Dynamic imaging of metastable reaction pathways in lithiated cobalt oxide electrodes

Li, Qianqian; Wu, Jinsong; Yao, Zhenpeng; Xu, Yaobin; Thackeray, Michael M.; Wolverton, Chris; Dravid, Vinayak P.

doi:10.1016/j.nanoen.2017.11.052

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

Journal Article · Thu Feb 01 00:00:00 EST 2018 · Nano Energy

DOI:https://doi.org/10.1016/j.nanoen.2017.11.052· OSTI ID:1478403

Li, Qianqian ^[1]; Wu, Jinsong ^[2]; Yao, Zhenpeng ^[3]; Xu, Yaobin ^[3]; Thackeray, Michael M. ^[4]; Wolverton, Chris ^[3]; Dravid, Vinayak P. ^[2]

Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering and NUANCE Center; Shanghai Univ. (China). Materials Genome Inst.
Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering and NUANCE Center
Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
Argonne National Lab. (ANL), Argonne, IL (United States). Electrochemical Energy Storage Dept.

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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: AC02-06CH11357; AC02-05CH11231; NNCI-1542205; DMR-1121262

OSTI ID:: 1478403

Journal Information:: Nano Energy, Vol. 44, Issue C; ISSN 2211-2855

Country of Publication:: United States

Language:: English

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