Ionically Cross‐Linked Proton Conducting Membranes for Fuel Cells

For improving stability without sacrificing ionic conductivity, ionically cross‐linked proton conducting membranes are fabricated from Na⁺‐form sulfonated poly(phthalazinone ether sulfone kentone) (SPPESK) and H⁺‐formed sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO). Ionically acid‐base cross‐linking between sulfonic acid groups in SPPO and phthalazone groups in SPPESK impart the composite membranes the good miscibility and electrochemical performance. In particular, the composite membranes possess proton conductivity of 60–110 mS cm⁻¹ at 30 °C. By controlling the protonation degree of SPPO within 40–100 %, the composite membranes with favorable cross‐linking degree are qualified for application in fuel cells. The maximum power density of the composite membrane reaches approximately 1100 mW cm⁻² at the current density of 2800 mA cm⁻² at 70 °C.     

Proton‐conductive membranes based on vanadium substituted heteropoly acids with Keggin structure and polymers

In this article, novel proton‐conducting composite membranes SPEEK/PW₁₁V and PVA/SiW₁₁V were synthesized from vanadium substituted heteropoly acids (H₄PW₁₁VO₄₀·8H₂O and H₅SiW₁₁VO₄₀·15H₂O, abbreviated as PW₁₁V and SiW₁₁V) and polymers (SPEEK or PVA) at the weight ratio 70 : 30. The membranes were characterized by the infrared spectroscopy, X‐ray powder diffraction, and scanning electron microscopy, which confirmed the maintenance of the Keggin framework and dispersion homogeneously in the polymer matrix without long‐range ordering. Their proton‐conducting properties were investigated with electrochemical impedance spectroscopy. The results show that the respective proton conductivities of SPEEK/PW₁₁V and PVA/SiW₁₁V membranes were in the order of 10^?2 and 10^?4 S cm^?1 at ambient temperature. The temperature dependence of the two composite membrane electrolytes exhibit Arrhenius behavior, and the observed activation energies to be 15.82 kJ mol^?1 for SPEEK/PW₁₁V and 14.40 kJ mol^?1 for PVA/SiW₁₁V, which indicates that the proton conduction complies with the Grotthuss mechanism. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42204.     

Novel Proton Conducting Membranes from the Combination of Sulfonated Polymers of Polyetheretherketones and Polyphosphazenes Doped with Sulfonated Single‐Walled Carbon Nanotubes

Intent on developing efficient proton exchange membranes used for direct methanol fuel cells as well as hydrogen fuel cells, a series of membranes based on sulfonated polyetheretherketone and sulfonated polyphosphazene‐graft copolymers is prepared by cross‐linking reaction because the former material has good enough mechanical property, while the latter is excellent in the proton transfer. The cross‐linked membranes combine the advantages of the two kinds of polymers. Among them, the membrane poly[(4‐trifluoromethylphenoxy)(4‐methylphenoxy)phosphazene]‐g‐poly {(styrene)₁₁‐r‐[4‐(4‐sulfobutyloxy)styrene]₃₃‐sulfonated poly(ether ether ketone)75 (CF₃‐PS₁₁‐PSBOS₃₃‐SPEEK75) shows a proton conductivity at 0.143 S cm⁻¹ under fully hydrated conditions at 80 °C and performs tensile strength about five times as much as did the sulfonated polyphosphazene membrane CF₃‐PS₁₁‐PSBOS₃₃. Further doping of sulfonated single‐walled carbon nanotubes (S‐SWCNTs) into the cross‐linked membranes on the screening of additives gives composite membrane CF₃‐PS₁₁‐PSBOS₃₃‐SPEEK75‐SWCNT possessing proton conductivity of 0.196 S cm⁻¹, even higher than that of Nafion 117 and a tensile strength comparable to that of Nafion 117. However, this significance of the composite membrane in the proton conduction is not observed in the test with a H₂/air fuel cell when it shows a maximal power density of 280 mW cm⁻² at 80 °C, whereas 294 mW cm⁻² is observed for CF₃‐PS₁₁‐PSBOS₃₃‐SPEEK75.

     

Single Radiation‐Induced Grafting Method for the Preparation of Two Proton‐ and Lithium Ion‐Conducting Membranes

Summary: Two distinct types of polymer electrolyte membranes for conducting protons and lithium ions have been prepared by a radiation‐induced grafting method. The polymer electrolyte precursor (PVDF‐g‐PS) is obtained by the simultaneous grafting of styrene onto poly(vinylidene fluoride) (PVDF) followed by one of two specific treatments. This includes sulfonation with a chlorosulfonic acid/dichloromethane mixture to obtain proton (H⁺)‐conducting membranes, or activation with LiPF₆/EC/DC liquid electrolyte to obtain lithium ion (Li⁺)‐conducting membranes. The chemical structure of the obtained electrolyte membranes is verified by FT‐IR spectroscopy. Differential scanning calorimetry is used to examine the changes in the crystallinity and the thermal properties of both electrolyte membranes during the preparation process. The thermal stability of both electrolyte membranes is also evaluated using thermal gravimetrical analysis. The obtained polymer electrolyte membranes achieve superior conductivity values: 1.61 × 10^?3 S · cm^?1 for Li⁺ and 5.95 × 10^?2 S · cm^?1 for H⁺ at room temperature at a polystyrene content of 50%. The results of this work suggest that high quality H⁺‐ and Li⁺‐conducting membranes can be obtained using a single radiation‐induced grafting method.

Schematic representation of the single root for preparation of Li⁺‐ and H⁺‐conducting membranes started by radiation‐induced grafting of styrene onto a PVDF film followed by chemical treatment.     

Nanocomposite hybrid membranes containing polyvinyl alcohol or poly(tetramethylene oxide) for fuel cell applications

New hybrid membranes containing polyvinyl alcohol (PVA) and poly(tetramethylene oxide) (PTMO) with heteropolyacid (HPA) as a hydrophilic inorganic modifier in an organic/inorganic matrix were developed for low-temperature proton exchange membrane fuel cells (PEMFCs). A maximum conductivity of 4.8 × 10⁻³ S cm⁻¹ was obtained at 80 °C and 75% RH for PVA/PWA/PTMO/H₃PO₄ (10/15/70/5 wt%), whereas the PVA/SiWA/MPTS/H₃PO₄ (50/10/10/30 wt%) membrane demonstrated a maximum conductivity of 8.5 × 10⁻³ S cm⁻¹ under identical conditions. These hybrid composite membranes were subsequently tested in a fuel cell. A maximum current density of 240 mA cm⁻² was produced at 70 °C for the PVA/PWA/PTMO/H₃PO₄ membrane, and the corresponding value for the PVA/SiWA/MPTS/H₃PO₄ membrane under identical conditions was 230 mA cm⁻². The small deviations in cell performance can be explained in terms of the variations in thickness of the membranes as well as differences in their conductivities. The fuel cell performances of these membranes decreased drastically when the temperature was increased to 100 °C.     

Enhanced proton conductivity from phosphoric acid‐incorporated 3D polyacrylamide‐graft‐starch hydrogel materials for high‐temperature proton exchange membranes

To enhance anhydrous proton conductivity of high‐temperature proton exchange membranes (PEMs), we report here the realization of H₃PO₄‐imbibed three‐dimensional (3D) polyacrylamide‐graft‐starch (PAAm‐g‐starch) hydrogel materials as high‐temperature PEMs using the unique absorption and retention of crosslinked PAAm‐g‐starch to concentrated H₃PO₄ aqueous solution. The 3D framework of PAAm‐g‐starch matrix provides enormous space to keep H₃PO₄ into the porous structure, which can be controlled by adjusting crosslinking agent and initiator dosages. Results show that the H₃PO₄ loading and therefore the proton conductivities of the membranes are significantly enhanced by increasing the amount of crosslinking agent and initiator dosages. Proton conductivities as high as 0.109 S cm^?1 at 180°C under fully anhydrous state are recorded. The high conductivities at high temperatures in combination with the simple preparation, low cost, and scalable matrices demonstrate the potential use of PAAm‐g‐starch hydrogel materials in high‐temperature proton exchange membrane fuel cells. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40622.     

Sulfonated graphene oxide‐doped proton conductive membranes based on polymer blends of highly sulfonated poly(ether ether ketone) and sulfonated polybenzimidazole

Simultaneously improving the proton conductivity and mechanical properties of a polymer electrolyte membrane is a considerable challenge in commercializing proton exchange membrane fuel cells. In response, we prepared a new series of miscible polymer blends and thus the corresponding crosslinked membranes based on highly sulfonated poly(ether ether ketone) and sulfonated polybenzimidazole. The blended membranes showed more compact structures, due to the acid‐base interactions between the two constituents, and improved mechanical and morphological properties. Further efforts by doping sulfonated graphene oxide (s‐GO) forming composite membranes led to not only significantly elevated proton conductivity and electrochemical performance, but also better mechanical properties. Notably, the composite membrane with the filler content of 15 wt % exhibited a proton conductivity of 0.217 S cm^?1 at 80 °C, and its maximum power density tested by the H₂/air single PEMFC cell at room temperature reached 171 mW cm^?2, almost two and half folds compared with that of the native membrane. As a result, these polymeric membranes provided new options as proton exchange membranes for fuel‐cell applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46547.     

Modification of sulfonated poly(ether ether ketone) membranes by impregnation with the ionic liquid 1‐butyl‐3‐methylimidazolium tetrafluoroborate for proton exchange membrane fuel cell applications

Sulfonated poly(ether ether ketone) (SPEEK) membranes were modified by impregnation with the ionic liquid (IL) 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMI.BF₄) by immersion into an IL aqueous solution for different periods of time. The modified membranes were investigated by thermogravimetric analyses (TGA), differential scanning calorimetry (DSC), ion exchange capacity (IEC), and conductivity. The SPEEK membrane immersed into the IL aqueous solution for 2 min showed greater dimensional and thermal stability than the pristine SPEEK membrane, and achieved higher decomposition temperatures. It also presented a higher conductivity value (1.0 mS cm^?1), indicating that BMI.BF₄ is a promoter of proton conductivity. The membrane electrode assembly (MEA) produced reached maximum values of power density of 0.13 W cm^?2 and current density of 0.54 A cm^?2 during fuel cell operation. The results indicate that the SPEEK membrane modified by immersion for 2 min is promising for use in a proton exchange membrane fuel cell. Its performance yielded values very close to those obtained with Nafion, which reaches maximum values of power density of 0.19 W cm^?2 and current density of 0.77 A cm^?2. POLYM. ENG. SCI. 56:1037–1044, 2016. © 2016 Society of Plastics Engineers     

Proton‐conducting blend membranes of crosslinked poly(vinyl alcohol)–sulfosuccinic acid ester and poly(1‐vinyl‐1,2,4‐triazole) for high temperature fuel cells

New type of composite membranes were synthesized by crosslinking of poly(vinyl alcohol) (PVA) with sulfosuccinic acid (SSA) and intercalating poly(1‐vinyl‐1,2,4‐triazole) (PVTri) into the resulting matrix. The complexed structure of the membranes was confirmed by Fourier transform infrared (FTIR) spectroscopy. The resulting hybrid membranes were transparent, flexible, and showed good thermal stability up to ～200°C. The proton conductivities of the membranes were investigated as a function of PVTri and SSA and operating temperature. The water/methanol uptake was measured and the results showed that solvent absorption of the materials increased with increasing PVTri content in the matrix. The proton conductivity of the membranes continuously increased with increasing SO₃H content, PVTri content, and the temperature. In the anhydrous state, the maximum proton conductivity is 7.7 × 10^?5 S/cm for PVA–SSA–PVTri‐1 and for PVA–SSA–PVTri‐3 is 1.6 × 10^?5 S/cm at 150°C. After humidification (RH = 100%), PVA–SSA–PVTri‐4 showed a maximum proton conductivity of 0.0028 S/cm at 60°C. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Preparation of PFSA‐PVA/PSf hollow fiber membrane for IPA/H2O pervaporation process

Using Na⁺ form of perfluorosulfonic acid (PFSA) and poly(vinyl alcohol) (PVA) as coating materials, polysulfone (PSf) hollow fiber ultrafiltration membrane as a substrate membrane, PFSA‐PVA/PSf hollow fiber composite membrane was fabricated by dip‐coating method. The membranes were post‐treated by two methods of heat treatment and by both heat treatment and chemical crosslinking. Maleic anhydride (MAC) aqueous solution was used as chemical crosslinking agent using 0.5 wt % H₂SO₄ as a catalyst. PFSA‐PVA/PSf hollow fiber composite membranes were used for the pervaporation (PV) separation of isopropanol (IPA)/H₂O mixture. Based on the experimental results, PFSA‐PVA/PSf hollow fiber composite membrane is suitable for the PV dehydration of IPA/H₂O solution. With the increment of heat treatment temperature, the separation factor increased and the total permeation flux decreased. The addition of PVA in PFSA‐PVA coating solution was favorable for the improvement of the separation factor of the composite membranes post‐treated by heat treatment. Compared with the membranes by heat treatment, the separation factors of the composite membranes post‐treated by both heat treatment and chemical crosslinking were evidently improved and reached to be about 520 for 95/5 IPA/water. The membranes post‐treated by heat had some cracks which disappeared after chemical crosslinking for a proper time. Effects of feed temperature on PV performance had some differences for the membranes with different composition of coating layer. The composite membranes with the higher mass fraction of PVA in PFSA‐PVA coating solution were more sensitive to temperature. It was concluded that the proper preparation conditions for the composite membranes were as follows: firstly, heated at 160°C for 1 h, then chemical crosslinking at 40°C for 3 h in 4% MAC aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of polybenzimidazole/α‐zirconium phosphate composites as proton exchange membrane

To improve the high‐temperature performance of proton exchange membranes, the polybenzimidazole (PBI)/α‐zirconium phosphate (α‐Zr(HPO₄)₂·nH₂O, α‐ZrP) proton exchange composite membranes were prepared in this study. PBI polymer containing a large amount of ether units has been synthesized from 3,3′‐ diaminobenzidine (DAB) and 4,4′‐oxybis (benzoic acid) by a direct polycondensation in polyphosphoric acid. The polymer exhibited a good solubility in most polar solvents. Inorganic proton conductor α‐ZrP nanoparticles have been obtained using a synthesis route involving separate nucleation and aging steps (SNAS). The effects of α‐ZrP doping content on the composite membrane performance were investigated. It was found that the introduction of ZrP improved the thermal stability of the composite membranes. The PBI/ZrP composite membranes exhibited excellent mechanical strength. The composite membrane with 10 wt% ZrP showed the highest proton conductivity of 0.192 S cm^?1 at 160°C under anhydrous condition. The proton conducting mechanism of the PBI/ZrP composite membranes was proposed to explain the proton transport phenomena. The experimental results suggested that the PBI/ZrP composite membranes may be a promising polymer electrolyte used in high temperature proton exchange membrane fuel cells (HT‐PEMFCs) under anhydrous condition. POLYM. ENG. SCI., 56:622–628, 2016. © 2016 Society of Plastics Engineers     

Preparation and Characterisation of Proton Exchange Membranes Based on Crosslinked Polybenzimidazole and Phosphoric Acid

Crosslinked polybenzimidazole (PBI) was synthesised via free radical polymerisation between N‐vinylimidazole and vinylbenzyl substituted PBI. The degree of crosslinking increases with increasing content of the crosslinker. The phosphoric acid doping behaviour, mechanical properties, proton conductivity and acid migration stability of crosslinked PBI and linear PBI are discussed. The results show that the acid doping ability decreases with increasing degree of crosslinking of PBI. The introduction of N‐vinylimidazole in PBI is beneficial to its oxidation stability. The mechanical stability of crosslinked PBI/H₃PO₄ membrane is better than that of linear PBI/H₃PO₄ membrane. The proton conductivity of the acid doped membranes can reach ∼10^–4 S cm^–1 for crosslinked PBI/H₃PO₄ composite membranes at 150 °C. The temperature dependence of proton conductivity of the acid doped membranes can be modelled by an Arrhenius relation. The proton conductivity of crosslinked PBI/H₃PO₄ composite membranes is a little lower than that of linear PBI/H₃PO₄ membranes with the same acid content. However, the migration stability of H₃PO₄ in crosslinked PBI/H₃PO₄ membranes is improved compared with that of linear PBI/H₃PO₄ membranes.     

New organic–inorganic hybrid membranes based on sulfonated polyimide/aminopropyltriethoxysilane doping with sulfonated mesoporous silica for direct methanol fuel cells

A series of novel composite methanol‐blocking polymer electrolyte membranes based on sulfonated polyimide (SPI) and aminopropyltriethoxysilane (APTES) doping with sulfonated mesoporous silica (S‐mSiO₂) were prepared by the casting procedure. The microstructure and properties of the resulting hybrid membranes were extensively characterized. The crosslinking networks of amino silica phase together with sulfonated mesoporous silica improved the thermal stability of the hybrid membranes to a certain extent in the second decomposition temperature (250–400°C). The composite membranes doping with sulfonated mesoporous silica (SPI/APTES/S‐mSiO₂) displayed superior comprehensive performance to the SPI and SPI/APTES membranes, in which the homogeneously embedded S‐mSiO₂ provided new pathways for proton conduction, rendered more tortuous pathways as well as greater resistance for methanol crossover. The hybrid membrane with 3 wt % S‐mSiO₂ into SPI/APTES‐4 (SPI/A‐4) exhibited the methanol permeability of 4.68 × 10^?6 cm² s^?1at 25°C and proton conductivity of 0.184 S cm^?1 at 80°C and 100%RH, while SPI/A‐4 membrane had the methanol permeability of 5.16 × 10^?6 cm² s^?1 at 25°C and proton conductivity of 0.172 S cm^?1 at 80°C and 100%RH and Nafion 117 exhibited the values of 8.80 × 10^?6 cm² s^?1 and 0.176 S cm^?1 in the same test conditions, respectively. The hybrid membranes were stable up to about 80°C and demonstrated a higher ratio of proton conductivity to methanol permeability than that of Nafion117. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Proton Conducting Membranes Based on Poly(2,2′‐imidazole‐5,5′‐bibenzimidazole)

Poly(2,2′‐imidazole‐5,5′‐bibenzimidazole) (PBI‐imi) was synthesized via the polycondensation between 3,3′,4,4′‐tetraaminobiphenyl and 4,5‐imidazole‐dicarboxylic acid. Effects of the reaction conditions on the intrinsic viscosity of the synthesized polymers were studied. The results show that the molecular weight of the polymers increases with increasing monomer concentration and reaction time, and then levels off. With higher reaction temperature, the molecular weight of the polymer is higher. With the additional imidazole group in the backbone, PBI‐imi shows improved phosphoric acid doping ability, as well as a little higher proton conductivity when compared with widely used poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] (PBI‐ph).Whereas, PBI‐imi and PBI‐ph have the similar chemical oxidation stability. PBI‐imi/3.0 H₃PO₄ composite membranes exhibit a proton conductivity as high as 10^–4 S cm^–1 at 150 °C under anhydrous condition. The temperature dependence of proton conductivity of acid doped PBI‐imi can be modeled by an Arrhenius equation.     

A redox‐mediator‐doped gel polymer electrolyte applied in quasi‐solid‐state supercapacitors

Methylene blue (MB) redox mediator was introduced into polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend host to prepare a gel polymer electrolyte (PVA‐PVP‐H₂SO₄‐MB) for a quasi‐solid‐state supercapacitor. The electrochemical properties of the supercapacitor with the prepared gel polymer electrolyte were evaluated by cyclic voltammetry, galvanostatic charge–discharge, electrochemical impedance spectroscopy, and self‐discharge measurements. With the addition of MB mediator, the ionic conductivity of gel polymer electrolyte increased by 56% up to 36.3 mS·cm^?1, and the series resistance reduced, because of the more efficient ionic conduction and higher charge transfer rate, respectively. The electrode specific capacitance of the supercapacitor with PVA‐PVP‐H₂SO₄‐MB electrolyte is 328 F·g^?1, increasing by 164% compared to that of MB‐undoped system at the same current density of 1 A·g^?1. Meanwhile, the energy density of the supercapacitor increases from 3.2 to 10.3 Wh·kg^?1. The quasi‐solid‐state supercapacitor showed excellent cyclability over 2000 charge/discharge cycles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39784.     

Synthesis and proton conductivity studies of 5‐aminotetrazole‐doped sulfonated polymer electrolyte membranes

This work reports the preparation and characterization of a new anhydrous proton conducting membrane based on poly(vinyl alcohol) (PVA), sulfosuccinic acid (SSA), and 5‐aminotetrazole (ATet) at various stoichiometric ratios. The proton conductivities of membranes were investigated as a function of ATet composition, SSA composition, and temperature. New anhydrous proton conducting membranes were characterized by infrared spectra, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), methanol permeability, and impedance measurements for proton conductivity. TGA showed that the samples were thermally stable up to 150°C. DSC results illustrated the homogeneity of the materials. Mechanical analysis showed that the storage modulus of the PVA–SSA–ATet blend polymer membranes decreased with increasing ATet content. The membranes with higher tetrazole content, or higher acid doping level presented the higher proton conductivity. PVA–SSA–ATet4 can exhibit an anhydrous proton conductivity of 1.7 × 10⁻³ S/cm at 130°C and the proton conductivity increased with increasing temperature and acid doping level. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Preparation and characterization of sulfonated block‐graft copolyimide/sulfonated polybenzimidazole blend membranes for fuel cell application

Polymer electrolyte blend membranes composed of sulfonated block‐graft polyimide (S‐bg‐PI) and sulfonated polybenzimidazole (sPBI) were prepared and characterized. The proton conductivity and oxygen permeability coefficient of the novel blend membrane S‐bg‐PI/sPBI (7 wt%) were 0.38 S cm^?1 at 90 °C and 98% relative humidity and 7.2 × 10^?13 cm³(STP) cm (cm² s cmHg)^?1 at 35 °C and 76 cmHg, respectively, while those of Nafion^® were 0.15 S cm^?1 and 1.1 × 10^?10 cm³(STP) cm (cm² s cmHg)^?1 under the same conditions. The apparent (proton/oxygen transport) selectivity calculated from the proton conductivity and the oxygen permeability coefficient in the S‐bg‐PI/sPBI (7 wt%) membrane was 300 times larger than that determined in the Nafion membrane. Besides, the excellent gas barrier properties based on an acid ? base interaction in the blend membranes are expected to suppress the generation of hydrogen peroxide and reactive oxygen species, which will degrade fuel cells during operation. The excellent proton conductivity and gas barrier properties of the novel membranes promise their application for future fuel cell membranes. © 2015 Society of Chemical Industry     

Preparation of water‐swollen hydrogel membranes for gas separation

Water‐swollen hydrogel (WSH) membranes for gas separation were prepared by the dip‐coating of asymmetric porous polyetherimide (PEI) membrane supports with poly(vinyl alcohol) (PVA)–glutaraldehyde (GA), followed by the crosslinking of the active layer by a solution method. Crosslinked PVA/GA film of different blend compositions (PVA/GA = 1/0.04, 0.06, 0.08, 0.10, 0.12 mol %) were characterized by differential scanning calorimetry (DSC) and their water‐swelling ratio. The swelling behavior of PVA/GA films of different blend compositions was dependent on the crosslinking density and chemical functional groups created by the reaction between PVA and GA, such as the acetal group, ether linkage, and unreacted pendent aldehydes in PVA. The permeation performances of the membranes swollen by the water vapor contained in a feed gas were investigated. The behavior of gas permeation through a WSH membrane was parallel to the swelling behavior of the PVA/GA film in water. The permeation rate of carbon dioxide through the WSH membranes was 10⁵ (cm³ cm^?2 s^?1 cmHg) and a CO₂/N₂ separation factor was about 80 at room temperature. The effect of the additive (potassium bicarbonate, KHCO₃) and catalyst (sodium arsenite, NaASO₂) on the permeation of gases through these WSH membranes was also studied. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1785–1791, 2001     

Modification of SPPESK proton exchange membranes through layer‐by‐layer self‐assembly

Sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) composite membranes are fabricated through electrostatic layer‐by‐layer (LbL) self‐assembly method with chitosan (CS) and phosphotungstic acid (PWA) to enhance the proton conductivity and stability. The results demonstrate that LbL self‐assembly has different effects on the SPPESK membrane substrates with different sulfonation degrees (DSs). It elevates proton conductivity of the SPPESK membrane of lower DS and enhances swelling stability of the SPPESK membrane of higher DS. For instance, at 80°C, proton conductivity of the SPPESK0.74/(CS/PWA)₁ membrane (lower DS) increases by 16%–96.49 mS cm^?1, and swelling ratio of the SPPESK1.01/(CS/PWA)₃ membrane (higher DS) decreases from 58 to 29%. Attribute to the electrostatic interaction and ion cross‐linking networks, permeability of the SPPESK0.74/(CS/PWA)₃ membrane and the SPPESK1.01/(CS/PWA)₅ membrane are reduced by 45 and 30%, respectively. The results indicate that the LbL self‐assembly has broadened the available DS range for fuel cell applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42867.     

Effect of organo clay content on proton conductivity and methanol transport through crosslinked PVA hybrid membrane for direct methanol fuel cell

In the present study, crosslinked poly(vinyl alcohol) (PVA) membranes were prepared using poly(styrene sulfonic acid-co-maleic acid) (PSSA_MA) (PVA:PSSA_MA = 1:7). The PSSA_MA was used both as a crosslinking agent and as a donor of the hydrophilic group (–SO₃H and/or –COOH). The hybrid membranes were prepared by modified clay such as Clay Na⁺, Clay 30B, and Clay 15A. The thermal, water uptake, proton and methanol transport properties of the hybrid membrane were found to be sensitive to the clay type and content. The hybrid membrane with Clay 30B shows higher proton conductivity than other hybrid membranes due to hydroxyethyl group. The membrane with Clay 15A showed the lowest methanol permeability due to lower specific gravity than other clay. Compared to the membrane without modified, the PVA/PSSA_MA/Clay 15A containing 4 wt% of Clay 15A showed both high proton conductivity (0.023 S/cm) and low methanol permeability (2.19 × 10^?7 cm²/s).