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Proton conducting membranes based on photopolymerizable monomers

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2011
786.pdf (259.5Kb)
Authors
Kellner, Michael
Radovanovic, Philip
Liska, Robert
Matović, Jovan
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Abstract
The proton exchange barrier or Proton Exchange Membrane (PEM) is the critical part of a fuel cell. The basic function of the membrane is to enable proton transport, while being simultaneously impermeable for electrons and gas. Typically, membranes for the PEM fuel cells (PEMFC) are made of perfluorocarbon-sulfonic acid monomers. The best known material of this class is Nafion which has a unique interpenetrating structure of hydrophobic perfluorocarbon regions providing thermal and chemical resistance, mechanical strength and diffusional resistance combined with hydrophilic regions of water clusters surrounding charged sulfonic acid groups which allow selective proton transport. For these reasons, Nafion is still considered the benchmark against which most of the new materials are compared [1]. At the molecular level, proton transport may follow two principal mechanisms: (a) diffusion mechanism via H3O+ ion as a carrier and (b) proton hopping mechanism (Grotthuss transport) [2]. Contemp...orary PEMFCs are exclusively based on the vehicle mechanism. PEMFCs produce water as a by-product and H+ ions moving from the anode to the cathode pull water molecules by an electro-osmotic drag force. In addition, membrane suffers from evaporation of water at working temperatures of 60-90ºC. Nafion effectively conducts protons only when imbibed by water within a narrow range, which limits the operating temperature of PEM fuel cells to around 80oC. However an operating temperature above 100ºC is a highly desirable goal. PEM membranes are not dimensionally stable since the material significantly swells upon water absorption. Therefore the aim of our proton conducting membrane is a rigid polymer with perpendicular nano channels which are filled with a conducting sulfonic polymer where conductivity is mainly achieved by the Grotthuss mechanism. Several monomers and crosslinker in a broad range of concentrations in water and 1-Methyl-2-pyrrolidone (NMP) respectively were screened for their mechanical properties, water uptake and conductivity in porous membranes by photo polymerization with a polar photo initiator. As conductive polymer, primarily poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS) and poly(2-sulfoethyl methacrylate) (PSEM) respectively as well as polymers of phosphonic acid containing monomers or newly synthesized monomers were used. The conductive monomers were crosslinked with varying hydrophobic and hydrophilic multifunctional monomers like N,N'-methylene bisacrylamide (MBA), 2-Propenoic acid, 2-methyl-, 1,1'-(1,10-decanediyl) ester (D3MA) or polyethyleneglycol diacrylates with two varying chainlengths (PEG-DA700, PEG-DA330). The advantage of several different building blocks with known characteristics is the possibility to tune the polymer to special needs of an application. For example, some polymer compositions have good conductivity at lower temperatures whereas other polymers develop better properties at elevated temperatures. The research leading to these results has received funding from the European Community's FP7- NMP Programme, under the Project Acronym MultiPlat and with Grant Agreement: N 228943 and the Austrian Federal Ministry of Science and Research. We thank 3M for providing us with samples of the PP membrane. 1/Hamrock, S.J. and M.A. Yandrasits, Proton Exchange Membranes for Fuel Cell Applications. 2006. 46(3): p. 219 - 244. 2/ Hoogers, G., Membranes and Ionomers, in Fuel Cell Technology Handbook G. Hoogers, Editor. 2002, CRC Press. p.

Keywords:
proton exchange barriers / proton exchange membranes / fuel cells / photopolymerizable monomers
Source:
ICOM 2011: Book of abstracts, 2011
Funding / projects:
  • MULTIPLAT - Biomimetic Ultrathin Structures as a Multipurpose Platform for Nanotechnology-Based Products (EU-228943)
[ Google Scholar ]
Handle
https://hdl.handle.net/21.15107/rcub_dais_789
URI
https://dais.sanu.ac.rs/123456789/789
Collections
  • Радови истраживача пре доласка у ИТН САНУ / Researchers' papers before joining ITS SASA
Institution/Community
Институт техничких наука САНУ / Institute of Technical Sciences of SASA
TY  - CONF
AU  - Kellner, Michael
AU  - Radovanovic, Philip
AU  - Liska, Robert
AU  - Matović, Jovan
PY  - 2011
UR  - https://dais.sanu.ac.rs/123456789/789
AB  - The proton exchange barrier or Proton Exchange Membrane (PEM) is the critical part of a fuel cell. The basic function of the membrane is to enable proton transport, while being simultaneously impermeable for electrons and gas. Typically, membranes for the PEM fuel cells (PEMFC) are made of perfluorocarbon-sulfonic acid monomers. The best known material of this class is Nafion which has a unique interpenetrating structure of hydrophobic perfluorocarbon regions providing thermal and chemical resistance, mechanical strength and diffusional resistance combined with hydrophilic regions of water clusters surrounding charged sulfonic acid groups which allow selective proton transport. For these reasons, Nafion is still considered the benchmark against which most of the new materials are compared [1]. At the molecular level, proton transport may follow two principal mechanisms: (a) diffusion mechanism via H3O+ ion as a carrier and (b) proton hopping mechanism (Grotthuss transport) [2]. Contemporary PEMFCs are exclusively based on the vehicle mechanism.
PEMFCs produce water as a by-product and H+ ions moving from the anode to the cathode pull water molecules by an electro-osmotic drag force. In addition, membrane suffers from evaporation of water at working temperatures of 60-90ºC. Nafion effectively conducts protons only when imbibed by water within a narrow range, which limits the operating temperature of PEM fuel cells to around 80oC. However an operating temperature above 100ºC is a highly desirable goal. PEM membranes are not dimensionally stable since the material significantly swells upon water absorption. Therefore the aim of our proton conducting membrane is a rigid polymer with perpendicular nano channels which are filled with a conducting sulfonic polymer where conductivity is mainly achieved by the Grotthuss mechanism. 
Several monomers and crosslinker in a broad range of concentrations in water and 1-Methyl-2-pyrrolidone (NMP) respectively were screened for their mechanical properties, water uptake and conductivity in porous membranes by photo polymerization with a polar photo initiator. As conductive polymer, primarily poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS) and poly(2-sulfoethyl methacrylate) (PSEM) respectively as well as polymers of phosphonic acid containing monomers or newly synthesized monomers were used. The conductive monomers were crosslinked with varying hydrophobic and hydrophilic multifunctional monomers like N,N'-methylene bisacrylamide (MBA), 2-Propenoic acid, 2-methyl-, 1,1'-(1,10-decanediyl) ester (D3MA) or polyethyleneglycol diacrylates with two varying chainlengths (PEG-DA700, PEG-DA330).
The advantage of several different building blocks with known characteristics is the possibility to tune the polymer to special needs of an application. For example, some polymer compositions have good conductivity at lower temperatures whereas other polymers develop better properties at elevated temperatures.
The research leading to these results has received funding from the European Community's FP7- NMP Programme, under the Project Acronym MultiPlat and with Grant Agreement: N 228943 and the Austrian Federal Ministry of Science and Research. We thank 3M for providing us with samples of the PP membrane. 

1/Hamrock, S.J. and M.A. Yandrasits, Proton Exchange Membranes for Fuel Cell Applications. 2006. 46(3): p. 219 - 244.
2/ Hoogers, G., Membranes and Ionomers, in Fuel Cell Technology Handbook G. Hoogers, Editor. 2002, CRC Press. p.
C3  - ICOM 2011: Book of abstracts
T1  - Proton conducting membranes based on photopolymerizable monomers
UR  - https://hdl.handle.net/21.15107/rcub_dais_789
ER  - 
@conference{
author = "Kellner, Michael and Radovanovic, Philip and Liska, Robert and Matović, Jovan",
year = "2011",
abstract = "The proton exchange barrier or Proton Exchange Membrane (PEM) is the critical part of a fuel cell. The basic function of the membrane is to enable proton transport, while being simultaneously impermeable for electrons and gas. Typically, membranes for the PEM fuel cells (PEMFC) are made of perfluorocarbon-sulfonic acid monomers. The best known material of this class is Nafion which has a unique interpenetrating structure of hydrophobic perfluorocarbon regions providing thermal and chemical resistance, mechanical strength and diffusional resistance combined with hydrophilic regions of water clusters surrounding charged sulfonic acid groups which allow selective proton transport. For these reasons, Nafion is still considered the benchmark against which most of the new materials are compared [1]. At the molecular level, proton transport may follow two principal mechanisms: (a) diffusion mechanism via H3O+ ion as a carrier and (b) proton hopping mechanism (Grotthuss transport) [2]. Contemporary PEMFCs are exclusively based on the vehicle mechanism.
PEMFCs produce water as a by-product and H+ ions moving from the anode to the cathode pull water molecules by an electro-osmotic drag force. In addition, membrane suffers from evaporation of water at working temperatures of 60-90ºC. Nafion effectively conducts protons only when imbibed by water within a narrow range, which limits the operating temperature of PEM fuel cells to around 80oC. However an operating temperature above 100ºC is a highly desirable goal. PEM membranes are not dimensionally stable since the material significantly swells upon water absorption. Therefore the aim of our proton conducting membrane is a rigid polymer with perpendicular nano channels which are filled with a conducting sulfonic polymer where conductivity is mainly achieved by the Grotthuss mechanism. 
Several monomers and crosslinker in a broad range of concentrations in water and 1-Methyl-2-pyrrolidone (NMP) respectively were screened for their mechanical properties, water uptake and conductivity in porous membranes by photo polymerization with a polar photo initiator. As conductive polymer, primarily poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS) and poly(2-sulfoethyl methacrylate) (PSEM) respectively as well as polymers of phosphonic acid containing monomers or newly synthesized monomers were used. The conductive monomers were crosslinked with varying hydrophobic and hydrophilic multifunctional monomers like N,N'-methylene bisacrylamide (MBA), 2-Propenoic acid, 2-methyl-, 1,1'-(1,10-decanediyl) ester (D3MA) or polyethyleneglycol diacrylates with two varying chainlengths (PEG-DA700, PEG-DA330).
The advantage of several different building blocks with known characteristics is the possibility to tune the polymer to special needs of an application. For example, some polymer compositions have good conductivity at lower temperatures whereas other polymers develop better properties at elevated temperatures.
The research leading to these results has received funding from the European Community's FP7- NMP Programme, under the Project Acronym MultiPlat and with Grant Agreement: N 228943 and the Austrian Federal Ministry of Science and Research. We thank 3M for providing us with samples of the PP membrane. 

1/Hamrock, S.J. and M.A. Yandrasits, Proton Exchange Membranes for Fuel Cell Applications. 2006. 46(3): p. 219 - 244.
2/ Hoogers, G., Membranes and Ionomers, in Fuel Cell Technology Handbook G. Hoogers, Editor. 2002, CRC Press. p.",
journal = "ICOM 2011: Book of abstracts",
title = "Proton conducting membranes based on photopolymerizable monomers",
url = "https://hdl.handle.net/21.15107/rcub_dais_789"
}
Kellner, M., Radovanovic, P., Liska, R.,& Matović, J.. (2011). Proton conducting membranes based on photopolymerizable monomers. in ICOM 2011: Book of abstracts.
https://hdl.handle.net/21.15107/rcub_dais_789
Kellner M, Radovanovic P, Liska R, Matović J. Proton conducting membranes based on photopolymerizable monomers. in ICOM 2011: Book of abstracts. 2011;.
https://hdl.handle.net/21.15107/rcub_dais_789 .
Kellner, Michael, Radovanovic, Philip, Liska, Robert, Matović, Jovan, "Proton conducting membranes based on photopolymerizable monomers" in ICOM 2011: Book of abstracts (2011),
https://hdl.handle.net/21.15107/rcub_dais_789 .

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