Revisiting the Mechanism Behind Transition-Metal Dissolution from Delithiated LiNixMnyCozO2 (NMC) Cathodes
Abstract
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.
- Authors:
-
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
- OSTI Identifier:
- 1607632
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the Electrochemical Society (Online)
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society (Online); Journal Volume: 167; Journal Issue: 2; Journal ID: ISSN 1945-7111
- Publisher:
- IOP Publishing
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; lithium-ion battery; transition metal dissolution
Citation Formats
Sahore, Ritu, O’Hanlon, Daniel C., Tornheim, Adam, Lee, Chang-Wook, Garcia, Juan C., Iddir, Hakim, Balasubramanian, Mahalingam, and Bloom, Ira. Revisiting the Mechanism Behind Transition-Metal Dissolution from Delithiated LiNixMnyCozO2 (NMC) Cathodes. United States: N. p., 2020.
Web. doi:10.1149/1945-7111/ab6826.
Sahore, Ritu, O’Hanlon, Daniel C., Tornheim, Adam, Lee, Chang-Wook, Garcia, Juan C., Iddir, Hakim, Balasubramanian, Mahalingam, & Bloom, Ira. Revisiting the Mechanism Behind Transition-Metal Dissolution from Delithiated LiNixMnyCozO2 (NMC) Cathodes. United States. https://doi.org/10.1149/1945-7111/ab6826
Sahore, Ritu, O’Hanlon, Daniel C., Tornheim, Adam, Lee, Chang-Wook, Garcia, Juan C., Iddir, Hakim, Balasubramanian, Mahalingam, and Bloom, Ira. Thu .
"Revisiting the Mechanism Behind Transition-Metal Dissolution from Delithiated LiNixMnyCozO2 (NMC) Cathodes". United States. https://doi.org/10.1149/1945-7111/ab6826. https://www.osti.gov/servlets/purl/1607632.
@article{osti_1607632,
title = {Revisiting the Mechanism Behind Transition-Metal Dissolution from Delithiated LiNixMnyCozO2 (NMC) Cathodes},
author = {Sahore, Ritu and O’Hanlon, Daniel C. and Tornheim, Adam and Lee, Chang-Wook and Garcia, Juan C. and Iddir, Hakim and Balasubramanian, Mahalingam and Bloom, Ira},
abstractNote = {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.},
doi = {10.1149/1945-7111/ab6826},
journal = {Journal of the Electrochemical Society (Online)},
number = 2,
volume = 167,
place = {United States},
year = {2020},
month = {1}
}
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