Home > Research > Publications & Outputs > Mesoscopic simulations of thein situNMR spectra...

Research

Electronic data

  • AuthorAcceptedManuscript

    Accepted author manuscript, 1.41 MB, PDF document

    Available under license: CC BY-NC: Creative Commons Attribution-NonCommercial 4.0 International License

Links

Text available via DOI:

Keywords

View graph of relations

Mesoscopic simulations of thein situNMR spectra of porous carbon based supercapacitors: electronic structure and adsorbent reorganisation effects

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Published

Standard

Mesoscopic simulations of thein situNMR spectra of porous carbon based supercapacitors: electronic structure and adsorbent reorganisation effects. / Sasikumar, A.; Belhboub, A.; Bacon, C. et al.
In: Physical Chemistry Chemical Physics, Vol. 23, No. 30, 14.08.2021, p. 15925-15934.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Harvard

Sasikumar, A, Belhboub, A, Bacon, C, Forse, AC, Griffin, JM, Grey, CP, Simon, P & Merlet, C 2021, 'Mesoscopic simulations of thein situNMR spectra of porous carbon based supercapacitors: electronic structure and adsorbent reorganisation effects', Physical Chemistry Chemical Physics, vol. 23, no. 30, pp. 15925-15934. https://doi.org/10.1039/d1cp02130c

APA

Sasikumar, A., Belhboub, A., Bacon, C., Forse, A. C., Griffin, J. M., Grey, C. P., Simon, P., & Merlet, C. (2021). Mesoscopic simulations of thein situNMR spectra of porous carbon based supercapacitors: electronic structure and adsorbent reorganisation effects. Physical Chemistry Chemical Physics, 23(30), 15925-15934. https://doi.org/10.1039/d1cp02130c

Vancouver

Sasikumar A, Belhboub A, Bacon C, Forse AC, Griffin JM, Grey CP et al. Mesoscopic simulations of thein situNMR spectra of porous carbon based supercapacitors: electronic structure and adsorbent reorganisation effects. Physical Chemistry Chemical Physics. 2021 Aug 14;23(30):15925-15934. Epub 2021 Jul 19. doi: 10.1039/d1cp02130c

Author

Sasikumar, A. ; Belhboub, A. ; Bacon, C. et al. / Mesoscopic simulations of thein situNMR spectra of porous carbon based supercapacitors : electronic structure and adsorbent reorganisation effects. In: Physical Chemistry Chemical Physics. 2021 ; Vol. 23, No. 30. pp. 15925-15934.

Bibtex

@article{897b6d6a503f4b78a60c757efc5390fd,
title = "Mesoscopic simulations of thein situNMR spectra of porous carbon based supercapacitors: electronic structure and adsorbent reorganisation effects",
abstract = "In situNMR spectroscopy is a powerful technique to investigate charge storage mechanisms in carbon-based supercapacitors thanks to its ability to distinguish ionic and molecular species adsorbed in the porous electrodes from those in the bulk electrolyte. The NMR peak corresponding to the adsorbed species shows a clear change of chemical shift as the applied potential difference is varied. This variation in chemical shift is thought to originate from a combination of ion reorganisation in the pores and changes in ring current shifts due to the changes of electronic density in the carbon. While previous Density Functional Theory calculations suggested that the electronic density has a large effect, the relative contributions of these two effects is challenging to untangle. Here, we use mesoscopic simulations to simulate NMR spectra and investigate the relative importance of ion reorganisation and ring currents on the resulting chemical shift. The model is able to predict chemical shifts in good agreement with NMR experiments and indicates that the ring currents are the dominant contribution. A thorough analysis of a specific electrode/electrolyte combination for which detailed NMR experiments have been reported allows us to confirm that local ion reorganisation has a very limited effect but the relative quantities of ions in pores of different sizes, which can change upon charging/discharging, can lead to a significant effect. Our findings suggest thatin situNMR spectra of supercapacitors may provide insights into the electronic structure of carbon materials in the future. ",
keywords = "Carbon, Density functional theory, Electrodes, Electrolytes, Electronic structure, Ions, Nuclear magnetic resonance spectroscopy, Porous materials, Supercapacitor, Superconducting materials, Applied potentials, Charging/discharging, Dominant contributions, Electronic density, Mesoscopic simulation, Molecular species, Porous electrodes, Relative contribution, Chemical shift",
author = "A. Sasikumar and A. Belhboub and C. Bacon and A.C. Forse and J.M. Griffin and C.P. Grey and P. Simon and C. Merlet",
year = "2021",
month = aug,
day = "14",
doi = "10.1039/d1cp02130c",
language = "English",
volume = "23",
pages = "15925--15934",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "30",

}

RIS

TY - JOUR

T1 - Mesoscopic simulations of thein situNMR spectra of porous carbon based supercapacitors

T2 - electronic structure and adsorbent reorganisation effects

AU - Sasikumar, A.

AU - Belhboub, A.

AU - Bacon, C.

AU - Forse, A.C.

AU - Griffin, J.M.

AU - Grey, C.P.

AU - Simon, P.

AU - Merlet, C.

PY - 2021/8/14

Y1 - 2021/8/14

N2 - In situNMR spectroscopy is a powerful technique to investigate charge storage mechanisms in carbon-based supercapacitors thanks to its ability to distinguish ionic and molecular species adsorbed in the porous electrodes from those in the bulk electrolyte. The NMR peak corresponding to the adsorbed species shows a clear change of chemical shift as the applied potential difference is varied. This variation in chemical shift is thought to originate from a combination of ion reorganisation in the pores and changes in ring current shifts due to the changes of electronic density in the carbon. While previous Density Functional Theory calculations suggested that the electronic density has a large effect, the relative contributions of these two effects is challenging to untangle. Here, we use mesoscopic simulations to simulate NMR spectra and investigate the relative importance of ion reorganisation and ring currents on the resulting chemical shift. The model is able to predict chemical shifts in good agreement with NMR experiments and indicates that the ring currents are the dominant contribution. A thorough analysis of a specific electrode/electrolyte combination for which detailed NMR experiments have been reported allows us to confirm that local ion reorganisation has a very limited effect but the relative quantities of ions in pores of different sizes, which can change upon charging/discharging, can lead to a significant effect. Our findings suggest thatin situNMR spectra of supercapacitors may provide insights into the electronic structure of carbon materials in the future.

AB - In situNMR spectroscopy is a powerful technique to investigate charge storage mechanisms in carbon-based supercapacitors thanks to its ability to distinguish ionic and molecular species adsorbed in the porous electrodes from those in the bulk electrolyte. The NMR peak corresponding to the adsorbed species shows a clear change of chemical shift as the applied potential difference is varied. This variation in chemical shift is thought to originate from a combination of ion reorganisation in the pores and changes in ring current shifts due to the changes of electronic density in the carbon. While previous Density Functional Theory calculations suggested that the electronic density has a large effect, the relative contributions of these two effects is challenging to untangle. Here, we use mesoscopic simulations to simulate NMR spectra and investigate the relative importance of ion reorganisation and ring currents on the resulting chemical shift. The model is able to predict chemical shifts in good agreement with NMR experiments and indicates that the ring currents are the dominant contribution. A thorough analysis of a specific electrode/electrolyte combination for which detailed NMR experiments have been reported allows us to confirm that local ion reorganisation has a very limited effect but the relative quantities of ions in pores of different sizes, which can change upon charging/discharging, can lead to a significant effect. Our findings suggest thatin situNMR spectra of supercapacitors may provide insights into the electronic structure of carbon materials in the future.

KW - Carbon

KW - Density functional theory

KW - Electrodes

KW - Electrolytes

KW - Electronic structure

KW - Ions

KW - Nuclear magnetic resonance spectroscopy

KW - Porous materials

KW - Supercapacitor

KW - Superconducting materials

KW - Applied potentials

KW - Charging/discharging

KW - Dominant contributions

KW - Electronic density

KW - Mesoscopic simulation

KW - Molecular species

KW - Porous electrodes

KW - Relative contribution

KW - Chemical shift

U2 - 10.1039/d1cp02130c

DO - 10.1039/d1cp02130c

M3 - Journal article

VL - 23

SP - 15925

EP - 15934

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 30

ER -