Parasitic structure defect blights sustainability of cobalt-free single crystalline cathodes

Yu, Lei; Dai, Alvin; Zhou, Tao; Huang, Weiyuan; Wang, Jing; Li, Tianyi; He, Xinyou; Ma, Lu; Xiao, Xianghui; Ge, Mingyuan; Amine, Rachid; Ehrlich, Steven N.; Ou, Xing; Wen, Jianguo; Liu, Tongchao; Amine, Khalil

doi:10.1038/s41467-024-55235-5

Parasitic structure defect blights sustainability of cobalt-free single crystalline cathodes

Journal Article · Mon Jan 06 00:00:00 EST 2025 · Nature Communications

DOI:https://doi.org/10.1038/s41467-024-55235-5· OSTI ID:2496747

Yu, Lei; Dai, Alvin; ; ; Wang, Jing; ; He, Xinyou; Ma, Lu; ; ; ; Ehrlich, Steven N.; ; ; ;

Abstract

Recent efforts to reduce battery costs and enhance sustainability have focused on eliminating Cobalt (Co) from cathode materials. While Co-free designs have shown notable success in polycrystalline cathodes, their impact on single crystalline (SC) cathodes remains less understood due to the significantly extended lithium diffusion pathways and the higher-temperature synthesis involved. Here, we reveal that removing Co from SC cathodes is structurally and electrochemically unfavorable, exhibiting unusual voltage fade behavior. Using multiscale diffraction and imaging techniques, we identify lithium-rich nanodomains (LRNDs) as a heterogeneous phase within the layered structure of Co-free SC cathodes. These LRNDs act as critical tipping points, inducing significant chemo-mechanical lattice strain and irreversible structural degradation, which exacerbates the voltage and capacity loss in electrochemical performance. Our findings highlight the considerable challenges of developing Co-free SC cathodes compared to polycrystalline ones and emphasize the need for new strategies to balance the interplay between cost, sustainability, and performance.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 2496747

Alternate ID(s):: OSTI ID: 2527300

Report Number(s):: BNL--227639-2025-JAAM; 434; PII: 55235

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 16; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

References (50)

Insights into Micromorphological Effects of Cation Disordering on Co‐Free Layered Oxide Cathodes Yu, Lei; Zhao, Hongan; Sun, Jingwen Advanced Functional Materials, Vol. 32, Issue 40 https://doi.org/10.1002/adfm.202204931	journal	July 2022
High Cycling Rate‐Induced Irreversible TMO₆ Slabs Glide in Co‐Free High‐Ni Layered Cathode Materials Yu, Lei; Huang, Yin; Han, Qiaofeng Advanced Functional Materials, Vol. 33, Issue 32 https://doi.org/10.1002/adfm.202301650	journal	May 2023
Controllable Solid Electrolyte Interphase in Nickel-Rich Cathodes by an Electrochemical Rearrangement for Stable Lithium-Ion Batteries Kim, Junhyeok; Lee, Jieun; Ma, Hyunsoo Advanced Materials, Vol. 30, Issue 5 https://doi.org/10.1002/adma.201704309	journal	December 2017
High‐Nickel NMA: A Cobalt‐Free Alternative to NMC and NCA Cathodes for Lithium‐Ion Batteries Li, Wangda; Lee, Steven; Manthiram, Arumugam Advanced Materials, Vol. 32, Issue 33 https://doi.org/10.1002/adma.202002718	journal	July 2020
In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes Zhao, Jianqing; Zhang, Wei; Huq, Ashfia Advanced Energy Materials, Vol. 7, Issue 3 https://doi.org/10.1002/aenm.201601266	journal	October 2016
Cobalt‐Free High‐Capacity Ni‐Rich Layered Li[Ni _0.9 Mn _0.1 ]O ₂ Cathode Aishova, Assylzat; Park, Geon‐Tae; Yoon, Chong S. Advanced Energy Materials, Vol. 10, Issue 4 https://doi.org/10.1002/aenm.201903179	journal	December 2019
A Comparative Investigation of Single Crystal and Polycrystalline Ni‐Rich NCMs as Cathodes for Lithium‐Ion Batteries Deng, Xianming; Zhang, Rui; Zhou, Kai ENERGY & ENVIRONMENTAL MATERIALS https://doi.org/10.1002/eem2.12331	journal	April 2022
Single-crystal nickel-rich layered-oxide battery cathode materials: synthesis, electrochemistry, and intra-granular fracture Qian, Guannan; Zhang, Youtian; Li, Linsen Energy Storage Materials, Vol. 27 https://doi.org/10.1016/j.ensm.2020.01.027	journal	May 2020
Breaking Free from Cobalt Reliance in Lithium-Ion Batteries Gourley, Storm William D.; Or, Tyler; Chen, Zhongwei iScience, Vol. 23, Issue 9 https://doi.org/10.1016/j.isci.2020.101505	journal	September 2020
Lithium-Ion Battery Supply Chain Considerations: Analysis of Potential Bottlenecks in Critical Metals Olivetti, Elsa A.; Ceder, Gerbrand; Gaustad, Gabrielle G. Joule, Vol. 1, Issue 2 https://doi.org/10.1016/j.joule.2017.08.019	journal	October 2017
Local structure and composition studies of Li1.2Ni0.2Mn0.6O2 by analytical electron microscopy Lei, C. H.; Bareño, J.; Wen, J. G. Journal of Power Sources, Vol. 178, Issue 1 https://doi.org/10.1016/j.jpowsour.2007.11.077	journal	March 2008
Insight into the origin of lithium/nickel ions exchange in layered Li(NixMnyCoz)O2 cathode materials Xiao, Yinguo; Liu, Tongchao; Liu, Jiajie Nano Energy, Vol. 49 https://doi.org/10.1016/j.nanoen.2018.04.020	journal	July 2018
Crack-free single-crystalline Ni-rich layered NCM cathode enable superior cycling performance of lithium-ion batteries Fan, Xinming; Hu, Guorong; Zhang, Bao Nano Energy, Vol. 70 https://doi.org/10.1016/j.nanoen.2020.104450	journal	April 2020
Constructing a stable interfacial phase on single-crystalline Ni-rich cathode via chemical reaction with phosphomolybdic acid Zou, Yu-Gang; Meng, Fanqi; Xiao, Dongdong Nano Energy, Vol. 87 https://doi.org/10.1016/j.nanoen.2021.106172	journal	September 2021
Analytical electron microscopy of Li1.2Co0.4Mn0.4O2 for lithium-ion batteries Wen, J. G.; Bareño, J.; Lei, C. H. Solid State Ionics, Vol. 182, Issue 1 https://doi.org/10.1016/j.ssi.2010.11.030	journal	February 2011
Ni/Li Disordering in Layered Transition Metal Oxide: Electrochemical Impact, Origin, and Control Zheng, Jiaxin; Ye, Yaokun; Liu, Tongchao Accounts of Chemical Research, Vol. 52, Issue 8 https://doi.org/10.1021/acs.accounts.9b00033	journal	June 2019
Impact of Microcrack Generation and Surface Degradation on a Nickel-Rich Layered Li[Ni _0.9 Co _0.05 Mn _0.05 ]O ₂ Cathode for Lithium-Ion Batteries Sun, Ho-Hyun; Manthiram, Arumugam Chemistry of Materials, Vol. 29, Issue 19 https://doi.org/10.1021/acs.chemmater.7b03268	journal	September 2017
Role of Superexchange Interaction on Tuning of Ni/Li Disordering in Layered Li(Ni _x Mn _y Co _z )O ₂ Zheng, Jiaxin; Teng, Gaofeng; Xin, Chao The Journal of Physical Chemistry Letters, Vol. 8, Issue 22 https://doi.org/10.1021/acs.jpclett.7b02498	journal	November 2017
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
High Nickel and No Cobalt─The Pursuit of Next-Generation Layered Oxide Cathodes Yu, Lei; Liu, Tongchao; Amine, Rachid ACS Applied Materials & Interfaces, Vol. 14, Issue 20 https://doi.org/10.1021/acsami.1c22091	journal	January 2022
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
Phase Transitions in the LiNi _0.5 Mn _0.5 O ₂ System with Temperature Hinuma, Yoyo; Meng, Ying S.; Kang, Kisuk Chemistry of Materials, Vol. 19, Issue 7 https://doi.org/10.1021/cm062903i	journal	April 2007
Layered Li _x Ni _y Mn _y Co _1-2 _y O ₂ Cathodes for Lithium Ion Batteries: Understanding Local Structure via Magnetic Properties Chernova, Natasha A.; Ma, Miaomiao; Xiao, Jie Chemistry of Materials, Vol. 19, Issue 19 https://doi.org/10.1021/cm0708867	journal	September 2007
Long-Range and Local Structure in the Layered Oxide Li _1.2 Co _0.4 Mn _0.4 O ₂ Bareño, J.; Balasubramanian, M.; Kang, S. H. Chemistry of Materials, Vol. 23, Issue 8 https://doi.org/10.1021/cm200250a	journal	April 2011
Cationic Ordering Coupled to Reconstruction of Basic Building Units during Synthesis of High-Ni Layered Oxides Zhang, Ming-Jian; Teng, Gaofeng; Chen-Wiegart, Yu-chen Karen Journal of the American Chemical Society, Vol. 140, Issue 39 https://doi.org/10.1021/jacs.8b06150	journal	August 2018
US aims for electric-car revolution — will it work? Tollefson, Jeff Nature, Vol. 616, Issue 7957 https://doi.org/10.1038/d41586-023-01255-y	journal	April 2023
Cobalt close-up Lindsay, David; Kerr, William Nature Chemistry, Vol. 3, Issue 6 https://doi.org/10.1038/nchem.1053	journal	May 2011
The path towards sustainable energy Chu, Steven; Cui, Yi; Liu, Nian Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4834	journal	December 2016
In situ inorganic conductive network formation in high-voltage single-crystal Ni-rich cathodes Fan, Xinming; Ou, Xing; Zhao, Wengao Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-25611-6	journal	September 2021
Rational design of mechanically robust Ni-rich cathode materials via concentration gradient strategy Liu, Tongchao; Yu, Lei; Lu, Jun Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-26290-z	journal	October 2021
Accurate structure models and absolute configuration determination using dynamical effects in continuous-rotation 3D electron diffraction data Klar, Paul B.; Krysiak, Yaşar; Xu, Hongyi Nature Chemistry, Vol. 15, Issue 6 https://doi.org/10.1038/s41557-023-01186-1	journal	April 2023
Performance and cost of materials for lithium-based rechargeable automotive batteries Schmuch, Richard; Wagner, Ralf; Hörpel, Gerhard Nature Energy, Vol. 3, Issue 4 https://doi.org/10.1038/s41560-018-0107-2	journal	April 2018
Building ultraconformal protective layers on both secondary and primary particles of layered lithium transition metal oxide cathodes Xu, Gui-Liang; Liu, Qiang; Lau, Kenneth K. S. Nature Energy, Vol. 4, Issue 6 https://doi.org/10.1038/s41560-019-0387-1	journal	May 2019
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
Introducing high-valence elements into cobalt-free layered cathodes for practical lithium-ion batteries Park, Geon-Tae; Namkoong, Been; Kim, Su-Bin Nature Energy, Vol. 7, Issue 10 https://doi.org/10.1038/s41560-022-01106-6	journal	September 2022
Long-life lithium-ion batteries realized by low-Ni, Co-free cathode chemistry Zhang, Rui; Wang, Chunyang; Zou, Peichao Nature Energy, Vol. 8, Issue 7 https://doi.org/10.1038/s41560-023-01267-y	journal	June 2023
Structural origin of the high-voltage instability of lithium cobalt oxide Li, Jianyuan; Lin, Cong; Weng, Mouyi Nature Nanotechnology, Vol. 16, Issue 5 https://doi.org/10.1038/s41565-021-00855-x	journal	February 2021
Origin of structural degradation in Li-rich layered oxide cathode Liu, Tongchao; Liu, Jiajie; Li, Luxi Nature, Vol. 606, Issue 7913 https://doi.org/10.1038/s41586-022-04689-y	journal	June 2022
Circular economy strategies for electric vehicle batteries reduce reliance on raw materials Baars, Joris; Domenech, Teresa; Bleischwitz, Raimund Nature Sustainability, Vol. 4, Issue 1 https://doi.org/10.1038/s41893-020-00607-0	journal	September 2020
Sustainable upcycling of spent LiCoO2 to an ultra-stable battery cathode at high voltage Wang, Junxiong; Jia, Kai; Ma, Jun Nature Sustainability, Vol. 6, Issue 7 https://doi.org/10.1038/s41893-023-01094-9	journal	March 2023
Electrolyte design for lithium-ion batteries with a cobalt-free cathode and silicon oxide anode Ko, Seongjae; Han, Xiao; Shimada, Tatau Nature Sustainability, Vol. 6, Issue 12 https://doi.org/10.1038/s41893-023-01237-y	journal	October 2023
Reducing cobalt from lithium-ion batteries for the electric vehicle era Ryu, Hoon-Hee; Sun, H. Hohyun; Myung, Seung-Taek Energy & Environmental Science, Vol. 14, Issue 2 https://doi.org/10.1039/D0EE03581E	journal	January 2021
(S)TEM-EELS as an advanced characterization technique for lithium-ion batteries Yu, Lei; Li, Matthew; Wen, Jianguo Materials Chemistry Frontiers, Vol. 5, Issue 14 https://doi.org/10.1039/D1QM00275A	journal	January 2021
Comparative study of polycrystalline and single-crystal NCM811 cathode materials: the role of crystal defects in electrochemical performance Zhu, Boyuan; Ning, Yadong; Xu, Ziyang Journal of Materials Chemistry A, Vol. 12, Issue 3 https://doi.org/10.1039/D3TA03290F	journal	January 2024
Three-dimensional rotation electron diffraction: software RED for automated data collection and data processing Wan, Wei; Sun, Junliang; Su, Jie Journal of Applied Crystallography, Vol. 46, Issue 6 https://doi.org/10.1107/S0021889813027714	journal	November 2013
Cobalt in lithium-ion batteries Li, Matthew; Lu, Jun Science, Vol. 367, Issue 6481 https://doi.org/10.1126/science.aba9168	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
Unrecoverable lattice rotation governs structural degradation of single-crystalline cathodes Huang, Weiyuan; Liu, Tongchao; Yu, Lei Science, Vol. 384, Issue 6698 https://doi.org/10.1126/science.ado1675	journal	May 2024
Is Cobalt Needed in Ni-Rich Positive Electrode Materials for Lithium Ion Batteries? Li, Hongyang; Cormier, Marc; Zhang, Ning Journal of The Electrochemical Society, Vol. 166, Issue 4 https://doi.org/10.1149/2.1381902jes	journal	January 2019

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