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Title: Influence of Inversion on Mg Mobility and Electrochemistry in Spinels

Abstract

Magnesium oxide and sulfide spinels have recently attracted interest as cathode and electrolyte materials for energy-dense Mg batteries, but their observed electrochemical performance depends strongly on synthesis conditions. In this study, using first-principles calculations and percolation theory, we explore the extent to which spinel inversion influences Mg 2+ ionic mobility in MgMn 2O 4 as a prototypical cathode, and MgIn 2S 4 as a potential solid electrolyte. We find that spinel inversion and the resulting changes of the local cation ordering give rise to both increased and decreased Mg 2+ migration barriers, along specific migration pathways, in the oxide as well as the sulfide. To quantify the impact of spinel inversion on macroscopic Mg 2+ transport, we determine the percolation thresholds in both MgMn 2O 4 and MgIn 2S 4. Furthermore, we analyze the impact of inversion on the electrochemical properties of the MgMn 2O 4 cathode via changes in the phase behavior, average Mg insertion voltages and extractable capacities, at varying degrees of inversion. In conclusion, our results confirm that inversion is a major performance limiting factor of Mg spinels and that synthesis techniques or compositions that stabilize the well-ordered spinel structure are crucial for the success of Mgmore » spinels in multivalent batteries.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2];  [2];  [3]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Department of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  3. Univ. of California, Berkeley, CA (United States). Department of Materials Sciences and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
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)
OSTI Identifier:
1476545
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 18; Related Information: © 2017 American Chemical Society.; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, Urban, Alexander, Bo, Shou-Hang, and Ceder, Gerbrand. Influence of Inversion on Mg Mobility and Electrochemistry in Spinels. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b02820.
Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, Urban, Alexander, Bo, Shou-Hang, & Ceder, Gerbrand. Influence of Inversion on Mg Mobility and Electrochemistry in Spinels. United States. doi:10.1021/acs.chemmater.7b02820.
Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, Urban, Alexander, Bo, Shou-Hang, and Ceder, Gerbrand. Thu . "Influence of Inversion on Mg Mobility and Electrochemistry in Spinels". United States. doi:10.1021/acs.chemmater.7b02820. https://www.osti.gov/servlets/purl/1476545.
@article{osti_1476545,
title = {Influence of Inversion on Mg Mobility and Electrochemistry in Spinels},
author = {Sai Gautam, Gopalakrishnan and Canepa, Pieremanuele and Urban, Alexander and Bo, Shou-Hang and Ceder, Gerbrand},
abstractNote = {Magnesium oxide and sulfide spinels have recently attracted interest as cathode and electrolyte materials for energy-dense Mg batteries, but their observed electrochemical performance depends strongly on synthesis conditions. In this study, using first-principles calculations and percolation theory, we explore the extent to which spinel inversion influences Mg2+ ionic mobility in MgMn2O4 as a prototypical cathode, and MgIn2S4 as a potential solid electrolyte. We find that spinel inversion and the resulting changes of the local cation ordering give rise to both increased and decreased Mg2+ migration barriers, along specific migration pathways, in the oxide as well as the sulfide. To quantify the impact of spinel inversion on macroscopic Mg2+ transport, we determine the percolation thresholds in both MgMn2O4 and MgIn2S4. Furthermore, we analyze the impact of inversion on the electrochemical properties of the MgMn2O4 cathode via changes in the phase behavior, average Mg insertion voltages and extractable capacities, at varying degrees of inversion. In conclusion, our results confirm that inversion is a major performance limiting factor of Mg spinels and that synthesis techniques or compositions that stabilize the well-ordered spinel structure are crucial for the success of Mg spinels in multivalent batteries.},
doi = {10.1021/acs.chemmater.7b02820},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 18,
volume = 29,
place = {United States},
year = {2017},
month = {8}
}

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Cited by: 22 works
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