Positive Role of Fluorine Impurity in Recovered LiNi0.6Co0.2Mn0.2O2 Cathode Materials

Zheng, Yadong; Zhang, Ruihan; Vanaphuti, Panawan; Liu, Yangtao; Yang, Zhenzhen; Wang, Yan

doi:10.1021/acsami.1c17341

Positive Role of Fluorine Impurity in Recovered LiNi_0.6Co_0.2Mn_0.2O₂ Cathode Materials

Journal Article · Fri Nov 19 00:00:00 EST 2021 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.1c17341· OSTI ID:1838890

^[1]; Zhang, Ruihan ^[1]; ^[1]; Liu, Yangtao ^[1]; Yang, Zhenzhen ^[2]; ^[1]

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

Lithium-ion battery (LIB) recycling is considered as an important component to enable industry sustainability. A massive number of LIBs in portable electronics, electric vehicles, and grid storage will eventually end up as wastes, leading to serious economic and environmental problems. Hence, tremendous efforts have been made to improve the hydrometallurgical recycling process because it is the most promising option for handling end-of-life LIBs owing to its wide applicability, low cost, and high productivity. Despite these advantages, some extra elements (Al, Fe, C, F, and so forth) remain as impurities in the removal process and are retained in the solution, which is a great challenge to obtain high-quality cathode materials. In this work, the impacts caused by fluorine impurity on the LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) cathode are intensively investigated via hydrometallurgical coprecipitation for the first time. Our results show that up to 1 at. % fluorine impurity brings a positive influence on the recovered material due to a higher Ni²⁺ ratio on the surface of cathode particles. In addition, the presence of fluoride ions during coprecipitation could lead to the formation of holes in cathode particles, which improves the rate capability and cyclability dramatically. Compared to the virgin material, the capacity of the NCM622 material with 0.2 at. % fluorine impurity is boosted by ~8% (167.7 mA h/g) with a remarkable capacity retention of 98.0% after 100 cycles at 0.33 C. Besides, the cathode with 0.2 at. % fluorine impurity shows a far better rate performance, especially at high rates (~7% increased at 5 C) than that of virgin. Furthermore, these results convince that a low concentration of fluorine impurity is desirable in the hydrometallurgical recycling process. More importantly, this study offers implications in the design of high-performance NCM622 cathode materials via coprecipitation production with ion doping in the near future.

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)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1838890

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 48 Vol. 13; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

Review on Synthesis, Characterization, and Electrochemical Properties of Fluorinated Nickel‐Cobalt‐Manganese Cathode Active Materials for Lithium‐Ion Batteries Breddemann, Ulf; Krossing, Ingo ChemElectroChem, Vol. 7, Issue 6 https://doi.org/10.1002/celc.202000029	journal	March 2020
Voltage Decay in Layered Li-Rich Mn-Based Cathode Materials Zhang, Kun; Li, Biao; Zuo, Yuxuan Electrochemical Energy Reviews, Vol. 2, Issue 4 https://doi.org/10.1007/s41918-019-00049-z	journal	August 2019
Degradation Mechanisms and Mitigation Strategies of Nickel-Rich NMC-Based Lithium-Ion Batteries Li, Tianyu; Yuan, Xiao-Zi; Zhang, Lei Electrochemical Energy Reviews, Vol. 3, Issue 1 https://doi.org/10.1007/s41918-019-00053-3	journal	October 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
Improved electrochemical property of Ni-rich LiNi0.6Co0.2Mn0.2O2 cathode via in-situ ZrO2 coating for high energy density lithium ion batteries Yao, Liu; Liang, Fengqing; Jin, Jun Chemical Engineering Journal, Vol. 389 https://doi.org/10.1016/j.cej.2020.124403	journal	June 2020
Synthetic optimization of Li[Ni1/3Co1/3Mn1/3]O2 via co-precipitation Lee, M. -H.; Kang, Y. -J.; Myung, S. -T. Electrochimica Acta, Vol. 50, Issue 4 https://doi.org/10.1016/j.electacta.2004.07.038	journal	December 2004
Unravelling the growth mechanism of hierarchically structured Ni1/3Co1/3Mn1/3(OH)2 and their application as precursors for high-power cathode materials Hua, Weibo; Liu, Wenyuan; Chen, Mingzhe Electrochimica Acta, Vol. 232 https://doi.org/10.1016/j.electacta.2017.02.105	journal	April 2017
The effect of Fe as an impurity element for sustainable resynthesis of Li[Ni1/3Co1/3Mn1/3]O2 cathode material from spent lithium-ion batteries Park, Sanghyuk; Kim, Duho; Ku, Heesuk Electrochimica Acta, Vol. 296 https://doi.org/10.1016/j.electacta.2018.11.001	journal	February 2019
Recycling of lithium-ion batteries: a novel method to separate coating and foil of electrodes Hanisch, Christian; Loellhoeffel, Thomas; Diekmann, Jan Journal of Cleaner Production, Vol. 108 https://doi.org/10.1016/j.jclepro.2015.08.026	journal	December 2015
Effect of impurities caused by a recycling process on the electrochemical performance of Li[Ni0.33Co0.33Mn0.33]O2 Krüger, S.; Hanisch, C.; Kwade, A. Journal of Electroanalytical Chemistry, Vol. 726 https://doi.org/10.1016/j.jelechem.2014.05.017	journal	July 2014
LiNi0.5Co0.2Mn0.3O2 hollow microspheres-synthesis, characterization and application as cathode materials for power lithium ion batteries Zhao, Xinxin; An, Liwei; Sun, Jiachen Journal of Electroanalytical Chemistry, Vol. 810 https://doi.org/10.1016/j.jelechem.2018.01.006	journal	February 2018
High-value utilization of graphite electrodes in spent lithium-ion batteries: From 3D waste graphite to 2D graphene oxide Yu, Jiadong; Lin, Minsong; Tan, Quanyin Journal of Hazardous Materials, Vol. 401 https://doi.org/10.1016/j.jhazmat.2020.123715	journal	January 2021
Recycling End-of-Life Electric Vehicle Lithium-Ion Batteries Chen, Mengyuan; Ma, Xiaotu; Chen, Bin Joule, Vol. 3, Issue 11 https://doi.org/10.1016/j.joule.2019.09.014	journal	November 2019
A closed loop process for recycling spent lithium ion batteries Gratz, Eric; Sa, Qina; Apelian, Diran Journal of Power Sources, Vol. 262, p. 255-262 https://doi.org/10.1016/j.jpowsour.2014.03.126	journal	September 2014
Synthesis of high performance LiNi1/3Mn1/3Co1/3O2 from lithium ion battery recovery stream Sa, Qina; Gratz, Eric; He, Meinan Journal of Power Sources, Vol. 282 https://doi.org/10.1016/j.jpowsour.2015.02.046	journal	May 2015
Significantly improving cycling performance of cathodes in lithium ion batteries: The effect of Al2O3 and LiAlO2 coatings on LiNi0.6Co0.2Mn0.2O2 Liu, Wen; Li, Xifei; Xiong, Dongbin Nano Energy, Vol. 44 https://doi.org/10.1016/j.nanoen.2017.11.010	journal	February 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
Surface engineering of LiNi0.8Mn0.1Co0.1O2 towards boosting lithium storage: Bimetallic oxides versus monometallic oxides Xu, Quan; Li, Xifei; Kheimeh Sari, Hirbod Maleki Nano Energy, Vol. 77 https://doi.org/10.1016/j.nanoen.2020.105034	journal	November 2020
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
Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries Chen, Xiangping; Chen, Yongbin; Zhou, Tao Waste Management, Vol. 38 https://doi.org/10.1016/j.wasman.2014.12.023	journal	April 2015
Facilitating the Operation of Lithium-Ion Cells with High-Nickel Layered Oxide Cathodes with a Small Dose of Aluminum Li, Jianyu; Li, Wangda; Wang, Shanyu Chemistry of Materials, Vol. 30, Issue 9 https://doi.org/10.1021/acs.chemmater.8b01077	journal	April 2018
Copper Impurity Effects on LiNi _1/3 Mn _1/3 Co _1/3 O ₂ Cathode Material Sa, Qina; Heelan, Joseph A.; Lu, Yuan ACS Applied Materials & Interfaces, Vol. 7, Issue 37 https://doi.org/10.1021/acsami.5b04426	journal	September 2015
Investigation of Fluorine and Nitrogen as Anionic Dopants in Nickel-Rich Cathode Materials for Lithium-Ion Batteries Binder, Jan O.; Culver, Sean P.; Pinedo, Ricardo ACS Applied Materials & Interfaces, Vol. 10, Issue 51 https://doi.org/10.1021/acsami.8b16049	journal	December 2018
Enhanced Electrochemical Performance of the Lithium-Manganese-Rich Cathode for Li-Ion Batteries with Na and F CoDoping Vanaphuti, Panawan; Chen, Jiajun; Cao, Jiayu ACS Applied Materials & Interfaces, Vol. 11, Issue 41 https://doi.org/10.1021/acsami.9b13838	journal	September 2019
Systematic Study of Al Impurity for NCM622 Cathode Materials Zhang, Ruihan; Zheng, Yadong; Yao, Zeyi ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 26 https://doi.org/10.1021/acssuschemeng.0c02965	journal	June 2020
Unveiling the Influence of Carbon Impurity on Recovered NCM622 Cathode Material Zheng, Yadong; Zhang, Ruihan; Vanaphuti, Panawan ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 17 https://doi.org/10.1021/acssuschemeng.1c01510	journal	April 2021
A Critical Review and Analysis on the Recycling of Spent Lithium-Ion Batteries Lv, Weiguang; Wang, Zhonghang; Cao, Hongbin ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 2 https://doi.org/10.1021/acssuschemeng.7b03811	journal	December 2017
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
Electron Transfer Mechanisms upon Lithium Deintercalation from LiCoO ₂ to CoO ₂ Investigated by XPS Dahéron, L.; Dedryvère, R.; Martinez, H. Chemistry of Materials, Vol. 20, Issue 2 https://doi.org/10.1021/cm702546s	journal	January 2008
Analysis of the Growth Mechanism of Coprecipitated Spherical and Dense Nickel, Manganese, and Cobalt-Containing Hydroxides in the Presence of Aqueous Ammonia van Bommel, Andrew; Dahn, J. R. Chemistry of Materials, Vol. 21, Issue 8 https://doi.org/10.1021/cm803144d	journal	April 2009
Mechanisms of Nucleation and Growth of Nanoparticles in Solution Thanh, Nguyen T. K.; Maclean, N.; Mahiddine, S. Chemical Reviews, Vol. 114, Issue 15 https://doi.org/10.1021/cr400544s	journal	July 2014
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
A reflection on lithium-ion battery cathode chemistry Manthiram, Arumugam Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15355-0	journal	March 2020
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
Recycling lithium-ion batteries from electric vehicles Harper, Gavin; Sommerville, Roberto; Kendrick, Emma Nature, Vol. 575, Issue 7781 https://doi.org/10.1038/s41586-019-1682-5	journal	November 2019
Closed Loop Recycling of Electric Vehicle Batteries to Enable Ultra-high Quality Cathode Powder Chen, Mengyuan; Zheng, Zhangfeng; Wang, Qiang Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-018-38238-3	journal	February 2019
Examining different recycling processes for lithium-ion batteries Ciez, Rebecca E.; Whitacre, J. F. Nature Sustainability, Vol. 2, Issue 2 https://doi.org/10.1038/s41893-019-0222-5	journal	February 2019
Hierarchical Porous LiNi1/3Co1/3Mn1/3O2 Nano-/Micro Spherical Cathode Material: Minimized Cation Mixing and Improved Li+ Mobility for Enhanced Electrochemical Performance Chen, Zhen; Wang, Jin; Chao, Dongliang Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep25771	journal	May 2016
Double-shelled hollow microspheres of LiMn2O4 for high-performance lithium ion batteries Ding, Yuan-Li; Zhao, Xin-Bing; Xie, Jian Journal of Materials Chemistry, Vol. 21, Issue 26 https://doi.org/10.1039/c1jm10924c	journal	January 2011
A novel method to recycle mixed cathode materials for lithium ion batteries Zou, Haiyang; Gratz, Eric; Apelian, Diran Green Chemistry, Vol. 15, Issue 5 https://doi.org/10.1039/c3gc40182k	journal	January 2013
LiNi1/3Co1/3Mn1/3O2 hollow nano-micro hierarchical microspheres with enhanced performances as cathodes for lithium-ion batteries Li, Jili; Cao, Chuanbao; Xu, Xingyan Journal of Materials Chemistry A, Vol. 1, Issue 38 https://doi.org/10.1039/c3ta12375h	journal	January 2013
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
Impurity removal with highly selective and efficient methods and the recycling of transition metals from spent lithium-ion batteries Peng, Fangwei; Mu, Deying; Li, Ruhong RSC Advances, Vol. 9, Issue 38 https://doi.org/10.1039/c9ra02331c	journal	January 2019
Revealing the correlation between structural evolution and Li ⁺ diffusion kinetics of nickel-rich cathode materials in Li-ion batteries Hong, Chaoyu; Leng, Qianyi; Zhu, Jianping Journal of Materials Chemistry A, Vol. 8, Issue 17 https://doi.org/10.1039/d0ta00555j	journal	January 2020
Factors that affect Li mobility in layered lithium transition metal oxides Kang, Kisuk; Ceder, Gerbrand Physical Review B, Vol. 74, Issue 9 https://doi.org/10.1103/PhysRevB.74.094105	journal	September 2006
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
R factors in Rietveld analysis: How good is good enough? Toby, Brian H. Powder Diffraction, Vol. 21, Issue 1 https://doi.org/10.1154/1.2179804	journal	March 2006

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode
electrochemistry
electrodes
fluorine
fluorine impurity
hydrometallurgical recycling
impurities
ions
lithium-ion batteries
materials