Mesoscale interplay among composition heterogeneity, lattice deformation, and redox stratification in single-crystalline layered oxide cathode

Xue, Zhichen; Wu, Feixiang; Ge, Mingyuan; Huang, Xiaojing; Chu, Yong S.; Pianetta, Piero; Liu, Yijin

doi:10.1016/j.esci.2024.100251

Title: Mesoscale interplay among composition heterogeneity, lattice deformation, and redox stratification in single-crystalline layered oxide cathode

Journal Article · 28 February 2024 · eScience

DOI: https://doi.org/10.1016/j.esci.2024.100251 · OSTI ID:2440588

Xue, Zhichen ^[1]; Wu, Feixiang ^[2]; Ge, Mingyuan ^[3]; Huang, Xiaojing ^[3]; Chu, Yong S. ^[3];

^[4]; Liu, Yijin ^[5]

Central South University, Changsha (China); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Central South University, Changsha (China)
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)
Univ. of Texas, Austin, TX (United States)

Single-crystalline layered oxide materials for lithium-ion batteries are featured by their excellent capacity retention over their polycrystalline counterparts, making them sought-after cathode candidates. Their capacity degradation, however, becomes more severe under high-voltage cycling, hindering many high-energy applications. It has long been speculated that the interplay among composition heterogeneity, lattice deformation, and redox stratification could be a driving force for the performance decay. The underlying mechanism, however, is not well-understood. In this study, we use X-ray microscopy to systematically examine single-crystalline NMC particles at the mesoscale. This technique allows us to capture detailed signals of diffraction, spectroscopy, and fluorescence, offering spatially resolved multimodal insights. Focusing on early high-voltage charging cycles, we uncover heterogeneities in valence states and lattice structures that are inherent rather than caused by electrochemical abuse. These heterogeneities are closely associated with compositional variations within individual particles. Our findings provide useful insights for refining material synthesis and processing for enhanced battery longevity and efficiency.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

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

OSTI ID:: 2440588

Report Number(s):: BNL--226038-2024-JAAM

Journal Information:: eScience, Journal Name: eScience Journal Issue: 4 Vol. 4; ISSN 2667-1417

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (35)

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
Chemical, Structural, and Electronic Aspects of Formation and Degradation Behavior on Different Length Scales of Ni‐Rich NCM and Li‐Rich HE‐NCM Cathode Materials in Li‐Ion Batteries de Biasi, Lea; Schwarz, Björn; Brezesinski, Torsten Advanced Materials, Vol. 31, Issue 26 https://doi.org/10.1002/adma.201900985	journal	April 2019
Revealing Roles of Co and Ni in Mn‐Rich Layered Cathodes Huang, Weiyuan; Lin, Cong; Zhang, Mingjian Advanced Energy Materials, Vol. 11, Issue 41 https://doi.org/10.1002/aenm.202102646	journal	October 2021
Crack-free single-crystalline Co-free Ni-rich LiNi0.95Mn0.05O2 layered cathode Ni, Lianshan; Guo, Ruiting; Fang, Susu eScience, Vol. 2, Issue 1 https://doi.org/10.1016/j.esci.2022.02.006	journal	January 2022
Syntheses, challenges and modifications of single-crystal cathodes for lithium-ion battery Zhang, Xinyue; Zhang, Yudong; Liu, Jiuding Journal of Energy Chemistry, Vol. 63 https://doi.org/10.1016/j.jechem.2021.10.022	journal	December 2021
Emerging X-ray imaging technologies for energy materials Cao, Chuntian; Toney, Michael F.; Sham, Tsun-Kong Materials Today, Vol. 34 https://doi.org/10.1016/j.mattod.2019.08.011	journal	April 2020
Enabling high rate performance of Ni-rich layered oxide cathode by uniform titanium doping Sun, Huabin; Cao, Zhilin; Wang, Tengrui Materials Today Energy, Vol. 13 https://doi.org/10.1016/j.mtener.2019.05.003	journal	September 2019
Selective dopant segregation modulates mesoscale reaction kinetics in layered transition metal oxide Qian, Guannan; Huang, Hai; Hou, Fuchen Nano Energy, Vol. 84 https://doi.org/10.1016/j.nanoen.2021.105926	journal	June 2021
Thick Electrode Design for Facile Electron and Ion Transport: Architectures, Advanced Characterization, and Modeling Arnot, David J.; Mayilvahanan, Karthik S.; Hui, Zeyu Accounts of Materials Research, Vol. 3, Issue 4 https://doi.org/10.1021/accountsmr.1c00281	journal	March 2022
Data-Driven Lithium-Ion Battery Cathode Research with State-of-the-Art Synchrotron X-ray Techniques Xue, Zhichen; Li, Jizhou; Pianetta, Piero Accounts of Materials Research, Vol. 3, Issue 8 https://doi.org/10.1021/accountsmr.2c00098	journal	July 2022
Delineating the Roles of Mn, Al, and Co by Comparing Three Layered Oxide Cathodes with the Same Nickel Content of 70% for Lithium-Ion Batteries Yi, Michael; Li, Wangda; Manthiram, Arumugam Chemistry of Materials, Vol. 34, Issue 2 https://doi.org/10.1021/acs.chemmater.1c03322	journal	January 2022
High-Energy Density Core–Shell Structured Li[Ni _0.95 Co _0.025 Mn _0.025 ]O ₂ Cathode for Lithium-Ion Batteries Jun, Do-Wook; Yoon, Chong S.; Kim, Un-Hyuck Chemistry of Materials, Vol. 29, Issue 12 https://doi.org/10.1021/acs.chemmater.7b01425	journal	May 2017
Identifying and Addressing Critical Challenges of High-Voltage Layered Ternary Oxide Cathode Materials Zhang, Shu; Ma, Jun; Hu, Zhenglin Chemistry of Materials, Vol. 31, Issue 16 https://doi.org/10.1021/acs.chemmater.9b01557	journal	June 2019
Structural Distortion-Induced Charge Gradient Distribution of Co Ions in Delithiated LiCoO ₂ Cathode Li, Shuai; Li, Kaili; Zheng, Jieyun The Journal of Physical Chemistry Letters, Vol. 10, Issue 24 https://doi.org/10.1021/acs.jpclett.9b02711	journal	November 2019
Capacity Fading Mechanisms in Ni-Rich Single-Crystal NCM Cathodes Ryu, Hoon-Hee; Namkoong, Been; Kim, Jae-Hyung ACS Energy Letters, Vol. 6, Issue 8 https://doi.org/10.1021/acsenergylett.1c01089	journal	July 2021
Degradation Mechanism of Ni-Rich Cathode Materials: Focusing on Particle Interior Park, Nam-Yung; Park, Geon-Tae; Kim, Su-Bin ACS Energy Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acsenergylett.2c01272	journal	June 2022
Structural Stability of Single-Crystalline Ni-Rich Layered Cathode upon Delithiation Han, Gi-Mun; Kim, Ye-Sung; Ryu, Hoon-Hee ACS Energy Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acsenergylett.2c01521	journal	August 2022
Morphology-Dependent Battery Performance of Ni-Rich Layered Cathodes: Single-Crystal versus Refined Polycrystal Ryu, Hoon-Hee; Lee, Soo-Been; Yoon, Chong S. ACS Energy Letters, Vol. 7, Issue 9, p. 3072-3079 https://doi.org/10.1021/acsenergylett.2c01670	journal	August 2022
Long-Lasting Ni-Rich NCMA Cathodes via Simultaneous Microstructural Refinement and Surface Modification Ryu, Hoon-Hee; Lim, Hyung-Woo; Kang, Gyeong-Cheol ACS Energy Letters, Vol. 8, Issue 3 https://doi.org/10.1021/acsenergylett.3c00083	journal	February 2023
Kinetic Origin of Planar Gliding in Single-Crystalline Ni-Rich Cathodes Meng, Xin-Hai; Lin, Ting; Mao, Huican Journal of the American Chemical Society, Vol. 144, Issue 25 https://doi.org/10.1021/jacs.2c03549	journal	June 2022
State-of-the-art characterization techniques for advanced lithium-ion batteries Lu, Jun; Wu, Tianpin; Amine, Khalil Nature Energy, Vol. 2, Issue 3 https://doi.org/10.1038/nenergy.2017.11	journal	March 2017
Surface regulation enables high stability of single-crystal lithium-ion cathodes at high voltage Zhang, Fang; Lou, Shuaifeng; Li, Shuang Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16824-2	journal	June 2020
High-nickel layered oxide cathodes for lithium-based automotive batteries Li, Wangda; Erickson, Evan M.; Manthiram, Arumugam Nature Energy, Vol. 5, Issue 1 https://doi.org/10.1038/s41560-019-0513-0	journal	January 2020
Understanding Co roles towards developing Co-free Ni-rich cathodes for rechargeable batteries Liu, Tongchao; Yu, Lei; Liu, Jiajie Nature Energy, Vol. 6, Issue 3 https://doi.org/10.1038/s41560-021-00776-y	journal	February 2021
Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte Xue, Weijiang; Huang, Mingjun; Li, Yutao Nature Energy, Vol. 6, Issue 5 https://doi.org/10.1038/s41560-021-00792-y	journal	March 2021
Bulk fatigue induced by surface reconstruction in layered Ni-rich cathodes for Li-ion batteries Xu, Chao; Märker, Katharina; Lee, Juhan Nature Materials, Vol. 20, Issue 1 https://doi.org/10.1038/s41563-020-0767-8	journal	August 2020
Fictitious phase separation in Li layered oxides driven by electro-autocatalysis Park, Jungjin; Zhao, Hongbo; Kang, Stephen Dongmin Nature Materials, Vol. 20, Issue 7 https://doi.org/10.1038/s41563-021-00936-1	journal	March 2021
Compositionally complex doping for zero-strain zero-cobalt layered cathodes Zhang, Rui; Wang, Chunyang; Zou, Peichao Nature, Vol. 610, Issue 7930 https://doi.org/10.1038/s41586-022-05115-z	journal	September 2022
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
A review on synthesis and engineering of crystal precursors produced via coprecipitation for multicomponent lithium-ion battery cathode materials Dong, Hongxu; Koenig, Gary M. CrystEngComm, Vol. 22, Issue 9 https://doi.org/10.1039/C9CE00679F	journal	January 2020
Synchrotron X-ray quantitative evaluation of transient deformation and damage phenomena in a single nickel-rich cathode particle Romano Brandt, León; Marie, John-Joseph; Moxham, Thomas Energy & Environmental Science, Vol. 13, Issue 10 https://doi.org/10.1039/D0EE02290J	journal	January 2020
PyXAS – an open-source package for 2D X-ray near-edge spectroscopy analysis Ge, Mingyuan; Lee, Wah-Keat Journal of Synchrotron Radiation, Vol. 27, Issue 2 https://doi.org/10.1107/S1600577520001071	journal	February 2020
Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode Bi, Yujing; Tao, Jinhui; Wu, Yuqin Science, Vol. 370, Issue 6522 https://doi.org/10.1126/science.abc3167	journal	December 2020
Synthesis of Single Crystal LiNi _0.5 Mn _0.3 Co _0.2 O ₂ for Lithium Ion Batteries Li, Jing; Li, Hongyang; Stone, Will Journal of The Electrochemical Society, Vol. 164, Issue 14 https://doi.org/10.1149/2.0401714jes	journal	January 2017
Synthesis of Single Crystal LiNi _0.88 Co _0.09 Al _0.03 O ₂ with a Two-Step Lithiation Method Li, Hongyang; Li, Jing; Zaker, Nafiseh Journal of The Electrochemical Society, Vol. 166, Issue 10 https://doi.org/10.1149/2.0681910jes	journal	January 2019

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