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Title: Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials

Abstract

© 2018 The Author(s). Redox phase transformations are relevant to a number of metrics pertaining to the electrochemical performance of batteries. These phase transformations deviate from and are more complicated than the conventional theory of phase nucleation and propagation, owing to simultaneous changes of cationic and anionic valence states as well as the polycrystalline nature of battery materials. Herein, we propose an integrative approach of mapping valence states and constructing chemical topographies to investigate the redox phase transformation in polycrystalline layered oxide cathode materials under thermal abuse conditions. We discover that, in addition to the three-dimensional heterogeneous phase transformation, there is a mesoscale evolution of local valence curvatures in valence state topographies. The relative probability of negative and positive local valence curvatures alternates during the layered-to-spinel/rocksalt phase transformation. The implementation of our method can potentially provide a universal approach to study phase transformation behaviors in battery materials and beyond.

Authors:
; ORCiD logo; ; ; ; ORCiD logo; ORCiD logo; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1478360
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English

Citation Formats

Mu, Linqin, Yuan, Qingxi, Tian, Chixia, Wei, Chenxi, Zhang, Kai, Liu, Jin, Pianetta, Piero, Doeff, Marca M., Liu, Yijin, and Lin, Feng. Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials. United States: N. p., 2018. Web. doi:10.1038/s41467-018-05172-x.
Mu, Linqin, Yuan, Qingxi, Tian, Chixia, Wei, Chenxi, Zhang, Kai, Liu, Jin, Pianetta, Piero, Doeff, Marca M., Liu, Yijin, & Lin, Feng. Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials. United States. doi:10.1038/s41467-018-05172-x.
Mu, Linqin, Yuan, Qingxi, Tian, Chixia, Wei, Chenxi, Zhang, Kai, Liu, Jin, Pianetta, Piero, Doeff, Marca M., Liu, Yijin, and Lin, Feng. Wed . "Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials". United States. doi:10.1038/s41467-018-05172-x. https://www.osti.gov/servlets/purl/1478360.
@article{osti_1478360,
title = {Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials},
author = {Mu, Linqin and Yuan, Qingxi and Tian, Chixia and Wei, Chenxi and Zhang, Kai and Liu, Jin and Pianetta, Piero and Doeff, Marca M. and Liu, Yijin and Lin, Feng},
abstractNote = {© 2018 The Author(s). Redox phase transformations are relevant to a number of metrics pertaining to the electrochemical performance of batteries. These phase transformations deviate from and are more complicated than the conventional theory of phase nucleation and propagation, owing to simultaneous changes of cationic and anionic valence states as well as the polycrystalline nature of battery materials. Herein, we propose an integrative approach of mapping valence states and constructing chemical topographies to investigate the redox phase transformation in polycrystalline layered oxide cathode materials under thermal abuse conditions. We discover that, in addition to the three-dimensional heterogeneous phase transformation, there is a mesoscale evolution of local valence curvatures in valence state topographies. The relative probability of negative and positive local valence curvatures alternates during the layered-to-spinel/rocksalt phase transformation. The implementation of our method can potentially provide a universal approach to study phase transformation behaviors in battery materials and beyond.},
doi = {10.1038/s41467-018-05172-x},
journal = {Nature Communications},
issn = {2041-1723},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:

Figures / Tables:

Fig. 1 Fig. 1: Direct visualization of the changing Ni valence state in Li0.4Ni0.4Mn0.4Co0.2O2 polycrystalline ensembles upon in situ heating. a The histogram of the local valence states of Ni (represented by the Ni K-edge X-ray absorption spectroscopy (XAS) absorption edge) over the entire field of view, with the heating pattern shownmore » in the inset. b–e The maps of the Ni valence states observed in situ, which are color coded to the local Ni valence state as indicated by the color map to the right of (e). The Ni valence states are represented by the Ni K-edge XAS absorption edge, where a higher energy and a lower edge energy represent a higher and a lower Ni valence states, respectively« less

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