All-solid-state lithium ion batteries may become long-term, stable, high-performance energy storage systems for the next generation of electric vehicles and consumer electronics, depending on the compatibility of electrode materials and suitable solid electrolytes. Nickel-rich layered oxides are nowadays the benchmark cathode materials for conventional lithium ion batteries because of their high storage capacity and the resulting high energy density, and their use in solid-state systems is the next necessary step. In this study, we present the successful implementation of a Li­[Ni,Co,Mn]­O2 material with high nickel content (LiNi0.8Co0.1Mn0.1O2, NCM-811) in a bulk-type solid-state battery with β-Li3PS4 as a sulfide-based solid electrolyte. We investigate the interface behavior at the cathode and demonstrate the important role of the interface between the active materials and the solid electrolyte for the battery performance. A passivating cathode/electrolyte interphase layer forms upon charging and leads to an irreversible first cycle capacity loss, corresponding to a decomposition of the sulfide electrolyte. In situ electrochemical impedance spectroscopy and X-ray photoemission spectroscopy are used to monitor this formation. We demonstrate that most of the interphase formation takes place in the first cycle, when charging to potentials above 3.8 V vs Li+/Li. The resulting overvoltage of the passivating layer is a detrimental factor for capacity retention. In addition to the interfacial decomposition, the chemomechanical contraction of the active material upon delithiation causes contact loss between the solid electrolyte and active material particles, further increasing the interfacial resistance and capacity loss. These results highlight the critical role of (electro-)­chemo-mechanical effects in solid-state batteries.

The very high ionic conductivity of Li10GeP2S12 (LGPS) makes it a potential solid electrolyte for lithium all-solid-state batteries. Besides the high ionic conductivity, another key requirement is the stability of the solid electrolyte against degradation reactions with the electrodes; here, we analyze the reaction of LGPS with lithium metal. In situ X-ray photoelectron spectroscopy (XPS), in combination with time-resolved electrochemical measurements offers detailed information on the chemical reactions at the Li/LGPS interface. The decomposition of Li10GeP2S12 leads to the formation of an interphase composed of Li3P, Li2S, and Li–Ge alloy, which is in perfect agreement with theoretical predictions, and an increase of the interfacial resistance. These results highlight the necessity to perform long-term, time-resolved electrochemical measurements when evaluating potential new solid electrolytes for solid-state batteries. The kinetics of this interphase growthcomparable to SEI formation on lithium anodes in liquid electrolytesseems to be governed by diffusion across the interphase, as a square root time dependence is observed.

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All-solid-state lithium-ion batteries have the potential to become an important class of next-generation electrochemical energy storage devices. However, for achieving competitive performance, a better understanding of the interfacial processes at the electrodes is necessary for optimized electrode compositions to be developed. In this work, the interfacial processes between the solid electrolyte (LiGePS) and the electrode materials (In/InLi and LiCoO) are monitored using impedance spectroscopy and galvanostatic cycling, showing a large resistance contribution and kinetic hindrance at the metal anode. The effect of different fractions of the solid electrolyte in the composite cathodes on the rate performance is tested. The results demonstrate the necessity of a carefully designed composite microstructure depending on the desired applications of an all-solid-state battery. While a relatively low mass fraction of solid electrolyte is sufficient for high energy density, a higher fraction of solid electrolyte is required for high power density.

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