气候变化领域集成服务门户(CCPortal): Deconvolution of intermixed redox processes in Ni-based cation-disordered Li-excess cathodes

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DOI	10.1039/d0ee03526b
	Deconvolution of intermixed redox processes in Ni-based cation-disordered Li-excess cathodes
	Huang T.-Y.; Crafton M.J.; Yue Y.; Tong W.; McCloskey B.D.
发表日期	2021
ISSN	17545692
起始页码	1553
结束页码	1562
卷号	14 期号:3
英文摘要	Cation-disordered rock-salt transition-metal oxides and oxyfluorides (DRX) have emerged as promising cathode materials for Li-ion batteries due to their potential to reach high energy densities and accommodate diverse, lower cost transition-metal chemistries compared to conventional layered oxide materials. However, the intricate local coordination environment in DRX also results in complex electrochemical electron transfer involving parallel mechanisms of transition-metal (TM) redox and oxygen (anionic) redox. Without decoupled and quantitative information of these intermixed redox processes, the origin of irreversibility, voltage hysteresis, and capacity fading is obscured, impeding the development of strategies to address these issues. Here we deconvolute the mixed redox processes in a Ni-based DRX, Li1.15Ni0.45Ti0.3Mo0.1O1.85F0.15, by combining 18O isotopic enrichment, differential electrochemical mass spectrometry (DEMS), and ex situ acid titration. The summation of TM-redox and oxygen-redox capacities measured through our approach agrees with the net electron transfer measured by the potentiostat. This study reveals much less Ni oxidation efficiency (59.5%) than its initially designed efficiency (100%) due to competition of oxygen redox, which can occur at potentials as low as 4.1 V (vs. Li/Li+). We propose that the chemical approach presented in this work and its future extension can resolve and quantify various mixed redox processes in different DRX, which allows clear correlations among material design, deconvoluted redox capacities, and battery performance. © 2021 The Royal Society of Chemistry.
英文关键词	Cathodes; Coordination reactions; Electron transitions; Electron transport properties; Lithium-ion batteries; Mass spectrometry; Mechanisms; Oxygen; Positive ions; Transition metal oxides; Voltage regulators; Differential electrochemical mass spectrometry; Electrochemical electron; High energy densities; Isotopic enrichment; Oxidation efficiency; Parallel mechanisms; Quantitative information; Transition metal chemistry; Transition metals; cation; deconvolution; electrode; nickel; redox conditions
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/190741
作者单位	Department of Chemical and Biomolecular Engineering, University of California-Berkeley, Berkeley, CA 94720, United States; Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, United States
推荐引用方式 GB/T 7714	Huang T.-Y.,Crafton M.J.,Yue Y.,et al. Deconvolution of intermixed redox processes in Ni-based cation-disordered Li-excess cathodes[J],2021,14(3).
APA	Huang T.-Y.,Crafton M.J.,Yue Y.,Tong W.,&McCloskey B.D..(2021).Deconvolution of intermixed redox processes in Ni-based cation-disordered Li-excess cathodes.Energy & Environmental Science,14(3).
MLA	Huang T.-Y.,et al."Deconvolution of intermixed redox processes in Ni-based cation-disordered Li-excess cathodes".Energy & Environmental Science 14.3(2021).