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Title: Impact of intermediate sites on bulk diffusion barriers: Mg intercalation in Mg 2Mo 3O 8

Abstract

The ongoing search for high voltage positive electrode materials for Mg batteries has been primarily hampered by poor Mg mobility in bulk oxide frameworks. Thus motivated by the presence of Mo 3 clusters that can facilitate charge redistribution and the presence of Mg in a non-preferred (tetrahedral) coordination environment, we have investigated the Mg (de)intercalation behavior in layered-Mg 2Mo 3O 8, a potential positive electrode. While no electrochemical activity is observed, chemical demagnesiation of Mg 2Mo 3O 8 is successful but leads to amorphization. Subsequent first-principles calculations predict a strong thermodynamic driving force for structure decomposition at low Mg concentrations and high activation barriers for bulk Mg diffusion, in agreement with experimental observations. Further analysis of the Mg diffusion pathway reveals an O–Mg–O dumbbell intermediate site that creates a high Mg 2+ migration barrier, indicating the influence of transition states on setting the magnitude of migration barriers.

Authors:
ORCiD logo [1];  [2];  [2];  [2];  [3]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (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
  2. Univ. of Waterloo, ON (Canada). Waterloo Inst. of Nanotechnology and Dept. of Chemistry
  3. 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
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Joint Center for Energy Storage Research (JCESR); Natural Sciences and Engineering Research Council of Canada (NSERC)
OSTI Identifier:
1474906
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 4; Journal Issue: 45; Related Information: © The Royal Society of Chemistry.; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gautam, Gopalakrishnan Sai, Sun, Xiaoqi, Duffort, Victor, Nazar, Linda F., and Ceder, Gerbrand. Impact of intermediate sites on bulk diffusion barriers: Mg intercalation in Mg2Mo3O8. United States: N. p., 2016. Web. doi:10.1039/c6ta07804d.
Gautam, Gopalakrishnan Sai, Sun, Xiaoqi, Duffort, Victor, Nazar, Linda F., & Ceder, Gerbrand. Impact of intermediate sites on bulk diffusion barriers: Mg intercalation in Mg2Mo3O8. United States. doi:10.1039/c6ta07804d.
Gautam, Gopalakrishnan Sai, Sun, Xiaoqi, Duffort, Victor, Nazar, Linda F., and Ceder, Gerbrand. Tue . "Impact of intermediate sites on bulk diffusion barriers: Mg intercalation in Mg2Mo3O8". United States. doi:10.1039/c6ta07804d. https://www.osti.gov/servlets/purl/1474906.
@article{osti_1474906,
title = {Impact of intermediate sites on bulk diffusion barriers: Mg intercalation in Mg2Mo3O8},
author = {Gautam, Gopalakrishnan Sai and Sun, Xiaoqi and Duffort, Victor and Nazar, Linda F. and Ceder, Gerbrand},
abstractNote = {The ongoing search for high voltage positive electrode materials for Mg batteries has been primarily hampered by poor Mg mobility in bulk oxide frameworks. Thus motivated by the presence of Mo3 clusters that can facilitate charge redistribution and the presence of Mg in a non-preferred (tetrahedral) coordination environment, we have investigated the Mg (de)intercalation behavior in layered-Mg2Mo3O8, a potential positive electrode. While no electrochemical activity is observed, chemical demagnesiation of Mg2Mo3O8 is successful but leads to amorphization. Subsequent first-principles calculations predict a strong thermodynamic driving force for structure decomposition at low Mg concentrations and high activation barriers for bulk Mg diffusion, in agreement with experimental observations. Further analysis of the Mg diffusion pathway reveals an O–Mg–O dumbbell intermediate site that creates a high Mg2+ migration barrier, indicating the influence of transition states on setting the magnitude of migration barriers.},
doi = {10.1039/c6ta07804d},
journal = {Journal of Materials Chemistry. A},
number = 45,
volume = 4,
place = {United States},
year = {Tue Oct 18 00:00:00 EDT 2016},
month = {Tue Oct 18 00:00:00 EDT 2016}
}

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Works referenced in this record:

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