Role of Long-Range Dispersion Forces in Modeling of MXenes as Battery Electrode Materials

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

We present a density functional theory study of stacked MXenes with the aim of assessing the accuracy of the most widely used exchange–correlation (xc) functionals for calculating properties relevant for battery electrode materials, namely, mechanical stability, open-circuit voltages, and lithium diffusion barriers. The open-circuit voltage results are nearly independent of the choice of xc-functional, while the lithium diffusion barriers are shown to be heavily dependent on the selected xc-functional, with diffusivities spanning 5 orders of magnitude. This is shown to be due to differences in the computed interlayer distances between the MXene monolayers, which are found to be linearly related to the diffusion barriers. This underlines the importance of starting from reliable crystal structures when modeling MXenes as battery electrode materials. Using an experimental reference materials database, we show a general trend in lattice parameter accuracy for 2D stacked materials with the chosen xc-functionals. Our results reveal that the optB88-vdW functional provides the best average accuracy for predicting the out-of-plane lattice parameter and hence also the best estimate for the transition-state barriers, while PBE with D3 damping performs only slightly worse on average.
Original languageEnglish
JournalThe Journal of Physical Chemistry Part C
Volume123
Issue number7
Pages (from-to)4064-4071
ISSN1932-7447
DOIs
Publication statusPublished - 2019

Cite this

@article{076d4adaec754e47a27eda063e186d3b,
title = "Role of Long-Range Dispersion Forces in Modeling of MXenes as Battery Electrode Materials",
abstract = "We present a density functional theory study of stacked MXenes with the aim of assessing the accuracy of the most widely used exchange–correlation (xc) functionals for calculating properties relevant for battery electrode materials, namely, mechanical stability, open-circuit voltages, and lithium diffusion barriers. The open-circuit voltage results are nearly independent of the choice of xc-functional, while the lithium diffusion barriers are shown to be heavily dependent on the selected xc-functional, with diffusivities spanning 5 orders of magnitude. This is shown to be due to differences in the computed interlayer distances between the MXene monolayers, which are found to be linearly related to the diffusion barriers. This underlines the importance of starting from reliable crystal structures when modeling MXenes as battery electrode materials. Using an experimental reference materials database, we show a general trend in lattice parameter accuracy for 2D stacked materials with the chosen xc-functionals. Our results reveal that the optB88-vdW functional provides the best average accuracy for predicting the out-of-plane lattice parameter and hence also the best estimate for the transition-state barriers, while PBE with D3 damping performs only slightly worse on average.",
author = "Tygesen, {Alexander S.} and Mohnish Pandey and Tejs Vegge and Thygesen, {Kristian Sommer} and Garc{\'i}a-Lastra, {Juan M.}",
year = "2019",
doi = "10.1021/acs.jpcc.8b11663",
language = "English",
volume = "123",
pages = "4064--4071",
journal = "The Journal of Physical Chemistry Part C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "7",

}

TY - JOUR

T1 - Role of Long-Range Dispersion Forces in Modeling of MXenes as Battery Electrode Materials

AU - Tygesen, Alexander S.

AU - Pandey, Mohnish

AU - Vegge, Tejs

AU - Thygesen, Kristian Sommer

AU - García-Lastra, Juan M.

PY - 2019

Y1 - 2019

N2 - We present a density functional theory study of stacked MXenes with the aim of assessing the accuracy of the most widely used exchange–correlation (xc) functionals for calculating properties relevant for battery electrode materials, namely, mechanical stability, open-circuit voltages, and lithium diffusion barriers. The open-circuit voltage results are nearly independent of the choice of xc-functional, while the lithium diffusion barriers are shown to be heavily dependent on the selected xc-functional, with diffusivities spanning 5 orders of magnitude. This is shown to be due to differences in the computed interlayer distances between the MXene monolayers, which are found to be linearly related to the diffusion barriers. This underlines the importance of starting from reliable crystal structures when modeling MXenes as battery electrode materials. Using an experimental reference materials database, we show a general trend in lattice parameter accuracy for 2D stacked materials with the chosen xc-functionals. Our results reveal that the optB88-vdW functional provides the best average accuracy for predicting the out-of-plane lattice parameter and hence also the best estimate for the transition-state barriers, while PBE with D3 damping performs only slightly worse on average.

AB - We present a density functional theory study of stacked MXenes with the aim of assessing the accuracy of the most widely used exchange–correlation (xc) functionals for calculating properties relevant for battery electrode materials, namely, mechanical stability, open-circuit voltages, and lithium diffusion barriers. The open-circuit voltage results are nearly independent of the choice of xc-functional, while the lithium diffusion barriers are shown to be heavily dependent on the selected xc-functional, with diffusivities spanning 5 orders of magnitude. This is shown to be due to differences in the computed interlayer distances between the MXene monolayers, which are found to be linearly related to the diffusion barriers. This underlines the importance of starting from reliable crystal structures when modeling MXenes as battery electrode materials. Using an experimental reference materials database, we show a general trend in lattice parameter accuracy for 2D stacked materials with the chosen xc-functionals. Our results reveal that the optB88-vdW functional provides the best average accuracy for predicting the out-of-plane lattice parameter and hence also the best estimate for the transition-state barriers, while PBE with D3 damping performs only slightly worse on average.

U2 - 10.1021/acs.jpcc.8b11663

DO - 10.1021/acs.jpcc.8b11663

M3 - Journal article

VL - 123

SP - 4064

EP - 4071

JO - The Journal of Physical Chemistry Part C

JF - The Journal of Physical Chemistry Part C

SN - 1932-7447

IS - 7

ER -