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Title: Dynamic imaging of metastable reaction pathways in lithiated cobalt oxide electrodes

Abstract

Understanding how lithium-ion batteries function down to the atomic level during charge and discharge cycling can provide valuable guidance to optimize structure-property relationships and to design and understand new electrode materials. Lithium insertion and reactions with the electrodes during charge and discharge cycling can occur via metastable structures with complex ordering and related non-equilibrium phenomena. Remarkably, these processes remain still poorly understood despite their significance in the operation of lithium battery systems in critical technologies. In this communication, we present the dynamics of lithium insertion into Co3O4 and the evolution of metastable phases as probed by in-situ transmission electron microscopy, in concert with first principles density functional theory calculations. We show that the initial lithium intercalation reaction occurs with the formation of several metastable and intermediate phases, followed by a sequence of conversion reactions that perturb and expand the cubic-close-packed oxygen array, ultimately generating an end-product of finely dispersed cobalt metal clusters within a Li2O matrix. The calculated non-equilibrium lithiation pathways corroborate with the experimental lithiation voltages, and explain the significant hysteresis that occurs during electrochemical cycling. The data provide new insights into the complexity of solid state lithium electrochemistry in metal oxides that are relevant to advancing lithium batterymore » technology.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technology; USDOE Office of Science - Energy Frontier Research Center - Center for Electrochemical Energy Science (CEES)
OSTI Identifier:
1473688
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 44; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
DFT calculation; conversion reaction electrode; in-situ lithiation; in-situ transmission electron microscopy; lithium-ion battery; metastable phase transformations

Citation Formats

Li, Qianqian, Wu, Jinsong, Yao, Zhenpeng, Xu, Yaobin, Thackeray, Michael M., Wolverton, Chris, and Dravid, Vinayak P. Dynamic imaging of metastable reaction pathways in lithiated cobalt oxide electrodes. United States: N. p., 2018. Web. doi:10.1016/j.nanoen.2017.11.052.
Li, Qianqian, Wu, Jinsong, Yao, Zhenpeng, Xu, Yaobin, Thackeray, Michael M., Wolverton, Chris, & Dravid, Vinayak P. Dynamic imaging of metastable reaction pathways in lithiated cobalt oxide electrodes. United States. https://doi.org/10.1016/j.nanoen.2017.11.052
Li, Qianqian, Wu, Jinsong, Yao, Zhenpeng, Xu, Yaobin, Thackeray, Michael M., Wolverton, Chris, and Dravid, Vinayak P. 2018. "Dynamic imaging of metastable reaction pathways in lithiated cobalt oxide electrodes". United States. https://doi.org/10.1016/j.nanoen.2017.11.052.
@article{osti_1473688,
title = {Dynamic imaging of metastable reaction pathways in lithiated cobalt oxide electrodes},
author = {Li, Qianqian and Wu, Jinsong and Yao, Zhenpeng and Xu, Yaobin and Thackeray, Michael M. and Wolverton, Chris and Dravid, Vinayak P.},
abstractNote = {Understanding how lithium-ion batteries function down to the atomic level during charge and discharge cycling can provide valuable guidance to optimize structure-property relationships and to design and understand new electrode materials. Lithium insertion and reactions with the electrodes during charge and discharge cycling can occur via metastable structures with complex ordering and related non-equilibrium phenomena. Remarkably, these processes remain still poorly understood despite their significance in the operation of lithium battery systems in critical technologies. In this communication, we present the dynamics of lithium insertion into Co3O4 and the evolution of metastable phases as probed by in-situ transmission electron microscopy, in concert with first principles density functional theory calculations. We show that the initial lithium intercalation reaction occurs with the formation of several metastable and intermediate phases, followed by a sequence of conversion reactions that perturb and expand the cubic-close-packed oxygen array, ultimately generating an end-product of finely dispersed cobalt metal clusters within a Li2O matrix. The calculated non-equilibrium lithiation pathways corroborate with the experimental lithiation voltages, and explain the significant hysteresis that occurs during electrochemical cycling. The data provide new insights into the complexity of solid state lithium electrochemistry in metal oxides that are relevant to advancing lithium battery technology.},
doi = {10.1016/j.nanoen.2017.11.052},
url = {https://www.osti.gov/biblio/1473688}, journal = {Nano Energy},
issn = {2211-2855},
number = C,
volume = 44,
place = {United States},
year = {Thu Feb 01 00:00:00 EST 2018},
month = {Thu Feb 01 00:00:00 EST 2018}
}