Sulfonated poly(ether sulfone) (SPES)/boron phosphate (BPO4) composite membranes for high-temperature proton-exchange membrane fuel cells

A new series of sulfonated poly(ether sulfone) (SPES)/boron phosphate (BPO₄) composite membranes for proton-exchange membrane fuel cells (PEMFCs) applications, with a BPO₄ content up to 40 wt%, were prepared by a sol–gel method using tripropylborate and phosphoric acid as precursors. Compared to a pure SPES membrane, BPO₄ doping in the membranes led to a higher thermal stability and glass-transition temperature (T_g) as revealed by TGA–FTIR, DSC and DMTA. Water uptake and oxidative stability were significantly increased by increasing the content of BPO₄. At both operating temperature conditions, namely 20 °C and 100 °C, the tensile strength of all the composite membranes were lower than that of the SPES membrane. However, even when the content of BPO₄ was as high as 30%, the composite membrane still possessed strength similar to the Nafion 112 membrane. SEM–EDX indicated that the BPO₄ particles were uniformly embedded throughout the SPES matrix, which may facilitate proton transport. Proton conductivities increased from 0.0065 to 0.022 S cm⁻¹ at room temperature as BPO₄ increased from 0 to 40%. The conductivities also increased with the temperature. The SPES/BPO₄ composite membrane is a promising candidate for PEMFCs applications, especially at higher temperatures.     

Nafion-impregnated electrospun polyvinylidene fluoride composite membranes for direct methanol fuel cells

Composite membranes consisting of polyvinylidene fluoride (PVdF) and Nafion have been prepared by impregnating various amounts of Nafion (0.3–0.5 g) into the pores of electrospun PVdF (5 cm × 5 cm) and characterized by scanning electron microscopy, differential scanning calorimetry, X-ray diffraction, and proton conductivity measurements. The characterization data suggest that the unique three-dimensional network structure of the electrospun PVdF membrane with fully interconnected fibers is maintained in the composite membranes, offering adequate mechanical properties. Although the composite membranes exhibit lower proton conductivity than Nafion 115, the composite membrane with 0.4 g Nafion exhibits better performance than Nafion 115 in direct methanol fuel cell (DMFC) due to smaller thickness and suppressed methanol crossover from the anode to the cathode through the membrane. With the composite membranes, the cell performance increases on going from 0.3 to 0.4 g Nafion and then decreases on going to 0.5 g Nafion due to the changes in proton conductivity.     

Novel composite electrolyte membranes consisting of fluorohydrogenate ionic liquid and polymers for the unhumidified intermediate temperature fuel cell

Novel composite electrolyte membranes consisting of [EMIm](FH)_nF (EMIm = 1-ethyl-3-methylimidazolium, n = 1.3 and 2.3) ionic liquids and fluorinated polymers were synthesized and their physical and electrochemical properties were measured under unhumidified conditions for their application to the intermediate temperature fuel cells. The ionic conductivities of composite membrane, P(VdF-co-HFP)/s-DFBP-HFDP/[EMIm](FH)_2.3F (1/0.3/1.75 in weight ratio), were 11.3 and 34.7 mS cm⁻¹ at 25 and 130 °C, respectively. The open circuit voltage (OCV) observed for the single cell using [EMIm](FH)_2.3F composite electrolyte was ∼1.0 V at 130 °C for over 5 h. The maximum power density of 20.2 mW cm⁻² was observed under the current of 60.1 mA cm⁻² at 120 °C. From the high thermal stability and high ionic conductivity, the fluorohydrogenate ionic liquid composite membranes are regarded as promising candidates for the electrolytes of the unhumidified intermediate temperature fuel cells.     

Fabrication of protic ionic liquid/sulfonated polyimide composite membranes for non-humidified fuel cells

We have demonstrated that a protic ionic liquid, diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]) functions as a proton conductor and is suitable for use as an electrolyte in H₂/O₂ fuel cells, which can be operated at temperatures higher than 100 °C under non-humidified conditions. In this study, in order to fabricate a polymer electrolyte fuel cell, matrix polymers for [dema][TfO] are explored and sulfonated polyimides (SPI), in which the sulfonic acid groups are in diethylmethylammonium form, are found to be highly compatible with [dema][TfO]. Polymer electrolyte membranes for non-humidified fuel cells are prepared by the solvent casting method using SPI and [dema][TfO]. The SPI, with an ion exchange capacity of 2.27 meq g⁻¹, can retain four times its own weight of [dema][TfO] and produces uniform, tough, and transparent composite membranes. The composite membranes have good thermal stability (>300 °C) and ionic conductivity (>10⁻² S cm⁻¹ at 120 °C when the [dema][TfO] content is higher than 67 wt%) under anhydrous conditions. In the H₂/O₂ fuel cell operation using a composite membrane without humidification, a current density higher than 240 mA cm⁻² is achieved with a maximum power density of 100 mW cm⁻² at 80 °C.     

Proton conductive inorganic-organic hybrid membranes functionalized with phosphonic acid for polymer electrolyte fuel cell

Proton conductive sol-gel derived hybrid membranes were synthesized from aromatic derivatives of methoxysilanes and ethyl 2-[3-(dihydroxyphosphoryl)-2-oxapropyl]acrylate (EPA). Two aromatic derivatives of methoxysilanes with different number of methoxy groups were used as the starting materials. Hybrid membranes from difunctional (methyldimethoxysilylmethyl)styrene (MDMSMS(D))/EPA revealed a higher chemical stability and mechanical properties than those from monofunctional (dimethylmethoxysilylmethyl)styrene (DMMSMS(M))/EPA. The membrane-electrode assembly (MEA) using the hybrid membranes as electrolytes worked as a fuel cell at 100 °C under saturated humidity. The DMMSMS(M)/EPA membrane-based MEA showed a larger current density than that from MDMSMS(D)/EPA. On the other hand, the MDMSMS(D)/EPA membrane-based MEA exhibited higher open circuit voltages than the DMMSMS(M)/EPA-based MEA, and was stable during fuel cell operation at 80 °C at least for 48 h.     

Silica-related membranes in fuel cell applications: An overview

Silica is the most common inorganic filler used in fuel cells, especially for proton exchange membrane fuel cell and direct alcohol fuel cell applications. Silica has played an important role in improving the performance of fuel cells by enhancing their membrane properties. Recently, silica has been widely implemented in different types of membranes, such as fluorinated membranes (Nafion), sulfonated membranes (SPEEK, SPS, SPAES, SPI) and other organic polymer matrixes. The incorporation of silica into membrane matrices has improved the thermal stability, mechanical strength, water retention capacity and proton conductivity of the membrane. This review describes the interactions between silica and different types of polymer matrices in fuel cells and how they boost fuel cell performance. In addition, this review also discusses the current challenges of silica-related membrane-based fuel cells and predicts the future prospects of silica in membrane-based fuel cell applications.     

Polybenzimidazole/zwitterion-coated polyamidoamine dendrimer composite membranes for direct methanol fuel cell applications

The zwitterion-coated polyamidoamine (ZC-PAMAM) dendrimer with ammonium and sulfonic acid groups has been synthesized and used as filler for the preparation of PBI-based composite membranes for direct methanol fuel cells. Polybenzimidazole (PBI)/ZC-PAMAM dendrimer composite membranes were prepared by casting a solution of PBI and ZC-PAMAM dendrimer, and then evaporating the solvent. The presence of ZC-PAMAM dendrimer was confirmed by FT-IR and energy-dispersive X-ray spectroscopy (EDS) mapping of sulfur and oxygen elements. The water uptake, swelling degree, proton conductivity, and methanol permeability of the membranes increased with the ZC-PAMAM dendrimer content. For the PBI/ZC-PAMAM-20 membrane with 20 wt% of ZC-PAMAM, it shows a proton conductivity of 1.83 × 10⁻² S/cm at 80 °C and a methanol permeability of 5.23 × 10⁻⁸ cm² s⁻¹. Consequently, the PBI/ZC-PAMAM-20 demonstrates a maximum power density of 26.64 mW cm⁻² in a single cell test, which was about 2-fold higher than Nafion-117 membrane under the same conditions.     

Chitosan/heteropolyacid composite membranes for direct methanol fuel cell

As inorganic proton conductors, phosphomolybdic acid (PMA), phosphotungstic acid (PWA) and silicotungstic acid (SiWA) are extremely attractive for proton-conducting composite membranes. An interesting phenomenon has been found in our previous experiments that the mixing of chitosan (CS) solution and different heteropolyacids (HPAs) leads to strong electrostatic interaction to form insoluble complexes. These complexes in the form of membrane (CS/PMA, CS/PWA and CS/SiWA composite membranes) have been prepared and evaluated as novel proton-conducting membranes for direct methanol fuel cells. Therefore, HPAs can be immobilized within the membranes through electrostatic interaction, which overcomes the leakage problem from membranes. CS/PMA, CS/PWA and CS/SiWA composite membranes were characterized for morphology, intermolecular interactions, and thermal stability by SEM, FTIR, and TGA, respectively. Among the three membranes, CS/PMA membrane was identified as ideal for DMFC as it exhibited low methanol permeability (2.7 × 10⁻⁷ cm² s⁻¹) and comparatively high proton conductivity (0.015 S cm⁻¹ at 25 °C).     

Electrospun multifunctional sulfonated carbon nanofibers for design and fabrication of SPEEK composite proton exchange membranes for direct methanol fuel cell application

Microstructural construction of a polymer/inorganic filler interface in organic/inorganic composite proton exchange membranes is a key to design of high performance proton conducting materials. Here, carbon nanofibers (CNFs) prepared through electrospun were successfully sulfonated to improve interfacial compatibility between the sulfonated poly(ether ether ketone) (SPEEK) and the sulfonated CNFs (SCNFs) via hydrogen bonding interaction. In addition, carbon nanofiber mats were successfully sheared into short lengths to facilitate dispersion of the SCNFs in the composite membranes. To demonstrate the effectiveness of the SCNFs on improvement of properties of the composite membranes, key physical quantities, i.e. mechanical strength, proton conductivity and methanol permeation were measured and systematically compared with the results of the neat SPEEK and Nafion 117 membranes. It was found that doping with the SCNFs of various contents could profoundly influence the physical properties of the composite membranes. In particular, mechanical strength, proton conductivity and methanol permeability prevention of the composite membranes were significantly enhanced upon incorporation of the SCNFs as fillers. The study provides useful insight into the investigation of the SCNFs based composite membranes for fuel cell applications.     

Nanostructured polypyrrole/carbon composite as Pt catalyst support for fuel cell applications

A novel catalyst support was synthesized by in situ chemical oxidative polymerization of pyrrole on Vulcan XC-72 carbon in naphthalene sulfonic acid (NSA) solution containing ammonium persulfate as oxidant at room temperature. Pt nanoparticles with 3–4 nm size were deposited on the prepared polypyrrole–carbon composites by chemical reduction method. Scanning electron microscopy and transmission electron microscopy measurements showed that Pt particles were homogeneously dispersed in polypyrrole–carbon composites. The Pt nanoparticles-dispersed catalyst composites were used as anodes of fuel cells for hydrogen and methanol oxidation. Cyclic voltammetry measurements of hydrogen and methanol oxidation showed that Pt nanoparticles deposited on polypyrrole–carbon with NSA as dopant exhibit better catalytic activity than those on plain carbon. This result might be due to the higher electrochemically available surface areas, electronic conductivity and easier charge-transfer at polymer/carbon particle interfaces allowing a high dispersion and utilization of deposited Pt nanoparticles.     

Sulfonated MWNT and imidazole functionalized MWNT/polybenzimidazole composite membranes for high-temperature proton exchange membrane fuel cells

Composite membranes used for proton exchange membrane fuel cells comprising of polybenzimidazole (PBI) and carbon nanotubes with certain functional groups were studied, because they could enhance both the mechanical property and fuel cell performance at the same time. In this study, sodium poly(4-styrene sulfonate) functionalized multiwalled carbon nanotubes (MWNT-poly(NaSS))/PBI and imidazole functionalized multiwalled carbon nanotubes (MWNT-imidazole)/PBI composite membranes were prepared. The functionalization of carbon nanotubes involving non-covalent modification and covalent modification were confirmed by FITR, XPS, Raman spectroscopy, and TGA. Compared to unmodified MWNTs and MWNT-poly(NaSS), MWNT-imidazole provided more significant mechanical reinforcement due to its better compatibility with PBI. For MWNT-poly(NaSS)/PBI and MWNT-imidazole/PBI composite membranes at their saturated doping levels, the proton conductivities were up to 5.1 × 10⁻² and 4.3 × 10⁻² S/cm at 160 °C under anhydrous condition respectively, which were slightly higher than pristine PBI (2.8 × 10⁻² S/cm). Also, MWNT-poly(NaSS)/PBI and MWNT-imidazole/PBI composite membranes showed relatively improved fuel cell performance at 170 °C compared to pristine PBI.     

Electrospun nanofibrous blend membranes for fuel cell electrolytes

We have synthesized the novel blend membranes composed of sulfonated polyimide nanofibers and sulfonated polyimide for proton exchange membrane fuel cell. The proton conductivities of the blend membrane containing nanofibers were measured as functions of the relative humidity and temperature using electrochemical impedance spectroscopy. The proton conductivity of the blend membrane indicated a higher value when compared to that determined for the blend membrane without nanofibers prepared with conventional solvent-casting method. In addition, the membrane stability, such as oxidative and hydrolytic stabilities, of the blend membrane containing nanofibers strongly depended on the amount of nanofiber and was significantly improved with an increase in nanofiber. Oxygen permeability of the membrane was also investigated under dry condition at 35 °C and 760 mm Hg. Oxygen permeability coefficient of the blend membrane slightly decreased when compared to that determined in the blend membrane without nanofibers. Consequently, nanofibers proved to be promising materials as a proton exchange membrane and the blend membrane containing nanofibers may have potential application for use in fuel cells.     

Novel nanofiber-based triple-layer proton exchange membranes for fuel cell applications

New types of triple-layer membranes were fabricated using multi-step impregnation of Nafion in electrospun webs based on bead-free nanofibers of sulfonated poly(ether sulfone) (SPES). The results showed that the fabricated nanofiber-filled membrane owing to its reduced methanol permeability as well as sufficient proton conductivity and membrane selectivity can be used as a promising proton exchange membrane for direct methanol fuel cell (DMFC) applications. The single cell DMFC performance results revealed that the SPES nanofiber-based triple-layer membranes have higher electrochemical performance than commercial Nafion membranes.     

Novel quaternized polysulfone/ZrO2 composite membranes for solid alkaline fuel cell applications

A novel composite anion exchange membrane, zirconia incorporated quaternized polysulfone (designated as QPSU/ZrO₂), is prepared by solution casting method. The characteristic properties of the QPSU/ZrO₂ composite polymer membranes are investigated by thermogravimetric analysis, X-ray diffraction and electrochemical impedance spectroscopy. The morphology of the composite membrane is observed by SEM and TEM studies. A study of an alkaline membrane fuel cell (AMFC) operating with hydroxide ion conducting membrane is reported. Evaluation of the fuel cell is performed using membrane electrode assemblies made up of carbon supported platinum (Vulcan XC-72) anode and platinum cathode catalysts and QPSU/ZrO₂ composite membrane. Experimental results indicate that the AMFC employing a cheap non-perflourinated (QPSU/ZrO₂) composite polymer membrane shows better electrochemical performance. The maximum power density observed is 250 mW/cm² for QPSU/10% ZrO₂ at 60 °C. The QPSU/ZrO₂ composite membrane constitutes a good candidate for alkaline membrane fuel cell applications.     

Crosslinked sulfonated poly(arylene ether sulfone) membranes for fuel cell application

A series of sulfonated poly(arylene ether sulfone) with photocrosslinkable moieties is successfully synthesized by direct copolymerization of 3,3′-disulfonated 4,4′-difluorodiphenyl sulfone (SDFDPS) and 4,4′-difluorodiphenyl sulfone (DFDPS) with 4,4′-biphenol (BP) and 1,3-bis-(4-hydroxyphenyl) propenone (BHPP). The content of crosslinkable moieties in the polymer repeat unit is controlled from 0 to 10 mol% by changing the monomer feed ratio of BHPP to BP. The polymer membranes can be crosslinked by irradiating UV with a wavelength of 365 nm. From FT-IR analysis, it can be identified that UV crosslinking mainly occurs due to the combination reaction of radicals that occurs in conjunction with the breaking of the carbon–carbon double bonds (–CH = CH-) of the chalcone moieties in the backbone. Consequently, a new bond is created to form cyclobutane. The crosslinked membranes show less water uptake, a lower level of methanol permeability, and good thermal and mechanical properties compared to pristine (non-crosslinked) membranes while maintaining a reasonable level of proton conductivity. Finally, the fuel cell performance of the crosslinked membranes is comparable to that of the Nafion 115 membrane, demonstrating that these membranes are promising candidates for use as polymer electrolyte membranes in DMFCs.     

Proton-conducting composite membranes of chitosan and sulfonated polysulfone for fuel cell application

Crosslinked composite membrane having a thin chitosan (CS) layer on microporous polysulfone (PSF) substrate was synthesized and assessed for its applicability in fuel cells. This composite (PSF/CS) was extensively characterized for morphology, intermolecular interactions, thermal stability, and physico-mechanical properties using SEM, XRD, FTIR, TGA and sorption studies, respectively. Since studies indicated a lack of interaction between the two polymers, efforts were made to enhance the interaction between polysulfone support and chitosan through surface modification of polysulfone. This rendered a novel type of composite (SPSF/CS) derived by surface modification of polysulfone substrate prior to casting of chitosan layer on it. Proton conductivity of both the composites, PSF/CS and SPSF/CS, was determined and compared with respective values of commercial Nafion 117. These composites exhibited an increase in conductivity with an increase in temperature. The composite, SPSF/CS exhibited high Ion Exchange Capacity (IEC) and proton conductivity higher than Nafion 117 at temperature above 100 °C. The membrane also showed adequate geometrical and thermal stabilities and can therefore be considered as a potential alternative fuel cell membrane especially for high temperature operations.     

Properties and fuel cell performance of a Nafion-based,sulfated zirconia-added,composite membrane

The effect of an acidic inorganic additive, i.e. sulfated zirconia, on Nafion-based polymer electrolytes is evaluated by comparing the properties in terms of conductivity and fuel cell performance of a composite sulfated zirconia-added Nafion membrane with those of an additive-free Nafion membrane. The peculiar surface properties of the selected filler promote a higher hydration level and a higher conductivity for the composite membrane under unsaturated conditions, i.e. at 20% RH. Tests on H₂-air fully humidified cells, monitored at 70 °C and at atmospheric pressure, reveal small differences when passing from a plain Nafion to a composite Nafion/sulfated zirconia membrane as electrolyte. However, remarkably great improvements are observed for the composite membrane-based cell when the comparison tests are run at low relative humidity and high temperature, this outlining the beneficial role of the sulfated zirconia additive.     

Recent advances in designing and tailoring nanofiber composite electrolyte membranes for high-performance proton exchange membrane fuel cells

As the critical component of proton exchange membrane fuel cell (PEMFC), proton exchange membrane (PEM) determine its overall performance. Current PEMs hardly meet the operating requirements of fuel cells, limiting their commercial applications. With the development of nanocomposite technology, nanofibers introduced into PEMs to prepare nanofiber composite proton exchange membranes (NCPEMs) have been widely studied. In an NCPEM, nanofibers can form long-range channels for proton transport, and reinforced skeleton to reach the target performance of PEMFCs. Focusing on NCPEM, this paper reviews on recent progresses in nanofiber preparation and NCPEM preparation techniques. Furthermore, different types of nanofibers incorporated into NCPEMs are reviewed in terms of fiber composition. The challenges and future perspectives regarding NCPEMs are also discussed.     

Alkaline anion-exchange polymer membrane with grid-plug microstructure for hydrogen fuel cell application

Porous polysulfone membrane, prepared by a phase-inversion technique, is filled with (3-acrylamidopropyl)trimethylammonium chloride and N,N′-methylenebisacrylamide via interfacial diffusion. The impregnated membrane is then subjected to UV-irradiation for polymerizing monomers that are entrapped in pore channels of the membrane. This in-situ polymerization engenders a grid-plug microstructure, where the grid is polysulfone and the plugs are an ion (OH⁻) conducting phase. As the plugs are extensively interconnected and non-tortuous throughout the membrane matrix, the ion-conducting phase sustains a power density as high as 55 mW cm⁻² at 60 °C. Thermal analysis indicates that the pore-filling condition affects the packing density of the plugs that in turn, impacts on ion transport flux.