An effective strategy for the preparation of a wide-temperature-range proton exchange membrane based on polybenzimidazoles and polyacrylamide hydrogels

Yin, Bibo; Wu, Yingnan; Liu, Chunfa; Wang, Peng; Wang, Lei; Sun, Guoxing

doi:10.1039/d0ta08872b

Cited by 64 publications

(40 citation statements)

References 51 publications

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“…PA-doped polybenzimidazole (PBI) membranes are proved to be the most promising candidate for high-temperature PEM fuel cells because of their high PA doping levels, outstanding conductivity, excellent mechanical properties, and superior thermal stability (Figure C) . Numerous modified PA-doped PBI membranes with enhanced performances have also been reported. , The goal was to increase the doping level while ensuring good mechanical properties, to prevent acid leaching and catalyst poisoning, and to eliminate performance degradation, thereby improving long-term stability under severe conditions. Meanwhile, it must be mentioned that in the case of phosphonic acid-functionalized systems some water activity is required to prevent the systems from condensation.…”

Section: Conductivity and Stability Of High-temperature Pemsmentioning

confidence: 99%

Current Challenges and Perspectives of Polymer Electrolyte Membranes

Zhang

et al. 2022

Macromolecules

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Polymer electrolyte membranes are charged polymers in the membrane shape, which can separate the anode reaction from the cathode reaction, allowing the fabrication of compact and highly efficient electrochemical devices. In recent years, great success has been witnessed in the development of advanced polymer electrolyte membranes, driven by the fast development of fuel cells that promise a clean and highly efficient sustainable energy supply. However, drawbacks limiting the widespread adoption of polymer electrolyte membranes still exist. These include the high cost of fluorinated polymer electrolyte membranes, the poor ion transport capability of non-fluorinated aromatic polymer-based polymer electrolyte membranes (especially under low-humidity conditions), the insufficient durability, and the function-led design of advanced polymer electrolyte membranes for applications beyond fuel cells. Herein we briefly discuss several important challenges that should be solved before polymer electrolyte membranes could be extensively adopted in real-world applications. These challenges include how to break through the limitation of phase-separation polymer electrolyte membrane design strategy on further increasing membrane conductivity, how to develop proton exchange membranes for high-temperature and low-humidity working environments, and how to design an alkaline-resistant anion exchange membrane and target its applications beyond hydrogen fuel cells. We also introduce breakthroughs made in these aspects during the past few years and suggest future directions that require extra attention.

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Section: Conductivity and Stability Of High-temperature Pemsmentioning

confidence: 99%

Current Challenges and Perspectives of Polymer Electrolyte Membranes

Zhang

et al. 2022

Macromolecules

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“…The PAM hydrogels are very susceptible to H 2 O 2 attacks. [13] However, the high stability of porous carbon-ZrO 2 promoted the oxidative stabilities of the BHC membranes; they exhibits a weight loss of only 10% after 100 h.…”

Section: Thermal and Chemical Stabilities As Well As The Mechanical Properties Of The Membranesmentioning

confidence: 99%

“…[12] To address the aforementioned issue, our group incorporated polyacrylamide (PAM) hydrogels into poly(4,4′-diphenylether-5,5′-bibenzimidazole) (OPBI), named OPBI-AM, to prepare a wide-temperature-range PEM. [13] The OPBI-AM membrane was self-assembled from OPBI and acrylamide, after which PAM was naturally formed beneath OPBI. The water and PA absorptions of the PAM hydrogels improved the low-and hightemperature conductivities of OPBI-AM, they also accounted for the large swell ratio of PEM, which severely deteriorated the performance and durability of PEMFC.…”

mentioning

confidence: 99%

Construction of Stable Wide‐Temperature‐Range Proton Exchange Membranes by Incorporating a Carbonized Metal–Organic Frame into Polybenzimidazoles and Polyacrylamide Hydrogels

Yin

Liang

et al. 2021

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Fuel cells (FCs) are promising energy devices owing to their high efficiency and minimized pollutant emission. Among the various types of FCs, the proton exchange membrane fuel cell-based ones (PEMFC) are attractive in automobile, portable, and transportation power applications. [1][2][3][4] Presently, high-temperature PEMFCs (HT-PEMFCs) operating at >140 °C are greatly interesting because of their high carbon monoxide tolerance, high electrode kinetics, and simplified water/thermal management systems. [5][6][7] Phosphoric acid-doped polybenzimidazole (PA-PBI) is a promising candidate for high-temperature proton exchange membrane (HT-PEM) owing to its excellent chemical and thermal stabilities, as well as good protonconducting capability, at elevated temperatures and low humidity. [8][9][10] However, the rapid decrease in the proton-conducting capability of PA-PBI at a low temperature (<100 °C) owing to fast loss of phosphoric acid caused by water accumulated in the frequent cold start-ups (condensate water) and oxygen reduction reactions (water produced by the chemical reaction) at the FCs cathode during normal vehicle drive cycles, has limited their application in FC electric vehicles (FCEVs). [11] In the PA-PBI membrane, the interaction energy of PA-water is much stronger than interaction energy between PA-BI and two PAs. The water molecules from the environment penetrate into the PA cluster of PA-PBI until the base polymers cannot hold the water and PA and bring "loosely bound" PA molecules out of the membrane (PA leaching). [12] To address the aforementioned issue, our group incorporated polyacrylamide (PAM) hydrogels into poly(4,4′-diphenylether-5,5′-bibenzimidazole) (OPBI), named OPBI-AM, to prepare a wide-temperature-range PEM. [13] The OPBI-AM membrane was self-assembled from OPBI and acrylamide, after which PAM was naturally formed beneath OPBI. The water and PA absorptions of the PAM hydrogels improved the low-and hightemperature conductivities of OPBI-AM, they also accounted for the large swell ratio of PEM, which severely deteriorated the performance and durability of PEMFC. This cold start-up challenge must be improved. The introduction of branched Proton exchange membrane fuel cells (PEMFCs) are promising devices for clean power generation in fuel cell electric vehicles applications. The further request of high-efficiency and cost competitive technology make high-temperature proton exchange membranes utilizing phosphoric aciddoped polybenzimidazole be favored because they can work well up to 180 °C without extra humidifier. However, they face quick loss of phosphoric acid below 120 °C and resulting in the limits of commercialization. Herein UiO-66 derived carbon (porous carbon-ZrO 2 ), comprising branched poly(4,4′-diphenylether-5,5′-bibenzimidazole) and polyacrylamide hydrogels self-assembly (BHC1-4) membranes for wide-temperature-range operation (80-160 °C) is presented. These two-phase membranes contained the hygroscopicity of polyacrylamide hydrogels improve the low-temperature proton conductiv...

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“…5a) containing the bipyridine units and basic sites of BIs to absorb PA; as a result, proton conductivity improves. Other acid-absorbing media in a PBI membrane matrix, such as threedimensional network polyacrylamide hydrogels, can occupy additional PA to retain the amount of water to transfer protons in both high-and low-temperature ranges [169]. A high proton conductivity ranging from 0.0159 to 0.104 S cm −1 is achieved in the temperature range of 40 to 180°C, and it remains stable for 120 h. The maximum peak power densities of 200 and 560 mW cm −2 are obtained at 80 and 160°C under anhydrous conditions, respectively.…”

Section: Pa-doped Composite Membranesmentioning

confidence: 99%

Structural architectures of polymer proton exchange membranes suitable for high-temperature fuel cell applications

2021

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High-temperature proton exchange membrane (HT-PEM) fuel cells offer more advantages than low-temperature PEM fuel cells. The ideal characteristics of HT-PEMs are high conductivities, low-humidity operation conditions, adequate mechanical properties, and competitive costs. Various molecular moieties, such as benzimidazole, benzothiazole, imide, and ether ether ketone, have been introduced to polymer chain backbones to satisfy the application requirements for HT-PEMs. The most common sulfonated polymers based on the main chain backbones have been employed to improve the rties. Side group/chain engineering, includ crosslinking, has been widely applied to HT-PEMs to further improve their proton conductivity, thermal stability, and mechanical properties. Currently, phosphoric acid-doped polybenzimidazole is the most successful polymer material for application in HT-PEMs. The compositing/blending modification methods of polymers are effective in obtaining high PA-doping levels and superior mechanical properties. In this review, the current progress of various membrane materials used for HT-PEMs is summarized. The synthesis and performance characteristics of polymers containing specific moieties in the chain backbones applied to HT-PEMs are discussed systemically. Various modification approaches and their deficiencies associated with HT-PEMs are analyzed and clarified. Prospects and future challenges are also presented.

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An effective strategy for the preparation of a wide-temperature-range proton exchange membrane based on polybenzimidazoles and polyacrylamide hydrogels

Abstract: OPBI-0.8AM membrane can operate from 80–160 °C which break through the limits of existing HT-PEMFCs materials.

Cited by 64 publications

References 51 publications

Current Challenges and Perspectives of Polymer Electrolyte Membranes

Current Challenges and Perspectives of Polymer Electrolyte Membranes

Construction of Stable Wide‐Temperature‐Range Proton Exchange Membranes by Incorporating a Carbonized Metal–Organic Frame into Polybenzimidazoles and Polyacrylamide Hydrogels

Structural architectures of polymer proton exchange membranes suitable for high-temperature fuel cell applications

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