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.

低甲醇透过直接甲醇燃料电池

直接甲醇燃料电池(DMFC)是一种清洁能源,具有高效、安全、无污染等优点[1～3],因此受到广泛关注。目前,在DMFC中广泛使用Nafion膜作为电解质膜,但甲醇透过Nafion膜后,不但氧阴极处产生混合电位,引起阴极催化剂中毒,导致阴极极化增加,电池性能降低,而且透过的甲醇未经反应从电池中排出,既浪费燃料又污染环境。甲醇透过Nafion膜是阻碍Nafion膜型直接甲醇燃料电池应用的主要技术问题之一[4,5]。为解决Nafion膜的甲醇透过问题,Pu等[6] 将一层致密的不透甲醇的质子导体夹在 2层Nafion膜之间形成复合电解质膜来消除甲醇透过。但是由于不同层之间的结合和膜厚度的增加,会使电解质膜的导质子性能降低。Won等[7] 和Yoon等[8] 采用刻蚀溅射法在Nafion膜表面修饰一层金属钯来降低甲醇透过,但该方法存在钯和Nafion膜表面结合不牢固和钯的用量相对较大等缺点。本文首次报道采用化学镀钯修饰Nafion膜的方法来降低甲醇透过率。Pd(NH3 )4 Cl2 和NaBH4均为上海试剂一厂产品 ,其它试剂均为分析纯。所有的溶液均用三次蒸馏水配制。

碳纳米管负载铂催化剂的制备及其对甲醇的电催化氧化研究

Pt金属是直接甲醇燃料电池(DMFC)常用的催化剂犤1～3犦。为了尽可能减少Pt金属用量,提高Pt的分散度,人们总是选择具有高表面积的基质,如石墨、碳黑、活性碳、分子筛、质子交换膜等,作为Pt金属的载体犤3～5犦。最初,人们以为载体的作用仅仅是提供表面积和多孔气体扩散电极的骨架,使Pt微粒可以有更大的比表面积与反应物接触,但是现在普遍认为犤1犦,当Pt金属负载在活性炭上时,它们中的催化性能有一部分应归结于金属和载体之间的相互作用,因此,载体的形貌及物理化学性质直接影响着催化剂对甲醇的电催化氧化活性。碳纳米管(CNTs)由于其拥有纳米级管腔结构、较高的比表面积、类石墨的多层管壁等特点,使它在做催化剂载体方面有着良好的应用前景犤6～9犦。CheGuangli等人犤6犦在探索CNTs的潜在用途时,曾研究了将Pt、Ru、PtRu等金属或合金沉积在CNTs的内壁,并讨论了其在DMFC上的潜在用途。本文通过液相化学还原的方法制得Pt载量为20%的Pt/CNTs催化剂,并研究了预处理对催化剂形貌、表面基团及其对甲醇电催化氧化性能的影响。1实验部分1.1试剂和仪器实验所用试剂均为分析纯,所有溶液均用三次蒸馏水配制。

直接甲醇燃料电池阴极电催化剂的研究进展

直接甲醇燃料电池 (DMFC)功率密度高 ,燃料甲醇价格低廉、储存和携带方便 ,特别适合作为电动车和小型电子设备的电源 ,是目前燃料电池研究领域的一个热点。本文介绍了 40年来DMFC阴极电催化剂的发展历史及现状 ,并针对目前严重影响DMFC性能的“甲醇透过”问题 ,阐述了研制耐甲醇阴极电催化剂的重要性 ,讨论了今后DMFC阴极电催化剂的发展趋势。

Electrocatalytic performance of Pt-TiO2/C complex catalysts for oxidation of methanol

It is reported for the first time that the Pt-TiO2/C catalyst prepared with chemical reduction and sol-gel method showed the excellent electrocatalytic activity and stability for the electrooxidation of methanol. When the atom ratio of Ti to Pt in the catalysts is 1/2, the catalysts showed the best electrocatalytic properties. After the catalyst is treated at 500 degreesC, the performance is further improved. It is hopeful to use the catalyst in the pratical DMFC.

固相反应法制备的Pt/C催化剂对乙醇氧化的电催化活性研究

直接甲醇燃料电池（DMFC）由于具有燃料来源丰富、价格低廉、易于携带储存等优点,近年来一直是世界上许多国家研究和开发的热点[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,必须探索寻找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,因此很有可能用作为替代甲醇作DMFC的燃料.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研究[2-7].其中,对乙醇电催化氧化活性较好的有pt[2-4]、pt-Ru[6-7]、Pt-Pd[5]和Pt-Mo[7]等催化剂.我们研究组报道了用固相反应法制得的Pt催化剂对甲醇氧化的电催化活性要优于用常规液

碳载Pt-TiO_2复合催化剂对甲醇氧化的电催化性能

报道了通过化学还原和溶胶 -凝胶法制备不同组成的 Pt-Ti O2 /C催化剂及其对甲醇的氧化反应 .结果表明 ,该催化剂具有很好的电催化活性和稳定性 .催化剂中的 Ti和 Pt的原子比为 1 /2时 ,催化剂的性能最好 .在 5 0 0℃下热处理后 ,催化剂的性能得到进一步的改善 .这种催化剂有望能在 DMFC中获得实际使用.

碳载Pt-TiO_2阳极催化剂对甲醇氧化的电催化活性和稳定性

近年来,直接甲醇燃料电池（DMFC）由于使用液体燃料而越来越受到重视,但目前DMFC存在的一个普遍的问题是常用的Pt阳极催化剂易被甲醇氧化的中间产物所毒化.因此,一些研究者研究了能抗甲醇氧化的中间产物毒化的Pt二元合金或Pt和过渡金属氧化物复合催化剂,如Pt-Ru[1]、Pt-Sn[2]、Pt-WOx[3]等.考虑至TiO2在酸性溶液中的稳定性,Hamnett研究组[4]和我们研究组[5]发现pt-TiO2/Ti复合电极对甲醇氧化有很好的电催化活性和抗中毒的能力.本文报道了制备能在DMFC中实际使用的碳载Pt-TiO2催化剂（Pt-TiO2/C）的方法和比较了Pt-TiO2/C和Pt/C电极对甲醇氧化的电催化活性和稳定性.用固相法制备含Pt20％的Pt/C催化剂[6],将制得的pt/C催化剂和Ti（OBu）4按摩尔比1:1的比例悬浮在乙醇中,超声波震荡并加水,使Ti（OBu）4完全水解成TiO2,并均匀沉积到Pt/C催化剂上,洗涤,真空干燥,500℃热处理

直接甲醇燃料电池中碳载Pt-TiO_2阳极复合催化剂的研究

首次报道了通过化学还原和溶胶 凝胶法制备了直接甲醇燃料电池 (DMFC)中Pt TiO2 /C阳极复合催化剂对甲醇氧化呈现出了很好的电催化活性和稳定性 .研究了催化剂的组份和制备条件对催化剂性能的影响 .这种催化剂有望能在DMFC实际使用 .

A study of dimethylferrocene diffusion and electrode kinetics using microelectrode voltammetry in poly(ethylene glycol) solvent

The heterogeneous electron transfer rate constant (k(s)) of dimethylferrocene (DMFc) was estimated using cyclic voltammetric peak potential separations taken typically in a mixed diffusion geometry regime in a polyelectrolyte, and the diffusion coefficient (D) of DMFc was obtained using a steady-state voltammogram. The heterogeneous electron transfer rate constant and diffusion coefficient are both smaller by about 100-fold in the polymeric solvent than in the monomeric solvent. The results are in agreement with the difference of longitudinal dielectric relaxation time (tau(L)) in the two kinds of solvents, poly(ethylene glycol) (PEG) and CH3CN, indicating that k(s) varies inversely with tau(L); k(s), is proportional to D of DMFc. Both D and k(s) of DMFc in PEG containing different supporting electrolytes and at different temperatures have been estimated. These results show that D and k(s) of DMFc increase with increasing temperature in the polyelectrolyte, whereas they vary only slightly with changing the supporting electrolyte.