Novel composite membrane based on zirconium phosphate-ionic liquids for high temperature PEM fuel cells

Composite membranes composed of zirconium phosphate (ZrP) and imidazolium-based ionic liquids (IL), supported on polytetrafluoroethylene (PTFE) were prepared and evaluated for their application in proton exchange membrane fuel cells (PEM) operating at 200 °C. The experimental results reported here demonstrate that the synthesized membrane has a high proton conductivity of 0.07 S cm^?1, i.e, 70% of that reported for Nafion. Furthermore, the composite membranes possess a very high proton conductivity of 0.06 S cm^?1 when processed at 200 °C under completely anhydrous conditions. Scanning electron microscopy (SEM) images indicate the formation of very small particles, with diameters in the range of 100–300 nm, within the confined pores of PTFE. Thermogravimetric analysis (TGA) reveals a maximum of 20% weight loss up to 500 °C for the synthesized membrane. The increase in proton conductivity is attributed to the creation of multiple proton conducting paths within the membrane matrix. The IL component is acting as a proton bridge. Therefore, these membranes have potential for use in PEM fuel cells operating at temperatures around 200 °C.     

Enhanced proton conductivity from phosphoric acid-imbibed crosslinked 3D polyacrylamide frameworks for high-temperature proton exchange membranes

To enhance the proton conductivity of high-temperature proton exchange membranes (PEMs), one promising approach is to increase the proton conductor loading per unit membrane. The objectives of this research are to demonstrate the feasibility of the concept and realize H₃PO₄-imbibed polyacrylamide (PAM) frameworks as high-temperature PEMs using the unique absorption and retention of crosslinked PAM to H₃PO₄ aqueous solution. The 3D framework of PAM provides space to hold H₃PO₄ into the porous structure, which can be controlled by adjusting the polymerization process and crosslinking agent and initiator dosages. Results show that the H₃PO₄ loadings and therefore the conductivities of the membranes are significantly enhanced by expanding the size of pore structure. Proton conductivities as high as 0.0749 S cm⁻¹ at ambient-temperature and fully hydrated state and 0.0635 S cm⁻¹ at 183 °C under anhydrous atmosphere are recorded. The high conductivities at high temperatures in combination with the simple preparation, low cost, scalable hosts and proton conductors demonstrate the potential use of hydrogel materials in high-temperature PEMs.     

Enhanced proton conductivities of chitosan-based membranes by inorganic solid superacid SO42−–TiO2 coated carbon nanotubes

To increase proton conductivity of chitosan (CS) based polymer electrolyte membranes, a novel nanofiller-solid superacide SO₄^2--TiO₂ (STi) coated carbon nanotubes (STi@CNTs) are introduced into CS matrix to fabricate membranes for polymer electrolyte membrane fuel cells (PEMFCs). Owing to the STi coating, the dispersion ability of CNTs and interfacial bonding are obviously improved, hence, CNTs can more fully play their reinforcing role, which makes the CS/STi@CNTs composite membranes exhibit better mechanical properties than that of pure CS membrane. More importantly, STi possesses excellent proton transport ability and may create facile proton transport channels in the membranes with the help of high aspect ratio of CNTs. Particularly, the CS/STi@CNTs-1 membrane (1 wt% STi@CNTs loading) obtains the highest proton conductivity of 4.2 × 10⁻² S cm^–1 at 80 °C, enhancing by 80% when compared with that of pure CS membrane. In addition, the STi@CNTs also confer the composite membranes low methanol crossover and outstanding cell performance. The maximum power density of the CS/STi@CNTs-1 membrane is 60.7 mW cm⁻² (5 M methanol concentration, 70 °C), while pure CS membrane produces the peak power density of only 39.8 mW cm⁻².     

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.     

Development of anion conducting zeolitic imidazolate framework bottle around ship incorporated with ionic liquids

Imidazolium based ionic liquids (denoted BMIM-ILs) with the altering anions (OH⁻, HCO₃⁻ and AcO⁻) as ionic carriers were synthesized and bottle around ship introduced into the cages of zeolite-type metal organic frameworks (ZIF-8) as porous host, resulting in a series of anion-containing composites (BMIM-ILs/ZIF-8) with anion conducting. Bottle around ship method could integrate with the superiorities of BMIM-ILs and ZIF-8 for more excelling conduction and quite eliminate IL leakage. Besides, the hybrid membranes combined BMIM-ILs/ZIF-8 as fillers with polymer blends consisting of polyvinylidene fluoride (PVDF) and polyvinylpyrrolidone (PVP) as matrix were assembled with varying weight percentages. The structures of the prepared composites and hybrid membranes were inspected. It should be noted that ZIF-8 encapsulating into BMIM-OH (6.8 × 10⁻⁴ S cm⁻¹) and BMIM-HCO₃ (1.08 × 10⁻³ S cm⁻¹) reveal two orders of magnitude increase in conductivity-values comparison to that of the parent framework (2.3× 10⁻⁵ S cm⁻¹) at 353 K and ∼98% relative humidity (RH). The hybrid membrane containing 30%BMIM-OH/ZIF-8 has the advantage in proton conductivity of 1.02 × 10⁻³ S cm⁻¹ at 353 K and ∼98% RH, which is 6.49 times higher than that of the ZIF-8/PVP/PVDF. The activation energies (E_a) of BMIM-OH/ZIF-8 and its hybrid membrane are calculated to be 0.15 eV and 0.23 eV, respectively. They could be regarded as a fast-ion conductor on the ground of high conduction and low activation energy, which make them bright outlooks and wonderful potential for electrochemical devices.     

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.     

Incorporation of H3PO4 into three-dimensional polyacrylamide-graft-starch hydrogel frameworks for robust high-temperature proton exchange membrane fuel cells

To enhance the anhydrous proton conductivities of proton exchange membranes, we report here the incorporation of H₃PO₄ into three-dimensional (3D) framework of polyacrylamide-graft-starch (PAAm-g-starch) hydrogel materials using extraordinary absorption of hydrogels to H₃PO₄ aqueous solution. Intrinsic microporous structure can close to seal H₃PO₄ molecules in the interconnected 3D frameworks of PAAm-g-starch after suffering from dehydration. The hydrogel membranes are thoroughly characterized by morphology observation, thermal stability, swelling kinetics, proton-conducting performances as well as electrochemical behaviors. The results show that the H₃PO₄ loadings and therefore the proton conductivities of the hydrogel membranes are dramatically enhanced by employing PAAm-g-starch matrix. H₃PO₄ loading of 88.68 wt% and an anhydrous proton conductivity as high as 0.046 S cm⁻¹ at 180 °C are recorded. A fuel cell using a thick membrane shows a peak power density of 517 mW cm⁻² at 180 °C by feeding with H₂/O₂ streams. The high H₃PO₄ loading, reasonable proton conductivity in combination with simple preparation, low cost and scalable matrix demonstrates the potential use of PAAm-g-starch hydrogel membranes in high-temperature proton exchange membrane fuel cells.     

Pore size tuning of Nafion membranes by UV irradiation for enhanced proton conductivity for fuel cell applications

The influence of optimal ultraviolet irradiation of Nafion membranes in enhancing proton conductivity and performance of passive micro-direct methanol fuel cells with silicon micro-flow channels is investigated for the first time. Initially, Nafion membranes are irradiated with different doses of ultraviolet radiation ranging within 0–400 mJ cm⁻² and their water uptake, swelling-ratios, porosity, and proton conductivities are measured using standard procedure. Results show that there is an enhancement in proton conductivity with an optimal dose of 198 mJ cm⁻² ultraviolet radiation. This enhancement is due to optimum photo-crosslinking of –SO₃H species resulting in maximum pore-size which facilitates enhanced proton-hopping from one –SO₃H site to another in the hydrophilic channel. Nafion membranes with three different thicknesses (50 μm, 90 μm and 183 μm) are irradiated with ultraviolet radiation with 198 mJ cm⁻² dose and passive micro-direct methanol fuel cells are assembled with irradiated Nafion proton exchange membranes. The polarization plots are obtained for the assembled devices. Results show an enhancement of power density of devices nearly by a factor of 1.2–1.5 with optimally irradiated membranes indicating that optimum dose of ultraviolet irradiation of Nafion membranes is an effective technique for power enhancement of proton exchange membrane fuel cells which use fuels like methanol, ethanol and hydrogen.     

High temperature proton exchange porous membranes based on polybenzimidazole/ lignosulfonate blends: Preparation,morphology and physical and proton conductivity properties

Porous polybenzimidazole (PBI) based blend membranes were prepared by adding different amounts of lignosulfonate (LS) in the presence of LiCl salt. The morphology characteristics of the PBI/LS blends were investigated by FT-IR, atomic force microscopy (AFM) and scanning electron microscopy (SEM) analyses. The relation between the membrane morphology and membrane proton conductivity was studied. Results showed that LS content has a significant influence on the membrane morphology. High amount of LS in the blend created micro-pores within the membrane where increase in the LS content up to 20 wt% resulted in membranes containing pores with a mean diameter of about 0.8 μm. The resulting PBI/LS (0–20 wt%) membranes indicated high PA doping levels, ranging from 3 to 16 mol of PA per mole of PBI repeat units, which contributed to their unprecedented high proton conductivities of 4–96 mS cm⁻¹, respectively, at 25 °C. The effect of temperature on the proton conductivity of blends was also investigated. The results showed that by rising the temperature, the proton conductivity increases in PBI/LS blends. In the blend containing 20 wt% LS, proton conductivity increased from 98 mS cm⁻¹ at 25 °C to 187 mS.cm⁻¹at 160 °C which can be considered as an excellent candidate for use in both high and low temperature proton exchange membrane fuel cells.     

Constructing interconnected nanofibers@ZIF-67 superstructure in nafion membranes for accelerating proton transport and confining methanol permeation

A high-performance proton exchange membrane was successfully prepared by incorporating an interconnected PMIA nanofiber@ZIF-8 network (ZHNFs) into Nafion solution, in which the unique ZHNFs were fabricated via in-situ growth of ZIF-67 on the surface of hierarchical PMIA nanofibers (HNFs) with multiscale nanofibers and high hydrophilicity. The hybrid membrane presents an outstanding performance with a peak proton conductivity of 0.277 S cm⁻¹ at 80 °C, 100RH% and a decreased methanol permeability of 1.415 × 10⁻⁷ cm² s⁻¹, implying a promising application in direct methanol fuel cells. The superior performance of the membranes could be due to the interconnected structure, high specific surface area of 122.637 m² g⁻¹ and active chemical bond of (−N–H) of ZHNFs. Specifically, the 3D interconnected structure of ZHNFs provides consecutive conduction path for protons, ensuring the improvement of proton conductivity. The effective interfacial acid-base pairs (−N–H ^… −SO₃H) formed via the tight interactions between the –N–H bonds in ZHNFs and –SO₃H groups in Nafion matrix could effectively ameliorate the compatibility of the nanofiber fillers and Nafion matrix, further promoting the methanol barrier of the hybrid membranes. Moreover, the generated acid-base pairs are beneficial for the efficient and rapid proton transfer via providing abundant proton conducting sites.     

A highly proton conductive membrane based on hydrolyzed NbCl5 and phytic acid

It is vital to choose economical and environmentally friendly proton conductive materials to improve the performance of proton exchange membranes, which occupies a unique position in proton exchange membrane fuel cells. This paper reports a new proton conductive nanocomposite, that was named NbO₂(OH)-PA prepared from phytic acid (PA) and NbCl₅. NbO₂(OH)-PA showed an excellent proton conductivity of 135 mS cm⁻¹ at 85 °C and 97% relative humidity. In addition, NbO₂(OH)-PA was combined with sulfonated poly (ether ketone) (SPEEK) in different proportions to form proton conductive membranes, that are labeled SPEEK-x NbO₂(OH)-PA. SPEEK-0.9% NbO₂(OH)-PA exhibited the best proton conductivity of 0.17 S cm⁻¹ at 80 °C in water. This work may provide new ideas for improving proton conductivity of membranes through simple methods.     

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.     

Performance of PEMFC with new polyvinyl-ionic liquids based membranes as electrolytes

Polymer Electrolyte Membrane Fuel Cells (PEMFC) represent a key technology for sustainable energy production due to their high efficiency and low environmental impact. The use of task specific protic ionic liquids as electrolytes is gaining interest due to their high conductivity and thermal and electrochemical stability under anhydrous conditions. Ionic liquids with the imidazolium cation exhibit a high electrochemical stability, besides sulfonic groups can be incorporated to the cation as side chains acting as carriers in order to facilitate the proton transport. Moreover suitable anions such as Tf₂N and OTf provide high ionic conductivity. In this work, two different types of membranes based on protic ionic liquids have been tested in PEMFC under anhydrous conditions i) Nafion membranes impregnated with the protic ionic liquids 1-methyl-3-(4-sulfobutyl)-imidazolium bis(trifluoromethylsulfonyl)-imide ([HSO₃-BMIm][NTf₂]) and 1-butyl-3-(4-sulfobutyl)-imidazolium trifluoromethanesulfonate ([HSO₃-BBIm][OTf]) and, ii) membranes based on the polymerization of the specifically designed ionic liquid 1-(4-sulfobutyl)-3-vinylimidazolium trifluoromethanesulfonate ([HSO₃-BVIm][OTf]). The influence of different operation variables such as cell temperature, gas humidity and membrane thickness on the performance of the PEMFC has been analyzed, and the resistance exerted by the electrolyte was determined using electrical impedance spectroscopy. Nafion membranes impregnated with [HSO₃-BBIm][OTf] achieve current densities of 217 mA/cm² under anhydrous conditions at 25 °C whereas [HSO₃-BVIm][OTf] polymerized electrolytes provide current densities of 154 mA/cm² at the same conditions. This is the first report that describes the application of designed polymerized protic ionic liquids membranes for fuel cells. Although some improvements in terms of thermal and mechanical stability should be achieved, this first approach presents a promising electrolyte with challenging characteristics.     

Crosslinked poly (isatin biphenyl spirofluorene) membranes for proton conduction over a wide temperature range from −40 to 160 °C

It is desired to develop proton exchange membranes (PEMs) working in a wide temperature range considering the practical working condition of devices using the PEMs as the electrolyte. Herein, a novel polymer of poly (isatin biphenyl spirofluorene) (PIBS) is first synthesized and it is afterwards crosslinked by 1,3-bis(4-piperidyl) propane (P) to fabricate membranes. The membranes can work in a temperature range of −40 to 160 °C after doping with phosphoric acid (PA). The proton conductivity of the PA doped membrane reaches 4.4 × 10⁻³ S cm⁻¹ at −40 °C under 80% relative humidity (RH) and 0.16 S cm⁻¹ at 160 °C without humidifying. We demonstrate the uses of the prepared PA doped PIBS-P membranes as membrane electrolytes in single fuel cells within 100–160 °C under anhydrous condition, and in water electrolytic cells within −20 to 60 °C, respectively.     

Long-term durable solid state electrolyte membranes based on a metal–organic framework with phosphotungstic acid confined in the mesoporous cages

In this study, phosphotungstic acid-encapsulated MIL-101 (Fe) (HPW@MIL-100 (Fe)) was synthesized by the in-situ direct hydrothermal method. Due to the large mesoporous cages and small microporous windows of MIL-100 (Fe), HPW could be well loaded and confined in the cages of MIL-100 (Fe). Furthermore, novel hybrid proton exchange membranes were fabricated by incorporating HPW@MIL-100 (Fe) into sulfonated poly (arylene ether ketone sulfone) containing carboxyl groups (C-SPAEKS) matrix. The structures of MIL-100 (Fe), HPW@MIL-100 (Fe), C-SPAEKS, and hybrid membranes were characterized by XRD and FT-IR. The HPW@MIL-100 (Fe), with a large amount of phosphotungstic acid in cages, could enhance the proton conductivities of hybrid membranes. The hybrid membrane with 4% content of HPW@MIL-100 (Fe) achieved a high proton conductivity of 0.072 S cm⁻¹ at 80 °C and 100% relative humidity, which was 1.8 times higher than that of pure C-SPAEKS (0.040 S cm⁻¹) at the same conditions. Meanwhile, the introduced HPW@MIL-100 (Fe) fillers improved the dimensional stability of hybrid membranes. These results indicate that introduction of MIL-100 (Fe) materials loaded with HPW plays an important role in improving the comprehensive performance and this series of hybrid membranes have potential as proton exchange membranes.     

Application of phosphoric acid and phytic acid-doped bacterial cellulose as novel proton-conducting membranes to PEMFC

Novel proton-conducting polymer electrolyte membranes have been prepared from bacterial cellulose by incorporation of phosphoric acid (H₃PO₄/BC) and phytic acid (PA/BC). H₃PO₄ and PA were doped by immersing the BC membranes directly in the aqueous solution of H₃PO₄ and PA, respectively. Characterizations by FTIR, TG, TS and AC conductivity measurements were carried out on the membrane electrolytes consisting of different H₃PO₄ or PA doping level. The ionic conductivity showed a sensitive variation with the concentration of the acid in the doping solution through the changes in the contents of acid and water in the membranes. Maximum conductivities up to 0.08 S cm⁻¹ at 20 °C and 0.11 S cm⁻¹ at 80 °C were obtained for BC membranes doped from H₃PO₄ concentration of 6.0 mol L⁻¹ and, 0.05 S cm⁻¹ at 20 °C and 0.09 S cm ⁻¹ at 60 °C were obtained for BC membranes doped from PA concentration of 1.6 mol L⁻¹. These types of proton-conducting membranes share not only the good mechanical properties but also the thermal stability. The temperature dependences of the conductivity follows the Arrhenius relationship at a temperature range from 20 to 80 °C and, the apparent activation energies (E_a) for proton conduction were found to be 4.02 kJ mol⁻¹ for H₃PO₄/BC membrane and 11.29 kJ mol⁻¹ for PA/BC membrane, respectively. In particular, the membrane electrode assembly fabricated with H₃PO₄/BC and PA/BC membranes reached the initial power densities of 17.9 mW cm⁻² and 23.0 mW cm⁻², which are much higher than those reported in literature in a real H₂/O₂ fuel cell at 25 °C.     

Nafion/Pd–SiO2 nanofiber composite membranes for direct methanol fuel cell applications

One of the major challenges for direct methanol fuel cells is the problem of methanol crossover. With the aim of solving this problem without adverse effects on the membrane conductivity, Nafion/Palladium–silica nanofiber (N/Pd–SiO₂) composite membranes with various fiber loadings were prepared by a solution casting method. The silica-supported palladium nanofibers had diameters ranging from 100 nm to 200 nm and were synthesized by a facile electro-spinning method. The thermal properties, ionic exchange capacities, water uptake, proton conductivities, methanol permeabilities, chemical structures, and micro-structural morphologies were determined for the prepared membranes. It was found that the transport properties of the membranes were affected by the fiber loading. All of the composite membranes showed higher water uptake and ion exchange capacities compared to commercial Nafion 117 and proved to be thermally stable for use as proton exchange membranes. The composite membranes with optimum fiber content (3 wt%) showed an improved proton conductivity of 0.1292 S cm⁻¹ and a reduced methanol permeability of 8.36 × 10⁻⁷ cm² s⁻¹. In single cell tests, it was observed that, the maximum power density measured with composite membrane is higher than those of commercial Nafion 117.     

Preparation of polybenzimidazole/ZIF-8 and polybenzimidazole/UiO-66 composite membranes with enhanced proton conductivity

Metal-organic frameworks (MOFs) are considered emerging materials as they further improve the various properties of polymer membranes used in energy applications, ranging from electrochemical storage and purification of hydrogen to proton exchange membrane fuel cells. Herein, we fabricate composite membranes consisting of polybenzimidazole (PBI) polymer as a matrix and MOFs as filler. Synthesis of ZIF-8 and UiO-66 MOFs are conducted through a typical solvothermal method, and composite membranes are fabricated with different MOF compositions (e.g., 2.5, 5.0, 7.5, and 10.0 wt %). We report a significant improvement in proton conductivity compared with the pristine PBI; for example, more than a three-fold increase in conductivity is observed when the PBI-UiO66 (10.0 wt %) and PBI-ZIF8 (10.0 wt %) membranes are tested at 160 °C. Proton conductivities of the composite membranes vary between 0.225 and 0.316 S cm^?1 at 140 and 160 °C. For the comparison, pure PBI exhibits 0.060 S cm^?1 at 140 °C and 0.083 S cm^?1 at 160 °C. However, we also report a decrease in permeability and mechanical stability with the composite membranes.     

Synthesis of (Si-PWA)-PVA/PTFE high-temperature proton-conducting composite membrane for DMFC

The inorganic silica immobilized PWA based (Si-PWA)-PVA/PTFE composite membrane was developed by an amalgamation of pore filling and layer by layer (LBL) casting. The composition of the top layer was optimized to be 0.3 M PWA: 0.2 M TEOS: 0.15PVA concerning to proton-conductivity and methanol permeability of the membrane. Surface morphological studies and elemental analysis were carried out by using SEM-EDX. The FT-IR and XRD analysis had confirmed the intercalation of sol with PTFE. Thermal deformation of the membrane was studied by TGA and it is stable up to 180 °C. Ion exchange capacity and water uptake were determined to be 2.38 meq per gram and 21.7%. The membrane has exhibited maximum proton conductivity of 41.2 mS cm⁻¹ at 100 °C. The membrane has significantly lower methanol permeability of 3.2 × 10⁻⁷ cm² S⁻¹ compared to that of Nafion117 (7.9 × 10⁻⁷ cm² S⁻¹) at 28 °C and the same trend was observed at 40, 60, and 80 °C. The (Si-PWA)-PVA/PTFE composite membrane is showed enhanced proton conductivity and lower methanol permeability at elevated temperatures.     

Influence of composition and acid treatment on proton conduction of composite polybenzimidazole membranes

Inorganic/organic composite membranes formed by polybenzimidazole, silicotungstic acid and silica with different ratio between them have been prepared and characterized before and after treatment in phosphoric acid in order to evaluate the influence of composition and acid treatment on some main characteristics of the membranes. In particular the proton conductivity, the mechanical stability and the structural characteristics of the membranes were evaluated. Silica behaved as a support on which the heteropolyacid remained blocked in finely dispersed state and as an adsorbent for water, thus determining a beneficial effect on proton conduction. The membrane with 50 wt.% of SiWA–SiO₂/PBI, mechanically stable, gave proton conductivity of 1.2×10⁻³ S cm⁻¹ at 160°C and 100% relative humidity. After treatment with phosphoric acid the proton conductivity of membranes increased to 2.23×10⁻³ S cm⁻¹ under the same test conditions. All the materials prepared had amorphous structure.