Durability of Pt/C and Pt/MC-PEDOT catalysts under simulated start-stop cycles in polymer electrolyte fuel cells

A composite of mesoporous carbon (MC) with poly(3,4-ethylenedioxythiophene) (PEDOT) is studied as catalyst support for platinum nanoparticles. The durability of commercial Pt/carbon and Pt/MC-PEDOT as cathode catalyst is investigated by invoking air-fuel boundary at the anode side so as to foster carbon corrosion at the cathode side of a polymer electrolyte fuel cell (PEFC). Pt/MC-PEDOT shows higher resistance to carbon corrosion in relation to Pt/C. Electrochemical techniques such as cyclic voltammetry (CV) and impedance measurements are used to evaluate the extent of degradation in the catalyst layer. It is surmised that the resistance of MC-PEDOT as catalyst support toward electrochemical oxidation makes Pt/MC-PEDOT a suitable and stable cathode catalyst for PEFCs.

低甲醇透过直接甲醇燃料电池(Low Methanol Crossover Direct Methanol Fuel Cell)

直接甲醇燃料电池与间接甲醇燃料电池相比，体积更小，重量更轻，因此在一些领域有诱人的应用前景。但是，在它们实际应用之前，必须解决一些具体的技术难题。目前，甲醇从阳极透过到阴极是影响电池性能的主要难题之一，另外，催化剂和电极的制备方法也对电池的性能有重要的影响。本论文的主要目的在于研制低甲醇透过直接甲醇燃料电池并有效地提高电池的性能。为了减小甲醇在Nafion117膜中的透过，提出并研制了铭纳米粒子修饰的Nafion复合膜，该方法包括与[Pd(NH_4)_4]~(2+)离子的离子交换过程和化学还原过程。研究了一种制备高分散性铂基催化剂的方法。另外我们还研究并分析了不同的电池运行参数，例如温度、甲醇浓度等，刘一电池性能和甲醇透过的影响。主要结果如下：1.采用离子交换还原法在Nafionll7膜内部沉积纳米把粒子，制备成高聚物电解质复合膜。研究了镀把前后Nafion膜表面形态、甲醇透过和膜的电导的变化和对直接甲醇燃料电池的性能的影响等。由于把纳米粒子阻碍了甲醇透过，同时，由于它对氢离子的强吸引力，不但不对氢离子的透过产生影响，而且还提高了膜佩狗电导。所以镀把后电解质膜的甲醇透过减少，膜电导增加，无论在低电流密度区还是在高电流密度区，电池性能都有效地提高。2.研究了一种制备高分散性铂基催化剂的新方法一预沉淀还原法。并采用TEM,XRD和电化学等技术来表征催化剂中铂的粒径、晶态结构和催化活性：与传统的化学还原法相比，因为该方法在化学还原过程中反应物与载体的作用力得到增强，所以采用该方法制备的催化剂铂分散性更好、晶态结构更低、粒径更小并且催化活性更好。该方法在直接甲醇燃料一电池中有应用价值。3.研究并分析了不同的电池运行参数，例如温度、甲醇浓度等，对电池性能和甲醇透过的影响。研究发现当电池运行温度增加时，电池性能提高，甲醇透过增加；甲醇浓度增加时，甲醇透过增加，但是，甲醇浓度对电池性能有不同的影响，在低甲醇浓度区，甲醇浓度增加，电池性能提高；在高甲醇浓度区，甲醇浓度增加，电池性能降低；存在一个最佳甲醇浓度，在该甲醇浓度的条件下，电池的性能最高。实验结果为：采用Nafion117膜时，电池的最佳甲醇浓度为2. 0 mol/L，采用镀把Nafion117膜时，电池的最佳甲醇浓度高于4.0 mol/Lo

Synthesis and characterization of carbon black supported Pt-Ru alloy as a model catalyst for fuel cells

A set of bimetallic Pt-Ru catalysts prepared by co-impregnation of carbon black with ruthenium(III) chloride hydrate and hydrogen hexachloroplatinate(IV) hydrate were investigated by temperature-programmed reduction (TPR), chemisorption of hydrogen, transmission electron microscopy (TEM), microcalorimetry of adsorbed CO and a structure-sensitive reaction (n-hexane conversion). The results showed that the volumetric capacities for CO and H-2 adsorption is influenced in the bimetallic Pt-Ru catalysts by the formation of a Pt-Ru alloy. The n-hexane reaction revealed that the reaction mechanism for the pure Pt catalyst mainly occurs via cyclic isomerization and aromatization due to the presence of bigger Pt surface ensembles, whereas the Pt-Ru catalysts exhibited predominantly bond-shift isomerization by the diluting effect of Ru metal addition. The differential heats of CO chemisorption on Pt-Ru catalysts fell between the two monometallic Pt and Ru catalysts extremes. (C) 2004 Elsevier B.V. All rights reserved.

Performance improvement in direct methanol fuel cell cathode using high mesoporous area catalyst support

Black Pearls 2000 (designated as BP- 2000) and Vulcan XC-72 (designated as XC-72) carbon blacks were chosen as supports to prepare 40 wt % (the targeted value) Pt/C catalysts by a modified polyol process. The carbon blacks were characterized by N-2 adsorption and Fourier tranform infrared spectroscopy. The prepared catalysts were characterized by inductively coupled plasma atomic emission spectroscopy, transmission electron microscopy, scanning electron microscopy (SEM), in situ cyclic voltammetry, and current-voltage curves. On BP- 2000, Pt nanoparticles were larger in size and more unevenly distributed than on XC-72. It was observed by SEM that the corresponding catalyst layer on BP- 2000 was thicker than that of XC-72 based catalyst at almost the identical catalyst loading. And the BP- 2000 supported catalyst gave a better single cell performance at high current densities. These results suggest that the performance improvement is due to the enhanced oxygen diffusion and water removal capability when BP- 2000 is used as cathode catalyst support. (C) 2004 The Electrochemical Society.

Novel synthesis of highly active Pt/C cathode electrocatalyst for direct methanol fuel cell

A 40 wt% Pt/C cathode electrocatalyst with controlled Pt particle size of similar to 2.9 nm showing better performance than commercial catalyst for direct methanol fuel cell was prepared by a polyol process with water but without using stabilizing agent.

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.

Sulfonated poly(arylene-co-imide)s as water stable proton exchange membrane materials for fuel cells

A novel sulfonated poly(arylene-co-imide)s were synthesized by Ni(0) catalytic copolymerization of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and naphthalimide dichloride monomer. The synthesized copolymers with the - SO3H group on the side-chain of polymers possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. Because of the introduction of electron donating phenoxy groups into naphthalimide moieties, the hydrolysis of the imide rings was depressed. The resulting copolymers exhibited excellent water stability. The copolymer membranes display no apparently change in appearance, flexibility, and toughness after a soaking treatment in pressurized water at 140 degrees C for 250 h.

Synthesis and properties of water stable poly[bis(benzimidazobenzisoquinolinone)] ionomers for proton exchange membranes fuel cells

A novel sulfonated tetraamine, di(triethylammonium)-4,4'-bis(3,4-diaminophenoxy)biphenyl-3,3'-disulfonate (BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4'-dihydroxybiphenyl with 5-chloro-2-nitroaniline, followed by sulfonation and reduction. A high-temperature polycondensation of sulfonated tetraamine, non-sulfonated tetraamine (4,4 -bis(3,4-aminophenoxy)biphenyl) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (a) or 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianydride (b) gave the poly[bis(benzimidazobenzisoquinolinones)] ionomers SPBIBI-a(x) or SPBIBI-b(x), where x refers to the molar percentage of the sulfonated tetraamine monomer. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The ionomer membranes displayed excellent dimensional and hydrolytic stabilities.