Formation of Surface Impurities on Lithium–Nickel–Manganese–Cobalt Oxides in the Presence of CO2 and H2O

Fang, Zongtang; Confer, Matthew P.; Wang, Yixiao; Wang, Qiang; Kunz, M. Ross; Dufek, Eric J.; Liaw, Boryann; Klein, Tonya M.; Dixon, David A.; Fushimi, Rebecca

doi:10.1021/jacs.1c03812

Title: Formation of Surface Impurities on Lithium–Nickel–Manganese–Cobalt Oxides in the Presence of CO₂ and H₂O

Journal Article · Fri Jul 02 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c03812· OSTI ID:1821481

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Idaho National Lab. (INL), Idaho Falls, ID (United States)
Univ. of Alabama, Tuscaloosa, AL (United States)

Surface impurities involving parasitic reactions and gas evolution contribute to the degradation of high Ni content LiNi_xMn_yCo_zO₂ (NMC) cathode materials. The transient kinetic technique of Temporal Analysis of Products (TAP), density functional theory, and infrared spectroscopy have been used to study the formation of surface impurities on varying nickel content NMC materials (NMC811, NMC622, NMC532, NMC433, NMC111) in the presence of CO₂ and H₂O. CO₂ reactivity on a clean surface as characterized by CO₂ conversion rate in the TAP reactor follows the order: NMC811 > NMC622 > NMC532 > NMC433 > NMC111. The capacity of CO₂ uptake follows a different order: NMC532 > NMC433 > NMC622 > NMC811 > NMC111. Moisture pretreatment slows down the direct CO₂ adsorption process and creates additional active sites for CO₂ adsorption. Electronic structure calculations predict that the (012) surface is more reactive than the ($$10\bar{1}4$$) surface for CO₂ and H₂O adsorption. CO₂ adsorption leading to carbonate formation is exothermic with formation of ion pairs. The average CO₂ binding energies on the different materials follow the CO₂ reactivity order. Water hydroxylates the (012) surface and surface OH groups favor bicarbonate formation. Water creates more active sites for CO₂ adsorption on the ($$10\bar{1}4$$) surface due to hydrogen bonding. The composition of surface impurities formed in ambient air exposure is dependent on water concentration and the percentage of different crystal planes. Different surface reactivities suggest that battery performance degradation due to surface impurities can be mitigated by precise control of the dominant surfaces in NMC materials.

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Research Organization:: Idaho National Lab. (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 1821481

Report Number(s):: INL/JOU-21-63084-Rev-000; TRN: US2214347

Journal Information:: Journal of the American Chemical Society, Vol. 143, Issue 27; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Transient Kinetics
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Inorganic carbon compounds
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Title: Formation of Surface Impurities on Lithium–Nickel–Manganese–Cobalt Oxides in the Presence of CO2 and H2O

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Title: Formation of Surface Impurities on Lithium–Nickel–Manganese–Cobalt Oxides in the Presence of CO₂ and H₂O