Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide

Zhang, Jin; Wang, Qinchao; Li, Shaofeng; Jiang, Zhisen; Tan, Sha; Wang, Xuelong; Zhang, Kai; Yuan, Qingxi; Lee, Sang-Jun; Titus, Charles J.; Irwin, Kent D.; Nordlund, Dennis; Lee, Jun-Sik; Pianetta, Piero; Yu, Xiqian; Xiao, Xianghui; Yang, Xiao-Qing; Hu, Enyuan; Liu, Yijin

doi:10.1038/s41467-020-20198-w

Title: Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide

Journal Article · 10 December 2020 · Nature Communications

DOI: https://doi.org/10.1038/s41467-020-20198-w · OSTI ID:1735389

Zhang, Jin; Wang, Qinchao; Li, Shaofeng; Jiang, Zhisen;

; Wang, Xuelong; Zhang, Kai;

;

; Pianetta, Piero;

;

Abstract Lithium-rich nickel-manganese-cobalt (LirNMC) layered material is a promising cathode for lithium-ion batteries thanks to its large energy density enabled by coexisting cation and anion redox activities. It however suffers from a voltage decay upon cycling, urging for an in-depth understanding of the particle-level structure and chemical complexity. In this work, we investigate the Li _1.2 Ni _0.13 Mn _0.54 Co _0.13 O ₂ particles morphologically, compositionally, and chemically in three-dimensions. While the composition is generally uniform throughout the particle, the charging induces a strong depth dependency in transition metal valence. Such a valence stratification phenomenon is attributed to the nature of oxygen redox which is very likely mostly associated with Mn. The depth-dependent chemistry could be modulated by the particles’ core-multi-shell morphology, suggesting a structural-chemical interplay. These findings highlight the possibility of introducing a chemical gradient to address the oxygen-loss-induced voltage fade in LirNMC layered materials.

View Journal Article

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: National Key Research & Development Program of China; National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; SC0012704

OSTI ID:: 1735389

Report Number(s):: BNL-220716-2020--JAAM; 6342; PII: 20198

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 11; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

References (52)

High‐Voltage Charging‐Induced Strain, Heterogeneity, and Micro‐Cracks in Secondary Particles of a Nickel‐Rich Layered Cathode Material Mao, Yuwei; Wang, Xuelong; Xia, Sihao Advanced Functional Materials, Vol. 29, Issue 18 https://doi.org/10.1002/adfm.201900247	journal	March 2019
New Insights into Improving Rate Performance of Lithium-Rich Cathode Material Wang, Yongqing; Yang, Zhenzhong; Qian, Yumin Advanced Materials, Vol. 27, Issue 26 https://doi.org/10.1002/adma.201500956	journal	May 2015
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
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
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
Nanoscale elemental sensitivity study of Nd ₂ Fe ₁₄ B using absorption correlation tomography : Nanoscale Elemental Sensitivity Study of N Kao, Thomas L.; Shi, Crystal Y.; Wang, Junyue Microscopy Research and Technique, Vol. 76, Issue 11 https://doi.org/10.1002/jemt.22273	journal	August 2013
Quantifying the heterogeneity of shale through statistical combination of imaging across scales Semnani, Shabnam J.; Borja, Ronaldo I. Acta Geotechnica, Vol. 12, Issue 6 https://doi.org/10.1007/s11440-017-0576-7	journal	August 2017
Li-Rich Layered Oxides and Their Practical Challenges: Recent Progress and Perspectives Hu, Sijiang; Pillai, Anoop. S.; Liang, Gemeng Electrochemical Energy Reviews, Vol. 2, Issue 2 https://doi.org/10.1007/s41918-019-00032-8	journal	March 2019
Heterogeneous damage in Li-ion batteries: Experimental analysis and theoretical modeling Xu, Rong; Yang, Yang; Yin, Fei Journal of the Mechanics and Physics of Solids, Vol. 129 https://doi.org/10.1016/j.jmps.2019.05.003	journal	August 2019
Charging Up Lithium-Ion Battery Cathodes Johnson, Christopher S. Joule, Vol. 2, Issue 3 https://doi.org/10.1016/j.joule.2018.02.020	journal	March 2018
High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions Dai, Kehua; Wu, Jinpeng; Zhuo, Zengqing Joule, Vol. 3, Issue 2 https://doi.org/10.1016/j.joule.2018.11.014	journal	February 2019
Thermal stress-induced charge and structure heterogeneity in emerging cathode materials Alvarado, Judith; Wei, Chenxi; Nordlund, Dennis Materials Today, Vol. 35 https://doi.org/10.1016/j.mattod.2019.11.009	journal	May 2020
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
Chemomechanical interplay of layered cathode materials undergoing fast charging in lithium batteries Xia, Sihao; Mu, Linqin; Xu, Zhengrui Nano Energy, Vol. 53 https://doi.org/10.1016/j.nanoen.2018.09.051	journal	November 2018
Electrochemical Characteristics of Layered Transition Metal Oxide Cathode Materials for Lithium Ion Batteries: Surface, Bulk Behavior, and Thermal Properties Tian, Chixia; Lin, Feng; Doeff, Marca M. Accounts of Chemical Research, Vol. 51, Issue 1 https://doi.org/10.1021/acs.accounts.7b00520	journal	December 2017
Mesoscale Battery Science: The Behavior of Electrode Particles Caught on a Multispectral X-ray Camera Wei, Chenxi; Xia, Sihao; Huang, Hai Accounts of Chemical Research, Vol. 51, Issue 10 https://doi.org/10.1021/acs.accounts.8b00123	journal	June 2018
Atomic-Resolution Visualization of Distinctive Chemical Mixing Behavior of Ni, Co, and Mn with Li in Layered Lithium Transition-Metal Oxide Cathode Materials Yan, Pengfei; Zheng, Jianming; Lv, Dongping Chemistry of Materials, Vol. 27, Issue 15 https://doi.org/10.1021/acs.chemmater.5b02016	journal	July 2015
Mesoscale Chemomechanical Interplay of the LiNi _0.8 Co _0.15 Al _0.05 O ₂ Cathode in Solid-State Polymer Batteries Besli, Münir M.; Xia, Sihao; Kuppan, Saravanan Chemistry of Materials, Vol. 31, Issue 2 https://doi.org/10.1021/acs.chemmater.8b04418	journal	December 2018
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
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
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
Surface-to-Bulk Redox Coupling through Thermally Driven Li Redistribution in Li- and Mn-Rich Layered Cathode Materials Li, Shaofeng; Lee, Sang-Jun; Wang, Xuelong Journal of the American Chemical Society, Vol. 141, Issue 30 https://doi.org/10.1021/jacs.9b05349	journal	July 2019
Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling Yang, Feifei; Liu, Yijin; Martha, Surendra K. Nano Letters, Vol. 14, Issue 8 https://doi.org/10.1021/nl502090z	journal	July 2014
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander Nature Chemistry, Vol. 8, Issue 7 https://doi.org/10.1038/nchem.2524	journal	May 2016
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
Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries Lin, Feng; Nordlund, Dennis; Li, Yuyi Nature Energy, Vol. 1, Issue 1 https://doi.org/10.1038/nenergy.2015.4	journal	January 2016
Origin of voltage decay in high-capacity layered oxide electrodes Sathiya, M.; Abakumov, A. M.; Foix, D. Nature Materials, Vol. 14, Issue 2 https://doi.org/10.1038/nmat4137	journal	December 2014
Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides Gent, William E.; Lim, Kipil; Liang, Yufeng Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-02041-x	journal	December 2017
Structural absorption by barbule microstructures of super black bird of paradise feathers McCoy, Dakota E.; Feo, Teresa; Harvey, Todd Alan Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-017-02088-w	journal	January 2018
Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes Assat, Gaurav; Foix, Dominique; Delacourt, Charles Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-02291-9	journal	December 2017
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
Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials Xu, Zhengrui; Jiang, Zhisen; Kuai, Chunguang Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-13884-x	journal	January 2020
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
Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging Singer, A.; Zhang, M.; Hy, S. Nature Energy, Vol. 3, Issue 8 https://doi.org/10.1038/s41560-018-0184-2	journal	July 2018
Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release Hu, Enyuan; Yu, Xiqian; Lin, Ruoqian Nature Energy, Vol. 3, Issue 8 https://doi.org/10.1038/s41560-018-0207-z	journal	July 2018
Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides Hong, Jihyun; Gent, William E.; Xiao, Penghao Nature Materials, Vol. 18, Issue 3 https://doi.org/10.1038/s41563-018-0276-1	journal	February 2019
Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes House, Robert A.; Maitra, Urmimala; Pérez-Osorio, Miguel A. Nature, Vol. 577, Issue 7791 https://doi.org/10.1038/s41586-019-1854-3	journal	December 2019
Insitu nanotomography and operando transmission X-ray microscopy of micron-sized Ge particles Weker, J. Nelson; Liu, N.; Misra, S. Energy Environ. Sci., Vol. 7, Issue 8 https://doi.org/10.1039/C4EE01384K	journal	January 2014
Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries Tsai, Ping-Chun; Wen, Bohua; Wolfman, Mark Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C8EE00001H	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
Computational investigation of chalcogenide spinel conductors for all-solid-state Mg batteries Koettgen, Julius; Bartel, Christopher J.; Ceder, Gerbrand Chemical Communications, Vol. 56, Issue 13 https://doi.org/10.1039/C9CC09510A	journal	January 2020
Li₂MnO₃-stabilized LiMO₂ (M = Mn, Ni, Co) electrodes for lithium-ion batteries Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S. Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125 https://doi.org/10.1039/b702425h	journal	January 2007
Three-dimensional mapping of nickel oxidation states using full field x-ray absorption near edge structure nanotomography Nelson, George J.; Harris, William M.; Izzo, John R. Applied Physics Letters, Vol. 98, Issue 17 https://doi.org/10.1063/1.3574774	journal	April 2011
High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source Qiao, Ruimin; Li, Qinghao; Zhuo, Zengqing Review of Scientific Instruments, Vol. 88, Issue 3 https://doi.org/10.1063/1.4977592	journal	March 2017
Soft X-ray spectroscopy with transition-edge sensors at Stanford Synchrotron Radiation Lightsource beamline 10-1 Lee, Sang-Jun; Titus, Charles J.; Alonso Mori, Roberto Review of Scientific Instruments, Vol. 90, Issue 11 https://doi.org/10.1063/1.5119155	journal	November 2019
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
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
TXM-Wizard : a program for advanced data collection and evaluation in full-field transmission X-ray microscopy Liu, Yijin; Meirer, Florian; Williams, Phillip A. Journal of Synchrotron Radiation, Vol. 19, Issue 2 https://doi.org/10.1107/S0909049511049144	journal	January 2012
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
Layered Li[Ni[sub x]Co[sub 1−2x]Mn[sub x]]O[sub 2] Cathode Materials for Lithium-Ion Batteries Lu, Zhonghua; MacNeil, D. D.; Dahn, J. R. Electrochemical and Solid-State Letters, Vol. 4, Issue 12 https://doi.org/10.1149/1.1413182	journal	January 2001
Depth-Dependent Redox Behavior of LiNi _0.6 Mn _0.2 Co _0.2 O ₂ Tian, Chixia; Nordlund, Dennis; Xin, Huolin L. Journal of The Electrochemical Society, Vol. 165, Issue 3 https://doi.org/10.1149/2.1021803jes	journal	January 2018
Fingerprint Oxygen Redox Reactions in Batteries through High-Efficiency Mapping of Resonant Inelastic X-ray Scattering Wu, Jinpeng; Li, Qinghao; Sallis, Shawn Condensed Matter, Vol. 4, Issue 1 https://doi.org/10.3390/condmat4010005	journal	January 2019

Similar Records

Structural evolution at the oxidative and reductive limits in the first electrochemical cycle of Li_1.2Ni_0.13Mn_0.54Co_0.13O₂

Journal Article · 2020 · Nature Communications · OSTI ID:1631047

Yin, Wei; Grimaud, Alexis; Rousse, Gwenaelle; +8 more

High-Voltage Charging-Induced Strain, Heterogeneity, and Micro-Cracks in Secondary Particles of a Nickel-Rich Layered Cathode Material

Journal Article · 2019 · Advanced Functional Materials · OSTI ID:1498873

Mao, Yuwei; Wang, Xuelong; Xia, Sihao; +16 more

Modulating the Surface Ligand Orientation for Stabilized Anionic Redox in Li‐Rich Oxide Cathodes

Journal Article · 2021 · Advanced Energy Materials · OSTI ID:1804575

Liu, Yanchen; Zhu, He; Zhu, Hekang; +14 more

Related Subjects

25 ENERGY STORAGE
batteries
lithium-rich layered
spectro-imaging

Title: Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide

Citation Formats

References (52)

Similar Records

Related Subjects