Decomposition of PVDF to delaminate cathode materials from end-of-life lithium-ion battery cathodes

Ji, Yi; Jafvert, Chad T.; Zyaykina, Nadezhda N.; Zhao, Fu

doi:10.1016/j.jclepro.2022.133112

Decomposition of PVDF to delaminate cathode materials from end-of-life lithium-ion battery cathodes

Journal Article · Tue Jul 12 00:00:00 EDT 2022 · Journal of Cleaner Production

DOI:https://doi.org/10.1016/j.jclepro.2022.133112· OSTI ID:1981660

^[1]; ^[1]; Zyaykina, Nadezhda N. ^[1]; Zhao, Fu ^[1]

Purdue University, West Lafayette, IN (United States)

The growing demand of electric vehicles and rapid consumption of rechargeable lithium-ion batteries (LIBs) require recycling of spent cathode active materials (CAMs) to reduce hazardous wastes and supply raw materials to LIB production. To separate CAMs from the cathode, direct calcination of polyvinylidene fluoride (PVDF) binder is widely applied, which leads to high energy consumption and release of toxic hydrogen fluoride. It is desirable to have an environmentally friendly and effective alternative to traditional direct calcination. In this study, five lithium salts, LiOAc (lithium acetate), LiNO₃, LiCl, Li₂CO₃, and Li₂SO₄, were deployed and compared for their performance in recycling CAMs. A peel-off efficiency of up to 98.5% was achieved at a LiOAc to LiNO₃ molar ratio of 3:2, salt to cathode mass ratio of 10:1, and temperature of 300 °C at a holding time of 30 min. This system avoids corrosive chemicals and minimizes particle agglomeration of recycled products. Compared with sodium salt systems (NaOAc-NaNO₃) or direct calcination, the LiOAc-LiNO₃ system prevented high reaction temperature or further lithium loss and minimized crystal structure and morphological changes. In conclusion, a decomposition mechanism of PVDF through adsorption of HF and fluorine substitution was proposed.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States). Critical Materials Institute (CMI)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1981660

Journal Information:: Journal of Cleaner Production, Journal Name: Journal of Cleaner Production Journal Issue: C Vol. 367; ISSN 0959-6526

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (37)

Ambient‐Pressure Relithiation of Degraded Li _x Ni _0.5 Co _0.2 Mn _0.3 O ₂ (0 < x < 1) via Eutectic Solutions for Direct Regeneration of Lithium‐Ion Battery Cathodes Shi, Yang; Zhang, Minghao; Meng, Ying Shirley Advanced Energy Materials, Vol. 9, Issue 20 https://doi.org/10.1002/aenm.201900454	journal	April 2019
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
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
Oxidation of acetate ions by nitrate and nitrite melts Burke, J. D.; Kerridge, D. H. Journal of Inorganic and Nuclear Chemistry, Vol. 37, Issue 3 https://doi.org/10.1016/0022-1902(75)80533-1	journal	March 1975
Optimizing the interface engineering and structural stability of nickel-rich layered oxide cathode by dual-function modification Zhu, Ziyi; Duan, Jianguo; Zhang, Jufeng Chemical Engineering Journal, Vol. 430 https://doi.org/10.1016/j.cej.2021.132908	journal	February 2022
Direct regeneration of spent LiFePO4 cathode materials with pre-oxidation and V-doping Liu, Peiwen; Zhang, Yannan; Dong, Peng Journal of Alloys and Compounds, Vol. 860 https://doi.org/10.1016/j.jallcom.2020.157909	journal	April 2021
Rational analysis applied to calculate the unknown stoichiometry of Li-ternary oxides blended to Li-mono oxides in cathode material mixtures Sita, Lucas Evangelista; da Silva, Stephany Pires; dos Santos, Caroline Santana Journal of Alloys and Compounds, Vol. 877 https://doi.org/10.1016/j.jallcom.2021.160230	journal	October 2021
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
Recycling of spent LiCoO2 materials by electrolytic leaching of cathode electrode plate Zhou, Siyuan; Zhang, Yingjie; Meng, Qi Journal of Environmental Chemical Engineering, Vol. 9, Issue 1 https://doi.org/10.1016/j.jece.2020.104789	journal	February 2021
Economic and environmental characterization of an evolving Li-ion battery waste stream Wang, Xue; Gaustad, Gabrielle; Babbitt, Callie W. Journal of Environmental Management, Vol. 135 https://doi.org/10.1016/j.jenvman.2014.01.021	journal	March 2014
A green process for exfoliating electrode materials and simultaneously extracting electrolyte from spent lithium-ion batteries He, Kai; Zhang, Zhi-Yuan; Alai, Lagu Journal of Hazardous Materials, Vol. 375 https://doi.org/10.1016/j.jhazmat.2019.03.120	journal	August 2019
A low-toxicity and high-efficiency deep eutectic solvent for the separation of aluminum foil and cathode materials from spent lithium-ion batteries Wang, Mengmeng; Tan, Quanyin; Liu, Lili Journal of Hazardous Materials, Vol. 380 https://doi.org/10.1016/j.jhazmat.2019.120846	journal	December 2019
Selectively peeling of spent LiFePO4 cathode by destruction of crystal structure and binder matrix for efficient recycling of spent battery materials He, Kai; Zhang, Zhi-Yuan; Zhang, Fu-Shen Journal of Hazardous Materials, Vol. 386 https://doi.org/10.1016/j.jhazmat.2019.121633	journal	March 2020
Structure and performance of LiFePO4 cathode materials: A review Zhang, Wei-Jun Journal of Power Sources, Vol. 196, Issue 6 https://doi.org/10.1016/j.jpowsour.2010.11.113	journal	March 2011
Recovery and heat treatment of the Li(Ni1/3Co1/3Mn1/3)O2 cathode scrap material for lithium ion battery Song, Dawei; Wang, Xiaoqing; Zhou, Enlou Journal of Power Sources, Vol. 232 https://doi.org/10.1016/j.jpowsour.2012.10.072	journal	June 2013
Recovery of cathode materials from spent lithium-ion batteries using eutectic system of lithium compounds Ji, Yi; Jafvert, Chad T.; Zhao, Fu Resources, Conservation and Recycling, Vol. 170 https://doi.org/10.1016/j.resconrec.2021.105551	journal	July 2021
Sustainable recycling of cathode scraps via Cyrene-based separation Bai, Yaocai; Hawley, W. Blake; Jafta, Charl J. Sustainable Materials and Technologies, Vol. 25 https://doi.org/10.1016/j.susmat.2020.e00202	journal	September 2020
Separation of the cathode materials from the Al foil in spent lithium-ion batteries by cryogenic grinding Wang, Haifeng; Liu, Jiangshan; Bai, Xuejie Waste Management, Vol. 91 https://doi.org/10.1016/j.wasman.2019.04.058	journal	May 2019
Probing the Reaction Mechanism of Aluminum/Poly(vinylidene fluoride) Composites DeLisio, Jeffery B.; Hu, Xiuli; Wu, Tao The Journal of Physical Chemistry B, Vol. 120, Issue 24 https://doi.org/10.1021/acs.jpcb.6b01100	journal	June 2016
Studies of Spinel-to-Layered Structural Transformations in LiMn ₂ O ₄ Electrodes Charged to High Voltages Leifer, Nicole; Schipper, Florian; Erickson, Evan M. The Journal of Physical Chemistry C, Vol. 121, Issue 17 https://doi.org/10.1021/acs.jpcc.7b00929	journal	April 2017
Resolving the Compositional and Structural Defects of Degraded LiNi _x Co _y Mn _z O ₂ Particles to Directly Regenerate High-Performance Lithium-Ion Battery Cathodes Shi, Yang; Chen, Gen; Liu, Fang ACS Energy Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsenergylett.8b00833	journal	June 2018
Revealing the Dissolution Mechanism of Polyvinylidene Fluoride of Spent Lithium-Ion Batteries in Waste Oil-Based Methyl Ester Solvent Wang, Mengmeng; Tan, Quanyin; Liu, Lili ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 19 https://doi.org/10.1021/acssuschemeng.0c02072	journal	April 2020
Dual-Function Regeneration of Waste Lithium Cobalt Oxide for Stable High Voltage Cycle Performance Fei, Zitong; Zhang, Yingjie; Meng, Qi ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 33 https://doi.org/10.1021/acssuschemeng.1c03266	journal	August 2021
Sustainable Recycling and Regeneration of Cathode Scraps from Industrial Production of Lithium-Ion Batteries Zhang, Xiaoxiao; Xue, Qing; Li, Li ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 12 https://doi.org/10.1021/acssuschemeng.6b01948	journal	October 2016
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
A Facile, Environmentally Friendly, and Low-Temperature Approach for Decomposition of Polyvinylidene Fluoride from the Cathode Electrode of Spent Lithium-ion Batteries Wang, Mengmeng; Tan, Quanyin; Liu, Lili ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 15 https://doi.org/10.1021/acssuschemeng.9b01546	journal	July 2019
Toxicity Identification and Evolution Mechanism of Thermolysis-Driven Gas Emissions from Cathodes of Spent Lithium-Ion Batteries Chen, Yongming; Liu, Nannan; Jie, Yafei ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 22 https://doi.org/10.1021/acssuschemeng.9b03739	journal	November 2019
Reactions between sodium carboxylic acid salts and molten sodium nitrate and sodium nitrite Kozlowski, Theodore R.; Bartholomew, Roger F. Inorganic Chemistry, Vol. 7, Issue 11 https://doi.org/10.1021/ic50069a015	journal	November 1968
Stereochemistry and Mechanism in Reactions of Silver Salts with Alkyl Halides. The Reaction of Silver Nitrate with Alkyl Halides^1,2 Kornblum, Nathan; Hardies, Donald E. Journal of the American Chemical Society, Vol. 88, Issue 8 https://doi.org/10.1021/ja00960a025	journal	April 1966
Halogen Bonding in Fluoroalkylhalides: A Quantum Chemical Study of Increasing Fluorine Substitution Valerio, Gabriele; Raos, Guido; Meille, Stefano V. The Journal of Physical Chemistry A, Vol. 104, Issue 8 https://doi.org/10.1021/jp993415j	journal	February 2000
Ten years left to redesign lithium-ion batteries Turcheniuk, Kostiantyn; Bondarev, Dmitry; Singhal, Vinod Nature, Vol. 559, Issue 7715 https://doi.org/10.1038/d41586-018-05752-3	journal	July 2018
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
LiCoO ₂ : recycling from spent batteries and regeneration with solid state synthesis Nie, Hehe; Xu, Long; Song, Dawei Green Chemistry, Vol. 17, Issue 2 https://doi.org/10.1039/C4GC01951B	journal	January 2015
Effects of an ionic liquid and processing conditions on the β-polymorph crystal formation in poly(vinylidene fluoride) Pickford, Tom; Gu, Xu; Heeley, Ellen L. CrystEngComm, Vol. 21, Issue 36 https://doi.org/10.1039/C9CE01051C	journal	January 2019
Alkali Attack of Glass Surfaces by Molten Salts Bartholomew, Roger F.; Kozlowski, Theodore R. Journal of the American Ceramic Society, Vol. 50, Issue 2 https://doi.org/10.1111/j.1151-2916.1967.tb15051.x	journal	February 1967
Phase Diagram of Li[sub x]FePO[sub 4] Dodd, J. L.; Yazami, R.; Fultz, B. Electrochemical and Solid-State Letters, Vol. 9, Issue 3 https://doi.org/10.1149/1.2164548	journal	January 2006
Multi-Particle Model for a Commercial Blended Lithium-Ion Electrode Mao, Z.; Farkhondeh, M.; Pritzker, M. Journal of The Electrochemical Society, Vol. 163, Issue 3 https://doi.org/10.1149/2.0321603jes	journal	December 2015

Similar Records

Environmentally sustainable lithium-ion battery cathode binders based on cellulose nanocrystals

Journal Article · Thu Aug 15 20:00:00 EDT 2024 · Journal of Materials Chemistry. A · OSTI ID:2434330

Cathodic polarization of sulfur in molten salts

Journal Article · Sat Nov 30 23:00:00 EST 1985 · Sov. Electrochem. (Engl. Transl.); (United States) · OSTI ID:5289512

Related Subjects

25 ENERGY STORAGE
Cathode materials
Engineering
Environmental Sciences & Ecology
Lithium salts
Lithium-ion battery
PVDF decomposition
Science & Technology - Other Topics

Decomposition of PVDF to delaminate cathode materials from end-of-life lithium-ion battery cathodes

Citation Formats

References (37)

Similar Records

Related Subjects