Polymer electrolyte membrane from polybenzimidazoles: Influence of tetraamine monomer structure

Sana, Balakondareddy; Jana, Tushar

doi:10.1016/j.polymer.2018.01.029

Cited by 30 publications

(23 citation statements)

References 50 publications

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“…The third weight loss, starting from 500 °C, corresponds to the main chain degradation of the PyOPBI polymers. 37 Overall, the thermal stability clearly shows the dependence on the structure of the polymers. The pendant type structure clearly increases the thermal stability of the PyOPBIs, and the highest stability is shown by Ph(CF 3 )PyOPBI polymer because of the presence of a bulky trifluoro group in the backbone.…”

Section: Synthesis Of Aryl Ether Type Pyopbi Polymers Andmentioning

confidence: 96%

“…In this regard, we have recently attempted to functionalize the backbone with various functionalities and introduce crosslinking in the chains, and we could improve the stability of the PyPBI in concentrated PA quite significantly. 37,38 Herein, we hypothesize that introduction of bulky groups in the PyPBI backbone may result in more open "spongelike" structure that can hold considerable amount of PA and maintain original shape. In order to design "spongelike" microstructure, one has to choose the polymer structure in such a way that the microstructure should provide "free volume" and a rugged framework to maintain the mechanical strength.…”

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Pyridine-Bridged Polybenzimidazole for Use in High-Temperature PEM Fuel Cells

Harilal

Shukla

Ghosh

et al. 2021

ACS Appl. Energy Mater.

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Although pyridine bridged oxypolybenzimidazole (PyOPBI) membranes are considered to be promising hightemperature proton exchange membrane (HT-PEM) materials that have the potential to overcome many obstacles such as solubility, membrane processability, cost, etc., of the mainstream conventional polybenzimidazole (PBI)-based HT-PEM, the weak structural stability of PyOPBI in concentrated phosphoric acid (PA) and poor dimensional and mechanical stability have been the crucial issues restraining the performance. To mitigate these bottlenecks, in this work, we successfully synthesized three types of PyOPBIs with flexible aryl ether backbones and bulky substituents by polycondensation reaction of various aryl diacids and pyridine-bridged tetraamine 2,6-bis(3′,4′-diaminophenyl)-4-phenylpyridine (PyTAB) in Eaton's reagent followed by casting as HT-PEMs. Three designed bulky substitute containing PyOPBI membranes showed considerably high PA loading capacity (16−22 mol of PA/repeat unit) and proton conductivity (0.04−0.078 S/cm) at 180 °C as compared to earlier reported unsubstituted PyOPBI membranes (14 mol of PA/repeat unit and 0.007 S/cm at 180 °C). In addition, the obtained membranes showcased good chemical, mechanical, thermal, and long-term conductivity stabilities and outstanding stability in concentrated PA. The pendent groups and the bulkiness of the backbone are believed to be the cause behind better stability and facilitating proton transport that results in higher proton conductivity. The single cell made from the membrane electrode assembly of these bulky substituted PyOPBI membranes displayed a peak power density in the range of 144−240 mW cm −2 under H 2 /O 2 at 160 °C, which is considerably higher than that for unsubstituted PyOPBI membrane (90.4 mW cm −2 ). Overall, the current results provide an effective strategy to explore the benefits of structural modulation of PyOPBI using various structurally divergent diacids to enhance HT-PEM properties and suggest a scalable route for the advancement of PBI-based HT-PEM fuel cells.

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Section: Synthesis Of Aryl Ether Type Pyopbi Polymers Andmentioning

confidence: 96%

Section: ■ Introductionmentioning

confidence: 99%

Pyridine-Bridged Polybenzimidazole for Use in High-Temperature PEM Fuel Cells

Harilal

Shukla

Ghosh

et al. 2021

ACS Appl. Energy Mater.

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“…The rigid aromatic structure in polybenzimidazole (PBI) contributes to its good chemical stability, high mechanical strength, and remarkable thermal stability. Owing to these characteristics, polybenzimidazole-based (PBI-based) membranes have been intensively explored for use in fuel cells, water electrolysis, and flow batteries [67][68][69].…”

Section: Polybenzimidazole (Pbi)mentioning

confidence: 99%

Membrane-Based Electrolysis for Hydrogen Production: A Review

et al. 2021

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Hydrogen is a zero-carbon footprint energy source with high energy density that could be the basis of future energy systems. Membrane-based water electrolysis is one means by which to produce high-purity and sustainable hydrogen. It is important that the scientific community focus on developing electrolytic hydrogen systems which match available energy sources. In this review, various types of water splitting technologies, and membrane selection for electrolyzers, are discussed. We highlight the basic principles, recent studies, and achievements in membrane-based electrolysis for hydrogen production. Previously, the NafionTM membrane was the gold standard for PEM electrolyzers, but today, cheaper and more effective membranes are favored. In this paper, CuCl–HCl electrolysis and its operating parameters are summarized. Additionally, a summary is presented of hydrogen production by water splitting, including a discussion of the advantages, disadvantages, and efficiencies of the relevant technologies. Nonetheless, the development of cost-effective and efficient hydrogen production technologies requires a significant amount of study, especially in terms of optimizing the operation parameters affecting the hydrogen output. Therefore, herein we address the challenges, prospects, and future trends in this field of research, and make critical suggestions regarding the implementation of comprehensive membrane-based electrolytic systems.

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“…The solid was dried in vacuum at 80 °C overnight and then recrystallized from an EtOH:H 2 O mixture (3:7 v/v) obtaining fine needlelike crystals, which were washed thoroughly with the cold crystallization mixture and then dried at 80 °C under vacuum for 24 pyrrolidone and 5 mL of dry toluene, and the resulting solution was stirred for 10 min at room temperature under an argon atmosphere. The temperature of the oil bath was slowly raised to 150 °C and left distilling out the water for 4 h before raising the temperature to 190 °C and continuing the reaction for 40 h. The viscous solution was cooled down to room temperature, diluted with 2 mL of dry N-methyl-2-pyrrolidone, and then precipitated in 300 mL of distilled water.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Chemical modification of the commercially available poly [2,2′- m -(phenylene)-5,5′-(bibenzimidazole)] structure was among the first strategies. Modifications of the molecular structure by addition of basic as well as acidic groups were attempted to increase the doping capacity of the membranes., − Another approach studied was the structural stabilization via blending or copolymerization of polybenzimidazoles. − Beneficial effects have been obtained also by the addition of free volume elements such as nanoparticles ,, or by producing porous membranes , which are capable of stabilizing the PA inside the membrane, limiting both swelling and leaking of the acid. One of the most effective and straightforward strategies to improve the mechanical stability of the PBI–PA membranes at high doping level is covalent cross-linking.…”

Section: Introductionmentioning

confidence: 99%

Highly Stable Membranes of Poly(phenylene sulfide benzimidazole) Cross-Linked with Polyhedral Oligomeric Silsesquioxanes for High-Temperature Proton Transport

Viviani

Fluitman

Loos

et al. 2020

ACS Appl. Energy Mater.

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Poly(phenylene sulfide benzimidazole) has been synthesized and tested as a potential material for high-temperature proton transport. A high content of sulfide bonds has been implemented in the polymer chains to endow a high antioxidant capacity and, in combination with bulky benzimidazole pendant units, to significantly suppress crystallinity and thereby improve the solubility in highly polar aprotic solvents. The amorphous polymer has high thermal stability and high glass transition temperature (T g ). Freestanding, insoluble, and robust membranes were obtained via thermal cross-linking of the benzimidazole moieties with octaglycidyl polyhedral oligomeric silsesquioxane (g-POSS). The series of hybrid networks (cPPSBi_X, with X being the g-POSS content wt %) showed excellent oxidative stability, with cPPSBi_15 having weight loss lower than 5% after 264 h in Fenton's reagent at 80 °C. Elastic moduli as high as 868 MPa with reduced strain at break (1.8%) were obtained. After doping the membranes with phosphoric acid, proton conductivity in the range of 2.3 × 10 −2 S cm −1 at 180 °C was obtained, and the membranes show a stress at break of 2.3 MPa. Dimensional and mechanical stability were maintained also at high doping levels thanks to the inclusion of g-POSS which provides the resulting hybrid networks with increased free volume and high cross-link density.

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Polymer electrolyte membrane from polybenzimidazoles: Influence of tetraamine monomer structure

Cited by 30 publications

References 50 publications

Pyridine-Bridged Polybenzimidazole for Use in High-Temperature PEM Fuel Cells

Pyridine-Bridged Polybenzimidazole for Use in High-Temperature PEM Fuel Cells

Membrane-Based Electrolysis for Hydrogen Production: A Review

Highly Stable Membranes of Poly(phenylene sulfide benzimidazole) Cross-Linked with Polyhedral Oligomeric Silsesquioxanes for High-Temperature Proton Transport

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