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Title: First-Principles Study of the Voltage Profile and Mobility of Mg Intercalation in a Chromium Oxide Spinel

Abstract

The development of Mg batteries, which can potentially achieve higher energy densities than Li-ion systems, is in need of cathodes that can reversibly intercalate Mg 2+ and exhibit a higher energy density than the state-of-the-art Chevrel and thio-spinel cathodes. Recent theoretical and experimental studies indicate that the oxide spinel family presents a set of promising Mg cathodes. Here specifically, in this work, we investigate Mg intercalation into the spinel-MgxCr 2O 4 system. Using first-principles calculations in combination with a cluster expansion model and the nudged elastic band theory, we calculate the voltage curve for Mg insertion at room temperature and the activation barriers for Mg diffusion, respectively, at different Mg concentrations in the Cr 2O 4 structure. Our results identify a potential limitation to Mg intercalation in the form of stable Mg-vacancy orderings in the Cr 2O 4 lattice, which exhibit high migration barriers for Mg diffusion in addition to a steep voltage change. Additionally, we propose cation substitution as a potential mechanism that can be used to suppress the formation of the stable Mg-vacancy ordering, which can eventually enable the practical usage of Cr 2O 4 as a Mg-cathode.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2];  [1]
  1. 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
  2. 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
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1476611
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 1; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE

Citation Formats

Chen, Tina, Sai Gautam, Gopalakrishnan, Huang, Wenxuan, and Ceder, Gerbrand. First-Principles Study of the Voltage Profile and Mobility of Mg Intercalation in a Chromium Oxide Spinel. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b04038.
Chen, Tina, Sai Gautam, Gopalakrishnan, Huang, Wenxuan, & Ceder, Gerbrand. First-Principles Study of the Voltage Profile and Mobility of Mg Intercalation in a Chromium Oxide Spinel. United States. doi:10.1021/acs.chemmater.7b04038.
Chen, Tina, Sai Gautam, Gopalakrishnan, Huang, Wenxuan, and Ceder, Gerbrand. Tue . "First-Principles Study of the Voltage Profile and Mobility of Mg Intercalation in a Chromium Oxide Spinel". United States. doi:10.1021/acs.chemmater.7b04038. https://www.osti.gov/servlets/purl/1476611.
@article{osti_1476611,
title = {First-Principles Study of the Voltage Profile and Mobility of Mg Intercalation in a Chromium Oxide Spinel},
author = {Chen, Tina and Sai Gautam, Gopalakrishnan and Huang, Wenxuan and Ceder, Gerbrand},
abstractNote = {The development of Mg batteries, which can potentially achieve higher energy densities than Li-ion systems, is in need of cathodes that can reversibly intercalate Mg2+ and exhibit a higher energy density than the state-of-the-art Chevrel and thio-spinel cathodes. Recent theoretical and experimental studies indicate that the oxide spinel family presents a set of promising Mg cathodes. Here specifically, in this work, we investigate Mg intercalation into the spinel-MgxCr2O4 system. Using first-principles calculations in combination with a cluster expansion model and the nudged elastic band theory, we calculate the voltage curve for Mg insertion at room temperature and the activation barriers for Mg diffusion, respectively, at different Mg concentrations in the Cr2O4 structure. Our results identify a potential limitation to Mg intercalation in the form of stable Mg-vacancy orderings in the Cr2O4 lattice, which exhibit high migration barriers for Mg diffusion in addition to a steep voltage change. Additionally, we propose cation substitution as a potential mechanism that can be used to suppress the formation of the stable Mg-vacancy ordering, which can eventually enable the practical usage of Cr2O4 as a Mg-cathode.},
doi = {10.1021/acs.chemmater.7b04038},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 1,
volume = 30,
place = {United States},
year = {2017},
month = {12}
}

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Cited by: 14 works
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Figures / Tables:

Figure 1 Figure 1: (a) Structure of fully magnesiated MgCr2O4 spinel conventional cell, with Mg in tetrahedral (orange) and Cr in octahedral (blue) coordination. All vertices of polyhedra are occupied by O (not shown). (b) MgCr2O4 spinel structure demonstrating full, half full, and empty tunnels, as viewed along the ⟨110⟩ direction.

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.