Fingerprint oxygen redox reactions in batteries through high-efficiency mapping of resonant inelastic X-ray scattering (mRIXS)

Abstract: Realizing reversible reduction-oxidation (Redox) reactions of lattice oxygen in batteries is a promising way to improve the energy and power density. However, conventional oxygen absorption spectroscopy fails to distinguish the critical oxygen chemistry in oxide-based battery electrodes. Therefore, high-efficiency full-range mapping of resonant inelastic X-ray scattering (mRIXS) has been developed as a reliable probe of oxygen redox reactions. Here, based on mRIXS results collected from a series of Li1.17Ni0.21Co0.08Mn0.54O2 electrodes at different electrochemical states and its comparison with peroxides, we provide a comprehensive analysis of five components observed in the mRIXS results. While almost all the components change upon electrochemical cycling, comparison with peroxide species show that only two evolving features correspond to the critical oxidized oxygen states. One is a specific feature at 531.0eV excitation and 523.7eV emission energy, the other is a low-energy loss feature. We show that both features evolve with electrochemical cycling of Li1.17Ni0.21Co0.08Mn0.54O2 electrodes, and could be used for characterizing oxygen redox states in battery electrodes. This work is the first benchmark for a complete assignment of all the important mRIXS features collected from battery materials, which provides guidelines for future studies in characterization, analysis and theoretical calculation for probing and understanding oxygen redox reactions.