Efficient separation and coprecipitation for simplified cathode recycling

Yu, Lu; Bai, Yaocai; Essehli, Rachid; Bisht, Anuj; Belharouak, Ilias

doi:10.1016/j.ensm.2023.103025

Efficient separation and coprecipitation for simplified cathode recycling

Journal Article · Mon Oct 30 00:00:00 EDT 2023 · Energy Storage Materials

DOI:https://doi.org/10.1016/j.ensm.2023.103025· OSTI ID:2217723

^[1]; ^[1]; Essehli, Rachid ^[1]; ^[1]; ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Hydrometallurgical recycling of spent lithium-ion batteries is among the most promising recovery approaches. The current hydrometallurgical method for battery recycling faces challenges such as complex separation and precipitation processes, and environmental concerns from the use of caustic inorganic acid and hazardous hydrogen peroxide. Our proposed modified method, namely polyol-metallurgy, uses citric acid in ethylene glycol as dual-function green solution to overcome these obstacles. This bifunctional solution leaches valuable metal ions from cathode materials (e.g., LiCoO₂), and then acts as chelating agents to selectively precipitate cobalt through an esterification reaction, without the need for additional precipitation agents. The leaching efficiency of cobalt and lithium reaches 99.55% and 97.65%, respectively, and more than 96% of cobalt could be directly self-precipitated and recovered. Further, the unique characteristics of the dual-function solution also avoids impurities from Al foils and PVDF/carbon black films, enabling the simple separation process. Therefore, the process can be completed in one-pot system with efficient leaching, separation and coprecipitation, making it more efficient and feasible for operation than existing alternatives.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Wind Energy Technologies Office

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2217723

Alternate ID(s):: OSTI ID: 2205270

Journal Information:: Energy Storage Materials, Journal Name: Energy Storage Materials Vol. 63; ISSN 2405-8297

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (51)

Boosting the Recycling Efficiency of Spent Lithium‐Ion Battery Cathodes Using a Green Reductant Rose, Satchit; Xu, Panpan; Gao, Hongpeng Advanced Energy and Sustainability Research, Vol. 2, Issue 8 https://doi.org/10.1002/aesr.202100040	journal	May 2021
Sustainable Lithium‐Metal Battery Achieved by a Safe Electrolyte Based on Recyclable and Low‐Cost Molecular Sieve Chang, Zhi; Qiao, Yu; Yang, Huijun Angewandte Chemie International Edition, Vol. 60, Issue 28 https://doi.org/10.1002/anie.202104124	journal	June 2021
Selective Extraction of Transition Metals from Spent LiNi_xCo_yMn_1−x−yO₂ Cathode via Regulation of Coordination Environment Chang, Xin; Fan, Min; Gu, Chao‐Fan Angewandte Chemie International Edition, Vol. 61, Issue 24 https://doi.org/10.1002/anie.202202558	journal	April 2022
Sustainable Direct Recycling of Lithium‐Ion Batteries via Solvent Recovery of Electrode Materials Bai, Yaocai; Muralidharan, Nitin; Li, Jianlin ChemSusChem, Vol. 13, Issue 21 https://doi.org/10.1002/cssc.202001479	journal	September 2020
A brief review on hydrometallurgical technologies for recycling spent lithium-ion batteries: Technologies for recycling spent lithium-ion batteries Chagnes, Alexandre; Pospiech, Beata Journal of Chemical Technology & Biotechnology, Vol. 88, Issue 7 https://doi.org/10.1002/jctb.4053	journal	April 2013
Effect of Sn precursor on the synthesis of SnO2 and Sb-doped SnO2 particles via polymeric precursor method López Morales, Francisco; Zayas, Teresa; Contreras, Oscar E. Frontiers of Materials Science, Vol. 7, Issue 4 https://doi.org/10.1007/s11706-013-0227-3	journal	November 2013
Comparision of Different Reductants in Leaching of Spent Lithium Ion Batteries Meshram, Pratima; Pandey, Banshi Dhar JOM, Vol. 68, Issue 10, p. 2613-2623 https://doi.org/10.1007/s11837-016-2032-9	journal	July 2016
Comprehensive study of a versatile polyol synthesis approach for cathode materials for Li-ion batteries Chung, Hyeseung; Grenier, Antonin; Huang, Ricky Nano Research, Vol. 12, Issue 9 https://doi.org/10.1007/s12274-019-2494-5	journal	August 2019
Recovery of Co and Li from spent lithium-ion batteries by combination method of acid leaching and chemical precipitation Zhu, Shu-guang; He, Wen-zhi; Li, Guang-ming Transactions of Nonferrous Metals Society of China, Vol. 22, Issue 9 https://doi.org/10.1016/S1003-6326(11)61460-X	journal	September 2012
Synergistic leaching of valuable metals from spent Li-ion batteries using sulfuric acid- l-ascorbic acid system Chen, Dongdong; Rao, Shuai; Wang, Dongxing Chemical Engineering Journal, Vol. 388 https://doi.org/10.1016/j.cej.2020.124321	journal	May 2020
A combined recovery process of metals in spent lithium-ion batteries Li, Jinhui; Shi, Pixing; Wang, Zefeng Chemosphere, Vol. 77, Issue 8 https://doi.org/10.1016/j.chemosphere.2009.08.040	journal	November 2009
Environmental impact of spent lithium ion batteries and green recycling perspectives by organic acids – A review Meshram, Pratima; Mishra, Abhilash Chemosphere, Vol. 242, p. 125291 https://doi.org/10.1016/j.chemosphere.2019.125291	journal	March 2020
In situ electrochemically generated composite-type CoOx/WOx in self-activated cobalt tungstate nanostructures: implication for highly enhanced electrocatalytic oxygen evolution Tian, Tian; Jiang, Jing; Ai, Lunhong Electrochimica Acta, Vol. 224 https://doi.org/10.1016/j.electacta.2016.11.173	journal	January 2017
A review of recycling spent lithium-ion battery cathode materials using hydrometallurgical treatments Jung, Joey Chung-Yen; Sui, Pang-Chieh; Zhang, Jiujun Journal of Energy Storage, Vol. 35 https://doi.org/10.1016/j.est.2020.102217	journal	March 2021
A reusable deep eutectic solvent for the regeneration of Li and Co metals from spent lithium-ion batteries Li, Honghu; Chen, Nuoya; Liu, Weifeng Journal of Alloys and Compounds, Vol. 966 https://doi.org/10.1016/j.jallcom.2023.171517	journal	December 2023
An atom-economic process for the recovery of high value-added metals from spent lithium-ion batteries Chen, Xiangping; Fan, Bailin; Xu, Liping Journal of Cleaner Production, Vol. 112 https://doi.org/10.1016/j.jclepro.2015.10.132	journal	January 2016
Vacuum pyrolysis and hydrometallurgical process for the recovery of valuable metals from spent lithium-ion batteries Sun, Liang; Qiu, Keqiang Journal of Hazardous Materials, Vol. 194 https://doi.org/10.1016/j.jhazmat.2011.07.114	journal	October 2011
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
Recycled cathode materials enabled superior performance for lithium-ion batteries Ma, Xiaotu; Chen, Mengyuan; Zheng, Zhangfeng Joule, Vol. 5, Issue 11 https://doi.org/10.1016/j.joule.2021.09.005	journal	November 2021
Recovery of metals from spent lithium-ion batteries with organic acids as leaching reagents and environmental assessment Li, Li; Dunn, Jennifer B.; Zhang, Xiao Xiao Journal of Power Sources, Vol. 233 https://doi.org/10.1016/j.jpowsour.2012.12.089	journal	July 2013
Succinic acid-based leaching system: A sustainable process for recovery of valuable metals from spent Li-ion batteries Li, Li; Qu, Wenjie; Zhang, Xiaoxiao Journal of Power Sources, Vol. 282 https://doi.org/10.1016/j.jpowsour.2015.02.073	journal	May 2015
Economical recycling process for spent lithium-ion batteries and macro- and micro-scale mechanistic study Li, Li; Bian, Yifan; Zhang, Xiaoxiao Journal of Power Sources, Vol. 377 https://doi.org/10.1016/j.jpowsour.2017.12.006	journal	February 2018
Recycling of lithium-ion batteries: Recent advances and perspectives Huang, Bin; Pan, Zhefei; Su, Xiangyu Journal of Power Sources, Vol. 399 https://doi.org/10.1016/j.jpowsour.2018.07.116	journal	September 2018
A simple and facile method to synthesize Co3O4 nanoparticles from metal benzoate dihydrazinate complex as a precursor Thangavelu, Kavitha; Parameswari, K.; Kuppusamy, K. Materials Letters, Vol. 65, Issue 10 https://doi.org/10.1016/j.matlet.2011.02.047	journal	May 2011
Energy and environmental aspects in recycling lithium-ion batteries: Concept of Battery Identity Global Passport Bai, Yaocai; Muralidharan, Nitin; Sun, Yang-Kook Materials Today, Vol. 41 https://doi.org/10.1016/j.mattod.2020.09.001	journal	December 2020
The effect of ethylene glycol/citric acid molar ratio in the initial precursor of TiO2 nanoparticle paste synthesized by a polymerizable complex method on the photovoltaic properties of dye-sensitized solar cells Mashreghi, A.; Davoudi, F. Materials Science in Semiconductor Processing, Vol. 30 https://doi.org/10.1016/j.mssp.2014.11.001	journal	February 2015
Anodic behaviour of tin in citrate solutions: The IR and XPS study on the composition of the passive layer Tselesh, A. S. Thin Solid Films, Vol. 516, Issue 18 https://doi.org/10.1016/j.tsf.2007.11.118	journal	July 2008
Use of mild organic acid reagents to recover the Co and Li from spent Li-ion batteries Nayaka, Girish Praveen; Pai, Karkala Vasantakumar; Manjanna, Jayappa Waste Management, Vol. 51 https://doi.org/10.1016/j.wasman.2015.12.008	journal	May 2016
Organic reductants based leaching: A sustainable process for the recovery of valuable metals from spent lithium ion batteries Chen, Xiangping; Guo, Chunxiu; Ma, Hongrui Waste Management, Vol. 75 https://doi.org/10.1016/j.wasman.2018.01.021	journal	May 2018
Bioinspired Cobalt–Citrate Metal–Organic Framework as an Efficient Electrocatalyst for Water Oxidation Jiang, Jing; Huang, Lan; Liu, Xiaomin ACS Applied Materials & Interfaces, Vol. 9, Issue 8 https://doi.org/10.1021/acsami.6b16534	journal	February 2017
Recycling Strategies for Spent Li-Ion Battery Mixed Cathodes Natarajan, Subramanian; Aravindan, Vanchiappan ACS Energy Letters, Vol. 3, Issue 9 https://doi.org/10.1021/acsenergylett.8b01233	journal	August 2018
Recovery of Cathode Materials and Aluminum Foil Using a Green Solvent Bai, Yaocai; Essehli, Rachid; Jafta, Charl J. ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 17 https://doi.org/10.1021/acssuschemeng.1c01293	journal	April 2021
Significant Improvement in Dissolving Lithium-Ion Battery Cathodes Using Novel Deep Eutectic Solvents at Low Temperature Chen, Yu; Wang, Yanlong; Bai, Yue ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 38 https://doi.org/10.1021/acssuschemeng.1c04220	journal	September 2021
Simultaneous Recycling of Critical Metals and Aluminum Foil from Waste LiNi_1/3Co_1/3Mn_1/3O₂ Cathode via Ethylene Glycol–Citric Acid System Zeng, Guisheng; Yao, Junxia; Liu, Chunli ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 48 https://doi.org/10.1021/acssuschemeng.1c04806	journal	November 2021
Hydrometallurgical Processes for Recycling Spent Lithium-Ion Batteries: A Critical Review Yao, Yonglin; Zhu, Meiying; Zhao, Zhuo ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 11 https://doi.org/10.1021/acssuschemeng.8b03545	journal	September 2018
Template-Free Synthesis of Amorphous Double-Shelled Zinc–Cobalt Citrate Hollow Microspheres and Their Transformation to Crystalline ZnCo₂O₄ Microspheres Xie, Qingshui; Li, Feng; Guo, Huizhang ACS Applied Materials & Interfaces, Vol. 5, Issue 12 https://doi.org/10.1021/am400696x	journal	June 2013
Development of a Stable MnCo ₂ O ₄ Cocatalyst for Photocatalytic CO ₂ Reduction with Visible Light Wang, Sibo; Hou, Yidong; Wang, Xinchen ACS Applied Materials & Interfaces, Vol. 7, Issue 7 https://doi.org/10.1021/am508766s	journal	February 2015
Anodization, Precursor Route to Flowerlike Patterns Composed of Nanoporous Tin Oxide Nanostrips on Tin Substrate Feng, Shuanglong; Tang, Yiwen; Xiao, Ting The Journal of Physical Chemistry C, Vol. 113, Issue 12 https://doi.org/10.1021/jp809282w	journal	March 2009
Formation of Amorphous Zinc Citrate Spheres and Their Conversion to Crystalline ZnO Nanostructures Cho, Seungho; Jang, Ji-Wook; Jung, Alum Langmuir, Vol. 27, Issue 1 https://doi.org/10.1021/la103600c	journal	December 2010
Deep eutectic solvents for cathode recycling of Li-ion batteries Tran, Mai K.; Rodrigues, Marco-Tulio F.; Kato, Keiko Nature Energy, Vol. 4, Issue 4 https://doi.org/10.1038/s41560-019-0368-4	journal	April 2019
Polyol synthesis of nanoparticles: status and options regarding metals, oxides, chalcogenides, and non-metal elements Dong, H.; Chen, Y. -C.; Feldmann, C. Green Chemistry, Vol. 17, Issue 8 https://doi.org/10.1039/C5GC00943J	journal	January 2015
Non-precious cobalt oxalate microstructures as highly efficient electrocatalysts for oxygen evolution reaction Liu, Xiaomin; Jiang, Jing; Ai, Lunhong Journal of Materials Chemistry A, Vol. 3, Issue 18 https://doi.org/10.1039/C5TA01012H	journal	January 2015
The polyol process: a unique method for easy access to metal nanoparticles with tailored sizes, shapes and compositions Fiévet, F.; Ammar-Merah, S.; Brayner, R. Chemical Society Reviews, Vol. 47, Issue 14 https://doi.org/10.1039/C7CS00777A	journal	January 2018
Toward sustainable and systematic recycling of spent rechargeable batteries Zhang, Xiaoxiao; Li, Li; Fan, Ersha Chemical Society Reviews, Vol. 47, Issue 19 https://doi.org/10.1039/C8CS00297E	journal	January 2018
Lithium fluoride recovery from cathode material of spent lithium-ion battery Zheng, Ying; Song, Wei; Mo, Wen-ting RSC Advances, Vol. 8, Issue 16 https://doi.org/10.1039/C8RA00061A	journal	January 2018
A novel method for screening deep eutectic solvent to recycle the cathode of Li-ion batteries Wang, Shubin; Zhang, Zuotai; Lu, Zhouguang Green Chemistry, Vol. 22, Issue 14 https://doi.org/10.1039/D0GC00701C	journal	January 2020
A facile synthesis and lithium storage properties of Co3O4–C hybrid core-shell and hollow spheres Zhong, Yeteng; Wang, Xi; Jiang, Kecheng Journal of Materials Chemistry, Vol. 21, Issue 44 https://doi.org/10.1039/c1jm12765a	journal	January 2011
Hydrometallurgical process for the recovery of metal values from spent lithium-ion batteries in citric acid media Chen, Xiangping; Zhou, Tao Waste Management & Research, Vol. 32, Issue 11 https://doi.org/10.1177/0734242X14557380	journal	October 2014
The Sol-Gel Method: Pathway to Ultrapure and Homogeneous Mixed Metal Oxide Nanoparticles Sharma, M.; Pathak, M.; Kapoor, P. N. Asian Journal of Chemistry, Vol. 30, Issue 7 https://doi.org/10.14233/ajchem.2018.20845	journal	January 2018
Preparation of La_1−zSr_zCo_1−yFe_yO_3−x thin films, membranes, and coatings on dense and porous substrates Liu, Meilin; Wang, Dongsheng Journal of Materials Research, Vol. 10, Issue 12 https://doi.org/10.1557/JMR.1995.3210	journal	December 1995
Determination of Lead(II) Using Glassy Carbon Electrode Modified with Hexagonal Co3O4 Microparticles Liu, Jingmin; Jin, Riya International Journal of Electrochemical Science, Vol. 13, Issue 11 https://doi.org/10.20964/2018.11.45	journal	November 2018

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References (51)

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