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Title: Hybrid DFT investigation of the energetics of Mg ion diffusion in α-MoO3

Abstract

We report that rechargeable batteries that utilize divalent Mg ions as the charge carrier species can in principle achieve substantially greater volumetric energy densities than conventional Li-ion batteries. One significant impediment to the development of commercially viable Mg-ion batteries is the slow rate of Mg ion diffusion through otherwise promising cathode materials. Accurate prediction of the activation energies associated with this diffusion process using density functional theory (DFT) is especially challenging due to self-interaction errors intrinsic to DFT that lead to over-delocalization of the d-electrons. One effective but highly computationally demanding approach to reducing self-interaction errors is the use of hybrid functionals, which incorporate a fraction of exact Hartree–Fock exchange. In this work, we assess the effects of exact exchange on computed activation energies for ion diffusion in one potential cathode material, α-MoO3. In contrast to previous studies that primarily utilize non-hybrid functionals, we perform nudged elastic band calculations in which the nuclear coordinates are fully converged using both hybrid functionals and k-point sampling. Additionally, it is found that while non-hybrid functionals indicate the existence of thermodynamically accessible channels for bulk Mg ion diffusion in all three dimensions, hybrid functionals predict that some of these channels are largely inaccessible undermore » typical charge/discharge conditions. Furthermore, it is demonstrated that certain commonly used approximations for incorporating the effects of Hartree–Fock exchange are inadequate for this system, including DFT+U calculations and the use of single-point hybrid calculations using atomic positions obtained using non-hybrid functionals.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Molecular Sciences Software Institute, Blacksburg, VA (Untied States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research, Molecular Foundry
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1497952
Alternate Identifier(s):
OSTI ID: 1471750; OSTI ID: 1490609
Report Number(s):
LLNL-JRNL-756999
Journal ID: ISSN 1463-9076; PPCPFQ; 944677
Grant/Contract Number:  
AC52-07NA27344; AC02-05CH11231; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 38; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE

Citation Formats

Barnes, Taylor A., Wan, Liwen F., Kent, Paul R. C., and Prendergast, David. Hybrid DFT investigation of the energetics of Mg ion diffusion in α-MoO3. United States: N. p., 2018. Web. doi:10.1039/C8CP05511D.
Barnes, Taylor A., Wan, Liwen F., Kent, Paul R. C., & Prendergast, David. Hybrid DFT investigation of the energetics of Mg ion diffusion in α-MoO3. United States. doi:10.1039/C8CP05511D.
Barnes, Taylor A., Wan, Liwen F., Kent, Paul R. C., and Prendergast, David. Fri . "Hybrid DFT investigation of the energetics of Mg ion diffusion in α-MoO3". United States. doi:10.1039/C8CP05511D. https://www.osti.gov/servlets/purl/1497952.
@article{osti_1497952,
title = {Hybrid DFT investigation of the energetics of Mg ion diffusion in α-MoO3},
author = {Barnes, Taylor A. and Wan, Liwen F. and Kent, Paul R. C. and Prendergast, David},
abstractNote = {We report that rechargeable batteries that utilize divalent Mg ions as the charge carrier species can in principle achieve substantially greater volumetric energy densities than conventional Li-ion batteries. One significant impediment to the development of commercially viable Mg-ion batteries is the slow rate of Mg ion diffusion through otherwise promising cathode materials. Accurate prediction of the activation energies associated with this diffusion process using density functional theory (DFT) is especially challenging due to self-interaction errors intrinsic to DFT that lead to over-delocalization of the d-electrons. One effective but highly computationally demanding approach to reducing self-interaction errors is the use of hybrid functionals, which incorporate a fraction of exact Hartree–Fock exchange. In this work, we assess the effects of exact exchange on computed activation energies for ion diffusion in one potential cathode material, α-MoO3. In contrast to previous studies that primarily utilize non-hybrid functionals, we perform nudged elastic band calculations in which the nuclear coordinates are fully converged using both hybrid functionals and k-point sampling. Additionally, it is found that while non-hybrid functionals indicate the existence of thermodynamically accessible channels for bulk Mg ion diffusion in all three dimensions, hybrid functionals predict that some of these channels are largely inaccessible under typical charge/discharge conditions. Furthermore, it is demonstrated that certain commonly used approximations for incorporating the effects of Hartree–Fock exchange are inadequate for this system, including DFT+U calculations and the use of single-point hybrid calculations using atomic positions obtained using non-hybrid functionals.},
doi = {10.1039/C8CP05511D},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 38,
volume = 20,
place = {United States},
year = {2018},
month = {9}
}

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