Underlying limitations behind impedance rise and capacity fade of single crystalline Ni-rich cathodes synthesized via a molten-salt route

Azhari, Luqman; Meng, Zifei; Yang, Zhenzhen; Gao, Guanhui; Han, Yimo; Wang, Yan

doi:10.1016/j.jpowsour.2022.231963

Underlying limitations behind impedance rise and capacity fade of single crystalline Ni-rich cathodes synthesized via a molten-salt route

Journal Article · Wed Aug 17 00:00:00 EDT 2022 · Journal of Power Sources

DOI:https://doi.org/10.1016/j.jpowsour.2022.231963· OSTI ID:1902347

^[1]; ^[1]; Yang, Zhenzhen ^[2]; Gao, Guanhui ^[3]; Han, Yimo ^[3]; ^[1]

Worcester Polytechnic Institute, MA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Rice Univ., Houston, TX (United States)

Layered oxide LiNi_xMn_yCo_zO₂ (NMC) cathodes are often synthesized as polycrystalline secondary particles. Due to intergranular fracture stemming from volume changes of randomly oriented primary particles during charge/discharge, the synthesis of larger single-crystalline cathodes is of high interest. In this work, molten salt assisted growth of micron-sized Ni-rich crystals is achieved with excellent crystallinity, low cation mixing, and negligible impurities. However, electrochemical performance is compromised by high surface reactivity resulting in decomposition of electrolyte and subsequent formation of a thick CEI layer. While intergranular fracture is eliminated, planar gliding and severe intragranular fracture along the (003) plane occurs in the high voltage region within the first few cycles and is associated primarily with H2 to H3 structural transitions. In addition, H2 to H3 transitions are highly irreversible with cyclic voltammograms revealing polarization growth within <5 cycles. Subsequently, the single-crystalline material exhibited markedly reduced available capacity and enhanced capacity fade from sharp impedance growth compared to its polycrystalline counterpart. Here, this work furthers a fundamental understanding into the limitations of single-crystalline Ni-rich cathodes, and the obstacles limiting the advantages offered by the single-crystalline morphology.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); Ford Motor Company

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1902347

Journal Information:: Journal of Power Sources, Journal Name: Journal of Power Sources Vol. 545; ISSN 0378-7753

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Improved Cycling Stability of Li[Ni _0.90 Co _0.05 Mn _0.05 ]O ₂ Through Microstructure Modification by Boron Doping for Li-Ion Batteries Park, Kang-Joon; Jung, Hun-Gi; Kuo, Liang-Yin Advanced Energy Materials, Vol. 8, Issue 25 https://doi.org/10.1002/aenm.201801202	journal	July 2018
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
Next‐Generation Cobalt‐Free Cathodes – A Prospective Solution to the Battery Industry's Cobalt Problem Muralidharan, Nitin; Self, Ethan C.; Dixit, Marm Advanced Energy Materials, Vol. 12, Issue 9 https://doi.org/10.1002/aenm.202103050	journal	January 2022
Tuning Cobalt‐Free Nickel‐Rich Layered LiNi_0.9Mn_0.1O₂Cathode Material for Lithium‐Ion Batteries Ma, Rui; Zhao, Zhikun; Fu, Jiale ChemElectroChem, Vol. 7, Issue 12 https://doi.org/10.1002/celc.202000443	journal	June 2020
Assessing Long‐Term Cycling Stability of Single‐Crystal Versus Polycrystalline Nickel‐Rich NCM in Pouch Cells with 6 mAh cm ⁻² Electrodes Zhao, Wengao; Zou, Lianfeng; Zhang, Leiting Small, Vol. 18, Issue 14 https://doi.org/10.1002/smll.202107357	journal	February 2022
Research Progress of Single‐Crystal Nickel‐Rich Cathode Materials for Lithium Ion Batteries You, Bianzheng; Wang, Zhixing; Shen, Fang Small Methods, Vol. 5, Issue 8 https://doi.org/10.1002/smtd.202100234	journal	July 2021
Evaluating single-crystal and polycrystalline NMC811 electrodes in lithium-ion cells via non-destructive EIS alone Saunders, Luke; Wang, Jiabin; Stimming, Ulrich Journal of Applied Electrochemistry, Vol. 52, Issue 9 https://doi.org/10.1007/s10800-022-01713-x	journal	May 2022
Automotive Li-Ion Batteries: Current Status and Future Perspectives Ding, Yuanli; Cano, Zachary P.; Yu, Aiping Electrochemical Energy Reviews, Vol. 2, Issue 1 https://doi.org/10.1007/s41918-018-0022-z	journal	January 2019
Building Safe Lithium-Ion Batteries for Electric Vehicles: A Review Duan, Jian; Tang, Xuan; Dai, Haifeng Electrochemical Energy Reviews, Vol. 3, Issue 1 https://doi.org/10.1007/s41918-019-00060-4	journal	December 2019
Quantitative analysis of Ni2+/Ni3+ in Li[NixMnyCoz]O2 cathode materials: Non-linear least-squares fitting of XPS spectra Fu, Zewei; Hu, Juntao; Hu, Wenlong Applied Surface Science, Vol. 441 https://doi.org/10.1016/j.apsusc.2018.02.114	journal	May 2018
The cathode–electrolyte interface in the Li-ion battery Edström, K.; Gustafsson, T.; Thomas, J. O. Electrochimica Acta, Vol. 50, Issue 2-3 https://doi.org/10.1016/j.electacta.2004.03.049	journal	November 2004
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
Bulk and surface degradation in layered Ni-rich cathode for Li ions batteries: Defect proliferation via chain reaction mechanism Yang, Chengkai; Shao, Ruiwen; Wang, Qian Energy Storage Materials, Vol. 35 https://doi.org/10.1016/j.ensm.2020.11.016	journal	March 2021
A perspective on single-crystal layered oxide cathodes for lithium-ion batteries Langdon, Jayse; Manthiram, Arumugam Energy Storage Materials, Vol. 37 https://doi.org/10.1016/j.ensm.2021.02.003	journal	May 2021
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
Mechanical and physical properties of LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC) Cheng, Eric Jianfeng; Hong, Kicheol; Taylor, Nathan John Journal of the European Ceramic Society, Vol. 37, Issue 9 https://doi.org/10.1016/j.jeurceramsoc.2017.03.048	journal	August 2017
Mechanical properties of cathode materials for lithium-ion batteries Stallard, Joe C.; Wheatcroft, Laura; Booth, Samuel G. Joule, Vol. 6, Issue 5 https://doi.org/10.1016/j.joule.2022.04.001	journal	May 2022
Minimization of the cation mixing in Li1+x(NMC)1−xO2 as cathode material Zhang, Xiaoyu; Jiang, W. J.; Mauger, A. Journal of Power Sources, Vol. 195, Issue 5 https://doi.org/10.1016/j.jpowsour.2009.09.029	journal	March 2010
Designing principle for Ni-rich cathode materials with high energy density for practical applications Xia, Yu; Zheng, Jianming; Wang, Chongmin Nano Energy, Vol. 49 https://doi.org/10.1016/j.nanoen.2018.04.062	journal	July 2018
Understanding fundamental effects of Cu impurity in different forms for recovered LiNi0.6Co0.2Mn0.2O2 cathode materials Zhang, Ruihan; Meng, Zifei; Ma, Xiaotu Nano Energy, Vol. 78 https://doi.org/10.1016/j.nanoen.2020.105214	journal	December 2020
A universal etching method for synthesizing high-performance single crystal cathode materials Ma, Xiaotu; Vanaphuti, Panawan; Fu, Jinzhao Nano Energy, Vol. 87 https://doi.org/10.1016/j.nanoen.2021.106194	journal	September 2021
Growth Manner of Octahedral-Shaped Li(Ni _1/3 Co _1/3 Mn _1/3 )O ₂ Single Crystals in Molten Na ₂ SO ₄ Kimijima, Takeshi; Zettsu, Nobuyuki; Teshima, Katsuya Crystal Growth & Design, Vol. 16, Issue 5 https://doi.org/10.1021/acs.cgd.5b01723	journal	April 2016
Oxygen Anion Solubility as a Factor in Molten Flux Crystal Growth, Synthesis, and Characterization of Four New Reduced Lanthanide Molybdenum Oxides: Ce_4.918(3)Mo₃O₁₆, Pr_4.880(3)Mo₃O₁₆, Nd_4.910(3)Mo₃O₁₆, and Sm_4.952(3)Mo₃O₁₆ Cortese, Anthony J.; Abeysinghe, Dileka; Wilkins, Branford Crystal Growth & Design, Vol. 16, Issue 8 https://doi.org/10.1021/acs.cgd.6b00201	journal	July 2016
Effects of Alkali Cations and Sulfate/Chloride Anions on the Flux Growth of {001}-Faceted β-Li₂TiO₃ Crystals Xiao, Xiong; Hayashi, Fumitaka; Yubuta, Kunio Crystal Growth & Design, Vol. 17, Issue 3 https://doi.org/10.1021/acs.cgd.6b01504	journal	January 2017
Reaction Heterogeneity in LiNi _0.8 Co _0.15 Al _0.05 O ₂ Induced by Surface Layer Grenier, Antonin; Liu, Hao; Wiaderek, Kamila M. Chemistry of Materials, Vol. 29, Issue 17 https://doi.org/10.1021/acs.chemmater.7b02236	journal	August 2017
Evolution of Structure and Lithium Dynamics in LiNi _0.8 Mn _0.1 Co _0.1 O ₂ (NMC811) Cathodes during Electrochemical Cycling Märker, Katharina; Reeves, Philip J.; Xu, Chao Chemistry of Materials, Vol. 31, Issue 7 https://doi.org/10.1021/acs.chemmater.9b00140	journal	March 2019
Tuning the Li/Ni Disorder of the NMC811 Cathode by Thermally Driven Competition between Lattice Ordering and Structure Decomposition Wang, Ting; Ren, Keliang; Xiao, Wei The Journal of Physical Chemistry C, Vol. 124, Issue 10 https://doi.org/10.1021/acs.jpcc.0c00720	journal	February 2020
Changing Established Belief on Capacity Fade Mechanisms: Thorough Investigation of LiNi _1/3 Co _1/3 Mn _1/3 O ₂ (NCM111) under High Voltage Conditions Kasnatscheew, Johannes; Evertz, Marco; Streipert, Benjamin The Journal of Physical Chemistry C, Vol. 121, Issue 3 https://doi.org/10.1021/acs.jpcc.6b11746	journal	January 2017
Simultaneous Enhancement of Interfacial Stability and Kinetics of Single-Crystal LiNi _0.6 Mn _0.2 Co _0.2 O ₂ through Optimized Surface Coating and Doping Bao, Wenda; Qian, Guannan; Zhao, Lianqi Nano Letters, Vol. 20, Issue 12 https://doi.org/10.1021/acs.nanolett.0c03778	journal	November 2020
Revealing Mechanism of Li ₃ PO ₄ Coating Suppressed Surface Oxygen Release for Commercial Ni-Rich Layered Cathodes Gan, Qingmeng; Qin, Ning; Wang, Zhenyu ACS Applied Energy Materials, Vol. 3, Issue 8 https://doi.org/10.1021/acsaem.0c00859	journal	July 2020
Comprehensive Study of Al- and Zr-Modified LiNi _0.8 Mn _0.1 Co _0.1 O ₂ through Synergy of Coating and Doping Gao, Yan; Park, Jonghyun; Liang, Xinhua ACS Applied Energy Materials, Vol. 3, Issue 9 https://doi.org/10.1021/acsaem.0c01420	journal	August 2020
Modified Nickel-Rich Cathodes via Conformal Nanoparticle Coating of Precursors Using a Single Reactor Process Azhari, Luqman; Arsenault, Renata; Gao, Guanhui ACS Applied Energy Materials, Vol. 4, Issue 12 https://doi.org/10.1021/acsaem.1c03257	journal	December 2021
Effect of Particle Size on LiNi_0.6Mn_0.2Co_0.2O₂ Layered Oxide Performance in Li-Ion Batteries Soloy, Adrien; Flahaut, Delphine; Allouche, Joachim ACS Applied Energy Materials, Vol. 5, Issue 5 https://doi.org/10.1021/acsaem.1c03924	journal	May 2022
Surface-Modified Quaternary Layered Ni-Rich Cathode Materials by Li₂ZrO₃ for Improved Electrochemical Performance for High-Power Li-Ion Batteries Jeyakumar, Juliya; Wu, Yi-Shiuan; Wu, She-Huang ACS Applied Energy Materials, Vol. 5, Issue 4 https://doi.org/10.1021/acsaem.2c00224	journal	April 2022
Controlling Ni²⁺ from the Surface to the Bulk by a New Cathode Electrolyte Interphase Formation on a Ni-Rich Layered Cathode in High-Safe and High-Energy-Density Lithium-Ion Batteries Yeh, Nan-Hung; Wang, Fu-Ming; Khotimah, Chusnul ACS Applied Materials & Interfaces, Vol. 13, Issue 6 https://doi.org/10.1021/acsami.0c22295	journal	February 2021
Demonstrating Apparently Inconspicuous but Sensitive Impacts on the Rollover Failure of Lithium-Ion Batteries at a High Voltage Klein, Sven; Bärmann, Peer; Stolz, Lukas ACS Applied Materials & Interfaces, Vol. 13, Issue 48 https://doi.org/10.1021/acsami.1c17408	journal	November 2021
From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes Han, Binghong; Key, Baris; Lapidus, Saul H. ACS Applied Materials & Interfaces, Vol. 9, Issue 47 https://doi.org/10.1021/acsami.7b13597	journal	November 2017
Nasicon-Type Surface Functional Modification in Core–Shell LiNi _0.5 Mn _0.3 Co _0.2 O ₂ @NaTi ₂ (PO ₄ ) ₃ Cathode Enhances Its High-Voltage Cycling Stability and Rate Capacity toward Li-Ion Batteries Liang, Longwei; Sun, Xuan; Wu, Chen ACS Applied Materials & Interfaces, Vol. 10, Issue 6 https://doi.org/10.1021/acsami.7b15808	journal	January 2018
Targeted Surface Doping with Reversible Local Environment Improves Oxygen Stability at the Electrochemical Interfaces of Nickel-Rich Cathode Materials Steiner, James D.; Cheng, Hao; Walsh, Julia ACS Applied Materials & Interfaces, Vol. 11, Issue 41 https://doi.org/10.1021/acsami.9b14729	journal	October 2019
Degradation Mechanism of Ni-Enriched NCA Cathode for Lithium Batteries: Are Microcracks Really Critical? Park, Kang-Joon; Hwang, Jang-Yeon; Ryu, Hoon-Hee ACS Energy Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsenergylett.9b00733	journal	May 2019
High Performance Cathode Recovery from Different Electric Vehicle Recycling Streams Zheng, Zhangfeng; Chen, Mengyuan; Wang, Qiang ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 11 https://doi.org/10.1021/acssuschemeng.8b02405	journal	September 2018
Lithium Nickel Cobalt Manganese Oxide Synthesized Using Alkali Chloride Flux: Morphology and Performance As a Cathode Material for Lithium Ion Batteries Kim, Yongseon ACS Applied Materials & Interfaces, Vol. 4, Issue 5 https://doi.org/10.1021/am300386j	journal	April 2012
Activation Mechanism of LiNi _0.80 Co _0.15 Al _0.05 O ₂ : Surface and Bulk Operando Electrochemical, Differential Electrochemical Mass Spectrometry, and X-ray Diffraction Analyses Robert, Rosa; Bünzli, Christa; Berg, Erik J. Chemistry of Materials, Vol. 27, Issue 2 https://doi.org/10.1021/cm503833b	journal	January 2015
Interfacial Origin of Performance Improvement and Fade for 4.6 V LiNi _0.5 Co _0.2 Mn _0.3 O ₂ Battery Cathodes Lee, Yu-Mi; Nam, Kyoung-Mo; Hwang, Eui-Hyung The Journal of Physical Chemistry C, Vol. 118, Issue 20 https://doi.org/10.1021/jp501670g	journal	May 2014
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
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
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
Stabilizing nickel-rich layered oxide cathodes by magnesium doping for rechargeable lithium-ion batteries Li, Hang; Zhou, Pengfei; Liu, Fangming Chemical Science, Vol. 10, Issue 5 https://doi.org/10.1039/C8SC03385D	journal	January 2019
Single-crystal based studies for correlating the properties and high-voltage performance of Li[Ni _x Mn _y Co _1−x−y ]O ₂ cathodes Zhu, Jian; Chen, Guoying Journal of Materials Chemistry A, Vol. 7, Issue 10 https://doi.org/10.1039/C8TA10329A	journal	January 2019
Revealing the degradation mechanism of Ni-rich cathode materials after ambient storage and related regeneration method Lv, Congjie; Li, Zhenguo; Ren, Xiaoning Journal of Materials Chemistry A, Vol. 9, Issue 7 https://doi.org/10.1039/D0TA10378K	journal	January 2021
Prospects and limitations of single-crystal cathode materials to overcome cross-talk phenomena in high-voltage lithium ion cells Klein, Sven; Bärmann, Peer; Fromm, Olga Journal of Materials Chemistry A, Vol. 9, Issue 12 https://doi.org/10.1039/D0TA11775G	journal	January 2021
Powder Characteristics of Pb(Mg1/3Nb2/3)O3 Prepared by Molten Salt Synthesis Yoon, Ki Hyun; Cho, Yong-Soo; Lee, Dong-Heon Journal of the American Ceramic Society, Vol. 76, Issue 5 https://doi.org/10.1111/j.1151-2916.1993.tb03770.x	journal	May 1993
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
All-Dry Synthesis of Single Crystal NMC Cathode Materials for Li-Ion Batteries Zheng, Lituo; Bennett, J. Craig; Obrovac, M. N. Journal of The Electrochemical Society, Vol. 167, Issue 13 https://doi.org/10.1149/1945-7111/abbcb1	journal	October 2020
Temperature-Swing Synthesis of Large-Size Single-Crystal LiNi _0.6 Mn _0.2 Co _0.2 O ₂ Cathode Materials Qian, Guannan; Li, Zhiyuan; Meng, Dechao Journal of The Electrochemical Society, Vol. 168, Issue 1 https://doi.org/10.1149/1945-7111/abdde0	journal	January 2021
Effect of Lithiation upon the Shear Strength of NMC811 Single Crystals Stallard, Joe C.; Vema, Sundeep; Hall, David S. Journal of The Electrochemical Society, Vol. 169, Issue 4 https://doi.org/10.1149/1945-7111/ac6244	journal	April 2022
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
Synthesis of Single Crystal LiNi _0.6 Mn _0.2 Co _0.2 O ₂ with Enhanced Electrochemical Performance for Lithium Ion Batteries Li, Hongyang; Li, Jing; Ma, Xiaowei Journal of The Electrochemical Society, Vol. 165, Issue 5 https://doi.org/10.1149/2.0951805jes	journal	January 2018
Comparison of Single Crystal and Polycrystalline LiNi _0.5 Mn _0.3 Co _0.2 O ₂ Positive Electrode Materials for High Voltage Li-Ion Cells Li, Jing; Cameron, Andrew R.; Li, Hongyang Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.0991707jes	journal	January 2017
Superior Cycle Stability of Single Crystal Nickel-Rich Layered Oxides with Micron-Scale Grain Size as Cathode Material for Lithium Ion Batteries Yang, Cheng International Journal of Electrochemical Science https://doi.org/10.20964/2020.06.03	journal	June 2020
Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries Teichert, Philipp; Eshetu, Gebrekidan Gebresilassie; Jahnke, Hannes Batteries, Vol. 6, Issue 1 https://doi.org/10.3390/batteries6010008	journal	January 2020
On the Sensitivity of the Ni-rich Layered Cathode Materials for Li-ion Batteries to the Different Calcination Conditions Ronduda, Hubert; Zybert, Magdalena; Szczęsna-Chrzan, Anna Nanomaterials, Vol. 10, Issue 10 https://doi.org/10.3390/nano10102018	journal	October 2020

Similar Records

Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode

Journal Article · Thu Dec 10 23:00:00 EST 2020 · Science · OSTI ID:1735502

Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode

Journal Article · Wed Dec 09 23:00:00 EST 2020 · Science · OSTI ID:1734972

Related Subjects

25 ENERGY STORAGE
Li-ion battery
LiNi0.8Mn0.1Co0.1O
NMC
Single-crystal
intragranular fracture

Underlying limitations behind impedance rise and capacity fade of single crystalline Ni-rich cathodes synthesized via a molten-salt route

Citation Formats

References (62)

Similar Records

Related Subjects