标题：High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions
作者：Dai, Kehua; Wu, Jinpeng; Zhuo, Zengqing; Li, Qinghao; Sallis, Shawn; Mao, Jing; Ai, Guo; Sun, Chihang; Li, Zaiyuan; Gent, William E. 更多 作者机构：[Dai, Kehua; Sun, Chihang; Li, Zaiyuan] Northeastern Univ, Sch Met, Shenyang 110819, Liaoning, Peoples R China.; [Dai, Kehua; Wu, Jinpeng; Zhuo, Zen 更多
通讯作者：Liu, Gao;Yang, WL;Liu, G
通讯作者地址：[Yang, WL]Lawrence Berkeley Natl Lab, Adv Light Source, Berkeley, CA 94720 USA;[Liu, G]Lawrence Berkeley Natl Lab, Energy Storage & Distributed Resour 更多
关键词：anionic redox reaction; cathode material; layered oxide; Li-ion battery; Li-rich material; mapping of resonant inelastic X-ray scattering (mRIXS); Na-ion battery; quantification; reversibility of oxygen redox; soft X-ray spectroscopy
摘要：The reversibility and cyclability of anionic redox in battery electrodes hold the key to its practical employments. Here, through mapping of resonant inelastic X-ray scattering (mRIXS), we have independently quantified the evolving redox states of both cations and anions in Na2/3Mg1/3Mn2/3O2. The bulk Mn redox emerges from initial discharge and is quantified by inverse partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn activities likely lead to the voltage fade. O-K super-partial fluorescence yield (sPFY) analysis of mRIXS shows 79% lattice oxygen redox reversibility during the initial cycle, with 87% capacity sustained after 100 cycles. In Li1.17Ni0.21Co0.08Mn0.54O2, lattice oxygen redox is 76% initial-cycle reversible but with only 44% capacity retention after 500 cycles. These results unambiguously show the high reversibility of lattice oxygen redox in both Li-ion and Na-ion systems. The contrast between Na2/3Mg1/3Mn2/3O2 and Li1.17Ni0.21Co0.08Mn0.54O2 systems suggests the importance of distinguishing lattice oxygen redox from other oxygen activities for clarifying its intrinsic properties.