Self-assembled polyelectrolyte multilayered films on Nafion with lowered methanol cross-over for DMFC applications

The paper is concerned with the deposition of self-assembled polyelectrolyte multilayer on Nafion membrane by layer-by-layer (LbL) technique with lowered methanol cross-over for direct methanol fuel cell (DMFC) applications. The formation of self-assembled multilayered film on Nafion was characterized by UV–vis spectroscopy and it was found that the polyelectrolyte layers growth on the Nafion surface regularly. Furthermore, the proton conductivity and methanol cross-over measurements were carried out for characterization of the LbL self-assembled composite membranes. The results showed that the concentration and pH of the polyelectrolytes significantly affect the proton conductivity and methanol barrier properties of the composite membranes. 10⁻¹ monomol polyelectrolyte concentration and pH 1.8 was found to be optimum deposition conditions considering proton conductivity and methanol permeation properties of the LbL self-assembled composite membranes. The methanol permeability of the 10 bi-layers of PAH1.8/PSS1.8 deposited LbL self-assembly composite membrane was significantly suppressed and found to be 4.41 × 10⁻⁷ cm²/s while the proton conductivity value is in acceptable range for fuel cell applications.     

Transport properties of composite membranes containing silicon dioxide and Nafion

Silicon dioxide (SiO₂) nanoparticles were incorporated into Nafion 115 membranes using the sol–gel method in order to investigate their effect on water retention/transport, proton concentration, effective proton mobility, and proton conductivity. By adjusting the sol–gel reaction time, Nafion/SiO₂ membranes were fabricated with SiO₂ content ranging from 5.9 to 33.3 wt%. Because the density of the membranes decreased with increasing SiO₂ content and because dimensional changes with swelling in water of the composite membranes were less than that of unmodified Nafion 115 despite having increased water content, the theory that rigid scaffolding is formed inside the membrane is supported. Water content increases with increasing SiO₂ content due to void space formed inside the membrane. This increase in water content dilutes the protons in the membrane leading to lower proton concentration and therefore lower proton conductivity. A decreasing effective proton mobility with increasing SiO₂ content, likely due to an increase in the tortuosity of the proton-conducting pathway, also contributes to the decreasing conductivity. However, as evidenced by the similar water vapour permeance values, the SiO₂ nanoparticles do not increase the effective tortuosity of the water vapour transmission pathways.     

Integration of a highly ordered gold nanowires array with glucose oxidase for ultra-sensitive glucose detection

A highly sensitive amperometric nanobiosensor has been developed by integration of glucose oxidase (GO_x) with a gold nanowires array (AuNWA) by cross-linking with a mixture of glutaraldehyde (GLA) and bovine serum albumin (BSA). An initial investigation of the morphology of the synthesized AuNWA by field emission scanning electron microscopy (FESEM) and field emission transmission electron microscopy (FETEM) revealed that the nanowires array was highly ordered with rough surface, and the electrochemical features of the AuNWA with/without modification were also investigated. The integrated AuNWA–BSA–GLA–GO_x nanobiosensor with Nafion membrane gave a very high sensitivity of 298.2 μA cm⁻² mM⁻¹ for amperometric detection of glucose, while also achieving a low detection limit of 0.1 μM, and a wide linear range of 5–6000 μM. Furthermore, the nanobiosensor exhibited excellent anti-interference ability towards uric acid (UA) and ascorbic acid (AA) with the aid of Nafion membrane, and the results obtained for the analysis of human blood serum indicated that the device is capable of glucose detection in real samples.     

In situ IR reflectance absorption spectroscopy studies of the effect of Nafion on CO adsorption and electrooxidation at Pt nanoparticles

We have synthesized colloidal Pt nanoparticles with a mean particle size of 2.6±0.4 nm by reducing PtCl₂ dissolved in N,N-dimethylacetamide with t-BuMe₂SiH. The latter compound acted both as a reducing agent and a stabilizer of the Pt nanoparticles. Pt nanoparticles were deposited onto the Au substrate and IR reflectance absorption spectroscopy (IRRAS) was applied to investigate CO adsorption and oxidation at the surface of the catalyst. The reactivity of the catalyst covered with Nafion was compared with the reactivity of the catalyst without Nafion. In addition, the reactivity of the colloidal Pt was compared with the reactivity of bulk polycrystalline Pt. We found that CO oxidation proceeds at lower over-potentials at nanoparticles than at polycrystalline Pt. The IRRAS data indicate that the difference in the reactivity may be explained by a different mechanism of the oxidation reaction; Langmuir–Hinshelwood at Pt nanoparticles and island formation and growth at polycrystalline Pt. We have also observed that a film of Nafion slows down the CO oxidation reaction. The IRRAS spectra for CO adsorbed at Pt nanoparticles covered by Nafion were significantly different from the spectra recorded for the nanoparticles in the absence of Nafion. The spectroscopic features suggest that in the presence of Nafion the nanoparticles experience regions of lower and higher proton concentration.This paper is dedicated to Prof. G. Horanyi on the occasion of his 70th birthday and in recognition of his contribution to electrochemistry.     

Reinforced and self-humidifying composite membrane for fuel cell applications

A novel preparation method for a composite proton exchange membrane with reinforced strength and self-humidifying property was developed. Using self-assembly method, highly dispersed poly(diallyldimethylammonium chloride) (PDDA) stabilized Pt nanoparticles were mounted onto the pores of poly(tetrafluoroethylene) (PTFE) porous film to serve the self-humidifying purpose. With Pt nanoparticles fixed on the PTFE pores, the potential problem of any short circuit because of the use of metal nanoparticles can be prevented. Pt-PDDA/PTFE substrate in the composite membrane can enhance the mechanical strength of the membrane and distribute self-humidifying layer adjacent to the anode side. Compared with the cells fabricated with conventional Nafion^® and PTFE/Nafion membranes, the performance of the cells with this composite membrane is dramatically improved under dry conditions. Electrochemical impedance spectroscopy technique revealed that these self-humidifying composite membranes could minimize membrane conductivity loss under dry conditions.     

Synthesis and anhydrous proton conductivity of poly(5-vinyltetrazole) prepared by free radical polymerization

5-Vinyltetrazole (VT)-based polymer is mainly produced by ‘click chemistry’ from polyacrylonitrile due to the unavailability of 5-vinyltetrazole monomer, which usually produces copolymers of VT and acrylonitrile rather than pure poly(5-vinyltetrazole) (PVT). In present work, VT was synthesized from 5-(2-chloroethyl)tetrazole via dehydrochlorination. A series of PVT with different molecular weight were synthesized by normal free radical polymerization. The chemical structures of VT and PVT were characterized by ¹H NMR and FTIR. PVT without any doped acid exhibits certain proton conductivity at higher temperature and anhydrous state. The proton conductivity of PVT decreases at least 2 orders of magnitude after methylation of tetrazole. PVT and PVT/H₃PO₄ composite membranes are thermally stable up to 200 °C. The glass transition temperature (T_g) of PVT/xH₃PO₄ composite membranes is shifted from 90 °C for x = 0.5 to 55 °C for x = 1. The temperature dependence of DC conductivity for pure PVT exhibits a simple Arrhenius behavior in the temperature range of 90–160 °C, while PVT/xH₃PO₄ composite membranes with higher H₃PO₄ concentration can be fitted by Vogel–Tamman–Fulcher (VTF) equation. PVT/1.0H₃PO₄ exhibits an anhydrous proton conductivity of 3.05 × 10⁻³ at 110 °C. The transmission of the PVT/xH₃PO₄ composite membrane is above 85% in the wavelength of visible light and changes little with acid contents. Thus, PVT/xH₃PO₄ composite membranes have potential applications not only in intermediate temperature fuel cells but also in solid electrochromic device.     

Properties of PWA/ZrO2-doped phosphosilicate glass composite membranes for low-temperature H2/O2 fuel cell applications

Phosphosilicate doped with a mixture of phosphotungstic acid and zirconium oxide (PWA/ZrO₂–P₂O₂–SiO₂) was investigated as potential glass composite membranes for use as H₂/O₂ fuel cell electrolytes. The glass membranes were studied with respect to their structural and thermal properties, proton conductivity, pore characteristics, hydrogen permeability, and performance in fuel cell tests. Thermal analysis including TG and DTA confirmed that the glass was thermally stable up to 400 °C. The dependence of the conductivity on the humidity was discussed based on the PWA content in the glass composite membranes. The proton transfer in the nanopores of the PWA/ZrO₂–P₂O₅–SiO₂ glasses was investigated and it was found that a glass with a pore size of ∼3 nm diameters was more appropriate for fast proton conduction. The hydrogen permeability rate was calculated at various temperatures, and was found to be comparatively higher than for membranes based on Nafion^®. The performance of a membrane electrolyte assembly (MEA) was influenced by its PWA content; a power density of 43 mW/cm² was obtained at 27 °C and 30% relative humidity for a PWA/ZrO₂–P₂O₅–SiO₂ glass membrane with a composition of 6–2–5–87 mol% and 0.2 mg/cm² of Pt/C loaded on the electrode.     

Characterization and performance of proton exchange membranes for direct methanol fuel cell: Blending of sulfonated poly(ether ether ketone) with charged surface modifying macromolecule

Modification of sulfonated poly(ether ether ketone) (SPEEK) membrane was attempted by blending charged surface modifying macromolecule (cSMM). The modified membrane was tested for direct methanol fuel cell (DMFC) application; i.e. a SPEEK/cSMM blend membrane was compared to a SPEEK membrane and a Nafion 112 membrane for the thermal and mechanical stability, methanol permeability, and proton conductivity. Thermal and mechanical stability of the blended membrane were slightly reduced from the SPEEK membrane but still higher than the Nafion 112 membrane. The blend membrane was found to be promising for DMFC applications because of its lower methanol diffusivity (2.75 × 10⁻⁷ cm² s⁻¹) and higher proton conductivity (6.4 × 10⁻³ S cm⁻¹), than the SPEEK membrane. A plausible explanation was given for the favorable effect of cSMM blending.     

Synthesis and characterization of poly(aryl ether ketone) ionomers with sulfonic acid groups on pendant aliphatic chains for proton-exchange membrane fuel cells

A series of parent poly(aryl ether ketone)s bearing different content of unsaturated pendant propenyl groups were synthesized via nucleophilic substitution polymerization from 3,3′-diallyl-4,4′-dihydroxybiphenyl, 9,9′-bis(4-hydroxyphenyl) fluorene and 4,4′-difluorobenzophenone. The polymers with pendant aliphatic sulfonic acid groups were further synthesized by free radical thiol-ene coupling reactions between 3-mercapto-1-propanesulfonic sodium and the parent propenyl functional copolymers. The resulting sulfonated polymers with high inherent viscosity (1.83-4.69 dL/g) were soluble in polar organic solvents and can form flexible and transparent membranes by casting from their solutions. The copolymers with different ion exchange capacity could be conveniently synthesized by varying the monomers ratios. Transmission electron microscopy (TEM) was used to examine the microstructures of the membrane and the results revealed that significant hydrophilic/hydrophobic microphase separation with spherical, uniform-sized (5-10 nm) and well-dispersed hydrophilic domains was afforded. The proton conductivities of the as-prepared membranes and the state-of-the-art Nafion 117 membrane in fully hydrated state were investigated. The results revealed that the proton conductivity of the synthesized membranes increased more remarkably than that of Nafion 117 membrane with increasing temperature. The membrane with 1.69 mequiv/g of IEC had a conductivity of 2.5 × 10⁻² Scm⁻¹ at 100 °C. The membranes also possessed excellent mechanical properties, good thermal, oxidative, hydrolytic and dimensional stabilities.     

Preparation of Nafion/PTFE/Zr(HPO4)2 composite membranes by direct impregnation method

The viscosities of as received 5.1 wt.% Nafion solutions (EW = 1100, Du Pont Co) blended with various concentrations of ZrOCl₂ were studied. We show the solution viscosity decreases as the wt. ratio of [ZrOCl₂]/[Nafion] is increased from 0.0 to 0.03, then the viscosity does not change significantly as the wt. ratio of [ZrOCl₂]/[Nafion] is increased from 0.03 to 0.16, and then the viscosity increases dramatically as the wt. ratio of [ZrOCl₂]/[Nafion] is increased above 0.16. Four Nafion solutions consisting of 5.1 wt.% Nafion and ZrOCl₂ with [ZrOCl₂]/[Nafion] wt. ratios of 0.019–0.24 were used with porous poly(tetrafluoroethylene) (PTFE) film to prepare zirconium hydrogenphosphate (ZrP) hybridized Nafion/PTFE (NF–ZrP) composite membranes by direct impregnating porous PTFE in Nafion/ZrOCl₂ solutions. The influence of [ZrOCl₂]/[Nafion] wt. ratio of Nafion/ZrOCl₂ solution on the membrane morphology of NF–ZrP and polyelectrolyte membrane fuel cell (PEMFC) performance at temperatures of 110–130 °C with relative humidity of 51.7–28.8% RH was investigated.     

Preparation of Nafion/sulfonated poly(phenylsilsesquioxane) nanocomposite as high temperature proton exchange membranes

Nafion/sulfonated poly(phenylmethyl silsesquioxane) (sPPSQ) composite membranes are fabricated using homogeneous dispersive mixing and a solvent casting method for direct dimethyl ether fuel cell (DDMEFC) applications operated above 100 °C. The inorganic conducting filler, sPPSQ significantly affects the characteristics in the nanocomposite membranes by functionalization with an organic sulfonic acid to PPSQ. Moreover, sPPSQ content plays an important role in membrane properties such as microstructure, proton conductivity, fuel crossover, and single cell performance test. With increasing sPPSQ content in the nanocomposite membrane, the proton conductivity increased and fuel crossover decreased. However, in a higher temperature range above 110 °C, Nafion/sPPSQ 5 wt.% composite membrane has the highest proton conductivity. Also, the DME permeability for the composite membrane with higher sPPSQ content increased sharply. The excessive sPPSQ content caused a large aggregation of inorganic fillers, leading to the deterioration of membrane properties. In this study, the optimal sPPSQ content for maximizing the DDMEFC performance was 5 wt.%. Our nanocomposite membranes demonstrated proton conductivities as high as 1.57 × 10⁻¹ S/cm at 120 °C, which is higher than that of Nafion. The cell performances were compared to Nafion/sPPSQ composite membrane with Nafion 115, and the composite membrane with sPPSQ yielded better cell performance than Nafion 115 at temperatures ranging from 100 to 120 °C and at pressures from 1 to 2 bar.     

A novel composite Nafion membrane for direct alcohol fuel cells

Trifluoromethanesulfonic acid or triflate acid, chemical formula CF₃SO₃H, is regarded as one of the strongest acids and resembles Nafion^® in structure. Erbium triflate, a lanthanum salt of triflate, is thermally stable. This paper reports data on the formation of membranes by the fixation of erbium triflate salts (ErTfO) into the Nafion structure. Five different loadings of ErTfO were used to fabricate ErTfO/Nafion composite membranes and these were characterized, extensively for possible use in direct alcohol fuel cells. The membranes were characterized using XRD, TGA, FTIR, and for mechanical strength, water uptake, ion exchange capacity, alcohol uptake, swelling, proton conductivity, alcohol permeability and oxygen stability. The ErTfO/Nafion composite membranes reduced alcohol permeability by 77–80%. The proton conductivity of 3% ErTfO/Nafion composite membranes was 38% higher than that of a pure cast Nafion membrane. The oxygen stability of the ErTfO/Nafion composite membranes was higher than pure cast Nafion. However, the mechanical strength of 7% and 9% ErTfO/Nafion was lower than that of pure cast Nafion. The composite membrane was chemically stable and has potential for use in direct alcohol fuel cells.     

Anhydrous proton conducting membranes based on crosslinked graft copolymer electrolytes

A comb-like copolymer consisting of a poly(vinylidene fluoride-co-chlorotrifluoroethylene) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. P(VDF-co-CTFE)-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP) using CTFE units as a macroinitiator. Successful synthesis and a microphase-separated structure of the copolymer were confirmed by proton nuclear magnetic resonance (¹H NMR), FT-IR spectroscopy, and transmission electron microscopy (TEM). This comb-like polymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the –OH groups of PHEA and the –COOH groups of IDA. Upon doping with phosphoric acid (H₃PO₄) to form imidazole–H₃PO₄ complexes, the proton conductivity of the membranes continuously increased with increasing H₃PO₄ content. A maximum proton conductivity of 0.015 S/cm was achieved at 120 °C under anhydrous conditions. In addition, these P(VDF-co-CTFE)-g-PHEA/IDA/H₃PO₄ membranes exhibited good mechanical properties (765 MPa of Young's modulus), and high thermal stability up to 250 °C, as determined by a universal testing machine (UTM) and thermal gravimetric analysis (TGA), respectively.     

Novel proton-conductive nanochannel membranes with modified SiO2 nanospheres for direct methanol fuel cells

A novel approach is proposed to prepare a proton-conductive nanochannel membrane based on polyvinylidene difluoride (PVDF) porous membrane with modified SiO₂ nanospheres. The hydrophilic PVDF porous membrane with a 450-nm inner pore size was chosen as the supporting structure. Pristine SiO₂ with a uniform particle size of 95–110 nm was synthesized and functionalized with –NH₂ and –COOH, respectively. Through-plane channels of porous membrane and arranged functional nanoparticles in pores could contribute to constituting efficient proton transfer channels. The characteristics such as morphology, thermal stability, water uptake, dimensional swelling, proton conductivity and methanol permeability as proton exchange membranes, of the SiO₂ nanospheres, and the composite membrane were investigated. The formation of ionic channels in membrane enhanced the water uptakes and proton conduction abilities of the composite membranes. PVDF/Nafion/SiO₂–NH₂ exhibited superior proton conductivities (0.21 S cm^?1) over other samples due to several proton sites and the acid–base pairs formed between –NH₂ and –SO₃H. Furthermore, all the composite membranes exhibited improved methanol resistance compared with Nafion. Therefore, such a design based on porous membrane provided feasibility for high-performance proton exchange membrane in fuel cell applications.     

Polyelectrolyte-based electrochemiluminescence enhancement for Ru(bpy)3 loaded by SiO2 nanoparticle carrier and its high sensitive immunoassay

In this paper the strong electrochemiluminescence (ECL) nanoparticles have been prepared based on the anionic polyelectrolyte sodium polyacrylate (PAA)-ECL enhancement for Ru(bpy)₃²⁺, which were loaded by the carrier of SiO₂ nanoparticle. There were two kinds of Ru(bpy)₃²⁺ for the as-prepared nanoparticles, the doped one and the exchanged one. The former was loaded inside the ECL nanoparticles by doping, in a form of ion-pair macromolecules PAA–Ru(bpy)₃²⁺. The corresponding ECL was enhanced about 2 times owing to the doping increase of Ru(bpy)₃²⁺. The latter was loaded on the PAA-doped Nafion membrane by ion exchange. The corresponding ECL was enhanced about 3 times owing to the ion-exchanging increase of Ru(bpy)₃²⁺. At the same time, ECL intensity of the doped-inside Ru(bpy)₃²⁺ was further enhanced 13 times because polyelectrolyte PAA in the doped membrane could obviously enhance electron transfer between the doped Ru(bpy)₃²⁺ and the working electrode. Furthermore, based on hydrophobic regions of the doped membrane antibody labeling could be easily realized by the as-prepared nanoparticles and then a high sensitive ECL immunoassay for HBsAg was developed. The linear range was between 1.0 and 100 pg mL⁻¹ (R² = 0.9912). The detection limit could be as low as 0.11 pg mL⁻¹ (signal-to-noise ratio = 3).     

A chitosan–polypyrrole magnetic nanocomposite as μ-sorbent for isolation of naproxen

An extracting medium based on chitosan–polypyrrole (CS–PPy) magnetic nanocomposite was synthesized by chemical polymerization of pyrrole at the presence of chitosan magnetic nanoparticles (CS-MNPs) for micro-solid phase extraction. In this work, magnetic nanoparticles, the modified CS-MNPs and different types of CS–PPy magnetic nanocomposites were synthesized. Extraction efficiency of the CS–PPy magnetic nanocomposite was compared with the CS-MNPs and Fe₃O₄ nanoparticles for the determination of naproxen in aqueous samples, via quantification by spectrofluorimetry. The scanning electron microscopy images obtained from all the prepared nanocomposites revealed that the CS–PPy magnetic nanocomposite possess more porous structure. Among different synthesized magnetic nanocomposites, CS–PPy magnetic nanocomposite showed a prominent efficiency. Influencing parameters on the morphology of CS–PPy magnetic nanocomposite such as weight ratio of components was also assayed. In addition, effects of different parameters influencing the extraction efficiency of naproxen including desorption solvent, desorption time, amount of sorbent, ionic strength, sample pH and extraction time were investigated and optimized. Under the optimum condition, a linear calibration curve in the range of 0.04–10 μg mL⁻¹ (R² = 0.9996) was obtained. The limits of detection (3S_b) and limits of quantification (10S_b) of the method were 0.015 and 0.04 μg mL⁻¹ (n = 3), respectively. The relative standard deviation for water sample spiked with 0.1 μg mL⁻¹ of naproxen was 3% (n = 5) and the absolute recovery was 92%. The applicability of method was extended to the determination of naproxen in tap water, human urine and plasma samples. The relative recovery percentages for these samples were in the range of 56–99%.     

Systematic investigation on new SrCo1−yNbyO3−δ ceramic membranes with high oxygen semi-permeability

SrCo_1−yNb_yO_3−δ (y = 0.025–0.4) were synthesized for oxygen separation application. The crystal structure, phase stability, oxygen nonstoichiometry, electrical conductivity, and oxygen permeability of the oxides were systematically investigated. Cubic perovskite, with enhanced phase stability at higher Nb concentration, was obtained at y = 0.025–0.2. However, the further increase in niobium concentration led to the formation of impurity phase. The niobium doping concentration also had a significant effect on electrical conductivity and oxygen permeability of the membranes. SrCo_0.9Nb_0.1O_3−δ exhibited the highest electrical conductivity and oxygen permeability among the others. It reached a permeation flux of ∼2.80 × 10⁻⁶ mol cm⁻² s⁻¹ at 900 °C for a 1.0-mm membrane under an air/helium oxygen gradient. The further investigation demonstrated the oxygen permeation process was mainly rate-limited by the oxygen bulk diffusion process.     

Synthesis and characterization of P2O5–ZrO2–SiO2 membranes doped with tungstophosphoric acid (PWA) for applications in PEMFC

Homogeneous, transparent and crack-free P₂O₅–ZrO₂ and P₂O₅–ZrO₂–SiO₂ membranes have been synthesized by the sol–gel process. A first step has been oriented to the optimization of the synthesis and characterization of different compositions by TGA, FE-SEM, FTIR and EIS to choose the best inorganic composition in terms of chemical and mechanical stability, and proton conductivity. The addition of SiO₂ improves the mechanical and chemical stability. On the other hand, compositions with higher content in P₂O₅ have demonstrated lower mechanical and chemical stability against water, but higher proton conductivity. The water retention and high porosity of inorganic membranes leads to high proton conductivity, 10⁻² S/cm, at 140 °C and 100% relative humidity. The second step has been focused in the study of doped inorganic membranes of molar composition 99.65(40P₂O₅–20ZrO₂–40SiO₂)–0.35PWA. The high homogeneity, transparency and SEM-EDX analysis of these membranes indicates no phase separation suggesting that PWA is well dispersed in the inorganic structure. The incorporation of PWA in sol–gel oxides provides an increase of the proton conductivity at low relative humidity due to the adequate distribution of PWA in the inorganic network. Conductivity increases in two orders of magnitude at low humidity (10⁻⁴ S/cm at 50 °C and 62% RH) compared with undoped sol–gel oxide membranes.     

Methanol permeability in sulfonated poly(etheretherketone) membranes: A comparison with Nafion membranes

Partially sulfonated poly(etheretherketone) (SPEEK) samples were prepared by modification of corresponding poly(etheretherketone) (PEEK) with concentrated sulfuric acid. Membranes cast from these materials were evaluated as polymer electrolytes for direct methanol fuel cells (DMFCs). SPEEK membranes were characterized by ¹H NMR, FT-IR and TGA. The transverse proton conductivities increased from 4.1 to 9.3 × 10⁻³ S/cm with the increase of the degree of sulfonation (DS) from 0.59 to 0.93. These values were comparable with that of Nafion 117 membrane (1.0 × 10⁻² S/cm) measured under the same condition. Nearly one order magnitude difference between transverse conductivity and longitudinal conductivity was found. The methanol permeabilities of the SPEEK membranes were all lower than that of Nafion 117 membrane. The effects of temperature and methanol concentration on the methanol permeability were also studied. In addition, the selectivities of the SPEEK membranes for protons and methanol were all higher than that of Nafion 117 membrane.     

Custom-made sulfonated poly (vinylidene fluoride-co-hexafluoropropylene) nanocomposite membranes for vanadium redox flow battery applications

Sulfonated poly (vinylidene fluoride-co-hexafluoropropylene) (SPVDF-co-HFP) based nanocomposite proton exchange membranes (PEM) are fabricated by simple solution casting method using polydopamine coated exfoliated molybdenum disulfide (PDA-MoS₂) nanosheets as an alternative for Nafion® in vanadium redox flow batteries (VRFBs). PDA-MoS₂ is synthesized by the etching of exfoliated MoS₂ nanosheets with dopamine molecule by self-polymerization method. Various characteristic results clearly demonstrated that the incorporated PDA-MoS₂ nanosheets homogeneously distributed into the SPVDF-co-HFP matrix and the presence of NH/NH₂ group electrostatically interacts with SPVDF-co-HFP to form a strong acid-base pair and thus enhances the proton transport via Grotthuss type mechanism. Besides, the improvement in surface hydrophilicity provides the vehicle type conduction also. As a result, SPVDF-co-HFP/PM nanocomposite membranes showed higher proton conductivity in comparison with the pristine membrane. Especially SPVDF-co-HFP/PM-1 membrane demonstrated the excellent proton conductivity of 5.24 × 10⁻³ Scm⁻¹ at 25 °C, lower vanadium-ion permeability of 1.05 × 10⁻⁸ cm²min⁻¹ and highest membrane selectivity of 49.9 × 10⁴ Scm⁻³min. On the other hand, vanadium-ion stability of the membrane increased by adding the PD-MoS₂ content is attributed to their strong electrostatic attraction towards the polymer matrix. Overall results suggested that the SPVDF-co-HFP/PM-1 nanocomposite membrane is found to be a better alternative for commercially costly Nafion in VRFB applications.