Novel polyelectrolyte membranes for fuel and flow batteries: insights from simulations

Soumyadipta Sengupta, Giorgos Kritikos, Konstantinos Karatasos, Arun Venkatnathan, Rakesh Pant, Pavel Komarov, Alexey V. Lyulin

Research output: Chapter in Book/Report/Conference proceedingConference contributionAcademicpeer-review

2 Citations (Scopus)

Abstract

Recent experiments on polyelectrolyte membranes have clearly shown that at operating temperatures perfluoroimide acid (PFIA) has a higher electrical conductivity than widely used Nafion. In the present paper classical molecular-dynamics simulations were carried out to study the structural properties of both materials, and the proton and water transport in the corresponding membranes at T=300 K and T=353 K. In this temperature range, the temperature effects on the hydrated internal polyelectrolyte structure were found to be negligible. The PFIA has longer side chains across a wide range of hydration levels which would have promoted more trapping of water and hydronium ions in PFIA. Indeed, the average number of water molecules in the first hydration shell around the side-chain protogenic groups was found to be higher in PFIA than in Nafion. Our simulations showed the formation of large continuous water clusters and connected pore volumes in PFIA at high hydration levels which promotes conductivity. The diffusivity constants for hydronium ions and water increase with increasing hydration and increasing temperature. Unlike the experimental conductivities, the simulated data for PFIA were comparable to those of Nafion at high hydration levels. Note that the experimentally measured conductivity in PFIA is both due to vehicular transport of ions, which can be resolved using classical molecular dynamics, and structural Grotthuss diffusion, which cannot be resolved in our simulations. Interestingly, we observed a higher total number of water molecules in the first coordination shell around hydronium in PFIA than in Nafion at higher hydration levels. This should aid in more hydrogen bonding between hydronium and water in PFIA which, in turn, should help in structural diffusion. Finally, we discuss our preliminary results and some peculiarities of the proton transport in Nafion membranes filled with the graphene oxide nanoflakes.

LanguageEnglish
Title of host publication9th International Conference on Times of Polymers and Composites
Subtitle of host publicationFrom Aerospace to Nanotechnology
PublisherAmerican Institute of Physics
Number of pages4
ISBN (Electronic)9780735416970
DOIs
StatePublished - 11 Jul 2018
Event9th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology - Ischia, Naples, Italy
Duration: 17 Jun 201821 Jun 2018

Publication series

NameAIP Conference Proceedings
No.1
Volume1981
ISSN (Print)0094-243X

Conference

Conference9th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology
CountryItaly
CityIschia, Naples
Period17/06/1821/06/18

Fingerprint

electric batteries
membranes
acids
hydration
simulation
water
hydronium ions
conductivity
molecular dynamics
protons
operating temperature
diffusivity
temperature effects
molecules
graphene
ions
trapping
porosity
electrical resistivity
temperature

Keywords

  • flow battery
  • hydronium diffusion
  • molecular dynamics
  • nanocomposite
  • polyelectrolyte membrane

Cite this

Sengupta, S., Kritikos, G., Karatasos, K., Venkatnathan, A., Pant, R., Komarov, P., & Lyulin, A. V. (2018). Novel polyelectrolyte membranes for fuel and flow batteries: insights from simulations. In 9th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology [020004] (AIP Conference Proceedings; Vol. 1981, No. 1). American Institute of Physics. DOI: 10.1063/1.5045866
Sengupta, Soumyadipta ; Kritikos, Giorgos ; Karatasos, Konstantinos ; Venkatnathan, Arun ; Pant, Rakesh ; Komarov, Pavel ; Lyulin, Alexey V./ Novel polyelectrolyte membranes for fuel and flow batteries : insights from simulations. 9th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology. American Institute of Physics, 2018. (AIP Conference Proceedings; 1).
@inproceedings{d29925cdb47f436790f2f08f6522812f,
title = "Novel polyelectrolyte membranes for fuel and flow batteries: insights from simulations",
abstract = "Recent experiments on polyelectrolyte membranes have clearly shown that at operating temperatures perfluoroimide acid (PFIA) has a higher electrical conductivity than widely used Nafion. In the present paper classical molecular-dynamics simulations were carried out to study the structural properties of both materials, and the proton and water transport in the corresponding membranes at T=300 K and T=353 K. In this temperature range, the temperature effects on the hydrated internal polyelectrolyte structure were found to be negligible. The PFIA has longer side chains across a wide range of hydration levels which would have promoted more trapping of water and hydronium ions in PFIA. Indeed, the average number of water molecules in the first hydration shell around the side-chain protogenic groups was found to be higher in PFIA than in Nafion. Our simulations showed the formation of large continuous water clusters and connected pore volumes in PFIA at high hydration levels which promotes conductivity. The diffusivity constants for hydronium ions and water increase with increasing hydration and increasing temperature. Unlike the experimental conductivities, the simulated data for PFIA were comparable to those of Nafion at high hydration levels. Note that the experimentally measured conductivity in PFIA is both due to vehicular transport of ions, which can be resolved using classical molecular dynamics, and structural Grotthuss diffusion, which cannot be resolved in our simulations. Interestingly, we observed a higher total number of water molecules in the first coordination shell around hydronium in PFIA than in Nafion at higher hydration levels. This should aid in more hydrogen bonding between hydronium and water in PFIA which, in turn, should help in structural diffusion. Finally, we discuss our preliminary results and some peculiarities of the proton transport in Nafion membranes filled with the graphene oxide nanoflakes.",
keywords = "flow battery, hydronium diffusion, molecular dynamics, nanocomposite, polyelectrolyte membrane",
author = "Soumyadipta Sengupta and Giorgos Kritikos and Konstantinos Karatasos and Arun Venkatnathan and Rakesh Pant and Pavel Komarov and Lyulin, {Alexey V.}",
year = "2018",
month = "7",
day = "11",
doi = "10.1063/1.5045866",
language = "English",
series = "AIP Conference Proceedings",
publisher = "American Institute of Physics",
number = "1",
booktitle = "9th International Conference on Times of Polymers and Composites",
address = "United States",

}

Sengupta, S, Kritikos, G, Karatasos, K, Venkatnathan, A, Pant, R, Komarov, P & Lyulin, AV 2018, Novel polyelectrolyte membranes for fuel and flow batteries: insights from simulations. in 9th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology., 020004, AIP Conference Proceedings, no. 1, vol. 1981, American Institute of Physics, 9th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology, Ischia, Naples, Italy, 17/06/18. DOI: 10.1063/1.5045866

Novel polyelectrolyte membranes for fuel and flow batteries : insights from simulations. / Sengupta, Soumyadipta; Kritikos, Giorgos; Karatasos, Konstantinos; Venkatnathan, Arun; Pant, Rakesh; Komarov, Pavel; Lyulin, Alexey V.

9th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology. American Institute of Physics, 2018. 020004 (AIP Conference Proceedings; Vol. 1981, No. 1).

Research output: Chapter in Book/Report/Conference proceedingConference contributionAcademicpeer-review

TY - GEN

T1 - Novel polyelectrolyte membranes for fuel and flow batteries

T2 - insights from simulations

AU - Sengupta,Soumyadipta

AU - Kritikos,Giorgos

AU - Karatasos,Konstantinos

AU - Venkatnathan,Arun

AU - Pant,Rakesh

AU - Komarov,Pavel

AU - Lyulin,Alexey V.

PY - 2018/7/11

Y1 - 2018/7/11

N2 - Recent experiments on polyelectrolyte membranes have clearly shown that at operating temperatures perfluoroimide acid (PFIA) has a higher electrical conductivity than widely used Nafion. In the present paper classical molecular-dynamics simulations were carried out to study the structural properties of both materials, and the proton and water transport in the corresponding membranes at T=300 K and T=353 K. In this temperature range, the temperature effects on the hydrated internal polyelectrolyte structure were found to be negligible. The PFIA has longer side chains across a wide range of hydration levels which would have promoted more trapping of water and hydronium ions in PFIA. Indeed, the average number of water molecules in the first hydration shell around the side-chain protogenic groups was found to be higher in PFIA than in Nafion. Our simulations showed the formation of large continuous water clusters and connected pore volumes in PFIA at high hydration levels which promotes conductivity. The diffusivity constants for hydronium ions and water increase with increasing hydration and increasing temperature. Unlike the experimental conductivities, the simulated data for PFIA were comparable to those of Nafion at high hydration levels. Note that the experimentally measured conductivity in PFIA is both due to vehicular transport of ions, which can be resolved using classical molecular dynamics, and structural Grotthuss diffusion, which cannot be resolved in our simulations. Interestingly, we observed a higher total number of water molecules in the first coordination shell around hydronium in PFIA than in Nafion at higher hydration levels. This should aid in more hydrogen bonding between hydronium and water in PFIA which, in turn, should help in structural diffusion. Finally, we discuss our preliminary results and some peculiarities of the proton transport in Nafion membranes filled with the graphene oxide nanoflakes.

AB - Recent experiments on polyelectrolyte membranes have clearly shown that at operating temperatures perfluoroimide acid (PFIA) has a higher electrical conductivity than widely used Nafion. In the present paper classical molecular-dynamics simulations were carried out to study the structural properties of both materials, and the proton and water transport in the corresponding membranes at T=300 K and T=353 K. In this temperature range, the temperature effects on the hydrated internal polyelectrolyte structure were found to be negligible. The PFIA has longer side chains across a wide range of hydration levels which would have promoted more trapping of water and hydronium ions in PFIA. Indeed, the average number of water molecules in the first hydration shell around the side-chain protogenic groups was found to be higher in PFIA than in Nafion. Our simulations showed the formation of large continuous water clusters and connected pore volumes in PFIA at high hydration levels which promotes conductivity. The diffusivity constants for hydronium ions and water increase with increasing hydration and increasing temperature. Unlike the experimental conductivities, the simulated data for PFIA were comparable to those of Nafion at high hydration levels. Note that the experimentally measured conductivity in PFIA is both due to vehicular transport of ions, which can be resolved using classical molecular dynamics, and structural Grotthuss diffusion, which cannot be resolved in our simulations. Interestingly, we observed a higher total number of water molecules in the first coordination shell around hydronium in PFIA than in Nafion at higher hydration levels. This should aid in more hydrogen bonding between hydronium and water in PFIA which, in turn, should help in structural diffusion. Finally, we discuss our preliminary results and some peculiarities of the proton transport in Nafion membranes filled with the graphene oxide nanoflakes.

KW - flow battery

KW - hydronium diffusion

KW - molecular dynamics

KW - nanocomposite

KW - polyelectrolyte membrane

UR - http://www.scopus.com/inward/record.url?scp=85049942505&partnerID=8YFLogxK

U2 - 10.1063/1.5045866

DO - 10.1063/1.5045866

M3 - Conference contribution

T3 - AIP Conference Proceedings

BT - 9th International Conference on Times of Polymers and Composites

PB - American Institute of Physics

ER -

Sengupta S, Kritikos G, Karatasos K, Venkatnathan A, Pant R, Komarov P et al. Novel polyelectrolyte membranes for fuel and flow batteries: insights from simulations. In 9th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology. American Institute of Physics. 2018. 020004. (AIP Conference Proceedings; 1). Available from, DOI: 10.1063/1.5045866