Transformations at interfaces between solid-state electrolytes (SSEs) and lithium metal electrodes can lead to high impedance and capacity decay during cycling of solid-state batteries, but the links between structural/chemical/mechanical evolution of interfaces and electrochemistry are not well understood. Here, we use in situ X-ray computed tomography to reveal the evolution of mechanical damage within a Li1+x Al x Ge2–x (PO4)3 (LAGP) SSE caused by interphase growth during electrochemical cycling. The growth of an interphase with expanded volume drives fracture in this material, and the extent of fracture during cycling is found to be the primary factor causing the impedance increase, as opposed to the resistance of the interphase itself. Cracks are observed to initiate near the edge of the lithium/LAGP interface, which agrees with simulations. The chemomechanical effects of interphase growth studied here are expected to play a role in a variety of SSE materials, and this work is a step toward designing durable interfaces.

Despite progress in solid-state battery engineering, our understanding of the chemo-mechanical phenomena that govern electrochemical behavior and stability at solid-solid interfaces remains limited compared to solid-liquid interfaces. Here, we use operando synchrotron X-ray computed microtomography to investigate the evolution of lithium/solid-state electrolyte interfaces during battery cycling, revealing how the complex interplay between void formation, interphase growth, and volumetric changes determines cell behavior. Void formation during lithium stripping is directly visualized in symmetric cells, and the loss of contact at the interface between lithium and the solid-state electrolyte (Li 10 SnP 2 S 12) is found to be the primary cause of cell failure. Reductive interphase formation within the solid-state electrolyte is simultaneously observed, and image segmentation reveals that the interphase is redox-active upon charge. At the cell level, we postulate that global volume changes and loss of stack pressure occur due to partial molar volume mismatches at either electrode. These results provide new insight into how chemo-mechanical phenomena can impact cell performance, which is necessary to understand for the development of solid-state batteries. File list (2) download file view on ChemRxiv Manuscript Updated.pdf (1.08 MiB) download file view on ChemRxiv Supplementary Information.pdf (1.02 MiB)

The interfaces between many solid-state electrolytes (SSEs) and lithium metal are (electro)­chemically unstable, and improved understanding of how interfacial transformations influence electrochemical degradation is necessary to stabilize these interfaces and therefore enable a wider range of viable SSEs for batteries. Here, the (electro)­chemical reaction processes that occur at the interface between Li1.4Al0.4Ge1.6(PO4)3 (LAGP) electrolyte and lithium are studied using in situ transmission electron microscopy and ex situ techniques. The reaction of lithium with LAGP causes amorphization and volume expansion, which induce mechanical stress and fracture of the SSE along with a massive increase in impedance. The evolved interphase has a nonuniform morphology at high currents, which causes accelerated chemo-mechanical failure. This work demonstrates that the current-dependent nature of the reaction at the SSE/Li interface plays a crucial role in determining chemo-mechanical degradation mechanisms, with implications for understanding and controlling degradation in a wide variety of SSE materials with unstable interfaces.

No abstract

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.