Energy material - the role of silicotungstic acid and fly ash in sulfonated poly (ether sulfone) composites for PEMFC applications

The composite polymer electrolyte membranes were prepared from sulfonated poly (ether sulfone) (SPES), silicotungstic acid (STA) and fly ash (FA). Post sulfonation process was adopted to synthesize SPES using sulphuric and chlorosulfonic acid. The prepared electrolyte membranes were examined by water uptake capacity, swelling ratio, ion-exchange ability, proton conductivity, thermal stability and electrochemical performance for evaluating the pertinence of these membranes in fuel cell applications. As such the pristine membrane restricts with the proton conductivity of 0.042?S cm^?1 at 30?°C and 0.060?S cm^?1 at 90?°C while the polymer composite membrane, SP-STA-FA-10 reveals the maximum conductivity of 0.054?S cm^?1 at 30?°C and 0.073?S cm^?1 at 90?°C. It also exhibits good thermal stability than that of the pure membrane. The membrane electrode assemblies (MEAs) have been successfully developed from SPES as well as SP-STA-FA-10 membranes and their electrochemical performance were studied the wide range of current density. Herein, the composite membranes derived from SPES, STA and FA can be viable candidates for fuel cell applications.     

Modification of hydrophilic channels in Nafion membranes by DMBA: Mechanism and effects on proton conductivity

Modification of proton conductive channels (PCCs) in Nafion has been achieved with the assistance of 3, 4‐dimethylbenzaldehyde (DMBA). During annealing, ionic clusters develop from small isolated spheres (1.72 nm) to wide continuous channels (5.15 nm), and the crystallinity of Nafion/DMBA membranes is also improved from 17% to 32% as shown by X‐ray diffraction. Molecular dynamic simulation reveals that hydrogen bonding and hydrophobic interaction between DMBA and Nafion work synergistically to achieve better phase separation. The morphology–property relationship shows that, versus various PCCs width, the corresponding proton conductivities vary greatly from 0.079 to 0.139 S/cm at 80 °C. By carefully tuning the width of PCCs, the proton conductivity shows an improvement of 22–34% as compared with pristine Nafion. A significant enhancement on the maximum power density is achieved for the membrane electrode assembly on Nafion/DMBA‐8h (as high as 1018 mW/cm^?2), yielding an enhancement of 39% on pristine Nafion‐8h (730 mW/cm^?2). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 52, 1107–1117     

Hydrogen‐Bonded Organic Frameworks (HOFs): A New Class of Porous Crystalline Proton‐Conducting Materials

Two porous hydrogen‐bonded organic frameworks (HOFs) based on arene sulfonates and guanidinium ions are reported. As a result of the presence of ionic backbones appended with protonic source, the compounds exhibit ultra‐high proton conduction values (σ) 0.75× 10^?2 S cm^?1 and 1.8×10^?2 S cm^?1 under humidified conditions. Also, they have very low activation energy values and the highest proton conductivity at ambient conditions (low humidity and at moderate temperature) among porous crystalline materials, such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). These values are not only comparable to the conventionally used proton exchange membranes, such as Nafion used in fuel cell technologies, but is also the highest value reported in organic‐based porous architectures. Notably, this report inaugurates the usage of crystalline hydrogen‐bonded porous organic frameworks as solid‐state proton conducting materials.     

Electrospun multi-scale nanofiber network: hierarchical proton-conducting channels in Nafion composite proton exchange membranes

In this study, a unique multi-scale nanofiber membrane prepared by electrospinning with adding the tetrabutylammonium chloride (TBAC)  was applied to proton exchange membrane for direct methanol fuel cell. Three types of multi-scale nanofiber membranes of cellulose acetate (CA), nylon 6 (PA6) and poly-m-phenyleneisophthalamide (PMIA) were carefully selected as effective conductive fillers to be incorporated into Nafion as composite membranes (T-CA-Nafion, T-PA6-Nafion and T-PMIA-Nafion). At 80 °C, the proton conductivity of the multi-scale nanofiber composite membranes could reach 0.192 S cm^?1 (T-CA-Nafion), 0.287 S cm^?1 (T-PA6-Nafion) and 0.225 S cm^?1 (T-PMIA-Nafion), which were higher than that of the ordinary nanofiber composite membrane. At the same time, the methanol permeability was also significantly reduced. The above superiorities could be attributed to the following aspects: Firstly, the unique multi-scale nanofiber structure could provide hierarchically consecutive long-range channels for proton conducting. Meanwhile, the hydrophilicity of TBAC additives made the membrane with high water-absorbing capacity, which could be beneficial to provide more water molecule carriers for proton conduction via the Vehicle mechanism. Moreover, the cross-linked nanofiber network can be acted as barriers to further hinder methanol penetration. Specifically, the –NH (amido bonds in the PA6 and PMIA) groups could be interconnected with –SO₃H groups in Nafion matrix via electrostatic attractions, leading to the formation of effective –NH^…–SO₃H pairs in the composite membrane. The effective acid–base pairs can facilitate the proton hopping through Grotthuss mechanism, which also well illustrated the better proton conducting behavior of the T-PA6-Nafion and T-PMIA-Nafion membranes.

     

Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006     

Crosslinking effects on hybrid organic–inorganic proton conducting membranes based on sulfonated polystyrene and polysiloxane

New hybrid semi‐interpenetrating proton‐conducting membranes were obtained using sulfonated polystyrene (SPS) and inorganic–organic polysiloxane phases with the aim of improving the mechanical and thermal characteristics of the pristine polymer and to study the effects of crosslinking in the latter phase in several of their properties, mainly proton conductivity. Siloxane phases were prepared using poly(dimethylsiloxane) (PDMS) and PDMS with tetraethoxysilane (TEOS) or phenyltrimethoxysilane (PTMS) as crosslinking agents. To study the crosslinking effect, membranes were prepared with different TEOS:PDMS and PTMS:PDMS mole ratios. The films obtained were characterized by FTIR, ²⁹Si‐HPDEC MAS‐NMR, ¹³C‐CP‐MAS NMR, elemental and thermal analyses. Certain properties, such as water uptake (WU), ion exchange capacity (IEC) and the state of the water, were determined. The proton conductivity was measured at different temperatures (30°C and 80°C) and relative humidities (50–95%). The water content of the hybrid membranes declined significantly, compared with the SPS membranes, depending on the nature and amount of siloxane phase added. Nonetheless, the conductivity values remained relatively high (>100 mS cm^?1 at 80°C and 95% RH) when compared to Nafion®117 presumably because of the formation of well developed proton channels, which makes them potentially promising as proton exchange membranes for fuel cells. These membranes proved to be thermally stable up to 350°C. Scanning electron microscopy (SEM) and scanning electrochemical microscopy (SECM) were used to characterize the hybrid membranes microstructures; the latter provided contrast for the conductive domains. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and Characterization of Phenolphthalein‐Containing Sulfonated Poly(arylene ether phosphine oxide)s by Direct Polycondensation for Proton Exchange Membrane

A series of novel phenolphthalein‐containing sulfonated poly(arylene ether phosphine oxide)s (sPAEPP) with various sulfonation degrees were synthesized by direct polycondensation. The structure of sPAEPP was confirmed by ¹H‐NMR, ¹³C‐NMR, and IR spectroscopy. The high‐molecular weight of these polymers was determined by gel permeation chromatography (GPC). The transparent, tough, and flexible membranes could be achieved by solution casting. The macroscopic properties and microstructure of the obtained membranes were investigated in detail. The results showed that these sPAEPP membranes displayed excellent properties in terms of swelling, proton conductivity, and methanol permeability. For example, sPAEPP‐100 membrane exhibited an appropriate water uptake of 33.1%, a swelling ratio of only 11.7% (lower than 20.1% of Nafion 117), a proton conductivity of 0.11 S cm^?1 (similar to that of Nafion 117) at 80 °C, and a methanol permeability of 4.82 × 10^?7 cm² s^?1. Meanwhile, it also presented outstanding oxidative stability. Atomic force microscope (AFM) micrographs showed that the hydrophilic domains of the sPAEPP‐100 membrane formed connected and narrow ionic channels, which contributed to its high proton conductivity and good dimensional stability. As a result, sPAEPP‐100 membrane displays excellent application prospect for fuel cells. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1097–1104     

Synthesis and properties of novel polyimides from sulfonated binaphthalene dianhydride for proton exchange membranes

A sulfonated dianhydride monomer, 6,6′‐disulfonic‐4,4′‐binaphthyl‐1,1′,8,8′‐tetracarboxylic dianhydride (SBTDA), was successfully synthesized by direct sulfonation of the parent dianhydride, 4,4′‐binaphthyl‐1,1′,8,8′‐tetracarboxylic dianhydride (BTDA), using fuming sulfuric acid as the sulfonating reagent. A series of sulfonated homopolyimides were prepared from SBTDA and various common nonsulfonated diamines. The resulting polymer electrolytes, which contain ion conductivity sites on the deactivated positions of the aryl backbone rings, displayed high proton conductivities of 0.25–0.31 S cm^?1 at 80 °C. The oxidative stability test indicated that the attachment of the ? SO₃H groups onto the dianhydride units did not deteriorate the oxidative stability of the SPI membranes. The better membranes were achieved by the copolymerization of nonsulfonated diamine, SBTDA, and BTDA. Copolymer membrane synthesized from hexane‐1,6‐diamine, SBTDA, and BTDA displayed excellent water stability of more than 1000 h at 90 °C, while its proton conductivity was still at a high level (comparable to that of Nafion 117). Furthermore, the novel block copolymer ( II‐b ) displayed higher proton conductivity compared with the random one ( II‐r ) obviously, probably due to the slightly higher water uptake and better microphase separated morphology. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2820–2832, 2008     

Highly proton conducting proton‐exchange membranes based on fluorinated poly(arylene ether ketone)s with octasulfonated segments

A new bisphenol monomer containing a pair of electron‐rich tetra‐arylmethane units was designed and synthesized. Based on this monomer, along with commercial 4,4′‐(hexafluoroisopropylidene)diphenol A and 4,4′‐difluorobenzophenone, a series of novel poly(arylene ether ketone)s containing octasulfonated segments of varying molar percentage (x) (6F‐SPAEK‐x) were successfully synthesized by polycondensation reactions, followed by sulfonation. Tough, flexible, and transparent membranes, exhibiting excellent thermal stabilities and mechanical properties were obtained by casting. 6F‐SPAEK‐x samples exhibited appropriate water uptake and swelling ratios at moderate ion exchange capacities (IECs) and excellent proton conductivities. The highest proton conductivity (215 mS cm⁻¹) is observed for hydrated 6F‐SPAEK‐15 (IEC = 1.68 meq g⁻¹) at 100 °C, which is more than 1.5 times that of Nafion 117. Furthermore, the 6F‐SPAEK‐10 membrane exhibited comparable proton conductivity (102 mS cm⁻¹) to that of Nafion 117 at 80 °C, with a relatively low IEC value (1.26 meq g⁻¹). Even under 30% relative humidity, the 6F‐SPAEK‐20 membrane (2.06 meq g⁻¹) showed adequate conductivity (2.1 mS cm⁻¹) compared with Nafion 117 (3.4 mS cm⁻¹). The excellent comprehensive properties of these membranes are attributed to well‐defined nanophase‐separated structures promoted by strong polarity differences between highly ionized and fluorinated hydrophobic segments. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 25–37     

Structural modification of chitosan biopolymer as a novel polyelectrolyte membrane for green power generation

In the present study, a series of bioresource polyelectrolytes based on chitosan were synthesized and assessed for applicability in direct methanol fuel cells (DMFCs). A binary cross‐linking agent (sulfosuccinic acid/glutaraldehyde) was used for the structural modification of chitosan and membranes comprising various amounts of sulfosuccinic acid (0, 8, 12, and 16 wt% SSA/wt chitosan) were prepared. It was found that by increasing the sulfonate groups' content up to 16 wt%, proton conductivity and methanol permeability properties reach the values of 0.0452 S cm^?1 and 9.6 × 10^?7 cm² sec^?1, respectively. Based on the membrane selectivity evaluation and activation energy measurements of proton conduction, the optimum composition of cross‐linking agent was determined. The optimum composition resulted in a relatively high proton conductivity of 0.0452 S cm^?1 and a low methanol permeability of 9.6 × 10^?7 cm² sec^?1. Moreover, the optimum proton exchange membrane exhibited selectivity value of 47,100 in comparison with the corresponding value of 40,500 for Nafion® 117. The fabricated membranes showed acceptable oxidative and hydrolytic stability. Furthermore, single cell DMFC performance test revealed a power density of 17 mW cm^?2 at 30°C and 41 mW cm^?2 at 60°C in a 2 M methanol feed. Hence, prepared proton‐conducting bioresource ionomers could have promising potential in the field of green power generation as a low cost and biodegradable polyelectrolyte. Copyright © 2009 John Wiley & Sons, Ltd.     

Property improvement of nanocellulose‐reinforced proton exchange nanocomposite membrane coated with tetraethyl orthosilicate

Study on proton exchange membrane (PEM) with the aim toward excellent battery performance of PEM for fuel cells has attracted increasing attention. In this work, nanocellulose (CNC) aminated by KH792 noted as NN was prepared. CNC or NN/sulfophenylated poly(ether ether ketone ketone) (sPEEKK) nanocomposite membrane (SN) or (SNN) were produced by solution mixing. SNN was further coated with tetraethyl orthosilicate (TEOS) to obtain SNNT. The properties of sPEEKK, SN, SNN, and SNNT membranes were thoroughly investigated. The proton conductivity of SN4 was 0.22 S·cm^?1 at 90 °C, while a proton conductivity of 0.30 S·cm^?1 was obtained for SNN4, and an even higher value of 0.36 S·cm^?1 at 90 °C was obtained for the TEOS‐coated SNN4 (SNN4T). Meanwhile, SNN4T showed high thermal stability, and its T_d5 was as high as 318.2 °C. Furthermore, the composite membrane coated with TEOS also presented excellent oxidative stability. The mass of SNN2T after treated in Fenton agent for 1 h at 80 °C was still retained 96.2%, and it was not fully dissolved until 11 h. It was illustrated that aminated CNC/sPEEKK nanocomposite membranes coated with TEOS is a kind of promising materials as PEMs for fuel cells. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2190–2200     

Enhanced proton conductivity of polymer electrolyte membrane doped with titanate nanotubes

Nafion-titanate nanotubes composite membranes were prepared through a casting process. With the addition of 5 wt.%, the nanotubes were homogenously distributed in Nafion solution. The formed composite membrane showed a comparable mechanical strength to Nafion membrane. The proton conductivity of the composite membrane without external humidification is higher than that of the Nafion membrane, reaching 0.034 Scm^?1 and 0.01 Scm^?1 at 100 °C and 120 °C, respectively. The improved proton conductivity was attributed to the great water retention ability of the doped nanotubes.     

Optimal method for preparing sulfonated polyaryletherketones with high ion exchange capacity by acid-catalyzed crosslinking for proton exchange membrane fuel cells

Sulfonated polyaryletherketones (SPAEK) bearing four sulfonic acid groups on the phenyl side groups were synthesized. The benzophenone moiety of polymer backbone was further reduced to benzydrol group with sodium borohydride. The membranes were crosslinked by acid-catalyzed Friedel-Crafts reaction without sacrifice of sulfonic acid groups and ion exchange capacity (IEC) values. Crosslinked membranes with the same IEC value but different water uptake could be prepared. The optimal crosslinking condition was investigated to achieve lower water uptake, better chemical stability (Fenton's test), and higher proton conductivity. In addition, the hydrophilic ionic channels from originally course and disordered could be modified to be narrow and continuous by this crosslinking method. The crosslinked membranes, CS4PH-40-PEKOH (IEC = 2.4 meq./g), reduced water uptake from 200 to 88% and the weight loss was reduced from 11 to 5% during the Fenton test compared to uncrosslinked one (S4PH-40-PEK). The membrane showed comparable proton conductivity (0.01–0.19 S/cm) to Nafion 212 at 80°C from low to high relative humidity (RH). Single H₂/O₂ fuel cell based on the crosslinked SPAEK with catalyst loading of 0.25 mg/cm² (Pd/C) exhibited a peak power density of 220.3 mW/cm², which was close to that of Nafion 212 (214.0 mW/cm²) at 80°C under 53% RH. These membranes provide a good option as proton exchange membrane with high ion exchange capacity for fuel cells.     

Synthesis and properties of novel sulfonated (co)polyimides bearing sulfonated aromatic pendant groups for PEFC applications

Novel sulfonated diamines bearing aromatic pendant groups, namely, 3,5‐diamino‐3′‐sulfo‐4′‐(4‐sulfophenoxy) benzophenone (DASSPB) and 3,5‐diamino‐3′‐sulfo‐4′‐(2,4‐disulfophenoxy) benzophenone (DASDSPB), were successfully synthesized. Novel side‐chain‐type sulfonated (co)polyimides (SPIs) were synthesized from these two diamines, 1,4,5,8‐naphthalene tetracarboxylic dianhydride (NTDA) and nonsulfonated diamines such as 4,4′‐bis(3‐aminophenoxy) phenyl sulfone (BAPPS). Tough and transparent membranes of SPIs with ion exchange capacity of 1.5–2.9 meq g^?1 were prepared. They showed good solubility and high thermal stability up to 300 °C. They showed isotropic membrane swelling in water, which was different from the main‐chain‐type and sulfoalkoxy‐based side‐chain‐type SPIs. The relative humidity (RH) and temperature dependence of proton conductivity were examined. At low RH, the novel SPI membranes showed much higher conductivity than the sulfoalkoxy‐based SPIs. They showed comparable or even higher proton conductivity than Nafion 112 in water at 60 °C (>0.10 S cm^?1). The membrane of NTDA‐DASDSPB/BAPPS (1/1)‐s displayed reasonably high proton conductivities of 0.05 and 0.30 S cm^?1 at 50 and 100% RH, respectively, at 120 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2862–2872, 2006     

Phosphoric acid‐doped imidazolium ionomers with enhanced stability for anhydrous proton‐exchange membrane applications

Phosphoric acid‐doped crosslinked proton‐conducting membranes with high anhydrous proton conductivity, and good chemical stability in phosphoric acid were synthesized and characterized. The synthetic procedure of the acid‐doped composite membranes mainly involves the in situ crosslinking of polymerizable monomer oils (styrene and acrylonitrile) and vinylimidazole, and followed by the sulfonation of pendant imidazole groups with butanesultone, and further doped with phosphoric acid. The resultant phosphoric acid‐doped composite electrolyte membranes are flexible and show high thermal stability and high‐proton conductivity up to the order of 10^?2 S cm^?1 at 160 °C under anhydrous conditions. The phosphoric acid uptake, swelling degree, and proton conductivity of the composite membranes increase with the vinylimidazole content. The resultant composite membranes also show good oxidative stability in Fenton's reagent (at 70 °C), and quite good chemical stability in phosphoric acid (at 160 °C). The properties of the prepared electrolyte membranes indicate their promising prospects in anhydrous proton‐exchange membrane applications. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013 , 51, 1311–1317     

Synthesis and characterization of poly(arylene ether ketone)s bearing pendant sulfonic acid groups for proton exchange membrane materials

A bisphenol monomer (2,5‐dimethoxy)phenylhydroquinone was prepared and further polymerized to obtain poly(arylene ether ketone) copolymers containing methoxy groups. After demethylation and sulfobutylation, a series of novel poly(arylene ether ketone)s bearing pendant sulfonic acid group (SPAEKs) with different sulfonation content were obtained. The chemical structures of all the copolymers were analyzed by ¹H NMR and ¹³C NMR spectra. Flexible and tough membranes with reasonably good mechanical properties were prepared. The resulting side‐chain‐type SPAEK membranes showed good dimensional stability, and their water uptake and swelling ratio were lower than those of conventional main‐chain‐type SPAEK membranes with similar ion exchange capacity. Proton conductivities of these side‐chain‐type sulfonated copolymers were higher than 0.01 S/cm and increased gradually with increasing temperature. Their methanol permeability values were in the range of 1.97 × 10^?7–5.81 × 10^?7 cm²/s, which were much lower than that of Nafion 117. A combination of suitable proton conductivities, low water uptake, low swelling ratio, and high methanol resistance for these side‐chain‐type SPAEK films indicated that they may be good candidate material for proton exchange membrane in fuel cell applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Multiblock poly(Phenylene ether nitrile)s with pendant sulfoalkoxyl side chain for H2/air fuel cells at low humidity condition

A series of multiblock poly(phenylene ether nitrile)s with pendant sulfoalkoxyl side chains have been developed as proton exchange membranes for fuel cells. The membranes were obtained by a solution casting method and exhibited good thermal stability, flexibility, and mechanical strength. The membranes displayed well‐developed microphase separation, which largely contributed to their excellent ion conduction ability. One of the new membranes with a low ion exchange capacity of 1.57 mequiv g^?1 showed higher proton conductivity than Nafion 212 over the entire RH range (30–95%). The maximum power output generated in a single cell test reached up to 0.754, 0.640, and 0.414 W cm^?2 at 70 °C under 80%, 50%, and 30% RH conditions, respectively. The current density of the membrane obtained at 0.6 V (I _0.6) was as high as 640 mA cm^?2, which was much higher than that of Nafion 212 (375 mA cm^?2 at 30% RH), suggesting its superiority for a more rapid system start‐up. Furthermore, the in situ durability test at 50% RH was performed at a constant current loading, and the membrane did not show any significant voltage reduction over the 400 h testing period. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1940–1948     

Magnetic field‐induced alignment of polybenzimidazole microstructures to enhance proton conduction

Aligned polymer microstructures in the field of biomaterials, semiconductors, and ion‐conductive membranes expand steadily. Here, an alternative aligned polybenzimidazole (WM PBI) microstructures fabrication strategy based on the utilization of a weak magnetic field (0.3 T) via the solvent casting method is demonstrated. The anisotropic alignment is induced by the interaction of the π‐electron‐rich structure with the magnetic field. A ripple‐like structure was observed in the field‐emission scanning electron microscopy image for the WM PBI membrane, which depicted the successful alignment of the PBI structure toward magnetic field direction. Electrochemical studies revealed the bulk resistance of WM PBI with only 13.71 × 10³ Ω compared to the unaligned PBI (WOM PBI) (63.01 × 10³ Ω). WM PBI marked as the highest proton conductivity of 610.66 × 10^?6 S cm^?1, and it was proven that the external magnetic field does bring the impact toward the augmentation of the proton conductivity, which is useful in various future generation applications.     

Comparison of Electrochemical Synthesis of Ammonia by Using Sulfonated Polysulfone and Nafion Membrane with Sm1.5Sr0.5NiO4

Polysulfone (PSF) and sulfonated polysulfone (SPSF) were synthesized and characterized by IR spectrum. Sm_1.5Sr_0.5NiO₄ (SSN) and Ni‐Ce_0.8Sm_0.2O_2?δ (Ni‐SDC, Ni‐samarium doped ceria) were prepared and characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Ammonia was synthesized from wet hydrogen and dry nitrogen with applied voltage, using SSN as cathode, Ni‐SDC as anode, Nafion and SPSF as proton membrane respectively. The performances of Nafion and SPSF membranes in ammonia synthesis were investigated and compared at atmospheric pressure and low temperature (25–100°C). The results demonstrated that the proton conducting performances of Nafion and SPSF membranes were similar and the highest rates of evolution of ammonia were up to 1.05×10^?8 and 1.03×10^?8 mol·cm^?2·s^?1 respectively at 80°C and 2.5 V.     

Synthesis and Characterization of Sulfonated Polyimides Containing Trifluoromethyl Groups as Proton Exchange Membranes

A novel sulfonated diamine, 4,4′‐bis(4‐amino‐3‐trifluoromethylphenoxy) biphenyl 3,3′‐disulfonic acid (F‐BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4′‐dihydroxybiphenyl with 2‐chloro‐5‐nitrobenzotrifluoride, followed by reduction and sulfonation. A series of sulfonated polyimides of high molecular weight (SPI‐x, x represents the molar percentage of the sulfonated monomer) were prepared by copolymerization of 1,4,5,8‐naphathlenetetracarboxylic dianhydride (NTDA) with F‐BAPBDS and nonsulfonated diamine. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The copolymer membranes exhibited excellent oxidative stability due to the introducing of the CF₃ groups. The SPI membranes displayed desirable proton conductivity (0.52×10⁻¹–0.97×10⁻¹ S·cm⁻¹) and low methanol permeability (less than 2.8×10⁻⁷ cm²·s⁻¹). The highest proton conductivity (1.89×10⁻¹ S·cm⁻¹) was obtained for the SPI‐90 membrane at 80°C, with an IEC of 2.12 mequiv/g. This value is higher than that of Nafion 117 (1.7×10⁻¹ S·cm⁻¹). Furthermore, the hydrolytic stability of the obtained SPIs is better than the BDSA and ODADS based SPIs due to the hydrophobic CF₃ groups which protect the imide ring from being attacked by water molecules, in spite of its strong electron‐withdrawing behaviors.