Resolving complex intralayer transition motifs in high-Ni-content layered cathode materials for lithium-ion batteries

Wang, Chunyang; Wang, Xuelong; Zhang, Rui; Lei, Tianjiao; Kisslinger, Kim; Xin, Huolin L.

doi:10.1038/s41563-022-01461-5

Resolving complex intralayer transition motifs in high-Ni-content layered cathode materials for lithium-ion batteries

Journal Article · Thu Jan 26 00:00:00 UTC 2023 · Nature Materials

DOI:https://doi.org/10.1038/s41563-022-01461-5· OSTI ID:1963194

^[1]; Wang, Xuelong ^[2]; Zhang, Rui ^[1]; Lei, Tianjiao ^[1]; ^[3]; ^[1]

Univ. of California, Irvine, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

High-Ni-content layered materials are promising cathodes for next-generation lithium-ion batteries. However, investigating the atomic configurations of the delithiation-induced complex phase boundaries and their transitions remains challenging. Here, in this study, by using deep-learning-aided super-resolution electron microscopy, we resolve the intralayer transition motifs at complex phase boundaries in high-Ni cathodes. We reveal that an O3 → O1 transformation driven by delithiation leads to the formation of two types of O1–O3 interface, the continuous- and abrupt-transition interfaces. The interfacial misfit is accommodated by a continuous shear-transition zone and an abrupt structural unit, respectively. Atomic-scale simulations show that uneven in-plane Li+ distribution contributes to the formation of both types of interface, and the abrupt transition is energetically more favourable in a delithiated state where O1 is dominant, or when there is an uneven in-plane Li⁺ distribution in a delithiated O3 lattice. Moreover, a twin-like motif that introduces structural units analogous to the abrupt-type O1–O3 interface is also uncovered. The structural transition motifs resolved in this study provide further understanding of shear-induced phase transformations and phase boundaries in high-Ni layered cathodes.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1963194

Report Number(s):: BNL-224160-2023-JAAM

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 2 Vol. 22; ISSN 1476-1122

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

A High‐Performance Carbonate‐Free Lithium\|Garnet Interface Enabled by a Trace Amount of Sodium Fu, Xingjie; Wang, Tiantian; Shen, Wenzhong Advanced Materials, Vol. 32, Issue 26 https://doi.org/10.1002/adma.202000575	journal	May 2020
Narrowing the Gap between Theoretical and Practical Capacities in Li-Ion Layered Oxide Cathode Materials Radin, Maxwell D.; Hy, Sunny; Sina, Mahsa Advanced Energy Materials, Vol. 7, Issue 20 https://doi.org/10.1002/aenm.201602888	journal	July 2017
Microstructure‐Controlled Ni‐Rich Cathode Material by Microscale Compositional Partition for Next‐Generation Electric Vehicles Kim, Un‐Hyuck; Ryu, Hoon‐Hee; Kim, Jae‐Hyung Advanced Energy Materials, Vol. 9, Issue 15 https://doi.org/10.1002/aenm.201803902	journal	February 2019
Polycrystalline and Single Crystalline NCM Cathode Materials—Quantifying Particle Cracking, Active Surface Area, and Lithium Diffusion Trevisanello, Enrico; Ruess, Raffael; Conforto, Gioele Advanced Energy Materials, Vol. 11, Issue 18 https://doi.org/10.1002/aenm.202003400	journal	March 2021
Phase Behavior during Electrochemical Cycling of Ni‐Rich Cathode Materials for Li‐Ion Batteries Xu, Chao; Reeves, Philip J.; Jacquet, Quentin Advanced Energy Materials, Vol. 11, Issue 7 https://doi.org/10.1002/aenm.202003404	journal	December 2020
There and Back Again-The Journey of LiNiO ₂ as a Cathode Active Material Bianchini, Matteo; Roca-Ayats, Maria; Hartmann, Pascal Angewandte Chemie International Edition, Vol. 58, Issue 31 https://doi.org/10.1002/anie.201812472	journal	May 2019
Oxygen Vacancy Diffusion and Condensation in Lithium‐Ion Battery Cathode Materials Lee, Sanghan; Jin, Wooyoung; Kim, Su Hwan Angewandte Chemie International Edition, Vol. 58, Issue 31 https://doi.org/10.1002/anie.201904469	journal	June 2019
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
The formation mechanisms of growth twins in polycrystalline Al with high stacking fault energy Xue, S.; Fan, Z.; Chen, Y. Acta Materialia, Vol. 101 https://doi.org/10.1016/j.actamat.2015.08.046	journal	December 2015
A high-throughput infrastructure for density functional theory calculations Jain, Anubhav; Hautier, Geoffroy; Moore, Charles J. Computational Materials Science, Vol. 50, Issue 8 https://doi.org/10.1016/j.commatsci.2011.02.023	journal	June 2011
Three-Dimensional Atomic Structure of Grain Boundaries Resolved by Atomic-Resolution Electron Tomography Wang, Chunyang; Duan, Huichao; Chen, Chunjin Matter, Vol. 3, Issue 6 https://doi.org/10.1016/j.matt.2020.09.003	journal	December 2020
Resolving atomic-scale phase transformation and oxygen loss mechanism in ultrahigh-nickel layered cathodes for cobalt-free lithium-ion batteries Wang, Chunyang; Han, Lili; Zhang, Rui Matter, Vol. 4, Issue 6 https://doi.org/10.1016/j.matt.2021.03.012	journal	June 2021
Electrodeposition and Mechanical Stability at Lithium-Solid Electrolyte Interface during Plating in Solid-State Batteries Tu, Qingsong; Barroso-Luque, Luis; Shi, Tan Cell Reports Physical Science, Vol. 1, Issue 7 https://doi.org/10.1016/j.xcrp.2020.100106	journal	July 2020
Atomic-Scale Observation of O1 Faulted Phase-Induced Deactivation of LiNiO ₂ at High Voltage Wang, Chunyang; Zhang, Rui; Kisslinger, Kim Nano Letters, Vol. 21, Issue 8 https://doi.org/10.1021/acs.nanolett.1c00862	journal	April 2021
Chemomechanically Stable Ultrahigh-Ni Single-Crystalline Cathodes with Improved Oxygen Retention and Delayed Phase Degradations Wang, Chunyang; Zhang, Rui; Siu, Carrie Nano Letters, Vol. 21, Issue 22 https://doi.org/10.1021/acs.nanolett.1c03852	journal	November 2021
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
Co-Free Layered Cathode Materials for High Energy Density Lithium-Ion Batteries Voronina, Natalia; Sun, Yang-Kook; Myung, Seung-Taek ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00742	journal	May 2020
Structural Stability of LiNiO ₂ Cycled above 4.2 V Yoon, Chong S.; Jun, Do-Wook; Myung, Seung-Taek ACS Energy Letters, Vol. 2, Issue 5 https://doi.org/10.1021/acsenergylett.7b00304	journal	April 2017
High-Voltage Cycling Induced Thermal Vulnerability in LiCoO ₂ Cathode: Cation Loss and Oxygen Release Driven by Oxygen Vacancy Migration Sun, Congli; Liao, Xiaobin; Xia, Fanjie ACS Nano, Vol. 14, Issue 5 https://doi.org/10.1021/acsnano.0c02237	journal	April 2020
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
Oxygen-Release-Related Thermal Stability and Decomposition Pathways of Li _x Ni _0.5 Mn _1.5 O ₄ Cathode Materials Hu, Enyuan; Bak, Seong-Min; Liu, Jue Chemistry of Materials, Vol. 26, Issue 2 https://doi.org/10.1021/cm403400y	journal	December 2013
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
Deformation-induced structural transition in body-centred cubic molybdenum Wang, S. J.; Wang, H.; Du, K. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4433	journal	March 2014
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
In situ atomic-scale observation of twinning-dominated deformation in nanoscale body-centred cubic tungsten Wang, Jiangwei; Zeng, Zhi; Weinberger, Christopher R. Nature Materials, Vol. 14, Issue 6 https://doi.org/10.1038/nmat4228	journal	March 2015
Coupling of electrochemically triggered thermal and mechanical effects to aggravate failure in a layered cathode Yan, Pengfei; Zheng, Jianming; Chen, Tianwu Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04862-w	journal	June 2018
Hierarchical nickel valence gradient stabilizes high-nickel content layered cathode materials Lin, Ruoqian; Bak, Seong-Min; Shin, Youngho Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-22635-w	journal	April 2021
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
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
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
Injection of oxygen vacancies in the bulk lattice of layered cathodes Yan, Pengfei; Zheng, Jianming; Tang, Zhen-Kun Nature Nanotechnology, Vol. 14, Issue 6 https://doi.org/10.1038/s41565-019-0428-8	journal	April 2019
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
TEMImageNet training library and AtomSegNet deep-learning models for high-precision atom segmentation, localization, denoising, and deblurring of atomic-resolution images Lin, Ruoqian; Zhang, Rui; Wang, Chunyang Scientific Reports, Vol. 11, Issue 1 https://doi.org/10.1038/s41598-021-84499-w	journal	March 2021
High-voltage positive electrode materials for lithium-ion batteries Li, Wangda; Song, Bohang; Manthiram, Arumugam Chemical Society Reviews, Vol. 46, Issue 10 https://doi.org/10.1039/C6CS00875E	journal	January 2017
Structural elucidation of the degradation mechanism of nickel-rich layered cathodes during high-voltage cycling Lai, Jing; Zhang, Jun; Li, Zuowei Chemical Communications, Vol. 56, Issue 36 https://doi.org/10.1039/D0CC00327A	journal	January 2020
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Size-Dependent Grain-Boundary Structure with Improved Conductive and Mechanical Stabilities in Sub-10-nm Gold Crystals Wang, Chunyang; Du, Kui; Song, Kepeng Physical Review Letters, Vol. 120, Issue 18 https://doi.org/10.1103/PhysRevLett.120.186102	journal	May 2018
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Oriented attachment induces fivefold twins by forming and decomposing high-energy grain boundaries Song, Miao; Zhou, Gang; Lu, Ning Science, Vol. 367, Issue 6473 https://doi.org/10.1126/science.aax6511	journal	November 2019
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
NiO[sub 2] Obtained by Electrochemical Lithium Deintercalation from Lithium Nickelate: Structural Modifications Croguennec, L.; Pouillerie, C.; Delmas, C. Journal of The Electrochemical Society, Vol. 147, Issue 4 https://doi.org/10.1149/1.1393356	journal	January 2000
The Character of Dislocations in LiCoO[sub 2] Gabrisch, H.; Yazami, R.; Fultz, B. Electrochemical and Solid-State Letters, Vol. 5, Issue 6 https://doi.org/10.1149/1.1472257	journal	January 2002
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

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