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Revisiting the Mechanism Behind Transition-Metal Dissolution from Delithiated LiNixMnyCozO2 (NMC) Cathodes

Journal Article · · Journal of the Electrochemical Society (Online)
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  1. Argonne National Lab. (ANL), Lemont, IL (United States)
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Dissolution of transition metals (TMs) from lithium-ion battery cathodes under high-voltage conditions is a major issue affecting battery performance that is not well understood mechanistically. Here, this phenomenon is studied by chemically aging pristine and charged LiNi0.5Mn0.3Co0.2O2 (NMC532) cathodes in the presence of different solutions. The solution composition was varied by 1) adding water to a standard electrolyte, 2) replacing LiPF6 salt with lithium acetylacetonate (Li-acac), 3) and/or adding oxidatively unstable tris(2,2,2-trifluoroethyl) phosphite (TTFP) as an electrolyte additive. Our results demonstrate that while TM dissolution from pristine NMC532 cathodes is dominated by HF-attack, TM dissolution from charged NMC532 cathodes is affected by many other factors apart from HF-attack. We suggest that reduction of TMs due to chemical/electrochemical oxidation of the electrolyte at cathode/electrolyte interface, followed by formation of soluble TM-complexes with concomitant Li+ intercalation into the cathode, is the dominant mechanism of TM-dissolution at high voltage.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1607632
Journal Information:
Journal of the Electrochemical Society (Online), Journal Name: Journal of the Electrochemical Society (Online) Journal Issue: 2 Vol. 167; ISSN 1945-7111
Publisher:
IOP PublishingCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
lithium-ion battery
transition metal dissolution