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 · 11 December 2020 · Nature Communications

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

Zhang, Jin ^[1]; Wang, Qinchao ^[2]; Li, Shaofeng ^[3]; Jiang, Zhisen ^[3];

^[2]; Wang, Xuelong ^[2]; Zhang, Kai ^[4];

^[4];

^[3];

^[5];

^[3];

^[3]; Pianetta, Piero ^[3];

^[6];

^[7];

^[2];

^[3]

Chinese Academy of Sciences (CAS), Beijing (China). Inst. of High Energy Physics (IHEP), Beijing Synchrotron Radiation Facility; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Brookhaven National Lab. (BNL), Upton, NY (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Chinese Academy of Sciences (CAS), Beijing (China). Inst. of High Energy Physics (IHEP), Beijing Synchrotron Radiation Facility
Stanford Univ., CA (United States)
Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Physics, Beijing Key Lab. for New Energy Materials and Devices
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source

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_1.2Ni_0.13Mn_0.54Co_0.13O₂ 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 (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

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

Grant/Contract Number:: SC0012704; AC02-76SF00515; 2016YFA0400900; ECCS-1542152

OSTI ID:: 1735389

Alternate ID(s):: OSTI ID: 1737442; OSTI ID: 1779170

Report Number(s):: BNL-220716-2020-JAAM

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

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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–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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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

Cited By (1)

A transition-edge sensor-based x-ray spectrometer for the study of highly charged ions at the National Institute of Standards and Technology electron beam ion trap Szypryt, P.; O’Neil, G. C.; Takacs, E. Review of Scientific Instruments, Vol. 90, Issue 12 https://doi.org/10.1063/1.5116717	journal	December 2019

Similar Records

Toward the Stable and Reversible Lattice Oxygen Redox in Li-Rich Layered Oxides

Conference · 2019 · OSTI ID:1770710

Zhang, Minghao; Meng, Ying Shirley

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

Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance

Journal Article · 2017 · Advanced Energy Materials · OSTI ID:1369400

Kuppan, Saravanan; Shukla, Alpesh Khushalchand; Membreno, Daniel; +2 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 (50)

Cited By (1)

Similar Records

Related Subjects