Proton‐conducting blend membranes of crosslinked poly(vinyl alcohol)–sulfosuccinic acid ester and poly(1‐vinyl‐1,2,4‐triazole) for high temperature fuel cells

New type of composite membranes were synthesized by crosslinking of poly(vinyl alcohol) (PVA) with sulfosuccinic acid (SSA) and intercalating poly(1‐vinyl‐1,2,4‐triazole) (PVTri) into the resulting matrix. The complexed structure of the membranes was confirmed by Fourier transform infrared (FTIR) spectroscopy. The resulting hybrid membranes were transparent, flexible, and showed good thermal stability up to ～200°C. The proton conductivities of the membranes were investigated as a function of PVTri and SSA and operating temperature. The water/methanol uptake was measured and the results showed that solvent absorption of the materials increased with increasing PVTri content in the matrix. The proton conductivity of the membranes continuously increased with increasing SO₃H content, PVTri content, and the temperature. In the anhydrous state, the maximum proton conductivity is 7.7 × 10^?5 S/cm for PVA–SSA–PVTri‐1 and for PVA–SSA–PVTri‐3 is 1.6 × 10^?5 S/cm at 150°C. After humidification (RH = 100%), PVA–SSA–PVTri‐4 showed a maximum proton conductivity of 0.0028 S/cm at 60°C. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Novel composite polymer electrolyte membranes based on poly(vinyl phosphonic acid) and poly (5‐(methacrylamido)tetrazole)

Heterocyclic molecules are generally used in the proton conducting membranes as dopant or polymer side group due to their high proton transfer ability. Composite proton conducting membranes based on poly(vinylphosphonic acid) (PVPA) and poly(5‐(methacrylamido)tetrazole) (PMTet) were produced. The homopolymers, prepared from their corresponding monomers, were blended at several mol ratios to obtain the polymer electrolyte membranes. All samples were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), differantial scanning calorimetry (DSC), cyclic voltammetry (CV), and impedance analysis. Besides, the morphology of the membranes was studied by X‐ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). FTIR spectra confirmed the formation of hydrogen bonding network between PVPA and PMTet units. TGA showed that the polymer electrolyte membranes were thermally stable up to ～210°C. CV curves demonstrated the oxidative stability of the samples in 3 V region. In anhydrous conditions, the maximum proton conductivity was determined as 0.06 Scm^?1 at 150°C for PMTetP(VPA)₄. POLYM. ENG. SCI., 55:260–269, 2015. © 2014 Society of Plastics Engineers     

Novel membranes based on poly(5‐(methacrylamido)tetrazole) and sulfonated polysulfone for proton exchange membrane fuel cells

Proton‐exchange membrane fuel cells (PEMFC)s are increasingly regarded as promising environmentally benign power sources. Heterocyclic molecules are commonly used in the proton conducting membranes as dopant or polymer side group due to their high proton transfer ability. In this study, 5‐(methacrylamido)tetrazole monomer, prepared by the reaction of methacryloyl chloride with 5‐aminotetrazole, was polymerized via conventional free radical mechanism to achieve poly(5‐(methacrylamido)tetrazole) homopolymer. Novel composite membranes, SPSU‐PMTetX, were successfully produced by incorporating sulfonated polysulfone (SPSU) into poly(5‐(methacrylamido)tetrazole) (PMTet). The sulfonation of polysulfone was performed with trimethylsilyl chlorosulfonate and high degree of sulfonation (140%) was obtained. The homopolymers and composite membranes have been characterized by NMR, FTIR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). ¹H‐NMR and FTIR confirmed the sulfonation of PSU and the ionic interaction between sulfonic acid and poly(5‐(methacrylamido)tetrazole) units. TGA showed that the polymer electrolyte membranes are thermally stable up to ～190°C. Scanning electron microscopy analysis indicated the homogeneity of the membranes. This result was also supported by the appearance of a single T_g in the DSC curves of the blends. Water uptake and proton conductivity measurements were, as well, carried out. Methanol permeability measurements showed that the composite membranes have similar methanol permeability values with Nafion 112. The maximum proton conductivity of anhydrous SPSU‐PMTet0.5 at 150°C was determined as 2.2 × 10^?6 S cm^?1 while in humidified conditions at 20°C a value of 6 × 10^?3 S cm^?1 was found for SPSU‐PMTet2. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40107.     

Sulfonated poly(ether sulfone)/phosphotungstic acid/attapulgite composite membranes for direct methanol fuel cells

Novel composite sulfonated poly(ether sulfone)(SPES)/phosphotungstic acid (PWA)/attapulgite (AT) membranes were investigated for direct methanol fuel cells (DMFCs). Physical–chemical properties of the composite membranes were characterized by FTIR, DSC, TGA, SEM‐EDX, water uptake, tensile test, proton conductivity, and methanol permeability. Compared with a pure SPES membrane, PWA, and AT doping in the membrane led to a higher thermal stability and glass transition temperature (T_g) as revealed by TGA and DSC. Tensile test indicated that lower AT content (3%) in the composite can significantly increase the tensile strength, while higher AT loading demonstrated a smaller contribution on strength. Proper PWA and AT loadings in the composite membranes can increase the proton conductivity and lower the methanol cross‐over. The proton conductivity of the SPES‐P‐A 10% composite membrane reached 60% of the Nafion 112 membrane conductivity at room temperature while the methanol permeability was only one‐fourth of that of Nafion 112 membrane. This excellent performances of SPES/PWA/AT composite membranes could indicate a potential feasibility as a promising electrolyte for DMFC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Enhancing the Anhydrous Proton Conductivity of Boronic and Phosphonic Acid Functional Copolymers by Grafting With Flexible Spacers

Polymers comprised of phosphonic acid units are generally preferred for proton conducting membranes due to their high proton conductivity in humidified and anhydrous state. Polymers based on 4-vinylbenzene boronic acid and diisopropyl-p-vinylbenzyl phosphonate were synthesized and the phosphonate group was hydrolyzed. Boronic acid groups were grafted with polyethyleneglycol methyl ether (PEGME) to produce more flexible copolymers. The copolymerization and grafting reactions were verified by Fourier Transform infrared spectroscopy, thermogravimetric analysis and differential scanning calorimetry (DSC). The P content of the samples was analyzed with SEM–EDS. Thermograms indicate that the copolymers are thermally stable to 200 °C. In addition, grafting resulted in the inhibition of condensation of the acidic units. DSC results show that after grafting the copolymers have distinct melting temperatures corresponding to PEGME units, which are bound to the polymer. The ion exchange capacity and cyclic voltammetry of the copolymers results were measured. The proton conductivity of the copolymers was investigated in the anhydrous state. Although the copolymers have low proton conductivity (<10^?10 S/cm), they reached a value of 1.6 × 10^?6 S/cm after grafting with PEGME units. This demonstrated that the presence of flexible side units increased the proton conductivity at least five orders of magnitude. This idea can be used for designing the novel membranes for fuel cells.     

Synthesis and proton conductivity studies of methacrylate/methacrylamide‐based azole functional novel polymer electrolytes

Anhydrous polymer electrolytes based on azole functional methacrylates and methacrylamides have been produced for use in proton exchange membrane fuel cells (PEMFCs). Poly(methacryloyl chloride) (PMAC) was prepared first by free‐radical polymerization of methacryloyl chloride, followed by side chain functionalization with 5‐aminotetrazole (ATet), 3‐amino‐1,2,4‐triazole (ATri) and 1H‐1,2,4‐triazole (Tri). Finally, the obtained polymers were doped with triflic acid (TA) at stoichometric ratios of 1.0, 2.0 and 4.0 with respect to azole units, and the anhydrous polymer electrolytes were obtained. The membranes were characterized by FT‐IR, ¹³C‐NMR, and elemental analysis. Thermal behaviour of polymers was explored by TGA and DSC. The samples were thermally stable up to approximately 200 ^oC. Proton conductivity was measured by impedance spectroscopy. Trifilic acid doped poly(methacryloyl aminotetrazole) (PMAATet‐(TA)₄), poly(methacryloyl‐3‐amino‐1,2,4‐triazole) (PMA‐Tri‐(TA)₄), and poly(methacryloyl‐1,2,4‐triazole) (PMA‐ATri‐(TA)₄) showed maximum proton conductivities of 0.01 Scm^?1, 0.02 Scm^?1 and 8.7x10^?4 Scm^?1, respectively, at 150^°C and anhydrous conditions. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39915.     

Novel polymer electrolyte membranes based on semi‐interpenetrating blends of poly(vinyl alcohol) and sulfonated poly(ether ether ketone)

In this work, the properties of novel ionic polymer blends of crosslinked and sulfonated poly(vinyl alcohol) (PVA) and sulfonated poly(ether ether ketone) (SPEEK) are investigated. Crosslinking and sulfonation of PVA were carried out using sulfosuccinic acid (SSA) in the presence of dispersed SPEEK to obtain semi‐interpenetrating network blends. PVA–SSA/SPEEK blend membranes of different compositions were studied for their ion‐exchange capacity, proton conductivity, water uptake, and thermal and mechanical properties. The hydrated blend membranes show good proton conductivities in the range of 10^?3 to 10^?2 S/cm. When compared with pure component membranes, the PVA–SSA/SPEEK blend membranes also exhibit improvement in tensile strength, tensile modulus, and delay in the onset of thermal and chemical degradation. Semi‐interpenetrating nature of the blends is established from morphology and dynamic mechanical analysis. Morphology of the membranes was studied using scanning electron microscopy after selective chemical treatment. The dynamic mechanical properties of the membranes are examined to understand the miscibility characteristics of the blends. The relative proportions of PVA and SPEEK and the degree of crosslinking of PVA–SSA are important factors in determining the optimum properties for the blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Proton Conducting Membranes Based on Poly(2,2′‐imidazole‐5,5′‐bibenzimidazole)

Poly(2,2′‐imidazole‐5,5′‐bibenzimidazole) (PBI‐imi) was synthesized via the polycondensation between 3,3′,4,4′‐tetraaminobiphenyl and 4,5‐imidazole‐dicarboxylic acid. Effects of the reaction conditions on the intrinsic viscosity of the synthesized polymers were studied. The results show that the molecular weight of the polymers increases with increasing monomer concentration and reaction time, and then levels off. With higher reaction temperature, the molecular weight of the polymer is higher. With the additional imidazole group in the backbone, PBI‐imi shows improved phosphoric acid doping ability, as well as a little higher proton conductivity when compared with widely used poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] (PBI‐ph).Whereas, PBI‐imi and PBI‐ph have the similar chemical oxidation stability. PBI‐imi/3.0 H₃PO₄ composite membranes exhibit a proton conductivity as high as 10^–4 S cm^–1 at 150 °C under anhydrous condition. The temperature dependence of proton conductivity of acid doped PBI‐imi can be modeled by an Arrhenius equation.     

Preparation and characterization of crosslinked PVAL membranes loaded with boehmite nanoparticles for fuel cell applications

Composite proton conducting membranes were prepared by doping the membrane, prepared by crosslinking poly(vinyl alcohol) with sulfosuccinic acid (SSA), with boehmite [aluminum oxyhydroxide or γ‐AlO(OH)]. The effect of the SSA and boehmite content on the membrane performance was studied and the results showed that the values for the ion exchange capacity (IEC) of the membranes were in the range of 0.45–4.80 mmol g^?1, the water content and the Young's modulus were dependent on the amount of SSA and nanoparticles. The proton conductivity was in the range of 10^?4 to 10^?2 S cm^?1 at 25°C and was directly related to the quantity of sulfonate groups present in the membrane, while the hydrogen permeability at 30°C was in the range of 10^?13 to 10^?12 mol cm s^?1 cm^?2 bar. The proton exchange membrane fuel cell tests indicated that the composite membranes have good proton conductivity and very low hydrogen permeability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40148.     

Pervaporation separation of water–ethanol mixtures using metal‐ion‐exchanged poly(vinyl alcohol) (PVA)/sulfosuccinic acid (SSA) membranes

Poly(vinyl alcohol)/sulfosuccinic acid (PVA/SSA) membranes in the hydrogen form were converted to monovalent metal ion forms Li⁺, Na⁺, and K⁺. The effect of exchange with metal ions was investigated by measuring the swelling of water–ethanol (10/90) mixtures at 30 °C and by the pervaporative dehydration performance test for aqueous ethanol solutions with various ethanol concentrations at 30, 40, and 50 °C. In addition, electron spectroscopy for chemical analysis (ESCA) analysis was carried out to study the quantity of metal ions in membranes. From the ESCA analysis, the lithium ion quantity in the resulting membranes is greater than that of any other metal ions in question because of the easy diffusion of a smaller metal ion into the membrane matrix. The swelling ratio was in the following order: PVA/SSA‐Li⁺ > PVA/SSA‐Na⁺ > PVA/SSA‐K⁺ membranes. For pervaporation, the PVA/SSA‐Na⁺ membrane showed the lowest flux and highest separation factor for all aqueous ethanol solutions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1867–1873, 2002     

Preparation of inorganic–organic hybrid proton exchange membrane with chemically bound hydroxyethane diphosphonic acid

Proton‐conductive inorganic–organic hybrid intermediate‐temperature membranes were prepared from 3‐glycidoxypropyltrimethoxysilane (GPTMS) and 1‐hydroxyethane‐1,1‐diphosphonic acid (HEDPA) by sol–gel process. To prevent the leaching out of phosphonic acid, triethylamine was used as catalyst to promote the reaction of HEDPA and GPTMS to immobilize phosphonic acid groups. Fourier transform infrared spectra revealed that phosphonic acid groups of HEDPA were chemically bounded to organosiloxane network as a result of the reaction of P? OH of HEDPA and epoxy ring of GPTMS. TG‐DSC results indicated that the hybrid membranes were thermally stable up to 250°C. The proton conductivity of the hybrid membranes increased with temperature from 30 to 130°C. The proton conductivity of hybrid membrane with the molar ratio of GPTMS/HEDPA = 2/1 can reach up to 1.0 × 10^?3 S/cm under anhydrous condition at 130°C, which reveals that this membrane is a promising proton exchange membrane for intermediate‐temperature proton exchange membrane fuel cell. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of polybenzimidazole/α‐zirconium phosphate composites as proton exchange membrane

To improve the high‐temperature performance of proton exchange membranes, the polybenzimidazole (PBI)/α‐zirconium phosphate (α‐Zr(HPO₄)₂·nH₂O, α‐ZrP) proton exchange composite membranes were prepared in this study. PBI polymer containing a large amount of ether units has been synthesized from 3,3′‐ diaminobenzidine (DAB) and 4,4′‐oxybis (benzoic acid) by a direct polycondensation in polyphosphoric acid. The polymer exhibited a good solubility in most polar solvents. Inorganic proton conductor α‐ZrP nanoparticles have been obtained using a synthesis route involving separate nucleation and aging steps (SNAS). The effects of α‐ZrP doping content on the composite membrane performance were investigated. It was found that the introduction of ZrP improved the thermal stability of the composite membranes. The PBI/ZrP composite membranes exhibited excellent mechanical strength. The composite membrane with 10 wt% ZrP showed the highest proton conductivity of 0.192 S cm^?1 at 160°C under anhydrous condition. The proton conducting mechanism of the PBI/ZrP composite membranes was proposed to explain the proton transport phenomena. The experimental results suggested that the PBI/ZrP composite membranes may be a promising polymer electrolyte used in high temperature proton exchange membrane fuel cells (HT‐PEMFCs) under anhydrous condition. POLYM. ENG. SCI., 56:622–628, 2016. © 2016 Society of Plastics Engineers     

Synthesis and Characterization of a New Fluorine‐Containing Polybenzimidazole (PBI) for Proton‐Conducting Membranes in Fuel Cells

A new type of fluorine‐containing polybenzimidazole, namely poly(2,2′‐(2,2′‐bis(trifluoromethyl)‐4,4′‐biphenylene)‐5,5′‐bibenzimidazole) (BTBP‐PBI), was developed as a candidate for proton‐conducting membranes in fuel cells. Polymerization conditions were experimentally investigated to achieve high molecular weight polymers with an inherent viscosity (IV) up to 1.60 dl g^–1. The introduction of the highly twisted 2,2′‐disubstituted biphenyl moiety into the polymer backbone suppressed the polymer chain packing efficiency and improved polymer solubility in certain polar organic solvents. The polymer also exhibited excellent thermal and oxidative stability. Phosphoric acid (PA)‐doped BTBP‐PBI membranes were prepared by the conventional acid imbibing procedure and their corresponding properties such as mechanical properties and proton conductivity were carefully studied. The maximum membrane proton conductivity was approximately 0.02 S cm^–1 at 180 °C with a PA doping level of 7.08 PA/RU. The fuel cell performance of BTBP‐PBI membranes was also evaluated in membrane electrode assemblies (MEA) in single cells at elevated temperatures. The testing results showed reliable performance at 180 °C and confirmed the material as a candidate for high‐temperature polymer electrolyte membrane fuel cell (PEMFC) applications.     

Partially Sulfonated Poly(1,4‐phenylene ether‐ether‐sulfone) and Poly(vinylidene fluoride) Blend Membranes for Fuel Cells

Blend membranes based on high conductive sulfonated poly(1,4‐phenylene ether‐ether‐sulfone) (SPEES) and poly(vinylidene fluoride) (PVDF) having excellent chemical stability were prepared and characterized for direct methanol fuel cells. The effects of PVDF content on the proton conductivity, water uptake, and chemical stability of SPEES/PVDF blend membranes were investigated. The morphology, miscibility, thermal, and mechanical properties of blend membranes were also studied by means of scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA) measurements. The blend membrane containing 90 wt.% SPEES (degree of sulfonation – DS = 72%) and 10 wt.% PVDF (M_w = 180,000) exhibits optimum properties among various SPEES72/PVDF membranes. Addition of PVDF enhanced resistance of the SPEES membrane against peroxide radicals and methanol significantly without deterioration of its proton conductivity. It's proton conductivity at 80 °C and 100% relative humidity is higher than Nafion 115 while it's methanol permeability is only half of that of Nafion 115 at 80 °C. The direct methanol fuel cell performance of the SPEES membranes was better than that of Nafion 115 membrane at 80 °C.     

PWA/silica doped sulfonated poly(ether sulfone) composite membranes for direct methanol fuel cells

A novel sulfonated poly(ether sulfone) (SPES)/phosphotungstic acid (PWA)/silica composite membranes for direct methanol fuel cells (DMFCs) application were prepared. The structure and performance of the obtained membranes were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), water uptake, proton conductivity, and methanol permeability. Compared to a pure SPES membrane, PWA and SiO₂ doped membranes had a higher thermal stability and glass transition temperature (T_g) as revealed by TGA‐FTIR and DSC. The morphology of the composite membranes indicated that SiO₂ and PWA were uniformly distributed throughout the SPES matrix. Proper PWA and silica loadings in the composite membranes showed high proton conductivity and sufficient methanol permeability. The selectivity (the ratio of proton conductivity to methanol permeability) of the SPES‐P‐S 15% composite membrane was almost five times than that of Nafion 112 membrane. This excellent selectivity of SPES/PWA/silica composite membranes indicate a potential feasibility as a promising electrolyte for DMFC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Phosphonic acid functionalized siloxane crosslinked with 3‐glycidoxyproyltrimethoxysilane grafted polybenzimidazole high temperature proton exchange membranes

Phosphonic acid functionalized siloxane crosslinked with 3‐glycidoxypropyltrimethoxysilane (GPTMS) grafted polybenzimidazole (PBI) membranes are prepared by sol–gel process. The structure of the membranes is characterized by Fourier‐transform infrared spectroscopy and X‐ray diffraction spectroscopy. SEM images of the membranes show that the membranes are homogeneous and compact. The crosslinked membranes exhibit excellent thermal stability, chemical stability and mechanical property. The proton conductivity of the crosslinked membranes increases by an order of magnitude over range of 20 °C to 160 °C under anhydrous condition, which can reach 3.15 × 10^?2 S cm^?1 at 160 °C under anhydrous condition. The activation energy of proton conductivity for membranes decreases with increase of PBI, because the formation of hydrogen bond network between the phosphonic acid and the imidazole ring can enhance the continuity of hydrogen bond in the membrane. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44818.     

Proton conduction promoted by 1H-1,2,3-benzotriazole in non-humidified polymer membranes

Heterocyclic protogenic solvents are promising candidates in production of proton conductive non-humidified membranes. In this work, 1H-1,2,3-Benzotriazole, BTri which is a novel protogenic solvent was incorporated into Nafion and polyvinylphosphonic acid, PVPA to produce novel anhydrous membranes. The composite membranes were characterized using FTIR, TGA and DSC. TGA results confirmed the thermal stability of the membranes and DSC results verified the homogeneity of the materials. The proton conductivity of these polymer electrolyte membranes with respect to BTri content was investigated. 1H-1,2,3-Benzotriazole promoted the proton conductivity of the membranes reaching approximately 10⁻³ S/cm at 150 °C, under anhydrous conditions. Cyclic voltammetry (CV) results demonstrated that 1H-1,2,3-benzotriazole has broad electrochemical stability domain.     

Proton exchange composite membranes from blends of brominated and sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide)

New composite proton exchange membrane was prepared by mixing a 1‐methyl‐2‐pyrrolidone (NMP) solution of sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO) in sodium form and brominated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (BPPO) for hydrophilic‐hydrophobic balance, then casting the solution as a thin film, evaporating the solvent, and treating the membrane with aqueous hydrochloric acid. The resulting membranes were subsequently characterized using FTIR‐ATR, SEM‐EDXA, and TGA instrumentation as well as measurements of basic properties such as ion exchange capacity (IEC), water uptake, proton conductivity, methanol permeability, and single cell performance. Water uptake, IEC, proton conductivity, and methanol permeability all increased with a corresponding increase of SPPO content. By properly compromising the conductivity and methanol permeability, membranes with 60–80 wt % SPPO content exhibited comparable proton conductivity to that of Nafion^® 117, with only half the methanol permeability, thereby demonstrating higher single cell performance. The membranes developed in this study could thus be a suitable candidate electrolyte for proton exchange membrane fuel cells (PEMFCs). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Proton conducting polymer blends from poly(2,5‐benzimidazole) and poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)

Proton conducting polymer electrolyte membranes were produced by blending of poly(2,5‐benzimidazole) (ABPBI) and poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) (PAMPS) at several stoichiometric ratios with respect to polymer repeating units. The membranes were characterized by using Fourier transform infrared spectroscopy for interpolymer interactions and scanning electron microscope for surface morphology. Thermal stability of the materials was investigated by thermogravimetric analysis. Glass transition temperatures of the samples were measured via differential scanning calorimetry. The spectroscopic measurements and water uptake studies indicate a complexation between ABPBI and PAMPS that inhibited polymer exclusion up on swelling in excess water. Proton conductivities of the anhydrous and humidified samples were measured using impedance spectroscopy. The proton conductivity of the humidified ABPBI:PAMPS (1 : 2) blend showed a proton conductivity of 0.1 S/cm, which is very close to Nafion 117, at 20°C at 50% relative humidity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Salt‐leaching technique for the synthesis of porous poly(2,5‐benzimidazole) (ABPBI) membranes for fuel cell application

The first instance of synthesizing porous poly(2,5‐benzimidazole) (ABPBI) membranes for high‐temperature polymer electrolyte membrane fuel cells (HT‐PEMFCs), using solvent evaporation/salt‐leaching technique, is reported herein. Various ratios of sodium chloride/ABPBI were dissolved in methanesulfonic acid and cast into membranes by solvent evaporation, followed by porogen (salt) leaching by water washing. The membranes were characterized using SEM, FTIR, TGA, and DSC. The proton conductivity, water and acid uptake of the membranes were measured and the chemical stability was determined by Fenton's test. SEM images revealed strong dependence of sizes and shapes of pores on the salt/polymer ratios. Surface porosities of membranes were estimated with Nis Elements‐D software; bulk porosities were measured by the fluid resaturation method. Thermogravimetric analysis showed enhanced dopant uptake with introduction of porosity, without the thermal stability of the membrane compromised. Incorporating pores enhanced solvent uptake and retention because of capillarity effects, enhancing proton conductivities of PEMs. Upon acid doping, a maximum conductivity of 0.0181 S/cm was achieved at 130 °C for a porous membrane compared with 0.0022 S/cm for the dense ABPBI membrane at the same temperature. Results indicated that with judicious optimization of porogen/polymer ratios, porous ABPBI membranes formed by salt‐leaching could be suitably used in HT‐PEMFCs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45773.