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

Abstract

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.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1339136
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 162; Journal Issue: 6; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; degradation; intercalation; lithium ion

Citation Formats

Rinaldo, Steven G., Gallagher, Kevin G., Long, Brandon R., Croy, Jason R., Bettge, Martin, Abraham, Daniel P., Bareno, Javier, and Dees, Dennis W. Physical Theory of Voltage Fade in Lithium- and Manganese-Rich Transition Metal Oxides. United States: N. p., 2015. Web. doi:10.1149/2.0181506jes.
Rinaldo, Steven G., Gallagher, Kevin G., Long, Brandon R., Croy, Jason R., Bettge, Martin, Abraham, Daniel P., Bareno, Javier, & Dees, Dennis W. Physical Theory of Voltage Fade in Lithium- and Manganese-Rich Transition Metal Oxides. United States. https://doi.org/10.1149/2.0181506jes
Rinaldo, Steven G., Gallagher, Kevin G., Long, Brandon R., Croy, Jason R., Bettge, Martin, Abraham, Daniel P., Bareno, Javier, and Dees, Dennis W. 2015. "Physical Theory of Voltage Fade in Lithium- and Manganese-Rich Transition Metal Oxides". United States. https://doi.org/10.1149/2.0181506jes. https://www.osti.gov/servlets/purl/1339136.
@article{osti_1339136,
title = {Physical Theory of Voltage Fade in Lithium- and Manganese-Rich Transition Metal Oxides},
author = {Rinaldo, Steven G. and Gallagher, Kevin G. and Long, Brandon R. and Croy, Jason R. and Bettge, Martin and Abraham, Daniel P. and Bareno, Javier and Dees, Dennis W.},
abstractNote = {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.},
doi = {10.1149/2.0181506jes},
url = {https://www.osti.gov/biblio/1339136}, journal = {Journal of the Electrochemical Society},
issn = {0013-4651},
number = 6,
volume = 162,
place = {United States},
year = {Wed Mar 04 00:00:00 EST 2015},
month = {Wed Mar 04 00:00:00 EST 2015}
}

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Cited by: 25 works
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Works referenced in this record:

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Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes
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Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials
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Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes
journal, January 2020