In situ Visualization of State-of-Charge Heterogeneity within a LiCoO2 Particle that Evolves upon Cycling at Different Rates

Xu, Yahong; Hu, Enyuan; Zhang, Kai; Wang, Xuelong; Borzenets, Valery; Sun, Zhihong; Pianetta, Piero; Yu, Xiqian; Liu, Yijin; Yang, Xiao-Qing; Li, Hong

doi:10.1021/acsenergylett.7b00263

Title: In situ Visualization of State-of-Charge Heterogeneity within a LiCoO₂ Particle that Evolves upon Cycling at Different Rates

Journal Article · Fri May 05 00:00:00 EDT 2017 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.7b00263· OSTI ID:1358026

Xu, Yahong ^[1]; Hu, Enyuan ^[2]; Zhang, Kai ^[3]; Wang, Xuelong ^[4]; Borzenets, Valery ^[5]; Sun, Zhihong ^[6]; Pianetta, Piero ^[5];

^[4];

^[5]; Yang, Xiao-Qing ^[2];

^[4]

Donghua Univ., Shanghai (China). College of Mechanical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Chinese Academy of Sciences (CAS), Beijing (China). Inst. of High Energy Physics. Beijing Synchrotron Radiation Facility
Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Physics. Beijing National Lab. for Condensed Matter Physics
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource
Donghua Univ., Shanghai (China). College of Mechanical Engineering

For designing new battery systems with higher energy density and longer cycle life, it is important to understand the degradation mechanism of the electrode material, especially at the individual particle level. Using in situ transmission X-ray microscopy (TXM) coupled to a pouch cell setup, the inhomogeneous Li distribution as well as the formation, population, and evolution of inactive domains in a single LiCoO₂ particle were visualized in this paper as it was cycled for many times. It is found that the percentage of the particle that fully recovered to the pristine state is strongly related to the cycling rate. Interestingly, we also observed the evolution of the inactive region within the particle during long-term cycling. The relationship between morphological degradation and chemical inhomogeneity, including the formation of unanticipated Co metal phase, is also observed. Finally, our work highlights the capability of in situ TXM for studying the degradation mechanism of materials in LIBs.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Chinese Academy of Sciences (CAS), Beijing (China)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Science and Technology of China; National Key Research and Development Program of China; National Natural Science Foundation of China (NSFC); Open Research Foundation of State Key Laboratory of Digital Manufacturing Equipment and Technology (China); USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Contributing Organization:: Donghua Univ., Shanghai (China)

Grant/Contract Number:: SC0012704; AC02-76SF00515; 2016YFB0100300; 2016YFA0400900; 11535015; U1632110; Battery500 consortium

OSTI ID:: 1358026

Alternate ID(s):: OSTI ID: 1368569

Report Number(s):: BNL-113846-2017-JA; R&D Project: MA453MAEA

Journal Information:: ACS Energy Letters, Vol. 2, Issue 5; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 130 works

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References (36)

Understanding the Rate Capability of High-Energy-Density Li-Rich Layered Li _1.2 Ni _0.15 Co _0.1 Mn _0.55 O ₂ Cathode Materials Yu, Xiqian; Lyu, Yingchun; Gu, Lin Advanced Energy Materials, Vol. 4, Issue 5 https://doi.org/10.1002/aenm.201300950	journal	December 2013
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
The Origin of Capacity Fade in the Li ₂ MnO ₃ ·Li M O ₂ ( M = Li, Ni, Co, Mn) Microsphere Positive Electrode: An Operando Neutron Diffraction and Transmission X-ray Microscopy Study Chen, Chih-Jung; Pang, Wei Kong; Mori, Tatsuhiro Journal of the American Chemical Society, Vol. 138, Issue 28 https://doi.org/10.1021/jacs.6b03932	journal	July 2016
Short- and Long-Range Order in the Positive Electrode Material, Li(NiMn) _0.5 O ₂ : A Joint X-ray and Neutron Diffraction, Pair Distribution Function Analysis and NMR Study Bréger, Julien; Dupré, Nicolas; Chupas, Peter J. Journal of the American Chemical Society, Vol. 127, Issue 20 https://doi.org/10.1021/ja050697u	journal	May 2005
Lithium Batteries and Cathode Materials Whittingham, M. Stanley Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302 https://doi.org/10.1021/cr020731c	journal	October 2004
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Solid-State Redox Reactions of LiCoO[sub 2] (R3m) for 4 Volt Secondary Lithium Cells Ohzuku, Tsutomu Journal of The Electrochemical Society, Vol. 141, Issue 11 https://doi.org/10.1149/1.2059267	journal	January 1994
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
Five-dimensional visualization of phase transition in BiNiO ₃ under high pressure Liu, Yijin; Wang, Junyue; Azuma, Masaki Applied Physics Letters, Vol. 104, Issue 4 https://doi.org/10.1063/1.4863229	journal	January 2014
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries Lee, J.; Urban, A.; Li, X. Science, Vol. 343, Issue 6170 https://doi.org/10.1126/science.1246432	journal	January 2014
Applications of Hard X‐ray Full‐Field Transmission X‐ray Microscopy at SSRL Liu, Y.; Andrews, J. C.; Meirer, F. THE 10TH INTERNATIONAL CONFERENCE ON X‐RAY MICROSCOPY, AIP Conference Proceedings https://doi.org/10.1063/1.3625377	conference	January 2011
CoO₂, The End Member of the Li_xCoO₂ Solid Solution Amatucci, G. G.; Tarascon, J. M.; Klein, L. C. Journal of The Electrochemical Society, Vol. 143, Issue 3, p. 1114-1123 https://doi.org/10.1149/1.1836594	journal	January 1996
Explore the Effects of Microstructural Defects on Voltage Fade of Li- and Mn-Rich Cathodes Hu, Enyuan; Lyu, Yingchun; Xin, Huolin L. Nano Letters, Vol. 16, Issue 10 https://doi.org/10.1021/acs.nanolett.6b01609	journal	September 2016
Cobalt dissolution in LiCoO₂-based non-aqueous rechargeable batteries Amatucci, G. G.; Tarascon, J. M.; Klein, L. C. Solid State Ionics, Vol. 83, Issue 1-2, p. 167-173 https://doi.org/10.1016/0167-2738(95)00231-6	journal	January 1996
Suppression of Cobalt Dissolution from the LiCoO[sub 2] Cathodes with Various Metal-Oxide Coatings Kim, Yong Jeong; Cho, Jaephil; Kim, Tae-Joon Journal of The Electrochemical Society, Vol. 150, Issue 12 https://doi.org/10.1149/1.1627347	journal	January 2003
Improving the Capacity Retention of LiCoO[sub 2] Cycled to 4.5 V by Heat-Treatment Chen, Zhaohui; Dahn, J. R. Electrochemical and Solid-State Letters, Vol. 7, Issue 1 https://doi.org/10.1149/1.1628871	journal	January 2004
Zero-Strain Intercalation Cathode for Rechargeable Li-Ion Cell Cho, Jaephil; Kim, Yong Jeong; Kim, Tae-Joon Angewandte Chemie International Edition, Vol. 40, Issue 18, p. 3367-3369 https://doi.org/10.1002/1521-3773(20010917)40:18<3367::AID-ANIE3367>3.0.CO;2-A	journal	September 2001
The Li-Ion Rechargeable Battery: A Perspective Goodenough, John B.; Park, Kyu-Sung Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja3091438	journal	January 2013
Direct Atomic-Resolution Observation of Two Phases in the Li _1.2 Mn _0.567 Ni _0.166 Co _0.067 O ₂ Cathode Material for Lithium-Ion Batteries Yu, Haijun; Ishikawa, Ryo; So, Yeong-Gi Angewandte Chemie International Edition, Vol. 52, Issue 23 https://doi.org/10.1002/anie.201301236	journal	April 2013
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
Unravelling the Impact of Reaction Paths on Mechanical Degradation of Intercalation Cathodes for Lithium-Ion Batteries Li, Juchuan; Zhang, Qinglin; Xiao, Xingcheng Journal of the American Chemical Society, Vol. 137, Issue 43 https://doi.org/10.1021/jacs.5b06178	journal	October 2015
Three-dimensional imaging of chemical phase transformations at the nanoscale with full-field transmission X-ray microscopy Meirer, Florian; Cabana, Jordi; Liu, Yijin Journal of Synchrotron Radiation, Vol. 18, Issue 5 https://doi.org/10.1107/S0909049511019364	journal	July 2011
In Operando X-ray Diffraction and Transmission X-ray Microscopy of Lithium Sulfur Batteries Nelson, Johanna; Misra, Sumohan; Yang, Yuan Journal of the American Chemical Society, Vol. 134, Issue 14 https://doi.org/10.1021/ja2121926	journal	March 2012
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
Li _1.20 Mn _0.54 Co _0.13 Ni _0.13 O ₂ with Different Particle Sizes as Attractive Positive Electrode Materials for Lithium-Ion Batteries: Insights into Their Structure Koga, Hideyuki; Croguennec, Laurence; Mannessiez, Philippe The Journal of Physical Chemistry C, Vol. 116, Issue 25 https://doi.org/10.1021/jp301879x	journal	June 2012
Unsupervised Data Mining in nanoscale X-ray Spectro-Microscopic Study of NdFeB Magnet Duan, Xiaoyue; Yang, Feifei; Antono, Erin Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep34406	journal	September 2016
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
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
Corrosion/Fragmentation of Layered Composite Cathode and Related Capacity/Voltage Fading during Cycling Process Zheng, Jianming; Gu, Meng; Xiao, Jie Nano Letters, Vol. 13, Issue 8 https://doi.org/10.1021/nl401849t	journal	July 2013
Structural integrity—Searching the key factor to suppress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques Xu, Yahong; Hu, Enyuan; Yang, Feifei Nano Energy, Vol. 28 https://doi.org/10.1016/j.nanoen.2016.08.039	journal	October 2016
Staging Phase Transitions in Li[sub x]CoO[sub 2] Chen, Zhaohui; Lu, Zhonghua; Dahn, J. R. Journal of The Electrochemical Society, Vol. 149, Issue 12 https://doi.org/10.1149/1.1519850	journal	January 2002
Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries Yan, Pengfei; Zheng, Jianming; Gu, Meng Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14101	journal	January 2017
High-Performance, Layered, 3D-LiCoO2 Cathodes with a Nanoscale Co3O4 Coating via Chemical Etching Jeong, Sookyung; Park, Soojin; Cho, Jaephil Advanced Energy Materials, Vol. 1, Issue 3 https://doi.org/10.1002/aenm.201100029	journal	April 2011
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
LixCoO2 (0<x<-1): A new cathode material for batteries of high energy density Mizushima, K.; Jones, P. C.; Wiseman, P. J. Materials Research Bulletin, Vol. 15, Issue 6 https://doi.org/10.1016/0025-5408(80)90012-4	journal	June 1980
Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries Gu, Meng; Belharouak, Ilias; Zheng, Jianming ACS Nano, Vol. 7, Issue 1 https://doi.org/10.1021/nn305065u	journal	December 2012

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Origins of capacity and voltage fading of LiCoO ₂ upon high voltage cycling Jiang, Yuyuan; Qin, Changdong; Yan, Pengfei Journal of Materials Chemistry A, Vol. 7, Issue 36 https://doi.org/10.1039/c9ta06579b	journal	January 2019
Reviving lithium cobalt oxide-based lithium secondary batteries-toward a higher energy density Wang, Longlong; Chen, Bingbing; Ma, Jun Chemical Society Reviews, Vol. 47, Issue 17 https://doi.org/10.1039/c8cs00322j	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
Role and importance of surface heterogeneities in transport of particles in saturated porous media Shen, Chongyang; Jin, Yan; Zhuang, Jie Critical Reviews in Environmental Science and Technology, Vol. 50, Issue 3 https://doi.org/10.1080/10643389.2019.1629800	journal	June 2019
Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials Mu, Linqin; Yuan, Qingxi; Tian, Chixia Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05172-x	journal	July 2018
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
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
Review of Recent Development of In Situ/Operando Characterization Techniques for Lithium Battery Research Liu, Dongqing; Shadike, Zulipiya; Lin, Ruoqian Advanced Materials, Vol. 31, Issue 28 https://doi.org/10.1002/adma.201806620	journal	May 2019
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Title: In situ Visualization of State-of-Charge Heterogeneity within a LiCoO2 Particle that Evolves upon Cycling at Different Rates

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Title: In situ Visualization of State-of-Charge Heterogeneity within a LiCoO₂ Particle that Evolves upon Cycling at Different Rates