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Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals

Liu, Yuanyue and Merinov, Boris V. and Goddard, William A., III (2016) Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals. Proceedings of the National Academy of Sciences of the United States of America, 113 (14). pp. 3735-3739. ISSN 0027-8424. PMCID PMC4833228. doi:10.1073/pnas.1602473113.

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It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion–substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems.

Item Type:Article
Related URLs:
URLURL TypeDescription Information CentralArticle Paper
Liu, Yuanyue0000-0002-5880-8649
Merinov, Boris V.0000-0002-2783-4262
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2016 National Academy of Sciences. Contributed by William A. Goddard III, February 19, 2016 (sent for review January 25, 2016; reviewed by Yi Cui and Michael L. Klein). Published online before print March 21, 2016. Y.L. thanks Drs. Brandon Wood, Suhuai Wei, and Jiayu Wan for helpful discussions and Brandon Wood for providing access to the Lawrence Livermore National Laboratory computational resources, which were used for some of the computations (supported under the Laboratory Directed Research and Development Program). Most of the calculations were performed on National Energy Research Scientific Computing Center, a Department of Energy (DOE) Office of Science User Facility supported by the Office of Science of the US DOE under Contract DE-AC02-05CH11231. Y.L. acknowledges the support from Resnick Prize Postdoctoral Fellowship at Caltech. This research was funded by the Bosch Energy Research Network and by NSF (CBET 1512759). Reviewers: Y.C., Stanford University; and M.L.K., Temple University. The authors declare no conflict of interest. This article contains supporting information online at
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-05CH11231
Resnick Sustainability InstituteUNSPECIFIED
Bosch Energy Research NetworkUNSPECIFIED
Subject Keywords:energy storage; Na-ion battery; Mg-ion battery; quantum-mechanical calculations
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Issue or Number:14
PubMed Central ID:PMC4833228
Record Number:CaltechAUTHORS:20160323-103905765
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Official Citation:Yuanyue Liu, Boris V. Merinov, and William A. Goddard III Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals PNAS 2016 113 (14) 3735-3739; published ahead of print March 21, 2016, doi:10.1073/pnas.1602473113
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:65618
Deposited By: Tony Diaz
Deposited On:25 Mar 2016 17:44
Last Modified:05 May 2022 17:58

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