Synthesis and characterization of sulfonated polyphenylene containing DCTPE for PEMFC potential application

The synthesis of conjugated polyphenylenes containing tetraphenylethylene (PPTPE) moiety, their functionalization with sulfonic acid groups, and the measurement of apposite parameters for PEMs are described. The polymers were prepared by Ni-catalyzed carbon–carbon coupling reaction of dichlorotetraphenylethylene and 2,5-dichlorobenzophenone. These polymers have all carbon–carbon linkages without any ether linkage on polymer backbone, which were not attacked by nucleophiles (H₂O, hydrogen peroxide, hydroxide anion and radical), and the twisted structure provided good solubility in aprotic polar solvent. The sulfonic acid groups were introduced by sulfonation reaction with concentrated sulfuric acid. All these membranes were prepared from dimethylacetamide (DMAc) polymer solution. The membranes were studied by ion exchange capacity (IEC), water uptake, proton conductivity, and single cell performance. The chemical degradation test of the prepared membrane was performed by Fenton reagent, and compared with normal sulfonated poly(ether sulfone)s & Nafion.     

Sulfonated poly(ether sulfone) electrolytes structured with mesonaphthobifluorene graphene moiety for PEMFC

Sulfonated poly(ether sulfone)s containing a mixture of cis and trans mesonaphthobifluorene moiety were synthesized, and their properties were characterized. The mesonaphthobifluorene graphene moiety contained 6 phenyl rings and was conjugated together to form planar sheets of sp²-bonded carbon. Poly(arylene ether sulfone)s containing a mixture of cis and trans tetraphenyl ethylene units were synthesized by polycondensation, and converted into graphene by intramolecular Friedel–Craft cyclization with Lewis acid (FeCl₃). The sulfonation was taken selectively on mesonaphthobifluorene units with concentrated sulfuric acid. The structural properties of the sulfonated polymers were investigated by ¹H NMR spectroscopy. The membranes were studied with regard to ion exchange capacity (IEC), water uptake, and proton conductivity.     

Preparation and characterization of grafted propane sulfonic acid polyphenylene membrane via superacid-catalyzed reaction

A series of polyphenylene-based polyelectrolytes were synthesized from 2,2'-biphenol, and isatin by superacid catalyzed polyhydroxyalkylation reactions. Grafted sulfonated polyphenylenes were synthesized via K₂CO₃ catalyzed condensation reaction with 3-bromopropane sulfonic acid potassium salt. These polymers have all carbon–carbon linkages without any ether linkage on polymer backbone, which were not attacked by nucleophiles (H₂O, hydrogen peroxide, hydroxide anion and radical). Particularly, chemical modification to flexible sulfoalkyl groups implanted to a biphenol unit afforded better stability due to less reactive towards nucleophilic substitution reaction, and good proton mobility because of well phase separation. The structural properties of the synthesized polymers were investigated by ¹H NMR spectroscopy. The membranes were studied by ion exchange capacity (IEC), water uptake, dimensional stability as well as proton conductivity assessment. The chemical degradation test was performed by Fenton's reagent, and compared with the usual sulfonated poly(ether sulfone)s and Nafion.     

Characterization of highly sulfonated PEEK based membrane for the fuel cell application

In this study, poly(bisphenol-A-ether ketone) (PBAEK) is synthesized via nucleophilic aromatic substitution poly condensation between bisphenol A and 4,4-difluorobenzophenone, and the synthesized polymers are sulfonated using chlorosulfuric acid and suitable synthesis conditions for the temperature and sulfonating reagent content. The sulfonation degree of polymer is calculated using element analyses. The prepared sulfonated polymers are characterized for potential fuel cell applications through determining their water uptake, proton conductivity, and thermal stability. The significant advantage of the synthesized sulfonated PBAEK (sPBAEK) is its better solubility relative to commercial PEEK in various solvents, because sPBAEK backbones contain bisphenol A. The water uptake of the membrane increases with increases in the sulfonation degree. The sPBAEK membrane exhibits increased proton conductivity compared with the PBAEK membrane at 100% relative humidity conditions. As the sulfonation degree increases, the proton conductivity increases due to the increasing content in the hydrophilic domain. This property allows the prepared membranes to be potential candidates for proton exchange membrane fuel cells.     

Block copolymers combining semi-fluorinated poly(arylene ether) and sulfonated poly(arylene ether sulfone) segments for proton exchange membranes

A series of aromatic multiblock copolymers based on alternating segments of hydrophilic sulfonated polysulfone (PSU) and hydrophobic polyfluoroether (PFE) were prepared and characterized as proton exchange membranes. PSU precursor blocks were synthesized by polycondensation of dichlorodiphenylsulfone and resorcinol, and PFE precursor blocks were prepared by combining decafluorobiphenyl and isopropylidenediphenol. After preparation of the multiblock copolymers via a mild coupling reaction of the precursor blocks, the resorcinol units of the PSU blocks were selectively and almost completely sulfonated under mild reaction conditions using trimethylsilylchlorosulfonate. Transparent and robust membranes with different PSU-PFE copolymer compositions and ion-exchange capacities were cast from solution. Atomic force microscopy of the membranes revealed a distinct nanophase separated morphology. At 80 °C, the proton conductivity reached 10 mS cm⁻¹ under 65% relative humidity and 100 mS cm⁻¹ under fully hydrated conditions.     

Modification of carbon aerogel supports for PEMFC catalysts

Nitrogen enriched carbon aerogels and Co-based non-noble metal catalysts supported on carbon aerogels have been synthesized and tested using XPS, HRTEM, XRD and RDE techniques. XPS spectra of unmodified carbon aerogels indicated a presence of two oxygen O(1s) groups and five carbon C(1s) groups in deconvoluted spectra. XPS spectra of chemically modified samples indicated nitrogen N(1s) introduced in the carbon aerogel structure by acidic (HNO₃) or basic (NH₄OH) chemical treatment.Synthesis of aerogel supported Co catalysts performed by using Co-methoxy-tetra-phenylporfirin as a macrocyclic compound incorporated into the aerogel structure, and sintered at 700 and 900 °C in N₂, revealed the presence of Co-metal nano-particles with 20 nm diameter. HRTEM and diffraction patterns show a β-Co FCC structure with many {111}<110> micro-twins in the Co nano-particles. The electrochemical properties of the synthesized catalysts in O₂-free and O₂-saturated sulfuric and perchloric acid solutions, evaluated by a rotating disc electrode (RDE) technique, demonstrated catalytic activity in hydrogen oxidation and oxygen reduction reactions.     

Synthesis and characterization of crosslinked sulfonated poly(arylene ether sulfone) membranes for high temperature PEMFC applications

Sulfonated poly(arylene ether sulfone) copolymers containing carboxyl groups are prepared by an aromatic substitution polymerization reaction using phenolphthalin, 3,3′-disulfonated-4,4′-dichlorodiphenyl sulfone, 4,4′-dichlorodiphenyl sulfone and 4,4′-bisphenol A as polymer electrolyte membranes for the development of high temperature polymer electrolyte membrane fuel cells. Thin, ductile films are fabricated by the solution casting method, which resulted in membranes with a thickness of approximately 50 μm. Hydroquinone is used to crosslink the prepared copolymer in the presence of the catalyst, sodium hypophosphite. The synthesized copolymers and membranes are characterized by ¹H NMR, FT-IR, TGA, ion exchange capacity, water uptake and proton conductivity measurements. The water uptake and proton conductivity of the membranes are decreased with increasing the degree of crosslinking which is determined by phenolphthalin content in the copolymer (0-15 mol%). The prepared membranes are tested in a 9 cm² commercial single cell at 80 °C and 120 °C in humidified H₂/air under different relative humidity conditions. The uncrosslinked membrane is found to perform better than the crosslinked membranes at 80 °C; however, the crosslinked membranes perform better at 120 °C. The crosslinked membrane containing 10 mol% of phenolphthalin (CPS-PP10) shows the best performance of 600 mA cm⁻² at 0.6 V and better performance than the commercial Nafion^® 112 (540 mA cm⁻² at 0.6 V) at 120 °C and 30 % RH.     

Novel proton exchange membranes based on proton conductive sulfonated PAMPS/PSSA-TiO2 hybrid nanoparticles and sulfonated poly (ether ether ketone) for PEMFC

Nanocomposite membranes based on sulfonated poly (ether ether ketone) (SPEEK) and sulfonated core-shell TiO₂ nanoparticles were prepared. TiO₂ nanoparticles were sulfonated by redox polymerization method by using sodium styrene sulfonate (SSA) and 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) monomers. The resultant hybrid nanoparticles (PAMPS-gTiO₂ and PSSA-g-TiO₂) were introduced to SPEEK with a sulfonation degree of 68%. Grafting of sulfonated polymers onto TiO₂ nanoparticles enhanced the content of proton transport sites in the membrane, leading to an increase in proton conductivity and power density. Besides, the mechanical and dimensional stabilities of the nanocomposite membranes were also improved compared with pure SPEEK membrane. The maximum power density for membranes containing 7.5 wt% of PAMPS-gTiO₂ and PSSA-g-TiO₂ nanoparticles at 80 °C obtained 283 mW cm⁻² and 245 mW cm⁻², respectively.     

Synthesis and characterization of sulfonated poly (arylene ether ketone sulfone) block copolymers containing multi-phenyl for PEMFC

Sulfonated multi-block copolymers (SMBPs) were successfully synthesized from precursors of hydrophilic and hydrophobic block oligomers. The hydrophilic block oligomer was synthesized using 1,2-bis(4-fluorobenzoyl)-3,4,5,6-tetraphenylbenzene (BFBTPB) and 4,4′-(2,2-diphenylethenylidene) diphenol (DHTPE). The hydrophobic block oligomer was prepared by bis(4-hydroxyphenyl) sulfone and bis(4-fluorophenyl) sulfone. The sulfonation was taken selectively on hydrophilic block segment as well as para position of the pendant phenyl groups with concentrated sulfuric acid. To control the IEC the stoichiometry mole ratios were changed with hydrophilic blocks of 10, 13 and 17 mol%. The structural properties of SMBPs were studied by FT-IR, ¹H NMR spectroscopy, thermogravimetric analysis (TGA), and atomic force microscope (AFM). The water uptakes were 9.7–42.3% at 30 °C and 14.3%–70.4% at 80 °C with changing the ion exchange capacities. The resulted ion exchange capacities (IEC) were 1.09–1.63 meq./g. The highest power density of a fuel cell using SMBP 17 (IEC = 1.63 meq./g) and Nafion 211 was 0.41 and 0.45 W/cm², respectively, at 0.6 V.     

Proton-conducting composite membranes based on polybenzimidazole and sulfonated mesoporous organosilicate

Sulfonated mesoporous organosilicate (s-MPOs) was synthesized by the one-step sol–gel method as a novel inorganic additive derived for use in the fuel cell. TEM observations revealed that the s-MPOs has well-ordered structure and many SO₃H groups on the inner surface of the mesopores. The s-MPOs was added to the proton-conductive polymer matrix, polybenzimidazole (PBI) in the presence of H₃PO₄, and the proton conductivities were measured at 60–100 °C under controlled humidity. The PBI composites filled with only 1 wt% of s-MPOs gave proton conductivity more than 10-times higher than the original PBI/H₃PO₄ membrane. The s-MPOs possessing many SO₃H groups were able to form effective proton conductive pathways via its periodic structure and to improve the conductivity. The greatest conductivity was estimated to be 0.21 S cm⁻¹ at 80 °C and 98 %RH in case of a PBI/s-MPOs20 (incl. approx. 20 mol% of the SO₃H units in MPS) composite.     

Synthesis of sulfonated poly(diketonephenylene)s containing dibenzoyl moiety via Ni/Zn catalyst

The new monomer, 1,2-bis(4-chlorobenzoyl)-3,6-diphenylbenzene, was synthesized from the Frieldel–Craft reaction of chlorobenzene and fumaryl chloride followed by the Diels–Alder reaction. Poly(diketonephenylene)s containing the dibenzoyl moiety in the side chains were synthesized from 1,2-bis(4-chlorobenzoyl)-3,6-diphenylbenzene and 1,4-dichloro-2,5-dibenzoylbenzene as a reactive monomer. The polymerization was performed employing a Ni/Zn catalyzed carbon–carbon coupling reaction followed by a sulfonation reaction with chlorosulfuric acid. These polymers consisted of diketone in the main chain and dibenzoyl in the side chain, which consisted of four active phenyl groups for sulfonation. A series of membranes was studied via ¹H NMR spectroscopy, ion exchange capacity (IEC), water uptake, and proton conductivity analyses. The thermal and chemical stability of the prepared membrane is then characterized through a thermogravimetric investigation.     

Single-step synthesis of sulfonated polyoxadiazoles and their use as proton conducting membranes

A single-step approach for the synthesis of sulfonated polyoxadiazoles from hydrazine sulfate was developed using non-sulfonated diacids in polyphosphoric acid. The post-sulfonation conditions were optimized by varying reaction time, medium and reagent concentrations in sulfuric acid, oleum and/or their mixtures. For the first time, a series of sulfonated polyoxadiazoles with ion exchange capacity (IEC) ranging from 1.26 to 2.7 meqiv. g⁻¹ and high molecular weight (about 40,0000 g mol⁻¹) were synthesized. The structures of the polymers were characterized by elemental analysis, ¹H NMR, and FTIR. Sulfonated polyoxadiazole membranes with high thermal stability indicated by observed glass-transition temperatures (T_g) ranging from 364 to 442 °C in sodium salt form and from 304 to 333 °C in acid form and with high mechanical properties (storage modulus about 3 GPa at 300 °C) have been prepared. The membrane stability to oxidation was investigated by soaking the film in Fenton's reagent at 80 °C for 1 h. The sulfonated polyoxadiazole membranes exhibited high oxidative stability, retaining 98–100% of their weight after the test. Proton conductivity values with the order of magnitude of 10⁻¹ to 10⁻² S cm⁻¹ at 80 °C and with relative humidity ranging from 100% to 20% were obtained.     

Characterization of polyethyleneterephthalate (PET) based proton exchange membranes prepared by UV-radiation-induced graft copolymerization of styrene

Polymer electrolyte membranes (PEMs) were successfully prepared by simultaneous ultraviolet (UV) radiation-induced graft copolymerization of styrene (35 vol.% concentration) onto poly(ethyleneterephthalate) (PET) film, followed by sulfonation on the styrene monomer units in the grafting chain using 0.05 M chlorosulfonic acid (ClSO₃H). The radiation grafting and the sulfonation have been confirmed by titrimetric and gravimetric analyses as well as Fourier Transform Infrared (FTIR) spectroscopy. The maximum ion-exchange capacity (IEC) of the PEM was measured to be 0.04385 mmol g⁻¹ at its highest level of grafting and sulfonation. They exhibited high thermal and mechanical properties as well as oxidative stability. They are highly stable in H₂SO₄ solutions and can be used in the acidic fuel cells. The membranes showed low water uptake as well as low proton conductivity than Nafion. In this study, the preparation of PEMs from commodity-type polymers is found to be very inexpensive and is a suitable candidate for applications in fuel cells.     

Polymer electrolyte membranes containing titanate nanotubes for elevated temperature fuel cells under low relative humidity

Nafion-titanate nanotubes composite membranes prepared through casting process have been investigated as electrolytes for polymer electrolyte membrane fuel cell applications under low relative humidity. The glass transition temperature and the decomposition temperature of composite membrane at dry state are higher than those of pristine Nafion membrane. Cracks have been observed in the membrane at the concentration of nanotubes above 5 wt.%. The maximum proton conductivity at 100 °C and 50% relative humidity is observed with the concentration of doped titanate nanotubes of 5 wt.%. Solid nuclear magnetic resonance spectrum is applied to qualitatively characterize the status of water inside the membrane at different temperatures. The power densities at 0.8 V for cell assembled from composite membrane containing 5 wt.% of titanate nanotubes are about 13% and 35% higher than that for plain Nafion cells under 50% relative humidity at 65 °C and 90 °C, respectively.     

Novel aryloxy-polybenzimidazoles as proton conducting membranes for high temperature PEMFCs

Polybenzimidazole (PBI) is the material of choice to fabricate proton exchange membranes for high temperature PEMFCs. Among the most recent trends in the design of PBI polymers, we recall the introduction of oxygen atoms in the polymer backbone. In fact, the presence of ether groups improves the polymer solubility in polar solvents and, consequently, the membrane and MEA processability. In addition, it provides reactive points for functionalization processes and further chemical modifications. Here we reported on the synthesis and characterization of new arylether-based PBIs, and namely Poly 1,4-bis-(4-(1H,1′H-2,5′-bibenzo[d]imidazol-2′-yl)phenoxy)benzene and Poly 2′,2″-(4,4′-oxybis(4,1-phenylene))bis(1H,1′H-2,5′-bibenzo[d]imidazole), labelled in the following as PBI-108 and PBI-109, respectively. The polymers differ for the number of the ether-based spacers, which are one in case of PBI-108, and two for PBI-109. The H₃PO₄-doped membranes were characterised in terms of thermal and chemical stability, proton conductivity and fuel cell performances. In particular, the MEAs properties were investigated with respect to the acid doping level of the electrodes, temperature, pressure and gas flow rates.The monomer structure does not remarkably affect the electrochemical properties of the membranes. However, the PBI-109 membrane is chemically more stable in presence of oxy- and hydroxyl-free radicals with respect to PBI-108 and oxygen-free PBI systems. Proton conductivity of 8 mS cm⁻¹ was measured at 120 °C and RH = 50% in the case of aryloxy-PBI with the shorter spacer. The power density increases with temperature, pressure and air stoichiometry. Values as high as to 400 mW cm⁻¹ were measured at 150 °C, λ_air = 6 and a backpressure of 2 bar.     

Numerical study for in-plane gradient effects of cathode gas diffusion layer on PEMFC under low humidity condition

A numerical study about in-plane porosity and contact angle gradient effects of cathode gas diffusion layer (GDL) on polymer electrolyte membrane fuel cell (PEMFC) under low humidity condition below 50% relative humidity is performed in this work. Firstly, a numerical model for a fuel cell is developed, which considers mass transfer, electrochemical reaction, and water saturation in cathode GDL. For water saturation in cathode GDL, porosity and contact angle of GDL are also considered in developing the model. Secondly, current density distribution in PEMFC with uniform cathode GDL is scrutinized to design the gradient cathode GDL. Finally, current density distributions in PEMFC with gradient cathode GDL and uniform cathode GDL are compared. At the gas inlet side, the current density is higher in GDL with a gradient than GDL with high porosity and large contact angle. At the outlet side, the current density is higher in GDL with a gradient than GDL with low porosity and small contact angle. As a result, gradient cathode GDL increases the maximum power by 9% than GDL with low porosity and small contact angle. Moreover, gradient cathode GDL uniformizes the current density distribution by 4% than GDL with high porosity and large contact angle.     

Proton conducting sol-gel sulfonated membranes produced from 2-allylphenol, 3-glycidoxypropyl trimethoxysilane and tetraethyl orthosilicate

An important research area in proton exchange membrane fuel cells (PEMFC) is devoted to the development of low cost membranes able to work at temperatures higher than 100 °C. In this work, homogeneous, transparent and crack-free hybrid membranes have been synthesized using tetraethyl orthosilicate (TEOS), 3-glycidoxipropyl trimethoxysilane (GPTMS) and 2-allylphenol (AP) as precursors. The synthesis of proton conducting membranes was performed by a post-sulfonation method using trimethylsilyl chlorosulfonate as a mild sulfonating agent. The water retention properties provided by sulfonate and hydroxyl groups and the high porosity leads to relatively high proton conductivity (maximum values around 1.3 × 10⁻³ S cm⁻¹ at 140 °C and 100% RH) for membranes treated at 180 °C and sulfonated for 2 h.     

Chelating agent assisted heat treatment of carbon supported cobalt oxide nanoparticle for use as cathode catalyst of polymer electrolyte membrane fuel cell (PEMFC)

Cobalt-based catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cell (PEMFC) have been successfully incorporated cobalt oxide (Co₃O₄) onto Vulcan XC-72 carbon powder by thermal decomposition of Co-ethylenediamine complex (ethylenediamine, NH₂CH₂CH₂NH₂, denoted en) at 850 °C. The catalysts were prepared by adsorbing the cobalt complexes [Co(en)(H₂O)₄]³⁺, [Co(en)₂(H₂O)₂]³⁺ and [Co(en)₃]³⁺ on commercial XC-72 carbon black supports, loading amount of Co with respect to carbon black was about 2%, the resulting materials have been pyrolyzed under nitrogen atmosphere to create CoO_x/C catalysts, donated as E1, E2, and E3, respectively. The composite materials were characterized using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). Chemical compositions of prepared catalysts were determined using inductively-coupled plasma-atomic emission spectroscopy (ICP-AES). The catalytic activities for ORR have been analyzed by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The electrocatalytic activity for oxygen reduction of E2 is superior to that of E1 and E3. Membrane electrode assemblies (MEAs) containing the synthesized CoO_x/C cathode catalysts were fabricated and evaluated by single cell tests. The E2 cathode performed better than that of E1 and E3 cathode. This can be attributed to the enhanced activity for ORR, in agreement with the composition of the catalyst that CoO co-existed with Co₃O₄. The maximum power density 73 mW cm⁻² was obtained at 0.3 V with a current density of 240 mA cm⁻² for E2 and the normalized power density of E2 is larger than that that of commercial 20 wt.% Pt/C-ETEK.     

Cross-linked miscible blend membranes of sulfonated poly(arylene ether sulfone) and sulfonated polyimide for polymer electrolyte fuel cell applications

Cross-linked miscible blend (CMB) membranes were prepared from sulfonated poly(arylene ether sulfone) (SPAES) and sulfonated polynaphthalimide (SPI). They were transparent and insoluble in solvents. They showed the intermediate properties between SPAES and SPI concerning mechanical strength, water uptake, membrane swelling and proton conductivity. As for membrane swelling and proton conductivity, SPAES was almost isotropic, whereas SPI was highly anisotropic. CMB membranes were moderately anisotropic and had the advantages of the smaller in-plane membrane swelling and the larger through-plane conductivity compared to SPAES and SPI, respectively. Polymer electrolyte fuel cell performance of CMB2 membrane with an equal weight ratio of SPAES/SPI and an ion exchange capacity (IEC) of 1.74 meq g⁻¹ was investigated, compared to SPI membrane (R1) with a slightly higher IEC of 1.86 meq g⁻¹. At 90 °C, 0.1 MPa and relatively high humidification of 82/68% RH or 0.2 MPa and low humidification of 50-30% RH, CMB2 showed the reasonably high cell performances. At 110 °C and 50-33% RH, the cell performance was fairly high only at a high pressure of 0.3 MPa, but low at 0.2-0.15 MPa. At these conditions, the cell performance was better for CMB2 than for R1 due to the more effective back-diffusion of water formed at cathode into membrane. CMB2 showed the fairly high PEFC durability at 110 °C.