Lithium Species in Electrochemically Lithiated and Delithiated Silicon Oxycarbides

摘要

The work described herein deals with efforts to make a persuasive correlation between structural characteristics and electrochemical lithium storage for a silicon oxycarbide prepared from poly(methylhydrogensiloxane) and divinylben- zene. Structural characterization reveals that the silicon oxycarbide includes excess free carbon in an amorphous network. The reversibility of lithiation and delithiation in the silicon oxycarbide reaches 74% between 0.005 and 3 V relative to lithium at the first cycle but falls to only ca. 30% between 0.4 and 3 V, We found two resonances at 0 and 2.4 ppm in the ~7Li magic angle spinning nuclear magnetic resonance spectrum of the silicon oxycarbide lithiated to 0.4 V, whose contributions are 67 and 33%, respectively, and thus are in good agreement with the reversibility observed between 0.4 and 3 V. The fully lithiated silicon oxycarbide shows a single resonance at ca. 3-9 ppm, which tends to broaden at lower temperatures to -120 °C, whereas the fully delithiated silicon oxycarbide has a single resonance at 0 ppm. These results indicate that both reversible and irreversible lithium species have ionic natures. The Li K edge in electron energy loss spectroscopy does not show clearly any identified near-edge fine structures in the inner part of the silicon oxycarbide after delithiation. Near the surface, on the other hand, LiF and oxygen- and phosphorus-containing compounds were found to be the major constituents of a solid electrolyte interface (SEI) layer. Over repeated lithiation and delithiation, the SEI layer appears to become thick, which should in part trigger capacity fading.