Preventing Structural Rearrangements on Battery Cycling: A First-Principles Investigation of the Effect of Dopants on the Migration Barriers in Layered Li0.5MnO2

Ieuan D. Seymour; David J. Wales; Clare P. Grey

doi:10.1021/acs.jpcc.6b05307

Preventing Structural Rearrangements on Battery Cycling: A First-Principles Investigation of the Effect of Dopants on the Migration Barriers in Layered Li_0.5MnO₂

Ieuan D. Seymour, David J. Wales, Clare P. Grey^*

^*Corresponding author for this work

Chemistry

University of Cambridge

Research output: Contribution to journal › Article › peer-review

16 Citations (Scopus)

Abstract

Layered LiMnO₂ is a potential Li ion cathode material that is known to undergo a layered to spinel transformation upon delithiation, as a result of Mn migration. A common strategy to improve the structural stability of LiMnO₂ has been to replace Mn with a range of metal dopants, although the mechanism by which each dopant stabilizes the structure is not well understood. In this work we characterize ion-migration barriers using hybrid eigenvector-following (EF) and density functional theory to study how trivalent dopants (Al³⁺, Cr³⁺, Fe³⁺, Ga³⁺, Sc³⁺, and In³⁺) affect Mn migration during the initial stage of the layered to spinel transformation in Li_0.5MnO₂. We demonstrate that dopants with small ionic radii, such as Al³⁺ and Cr³⁺, can increase the barrier for migration, but only when they are located in the first cation coordination sphere of Mn. We also demonstrate how the hybrid EF approach can be used to study the migration barriers of dopant species within the structure of Li_0.5MnO₂ efficiently. The transition state searching methodology described in this work will be useful for studying the effects of dopants on structural transformation mechanisms in a wide range of technologically interesting energy materials.

Original language	English
Pages (from-to)	19521-19530
Number of pages	10
Journal	Journal of Physical Chemistry C
Volume	120
Issue number	35
Early online date	19 Aug 2016
DOIs	https://doi.org/10.1021/acs.jpcc.6b05307
Publication status	Published - 8 Sept 2016

Bibliographical note

Funding Information:
this work used the ARCHER UK National Supercomputing Service. Research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract DE-AC02-98CH10886. C.P.G. acknowledges the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award #DE-SC0012583. I.D.S. acknowledges funding from NECCES and the Geoffrey Moorhouse Gibson Studentship in Chemistry from Trinity College Cambridge

Publisher Copyright:
© 2016 American Chemical Society.

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10.1021/acs.jpcc.6b05307

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title = "Preventing Structural Rearrangements on Battery Cycling: A First-Principles Investigation of the Effect of Dopants on the Migration Barriers in Layered Li0.5MnO2",

abstract = "Layered LiMnO2 is a potential Li ion cathode material that is known to undergo a layered to spinel transformation upon delithiation, as a result of Mn migration. A common strategy to improve the structural stability of LiMnO2 has been to replace Mn with a range of metal dopants, although the mechanism by which each dopant stabilizes the structure is not well understood. In this work we characterize ion-migration barriers using hybrid eigenvector-following (EF) and density functional theory to study how trivalent dopants (Al3+, Cr3+, Fe3+, Ga3+, Sc3+, and In3+) affect Mn migration during the initial stage of the layered to spinel transformation in Li0.5MnO2. We demonstrate that dopants with small ionic radii, such as Al3+ and Cr3+, can increase the barrier for migration, but only when they are located in the first cation coordination sphere of Mn. We also demonstrate how the hybrid EF approach can be used to study the migration barriers of dopant species within the structure of Li0.5MnO2 efficiently. The transition state searching methodology described in this work will be useful for studying the effects of dopants on structural transformation mechanisms in a wide range of technologically interesting energy materials.",

author = "Seymour, {Ieuan D.} and Wales, {David J.} and Grey, {Clare P.}",

note = "Funding Information: this work used the ARCHER UK National Supercomputing Service. Research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract DE-AC02-98CH10886. C.P.G. acknowledges the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award #DE-SC0012583. I.D.S. acknowledges funding from NECCES and the Geoffrey Moorhouse Gibson Studentship in Chemistry from Trinity College Cambridge Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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N1 - Funding Information: this work used the ARCHER UK National Supercomputing Service. Research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract DE-AC02-98CH10886. C.P.G. acknowledges the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award #DE-SC0012583. I.D.S. acknowledges funding from NECCES and the Geoffrey Moorhouse Gibson Studentship in Chemistry from Trinity College Cambridge Publisher Copyright: © 2016 American Chemical Society.

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N2 - Layered LiMnO2 is a potential Li ion cathode material that is known to undergo a layered to spinel transformation upon delithiation, as a result of Mn migration. A common strategy to improve the structural stability of LiMnO2 has been to replace Mn with a range of metal dopants, although the mechanism by which each dopant stabilizes the structure is not well understood. In this work we characterize ion-migration barriers using hybrid eigenvector-following (EF) and density functional theory to study how trivalent dopants (Al3+, Cr3+, Fe3+, Ga3+, Sc3+, and In3+) affect Mn migration during the initial stage of the layered to spinel transformation in Li0.5MnO2. We demonstrate that dopants with small ionic radii, such as Al3+ and Cr3+, can increase the barrier for migration, but only when they are located in the first cation coordination sphere of Mn. We also demonstrate how the hybrid EF approach can be used to study the migration barriers of dopant species within the structure of Li0.5MnO2 efficiently. The transition state searching methodology described in this work will be useful for studying the effects of dopants on structural transformation mechanisms in a wide range of technologically interesting energy materials.

AB - Layered LiMnO2 is a potential Li ion cathode material that is known to undergo a layered to spinel transformation upon delithiation, as a result of Mn migration. A common strategy to improve the structural stability of LiMnO2 has been to replace Mn with a range of metal dopants, although the mechanism by which each dopant stabilizes the structure is not well understood. In this work we characterize ion-migration barriers using hybrid eigenvector-following (EF) and density functional theory to study how trivalent dopants (Al3+, Cr3+, Fe3+, Ga3+, Sc3+, and In3+) affect Mn migration during the initial stage of the layered to spinel transformation in Li0.5MnO2. We demonstrate that dopants with small ionic radii, such as Al3+ and Cr3+, can increase the barrier for migration, but only when they are located in the first cation coordination sphere of Mn. We also demonstrate how the hybrid EF approach can be used to study the migration barriers of dopant species within the structure of Li0.5MnO2 efficiently. The transition state searching methodology described in this work will be useful for studying the effects of dopants on structural transformation mechanisms in a wide range of technologically interesting energy materials.

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Preventing Structural Rearrangements on Battery Cycling: A First-Principles Investigation of the Effect of Dopants on the Migration Barriers in Layered Li_0.5MnO₂

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