Electrochemical Lithiation/Delithiation of ZnO in 3D-Structured Electrodes: Elucidating the Mechanism and the Solid Electrolyte Interphase Formation

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 (q(ZnO) = 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.

Automated summary

Active materials like ZnO show promise as a replacement for graphite anodes in lithium-ion batteries, offering high lithium-ion diffusion and rapid reaction kinetics. However, research on the reaction mechanisms and solid electrolyte interphase formation in ZnO remains contradictory and limited. This study presents findings on lithiation, delithiation, and SEI formation with ZnO in ether-based electrolytes, clarifying the misunderstanding of the reaction mechanism and revealing simultaneous conversion and alloy reactions in the electrode bulk, as well as the formation of a double-layered SEI on the surface.