Following the in-plane disorder of sodiated hard carbon through operando total scattering

Jette K. Mathiesen, Ronald Väli, Meelis Härmas, Enn Lust, Jon Fold Von Bülow, Kirsten M.Ø. Jensen, Poul Norby*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Successfully enabling a new battery technology, such as sodium-ion batteries, requires a thorough understanding of the functional properties of its building blocks. Knowing how the electrode materials behave upon operation is crucial to gain insight into how the battery technologies can be improved for optimal usage. Here we examine with X-ray total scattering and subsequent pair distribution function (PDF) analysis the structural response of hard carbon upon operation, which has been proposed as a possible electrode material for sodium ion batteries. PDF analysis reveals a clear correlation between the interplane and in-plane interatomic distances and the state of charge. The change in in-plane graphene behaviour corresponds to a reversible charge transfer between sodium and the antibonding orbitals in the upper π band of the graphene sheet, resulting in in-plane elongation and contraction upon cycling. As a result of the introduction of sodium into the structure upon discharge, the hard carbon structure is found to become increasingly disordered resulting in the initial structure not being able to fully recover upon desodiation. The more pronounced structural impact upon sodiation than seen in lithiated hard carbon suggests a larger electron transfer impact on the structure by influencing the π-orbitals of the neighboring, conjugated benzene rings. This means that the electron transfer cannot be described as a local electron transfer contribution as might be the case of lithium, but instead as a more delocalized contribution, in which the local structure of graphene experiences a larger change upon sodiation.

Original languageEnglish
JournalJournal of Materials Chemistry A
Volume7
Issue number19
Pages (from-to)11709-11717
Number of pages9
ISSN2050-7488
DOIs
Publication statusPublished - 2019

Cite this

Mathiesen, J. K., Väli, R., Härmas, M., Lust, E., Fold Von Bülow, J., Jensen, K. M. Ø., & Norby, P. (2019). Following the in-plane disorder of sodiated hard carbon through operando total scattering. Journal of Materials Chemistry A, 7(19), 11709-11717. https://doi.org/10.1039/c9ta02413a
Mathiesen, Jette K. ; Väli, Ronald ; Härmas, Meelis ; Lust, Enn ; Fold Von Bülow, Jon ; Jensen, Kirsten M.Ø. ; Norby, Poul. / Following the in-plane disorder of sodiated hard carbon through operando total scattering. In: Journal of Materials Chemistry A. 2019 ; Vol. 7, No. 19. pp. 11709-11717.
@article{10afeeee5be04571b30a3aedf940c92d,
title = "Following the in-plane disorder of sodiated hard carbon through operando total scattering",
abstract = "Successfully enabling a new battery technology, such as sodium-ion batteries, requires a thorough understanding of the functional properties of its building blocks. Knowing how the electrode materials behave upon operation is crucial to gain insight into how the battery technologies can be improved for optimal usage. Here we examine with X-ray total scattering and subsequent pair distribution function (PDF) analysis the structural response of hard carbon upon operation, which has been proposed as a possible electrode material for sodium ion batteries. PDF analysis reveals a clear correlation between the interplane and in-plane interatomic distances and the state of charge. The change in in-plane graphene behaviour corresponds to a reversible charge transfer between sodium and the antibonding orbitals in the upper π band of the graphene sheet, resulting in in-plane elongation and contraction upon cycling. As a result of the introduction of sodium into the structure upon discharge, the hard carbon structure is found to become increasingly disordered resulting in the initial structure not being able to fully recover upon desodiation. The more pronounced structural impact upon sodiation than seen in lithiated hard carbon suggests a larger electron transfer impact on the structure by influencing the π-orbitals of the neighboring, conjugated benzene rings. This means that the electron transfer cannot be described as a local electron transfer contribution as might be the case of lithium, but instead as a more delocalized contribution, in which the local structure of graphene experiences a larger change upon sodiation.",
author = "Mathiesen, {Jette K.} and Ronald V{\"a}li and Meelis H{\"a}rmas and Enn Lust and {Fold Von B{\"u}low}, Jon and Jensen, {Kirsten M.{\O}.} and Poul Norby",
year = "2019",
doi = "10.1039/c9ta02413a",
language = "English",
volume = "7",
pages = "11709--11717",
journal = "Journal of Materials Chemistry A",
issn = "2050-7488",
publisher = "RSC Publications",
number = "19",

}

Mathiesen, JK, Väli, R, Härmas, M, Lust, E, Fold Von Bülow, J, Jensen, KMØ & Norby, P 2019, 'Following the in-plane disorder of sodiated hard carbon through operando total scattering', Journal of Materials Chemistry A, vol. 7, no. 19, pp. 11709-11717. https://doi.org/10.1039/c9ta02413a

Following the in-plane disorder of sodiated hard carbon through operando total scattering. / Mathiesen, Jette K.; Väli, Ronald; Härmas, Meelis; Lust, Enn; Fold Von Bülow, Jon; Jensen, Kirsten M.Ø.; Norby, Poul.

In: Journal of Materials Chemistry A, Vol. 7, No. 19, 2019, p. 11709-11717.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Following the in-plane disorder of sodiated hard carbon through operando total scattering

AU - Mathiesen, Jette K.

AU - Väli, Ronald

AU - Härmas, Meelis

AU - Lust, Enn

AU - Fold Von Bülow, Jon

AU - Jensen, Kirsten M.Ø.

AU - Norby, Poul

PY - 2019

Y1 - 2019

N2 - Successfully enabling a new battery technology, such as sodium-ion batteries, requires a thorough understanding of the functional properties of its building blocks. Knowing how the electrode materials behave upon operation is crucial to gain insight into how the battery technologies can be improved for optimal usage. Here we examine with X-ray total scattering and subsequent pair distribution function (PDF) analysis the structural response of hard carbon upon operation, which has been proposed as a possible electrode material for sodium ion batteries. PDF analysis reveals a clear correlation between the interplane and in-plane interatomic distances and the state of charge. The change in in-plane graphene behaviour corresponds to a reversible charge transfer between sodium and the antibonding orbitals in the upper π band of the graphene sheet, resulting in in-plane elongation and contraction upon cycling. As a result of the introduction of sodium into the structure upon discharge, the hard carbon structure is found to become increasingly disordered resulting in the initial structure not being able to fully recover upon desodiation. The more pronounced structural impact upon sodiation than seen in lithiated hard carbon suggests a larger electron transfer impact on the structure by influencing the π-orbitals of the neighboring, conjugated benzene rings. This means that the electron transfer cannot be described as a local electron transfer contribution as might be the case of lithium, but instead as a more delocalized contribution, in which the local structure of graphene experiences a larger change upon sodiation.

AB - Successfully enabling a new battery technology, such as sodium-ion batteries, requires a thorough understanding of the functional properties of its building blocks. Knowing how the electrode materials behave upon operation is crucial to gain insight into how the battery technologies can be improved for optimal usage. Here we examine with X-ray total scattering and subsequent pair distribution function (PDF) analysis the structural response of hard carbon upon operation, which has been proposed as a possible electrode material for sodium ion batteries. PDF analysis reveals a clear correlation between the interplane and in-plane interatomic distances and the state of charge. The change in in-plane graphene behaviour corresponds to a reversible charge transfer between sodium and the antibonding orbitals in the upper π band of the graphene sheet, resulting in in-plane elongation and contraction upon cycling. As a result of the introduction of sodium into the structure upon discharge, the hard carbon structure is found to become increasingly disordered resulting in the initial structure not being able to fully recover upon desodiation. The more pronounced structural impact upon sodiation than seen in lithiated hard carbon suggests a larger electron transfer impact on the structure by influencing the π-orbitals of the neighboring, conjugated benzene rings. This means that the electron transfer cannot be described as a local electron transfer contribution as might be the case of lithium, but instead as a more delocalized contribution, in which the local structure of graphene experiences a larger change upon sodiation.

U2 - 10.1039/c9ta02413a

DO - 10.1039/c9ta02413a

M3 - Journal article

AN - SCOPUS:85065874183

VL - 7

SP - 11709

EP - 11717

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

SN - 2050-7488

IS - 19

ER -

Mathiesen JK, Väli R, Härmas M, Lust E, Fold Von Bülow J, Jensen KMØ et al. Following the in-plane disorder of sodiated hard carbon through operando total scattering. Journal of Materials Chemistry A. 2019;7(19):11709-11717. https://doi.org/10.1039/c9ta02413a