High proton conductive advanced hybrid membrane based on sulfonated Si-SBA-15

Composite membranes based on Sulfonated poly(ether ether ketone) (SPEEK) and sulfonated organically modified Si-SBA-15 (S-SBA-15) were investigated with the purpose of increasing the proton conductivity. The novelty of the composite membranes was attributed to two special structures and different ion exchange capacities (IEC) of S-SBA-15 fillers, which were embedded in membranes. The typical hexagonal channels array of S-SBA-15 was confirmed by XRD and TEM. The regular vermiculate and amorphous structures of the inorganic fillers were proved by SEM. Composite membranes were prepared through common solvent casting method. SEM images indicated that the inorganic filler with regular structure dispersed homogeneously in the composite membranes, but the amorphous filler caused an agglomeration phenomenon at the same loading content.

Facile synthesis of PtRu/C electrocatalyst with high activity and high loading for passive direct methanol fuel cell by synergetic effect of ultrasonic radiation and mechanical stirring

The PtRu/C electrocatalyst with high loading (PtRu of 60 wt%) was prepared by synergetic effect of ultrasonic radiation and mechanical stirring. Physicochemical characterizations show that the size of PtRu particles of as-prepared PtRu/C catalyst is only several nanometers (2-4 nm), and the PtRu nanoparticles were homogeneously dispersed on carbon surface. Electrochemistry and single passive direct methanol fuel cell (DMFC) tests indicate that the as-prepared PtRu/C electrocatalyst possessed larger electrochemical active surface (EAS) area and enhanced electrocatalytic activity for methanol oxidation reaction (MOR). The enhancement could be attributed to the synergetic effect of ultrasound radiation and mechanical stirring, which can avoid excess concentration of partial solution and provide a uniform environment for the nucleation and growth of metal particles simultaneously hindering the agglomeration of PtRu particles on carbon surface.

Pore-filling membrane for direct methanol fuel cells based on sulfonated poly(styrene-ran-ethylene) and porous polyimide matrix

We have synthesized a porous co-polyimide film by coagulating a polyimide precursor in the non-solvent and thermal imidization. Factors affecting the morphology, pore size, porosity, and mechanical strength of the film were discussed. The porous polyimide matrix consists of a porous top layer and a spongy sub-structure with micropores. It is used as a porous matrix to construct sulfonated poly(styrene-ran-ethylene) (SPSE) infiltrated composite membrane for direct methanol fuel cell (DMFC) application. Due to the complete inertness to methanol and the very high mechanical strength of the polyimide matrix, the swelling of the composite membrane is greatly suppressed and the methanol crossover is also significantly reduced, while high proton conductivity is still maintained. Because of its higher proton conductivity and less methanol permeability, single fuel cell performance test demonstrated that this composite membrane outperformed Nafion membrane.

稀土离子对甲醇电氧化的影响

直接甲醇燃料电池(DMFC)是以固体聚合物为电解质,阳极以液相甲醇或蒸气相甲醇进料,阴极以空气或氧气为氧化剂.DMFC具有原料甲醇易储存、电池的理论电压高和能量效率高等特点,适于作电动车电源和便携式电源,具有广阔的发展前景.然而,在DMFC中,甲醇的阳极氧化涉及6个电子的传递过程,比氢气的氧化更困难,由于存在较高的阳极过电位,使得电池的实际输出电压低于理论电压;更为重要的是甲醇的部分氧化中间产物(CO)易使电催化剂中毒,因此,高效的阳极电催化剂一直是DMFC中的重要研究领域之一[1~7].目前解决这一问题的途径主要集中在对电催化剂的研究和改进上,如性能较好的Pt/Metal(oxide),即Pt复合金属或金属氧化物催化剂.稀土元素Ln系位于元素周期表中的B族,具有丰富的d轨道和f轨道电子,因此可以作为催化剂中的第二种金属元素加以研究.将稀土元素及其氧化物用于较低温度(250℃)下催化CO的化学氧化反应已早有研究[8].目前,已经有将Rh/Sm和Pt/Sm合金应用于CO的催化氧化反应的研究报道[9].本文选择几种稀土离子作为添加剂,研究了稀土离子对甲醇电氧化反应的影响.1实验部分1.1试剂与仪器甲醇(优级纯),...

不同载量Pt/C催化剂制备及其对甲醇氧化的电催化活性

用甲醇作溶剂,SnCl2作还原剂,采用改进的有机溶胶方法制备了用于直接甲醇燃料电池(DMFC)中甲醇氧化的炭载Pt(Pt/C)催化剂。制得的Pt/C催化剂中的Pt粒子具有高度的均一性和良好的分散度。通过控制溶剂的蒸发温度,能够获得Pt粒子平均粒径基本相同、Pt载质量分数为10%～60%的Pt/C催化剂,粒径为3.3～4.3nm。将获得的催化剂通过涂膜-热压法制备成DMFC膜电极,研究了Pt载量对甲醇电催化氧化性能的影响。结果表明,质量分数为40%的Pt/C催化剂对甲醇的电催化氧化显示出优异的电催化性能。

Effect of pretreatment of black carbon on electrocatalytic activity of Pt/C catalyst for methanol oxidation

Direct methanol fuel cell (DMFC) has attracted wide attention due to its many advantages. However, its practical application is limited by the low electrocatalytic activity of the anodic Pt/C catalyst usually used for the methanol oxidation. In this paper, in order to increase the electrocatalytic performance of the Pt/C catalyst for the methanol oxidation, the black carbon, usually used as the supporter, was pretreated with CO2, air, HNO3 or H2O2. The cyclic voltarnmetric results indicated that the current densities of the anodic peak of methanol oxidation at the Pt/C catalysts with the black carbon pretreated with CO2,air, HN03, H202 and untreated black carbon were 39, 33, 32, 20 and 18 mA center dot cm(-2), respectively, illustrating that among the above five kinds of the Pt/C catalysts, the Pt/C catalyst with the black carbon pretreated with CO2 shows the best electrocatalytic activity and stability for the methanol oxidation. Its main reason is that the CO2 pretreatment could reduce the content of the oxygen-containing groups on the surface of the black carbon and increase the content of graphite in the black carbon, leading to the low resistance of the black carbon and the increase in the dispersion extent of the Pt particles in the Pt/C catalyst.

碳黑预处理对Pt/C催化剂对甲醇氧化电催化活性的影响

直接甲醇燃料电池(DMFC)由于具有较多的优点而受到广泛的关注.但是碳载Pt(Pt/C)阳极催化剂电催化活性低是限制其应用的一个主要问题.为了提高Pt/C催化剂对甲醇氧化的电催化性能,分别用CO2,空气,H2O2或HNO3对常用作为载体的VulcanXC-72碳黑进行预处理.结果表明,在用CO2,空气,HNO3,H2O2处理的及未处理的碳黑作载体制得的Pt/C催化剂电极上,甲醇氧化峰的峰电流密度顺序为39,33,32,20和18mA?cm-2,表明用CO2处理的碳载体制备的Pt/C催化剂对甲醇氧化有最好的电催化活性和稳定性.其主要原因是用CO2处理能减少碳黑表面的含氧基团和增加石墨化程度,而使碳黑的电阻降低及Pt粒子在碳黑上的分散性变好.

Sm~(3+)对甲醇电化学氧化反应的助催化作用

分别以相同面积的光滑 Pt电极和吸附了 Sm3+ 的铂电极作为工作电极 ,在酸性介质中采用循环伏安法对甲醇氧化进行测定 .结果表明 ,吸附了 Sm3+ 的 Pt电极上产生了更大的氧化电流 ,表明 Sm3+ 的加入对甲醇的电催化氧化起到了促进作用 .这一研究结果在直接甲醇燃料电池 ( DMFC)阳极催化剂研制方面具有较大的应用潜力

固相反应法制备Pt-Ru/C催化剂对乙醇氧化的电催化活性研究

引言近年来,直接甲醇燃料电池(DMFC)由于其燃料来源丰富、价格低廉、甲醇携带和储存安全方便等独特的优越性而越来越受到重视[1]。但是甲醇具有一定的毒性,因此要想实现DMFC在诸如手机、笔记本电脑以及电动车等可移动电源领域的应用,必须探索新的液体燃料以替代有毒性的甲醇。其中乙醇很易从农作物中大量生产,又无毒,因此很有可能用作替代甲醇的质子交换膜燃料电池燃料。近年来乙醇的电催化氧化已被众多的研究者从电催化和乙醇燃料电池的角度进行了广泛的研究[2,3]。但是乙醇在Pt电极上的氧化易导致强吸附物种CO毒化催化剂,Pt鄄Ru合金是目前强吸附毒化物种CO易氧化为CO2的最有效的电催化剂,因此近年来也有一些关于Pt鄄Ru合金催化剂对乙醇的电化学氧化的研究[4~6]。我们研究组首次用固相反应法制备了Pt/C催化剂,发现所制得的Pt/C催化剂对甲醇[7]和乙醇[8]氧化的电催化性能要比用传统的液相反应法制得的Pt/C催化剂好很多。但Pt/C催化剂对甲醇和乙醇氧化的电催化活性还是较低,因此,本文首次研究了用固相反应法制备Pt鄄Ru/C催化剂及这种催化剂对乙醇氧化的电催化性能,发现用固相反应法制备的Pt鄄Ru/C催化剂对乙醇氧...

直接甲醇燃料电池的研究进展

综述了直接甲醇燃料电池 (DMFC)的几个方面研究进展 :如电催化剂、质子交换膜、膜电极集合体、电池结构以及电池性能等 ,论述了直接甲醇燃料电池的国内外研究现状及进展 ,分析了所存在的问题 ,预测了DMFC的发展方向及应用前景

Novel chemical synthesis of Pt-Ru-P electrocatalysts by hypophosphite deposition for enhanced methanol oxidation and CO tolerance in direct methanol fuel cell

A novel method was developed to prepare the highly active Pt-Ru-P/C catalyst. The deposition of phosphorus significantly increased electrochemical active surface (EAS) area of catalyst by reduces Pt-Ru particle size. TEM images show that Pt-Ru-P nanoparticles have an uniform size distribution with an average diameter of 2 nm. Cyclic voltammetry (CV), Chronoamperometry (CA), and CO stripping indicate that the presence of non-metal phosphorus as an interstitial species Pt-Ru-P/C catalyst shows high activity for the electro-oxidation of methanol, and exhibit enhanced performance in the oxidation of carbon monoxide compared with Pt-Ru/C catalyst. At 30 degrees C and pure oxygen was fed to the cathode, the maximum power density of direct methanol fuel cell (DMFC) with Pt-Ru-P/C and Pt-Ru/C catalysts as anode catalysts was 61.5 mW cm(-2) and 36.6 mW cm(-2), respectively. All experimental results indicate that Pt-Ru-P/C catalyst was the optimum anode catalyst for direct methanol fuel cell.

Preparation and properties of sulfonated poly(ether ether ketone)s (SPEEK)/polypyrrole composite membranes for direct methanol fuel cells

Polypyrrole (Ppy) was successfully introduced into methyl substituted sulfonated poly(ether ether ketone) (SPEEK) membranes by polymerization in SPEEK solutions to improve their methanol resistance. Uniform polypyrrole (Ppy) distributed composite membranes were formed by this method by the interaction between SPEEK and Ppy. The properties of the composite membranes were characterized in detail. The composite membranes show very good proton conductive capability (25 degrees C: 0.05-0.06s cm(-1)) and good methanol resistance (25 degrees C: 5.3 x 10(-7) 1.1 x 10(-6) cm(2) s(-1)). The methanol diffusion coefficients of composite membranes are much lower than that of pure SPEEK membranes (1.5 x 10(-6) cm(2) s(-1)). The composite membranes show very good potential usage in direct methanol fuel cells (DMFCs).

Effect of cations in solution on the oxidation of methanol on the surface of platinum electrode

The effect of metal cations in solution on the oxidation of methanol on the electrode surface of platinum is a neglected aspect to direct methanol fuel cell (DMFC). In this paper, a smooth platinum electrode absorbing metal cations as the working electrode was applied to investigate the methanol oxidation with the cyclic voltammetry (CV) in 1.0 mol L-1 H2SO4. From the analysis of experiment, it is found that the cations, Li+, Ce4+, Mn2+, Ni2+, Cu2+, have some negative effect on the catalytic oxidation of methanol on the surface of platinum. The degree of the effect from different cations was analyzed.

Preparation and simulation of an additional catalyst layer for direct methanol fuel cell

An additional anode catalyst layer with PtRu/C was hot pressed between two Nafion (R) 112 membranes and a conventional direct methanol fuel cell (DMFC) cathode/membrane/anode assembly with the above membranes as separator was fabricated. The additional catalyst layer formed an assistant cell with the cathode to prevent methanol crossover. A simple one-dimensional mathematical model was presented to describe the performance of this new type of membrane electrode assembly system. As seen from both experimental result and model analysis, the additional catalyst layer can not only effectively prevent the methanol crossover, but also generate electrical power with the crossover methanol. The percentage of output power of the assistant cell to the total power analyzed by the model is about 40% under usual condition, which is much higher than that from experimental result, indicating the potential of the development in the DMFC designing. It was also discovered that the electrical power generated from the assistant cell with crossover methanol could take higher percentage in total electrical power when the main DMFC current density became lower.

Physical and electrochemical characterizations of PtRu/C catalysts by spray pyrolysis for electrocatalytic oxidation of methanol

In this paper, it was reported that the carbon-supported Pt-Ru(Pt-Ru/C) catalyst used as the anodic catalyst in the direct methanol fuel cell (DMFC) was synthesized with a two-step spray pyrolysis (SP) method using the Pt and Ru metal salt as the precursors and polyethylene glycol (PEG) with the different molecular weights (Mw= 200,600,and 1000 analytical reagent) as cosolvent. PEG as a cosolvent plays a crucial role in producing PtRu/C catalysts. It was found that the Mw of PEG could affect the electrocatalytic activity of Pt-Ru and the morphology of the Pt-Ru particles in the Pt-Ru/C catalysts prepared with this method. When the Mw of PEG is 600, the Pt-Ru particles in the Pt-Ru/C catalyst prepared with this method possess the small average size, narrow size distribution, uniform dispersion, and high electrochemically active specific surface area. The electrocatalytic activity of the Pt-Ru/C catalyst prepared with this method using the cosolvent PEG with Mw = 600 for the methanol oxidation is much higher than that of the commercial E-TEK Pt-Ru/C catalyst. Therefore, the two-step SP method is an excellent method for the preparation of the Pt-Ru/C catalyst used in DMFCs.