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

Onderzoeksoutput: Hoofdstuk in Boek/Rapport/CongresprocedureConferentiebijdrageAcademicpeer review

Uittreksel

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.

TaalEngels
Titel9th International Conference on Times of Polymers and Composites
SubtitelFrom Aerospace to Nanotechnology
UitgeverijAmerican Institute of Physics
ISBN van elektronische versie9780735416970
DOI's
StatusGepubliceerd - 11 jul 2018
Evenement9th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology - Ischia, Naples, Italië
Duur: 17 jun 201821 jun 2018

Congres

Congres9th International Conference on Times of Polymers and Composites: From Aerospace to Nanotechnology
LandItalië
StadIschia, Naples
Periode17/06/1821/06/18

Vingerafdruk

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

Trefwoorden

    Citeer dit

    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] 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.
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    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.",
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    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, American Institute of Physics, Ischia, Naples, Italië, 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.

    Onderzoeksoutput: Hoofdstuk in Boek/Rapport/CongresprocedureConferentiebijdrageAcademicpeer review

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    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

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    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.

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    KW - hydronium diffusion

    KW - molecular dynamics

    KW - nanocomposite

    KW - polyelectrolyte membrane

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    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. Beschikbaar vanaf, DOI: 10.1063/1.5045866