Probing Mg Migration in Spinel Oxides
Abstract
Mg batteries utilizing oxide cathodes can theoretically surpass the energy density of current Li-ion technologies. The absence of functional devices so far has been ascribed to impeded Mg2+ migration within oxides, which severely handicaps intercalation reactions at the cathode. Broadly, knowledge of divalent cation migration in solid frameworks is surprisingly deficient. In this paper, we present a combined experimental and theoretical study of Mg migration within three spinel oxides, which reveal critical features that influence it. Experimental activation energies for a Mg2+ hop to an adjacent vacancy, as low as ~0.6 eV, are reported. These barriers are low enough to support functional electrodes based on the intercalation of Mg2+. Subsequent electrochemical experiments demonstrate that significant demagnesiation is indeed possible, but the challenges instead lie with the chemical stability of the oxidized states. Our findings enhance the understanding of cation transport in solid structures and renew the prospects of finding materials capable of high density of energy storage.
- Authors:
-
[2];
[3];
[4];
[7];
[9];
[10];
[2];
[8]
- Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Oxford (United Kingdom)
- Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
- Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Argonne National Lab. (ANL), Argonne, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Univ. of Illinois, Chicago, IL (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- ISIS Pulsed Neutron and Muon Source, Rutherford Appleton Laboratory, Didcot OX11 0QX, U.K.
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Science and Technology Facilities Council (STFC); Ramsay Memorial Trust
- OSTI Identifier:
- 1606525
- Alternate Identifier(s):
- OSTI ID: 1597692; OSTI ID: 1766478
- Report Number(s):
- PNNL-SA-129154
Journal ID: ISSN 0897-4756; 137865
- Grant/Contract Number:
- AC05-76RL01830; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 32; Journal Issue: 2; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Spinel; Oxides; Genetics; Electrodes; Transition metals
Citation Formats
Bayliss, Ryan D., Key, Baris, Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, Kwon, Bob Jin, Lapidus, Saul H., Dogan, Fulya, Adil, Abdullah A., Lipton, Andrew S., Baker, Peter J., Ceder, Gerbrand, Vaughey, John T., and Cabana, Jordi. Probing Mg Migration in Spinel Oxides. United States: N. p., 2019.
Web. https://doi.org/10.1021/acs.chemmater.9b02450.
Bayliss, Ryan D., Key, Baris, Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, Kwon, Bob Jin, Lapidus, Saul H., Dogan, Fulya, Adil, Abdullah A., Lipton, Andrew S., Baker, Peter J., Ceder, Gerbrand, Vaughey, John T., & Cabana, Jordi. Probing Mg Migration in Spinel Oxides. United States. https://doi.org/10.1021/acs.chemmater.9b02450
Bayliss, Ryan D., Key, Baris, Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, Kwon, Bob Jin, Lapidus, Saul H., Dogan, Fulya, Adil, Abdullah A., Lipton, Andrew S., Baker, Peter J., Ceder, Gerbrand, Vaughey, John T., and Cabana, Jordi. Thu .
"Probing Mg Migration in Spinel Oxides". United States. https://doi.org/10.1021/acs.chemmater.9b02450. https://www.osti.gov/servlets/purl/1606525.
@article{osti_1606525,
title = {Probing Mg Migration in Spinel Oxides},
author = {Bayliss, Ryan D. and Key, Baris and Sai Gautam, Gopalakrishnan and Canepa, Pieremanuele and Kwon, Bob Jin and Lapidus, Saul H. and Dogan, Fulya and Adil, Abdullah A. and Lipton, Andrew S. and Baker, Peter J. and Ceder, Gerbrand and Vaughey, John T. and Cabana, Jordi},
abstractNote = {Mg batteries utilizing oxide cathodes can theoretically surpass the energy density of current Li-ion technologies. The absence of functional devices so far has been ascribed to impeded Mg2+ migration within oxides, which severely handicaps intercalation reactions at the cathode. Broadly, knowledge of divalent cation migration in solid frameworks is surprisingly deficient. In this paper, we present a combined experimental and theoretical study of Mg migration within three spinel oxides, which reveal critical features that influence it. Experimental activation energies for a Mg2+ hop to an adjacent vacancy, as low as ~0.6 eV, are reported. These barriers are low enough to support functional electrodes based on the intercalation of Mg2+. Subsequent electrochemical experiments demonstrate that significant demagnesiation is indeed possible, but the challenges instead lie with the chemical stability of the oxidized states. Our findings enhance the understanding of cation transport in solid structures and renew the prospects of finding materials capable of high density of energy storage.},
doi = {10.1021/acs.chemmater.9b02450},
journal = {Chemistry of Materials},
number = 2,
volume = 32,
place = {United States},
year = {2019},
month = {12}
}
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