Transition Metal Dissolution in Lithium-Ion Cells: A Piece of the Puzzle

Son, Seoung-Bum; Zhang, Zhengcheng; Gim, Jihyeon; Johnson, Christopher S.; Tsai, Yifen; Kalensky, Michael; Lopykinski, Susan; Kahvecioglu, Ozgenur; Yang, Zhenzhen; Montoya, Anthony T.; Bloom, Ira

doi:10.1021/acs.jpcc.2c08234

Transition Metal Dissolution in Lithium-Ion Cells: A Piece of the Puzzle

Journal Article · Thu Jan 19 00:00:00 EST 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c08234· OSTI ID:2217014

^[1]; ^[1]; Gim, Jihyeon ^[1]; ^[1]; Tsai, Yifen ^[1]; Kalensky, Michael ^[1]; Lopykinski, Susan ^[1]; Kahvecioglu, Ozgenur ^[1]; ^[1]; ^[1]; ^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States)

Static leaching tests were performed using the chemically delithiated positive electrode materials, LiFePO₄, LiCoO₂, LiMn₂O₄, LiNiO₂, and LiNi_0.8Mn_0.1Co_0.1O₂. Instead of the common electrolyte, which contains LiPF₆, the solvent consisted of only ethylene carbonate (EC) and ethyl methyl carbonate (EMC), limiting the possible reactions to only those that depend on the solvent. The product liquids from these experiments showed that there were lithium-bearing species in common, such as Li(EC)⁺ and Li(EMC)⁺. Interestingly, we found evidence of electrolyte degradation products in both the positive-and negative-ion mass spectral results. The positive-ion results showed that the products tended to coordinate to lithium. In conclusion, the negative-ion results showed that most of the products tended to complex with transition metals. It was difficult to discern which positive ion was associated with which negative ion.

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), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2217014

Journal Information:: Journal of Physical Chemistry. C, Vol. 127, Issue 4; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Rapid Characterization of Lithium Ion Battery Electrolytes and Thermal Aging Products by Low-Temperature Plasma Ambient Ionization High-Resolution Mass Spectrometry Vortmann, Britta; Nowak, Sascha; Engelhard, Carsten Analytical Chemistry, Vol. 85, Issue 6 https://doi.org/10.1021/ac4001404	journal	March 2013
Dissolution kinetics of smithsonite ore as an alternative zinc source with an organic leach reagent Hurşit, Mehtap; Laçin, Oral; Saraç, Hanifi Journal of the Taiwan Institute of Chemical Engineers, Vol. 40, Issue 1 https://doi.org/10.1016/j.jtice.2008.07.003	journal	January 2009
Study on the influence of various factors in the hydrometallurgical processing of waste printed circuit boards for copper and gold recovery Birloaga, Ionela; De Michelis, Ida; Ferella, Francesco Waste Management, Vol. 33, Issue 4 https://doi.org/10.1016/j.wasman.2013.01.003	journal	April 2013
Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells Gummow, R. J.; de Kock, A.; Thackeray, M. M. Solid State Ionics, Vol. 69, Issue 1, p. 59-67 https://doi.org/10.1016/0167-2738(94)90450-2	journal	April 1994
Dissolution of Spinel Oxides and Capacity Losses in 4V Li / Li_xMn₂O₄ Cells Jang, Dong H.; Shin, Young J.; Oh, Seung M. Journal of The Electrochemical Society, Vol. 143, Issue 7, p. 2204-2211 https://doi.org/10.1149/1.1836981	journal	January 1996
Revisiting the Mechanism Behind Transition-Metal Dissolution from Delithiated LiNi _x Mn _y Co _z O ₂ (NMC) Cathodes Sahore, Ritu; O’Hanlon, Daniel C.; Tornheim, Adam Journal of The Electrochemical Society, Vol. 167, Issue 2 https://doi.org/10.1149/1945-7111/ab6826	journal	January 2020
Hydrolysis in the system LiPF6—propylene carbonate—dimethyl carbonate—H2O Plakhotnyk, Andriy V.; Ernst, Ludger; Schmutzler, Reinhard Journal of Fluorine Chemistry, Vol. 126, Issue 1 https://doi.org/10.1016/j.jfluchem.2004.09.027	journal	January 2005
Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells Gilbert, James A.; Shkrob, Ilya A.; Abraham, Daniel P. Journal of The Electrochemical Society, Vol. 164, Issue 2 https://doi.org/10.1149/2.1111702jes	journal	December 2016
X-ray Photoelectron Spectroscopy Study of Surface Films Formed on Li Electrodes Freshly Prepared in Alkyl Carbonate Solutions Schechter, Alex; Aurbach, Doron; Cohen, Hagay Langmuir, Vol. 15, Issue 9 https://doi.org/10.1021/la981048h	journal	April 1999
Quantitative Elucidation of the Non-Equilibrium Phase Transition in LiFePO₄ via the Intermediate Phase Yoshinari, Takahiro; Mori, Takuya; Otani, Kazufumi Chemistry of Materials, Vol. 31, Issue 18 https://doi.org/10.1021/acs.chemmater.9b00834	journal	July 2019
The mechanism of dissolution of minerals in acidic and alkaline solutions: Part I — A new theory of non-oxidation dissolution Crundwell, F. K. Hydrometallurgy, Vol. 149 https://doi.org/10.1016/j.hydromet.2014.06.009	journal	October 2014
The mechanism of dissolution of minerals in acidic and alkaline solutions: Part III. Application to oxide, hydroxide and sulfide minerals Crundwell, F. K. Hydrometallurgy, Vol. 149 https://doi.org/10.1016/j.hydromet.2014.06.008	journal	October 2014
Long-range ordering during delithiation of LiMn2O4 cathode material Björk, Helen; Gustafsson, Torbjörn; Thomas, John O. Journal of Materials Chemistry, Vol. 13, Issue 3 https://doi.org/10.1039/B210265J	journal	January 2003
Aging mechanisms of lithium cathode materials Wohlfahrt-Mehrens, M.; Vogler, C.; Garche, J. Journal of Power Sources, Vol. 127, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2003.09.034	journal	March 2004
Investigation of dissolution kinetics of zinc from smithsonite in 5-sulphosalicylic acid solution Wu, D. D.; Wen, S. M.; Yang, J. Canadian Metallurgical Quarterly, Vol. 54, Issue 1 https://doi.org/10.1179/1879139514y.0000000150	journal	September 2014
Ion chromatographic determination of hydrolysis products of hexafluorophosphate salts in aqueous solution Terborg, Lydia; Nowak, Sascha; Passerini, Stefano Analytica Chimica Acta, Vol. 714 https://doi.org/10.1016/j.aca.2011.11.056	journal	February 2012
Ring-Opening Polymerization of Ethylene Carbonate and Depolymerization of Poly(ethylene oxide- c o -ethylene carbonate) Lee, Jong-Chan; Litt, Morton H. Macromolecules, Vol. 33, Issue 5 https://doi.org/10.1021/ma9914321	journal	March 2000
Identification and formation mechanism of individual degradation products in lithium-ion batteries studied by liquid chromatography/electrospray ionization mass spectrometry and atmospheric solid analysis probe mass spectrometry: Identification of degradation products in LIBs by LC/ESI-MS and ASAP-MS Takeda, Sahori; Morimura, Wataru; Liu, Yi-Hung Rapid Communications in Mass Spectrometry, Vol. 30, Issue 15 https://doi.org/10.1002/rcm.7652	journal	July 2016
In Situ Structural and Electrochemical Study of Ni1−xCoxO2 Metastable Oxides Prepared by Soft Chemistry Tarascon, J. M.; Vaughan, G.; Chabre, Y. Journal of Solid State Chemistry, Vol. 147, Issue 1 https://doi.org/10.1006/jssc.1999.8465	journal	October 1999
Citric acid as an alternative lixiviant for zinc oxide dissolution Larba, R.; Boukerche, I.; Alane, N. Hydrometallurgy, Vol. 134-135 https://doi.org/10.1016/j.hydromet.2013.02.002	journal	March 2013
Capacity Fade Mechanisms and Side Reactions in Lithium-Ion Batteries Arora, Pankaj; White, Ralph E.; Doyle, Marc Journal of The Electrochemical Society, Vol. 145, Issue 10, p. 3647-3667 https://doi.org/10.1149/1.1838857	journal	January 1998
Identification of Electrolyte-Soluble Organic Cross-Talk Species in a Lithium-Ion Battery via a Two-Compartment Cell Sahore, Ritu; Dogan, Fulya; Bloom, Ira D. Chemistry of Materials, Vol. 31, Issue 8 https://doi.org/10.1021/acs.chemmater.9b00063	journal	March 2019
Clarification of Decomposition Pathways in a State‐of‐the‐Art Lithium Ion Battery Electrolyte through ¹³ C‐Labeling of Electrolyte Components Henschel, Jonas; Peschel, Christoph; Klein, Sven Angewandte Chemie International Edition, Vol. 59, Issue 15 https://doi.org/10.1002/anie.202000727	journal	February 2020
Alkaline leaching of lead and zinc by sodium hydroxide: kinetics modeling Seyed Ghasemi, Seyed Mahyar; Azizi, Asghar Journal of Materials Research and Technology, Vol. 7, Issue 2 https://doi.org/10.1016/j.jmrt.2017.03.005	journal	April 2018
Transition-Metal Dissolution from NMC-Family Oxides: A Case Study Morin, Hannah R.; Graczyk, Donald G.; Tsai, Yifen ACS Applied Energy Materials, Vol. 3, Issue 3 https://doi.org/10.1021/acsaem.9b02277	journal	February 2020
Electrochemical and Thermal Behavior of LiNi[sub 1−z]M[sub z]O[sub 2] (M = Co, Mn, Ti) Arai, Hajime Journal of The Electrochemical Society, Vol. 144, Issue 9 https://doi.org/10.1149/1.1837968	journal	January 1997
Lithium Ethylene Dicarbonate Identified as the Primary Product of Chemical and Electrochemical Reduction of EC in 1.2 M LiPF ₆ /EC:EMC Electrolyte Zhuang, Guorong V.; Xu, Kang; Yang, Hui The Journal of Physical Chemistry B, Vol. 109, Issue 37 https://doi.org/10.1021/jp052474w	journal	September 2005
The Formation Mechanism of Fluorescent Metal Complexes at the Li _x Ni _0.5 Mn _1.5 O _4−δ /Carbonate Ester Electrolyte Interface Jarry, Angélique; Gottis, Sébastien; Yu, Young-Sang Journal of the American Chemical Society, Vol. 137, Issue 10 https://doi.org/10.1021/ja5116698	journal	March 2015
Cationic Ring-Opening Polymerization of Cyclic Carbonates with Alkyl Halides To Yield Polycarbonate without the Ether Unit by Suppression of Elimination of Carbon Dioxide Ariga, Toshiro; Takata, Toshikazu; Endo, Takeshi Macromolecules, Vol. 30, Issue 4 https://doi.org/10.1021/ma9607325	journal	February 1997
Effect of overcharge on Li(Ni0.5Mn0.3Co0.2)O2 cathodes: NMP-soluble binder. II — Chemical changes in the anode Bloom, Ira; Bareño, Javier; Dietz Rago, Nancy Journal of Power Sources, Vol. 385 https://doi.org/10.1016/j.jpowsour.2017.12.015	journal	May 2018
Preparation of a new crystal form of manganese dioxide: λ-MnO₂ Hunter, James C. Journal of Solid State Chemistry, Vol. 39, Issue 2, p. 142-147 https://doi.org/10.1016/0022-4596(81)90323-6	journal	September 1981
Understanding Transition-Metal Dissolution Behavior in LiNi _0.5 Mn _1.5 O ₄ High-Voltage Spinel for Lithium Ion Batteries Pieczonka, Nicholas P. W.; Liu, Zhongyi; Lu, Peng The Journal of Physical Chemistry C, Vol. 117, Issue 31 https://doi.org/10.1021/jp405158m	journal	July 2013
Atomic resolution of lithium ions in LiCoO2 Shao-Horn, Yang; Croguennec, Laurence; Delmas, Claude Nature Materials, Vol. 2, Issue 7 https://doi.org/10.1038/nmat922	journal	June 2003
Mass Spectrometry Investigations on Electrolyte Degradation Products for the Development of Nanocomposite Electrodes in Lithium Ion Batteries Gireaud, Laurent; Grugeon, Sylvie; Pilard, Serge Analytical Chemistry, Vol. 78, Issue 11 https://doi.org/10.1021/ac051987w	journal	June 2006
Leaching of brannerite in the ferric sulphate system — Part 1: Kinetics and reaction mechanisms Gilligan, Rorie; Nikoloski, Aleksandar N. Hydrometallurgy, Vol. 156 https://doi.org/10.1016/j.hydromet.2015.05.016	journal	July 2015
Correlation between dissolution behavior and electrochemical cycling performance for LiNi1/3Co1/3Mn1/3O2-based cells Zheng, Honghe; Sun, Qingna; Liu, Gao Journal of Power Sources, Vol. 207 https://doi.org/10.1016/j.jpowsour.2012.01.122	journal	June 2012
Specific chemical rate constants for the acid dissolution of oxides and silicates Terry, Brian Hydrometallurgy, Vol. 11, Issue 3 https://doi.org/10.1016/0304-386x(83)90051-8	journal	December 1983
Thermal Decomposition of LiPF[sub 6]-Based Electrolytes for Lithium-Ion Batteries Campion, Christopher L.; Li, Wentao; Lucht, Brett L. Journal of The Electrochemical Society, Vol. 152, Issue 12 https://doi.org/10.1149/1.2083267	journal	January 2005
Spectroscopic Compositional Analysis of Electrolyte during Initial SEI Layer Formation Gourdin, Gerald; Collins, John; Zheng, Dong The Journal of Physical Chemistry C, Vol. 118, Issue 31 https://doi.org/10.1021/jp504181b	journal	July 2014
Kinetics of Li-ion transfer reaction at LiMn2O4, LiCoO2, and LiFePO4 cathodes Swiderska-Mocek, Agnieszka; Lewandowski, Andrzej Journal of Solid State Electrochemistry, Vol. 21, Issue 5 https://doi.org/10.1007/s10008-016-3499-6	journal	January 2017

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Transition Metal Dissolution in Lithium-Ion Cells: A Piece of the Puzzle

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