Synthesis and characterization of 3,3′‐disulfonated‐4,4′‐dichlorodiphenyl sulfone (SDCDPS) monomer for proton exchange membranes (PEM) in fuel cell applications

Sankır, Mehmet; Bhanu, V. A.; Harrison, William; Ghassemi, Hossein; Wiles, Kenton B.; Glass, Thomas E.; Brink, A. E.; Brink, M.; McGrath, James E.

doi:10.1002/app.22803

Cited by 82 publications

(58 citation statements)

References 14 publications

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“…The shifts of the protons the distribution of the sulfonic acid units in the polymer structure. [14] However, sulfonated statistical copolymers usually show low proton conductivities, especially at low water contents. The main reason for this is the poor connectivity (percolation) of the proton-conducting hydrated phase domain, in combination with a significant retardation of the water diffusion because of strong interactions with the sulfonic acid groups of the membrane.…”

Section: Hydroxy-terminated Paes Oligomersmentioning

confidence: 99%

Multiblock Copolymers with Highly Sulfonated Blocks Containing Di‐ and Tetrasulfonated Arylene Sulfone Segments for Proton Exchange Membrane Fuel Cell Applications

Takamuku¹,

Jannasch²

2011

Advanced Energy Materials

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(arylene ether sulfone)s with different block lengths and ionic contents are tailored for durable and proton-conducting electrolyte membranes. Two series of fully aromatic copolymers are prepared by coupling reactions between non-sulfonated hydrophobic precursor blocks and highly sulfonated hydrophilic precursor blocks containing either fully disulfonated diarylsulfone or fully tetrasulfonated tetraaryldisulfone segments. The sulfonic acid groups are exclusively introduced in ortho positions to the sulfone bridges to impede desulfonation reactions and give the blocks ion exchange capacities (IECs) of 4.1 and 4.6 meq. g −1 , respectively. Solvent cast block copolymer membranes show well-connected hydrophilic nanophase domains for proton transport and high decomposition temperatures above 310 °C under air. Despite higher IEC values, membranes containing tetrasulfonated tetraaryldisulfone segments display a markedly lower water uptake than the corresponding ones with disulfonated diarylsulfone segments when immersed in water at 100 °C, presumably because of the much higher chain stiffness and glass transition temperature of the former segments. The former membranes have proton conductivities in level of a perfluorosulfonic acid membrane (NRE212) under fully humidified conditions. A membrane with an IEC of 1.83 meq. g −1 reaches above 6 mS cm −1 under 30% relative humidity at 80 °C, to be compared with 10 mS cm −1 for NRE212 under the same conditions.solubilization of conductive polymers such as poly(thiophene)s. [4] Still, perhaps the most important application area of these robust polymers is currently as proton exchange membranes for polymer electrolyte fuel cells, which are highly energy efficient and potentially environmentally benign power devices. [5,6] Today, perfluorosulfonic acid polymers such as Nafion are considered as state-of-the-art membranes because of their high chemical stability and high proton conductivity under a wide humidity range at moderate operating temperatures. [7,8] Nevertheless, the Nafion membrane suffers from general disadvantages such as high cost, high fuel permeability and a low mechanical modulus. More seriously, the Nafion membrane has a tendency to dehydrate above 80 °C, leading to lower conductivities. It thus fails to meet the current industrial demands which call for operating temperatures above 100 °C. [9,10] Over the last decade, an extensive research effort has been directed toward developing alternative membranes based on sulfonated hydrocarbon polymers to overcome the drawbacks of Nafion. [11,12] The use of hydrocarbon-based monomers and building blocks has widely expanded the possibilities to vary and control the structure and function of the membranes in relation to fluorocarbon-based approaches. For example, a wide range of sulfonated high-performance aromatic polymers has been prepared and their films have subsequently been evaluated and demonstrated as prospective fuel cell membranes. Among these polymers, sulfonated poly(arylene ether sulfone)s (SPAESs) have been ex...

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Section: Hydroxy-terminated Paes Oligomersmentioning

confidence: 99%

Multiblock Copolymers with Highly Sulfonated Blocks Containing Di‐ and Tetrasulfonated Arylene Sulfone Segments for Proton Exchange Membrane Fuel Cell Applications

Takamuku¹,

Jannasch²

2011

Advanced Energy Materials

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“…The most extensively studied materials are the so-called BPSH-type materials, which are statistical random copolymers based on disulfonated poly(arylene ether sulfone)s [4][5][6]. BPSH-type copolymer systems utilize 3,3 -disulfonated-4,4 -dichlorodiphenylsulfone (SDCDPS) as the key monomer, which can facilitate precise control over the degree of sulfonation, and excellent stability of the sulfonic acid moieties [2,7]. Although PEMs based on BPSH-type materials display improved properties over Nafion ® under fully hydrated conditions with respect to conductivity, durability, and fuel cross-over, their proton conductivities under partially hydrated conditions have remained somewhat disappointing.…”

Section: Introductionmentioning

confidence: 99%

Development of multiblock copolymers with novel hydroquinone-based hydrophilic blocks for proton exchange membrane (PEM) applications

Lee

Lane

McGrath

2010

Journal of Power Sources

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“…The integration and appropriate analyses of the monomers and polymers allowed the composition of the various monomers to be defined using known reference protons. The sulfonation of the monomer was confirmed using 1 H NMR spectrum 40 and is shown in Figure 3. In the 1 H NMR spectra of the SDFDPS, there were three different aromatic protons.…”

Section: Resultsmentioning

confidence: 98%

Preparation and characterization of acid-acid blend membranes for direct methanol fuel cell applications

Park

et al. 2011

Macromol. Res.

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Acid-acid blend membranes were successfully prepared using two types of sulfonated poly(arylene ether sulfone) random copolymers with various ratios (SPAES-BP and SPAES-HPF). The blend membrane properties were investigated using proton nuclear magnetic resonance, thermogravimetric analysis, water uptake, methanol permeability, and proton conductivity measurements. The morphology of the blend membranes varied according to the SPAES-HPF ratio in the blending solution and the nanosized dispersion of the SPAES-HPF in the SPEAS-BP affected the improvement of acid-acid blend membrane properties. Consequentially, the water uptake and dimensional change decreased while the proton conductivity increased in the blend membranes involving a small amount SPAES-HPF compared with that of the SPAES-BP. For the direct methanol fuel cell performance, the power density of SPAES-BP(90)/SPAES-HPF(10) showed an enhancement of 145 mW/cm 2 over that of Nafion 115 (132 mW/cm 2 ).

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Synthesis and characterization of 3,3′‐disulfonated‐4,4′‐dichlorodiphenyl sulfone (SDCDPS) monomer for proton exchange membranes (PEM) in fuel cell applications

Cited by 82 publications

References 14 publications

Multiblock Copolymers with Highly Sulfonated Blocks Containing Di‐ and Tetrasulfonated Arylene Sulfone Segments for Proton Exchange Membrane Fuel Cell Applications

Multiblock Copolymers with Highly Sulfonated Blocks Containing Di‐ and Tetrasulfonated Arylene Sulfone Segments for Proton Exchange Membrane Fuel Cell Applications

Development of multiblock copolymers with novel hydroquinone-based hydrophilic blocks for proton exchange membrane (PEM) applications

Preparation and characterization of acid-acid blend membranes for direct methanol fuel cell applications

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