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Title: Electrochemomechanical Fatigue: Decoupling Mechanisms of Fracture-Induced Performance Degradation in Li XMn 2O 4

Abstract

Decades of Li-ion battery (LIB) research have identified mechanical and chemical culprits that limit operational lifetime of LIB electrodes. For example, severe capacity fade of unmodified Li XMn 2O 4 electrodes has been linked historically with Mn dissolution and, more recently, fracture of the electrochemically active particles. Mitigation approaches targeting both effects have prolonged cycle and calendar life, but the fundamental mechanistic sequences linking fracture to capacity fade in Li XMn 2O 4 and many other cathode materials remain ambiguous. Here, we investigate specifically the temporal correlations of fracture, capacity fade, and impedance growth to gain understanding of the interplay between these phenomena and the time scales over which they occur. By conducting controlled excursions into the cubic-tetragonal phase transformation regime of Li XMn 2O 4, we find that fracture contributes to impedance growth and capacity fade by two distinct mechanisms occurring over different time scales: (1) poorly conducting crack surfaces immediately hinder electronic conduction through the bulk of the electrode, and (2) capacity fades at a faster rate over multiple cycles, due plausibly to dissolution reactions occurring at newly formed electrode-electrolyte interfaces. The deconvolution of these effects in a well-studied cathode material such as Li XMn 2O 4 facilitatesmore » understanding of the complex relationship between mechanics and electrochemistry in LIB electrodes.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science & Engineering
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1464291
Alternate Identifier(s):
OSTI ID: 1509863
Grant/Contract Number:  
SC0002633; DMR-1419807
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 11; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; electrochemomechanical; fatigue; Li-ion battery

Citation Formats

McGrogan, Frank P., Raja, Shilpa N., Chiang, Yet-Ming, and Van Vliet, Krystyn J.. Electrochemomechanical Fatigue: Decoupling Mechanisms of Fracture-Induced Performance Degradation in LiXMn2O4. United States: N. p., 2018. Web. doi:10.1149/2.0191811jes.
McGrogan, Frank P., Raja, Shilpa N., Chiang, Yet-Ming, & Van Vliet, Krystyn J.. Electrochemomechanical Fatigue: Decoupling Mechanisms of Fracture-Induced Performance Degradation in LiXMn2O4. United States. doi:10.1149/2.0191811jes.
McGrogan, Frank P., Raja, Shilpa N., Chiang, Yet-Ming, and Van Vliet, Krystyn J.. Sat . "Electrochemomechanical Fatigue: Decoupling Mechanisms of Fracture-Induced Performance Degradation in LiXMn2O4". United States. doi:10.1149/2.0191811jes.
@article{osti_1464291,
title = {Electrochemomechanical Fatigue: Decoupling Mechanisms of Fracture-Induced Performance Degradation in LiXMn2O4},
author = {McGrogan, Frank P. and Raja, Shilpa N. and Chiang, Yet-Ming and Van Vliet, Krystyn J.},
abstractNote = {Decades of Li-ion battery (LIB) research have identified mechanical and chemical culprits that limit operational lifetime of LIB electrodes. For example, severe capacity fade of unmodified LiXMn2O4 electrodes has been linked historically with Mn dissolution and, more recently, fracture of the electrochemically active particles. Mitigation approaches targeting both effects have prolonged cycle and calendar life, but the fundamental mechanistic sequences linking fracture to capacity fade in LiXMn2O4 and many other cathode materials remain ambiguous. Here, we investigate specifically the temporal correlations of fracture, capacity fade, and impedance growth to gain understanding of the interplay between these phenomena and the time scales over which they occur. By conducting controlled excursions into the cubic-tetragonal phase transformation regime of LiXMn2O4, we find that fracture contributes to impedance growth and capacity fade by two distinct mechanisms occurring over different time scales: (1) poorly conducting crack surfaces immediately hinder electronic conduction through the bulk of the electrode, and (2) capacity fades at a faster rate over multiple cycles, due plausibly to dissolution reactions occurring at newly formed electrode-electrolyte interfaces. The deconvolution of these effects in a well-studied cathode material such as LiXMn2O4 facilitates understanding of the complex relationship between mechanics and electrochemistry in LIB electrodes.},
doi = {10.1149/2.0191811jes},
journal = {Journal of the Electrochemical Society},
issn = {0013-4651},
number = 11,
volume = 165,
place = {United States},
year = {2018},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1149/2.0191811jes

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Works referenced in this record:

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