New highly proton-conducting membrane poly(vinylpyrrolidone)(PVP) modified poly(vinyl alcohol)/2-acrylamido-2-methyl-1-propanesulfonic acid (PVA-PAMPS) for low temperature direct methanol fuel cells (DMFCs)

A new type of chemically cross-linked polymer blend membranes consisting of poly(vinyl alcohol) (PVA), 2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS) and poly(vinylpyrrolidone) (PVP) have been prepared and evaluated as proton conducting polymer electrolytes. The proton conductivity (σ) of the membranes was investigated as a function of cross-linking time, blending composition, water content and ion exchange capacity (IEC). Membranes were also characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), and the differential scanning calorimetry (DSC). Membrane swelling decreased with cross-linking time, accompanied by an improvement in mechanical properties and a small decrease in proton conductivity due to the reduced water absorption. The membranes attained 0.088 S cm⁻¹ of the proton conductivity and 1.63 mequiv g⁻¹ of IEC at 25±2 °C for a polymer composition PVA-PAMPS-PVP being 1:1:0.5 in mass, and a methanol permeability of 6.1×10⁻⁷ cm² s⁻¹, which showed a comparable proton conductivity to Nafion 117, but only one third of Nafion 117 methanol permeability under the same measuring conditions. The membranes displayed a relatively high oxidative durability without weight loss of the membranes (e.g. 100 h in 3% H₂O₂ solution and 20 h in 10% H₂O₂ solution at 60 °C). PVP, as a modifier, was found to play a crucial role in improving the above membrane performances.     

Direct synthesis of sulfonated poly(ether ether ketone ketone)s (SPEEKKs) proton exchange membranes for fuel cell application

A series of sulfonated poly(ether ether ketone ketone)s (SPEEKK)s based membranes have been prepared and evaluated for proton exchange membranes (PEM). The membranes show very good thermal and mechanical stabilities. The structures of membranes were studied with AFM. The membranes show very good proton conductive ability (25 °C: 0.007-0.04 s/cm) and methanol resistance (25 °C: 7.68×10⁻⁸ to 5.75×10⁻⁷ cm²/s). The methanol diffusion coefficients of membranes are much lower than that of Nafion (2×10⁻⁶ cm²/s). The SPEEKKs membranes show very good respective in direct methanol fuel cells (DMFC) usages.     

Hybrid proton-conducting membranes for polymer electrolyte fuel cells: Phosphomolybdic acid doped poly(2,5-benzimidazole)—(ABPBI-H3PMo12O40)

The synthesis and characterization of a novel hybrid organic-inorganic material formed by phosphomolybdic acid H₃PMo₁₂O₄₀ (PMo₁₂) and poly(2,5-benzimidazole) (ABPBI) is reported. This material, composed of two proton-conducting components, can be cast in the form of membranes from methanesulfonic acid (MSA) solutions. Upon impregnation with phosphoric acid, the hybrid membranes present higher conductivity than the best ABPBI polymer membranes impregnated in the same conditions. These electrolyte membranes are stable up to 200 °C, and have a proton conductivity of 3 × 10⁻² S cm⁻¹ at 185 °C without humidification. These properties make them very good candidates as membranes for polymer electrolyte membrane fuel cells (PEMFC) at temperatures of 100-200 °C.     

Nafion/Analcime and Nafion/Faujasite composite membranes for polymer electrolyte membrane fuel cells

The Nafion/zeolite composite membranes were synthesized for polymer electrolyte fuel cells (PEMFCs) by adding zeolite in the matrix of Nafion polymer. Two kinds of zeolites, Analcime and Faujasite, having different Si/Al ratio were used. The physico-chemical properties of the composite membranes such as water uptake, ion-exchange capacity, hydrogen permeability, and proton conductivity were determined. The fabricated composite membranes showed the significant improvement of all tested properties compared to that of pure Nafion membrane. The maximum proton conductivity of 0.4373 S cm⁻¹ was obtained from Nafion/Analcime (15%) at 80 °C which was 6.8 times of pure Nafion (0.0642 S cm⁻¹ at 80 °C). Conclusively, Analcime exhibited higher improvement than Faujasite.     

Proton exchange membranes based on sulfonated crosslinked polystyrene micro particles dispersed in poly(dimethyl siloxane)

Proton exchange membranes of sulfonated crosslinked polystyrene (SXLPS) particles dispersed in crosslinked poly(dimethyl siloxane) matrix were investigated. Three different sizes of particles—25, 8 and 0.08 μm—were used at loadings from 0 to 50 wt% and the influence of these variables on the water and methanol uptake and proton conductivity were observed. With the reduction in particle size in the composite membrane, more water or methanol uptake was observed. Three different states of water were revealed in the composite membranes by differential scanning calorimetry (DSC). The number of bound water molecules per SO₃H group was 11-15 in membranes with 8- and 25-μm SXLPS. The ratio of bound to unbound water molecules was more than one in these membranes, whereas it was less than one in membranes with 0.08-μm SXLPS. The proton conductivities of the membranes increased with the increase in particle loading. At particle loadings above 35 wt%, membranes containing 8-μm SXLPS had higher conductivity compared to 25-μm SXLPS at room temperature. The conductivity of membranes containing 0.08-μm SXLPS was restricted to 10⁻³ S/cm because of the inherently low IEC of the particles. Increasing the temperature from 30 to 80 °C drastically enhanced the conductivity of the composite membranes compared to Nafion^® 112. At 80 °C, conductivities as high as 0.11±0.04 S/cm were observed for membranes containing more than 30 wt% of 25-μm SXLPS particles.     

Solution-cast Nafion/montmorillonite composite membrane with low methanol permeability

Perfluorosulfonate ionomer dispersions in dimethylformamide solvent were used to form solution-cast membranes. Modified composite membranes were prepared with the addition of 1 and 5 wt.% montmorillonite salts. Measurements of water uptake, solubility and methanol permeation of the cast membranes were conducted. Tangential conductivities were measured directly on membranes fully immersed in deionized water by means of impedance spectroscopy. Results show that the addition of a low quantity of silicate did not alter the conductivity (94-96 mS cm⁻¹ at 25 °C), but produced a marked decrease of methanol permeability (−6%). Also a simple model was proposed to explain the increase of tangential conductivity with decreasing thickness of Nafion^® and recast membranes.     

Development of a new graded-porosity FeAl alloy by elemental reactive synthesis

A new graded-porosity FeAl alloy can be fabricated through Fe and Al elemental reactive synthesis. FeAl alloy with large connecting open pores and permeability were used as porous supports. The coating was obtained by spraying slurries consisting of mixtures of Fe powder and Al powder with 3-5 μm diameter onto porous FeAl support and then sintered at 1100 °C. The performances of the coating were compared in terms of thickness, pore diameter and permeability. With an increase in the coating thickness up to 200 μm, the changes of maximum pore size decreased from 23.6 μm to 5.9 μm and the permeability decreased from 184.2 m³ m^− 2 kPa^− 1 h^− 1 to 76.2 m³ m^− 2 kPa^− 1 h^− 1, respectively, for a sintering temperature equal to 1100 °C. The composite membranes have potential application for excellent filters in severe environments.     

Assembly of 8YSZ nanoparticles into gas-tight 1-2 μm thick 8YSZ electrolyte layers using wet coating methods

The application of a thin film electrolyte layer with a thickness in the micrometer range could greatly improve current solid oxide fuel cells (SOFCs) in terms of operating temperature and power output. Since the achievable minimal layer thickness with conventional powder coating methods is limited to ∼5 μm, a variety of thin film methods have been studied, but results on regular large-scale anode substrates are still lacking in the literature. In this paper, a wet coating process is presented for fabricating gas-tight 1-2 μm thick 8YSZ electrolyte layers on a regular NiO/8YSZ substrate, with a rough surface, a high porosity and a large pore size. These layers were deposited in a similar way as conventional suspension based layers, but the essential difference includes the use of coating liquids (nano-dispersion, sol) with a considerably smaller particle size (85 nm, 60 nm, 35 nm, 6 nm). Successful deposition of such layers was accomplished by means of an innovative coating process, which involves the preparation of a hybrid polyvinyl alcohol/8YSZ membrane by dip-coating or spin-coating and subsequently burning out the polymer part at 500 °C. Results from He leak tests confirmed that the sintered layers posses a very low number of defects and with values in the range 10⁻⁴-10⁻⁶ (hPa dm³)/(s cm²) the gas-tightness of the thin film layers is satisfactory for fuel cell operation. Moreover, preliminary results have also indicated a potential reduction of the sintering temperature from 1400 °C to the range 1200-1300 °C, using the presented coating process.     

Chitosan membranes filled by GPTMS-modified zeolite beta particles with low methanol permeability for DMFC

Uniform zeolite beta particles about 800 nm in diameter were synthesized by a hydrothermal method, and functionalized by γ-glycidoxypropyltrimethoxysilane (GPTMS). Subsequently, chitosan (CS) membranes filled by GPTMS-modified zeolite beta particles were prepared, and characterized by SEM, FT-IR, XRD and TGA. Compared with the pure CS and Nafion^®117 membrane, these CS/zeolite beta hybrid membranes show apparently the lower methanol permeability, which could be assigned to the better interfacial morphology and compatibility between the GPTMS-modified zeolite beta particles and chitosan matrix. In all the prepared CS/zeolite beta hybrid membranes, the CS membrane filled by 10 wt.% GPTMS-modified zeolite beta particles exhibits the lowest methanol permeability, which is 4.4 × 10⁻⁷ and 2.2 × 10⁻⁷ cm² s⁻¹ at 2 and 12 M methanol concentration, respectively. The proton conductivity of this hybrid membrane is 1.31 × 10⁻² S cm⁻¹, which is slightly lower than that of the pure CS membrane. The selectivity of CS/GPTMS-zeolite beta membranes is comparable with Nafion^® 117 at 2 M methanol concentration, and much higher at 12 M methanol concentration.     

Performance of an anode-supported tubular solid oxide fuel cell (SOFC) under pressurized conditions

An anode-supported tubular solid oxide fuel cell (SOFC) with a 15-μm thick YSZ electrolyte and an active area of 100 cm² was successfully fabricated by co-firing process, and the cell performance was measured under both atmospheric and pressurized conditions. The experimental results showed that the cell performance was significantly improved under the pressurized condition. When the pressure was increased from 1 to 6 atm, the maximum power density increased from 135.0 to 159.0 mW cm⁻² at 650 °C, and from 266.7 to 306.0 mW cm⁻² at 800 °C. The maximum power density at 800 °C and 4 atm was decreased from 334.8 to 273.9 mW cm⁻² when increasing the fuel utilization from 10% to 90%. Under the test condition of 70% fuel utilization, 800 °C and 4 atm, the cell could run stably at 0.7 V and 350 mA cm⁻² for 50 h, almost without any performance loss.     

Transport of helium in polycarbonate membranes

The transport of helium in membranes of poly(bisphenol A carbonate-co-4,4′-(3,3,5-trimethylcyclohexylidene)diphenyl carbonate) (PBCDC) is reported. The experimental values of the diffusion and permeability coefficients, under the upstream pressure of 176 cmHg, are (10.9±0.7)×10⁻⁶ cm² s⁻¹ and 61.4±0.5 barrers, respectively, at 30°C. Both coefficients obey Arrhenius behavior with activation energies of 1.9 and 3.0 kcal mol⁻¹, respectively. The dynamics of helium in the membranes was simulated using the transition state approach (TSA). Very good agreement between the theoretical and experimental values of the diffusion coefficient was found. However, the simulated solubility coefficient is nearly one order of magnitude higher than the experimental value.     

Sulfonated poly(ether ether ketone) membranes crosslinked with sulfonic acid containing benzoxazine monomer as proton exchange membranes

The incorporation of benzoxazine (Ba) or sulfonic acid containing benzoxazine (SBa) as a crosslinking agent in SPEEK proton exchange membrane (PEM) can substantially improve the SPEEK membrane performance. The SPEEK-SBa membranes give higher effective selectivity than corresponding SPEEK-Ba membranes under close crosslinker loading and thus are more suitable to be used in direct methanol fuel cells. The best achieved SPEEK-SBa composition (SBa40) gives reasonable proton conductivity (0.91 × 10⁻² S cm⁻¹) but significantly lower methanol permeability (6.5 × 10⁻⁸ S² cm⁻¹). The achieved effective selectivity (Φ = SPEEK-SBa40: 14.0 × 10⁴ S s cm⁻³) is substantially higher than the plain SPEEK (Φ = 7.24 × 10⁴ S s cm⁻³) which has great potential for practical applications in DMFCs.     

Anhydrous proton conducting polymer electrolytes based on poly(vinylphosphonic acid)-heterocycle composite material

The development of anhydrous proton conducting membrane is important for the operation of polymer electrolyte membrane fuel cell (PEMFC) at intermediate temperature (100-200 °C). In this study, we have investigated the acid-base hybrid materials by mixing of strong phosphonic acid polymer of poly(vinylphosphonic acid) (PVPA) with the high proton-exchange capacity and organic base of heterocycle, such as imidazole (Im), pyrazole (Py), or 1-methylimidazole (MeIm). As a result, PVPA-heterocycle composite material showed the high proton conductivity of approximately 10⁻³ S cm⁻¹ at 150 °C under anhydrous condition. In particular, PVPA-89 mol% Im composite material showed the highest proton conductivity of 7×10⁻³ S cm⁻¹ at 150 °C under anhydrous condition. Additionally, the fuel cell test of PVPA-89 mol% Im composite material using a dry H₂/O₂ showed the power density of approximately 10 mW cm⁻² at 80 °C under anhydrous conditions. These acid-base anhydrous proton conducting materials without the existence of water molecules might be possibly used for a polymer electrolyte membrane at intermediate temperature operations under anhydrous or extremely low humidity conditions.     

Proton conducting polydimethylsiloxane/zirconium oxide hybrid membranes added with phosphotungstic acid

Inorganic polymer based hybrid membranes consisting of zirconium oxide and polydimethylsiloxane (PDMS) have been synthesized by sol-gel processes. The organic/inorganic polymeric hybrid membranes showed thermal stability and flexibility up to 300 °C. The membrane becomes proton conducting polymer electrolyte when added with 12-phosphotungstic acid (PWA). The conductivity of the membranes was measured in the temperature range from room temperature to 150 °C under saturated humidity and a maximum conductivity of 5×10⁻⁵ S cm⁻¹ was obtained at 150 °C.     

Poly(vinyl alcohol)-based polymer electrolyte membranes for direct methanol fuel cells

We have prepared polymer electrolyte membranes (PEMs) from poly(vinyl alcohol) (PVA) and modified PVA polyanion containing 2 or 4 mol% of 2-methyl-1-propanesulfonic acid (AMPS) groups as a copolymer. The PEMs of various AMPS content and cross-linking conditions were prepared to determine the effect of AMPS content and cross-linking conditions on PEM properties. Proton conductivity and permeability of methanol through the PEMs increased with increasing AMPS content, C_AMPS, and with decreasing cross-linker concentration, C_GA, because of the increase in the water content. The permeability coefficient of methanol through the PEM prepared under the conditions of C_AMPS = 2.7 mol% and C_GA = 0.35 vol% was about 30 times lower than that of Nafion^®117 under the same measurement conditions. The proton permselectivity of the PEM, which is defined as the ratio of the proton conductivity to the permeability coefficient of methanol, gave a maximum value of 66 × 10³ S cm⁻³ s. The value is about three times higher than that of Nafion^®117.     

Synthesis and characterization of novel sulfonated polyimides from 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid

A novel sulfonated diamine monomer, 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid (BAPNDS), was synthesized. A series of sulfonated polyimide copolymers were prepared from BAPNDS, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and nonsulfonated diamine 4,4′-diaminodiphenyl ether (ODA). Flexible, transparent, and mechanically strong membranes were obtained. The membranes displayed slightly anisotropic membrane swelling. The dimensional change in thickness direction was larger than that in planar. The novel SPI membranes showed higher conductivity, which was comparable or even higher than Nafion 117. Membranes exhibited methanol permeability from 0.24 × 10⁻⁶ to 0.80 × 10⁻⁶ cm²/s at room temperature, which was much lower than that of Nafion (2 × 10⁻⁶ cm²/s). The copolymers were thermally stable up to 340 °C. These preliminary results have proved its potential availability as proton-exchange membrane for PEMFCs or DMFCs.     

Gel polymer electrolyte based on poly(acrylonitrile-co-styrene) and a novel organic iodide salt for quasi-solid state dye-sensitized solar cell

A gel polymer electrolyte based on poly(acrylonitrile-co-styrene) as polymer matrix and N-methyl pyridine iodide salt as I⁻ source was prepared. Controlling the concentration of polymer matrix of poly(acrylonitrile-co-styrene) at 17.5 wt.%, mixing the binary organic solvents mixture ethylene carbonate and propylene carbonate with 6:4 (w/w), and the concentration of N-methyl pyridine iodide and iodine with 0.5 and 0.05 M, respectively, the gel polymer electrolyte attains the maximum ionic conductivity (at 30 °C) of 4.63 mS cm⁻¹. Based on the gel polymer electrolyte, a quasi-solid state dye-sensitized solar cell was fabricated and its overall energy conversion efficiency of light-to-electricity of 3.10% was achieved under irradiation of 100 mW cm⁻².     

Preparation, characterization, and properties of new crosslinked proton-conducting membranes with polyoxyalkylene moieties

A new class of crosslinked proton-conducting membranes (CPMs) with polyoxyalkylene moieties was designed and prepared based on poly(styrene-co-maleic anhydride) modified with 2-aminoethanesulfonic acid sodium salt (AESA-Na) and polyoxyalkylenediamines (PEGDAs). The number density of the pendant of sulfonate group was controlled by the ratio of AESA-Na to PEGDA. The resulted membranes possess good mechanical strength and excellent flexibility. The structural characterizations of these membranes were confirmed by FT-IR and solid-state ¹³C NMR spectra. All these membranes exhibit a wholly amorphous morphology, and show a one-step weight loss from 350 °C, indicating their good thermal stability. The CPM sample with 1.25 mequiv SO₃H per gram reaches the proton conductivity of 0.21 S cm⁻¹ at 30 °C and 0.49 S cm⁻¹ at 95 °C, respectively. Moreover, these protonated membranes show adequate oxidative stability in Fenton's reagent at 30 °C.     

Polyvinylpyrrolidone-assisted synthesis of microscale C-LiFePO4 with high tap density as positive electrode materials for lithium batteries

Carbon-coated LiFePO₄ (C-LiFePO₄) with micron particle size (6 μm) and high tap density (1.6 g cm⁻³) was prepared from spherical FePO₄·2H₂O powder via the co-precipitation method. The C-LiFePO₄ powder was calcined at temperatures between 650 and 800 °C. The 6 μm C-LiFePO₄ prepared at 800 °C exhibited an excellent rate capability, delivering 150 mAh g⁻¹ on discharge at the 0.1 C-rate and 108 mAh g⁻¹ at the 5 C-rate. The volumetric capacity of the 6 μm C-LiFePO₄ corresponded to 225 mAh cm⁻³, since the large secondary particles (6 μm) C-LiFePO₄ sufficiently allowed tight packing of the particles. The 6 μm C-LiFePO₄ powder with high tap density makes an attractive positive electrode candidate for lithium-ion batteries designed for high energy density.     

Synthesis of sulfonated poly(arylene-co-naphthalimide)s as novel polymers for proton exchange membranes

A series of novel sulfonated poly(arylene-co-binaphthalimide)s (SPPIs) were successfully synthesized via Ni(0) catalytic coupling of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and bis(chloronaphthalimide)s. Bis(chloronaphthalimide)s were conveniently prepared from 5-chloro-1,8-naphthalic anhydride and various diamines. Tough and transparent SPPI membranes were prepared and the electrolyte properties of the copolymers were intensively investigated as were the effects of different diamine structures on the copolymer characterisitics. The copolymer membrane Ia-80, with an ion exchange capacity (IEC) of 2.50 meq g⁻¹, displayed a higher proton conductivity, i.e. 0.135 S cm⁻¹ at 20 °C, as compared to Nafion 117 (0.09 S cm⁻¹, 20 °C). The copolymer membrane Id-70, containing 3,3′-dimethyl-4,4′-methylenedianiline (DMMDA) units, exhibited excellent stability toward water and oxidation due to the introduction of hydrophobic methyl groups on the ortho-position of the imido bond in the copolymer. The mechanical property of Id-70 remained virtually unchanged after immersing membrane in pressured water at 140 °C for 24 h. Furthermore, the introduction of aliphatic segment a hexane-1,6-diamine (HDA) in copolymer led to a significant increase in proton conductivity and water uptake with increasing temperature; the proton conductivity of the Ic-70 membrane reached 0.212 S cm⁻¹ at 80 °C, which was higher than Nafion 117 as well as of the membranes based on aromatic diamines at equivalent IEC values. Consequently, these materials proved to be promising as proton exchange membranes.