Benedek, R. and Thackeray, M. M. and van de Walle, A. (2010) Pourbaix-like phase diagram for lithium manganese spinels in acid. Journal of Materials Chemistry, 20 (2). pp. 369-374. ISSN 0959-9428 http://resolver.caltech.edu/CaltechAUTHORS:20100203-111554200
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Calculations are performed on the free energies for proton-promoted reactions of the lithium-ion-battery electrode material LiMn_(2)O_4 spinel in acid, as a function of lithium excess and lithium deficiency relative to stoichiometry. In particular, we consider the dissolution reaction proposed by Hunter (J. Solid State Chem., 1981, 39, 142), in which protons react with lithium manganate spinel to form λ-MnO2, Li^+, and Mn^(2+) products. The calculations employ a hybrid method developed in previous work in which first principles total energy calculations are applied for the solid phases and free atom energies, and tabulated ionization and hydration energies for the aqueous species. A correction to the atomic energies, derived from analysis of binary oxide dissolution reactions, improves the accuracy of the results. A Pourbaix-like dissolution/stability phase diagram is constructed from the resultant reaction free energies.
|Additional Information:||© 2010 Royal Society of Chemistry. Received 16th July 2009; sccepted 8th October 2009; first published as an Advance Article on the web 9th November 2009. The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (‘‘Argonne’’). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. This work was supported at Argonne by the Office of FreedomCar and Vehicle Technologies (Batteries for Advanced Transportation Technologies (BATT) Program), U.S. Department of Energy. Axel van de Walle was supported by the National Science Foundation through TeraGrid computing resources provided by NCSA and SDSC under grant DMR060011N. Grants of computer time at the National Energy Research Supercomputer Center, Lawrence Berkeley Laboratory are gratefully acknowledged.|
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|Deposited By:||Jason Perez|
|Deposited On:||10 Feb 2010 22:01|
|Last Modified:||26 Dec 2012 11:44|
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