Physical Theory of Voltage Fade in Lithium- and Manganese-Rich Transition Metal Oxides

Rinaldo, Steven G.; Gallagher, Kevin G.; Long, Brandon R.; Croy, Jason R.; Bettge, Martin; Abraham, Daniel P.; Bareno, Javier; Dees, Dennis W.

doi:10.1149/2.0181506jes

Physical Theory of Voltage Fade in Lithium- and Manganese-Rich Transition Metal Oxides

Journal Article · Tue Mar 03 23:00:00 EST 2015 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.0181506jes· OSTI ID:1339136

Rinaldo, Steven G. ^[1]; Gallagher, Kevin G. ^[1]; Long, Brandon R. ^[1]; Croy, Jason R. ^[1]; Bettge, Martin ^[1]; Abraham, Daniel P. ^[1]; Bareno, Javier ^[1]; Dees, Dennis W. ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division

Lithium- and manganese-rich (LMR) transition metal oxide cathodes are of interest for lithium-ion battery applications due to their increased energy density and decreased cost. However, the advantages in energy density and cost are offset, in part, due to the phenomena of voltage fade. Specifically, the voltage profiles (voltage as a function of capacity) of LMR cathodes transform from a high energy configuration to a lower energy configuration as they are repeatedly charged (Li removed) and discharged (Li inserted). Here, we propose a physical model of voltage fade that accounts for the emergence of a low voltage Li phase due to the introduction of transition metal ion defects within a parent Li phase. The phenomenological model was re-cast in a general form and experimental LMR charge profiles were de-convoluted to extract the evolutionary behavior of various components of LMR capacitance profiles. Evolution of the voltage fade component was found to follow a universal growth curve with a maximal voltage fade capacity of ≈ 20% of the initial total capacity.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1339136

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 6 Vol. 162; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials Radin, Maxwell D.; Vinckeviciute, Julija; Seshadri, Ram Nature Energy, Vol. 4, Issue 8 https://doi.org/10.1038/s41560-019-0439-6	journal	July 2019
Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes Eum, Donggun; Kim, Byunghoon; Kim, Sung Joo Nature Materials, Vol. 19, Issue 4 https://doi.org/10.1038/s41563-019-0572-4	journal	January 2020
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