(Battery Division Early Career Award Sponsored by Neware Technology Limited) Understanding Interfacial Mechanisms that Govern Performance in Solid-State Batteries

Abstract

Solid-state batteries offer the promise of improved energy density and safety compared to lithium-ion batteries. Here, I will present our emerging understanding of the key differences between how high-capacity anode materials behave in solid-state batteries compared to in conventional liquid-electrolyte batteries. The electro-chemo-mechanical evolution of materials at solid-solid electrochemical interfaces is different than at solid/liquid interfaces, and contact evolution in particular plays a critical role in determining the behavior of solid-state batteries. I will focus on mechanisms governing lithium metal anodes (including lithium in the “anode-free” configuration) and alloy anodes. Lithium metal anodes in solid-state batteries are intrinsically limited by void formation during stripping and dendrite growth during plating. Anode-free solid-state batteries, in which there is no initial lithium metal at the anode interface, offer extremely high energy density, but there is a lack of understanding of how their behavior differs from excess-lithium electrodes. Using X-ray tomography, cryo-FIB, and finite-element modeling, we show that anode-free solid-state batteries are intrinsically limited by current concentrations at the end of stripping due to localized lithium depletion. This causes accelerated short circuiting compared to lithium-excess cells. Based on these results, the beneficial influence of metal alloy interfacial layers on controlling lithium evolution and mitigating contact loss from localized lithium depletion, including at low stack pressures, will be discussed. X-ray tomography is further shown to be particularly useful in observing the dynamic evolution of lithium metal, including void formation and filament growth. The second part of the talk focuses on alloy anodes. Alloy anodes typically exhibit fast capacity decay in lithium-ion batteries because of excessive solid-electrolyte interphase growth. We show that alloy anodes in solid-state batteries can exhibit improved interfacial stability and enhanced cyclability. Furthermore, in situ measurement of stack pressure evolution during cycling shows that the volume changes of alloy anodes can lead to large pressure swings within the cell, giving insight into electrode composite evolution. Based on these insights, we present a new design for dense foil alloy anodes. This design offers a paradigm that does away with slurry coating, potentially reducing manufacturing costs. Taken together, these findings show the importance of controlling chemo-mechanics and interfaces in solid-state batteries for improved energy storage capabilities.