Li Distribution Heterogeneity in Solid Electrolyte Li₁₀GeP₂S₁₂ upon Electrochemical Cycling Probed by ⁷Li MRI

All-solid-state rechargeable batteries embody the promise for high energy density, increased stability, and improved safety. However, their success is impeded by high resistance for mass and charge transfer at electrode–electrolyte interfaces. Li deficiency has been proposed as a major culprit for interfacial resistance, yet experimental evidence is elusive due to the challenges associated with noninvasively probing the Li distribution in solid electrolytes. In this Letter, three-dimensional ⁷Li magnetic resonance imaging (MRI) is employed to examine Li distribution homogeneity in solid electrolyte Li₁₀GeP₂S₁₂ within symmetric Li/Li₁₀GeP₂S₁₂/Li batteries. ⁷Li MRI and the derived histograms reveal Li depletion from the electrode–electrolyte interfaces and increased heterogeneity of Li distribution upon electrochemical cycling. Significant Li loss at interfaces is mitigated via facile modification with a poly­(ethylene oxide)/bis­(trifluoromethane)­sulfonimide Li salt thin film. This study demonstrates a powerful tool for noninvasively monitoring the Li distribution at the interfaces and in the bulk of all-solid-state batteries as well as a convenient strategy for improving interfacial stability.