Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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:
 [1]; ORCiD logo [2];  [1];  [3];  [2]; ORCiD logo [4]; ORCiD logo [3];  [5]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. Chinese Academy of Sciences (CAS), Beijing (China)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Stanford Univ., Stanford, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1463350
Alternate Identifier(s):
OSTI ID: 1478360
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231
Resource Type:
Accepted Manuscript
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
Subject:
25 ENERGY STORAGE

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.
Copy to clipboard
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. https://doi.org/10.1038/s41467-018-05172-x
Copy to clipboard
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. https://doi.org/10.1038/s41467-018-05172-x. https://www.osti.gov/servlets/purl/1463350.
Copy to clipboard
@article{osti_1463350,
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},
number = 1,
volume = 9,
place = {United States},
year = {Wed Jul 18 00:00:00 EDT 2018},
month = {Wed Jul 18 00:00:00 EDT 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1038/s41467-018-05172-x
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 47 works
Citation information provided by
Web of Science

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
All figures and tables (5 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Nonequilibrium Pathways during Electrochemical Phase Transformations in Single Crystals Revealed by Dynamic Chemical Imaging at Nanoscale Resolution
journal, December 2014

  • Yu, Young-Sang; Kim, Chunjoong; Liu, Yijin
  • Advanced Energy Materials, Vol. 5, Issue 7
  • DOI: 10.1002/aenm.201402040

Sodiation Kinetics of Metal Oxide Conversion Electrodes: A Comparative Study with Lithiation
journal, August 2015

Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials
journal, March 2018

Electrochemical stiffness in lithium-ion batteries
journal, August 2016

  • Tavassol, Hadi; Jones, Elizabeth M. C.; Sottos, Nancy R.
  • Nature Materials, Vol. 15, Issue 11
  • DOI: 10.1038/nmat4708

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016

  • Luo, Kun; Roberts, Matthew R.; Hao, Rong
  • Nature Chemistry, Vol. 8, Issue 7
  • DOI: 10.1038/nchem.2471

Mesoscale Phase Distribution in Single Particles of LiFePO 4 following Lithium Deintercalation
journal, April 2013

  • Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm400106k

A study of room-temperature LixMn1.5Ni0.5O4 solid solutions
journal, January 2015

  • Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep08027

Structural Transformations in High-Capacity Li 2 Cu 0.5 Ni 0.5 O 2 Cathodes
journal, March 2017

Ideal charge-density-wave order in the high-field state of superconducting YBCO
journal, December 2016

  • Jang, H.; Lee, W. -S.; Nojiri, H.
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 51
  • DOI: 10.1073/pnas.1612849113

3D elemental sensitive imaging using transmission X-ray microscopy
journal, February 2012

  • Liu, Yijin; Meirer, Florian; Wang, Junyue
  • Analytical and Bioanalytical Chemistry, Vol. 404, Issue 5
  • DOI: 10.1007/s00216-012-5818-9

Transformations and Decomposition of MnCO3 at Earth's Lower Mantle Conditions
journal, December 2016

Phase Change of Nickel Phosphide Catalysts in the Conversion of Cellulose into Sorbitol
journal, April 2012

Lithium Electrochemical Deintercalation from O2-LiCoO[sub 2]
journal, January 2002

  • Carlier, D.; Saadoune, I.; Ménétrier, M.
  • Journal of The Electrochemical Society, Vol. 149, Issue 10
  • DOI: 10.1149/1.1503075

Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles
journal, August 2016

Sodium Promoter Inducing a Phase Change in a Palladium Catalyst
journal, October 2012

  • Seriani, Nicola
  • The Journal of Physical Chemistry C, Vol. 116, Issue 43
  • DOI: 10.1021/jp308051v

Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li x FePO 4
journal, June 2015

Visualization and Quantification of Electrochemical and Mechanical Degradation in Li Ion Batteries
journal, October 2013

Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes
journal, June 2014

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials
journal, April 2018

Calculation of a phase diagram for the lithium oxide-aluminum oxide (LiO0.5-AlO1.5) system
journal, September 1979

  • Byker, Harlan J.; Eliezer, Isaac.; Eliezer, Naomi.
  • The Journal of Physical Chemistry, Vol. 83, Issue 18
  • DOI: 10.1021/j100481a009

Understanding the Degradation Mechanisms of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Material in Lithium Ion Batteries
journal, August 2013

  • Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun
  • Advanced Energy Materials, Vol. 4, Issue 1
  • DOI: 10.1002/aenm.201300787

Persistent State-of-Charge Heterogeneity in Relaxed, Partially Charged Li 1− x Ni 1/3 Co 1/3 Mn 1/3 O 2 Secondary Particles
journal, May 2016

  • Gent, William E.; Li, Yiyang; Ahn, Sungjin
  • Advanced Materials, Vol. 28, Issue 31
  • DOI: 10.1002/adma.201601273

Structural phase transformations in metallic grain boundaries
journal, May 2013

  • Frolov, Timofey; Olmsted, David L.; Asta, Mark
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2919

Reactivity and acidity of Li in lithium aluminum oxide (LiAlO2) phases
journal, January 1993

Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy
journal, February 2017

  • Kuppan, Saravanan; Xu, Yahong; Liu, Yijin
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14309

Transitions from Near-Surface to Interior Redox upon Lithiation in Conversion Electrode Materials
journal, January 2015

  • He, Kai; Xin, Huolin L.; Zhao, Kejie
  • Nano Letters, Vol. 15, Issue 2
  • DOI: 10.1021/nl5049884

Correlating Structural Changes and Gas Evolution during the Thermal Decomposition of Charged Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials
journal, January 2013

  • Bak, Seong-Min; Nam, Kyung-Wan; Chang, Wonyoung
  • Chemistry of Materials, Vol. 25, Issue 3
  • DOI: 10.1021/cm303096e

Tracking Non-Uniform Mesoscale Transport in LiFePO 4 Agglomerates During Electrochemical Cycling
journal, May 2015

  • Nelson Weker, Johanna; Li, Yiyang; Shanmugam, Rengarajan
  • ChemElectroChem, Vol. 2, Issue 10
  • DOI: 10.1002/celc.201500119

Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes
journal, September 2014

  • Li, Yiyang; El Gabaly, Farid; Ferguson, Todd R.
  • Nature Materials, Vol. 13, Issue 12
  • DOI: 10.1038/nmat4084

Thermal Stability and Structural Changes of Li4Mn5O12under Oxygen and Nitrogen Atmosphere
journal, January 1996

  • Takada, Toshimi; Hayakawa, Hiroshi; Kumagai, Toshiya
  • Journal of Solid State Chemistry, Vol. 121, Issue 1
  • DOI: 10.1006/jssc.1996.0012

Phase transitions of LiAlO2 at high pressure and high temperature
journal, August 2008

Structural Changes and Thermal Stability of Charged LiNi x Mn y Co z O 2 Cathode Materials Studied by Combined In Situ Time-Resolved XRD and Mass Spectroscopy
journal, December 2014

  • Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 24
  • DOI: 10.1021/am506712c

Phase evolution for conversion reaction electrodes in lithium-ion batteries
journal, February 2014

  • Lin, Feng; Nordlund, Dennis; Weng, Tsu-Chien
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4358

Visualization of anisotropic-isotropic phase transformation dynamics in battery electrode particles
journal, August 2016

  • Wang, Jiajun; Karen Chen-Wiegart, Yu-chen; Eng, Christopher
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12372

Probing three-dimensional sodiation–desodiation equilibrium in sodium-ion batteries by in situ hard X-ray nanotomography
journal, June 2015

  • Wang, Jiajun; Eng, Christopher; Chen-Wiegart, Yu-chen Karen
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8496

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014

  • Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4529

Visualization of electrochemically driven solid-state phase transformations using operando hard X-ray spectro-imaging
journal, April 2015

  • Li, Linsen; Chen-Wiegart, Yu-chen Karen; Wang, Jiajun
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7883

In operando tracking phase transformation evolution of lithium iron phosphate with hard X-ray microscopy
journal, August 2014

  • Wang, Jiajun; Chen-Wiegart, Yu-chen Karen; Wang, Jun
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5570

Mesoscale Phase Distribution in Single Particles of $LiFePO_{4}$ following Lithium Deintercalation
text, January 2013

  • Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/desy-2014-01931

Persistent State-of-Charge Heterogeneity in Relaxed, Partially Charged Li 1− x Ni 1/3 Co 1/3 Mn 1/3 O 2 Secondary Particles
journal, May 2016

  • Gent, William E.; Li, Yiyang; Ahn, Sungjin
  • Advanced Materials, Vol. 28, Issue 31
  • DOI: 10.1002/adma.201601273

Nonequilibrium Pathways during Electrochemical Phase Transformations in Single Crystals Revealed by Dynamic Chemical Imaging at Nanoscale Resolution
journal, December 2014

  • Yu, Young-Sang; Kim, Chunjoong; Liu, Yijin
  • Advanced Energy Materials, Vol. 5, Issue 7
  • DOI: 10.1002/aenm.201402040

Tracking Non-Uniform Mesoscale Transport in LiFePO 4 Agglomerates During Electrochemical Cycling
journal, May 2015

  • Nelson Weker, Johanna; Li, Yiyang; Shanmugam, Rengarajan
  • ChemElectroChem, Vol. 2, Issue 10
  • DOI: 10.1002/celc.201500119

Phase Change of Nickel Phosphide Catalysts in the Conversion of Cellulose into Sorbitol
journal, April 2012

Phase transitions of LiAlO2 at high pressure and high temperature
journal, August 2008

Structural Transformations in High-Capacity Li 2 Cu 0.5 Ni 0.5 O 2 Cathodes
journal, March 2017

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials
journal, April 2018

Correlating Structural Changes and Gas Evolution during the Thermal Decomposition of Charged Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials
journal, January 2013

  • Bak, Seong-Min; Nam, Kyung-Wan; Chang, Wonyoung
  • Chemistry of Materials, Vol. 25, Issue 3
  • DOI: 10.1021/cm303096e

Reactivity and acidity of Li in lithium aluminum oxide (LiAlO2) phases
journal, January 1993

Calculation of a phase diagram for the lithium oxide-aluminum oxide (LiO0.5-AlO1.5) system
journal, September 1979

  • Byker, Harlan J.; Eliezer, Isaac.; Eliezer, Naomi.
  • The Journal of Physical Chemistry, Vol. 83, Issue 18
  • DOI: 10.1021/j100481a009

Sodium Promoter Inducing a Phase Change in a Palladium Catalyst
journal, October 2012

  • Seriani, Nicola
  • The Journal of Physical Chemistry C, Vol. 116, Issue 43
  • DOI: 10.1021/jp308051v

Transitions from Near-Surface to Interior Redox upon Lithiation in Conversion Electrode Materials
journal, January 2015

  • He, Kai; Xin, Huolin L.; Zhao, Kejie
  • Nano Letters, Vol. 15, Issue 2
  • DOI: 10.1021/nl5049884

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016

  • Luo, Kun; Roberts, Matthew R.; Hao, Rong
  • Nature Chemistry, Vol. 8, Issue 7
  • DOI: 10.1038/nchem.2471

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014

  • Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4529

In operando tracking phase transformation evolution of lithium iron phosphate with hard X-ray microscopy
journal, August 2014

  • Wang, Jiajun; Chen-Wiegart, Yu-chen Karen; Wang, Jun
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5570

Probing three-dimensional sodiation–desodiation equilibrium in sodium-ion batteries by in situ hard X-ray nanotomography
journal, June 2015

  • Wang, Jiajun; Eng, Christopher; Chen-Wiegart, Yu-chen Karen
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8496

Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes
journal, September 2014

  • Li, Yiyang; El Gabaly, Farid; Ferguson, Todd R.
  • Nature Materials, Vol. 13, Issue 12
  • DOI: 10.1038/nmat4084

Electrochemical stiffness in lithium-ion batteries
journal, August 2016

  • Tavassol, Hadi; Jones, Elizabeth M. C.; Sottos, Nancy R.
  • Nature Materials, Vol. 15, Issue 11
  • DOI: 10.1038/nmat4708

A study of room-temperature LixMn1.5Ni0.5O4 solid solutions
journal, January 2015

  • Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep08027

Persistence of Jahn-Teller Distortion up to the Insulator to Metal Transition in LaMnO 3
journal, February 2011

Morphology of Critical Nuclei in Solid-State Phase Transformations
journal, June 2007

Visualization and Quantification of Electrochemical and Mechanical Degradation in Li Ion Batteries
journal, October 2013

Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes
journal, June 2014

Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles
journal, August 2016

Transformations and Decomposition of MnCO3 at Earth's Lower Mantle Conditions
journal, December 2016

Structural phase transformations in metallic grain boundaries
text, January 2012

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Deciphering the Cathode-Electrolyte Interfacial Chemistry in Sodium Layered Cathode Materials
    journal, October 2018

    Quantification of Heterogeneous Degradation in Li‐Ion Batteries
    journal, May 2019

    Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes
    journal, January 2020

    Chemomechanical behaviors of layered cathode materials in alkali metal ion batteries
    journal, January 2018

    • Xu, Zhengrui; Rahman, Muhammad Mominur; Mu, Linqin
    • Journal of Materials Chemistry A, Vol. 6, Issue 44
    • DOI: 10.1039/c8ta06875e

    Thermally driven mesoscale chemomechanical interplay in Li 0.5 Ni 0.6 Mn 0.2 Co 0.2 O 2 cathode materials
    journal, January 2018

    • Wei, Chenxi; Zhang, Yan; Lee, Sang-Jun
    • Journal of Materials Chemistry A, Vol. 6, Issue 45
    • DOI: 10.1039/c8ta08973f

    Probing and quantifying cathode charge heterogeneity in Li ion batteries
    journal, January 2019

    • Zhang, Yuxin; Yang, Zhijie; Tian, Chixia
    • Journal of Materials Chemistry A, Vol. 7, Issue 41
    • DOI: 10.1039/c9ta06977a

    Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries
    journal, January 2020

    • Teichert, Philipp; Eshetu, Gebrekidan Gebresilassie; Jahnke, Hannes
    • Batteries, Vol. 6, Issue 1
    • DOI: 10.3390/batteries6010008

    TOPAS and TOPAS-Academic : an optimization program integrating computer algebra and crystallographic objects written in C++
    journal, February 2018

    Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries
    text, January 2020

    • Teichert, Philipp; Eshetu, Gebrekidan Gebresilassie; Jahnke, Hannes
    • RWTH Aachen University
    • DOI: 10.18154/rwth-2020-04543

    NIR-II fluorescence microscopic imaging of cortical vasculature in non-human primates
    journal, January 2020

    • Cai, Zhaochong; Zhu, Liang; Wang, Mengqi
    • Theranostics, Vol. 10, Issue 9
    • DOI: 10.7150/thno.43533
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Fig. 1 (p. 3)figure
      Fig. 2 (p. 4)figure
      Fig. 3 (p. 4)figure
      Fig. 4 (p. 5)figure
      Fig. 5 (p. 5)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: