Polymer-Grafted Graphene Oxide/Polybenzimidazole Nanocomposites for Efficient Proton-Conducting Membranes

Das, Anupam; Mukherjee, Nilanjan; Jana, Tushar

doi:10.1021/acsanm.3c00834

Cited by 21 publications

(41 citation statements)

References 62 publications

(88 reference statements)

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“…The glass transition temperatures ( T g ) of the samples are obtained from the loss modulus ( E ″) and tan δ plots (Figure S12) and the corresponding values are summarized in Table S3 of the Supporting Information. Due to the formation of miscible blend membranes, loss modulus ( E ″) and tan δ plot exhibit only a single relaxation peak for m -PBI-P@MCOF composite MMMs, and the temperature associated with that peak is considered as the glass transition temperature ( T g ). − The T g value of m -PBI is 320 °C (loss modulus plot) and 340 °C (tan δ plot), respectively. The incorporation of P@MCOF fillers results slight decrement in the T g values, and with the increase in the P@MCOF loading gradual decrement in T g value is observed (Table S3) which might be due to the polymer-COF interactions present in the composite membrane matrix.…”

Section: Resultsmentioning

confidence: 99%

Nanoporous Covalent Organic Framework and Polybenzimidazole Composites for Proton Exchange Membranes

Das

Hazarika

Sana

et al. 2023

ACS Appl. Nano Mater.

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Fabrication and design of proton conduction nanochannels within the solid electrolyte materials is pivotal and challenging in order to develop an efficient proton exchange membrane (PEM) for the use in fuel cells. To address this, we have synthesized a melamine-based Schiff base network type porous covalent organic framework (MCOF) and impregnated phosphoric acid (H3PO4) as the electrolyte into the pores of the MCOF via the vacuum-assisted method. Unfortunately, a stable membrane did not form from H3PO4-loaded MCOF (P@MCOF), and hence, in order to make a strong membrane, mixed matrix membranes (MMMs) were fabricated using P@MCOF as nanofillers and [2,2′-(m-phenylene)-5,5′-benzimidazole] or m-PBI as the membrane forming polymer matrix. Formation of acid base pair occurred in the m-PBI-P@MCOF nanocomposite membrane owing to H-bonding interactions between the filler and polymer. Also, the acidic functionalities in the pores of P@MCOF provides abundant sites for labile proton transport, which enables uninterrupted proton conduction ion channels with low energy barrier in the nanocomposite membranes. Furthermore, all the composite membranes were immersed and loaded with phosphoric acid (PA) to increase electrolyte contents in the resulting MMM-based PEM. Superior proton conductivity, excellent thermal, thermo-mechanical and tensile strength, improved acid (PA) holding efficiency, and improved chemical stability of these PEMs, obtained from MMMs of m-PBI-P@MCOF, were observed in comparison with the PEM of pristine m-PBI. The proton conductivity of m-PBI-P@MCOF-10% membrane at 180 °C is 0.309 S cm–1, a five-fold increment with respect to pristine m-PBI proton conductivity (0.061 S cm–1) under the identical experimental condition. This work clearly illustrates the nature of H-bonded interactions between the nanofillers and polymers which efficiently enhanced proton conduction along with chemical and mechanical durability in the MMM materials.

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Section: Resultsmentioning

confidence: 99%

Nanoporous Covalent Organic Framework and Polybenzimidazole Composites for Proton Exchange Membranes

Das

Hazarika

Sana

et al. 2023

ACS Appl. Nano Mater.

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“…The composite membranes comprising polymer/GO have gained much attention in recent years due to their high surface areas comprised of hydrophilic functionalities which help in the proton transport . However, the agglomeration of GO in the composite resulting from the incompatibility between the surface functionalities present on GO and the polymer can affect the membrane properties .…”

Section: Nonfluorinated Arylene Polymer Membranesmentioning

confidence: 99%

“…Functionalization of GO with a surface grafted polymer chain is an effective method to enhance the properties of the GO/polymer composite membrane. Das et al used this strategy to modify the surface of GO by growing polymer chains on its surface and prepared polymer- g -GO/OPBI based nanocomposite membranes by varying the loading of the nanofiller into the polymer . The prepared nanocomposite membranes showed enhancements in properties such as proton conductivity, tensile strength, and thermal stability.…”

Section: Nonfluorinated Arylene Polymer Membranesmentioning

confidence: 99%

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A Critical Review of Electrolytes for Advanced Low- and High-Temperature Polymer Electrolyte Membrane Fuel Cells

Javed

González

Thangadurai

2023

ACS Appl. Mater. Interfaces

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In the 21st century, proton exchange membrane fuel cells (PEMFCs) represent a promising source of power generation due to their high efficiency compared with coal combustion engines and eco-friendly design. Proton exchange membranes (PEMs), being the critical component of PEMFCs, determine their overall performance. Perfluorosulfonic acid (PFSA) based Nafion and nonfluorinated-based polybenzimidazole (PBI) membranes are commonly used for low-and high-temperature PEMFCs, respectively. However, these membranes have some drawbacks such as high cost, fuel crossover, and reduction in proton conductivity at high temperatures for commercialization. Here, we report the requirements of functional properties of PEMs for PEMFCs, the proton conduction mechanism, and the challenges which hinder their commercial adaptation. Recent research efforts have been focused on the modifications of PEMs by composite materials to overcome their drawbacks such as stability and proton conductivity. We discuss some current developments in membranes for PEMFCs with special emphasis on hybrid membranes based on Nafion, PBI, and other nonfluorinated proton conducting membranes prepared through the incorporation of different inorganic, organic, and hybrid fillers.

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“…Syntheses of graphene oxide (GO), amine-modified GO (GO-EDA), and [3-benzylsulfanylthiocarbonylsufanyl-propionic acid] or BSPA RAFT agent, and the activation of the BSPA RAFT agent and its covalent attachment to the GO surface in order to synthesize GO-BSPA, are reported in detail in our earlier work. 39 We utilized identical batches of GO and RAFT-functionalized GO [GO−BSPA] for the development of PIL-g-GO materials in our current work. The synthesis of 3-butyl-1-vinylimidazolium iodide [VImBu][I] and 1butyl-2-methyl-1-(4-vinylbenzyl)imidazolium iodide [VBImBu][I] was performed following the literature−reported procedure, and characterization data are given in the Supporting Information (Figures S1 and S2).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Multicationic Anion-Exchange Membranes from Pyridine-Bridged Polybenzimidazole and Polymer-Ionic-Liquid-Grafted Graphene Oxide

Das,

Mukherjee,

Saraswat

et al. 2023

ACS Appl. Energy Mater.

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In this study, we functionalized the surface of graphene oxide (GO) nanosheets by grafting polymer ionic liquid (PIL) chains of varying structures and then utilized PIL-g-GO materials as nanofillers with poly-(butylated pyridinium benzimidazolium)iodide (PyPBI-BuI-OBA) in order to prepare hydroxide-ion-conducting mixed-matrix alkaline anion-exchange membranes with multiple ion-exchange sites. Three different ionic-liquidbased monomers, namely, [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MATMA), 3-butyl-1-vinylimidazolium iodide [VImBu][I], and 1butyl-2-methyl-1-(4-vinylbenzyl)imidazolium iodide [VBImBu][I], were polymerized on the activated GO surface via a surface-initiated reversible addition− fragmentation chain-transfer process to obtain three different types of PILgrafted GOs, namely, pMATMA-g-GO (GOPIL1), pVImBu-g-GO (GOPIL2), and pVBImBu-g-GO (GOPIL3). Exfoliation of GO sheets upon grafting of PIL was observed and verified by electron microscopic studies. The grafted PIL chains were found to have a narrow polydispersity index (Đ) and precise control over the molecular weight, confirming polymerization occuring through SI-RAFT technique. The amount of polymer grafted on the GO surface was determined by TGA analysis, and a strong dependence on the polymer structure was found. The mixed-matrix membranes (MMMs) were prepared by solution blending of PyPBI-BuI-OBA with varying loadings of GOPIL materials, and then MMMs were immersed in KOH to prepare alkaline anion-exchange membranes (AAEMs) consisting of imidazolium and pyridinium quaternary ammonium ion-exchange sites. Among all AAEMs, those with 2 wt % GOPIL2 and GOPIL3 exhibited superior hydroxide ion conductivities of 137 and 127 mS/cm, respectively, at 80 °C. The structural, chemical, thermal, mechanical, and conductive properties of the membranes remained unaltered after alkaline treatment at elevated temperatures. These AAEMs exhibited ∼90 and ∼80% retention of ion-exchange capacity (IEC) and ∼90 and ∼70% retention of OH − conductivity after alkaline treatment in 1 M KOH, at 60 °C for 500 h and in 5 M KOH, at 60 °C for 375 h, respectively. To the best of our knowledge, this will be the first report on the utilization of surface PIL-grafted GO nanosheets in AAEMs.

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Polymer-Grafted Graphene Oxide/Polybenzimidazole Nanocomposites for Efficient Proton-Conducting Membranes

Cited by 21 publications

References 62 publications

Nanoporous Covalent Organic Framework and Polybenzimidazole Composites for Proton Exchange Membranes

Nanoporous Covalent Organic Framework and Polybenzimidazole Composites for Proton Exchange Membranes

A Critical Review of Electrolytes for Advanced Low- and High-Temperature Polymer Electrolyte Membrane Fuel Cells

Multicationic Anion-Exchange Membranes from Pyridine-Bridged Polybenzimidazole and Polymer-Ionic-Liquid-Grafted Graphene Oxide

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