nature of the electrochemical reaction at the interface. This work shows the promise of interface engineering for a variety of SSE materials within solid-state batteries, while emphasizing the necessity of understanding how protection layers affect dynamic evolution of interfaces.