Experimental Investigation of boron phosphate Incorporated speek/pvdf blend membrane for proton exchange membrane fuel cells

The recent studies focused on the blend membranes to a great extent due to their capability of gathering some important polymer characteristic features. In this survey, boron phosphate (BP) doped sulfonated poly (ether ether ketone)/Poly (vinylidene fluoride) (SPEEK/PVDF) blend membrane having high ionic conduction capability was synthesized. The boron phosphate doping to the membrane matrix enhanced the membrane properties in terms of proton exchange membrane conditions. The sol-gel and casting method was used to synthesise the SPEEK/PVDF blend membrane. The characterization tests to observe the structure of the membrane, such as X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), FT-IR and mechanical/thermal stability tests were conducted. The membrane ionic transportation and water retention were improved directly by the addition of boron phosphate. The highest power density (242 mW cm^?2) and current density (400 mA cm^?2) at 0.6 V were obtained by SPEEK/PVDF/10BP, respectively. Additionally, the proton conductivity value of 39 mS cm^?1 was obtained for SPEEK/PVDF/10BP sample at 80 °C. The authors concluded that both boron phosphate additive and SPEEK/PVDF blend membrane have promising results for fuel cell future operations.     

Improved fuel cell properties of Nano-TiO2 doped Poly(Vinylidene fluoride) and phosphonated Poly(Vinyl alcohol) composite blend membranes for PEM fuel cells

Blend composite membranes are known as a good alternative to expensive Nafion membrane since they combine the superior properties of their components in a single structure. Herein, poly(vinylidene fluoride) (PVDF) - phosphonated polyvinyl alcohol (PPVA) blend membranes (90/10 by mass) were prepared with the solution casting method. Then, nano-TiO₂ were added at varying mass ratios (2, 5, 8, 10, and 15%) to improve the performance of the synthesized membranes. Characterization tests namely, Fourier Transform Infrared (FTIR), water uptake capacity, ion exchange capacity (IEC), proton conductivity, dynamic mechanic analysis, open-circuit voltage (OCV) measurements, and performance tests were conducted. PVDF/PPVA membrane containing 8% nano-TiO₂ exhibited the highest performance with 382.7 mA/cm² of current density and 225.4 mW cm⁻² of power density. The OCV measurements showed 8.57% voltage decrement at the end of 1000 h. Obtained results show the high potential of TiO₂ doped PVDF/PPVA membranes could be considered as a favorable candidate for fuel cells.     

Polybenzimidazole composite membranes containing imidazole functionalized graphene oxide showing high proton conductivity and improved physicochemical properties

Polymer composite membranes are fabricated using poly[2,2'-(m-phenylene)-5,5′-bibenzimidazole] (PBI) as a polymer matrix and imidazole functionalized graphene oxide (ImGO) as a filler material for high temperature proton exchange membrane fuel cell applications. ImGO is prepared by the reaction of o-phenylenediamine with graphene oxide (GO). The compatibility of ImGO with PBI matrix is found to be better than that of GO, and as a result PBI composite membrane having ImGO exhibits improved physicochemical properties and larger proton conductivity compared with pure PBI and PBI composite membrane having GO. For example, PBI composite membrane having 0.5 wt% of ImGO shows enhanced tensile strength (219.2 MPa) with minimal decrease of elongation at break value (28.8%) compared with PBI composite membrane having 0.5 wt% of GO (215.5 MPa, 15.4%) and pure PBI membrane without any filler (181.0 MPa, 34.8%). The proton conductivity of this membrane, at 150 °C under anhydrous condition, is 77.52 mS cm^?1.     

Incorporating graphene oxide to improve the performance of Nafion-mordenite composite membranes for a direct methanol fuel cell

The proton exchange membrane is one of the critical parts of a direct methanol fuel cell. High proton conductivity and low methanol permeability are required. To enhance the performance of a direct methanol fuel cell, graphene oxide was incorporated to Nafion-mordenite composite membranes to enhance the compatibility and to decrease methanol permeability. It was found that the membrane with silane grafted on graphene oxide-treated mordenite with a graphene oxide content of 0.05% presented the highest proton conductivity (0.0560 S·cm⁻¹, 0.0738 S·cm⁻¹ and 0.08645 S·cm⁻¹ at 30, 50, and 70 °C, respectively). This was about 1.6-fold of the recast Nafion and commercial Nafion 117 and was about 1.5-fold of that without graphene oxide incorporation. Finally, the operating condition was optimized using response surface methodology and the maximum power density was investigated. Power density of about 4-fold higher than that of Nafion 117 was obtained in this work at 1.84 M and 72 °C with a %Error between the model prediction and the fuel cell experiment of 0.082%.     

Effects of phosphotungstic acid on performance of phosphoric acid doped polyethersulfone-polyvinylpyrrolidone membranes for high temperature fuel cells

Heteropoly acids have been employed to increase the proton conductivity of phosphoric acid (PA) doped polymer membranes for high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). In this work, we develop a new composite membrane based on phosphotungstic acid (PWA) doped polyethersulfone-polyvinylpyrrolidone (PES-PVP) matrix, forming PWA/PES-PVP composite membrane for HT-PEMFCs. The homogeneous distribution of PWA on the PES-PVP membrane enhances its mechanical strength. In addition, there is a strong interaction between PWA and PA that is confirmed experimentally by the attenuated total reflectance Fourier Transform Infrared spectroscopy and semi-empirical quantum mechanics calculation. This enhances not only the PA uptake but also the proton conductivity of the PWA/PES-PVP composite membrane. ¹H nuclear magnetic resonance spectroscopy results elucidate that the high proton conductivity of the PA doped PWA/PES-PVP membranes is due to their higher proton content and mobility compared to the pristine PA doped PES-PVP membrane. The best results are observed on the PES-PVP composite membrane with addition of 5 wt% PWA, reaching proton conductivity of 1.44 × 10^?1 S cm^?1 and a peak power density of 416 mW cm^?2 at 160 °C and anhydrous conditions. PWA additives increase the proton conductivity and cell performance, demonstrating significantly positive effects on the acid-base composite membranes for high temperature polymer electrolyte membrane fuel cell applications.     

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.     

N-spirocyclic ammonium-functionalized graphene oxide-based anion exchange membrane for fuel cells

Graphene oxide (GO) is a potential material in the electrode and membrane of polymer electrolyte membrane fuel cells due to its unique structure and various oxygen-containing functional groups. A class of three-layered GO/poly (phenylene oxide) for AEMs was prepared in this work. GO was functionalized with highly stable 6-azonia-spiro [5.5]undecane groups and used as a fast hydroxide conductor, named ASU-GO. Functionalized by N-spirocyclic cations, poly (phenylene oxide) (PIPPO) was then combined with ASU-GO and GO to fabricate the ASU-GO/PIPPO and GO/PIPPO. Notably, the maximum hydroxide conductivity of the ASU-GO/PIPPO was 73.7 mS cm⁻¹ at 80 °C, which was 3 times higher than that of the GO/PIPPO. The enhancement in hydroxide conductivity was due to the changes in the hydroxide transport mechanism and the poor stacked structure of the ASU-GO layer. Only 10.8% drops in hydroxide conductivity of ASU-GP/PIPPO after the alkaline test (1 M KOH at 80 °C for 700 h). Furthermore, the ASU-GO/PIPPO-50 membrane showed a maximum peak power density of 102 mW cm⁻², demonstrating the prepared membrane was promising in the AEM applications.     

Study of deep oxidation and sulfonation of graphene oxide as low-temperature fuel cell electrolyte

In order improve the fuel cell performance of a free-standing graphene oxide (GO) membrane, the impacts of both the additional oxidation of GO and the modification with vinilsulfonic acid were investigated. The modification with vinilsulfonic acid was conducted with and without adding potassium persulfate, K₂S₂O₈, which is a radical initiator for the polymerization of vinylsulfonate. A total of six types of free-standing GO membranes with and without the oxidation and/or the modification were prepared. The oxidation and the modification additively increased the proton conductivity, and the oxidation significantly improved the durability of the fuel cell performance at 30 °C. The membrane of GOhvsi, of which GO was oxidized and modified with the initiator, showed very high in-plane proton conductivities at 30 °C, i.e., 0.54 S cm^?1 at RH 100%. The H₂–O₂ fuel cell using GOhvsi showed maximum power densities as high as 136 mW cm^?2 and 184 mW cm^?2 at 30 °C and 50 °C, respectively. The performance at 30 °C was stable for more than 20 h. The improved durability by the oxidation was attributed to the increased defects of carbon based on an XPS analysis. The TPD-MS analysis suggested that the oxygenated functional groups at the defects would increase the binding strength.     

Nanocomposite membrane electrolyte of polyaminobenzene sulfonic acid grafted single walled carbon nanotubes with sulfonated polyether ether ketone for direct methanol fuel cell

Nanocomposite membranes of sulfonated polyether ether ketone (sPEEK) are prepared with polyaminobenzene sulfonic acid grafted single-walled carbon nanotubes copolymer (PABS-SWCNT) and its zwitterion interactions are studied. The nanocomposite membranes are prepared through solution cast technique using PABS-SWCNT as additive in different weight % (0.1, 0.15, and 0.2) ratio. The additive and nanocomposite membranes are characterized for its surface morphology, composition, thermal and physico-chemical properties. The nanocomposite membrane comprising optimized content of PABS-SWCNT (0.15 wt %) shows improved proton conductivity and reduced methanol crossover resulting in enhanced DMFC peak power density of 150 mW cm⁻² in comparison to 110 mW cm⁻² for sPEEK and 80 mW cm⁻² for Nafion® 117 respectively. The improved durability till 100 h for sPEEK/PABS-SWCNT (0.15 wt %) compared to sPEEK and Nafion-117 confirms its viability in DMFC application.     

New anhydrous proton exchange membranes based on fluoropolymers blend imidazolium poly (aromatic ether ketone)s for high temperature polymer electrolyte fuel cells

The blend polymer membranes were synthesized from the methylimidazolium poly (aromatic ether ketone) (MeIm-PAEK) and fluoropolymers (PVDF and PVDF-HFP) with excellent thermal stability and improved dimensional stabilities for high-temperature polymer electrolyte fuel cells. The MeIm-PAEK exhibited good compatibility with PVDF or PVDF-HFP without phase separation. High phosphoric acid doping contents of the blend membranes were achieved at elevated temperatures with acceptable swellings. The acid doped blend membranes displayed lower dimensional swellings and higher mechanical strength compared to the MeIm-PAEK membrane, which allowed the blend membranes to obtain higher acid doping contents and proton conductivities. The MeIm-PAEK/10%PVDF membrane with a phosphoric acid doping content of 700 wt% showed a proton conductivity as high as 0.192 S cm^?1 at 180 °C under the non-humidified condition and a tensile strength of 4.3 MPa at room temperature.     

Simple design of PVA-based blend doped with SO4(PO4)-functionalised TiO2 as an effective membrane for direct borohydride fuel cells

Nanocomposite membranes for low-temperature fuel cells, specifically, direct borohydride fuel cells (DBFCs), are formulated from a ternary polymer blend of poly (vinyl alcohol), poly (vinyl pyrrolidone), and poly (ethylene oxide) with the incorporation of (SO₄–TiO₂) nanotubes and (PO₄–TiO₂) as doping agents. The functionalisation of TiO₂ is carried out by impregnation-calcination method. Structural and morphological characterisation by FTIR, TEM, SEM, EDX, ICP, and XRD confirmed the successful preparation of the doping materials and their incorporation into the polymer blend. The influence of SO₄–TiO₂ and PO₄–TiO₂ doping and their content on the physicochemical properties of the composite membranes is assessed. Water uptake and swelling degree gradually reduced to below 20% with increasing the concentration of TiO₂-based doping agent, while the ion exchange capacity raised 3.5 times compared to that of the undoped membrane. The increase of the doping agent content also increased the ionic conductivity, tensile strength and thermal stability of the membrane. DBFC using the composite membrane produced a maximum power density of 75 mW cm⁻², close to that using Nafion®117 membrane (81 mW cm⁻²) but at a significantly lower cost. The promising results obtained in this study pave the way for a simple, green and economic approach for the development of composite membranes for application in DBFCs.     

Sulfonated graphene oxide as an inorganic filler in promoting the properties of a polybenzimidazole membrane as a high temperature proton exchange membrane

A commercial perfluorinated sulfonic acid (PFSA) membrane, Nafion, shows outstanding conductivity under conditions of a fully humidified surrounding. Nevertheless, the use of Nafion membranes that operate only at low temperature (<100 °C) can lead to some disadvantages in PEMFC systems, such as a low impurity tolerance and slow kinetics. To overcome the above problems, this study introduces a highly durable composite membrane with an inorganic filler for a high-temperature proton exchange membrane fuel cell (HT-PEMFC) applications under anhydrous conditions. In this work, polybenzimidazole (PBI) is used as a polymer electrolyte membrane with the addition of a sulfonated graphene oxide (SGO) inorganic filler. The amount of SGO filler was varied (0.5–6 wt.%) to study its influence on proton conductivity at elevated temperature, mechanical stability as well as phosphoric acid doping level. In particular, PBI-SGO composite membranes exhibited higher the level of acid dopant and proton conductivities than those of the pure PBI membranes. The PBI-SGO 2 wt.% composite membrane displayed the highest proton conductivity, with a value of 9.142 mS cm⁻¹ at 25 °C, and it increased to 29.30 mS cm⁻¹ at 150 °C. The PBI-SGO 2 wt.% also displayed the maximum values in the acid doping level (11.63 mol of PA/PBI repeat unit) and mechanical stability (48.86 MPa) analyses. In the HT-PEMFC test, compared with a pristine PBI membrane, the maximum power density was increased by 40% with the use of a PBI composite membrane with 2 wt.% SGO. These results show that the PBI-SGO membrane has a great potential to be applied as an alternative membrane in HT-PEMFC applications, offering the possibility of improving impurity tolerance and kinetic reactions.     

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.     

Preparation of functional copolymer based composite membranes containing graphene oxide showing improved electrochemical properties and fuel cell performance

The objective of this work is to prepare a functional copolymer of poly(acrylonitrile)-co-poly(2-Acrylamido-2-methyl-1-propanesulfonic acid) (PAN-co-PAMPS) and impregnation of graphene oxide (GO) into the copolymer followed by crosslinking to prepare conetwork composite membranes by simple and cost effective solution casting method and evaluating their structural, morphological, thermal, and mechanical properties. The successful incorporation of different amounts of GO content (0.1–1 wt%) within the polymer matrix was confirmed by FT-IR spectroscopy, X-ray diffraction, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The mechanical properties of the prepared crosslinked composite membranes are found to be greatly enhanced by the addition of GO in the copolymer matrix. The thermogravimetric analysis (TGA) demonstrated considerable improvements in thermal stability for the composite membrane with low GO content. The effect of loading of GO in the copolymer matrix on proton conductivity and fuel cell performance has been studied systematically. The membranes prepared by mixing with 0.5 wt% GO in the copolymer followed by crosslinking exhibited maximum ionic conductivity (K^m), lower methanol permeability (P_M), and higher relative selectivity. This observed P_M value is much lower range from 3.02 × 10^?7 to 11.9 × 10^?7 cm²/s compared to the Nafion® 117 membrane (22 × 10^?7 cm²/s). The fuel cell performance in terms of maximum power density and current density and the durability of the crosslinked composite membranes have also been evaluated here. Low P_M, high K^m, and high selectivity values show that functional co-polymer/GO crosslinked co-network composite membrane is a promising alternative membrane separator to replace the expensive Nafion® 117 for proton exchange membrane fuel cells (PEMFCs) application.     

Performance of PVDF supported silica immobilized phosphotungstic acid membrane (Si-PWA/PVDF) in direct methanol fuel cell

PVDF supported silica-immobilized phosphotungstic acid membrane (Si-PWA/PVDF) was synthesized by impregnation of silica immobilized phosphotungstic acid particles in porous PVDF film. Pore size distribution as well as stability of membrane in oxidative environment was determined using Fenton's reagent test. Stability of membrane against leaching of PWA which provides ion exchanging capacity was also determined and found to be adequate. Properties which affect performance of membrane in DMFC like water uptake, methanol cross-over and proton conductivity were measured. Water uptake of the membrane increased from 30.3% to 37.9% as the temperature was increased from 25 °C to 80 °C. The proton conductivity of the membrane increased from 4.3 mS cm⁻¹ to 20 mS cm⁻¹ with increase in the temperature from 25 °C to 80 °C. Methanol uptake of the Si-PWA/PVDF membrane was low compared to Nafion membrane and changed by very small amount with increase in temperature. Effect of operating parameters on performance of direct methanol fuel cell (DMFC) with the synthesized Si-PWA/PVDF was determined. DMFC performance improved on increasing temperature. As the temperature was increased from 25 °C to 60 °C, open circuit voltage (OCV) increased from 0.685 V at 0.815 V and the peak power density increased from 21.4 mW cm⁻² to 44.0 mW cm⁻². Maximum peak power density was obtained with 1 M methanol concentration and 60% relative humidity. Peak power density decreased with further increase in both methanol concentration and relative humidity.     

An enhanced proton conductivity and reduced methanol permeability composite membrane prepared by sulfonated covalent organic nanosheets/Nafion

Sulfonated covalent organic nanosheets (SCONs) with a functional group (−SO₃H) are effective at reducing ion channels length and facilitating proton diffusion, indicating the potential advantage of SCONs in application for proton exchange membranes (PEMs). In this study, Nafion-SCONs composite membranes were prepared by introducing SCONs into a Nafion membrane. The incorporation of SCONs not only improved proton conductivity, but also suppressed methanol permeability. This was due to the even distribution of ion channels, formed by strong electrostatic interaction between the well dispersed SCONs and Nafion polymer molecules. Notably, Nafion-SCONs-0.6 was the best choice of composite membranes. It exhibited enhanced performance, such as high conductivity and low methanol permeability. The direct methanol fuel cell (DMFC) with Nafion-SCONs-0.6 membrane also showed higher power density (118.2 mW cm⁻²), which was 44% higher than the cell comprised of Nafion membrane (81.9 mW cm⁻²) in 2 M methanol at 60 °C. These results enabled us to work on building composite membranes with enhanced properties, made from nanomaterials and polymer molecules.     

Composite membrane by incorporating sulfonated graphene oxide in polybenzimidazole for high temperature proton exchange membrane fuel cells

The objective of this work is to examine the polybenzimidazole (PBI)/sulfonated graphene oxide (sGO) membranes as alternative materials for high-temperature proton exchange membrane fuel cell (HT-PEMFC). PBI/sGO composite membranes were characterized by TGA, FTIR, SEM analysis, acid doping&acid leaching tests, mechanical analysis, and proton conductivity measurements. The proton conductivity of composite membranes was considerably enhanced by the existence of sGO filler. The enhancement of these properties is related to the increased content of –SO₃H groups in the PBI/sGO composite membrane, increasing the channel availability required for the proton transport. The PBI/sGO membranes were tested in a single HT-PEMFC to evaluate high-temperature fuel cell performance. Amongst the PBI/sGO composite membranes, the membrane containing 5 wt. % GO (PBI/sGO-2) showed the highest HT-PEMFC performance. The maximum power density of 364 mW/cm² was yielded by PBI/sGO-2 membrane when operating the cell at 160 °C under non humidified conditions. In comparison, a maximum power density of 235 mW/cm² was determined by the PBI membrane under the same operating conditions. To investigate the HT-PEMFC stability, long-term stability tests were performed in comparison with the PBI membrane. After a long-term performance test for 200 h, the HT-PEMFC performance loss was obtained as 9% and 13% for PBI/sGO-2 and PBI membranes, respectively. The improved HT-PEMFC performance of PBI/sGO composite membranes suggests that PBI/sGO composites are feasible candidates for HT-PEMFC 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.     

PVDF-g-PSSA and Al2O3 composite proton exchange membranes

Poly(vinylidene fluoride) grafted polystyrene sulfonated acid (PVDF-g-PSSA) membranes doped with different amount of Al₂O₃ (PVDF/Al₂O₃-g-PSSA) were prepared based on the solution-grafting technique. The microstructure of the membranes was characterized by IR-spectra and scanning electron microscope (SEM). The thermal stability was measured by thermal gravity analysis (TGA). The degree of grafting, water-uptake, proton conductivity and methanol permeability were measured. The results show that the PVDF-g-PSSA membrane doped with 10% Al₂O₃ has a lower methanol permeability of 6.6 × 10⁻⁸ cm² s⁻¹, which is almost one-fortieth of that of Nafion-117, and this membrane has moderate proton conductivity of 4.5 × 10⁻² S cm⁻¹. Tests on cells show that a DMFC with the PVDF/10%Al₂O₃-g-PSSA has a better performance than Nafion-117. Although Al₂O₃ has some influence on the stability of the membrane, it can still be used in direct methanol fuel cells in the moderate temperature.     

Highly branched poly(arylene ether)/surface functionalized fullerene‐based composite membrane electrolyte for DMFC applications

Sulfonated branched polymer membranes have been gaining immense attention as the separator in energy‐related applications especially in fuel cells and flow batteries. Utilization of this branched polymer membranes in direct methanol fuel cell (DMFC) is limited because of large free volume and high methanol permeation. In the present work, sulfonated fullerene is used to improve the methanol barrier property of the highly branched sulfonated poly(ether ether ketone sulfone)s membrane without sacrificing its high proton conductivity. The existence of sulfonated fullerene with larger size and the usage of small quantity in the branched polymer matrix effectively prevent the methanol transportation channel across the membrane. The composite membrane with an optimized loading of sulfonated fullerene displays the highest proton conductivity of 0.332 S cm^?1 at 80°C. Radical scavenging property of the fullerene improves the oxidative stability of the composite membrane. Composite membrane exhibits the peak power density of 74.38 mW cm^?2 at 60°C, which is 30% larger than the commercial Nafion 212 membrane (51.78 mW cm^?2) at the same condition. From these results, it clearly depicts that sulfonated fullerene‐incorporated branched polymer electrolyte membrane emerges as a promising candidate for DMFC applications.