Effect of phosphonated triazine monomer additive in disulfonated poly (arylene ether sulfone) composite membranes for proton exchange membrane fuel cells

Thompson, Tiffany N; Arnett, Natalie Y.

doi:10.1016/j.polymer.2019.03.021

Cited by 9 publications

(5 citation statements)

References 34 publications

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“…The characteristic peak of the C-H bonds for methyl and methylene groups was absent around 2900 cm −1 . 53 In the 1 H NMR spectrum, only the characteristic peaks of the hydroxyl group on the phosphate group. And the ethyl peak of phosphonic acid ester groups was also not found in the 1 H and 13 C NMR spectrums.…”

Section: Resultsmentioning

confidence: 99%

Enhancing Proton Conductivity and Durability of Crosslinked PBI-Based High-Temperature PEM: Effectively Doping a Novel Cerium Triphosphonic-isocyanurate

Guo

Liu

Sun

et al. 2021

J. Electrochem. Soc.

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Acid doping is an effective way to enhance the proton conduction of high temperature polybenzimidazole (PBI) based proton exchange membranes (HTPEMs). To overcome the problem of acid leaching from the membranes, a cerium triphosphonic-isocyanurate (Ce-TOPT) proton conductor was synthesized and doped into a crosslinked PBI backbone (c-mPBI). The TOPT organic compound contains three –PO3H2 groups, which can be complexed with high valent metal ions (Ce4+/3+, Zr4+, Fe3+) to ensure its water-insolubility. Ce-TOPT(1:2) exhibited high ion exchange capacity (IEC, up to 2.2 meq. g−1) and good thermal stability. The organic-inorganic Ce-TOPT shown a high doping level in c-mPBI/CeTOPT membranes and consequently high proton conductivity of the membranes at high temperature and low relative humidity (RH). At 180 °C, the conductivity of c-mPBI/CeTOPT(50) could reach 0.125, 0.0885 and 0.0363 S cm−1 at 100% RH, 50% RH and anhydrous conditions, respectively. After water-washing for 48 h, the proton conductivity loss of c-mPBI/CeTOPT(50) was 4.6%. The good mechanical properties, proton conductivity, durability and membrane selectivity indicate that the crosslinked PBI-based membrane doped with Ce-TOPT is a potential candidate as HTPEMs.

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Section: Resultsmentioning

confidence: 99%

Enhancing Proton Conductivity and Durability of Crosslinked PBI-Based High-Temperature PEM: Effectively Doping a Novel Cerium Triphosphonic-isocyanurate

Guo

Liu

Sun

et al. 2021

J. Electrochem. Soc.

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“…To minimize the effect by residual solvents or absorbed water, all membranes were preheated at 120 °C 55 . All the membranes exhibit similar degradation curves where the first degradation curves at 250–300 °C are corresponding to the degradation of sulfonic acid groups and the second degradation curves at 450–550 °C are corresponding to the degradation of the polymer main backbone 10,54 . T d5 values where 5 wt% loss occurs were found to be 277.1 and 281.7 °C for cSPAES90‐1 and cSPAES90‐2 membranes, respectively, which are smaller than that of the SPAES70 membrane, 317.0 °C.…”

Section: Resultsmentioning

confidence: 99%

“…Therefore, SHPs with a high degree of sulfonation (DS) should be used for PEM preparation because high DS can help create the well‐formed interconnected hydrophilic channels in the membrane and have a high ion (H + ) carrier concentration, contributing to high proton conductivity. Although the high DS can increase the proton conductivity, it can lead to excessive water absorption with severe membrane swelling that decreases the stability and durability especially for the long‐term operation of PEM 10,11 . Thus, the introduction of cross‐linked structures into SHP membranes with high DS has been considered an effective strategy for enhancing dimensional stability and improving mechanical property, while attaining high proton conductivity 12–14 .…”

Section: Introductionmentioning

confidence: 99%

End‐group cross‐linked membranes based on highly sulfonated poly(arylene ether sulfone) with vinyl functionalized graphene oxide as a cross‐linker and a filler for proton exchange membrane fuel cell application

Kim

Kım

Han

et al. 2020

Journal of Polymer Science

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High-performance end-group cross-linked sulfonated poly(arylene ether sulfone) (SPAES) membranes are developed using thiolate-terminated SPAES with very high degree of sulfonation (DS) such as 90 mol% (SK-SPAES90) and vinyl functionalized graphene oxide (VGO) as a cross-linker and a filler through the thiol-Michael addition reaction. Since free-standing membranes for fuel cell application could not be prepared using the water soluble and highly proton conductive SPAES with high DS of 90 mol%, cross-linked SPAES90 membranes are intentionally prepared. The cross-linked membranes are found to have good physicochemical properties with excellent proton conductivity that can be applied for the proton exchange membrane. In particular, the cross-linked SPAES90 membrane prepared using 1.0 wt% of VGO exhibits better dimensional stability than a SPAES70 membrane from the linear SPAES with DS of 70 mol% and the proton conductivities of this membrane are larger than those of Nafion 211 at 80 C under different relative humidity conditions (40%-95%).

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“…1−5 It is well-known that the dehydration of the polymer material at high temperatures results in a decrease of proton conductivity, limiting its application to operation temperatures <100 °C. 6,7 In contrast to sulfonic acid groups, phosphonic acid units are known for their high thermal and chemical stabilities. 8−11 Phosphonated polymers were used and investigated by several research groups in the past.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Over the past decades, sulfonated polymers have been widely investigated in terms of their ion-transport mechanism. − It is well-known that the dehydration of the polymer material at high temperatures results in a decrease of proton conductivity, limiting its application to operation temperatures <100 °C. , In contrast to sulfonic acid groups, phosphonic acid units are known for their high thermal and chemical stabilities. − Phosphonated polymers were used and investigated by several research groups in the past. ,− Atanasov and Kerres . synthesized a highly phosphonated poly(pentafluorostyrene) (PWN2010) via nucleophilic aromatic substitution Michaelis-Arbuzov reaction.…”

Section: Introductionmentioning

confidence: 99%

Modification of Phosphonated Poly(pentafluorostyrene) toward Ductile Membranes for Electrochemical Applications

Stigler,

Wagner,

Thiele

et al. 2023

Macromolecules

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In terms of proton exchange membranes, phosphonated poly(pentafluorostyrene) (PWN) is an auspicious material. It provides a high ion-exchange capacity, good thermal and chemical stabilities, as well as reduced anhydride formation and high proton dissociation degree due to low pK a. One major drawback preventing the utilization in fuel cells as pure material lies in its poor mechanical stability. Therefore, the need for modifying the polymer structure arises. Herein, we have investigated a rapid and scalable postfunctionalization of poly(pentafluorostyrene) to mechanically modified PWN. Alkyl chains of different lengths ranging from a chain of 6 carbons (-C06) to 18 carbons (-C18) were introduced via para-fluoro-thiol reaction, followed by substitution of the residual para-fluor atoms with phosphonic acid groups via Michaelis-Arbuzov reaction. For the first time, we were able to produce free-standing PWN membranes. Via differential scanning calorimetry measurements, molecular dynamics simulation, and tensile testing, we have proven that the plasticization effect ascends with increasing alkyl chain length. Thereby, the alkyl modification also turned out to be thermally stable (>332 °C), demonstrated with TGA-FTIR measurements. The membrane with 68% phosphonic acid groups and 28% C18 alkyl chains showed a proton conductivity of 93.6 ± 6.9 mS cm–1 and outperformed the Nafion membrane (N-212), which exhibited a proton conductivity of 69.2 ± 6.21 mS cm–1 at 105 °C and a relative humidity of approximately 90%.

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Effect of phosphonated triazine monomer additive in disulfonated poly (arylene ether sulfone) composite membranes for proton exchange membrane fuel cells

Cited by 9 publications

References 34 publications

Enhancing Proton Conductivity and Durability of Crosslinked PBI-Based High-Temperature PEM: Effectively Doping a Novel Cerium Triphosphonic-isocyanurate

Enhancing Proton Conductivity and Durability of Crosslinked PBI-Based High-Temperature PEM: Effectively Doping a Novel Cerium Triphosphonic-isocyanurate

End‐group cross‐linked membranes based on highly sulfonated poly(arylene ether sulfone) with vinyl functionalized graphene oxide as a cross‐linker and a filler for proton exchange membrane fuel cell application

Modification of Phosphonated Poly(pentafluorostyrene) toward Ductile Membranes for Electrochemical Applications

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