Density Functional Theory Study of Ethylene Carbonate Adsorption on the (0001) Surface of Aluminum Oxide α-Al2O3

Brian Ramogayana; David Santos-Carballal; Khomotso P. Maenetja; Nora H. De Leeuw; Phuti E. Ngoepe

doi:10.1021/acsomega.1c03771

Density Functional Theory Study of Ethylene Carbonate Adsorption on the (0001) Surface of Aluminum Oxide α-Al₂O₃

Brian Ramogayana
, David Santos-Carballal
, Khomotso P. Maenetja
, Nora H. De Leeuw
, Phuti E. Ngoepe^*

^*Corresponding author for this work

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

Abstract

Surface coating is one of the techniques used to improve the electrochemical performance and enhance the resistance against decomposition of cathode materials in lithium-ion batteries. Despite several experimental studies addressing the surface coating of secondary Li-ion batteries using α-Al2O3, the reactivity of the material toward the electrolyte components is not yet fully understood. Here, we have employed calculations based on the density functional theory to investigate the adsorption of the organic solvent ethylene carbonate (EC) on the major α-Al2O3(0001) surface. During adsorption of a single EC molecule, it was found that it prefers to bind parallel to the surface through its carboxyl oxygen. As the surface coverage (θ) was increased up to a monolayer, we observed larger adsorption energies per EC molecule (Eads/NEC) for parallel interactions and a reduction for perpendicular interactions. We also noted that increasing the surface coverage with both parallel and perpendicularly interacting EC molecules led to a decrease of the surface free energies and hence increased stability of the α-Al2O3(0001) surface. Despite the larger Eads/NEC observed when the molecule was placed parallel to the surface, minimal charge transfer was calculated for single EC interactions and at higher surface coverages. The simulated scanning tunneling microscopy images are also presented for a clean corundum α-Al2O3 surface and after adsorption with different coverages of parallel and perpendicularly placed EC molecules.

Original language	English
Pages (from-to)	29577-29587
Number of pages	11
Journal	ACS Omega
Volume	6
Issue number	44
DOIs	https://doi.org/10.1021/acsomega.1c03771
Publication status	Published - 9 Nov 2021

Bibliographical note

Funding Information:
The authors acknowledge funding from the UK Economic and Social Research Council (ESRC grant no. ES/N013867/1) and the National Research Foundation South Africa for funding of a UK-SA Newton PhD partnership program. P.E.N. acknowledges the financial support of the DSI-NRF South African Research Chair Initiative, and N.H.d.L. acknowledges the UK Engineering and Physical Sciences Research Council (EPSRC grant EP/K009567) for funding. The authors acknowledge the use of the Centre for High-Performance Computing (CHPC) facility of South Africa in the completion of this work. They also appreciate the support received from DSI Energy Storage Research Development and Innovation Initiative, South Africa. This work was performed using the computational facilities of the Material Modelling Centre (MMC), University of Limpopo, Centre for High-Performance Computing, Cape Town, and the Supercomputing Facilities at Cardiff University operated by ARCCA on behalf of the HPC Wales and Supercomputing Wales (SCW) projects. All data are provided in full in the Results and Discussion section of this paper.

Publisher Copyright:
©

Funding

The authors acknowledge funding from the UK Economic and Social Research Council (ESRC grant no. ES/N013867/1) and the National Research Foundation South Africa for funding of a UK-SA Newton PhD partnership program. P.E.N. acknowledges the financial support of the DSI-NRF South African Research Chair Initiative, and N.H.d.L. acknowledges the UK Engineering and Physical Sciences Research Council (EPSRC grant EP/K009567) for funding. The authors acknowledge the use of the Centre for High-Performance Computing (CHPC) facility of South Africa in the completion of this work. They also appreciate the support received from DSI Energy Storage Research Development and Innovation Initiative, South Africa. This work was performed using the computational facilities of the Material Modelling Centre (MMC), University of Limpopo, Centre for High-Performance Computing, Cape Town, and the Supercomputing Facilities at Cardiff University operated by ARCCA on behalf of the HPC Wales and Supercomputing Wales (SCW) projects. All data are provided in full in the Results and Discussion section of this paper.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Access to Document

10.1021/acsomega.1c03771Licence: CC BY-NC-ND

acsomega.1c03771Final published version, 6.29 MBLicence: CC BY-NC-ND

Cite this

@article{9974ebf763ad4473aa479f429a16d2fd,

title = "Density Functional Theory Study of Ethylene Carbonate Adsorption on the (0001) Surface of Aluminum Oxide α-Al2O3",

abstract = "Surface coating is one of the techniques used to improve the electrochemical performance and enhance the resistance against decomposition of cathode materials in lithium-ion batteries. Despite several experimental studies addressing the surface coating of secondary Li-ion batteries using α-Al2O3, the reactivity of the material toward the electrolyte components is not yet fully understood. Here, we have employed calculations based on the density functional theory to investigate the adsorption of the organic solvent ethylene carbonate (EC) on the major α-Al2O3(0001) surface. During adsorption of a single EC molecule, it was found that it prefers to bind parallel to the surface through its carboxyl oxygen. As the surface coverage (θ) was increased up to a monolayer, we observed larger adsorption energies per EC molecule (Eads/NEC) for parallel interactions and a reduction for perpendicular interactions. We also noted that increasing the surface coverage with both parallel and perpendicularly interacting EC molecules led to a decrease of the surface free energies and hence increased stability of the α-Al2O3(0001) surface. Despite the larger Eads/NEC observed when the molecule was placed parallel to the surface, minimal charge transfer was calculated for single EC interactions and at higher surface coverages. The simulated scanning tunneling microscopy images are also presented for a clean corundum α-Al2O3 surface and after adsorption with different coverages of parallel and perpendicularly placed EC molecules.",

author = "Brian Ramogayana and David Santos-Carballal and Maenetja, \{Khomotso P.\} and \{De Leeuw\}, \{Nora H.\} and Ngoepe, \{Phuti E.\}",

note = "Funding Information: The authors acknowledge funding from the UK Economic and Social Research Council (ESRC grant no. ES/N013867/1) and the National Research Foundation South Africa for funding of a UK-SA Newton PhD partnership program. P.E.N. acknowledges the financial support of the DSI-NRF South African Research Chair Initiative, and N.H.d.L. acknowledges the UK Engineering and Physical Sciences Research Council (EPSRC grant EP/K009567) for funding. The authors acknowledge the use of the Centre for High-Performance Computing (CHPC) facility of South Africa in the completion of this work. They also appreciate the support received from DSI Energy Storage Research Development and Innovation Initiative, South Africa. This work was performed using the computational facilities of the Material Modelling Centre (MMC), University of Limpopo, Centre for High-Performance Computing, Cape Town, and the Supercomputing Facilities at Cardiff University operated by ARCCA on behalf of the HPC Wales and Supercomputing Wales (SCW) projects. All data are provided in full in the Results and Discussion section of this paper. Publisher Copyright: {\textcopyright} ",

year = "2021",

month = nov,

day = "9",

doi = "10.1021/acsomega.1c03771",

language = "English",

volume = "6",

pages = "29577--29587",

journal = "ACS Omega",

issn = "2470-1343",

publisher = "American Chemical Society",

number = "44",

}

TY - JOUR

T1 - Density Functional Theory Study of Ethylene Carbonate Adsorption on the (0001) Surface of Aluminum Oxide α-Al2O3

AU - Ramogayana, Brian

AU - Santos-Carballal, David

AU - Maenetja, Khomotso P.

AU - De Leeuw, Nora H.

AU - Ngoepe, Phuti E.

N1 - Funding Information: The authors acknowledge funding from the UK Economic and Social Research Council (ESRC grant no. ES/N013867/1) and the National Research Foundation South Africa for funding of a UK-SA Newton PhD partnership program. P.E.N. acknowledges the financial support of the DSI-NRF South African Research Chair Initiative, and N.H.d.L. acknowledges the UK Engineering and Physical Sciences Research Council (EPSRC grant EP/K009567) for funding. The authors acknowledge the use of the Centre for High-Performance Computing (CHPC) facility of South Africa in the completion of this work. They also appreciate the support received from DSI Energy Storage Research Development and Innovation Initiative, South Africa. This work was performed using the computational facilities of the Material Modelling Centre (MMC), University of Limpopo, Centre for High-Performance Computing, Cape Town, and the Supercomputing Facilities at Cardiff University operated by ARCCA on behalf of the HPC Wales and Supercomputing Wales (SCW) projects. All data are provided in full in the Results and Discussion section of this paper. Publisher Copyright: ©

PY - 2021/11/9

Y1 - 2021/11/9

N2 - Surface coating is one of the techniques used to improve the electrochemical performance and enhance the resistance against decomposition of cathode materials in lithium-ion batteries. Despite several experimental studies addressing the surface coating of secondary Li-ion batteries using α-Al2O3, the reactivity of the material toward the electrolyte components is not yet fully understood. Here, we have employed calculations based on the density functional theory to investigate the adsorption of the organic solvent ethylene carbonate (EC) on the major α-Al2O3(0001) surface. During adsorption of a single EC molecule, it was found that it prefers to bind parallel to the surface through its carboxyl oxygen. As the surface coverage (θ) was increased up to a monolayer, we observed larger adsorption energies per EC molecule (Eads/NEC) for parallel interactions and a reduction for perpendicular interactions. We also noted that increasing the surface coverage with both parallel and perpendicularly interacting EC molecules led to a decrease of the surface free energies and hence increased stability of the α-Al2O3(0001) surface. Despite the larger Eads/NEC observed when the molecule was placed parallel to the surface, minimal charge transfer was calculated for single EC interactions and at higher surface coverages. The simulated scanning tunneling microscopy images are also presented for a clean corundum α-Al2O3 surface and after adsorption with different coverages of parallel and perpendicularly placed EC molecules.

AB - Surface coating is one of the techniques used to improve the electrochemical performance and enhance the resistance against decomposition of cathode materials in lithium-ion batteries. Despite several experimental studies addressing the surface coating of secondary Li-ion batteries using α-Al2O3, the reactivity of the material toward the electrolyte components is not yet fully understood. Here, we have employed calculations based on the density functional theory to investigate the adsorption of the organic solvent ethylene carbonate (EC) on the major α-Al2O3(0001) surface. During adsorption of a single EC molecule, it was found that it prefers to bind parallel to the surface through its carboxyl oxygen. As the surface coverage (θ) was increased up to a monolayer, we observed larger adsorption energies per EC molecule (Eads/NEC) for parallel interactions and a reduction for perpendicular interactions. We also noted that increasing the surface coverage with both parallel and perpendicularly interacting EC molecules led to a decrease of the surface free energies and hence increased stability of the α-Al2O3(0001) surface. Despite the larger Eads/NEC observed when the molecule was placed parallel to the surface, minimal charge transfer was calculated for single EC interactions and at higher surface coverages. The simulated scanning tunneling microscopy images are also presented for a clean corundum α-Al2O3 surface and after adsorption with different coverages of parallel and perpendicularly placed EC molecules.

UR - https://www.scopus.com/pages/publications/85118863115

U2 - 10.1021/acsomega.1c03771

DO - 10.1021/acsomega.1c03771

M3 - Article

AN - SCOPUS:85118863115

SN - 2470-1343

VL - 6

SP - 29577

EP - 29587

JO - ACS Omega

JF - ACS Omega

IS - 44

ER -