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

Mu, Linqin; Yuan, Qingxi; Tian, Chixia; Wei, Chenxi; Zhang, Kai; Liu, Jin; Pianetta, Piero; Doeff, Marca M.; Liu, Yijin; Lin, Feng

doi:10.1038/s41467-018-05172-x

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

Journal Article · Wed Jul 18 00:00:00 EDT 2018 · Nature Communications

DOI:https://doi.org/10.1038/s41467-018-05172-x· OSTI ID:1463350

Mu, Linqin ^[1];

^[2]; Tian, Chixia ^[1]; Wei, Chenxi ^[3]; Zhang, Kai ^[2];

^[4];

^[3]; Doeff, Marca M. ^[5];

^[3];

^[1]

Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Chinese Academy of Sciences (CAS), Beijing (China)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Stanford Univ., Stanford, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

© 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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-76SF00515; AC02-05CH11231

OSTI ID:: 1463350

Alternate ID(s):: OSTI ID: 1478360

Journal Information:: Nature Communications, Vol. 9, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 47 works

Citation information provided by
Web of Science

References (47)

Nonequilibrium Pathways during Electrochemical Phase Transformations in Single Crystals Revealed by Dynamic Chemical Imaging at Nanoscale Resolution Yu, Young-Sang; Kim, Chunjoong; Liu, Yijin Advanced Energy Materials, Vol. 5, Issue 7 https://doi.org/10.1002/aenm.201402040	journal	December 2014
Sodiation Kinetics of Metal Oxide Conversion Electrodes: A Comparative Study with Lithiation He, Kai; Lin, Feng; Zhu, Yizhou Nano Letters, Vol. 15, Issue 9 https://doi.org/10.1021/acs.nanolett.5b01709	journal	August 2015
Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials Tian, Chixia; Xu, Yahong; Nordlund, Dennis Joule, Vol. 2, Issue 3 https://doi.org/10.1016/j.joule.2017.12.008	journal	March 2018
Electrochemical stiffness in lithium-ion batteries Tavassol, Hadi; Jones, Elizabeth M. C.; Sottos, Nancy R. Nature Materials, Vol. 15, Issue 11 https://doi.org/10.1038/nmat4708	journal	August 2016
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen Luo, Kun; Roberts, Matthew R.; Hao, Rong Nature Chemistry, Vol. 8, Issue 7 https://doi.org/10.1038/nchem.2471	journal	March 2016
Mesoscale Phase Distribution in Single Particles of LiFePO ₄ following Lithium Deintercalation Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin Chemistry of Materials, Vol. 25, Issue 9 https://doi.org/10.1021/cm400106k	journal	April 2013
A study of room-temperature LixMn1.5Ni0.5O4 solid solutions Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep08027	journal	January 2015
Structural Transformations in High-Capacity Li ₂ Cu _0.5 Ni _0.5 O ₂ Cathodes Ruther, Rose E.; Samuthira Pandian, Amaresh; Yan, Pengfei Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.6b05442	journal	March 2017
Ideal charge-density-wave order in the high-field state of superconducting YBCO Jang, H.; Lee, W. -S.; Nojiri, H. Proceedings of the National Academy of Sciences, Vol. 113, Issue 51 https://doi.org/10.1073/pnas.1612849113	journal	December 2016
Using Real-Time Electron Microscopy To Explore the Effects of Transition-Metal Composition on the Local Thermal Stability in Charged Li _x Ni _y Mn _z Co _{1– y – z} O ₂ Cathode Materials Hwang, Sooyeon; Kim, Seung Min; Bak, Seong-Min Chemistry of Materials, Vol. 27, Issue 11 https://doi.org/10.1021/acs.chemmater.5b00709	journal	May 2015
3D elemental sensitive imaging using transmission X-ray microscopy Liu, Yijin; Meirer, Florian; Wang, Junyue Analytical and Bioanalytical Chemistry, Vol. 404, Issue 5 https://doi.org/10.1007/s00216-012-5818-9	journal	February 2012
Transformations and Decomposition of MnCO3 at Earth's Lower Mantle Conditions Boulard, Eglantine; Liu, Yijin; Koh, Ai L. Frontiers in Earth Science, Vol. 4 https://doi.org/10.3389/feart.2016.00107	journal	December 2016
Phase Change of Nickel Phosphide Catalysts in the Conversion of Cellulose into Sorbitol Yang, Pengfei; Kobayashi, Hirokazu; Hara, Kenji ChemSusChem, Vol. 5, Issue 5 https://doi.org/10.1002/cssc.201100498	journal	April 2012
Lithium Electrochemical Deintercalation from O2-LiCoO[sub 2] Carlier, D.; Saadoune, I.; Ménétrier, M. Journal of The Electrochemical Society, Vol. 149, Issue 10 https://doi.org/10.1149/1.1503075	journal	January 2002
Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles Lim, Jongwoo; Li, Yiyang; Alsem, Daan Hein Science, Vol. 353, Issue 6299 https://doi.org/10.1126/science.aaf4914	journal	August 2016
Sodium Promoter Inducing a Phase Change in a Palladium Catalyst Seriani, Nicola The Journal of Physical Chemistry C, Vol. 116, Issue 43 https://doi.org/10.1021/jp308051v	journal	October 2012
Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li _x FePO ₄ Yu, Young-Sang; Kim, Chunjoong; Shapiro, David A. Nano Letters, Vol. 15, Issue 7 https://doi.org/10.1021/acs.nanolett.5b01314	journal	June 2015
Visualization and Quantification of Electrochemical and Mechanical Degradation in Li Ion Batteries Ebner, M.; Marone, F.; Stampanoni, M. Science, Vol. 342, Issue 6159 https://doi.org/10.1126/science.1241882	journal	October 2013
Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes Liu, H.; Strobridge, F. C.; Borkiewicz, O. J. Science, Vol. 344, Issue 6191 https://doi.org/10.1126/science.1252817	journal	June 2014
Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials Mu, Linqin; Lin, Ruoqian; Xu, Rong Nano Letters, Vol. 18, Issue 5 https://doi.org/10.1021/acs.nanolett.8b01036	journal	April 2018
Calculation of a phase diagram for the lithium oxide-aluminum oxide (LiO0.5-AlO1.5) system Byker, Harlan J.; Eliezer, Isaac.; Eliezer, Naomi. The Journal of Physical Chemistry, Vol. 83, Issue 18 https://doi.org/10.1021/j100481a009	journal	September 1979
Understanding the Degradation Mechanisms of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ Cathode Material in Lithium Ion Batteries Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun Advanced Energy Materials, Vol. 4, Issue 1 https://doi.org/10.1002/aenm.201300787	journal	August 2013
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 Gent, William E.; Li, Yiyang; Ahn, Sungjin Advanced Materials, Vol. 28, Issue 31 https://doi.org/10.1002/adma.201601273	journal	May 2016
In situ Visualization of State-of-Charge Heterogeneity within a LiCoO ₂ Particle that Evolves upon Cycling at Different Rates Xu, Yahong; Hu, Enyuan; Zhang, Kai ACS Energy Letters, Vol. 2, Issue 5 https://doi.org/10.1021/acsenergylett.7b00263	journal	April 2017
Combining In Situ Synchrotron X-Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium-Ion Batteries Nam, Kyung-Wan; Bak, Seong-Min; Hu, Enyuan Advanced Functional Materials, Vol. 23, Issue 8 https://doi.org/10.1002/adfm.201200693	journal	June 2012
Structural phase transformations in metallic grain boundaries Frolov, Timofey; Olmsted, David L.; Asta, Mark Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2919	journal	May 2013
Cathode Materials: Combining In Situ Synchrotron X-Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium-Ion Batteries (Adv. Funct. Mater. 8/ Nam, Kyung-Wan; Bak, Seong-Min; Hu, Enyuan Advanced Functional Materials, Vol. 23, Issue 8 https://doi.org/10.1002/adfm.201370042	journal	February 2013
Reactivity and acidity of Li in lithium aluminum oxide (LiAlO2) phases Dronskowski, Richard Inorganic Chemistry, Vol. 32, Issue 1 https://doi.org/10.1021/ic00053a001	journal	January 1993
Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy Kuppan, Saravanan; Xu, Yahong; Liu, Yijin Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14309	journal	February 2017
Transitions from Near-Surface to Interior Redox upon Lithiation in Conversion Electrode Materials He, Kai; Xin, Huolin L.; Zhao, Kejie Nano Letters, Vol. 15, Issue 2 https://doi.org/10.1021/nl5049884	journal	January 2015
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 Bak, Seong-Min; Nam, Kyung-Wan; Chang, Wonyoung Chemistry of Materials, Vol. 25, Issue 3 https://doi.org/10.1021/cm303096e	journal	January 2013
Tracking Non-Uniform Mesoscale Transport in LiFePO ₄ Agglomerates During Electrochemical Cycling Nelson Weker, Johanna; Li, Yiyang; Shanmugam, Rengarajan ChemElectroChem, Vol. 2, Issue 10 https://doi.org/10.1002/celc.201500119	journal	May 2015
Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes Li, Yiyang; El Gabaly, Farid; Ferguson, Todd R. Nature Materials, Vol. 13, Issue 12 https://doi.org/10.1038/nmat4084	journal	September 2014
Thermal Stability and Structural Changes of Li4Mn5O12under Oxygen and Nitrogen Atmosphere Takada, Toshimi; Hayakawa, Hiroshi; Kumagai, Toshiya Journal of Solid State Chemistry, Vol. 121, Issue 1 https://doi.org/10.1006/jssc.1996.0012	journal	January 1996
Phase transitions of LiAlO2 at high pressure and high temperature Lei, Li; He, Duanwei; Zou, Yongtao Journal of Solid State Chemistry, Vol. 181, Issue 8 https://doi.org/10.1016/j.jssc.2008.04.006	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 Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning ACS Applied Materials & Interfaces, Vol. 6, Issue 24 https://doi.org/10.1021/am506712c	journal	December 2014
Phase evolution for conversion reaction electrodes in lithium-ion batteries Lin, Feng; Nordlund, Dennis; Weng, Tsu-Chien Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4358	journal	February 2014
Visualization of anisotropic-isotropic phase transformation dynamics in battery electrode particles Wang, Jiajun; Karen Chen-Wiegart, Yu-chen; Eng, Christopher Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12372	journal	August 2016
Probing three-dimensional sodiation–desodiation equilibrium in sodium-ion batteries by in situ hard X-ray nanotomography Wang, Jiajun; Eng, Christopher; Chen-Wiegart, Yu-chen Karen Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8496	journal	June 2015
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries Lin, Feng; Markus, Isaac M.; Nordlund, Dennis Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4529	journal	March 2014
Visualization of electrochemically driven solid-state phase transformations using operando hard X-ray spectro-imaging Li, Linsen; Chen-Wiegart, Yu-chen Karen; Wang, Jiajun Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7883	journal	April 2015
In operando tracking phase transformation evolution of lithium iron phosphate with hard X-ray microscopy Wang, Jiajun; Chen-Wiegart, Yu-chen Karen; Wang, Jun Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5570	journal	August 2014
Mesoscale Phase Distribution in Single Particles of $LiFePO_{4}$ following Lithium Deintercalation Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/desy-2014-01931	text	January 2013
Ideal charge density wave order in the high-field state of superconducting YBCO Jang, H.; Lee, W. -S.; Nojiri, H. arXiv https://doi.org/10.48550/arxiv.1607.05359	text	January 2016
Persistence of Jahn-Teller Distortion up to the Insulator to Metal Transition in ${LaMnO}_{3}$ Baldini, M.; Struzhkin, V. V.; Goncharov, A. F. Physical Review Letters, Vol. 106, Issue 6 https://doi.org/10.1103/physrevlett.106.066402	journal	February 2011
Morphology of Critical Nuclei in Solid-State Phase Transformations Zhang, Lei; Chen, Long-Qing; Du, Qiang Physical Review Letters, Vol. 98, Issue 26 https://doi.org/10.1103/physrevlett.98.265703	journal	June 2007
Structural phase transformations in metallic grain boundaries Frolov, Timofey; Olmsted, David L.; Asta, Mark arXiv https://doi.org/10.48550/arxiv.1211.1756	text	January 2012

Cited By (10)

Deciphering the Cathode-Electrolyte Interfacial Chemistry in Sodium Layered Cathode Materials Mu, Linqin; Feng, Xu; Kou, Ronghui Advanced Energy Materials, Vol. 8, Issue 34 https://doi.org/10.1002/aenm.201801975	journal	October 2018
Quantification of Heterogeneous Degradation in Li‐Ion Batteries Yang, Yang; Xu, Rong; Zhang, Kai Advanced Energy Materials, Vol. 9, Issue 25 https://doi.org/10.1002/aenm.201900674	journal	May 2019
Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes Finegan, Donal P.; Vamvakeros, Antonis; Tan, Chun Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-14467-x	journal	January 2020
Chemomechanical behaviors of layered cathode materials in alkali metal ion batteries Xu, Zhengrui; Rahman, Muhammad Mominur; Mu, Linqin Journal of Materials Chemistry A, Vol. 6, Issue 44 https://doi.org/10.1039/c8ta06875e	journal	January 2018
Thermally driven mesoscale chemomechanical interplay in Li _0.5 Ni _0.6 Mn _0.2 Co _0.2 O ₂ cathode materials Wei, Chenxi; Zhang, Yan; Lee, Sang-Jun Journal of Materials Chemistry A, Vol. 6, Issue 45 https://doi.org/10.1039/c8ta08973f	journal	January 2018
Probing and quantifying cathode charge heterogeneity in Li ion batteries Zhang, Yuxin; Yang, Zhijie; Tian, Chixia Journal of Materials Chemistry A, Vol. 7, Issue 41 https://doi.org/10.1039/c9ta06977a	journal	January 2019
Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries Teichert, Philipp; Eshetu, Gebrekidan Gebresilassie; Jahnke, Hannes Batteries, Vol. 6, Issue 1 https://doi.org/10.3390/batteries6010008	journal	January 2020
TOPAS and TOPAS-Academic : an optimization program integrating computer algebra and crystallographic objects written in C++ Coelho, Alan A. Journal of Applied Crystallography, Vol. 51, Issue 1 https://doi.org/10.1107/S1600576718000183	journal	February 2018
Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries Teichert, Philipp; Eshetu, Gebrekidan Gebresilassie; Jahnke, Hannes RWTH Aachen University https://doi.org/10.18154/rwth-2020-04543	text	January 2020
NIR-II fluorescence microscopic imaging of cortical vasculature in non-human primates Cai, Zhaochong; Zhu, Liang; Wang, Mengqi Theranostics, Vol. 10, Issue 9 https://doi.org/10.7150/thno.43533	journal	January 2020