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
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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