Sulfonated poly(ether ether ketone) membranes with sulfonated graphene oxide fillers for direct methanol fuel cells

Sulfonated organosilane functionalized graphene oxides (SSi-GO) synthesized through the grafting of graphene oxide (GO) with 3-mercaptopropyl trimethoxysilane and subsequent oxidation have been used as a filler in sulfonated poly(ether ether ketone) (SPEEK) membranes. The incorporation of SSi-GOs greatly increases the ion-exchange capacity (IEC), water uptake, and proton conductivity of the membrane. With well-controlled contents of SSi-GOs, the composite membranes exhibit higher proton conductivity and lower methanol permeability than Nafion^® 112 and Nafion^® 115, making them particularly attractive as proton exchange membranes (PEMs) for direct methanol fuel cells (DMFC). The composite membrane with optimal SSi-GOs content exhibit over 38 and 17% higher power densities, respectively, than Nafion^® 112 and Nafion^® 115 membranes in DMFCs, offering the possibilities to reduce the DMFC membrane cost significantly while keeping high-performance.     

Nafion/nitrated sulfonated poly(ether ether ketone) membranes for direct methanol fuel cells

Sulfonated poly(ether ether ketone)s (SPEEKs) are substituted on the main chain of the polymer by nitro groups and blended with Nafion^® to attain composite membranes. The sulfonation, nitration and blending are achieved with a simple, inexpensive process, and the blended membranes containing the nitrated SPEEKs reveal a liquid-liquid phase separation. The blended membranes have a lower water uptake compared to recast Nafion^®, and the methanol permeability is reduced significantly to 4.29 × 10⁻⁷-5.34 × 10⁻⁷ cm² s⁻¹ for various contents of nitrated SPEEK for S63N17, and 4.72 × 10⁻⁷-7.11 × 10⁻⁷ cm² s⁻¹ for S63N38, with a maximum proton conductivity of ∼0.085 S cm⁻¹. This study examines the single-cell performance at 80 °C of Nafion^®/nitrated SPEEK membranes with various contents of nitrated SPEEK and a degree of nitration of 23-25 mW cm⁻² for S63N17 and 24-29 mW cm⁻² for S63N38. Both the power density and open circuit voltage are higher than those of Nafion^® 115 and recast Nafion^®.     

Preparation of nitrated sulfonated poly(ether ether ketone) membranes for reducing methanol permeability in direct methanol fuel cell applications

Sulfonated poly(ether ether ketone)s (SPEEKs) were further substituted on the polymer main chain by nitration. All sulfonation and nitration were achieved with an inexpensive and simple post substitute reaction. The nitrated SPEEKs have a high glass transition temperature and thermal decomposition temperature, and a lower water uptake than SPEEK, which provides sufficient mechanical strength without swelling in the direct methanol fuel cell (DMFC) application. The methanol permeability of nitrated SPEEKS is reduced to 1.76 × 10⁻⁷ cm² s⁻¹ for S53N22 and 1.86 × 10⁻⁷ cm² s⁻¹ for S63N17 with no loss of conductivity in the DMFC application, and a proton conductivity that reached 0.026 S cm⁻¹. The nitrated SPEEK membranes satisfy the requirements of proton-exchange membranes for the DMFC.     

Crosslinked sulfonated poly(ether ether ketone) proton exchange membranes for direct methanol fuel cell applications

In the present study, a series of the crosslinked sulfonated poly(ether ether ketone) (SPEEK) proton exchange membranes were prepared. The photochemical crosslinking of the SPEEK membranes was carried out by dissolving benzophenone and triethylamine photo-initiator system in the membrane casting solution and then exposing the resulting membranes after solvent evaporation to UV light. The physical and transport properties of crosslinked membranes were investigated. The membrane performance can be controlled by adjusting the photoirradiation time. The experimental results showed that the crosslinked SPEEK membranes with photoirradiation 10 min had the optimum performance for proton exchange membranes (PEMs). Compared with the non-crosslinked SPEEK membranes, the crosslinked SPEEK membranes with photoirradiation 10 min markedly improved thermal stabilities and mechanical properties as well as hydrolytic and oxidative stabilities, greatly reduced water uptake and methanol diffusion coefficients with only slight sacrifice in proton conductivities. Therefore, the crosslinked SPEEK membranes with photoirradiation 10 min were particularly promising as proton exchange membranes for direct methanol fuel cell (DMFC) applications.     

The effective methanol-blocking and proton conductivity membranes based on sulfonated poly (ether ether ketone ketone) and polyorganosilicon with functional groups

To solve the conflict between high proton conductivity and low methanol crossover of pristine sulfonated aromatic polymer membranes, the polyorganosilicon doped sulfonated poly (ether ether ketone ketone) (SPEEKK) composite membranes were prepared by introducing polyorganosilicon additive with various functional groups into SPEEKK in this study. Scanning electron microcopy (SEM) images showed the obtained membranes were compact. No apparent agglomerations, cracks and pinholes were observed in the SEM images of composite membranes. The good compatibility between polymer and additive led to the interconnection, thus producing new materials with great characteristics and enhanced performance. Besides, the dual crosslinked structure could be formed in composite membranes through the condensation of silanols and the strong interaction between matrix and additive. The formation of dual crosslinked structure optimized the water absorption, enhanced the hydrolytic stability and oxidative stability of membranes. Especially, the incorporation of additive improved the strength and flexibility of composite membranes at the same time, meaning that the life of the composite membranes might be extended during the fuel cell operation. Meanwhile, the proton conductivity improved with increasing additive content due to the loading of more available acidic groups. It is noteworthy that at 25% additive loading, the proton conductivity reached a maximum value of 5.4 × 10⁻² S cm⁻¹ at 25 °C, which exceeded the corresponding value of Nafion^@ 117 (5.0 × 10⁻² S cm⁻¹) under same experimental conditions. The composite membrane with 20 wt% additive was found to produce the highest selectivity (1.22 × 10⁵ S cm⁻³) with proton conductivity of 4.70 × 10⁻² S cm⁻¹ and methanol diffusion coefficient of 3.85 × 10⁻⁷ cm² s⁻¹, suggesting its best potential as proton exchange membrane for direct methanol fuel cell application. The main novelty of our work is providing a feasible and environment-friendly way to prepare the self-made polyorganosilicon with various functional groups and introducing it into SPEEKK to fabricate the dual crosslinked membranes. This design produces new materials with outstanding performance.     

Preparation of main-chain-type and side-chain-type sulfonated poly(ether ether ketone) membranes for direct methanol fuel cell applications

Novel main-chain-type and side-chain-type sulphonated poly(ether ether ketone)s (MS-SPEEKs) are synthesised by reacting the sulphonic acid groups of pristine SPEEKs with 2-aminoethanesulphonic acid to improve the nano-phase separated morphology of the material. ¹H NMR and FT-IR spectroscopy are employed to determine the structure and composition of main-chain-type and side-chain-type sulphonated polymers. Flexible and tough membranes with reasonable thermal properties are obtained. The MS-SPEEKs show good hydrolytic stability, and water uptake values ranging from 15% to 30% are observed. Compared to Nafion 117^®, the methanol permeability of the MS-SPEEKs is dramatically reduced to 8.83 × 10⁻⁸ cm² s⁻¹ to 3.31 × 10⁻⁷ cm² s⁻¹. The proton conductivity increases with increasing temperature, reaching 0.013-0.182 S cm⁻¹. A maximum power density and open circuit voltage of 115 mW cm⁻² and 0.830 V are obtained at 80 °C, respectively, which is significantly greater than the values generated with Nafion 117^®. The introduction of pendent side-chain-type sulphonic acid groups increases the single-cell performance by more than approximately 20%; thus, the lower water diffusivity, methanol permeability, electro-osmotic drag coefficient and high cell performance indicated that MS-SPEEK is a promising candidate for DMFC applications.     

Synthesis and characterization of proton exchange membranes based on sulfonated poly(fluorenyl ether nitrile oxynaphthalate) for direct methanol fuel cells

A series of sulfonated poly(fluorenyl ether nitrile oxynaphthalate) (SPFENO) copolymers with different degree of sulfonation (DS) are synthesized via nucleophilic polycondensation reactions with commercially available monomers. Incorporation of the naphthalanesulfonate group into the copolymers and their copolymer structures are confirmed by ¹H NMR spectroscopy. Thermal stability, mechanical properties, water uptake, swelling behavior, proton conductivity and methanol permeability of the SPFENO membranes are investigated with respect to their structures. The electrochemical performance of a direct methanol fuel cell (DMFC) assembled with the SPFENO membrane was evaluated and compared to a DMFC with a Nafion 117 membrane. The DMFC assembled with the SPFENO membrane of proper DS exhibits better electrochemical performance compared to the Nafion 117-based cell.     

Improving the proton conductivity of sulfonated poly (ether ether ketone) membranes by incorporating a crystalline nanoassembly of trimesic acid and melamine

A novel proton exchange membrane was synthesized by embedding a crystalline which was nano-assembled through trimesic acid and melamine (TMA·M) into the matrix of the sulfonated poly (ether ether ketone) (SPEEK) to enhance the proton conductivity of the SPEEK membrane. Fourier transform infrared indicated that hydrogen bonds existed between SPEEK and TMA·M. XRD and SEM indicated that TMA·M was uniformly distributed within the matrix of SPEEK, and no phase separation occurred. Thermogravimetric analysis showed that this membrane could be applied as high temperature proton exchange membrane until 250 °C. The dimensional stability and mechanical properties of the composite membranes showed that the performance of the composite membranes is superior to that of the pristine SPEEK. Since TMA·M had a highly ordered nanostructure, and contained lots of hydrogen bonds and water molecules, the proton conductivity of the SPEEK/TMA·M-20% reached 0.00513 S cm⁻¹ at 25 °C and relative humidity 100%, which was 3 times more than the pristine SPEEK membrane, and achieved 0.00994 S cm⁻¹ at 120 °C.     

Sulfonated poly(ether ether ketone) as an ionomer for direct methanol fuel cell electrodes

Sulfonated poly(ether ether ketone) has been investigated as an ionomer in the catalyst layer for direct methanol fuel cells (DMFC). The performance in DMFC, electrochemical active area (by cyclic voltammetry), and limiting capacitance (by impedance spectroscopy) have been evaluated as a function of the ion exchange capacity (IEC) and content (wt.%) of the SPEEK ionomer in the catalyst layer. The optimum IEC value and SPEEK ionomer content in the electrodes are found to be, respectively, 1.33 meq. g⁻¹ and 20 wt.%. The membrane-electrode assemblies (MEA) fabricated with SPEEK membrane and SPEEK ionomer in the electrodes are found to exhibit superior performance in DMFC compared to that fabricated with Nafion ionomer due to lower interfacial resistance in the MEA as well as larger electrochemical active area. The MEAs with SPEEK membrane and SPEEK ionomer also exhibit better performance than that with Nafion 115 membrane and Nafion ionomer due to lower methanol crossover and better electrode kinetics.     

Layer-by-layer self-assembly of polyaniline on sulfonated poly(arylene ether ketone) membrane with high proton conductivity and low methanol crossover

Sulfonated poly(arylene ether ketone) bearing carboxyl groups (SPAEK-C) membranes were first modified by alternating deposition of oppositely charged polyaniline (PANI) and phosphotungstic acid (PWA) via the layer-by-layer method in order to prevent the crossover of methanol in a direct methanol fuel cell. The methanol permeability of SPAEK-C–(PANI/PWA)₅ is 2 orders of magnitude less than those of Nafion 117 and pristine SPAEK-C. Furthermore, the modified membrane shows a proton conductivity of 0.093 Scm⁻¹ at 25 °C and 0.24 Scm⁻¹ at 80 °C, which are superior to those of Nafion 117 and pristine SPAEK-C. Fourier transform infrared spectroscopy confirms that PANI and PWA are assembled in the multilayers. The SEM images show the presence of thin PANI/PWA layers coated on the SPAEK-C membrane. Thermal stability, water uptake, water swelling, proton and electron conductivity at different temperature of the SPAEK-C and SPAEK-C-(PANI/PWA)_n membranes are also investigated.     

Cross-linked membranes based on sulfonated poly (ether ether ketone) (SPEEK)/Nafion for direct methanol fuel cells (DMFCs)

A series of cross-linked membranes based on SPEEK/Nafion have been prepared to improve methanol resistance and dimension stability of SPEEK membrane for the usage in the direct methanol fuel cells (DMFCs). Sulfonated diamine monomer is synthesized and used as cross-linker to improve the dispersion of Nafion in the composite membranes and decrease the negative effect of cross-linking on proton conductivity of membranes. FT-IR analysis shows that the cross-linking reaction is performed successfully. The effects of different contents of Nafion on the properties of cross-linked membranes are investigated in detail. All the cross-linked membranes show lower methanol permeability and better dimensional stability compared with the pristine SPEEK membrane. SPEEK-N30 with the 30 wt % Nafion shows a methanol permeability of 0.73 × 10⁻⁶ cm² s⁻¹ and a water uptake of 24.4% at 25 °C, which are lower than those of the pristine membrane. Meanwhile, the proton conductivity of SPEEK-N30 still remains at 0.041 S cm⁻¹ at 25 °C, which is comparable to that of the pristine SPEEK membrane. All the results indicate that these cross-linked membranes based on SPEEK/Nafion show good prospect for the use as proton exchange membranes.     

SPEEK/sulfonated cyclodextrin blend membranes for direct methanol fuel cell

In this paper, the blend membranes based on sulfonated poly(ether ether ketone) and sulfonated cyclodextrin as the proton conducting membranes for DMFCs usage are prepared and investigated. The incorporation of sulfonated cyclodextrin in SPEEK membranes is evaluated by the characteristic absorptions of FT-IR spectra. Thermal stability and micro-morphology of the blend membranes are determined by thermogravimetry analysis and scanning electron microscope tests. The properties of the blend membranes are investigated such as swelling behavior, methanol permeability and proton conduction as function of the fraction of sulfonated cyclodextrin. The methanol crossover could be suppressed by the incorporation of sulfonated cyclodextrin and the methanol permeability decreases when the methanol concentration increases from 2.5 M to 20 M. Proton conduction is also promoted by the introduction of sulfonated cyclodextrin and the proton conductivity increases with the increase of sulfonated cyclodextrin content. The calculated activation energy for proton conduction of the blend membranes is very low and the maximum value is 4.20 kJ mol⁻¹, which is much lower than that of Nafion 115 (9.15 kJ mol⁻¹, measured in our experiments). These data indicate that proton can transport easily through the blend membranes. The selectivity of the blend membranes, a compromise between proton conductivity and methanol permeability, is much higher than that of Nafion 115 at the sulfonated cyclodextrin content above 15 wt.%. The blend membranes with 15, 20, and 25 wt.% of sulfonated cyclodextrin are assembled in the practical DMFCs and their polarization curves with 2.5 M and 8.0 M methanol solution are determined, respectively. The membrane with 20 wt.% sulfonated cyclodextrin reaches the highest power density of 29.52 mW cm⁻² at 120 mA cm⁻² and 8.0 M methanol solution. These results suggest the potential usage of the SPEEK membranes incorporating with sulfonated cyclodextrin in DMFCs.     

A facile approach to prepare self-cross-linkable sulfonated poly(ether ether ketone) membranes for direct methanol fuel cells

Sulfonated poly(ether ether ketone) containing hydroxyl groups (SPEEK-OH) has been prepared for use as a proton exchange membrane (PEM) by reducing the carbonyl groups on the main chain of the polymers. With the goal of reducing water uptake and methanol permeability, a facile thermal-cross-linking process is used to obtain the cross-linked membranes. The properties of the cross-linked membranes with different cross-linked density are measured and compared with the pristine membrane. Notably, SPEEK-4 with the highest cross-linked density shows a water uptake of 39% and a methanol permeability of 2.52 × 10⁻⁷ cm² s⁻¹, which are much lower than those of the pristine membrane (63.2% and 5.37 × 10⁻⁷ cm² s⁻¹, respectively). These results indicate that this simple approach is very effective to prepare cross-linked proton exchange membranes for reducing water uptake and methanol permeability.     

Molecular structure and transport dynamics in Nafion and sulfonated poly(ether ether ketone ketone) membranes

An atomistic simulation technique is performed to investigate the molecular structure and transport dynamics inside a hydrated Nafion membrane and a hydrated sulfonated poly(ether ether ketone ketone) (SPEEKK) membrane. The simulation system consists of the representative fragments of the polymer electrolytes, hydronium ions and solvent molecules, such as water plus methanol molecules. Simulation results show that the hydrated SPEEKK has less phase separation among hydrophobic and hydrophilic regions in comparison with the Nafion. Those water channels formed in the SPEEKK are much narrower compared to those in the Nafion. These characteristics lead to a lower mobility of hydronium ions and water molecules and hence relatively lower diffusion coefficient of methanol in the SPEEKK. It results in the reduction of the methanol permeation problem in direct methanol fuel cells.     

Organic-inorganic crosslinked and hybrid membranes derived from sulfonated poly(arylene ether sulfone)/silica via sol-gel process

A series of covalently crosslinkable organic-inorganic hybrid membranes have been prepared from sulfonated poly(arylene ether sulfone) (SPAES) with pendant propenyl moiety and various amounts of vinyl substituted silica via sol-gel process which are then thermally crosslinked in the presence of benzoyl peroxide (BPO) initiator. The obtained membranes are characterized in terms of oxidative stability, thermal property, ion exchange capacity (IEC), water uptake, swelling ratio in methanol aqueous solution, proton conductivity, and methanol permeability coefficient. The results indicate that the oxidative stability and thermal stability of the hybrid membranes are improved. Moreover, introduction of silica reduces the water uptake and methanol swelling of membranes. The swelling ratio of membranes in 2 mol L⁻¹ methanol aqueous solution at 80 °C slowly decreases from 26 to 19% with the increase of SiO₂ content from 0 to 12 wt.%. Furthermore, with the increase in silica content, the methanol permeability coefficient of the hybrid membranes decreases at first and then increases. When the silica content reaches 8 wt.%, the methanol permeability coefficient is at the minimum of 6.02 × 10⁻⁷ cm² s⁻¹, a 2.64-fold decrease compared with that of the pristine SPAES membrane. Moreover, the proton conductivity is found to be at about 95% of that of pristine polymer at that silica content.     

Synthesis and properties of sulfonated poly(arylene ether ketone sulfone) containing amino groups/functional titania inorganic particles hybrid membranes for fuel cells

In this work, the organic-inorganic hybrid membranes were prepared. The synthesis and properties of the hybrid membranes were investigated. The sulfonated poly(arylene ether ketone sulfone) containing amino groups (Am-SPAEKS) was synthesized by nucleophilic polycondensation. The sol-gel method was used to prepared functional titania inorganic particles (L-TiO₂). The ¹H NMR and FT-IR were performed to verified the structure of Am-SPAEKS and L-TiO₂. The organic-inorganic hybrid membranes showed both good thermal stabilities and mechanical properties than that of Am-SPAEKS. The L-Am-15% membrane exhibited the highest Young's modulus (2262.71 MPa) and Yield stress (62.09 MPa). The distribution of L-TiO₂ particles was revealed by SEM. Compared to Am-SPAEKS, the hybrid membranes showed higher proton conductivities. The L-Am-15% exhibited the highest proton conductivity of 0.0879 S cm⁻¹ at 90 °C. The results indicate that the organic-inorganic hybrid membranes have potential for application in proton exchange membrane fuel cells.     

Sulfonated poly(arylene ether)s based proton exchange membranes for fuel cells

During the past decade proton exchange membrane fuel cells (PEMFCs) as one kind of the potential clean energy sources for electric vehicles and portable electronic devices are attracting more and more attentions. Although Nafion® membranes are considered as the benchmark of proton exchange membranes (PEMs), the drawbacks of Nafion® membranes restrict the commercialization in the practical application of PEMFCs. As of today, the attention is to focus on developing both high-performance and low-cost PEMs to replace Nafion® membranes. In all of these PEMs, sulfonated poly(arylene ether ketone)s (SPAEKs) and sulfonated poly(arylene ether sulfone)s (SPAESs) are the most promising candidates due to their excellent performance and low price. In this review, the efforts of SPAEK and SPAES membranes are classified and introduced according to the chemical compositions, the microstructures and configurations, as well as the composites with polymers and/or inorganic fillers. Specifically, several perspectives related to the modification and composition of SPAESs and SPAEKs are proposed, aiming to provide the development progress and the promising research directions in this field.     

Novel cross-linked sulfonated poly (arylene ether ketone) membranes for direct methanol fuel cell

To prepare a cross-linked proton exchange membrane with low methanol permeability and high proton conductivity, poly (vinyl alcohol) is first blended with sulfonated poly (arylene ether ketone) bearing carboxylic acid groups (SPAEK-C) and then heated to induce a cross-linking reaction between the carboxyl groups in SPAEK-C and the hydroxyl groups in PVA. Fourier transform infrared spectroscopy is used to characterize and confirm the structure of SPAEK-C and the cross-linked membranes. The proton conductivity of the cross-linked membrane with 15% PVA in weight reaches up to 0.18 S cm⁻¹ at 80 °C (100% relative humidity), which is higher than that of Nafion membrane, while the methanol permeability is nearly five times lower than Nafion. The ion-exchange capacity, water uptake and thermal stability are investigated to confirm their applicability in fuel cells.     

Sulfonated poly(arylene ether sulfone) as a methanol-barrier layer in multilayer membranes for direct methanol fuel cells

Novel poly(arylene ether sulfone) copolymers containing different amount of pendant sulfonic acid groups have been synthesized by an aromatic substitution polymerization reaction. The properties of the synthesized sulfonated poly(diphenylsulfone-diphenol) (SDPS-DP) copolymers depend on the sulfonic acid group content in the copolymers. Although all the copolymers show good thermal stability, low liquid uptake, and low methanol crossover, they exhibit lower proton conductivity than Nafion or sulfonated poly(ether ether ketone) (SPEEK). Taking advantage of the low methanol crossover, multilayer membranes consisting of the SDPS-DP copolymer as a methanol-barrier center layer and SPEEK as the proton-conducting outer layers have been fabricated and characterized. The SPEEK/SDPS-DP-60/SPEEK multilayer membranes with an optimized center layer thickness are found to exhibit better performance and higher power density in DMFC than plain SPEEK and Nafion 115 membranes.     

Enhancement of fuel cell properties in polyethersulfone and sulfonated poly (ether ether ketone) membranes using metal oxide nanoparticles for proton exchange membrane fuel cell

The proton exchange membrane (PEM) was synthesized using polyethersulfone (PES), sulfonated poly (ether ether ketone) (SPEEK) and nanoparticles. The metal oxide nanoparticles such as Fe₃O₄, TiO₂ and MoO₃ were added individually to the polymer blend (PES and SPEEK). The polymer composite membranes exhibit excellent features regarding water uptake, ion exchange capacity and proton conductivity than the pristine PES membrane. Since the presence of sulfonic acid groups provides by added SPEEK and the unique properties of inorganic nanoparticles (Fe₃O₄, TiO₂ and MoO₃) helps to interconnect the ionic domain by the absorption of more water molecules thereby enhance the conductivity value. The proton conductivity of PES, SPEEK, PES/SPEEK/Fe₃O₄, PES/SPEEK/TiO₂ and PES/SPEEK/MoO₃ membranes were 0.22 × 10^?4 S/cm, 5.18 × 10^?4 S/cm, 3.57 × 10^?4 S/cm, 4.57 × 10^?4 S/cm and 2.67 × 10^?4 S/cm respectively. Even though the blending of PES with SPEEK has reduced the conductivity value to a lesser extent, hydrophobic PES has vital role in reducing the solvent uptake, swelling ratio and improves hydrolytic stability. Glass transition temperature (T_g) of the membranes were determined from DSC thermogram and it satisfies the operating condition of fuel cell system which guarantees the thermal stability of the membrane for fuel cell application.