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Nickel, Manganese, and Cobalt Dissolution from Ni-Rich NMC and Their Effects on NMC622-Graphite Cells

Journal of the Electrochemical Society(2019)SCI 3区

Tech Univ Munich | BMW Grp | Univ Amsterdam

Cited 250|Views18
Abstract
Transition metal dissolution from the cathode active material and its deposition on the anode causes significant cell aging, studied most intensively for manganese. Owing to their higher specific energy, the current focus is shifting towards nickel-rich layered LiNixMnyCozO2 (NMC, x + y + z = 1) with x > 0.5, so that the effect of Ni dissolution on cell degradation needs to be understood. This study investigates the dissolution of transition metals from a NMC622 cathode and their subsequent deposition on a graphite anode using operando X-ray absorption spectroscopy. We show that in NMC622-graphite cells transition metals dissolve nearly stoichiometrically at potentials > 4.6 V, highlighting the significance of investigating Ni dissolution/deposition. Using NMC622-graphite full-cells with electrolyte containing the bis(trifluoromethane) sulfonimide (TFSI) salts of either Ni, Mn, or Co, we compare the detrimental impact of these metals on cell performance. Using in-situ and ex-situ XRD, we show that the aging mechanism induced by all three metals is the loss of cycleable lithium in the solid electrolyte interface (SEI) of the graphite. This loss is larger in magnitude when Mn is present in the electrolyte compared to Ni and Co, which we ascribe to a higher activity of deposited Mn towards SEI decomposition in comparison to Ni and Co. (C) The Author(s) 2019. Published by ECS.
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要点】:本文研究了富镍NMC622正极材料中过渡金属(镍、锰、钴)的溶解及其对NMC622-石墨电池性能的影响,发现锰的沉积对电池性能的负面影响最大。

方法】:作者使用原位X射线吸收光谱技术研究了过渡金属的溶解和沉积过程,并利用X射线衍射技术分析了不同金属对电池老化机制的影响。

实验】:通过使用含有镍、锰、钴TFSI盐的电解质的NMC622-石墨全电池进行实验,发现所有三种金属都会导致石墨电极固体电解质界面(SEI)中可循环锂的损失,其中锰对SEI的分解活性最高,导致电池性能下降最严重。