Implantation of Nafion (R) ionomer into polyvinyl alcohol/chitosan composites to form novel proton-conducting membranes for direct methanol fuel cells

A series of cost-effective, proton-conducting composite membranes, comprising of Nafion (R) ionomer, chitosan (CS). and polyvinyl alcohol (PVA), is successfully prepared. By taking advantage of the strong electrostatic interactions between Nafion (R) ionomer and CS component, Nafion ionomer is effectively implanted into the PVA/CS composite membranes, and improves proton conductivity of the PVA/CS composite membranes. Furthermore, this effect dramatically depends on the composition ratio of PVA/CS, and the optimum conductivity is obtained at the PVA/CS ratio of 1:1. The developed composite membranes exhibit much lower methanol permeability compared with the widely used Nafion (R) membrane, indicating that these novel membranes have great potential for direct methanol fuel cells (DMFCs).

PEDOT:PSS self-assembled films to methanol crossover reduction in Nafion (R) membranes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Co-assembly of a Nafion-Mesoporous Zirconium Phosphate Composite Membrane for PEM Fuel Cells

Synthesis of mesoporous zirconium phosphate (MZP) by co-assembly of a tri-block copolymer, namely pluronic-F127, as a structure-directing agent, and a mixture of zirconium butoxide and phosphorous trichloride as inorganic precursors is reported. MZP with a specific surface area of 84 m(2) g(-1) average pore diameter of about 17 nm and pore volume of 0.35 cm(3) g(-1) has been prepared, and characterised by X-ray diffraction (XRD) and transmission electron microscopy. Nafion-MZP composite membrane is obtained by employing MZP as a surface-functionalised solid-super-acid-proton-conducting medium as well as all inorganic filler with high affinity to absorb water and fast proton-transport across the electrolyte membrane even under low relative humidity (RH) conditions. The composite membranes have been evaluated in H-2/O-2 polymer electrolyte fuel cells (PEFCs) at varying RH values between 18 and 100%; a peak power density of 355 mW cm(-2) at a load current density of 1,100 mA cm(-2) is achieved with the PEFC employing Nafion-MZP composite membrane while operating at optimum temperature (70 degrees C) under 18% RH and ambient pressure. On operating the PEFC employing Nafion-MZP membrane electrolyte with hydrogen and air feeds at ambient pressure and a RH value of 18%, a peak power density of 285 mW cm(-2) at the optimum temperature (60 degrees C) is achieved. In contrast, operating under identical conditions, a peak power density of only similar to 170 mW cm(-2) is achieved with the PEFC employing Nafion-1135 membrane electrolyte.

Mordenite-incorporated PVA-PSSA membranes as electrolytes for DMFCs

Composite membranes with mordenite (MOR) incorporated in poly vinyl alcohol (PVA)–polystyrene sulfonic acid (PSSA) blend tailored with varying degree of sulfonation are reported. Such a membrane comprises a dispersed phase of mordenite and a continuous phase of the polymer that help tuning the flow of methanol and water across it. The membranes on prolonged testing in a direct methanol fuel cell (DMFC) exhibit mitigated methanol cross-over from anode to the cathode. The membranes have been tested for their sorption behaviour, ion-exchange capacity, electrochemical selectivity and mechanical strength as also characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Water release kinetics has been measured by magnetic resonance imaging (NMR imaging) and is found to be in agreement with the sorption data. Similarly, methanol release kinetics studied by volume-localized NMR spectroscopy (point resolved spectroscopy, PRESS) clearly demonstrates that the dispersion of mordenite in PVA–PSSA retards the methanol release kinetics considerably. A peak power-density of 74 mW/cm2 is achieved for the DMFC using a PVA–PSSA membrane electrolyte with 50% degree of sulfonation and 10 wt.% dispersed mordenite phase. A methanol cross-over current as low as 7.5 mA/cm2 with 2 M methanol feed at the DMFC anode is observed while using the optimized composite membrane as electrolyte in the DMFC, which is about 60% and 46% lower than Nafion-117 and PVA–PSSA membranes, respectively, when tested under identical conditions.

Novel organic-inorganic composite polymer-electrolyte membranes for DMFCs

Organic-inorganic composite membranes comprising Nation with inorganic materials such as silica, mesoporous zirconium phosphate (MZP) and mesoporous titanium phosphate (MTP) are fabricated and evaluated as proton-exchange-membrane electrolytes for direct methanol fuel cells (DMFCs). For Nation-silica composite membrane, silica is impregnated into Nation matrix as a sol by a novel water hydrolysis process precluding the external use of an acid. Instead, the acidic nature of Nation facilitates in situ polymerization reaction with Nation leading to a uniform composite membrane. The rapid hydrolysis and polymerization reaction while preparing zirconia and titania sols leads to uncontrolled thickness and volume reduction in the composite membranes, and hence is not conducive for casting membranes. Nafion-MZP and Nafion-MTP composite membranes are prepared by mixing pre-formed porous MZP and MTP with Nation matrix. MZP and MTP are synthesised by co-assembly of a tri-block co-polymer, namely pluronic-F127, as a structure-directing agent, and a mixture of zirconium butoxide/titanium isopropoxide and phosphorous trichloride as inorganic precursors. Methanol release kinetics is studied by volume-localized NMR spectroscopy (employing ``point resolved spectroscopy'', PRESS), the results clearly demonstrating that the incorporation of inorganic fillers in Nation retards the methanol release kinetics under osmotic drag. Appreciable proton conductivity with reduced methanol permeability across the composite membranes leads to improved performance of DMFCs in relation to commercially available Nafion-117 membrane.

Chitosan-polyvinyl alcohol-sulfonated polyethersulfone mixed-matrix membranes as methanol-barrier electrolytes for DMFCs

Chitosan (CS)-polyvinyl alcohol (PVA) cross-linked with sulfosuccinic acid (SSA) and modified with sulfonated polyethersulfone (SPES) mixed-matrix membranes are reported for their application in direct methanol fuel cells (DMFCs). Polyethersulfone (PES) is sulfonated by chlorosulfonic acid and factors affecting the sulfonation reaction, such as time and temperature, are studied. The ion-exchange capacity, degree of sulfonation, sorption, and proton conductivity for the mixed-matrix membranes are investigated. The mixed-matrix membranes are also characterised for their mechanical and thermal properties. The methanol-crossover flux across the mixed-matrix membranes is studied by measuring the mass balance of methanol using the density meter. The methanol cross-over for these membranes is found to be about 33% lower in relation to Nafion-117 membrane. The DMFC employing CS-PVA-SPES mixed-matrix membrane with an optimum content of 25 wt % SPES delivers a peak power-density of 5.5 mW cm-2 at a load current-density of 25 mA cm-2 while operating at 70 degrees C. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Degradation mechanism of polystyrene sulfonic acid membrane and application of its composite membranes in fuel cells

The lifetime behavior of a H-2/O-2 proton exchange membrane (PEM) fuel cell with polystyrene sulfonic acid (PSSA) membrane have been investigated in order to give an insight into the degradation mechanism of the PSSA membrane. The distribution of sulfur concentration in the cross section of the PSSA membrane was measured by energy dispersive analysis of X-ray, and the chemical composition of the PSSA membrane was characterized by infrared spectroscopy before and after the lifetime experiment. The degradation mechanism of the PSSA membrane is postulated as: the oxygen reduction at the cathode proceeds through some peroxide intermediates during the fuel cell operation, and these intermediates have strong oxidative ability and may chemically attack the tertiary hydrogen at the a carbon of the PSSA; the degradation of the PSSA membrane mainly takes place at the cathode side of the cell, and the loss of the aromatic rings and the SO3- groups simultaneously occurs from the PSSA membrane. A new kind of the PSSA-Nafion composite membrane, where the Nafion membrane is bonded with the PSSA membrane and located at the cathode of the cell, was designed to prevent oxidation degradation of the PSSA membrane in fuel cells. The performances of fuel cells with PSSA-Nafion101 and PSSA-recast Nafion composite membranes are demonstrated to be stable after 835 h and 240 h, respectively.

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 degrees C, as compared to Nafion 117 (0.09 S cm(-1), 20 degrees C).

Dispersions of carbon nanotubes in sulfonated poly[bis(benzimidazobenzisoquinolinones)] and their proton-conducting composite membranes

A sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBI) possessing a conjugated pyridinone ring was shown to be effective for dispersing multiwalled carbon nanotubes (MWCNTs) in DMSO. The dispersions in which the SPBIBI to MWCNTs mass ratio was 4:1 demonstrated the highest MWCNTs concentrations, i.e., 1.5-2.0 mg mL(-1), and were found to be stable for more than six months at room temperature. Through casting of these dispersions, MWCNTs/SPBIBI composite membranes were successfully fabricated on substrates as proton exchange membranes for fuel cell applications and showed no signs of macroscopic aggregation. The properties of composite membranes were investigated, and it was found that the homogeneous dispersion of the MWCNTs in the SPBIBI matrix altered the morphology structures of the composite membranes, which lead to the formation of more regular and smaller cluster-like ion domains.

Novel proton exchange membranes based on water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)]

Novel water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBIs) were synthesized from 6,6'-disulfonic-4,4'-binaphthy]-1,1',8,8'-tetracarboxylic dianhydride (SBTDA) and various aromatic ether tetraamines. The resulting polymers with IEC in the range of 2.17-2.87 mequiv g(-1) have a combination of desired properties such as high solubility in common organic solvents, film-forming ability, and excellent thermal and mechanical properties. Flexible and tough membranes, obtained by casting from m-cresol solution, had tensile strength, elongation at break, and tensile modulus values in the range of 87.6-98.4 MPa, 35.8-52.8%, and 0.94-1.07 GPa. SPBIBI membranes with a high degree of sulfonation displayed high proton conductivity and a good resistance to water swelling as well. SPBIBI-b with IEC of 2.80 mequiv g(-1) displayed the conductivity of 1.74 x 10(-1) S cm(-1) at 100 degrees C, which was comparable to that of Nafion (R) 117 (1.78 x 10(-1) S cm(-1), at 100 degrees C).