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Conversion/alloy active materials, such as ZnO, are one of the most promising candidates to replace graphite anodes in lithium-ion batteries. Besides a high specific capacity (qZnO = 987 mAh g-1), ZnO offers a high lithium-ion diffusion and fast reaction kinetics, leading to a high-rate capability, which is required for the intended fast charging of battery electric vehicles. However, lithium-ion storage in ZnO is accompanied by the formation of lithium-rich solid electrolyte interphase (SEI) layers, immense volume expansion, and a large voltage hysteresis. Nonetheless, ZnO is appealing as an anode material for lithium-ion batteries and is investigated intensively. Surprisingly, the conclusions reported on the reaction mechanism are contradictory and the formation and composition of the SEI are addressed in only a few works. In this work, we investigate lithiation, delithiation, and SEI formation with ZnO in ether-based electrolytes for the first time reported in the literature. The combination of operando and ex situ experiments (cyclic voltammetry, X-ray photoelectron spectroscopy, X-ray diffraction, coupled gas chromatography and mass spectrometry, differential electrochemical mass spectrometry, and scanning electron microscopy) clarifies the misunderstanding of the reaction mechanism. We evidence that the conversion and alloy reaction take place simultaneously inside the bulk of the electrode. Furthermore, we show that a two-layered SEI is formed on the surface. The SEI is decomposed reversibly upon cycling. In the end, we address the issue of the volume expansion and associated capacity fading by incorporating ZnO into a mesoporous carbon network. This approach reduces the capacity fading and yields cells with a specific capacity of above 500 mAh g-1 after 150 cycles.

Li-S cells can have high gravimetric energy densities above 300 Wh kg−1 when the electrodes and cell components are optimized. Low electrolyte/sulfur mass ratios or more generallly, the relative amount of electrolyte in a Li-S cell have an especially high impact on the achievable gravimetric energy density. A negative side effect of low electrolyte/sulfur ratios are low cycle numbers due to electrolyte decomposition and the possibility that electrolyte becomes inaccessible at the lithium metal anode when the lithium becomes more and more porous during cycling. Electrode thickness measurements were performed during cycling for various cell chemistries such as lithium-sulfur (Li-S) with different cathode sulfur loadings and porosities, lithium-hard carbon (Li-HC), lithium-silicon (Li-Si), prelithiated HC-sulfur (LiHC-S), prelithiated Si-sulfur (LiSi-S) and Li-ion. The thickness measurements provided information about mechanical stress and irreversible thickness changes. The thickness measurements also helped to explain different electrolyte decomposition behavior and they can be used to discuss the impact of thickness changes on gas analysis. The electrolyte decomposition of the Li-S standard electrolyte based on lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in dimethoxyethane (DME): dioxolane (DIOX) with LiNO3 was examined by online mass spectrometry (MS) within Li-S, Li-HC, Li-Si, LiSi-S and LiHC-S cells. Several electrolyte decomposition products were verified by post-mortem gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) of Li-S cells with cycled electrolyte.