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DOI	10.1039/d0ee03765f
	Towards controlling the reversibility of anionic redox in transition metal oxides for high-energy Li-ion positive electrodes
	Yu Y.; Karayaylali P.; Sokaras D.; Giordano L.; Kou R.; Sun C.-J.; Maglia F.; Jung R.; Gittleson F.S.; Shao-Horn Y.
发表日期	2021
ISSN	17545692
起始页码	2322
结束页码	2334
卷号	14 期号:4
英文摘要	Anionic redox in positive electrode materials in Li-ion batteries provides an additional redox couple besides conventional metal redox, which can be harvested to further boost the energy density of current Li-ion batteries. However, the requirement for the reversible anionic redox activity remains under debate, hindering the rational design of new materials with reversible anionic redox. In this work, we employed differential electrochemical mass spectrometry (DEMS) to monitor the release of oxygen and to quantify the reversibility of the anionic redox of Li2Ru0.75M0.25O3 (M = Ti, Cr, Mn, Fe, Ru, Sn, Pt, Ir) upon first charge. X-ray absorption spectroscopy, coupled with density functional theory (DFT) calculations, show that various substituents have a minimal effect on the nominal metal redox, yet more ionic substituents and reduced metal-oxygen covalency introduce irreversible oxygen redox, accompanied with easier distortion of the M-O octahedron and a smaller barrier for forming an oxygen dimer within the octahedron. Therefore, a strong metal-oxygen covalency is needed to enhance the reversible oxygen redox. We proposed an electron-phonon-coupled descriptor for the reversibility of oxygen redox, laying the foundation for high-throughput screening of novel materials that enable reversible anionic redox activity. This journal is © The Royal Society of Chemistry.
英文关键词	Density functional theory; Design for testability; Drug products; Electrodes; Ions; Mass spectrometry; Oxygen; Phonons; Redox reactions; Transition metal oxides; Transition metals; X ray absorption spectroscopy; Conventional metals; Differential electrochemical mass spectrometry; Electron phonon; High throughput screening; Novel materials; Positive electrode materials; Positive electrodes; Rational design; Lithium-ion batteries; electrochemical method; electrode; energy; oxide; redox conditions; transition element; Varanidae
语种	英语
来源期刊	Energy & Environmental Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/190692
作者单位	Department of Materials Science and Engineering, MIT, Cambridge, MA 02139, United States; Department of Mechanical Engineering, MIT, Cambridge, MA 02139, United States; SLAC National Accelerator Laboratory, Menlo Park, CA 94025, United States; Research Laboratory of Electronics, MIT, Cambridge, MA 02139, United States; Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439, United States; BMW Group, Petuelring 130, Munich, 80788, Germany; BMW Group Technology Office USA, 2606 Bayshore Parkway, Mountain View, CA 94043, United States
推荐引用方式 GB/T 7714	Yu Y.,Karayaylali P.,Sokaras D.,et al. Towards controlling the reversibility of anionic redox in transition metal oxides for high-energy Li-ion positive electrodes[J],2021,14(4).
APA	Yu Y..,Karayaylali P..,Sokaras D..,Giordano L..,Kou R..,...&Shao-Horn Y..(2021).Towards controlling the reversibility of anionic redox in transition metal oxides for high-energy Li-ion positive electrodes.Energy & Environmental Science,14(4).
MLA	Yu Y.,et al."Towards controlling the reversibility of anionic redox in transition metal oxides for high-energy Li-ion positive electrodes".Energy & Environmental Science 14.4(2021).