Study of the Na Storage Mechanism in Silicon Oxycarbide—Evidence for Reversible Silicon Redox Activity

Advanced anode materials with high electrochemical performance are necessary for the development of competitive sodium-ion batteries. Much attention is focussed on materials that undergo a reversible alloying reaction with sodium and thus possess high capacities. Silicon-based compounds are interesting candidates for anode materials, but only show a relatively low electrochemical performance with sodium. Controversial reports are available about the electrochemical interaction between Na and silicon, which encouraged us to investigate the sodium-storage mechanism in a silicon-based material in detail. Here, we report the result of a systematic investigation of the electrochemical sodium ion storage process in silicon oxycarbide supported by ex-situ X-ray photoelectron spectroscopy (XPS) and magic-angle spinning nuclear magnetic resonance (MAS NMR). The comparison of the pristine and HF-etched silicon oxycarbide shows that the silicon is active, but not via an alloying process. Instead, the results reveal an irreversible structural change and amorphization of SiCO upon the initial sodium uptake and support the existence of reversible conversion and insertion-based reactions afterwards. Submitted: 19.01.2018 *Corresp. authors: E-mail: stefano.passerini@kit.edu; daniel.buchholz@kit.edu

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