Gas diffusion electrodes for polymer electrolyte fuel cells using novel organic/inorganic hybrid electrolytes: effect of carbon black addition in the catalyst layer

We have prepared novel gas diffusion electrodes for polymer electrolyte fuel cells (PEFC) using new organic/inorganic hybrid electrolytes. The catalyst layers were prepared by mixing 3-(trihydroxysilyl)-1-propanesulfonic acid [(THS)Pro-SO₃H], 1,8-bis(triethoxysilyl) octane (TES-Oct), Pt loaded carbon black (Pt-CB) and water, followed by a sol-gel reaction. It was found that addition of uncatalyzed carbon black (u-CB) into the cathode catalyst layer enhanced the performance at high current density region, due to an increase in the gas diffusion rate. The optimum volume ratio of u-CB/Pt-CB was found to be 0.1, at which the gas diffusivity and the catalyst utilization are well balanced.     

The electrochemical reduction of VO2 in acidic solution at high overpotentials

An investigation has been carried out to attempt to understand the unusually low apparent symmetry factor observed during the reduction of V(5) at higher overpotentials at carbon electrodes (typically <0.13, or >460 mV decade⁻¹). This reaction is of interest because it occurs in vanadium redox-flow batteries (VRBs) during discharge. Polarisation curves were measured using a rotating disk electrode (RDE). The reaction was not solution mass transport controlled, was pH independent (ca from 0 to 1), and the observed Tafel slope was unaffected by V(5) concentration over a range from 0.031 to 280 mM. Electrode double layer capacitance measurements were also carried out in sulphuric acid with and without vanadium. These tests showed that the presence of V(5) caused a suppression of the normal carbon surface quinone pseudocapacitance, as well as the appearance of two new pseudocapacitance peaks, one around 0.175-0.2 V and the other around 0.675-0.725 V versus SCE. The observed results do not appear consistent with a precipitated film causing diffusion limitations or causing IR drop. A model is developed to try to explain the data, which involves electron transfer through an adsorbed layer of vanadium.     

Comparison of platinum with IrO2–Ta2O5 system for the stannous ion consumption in methane sulfonic acid baths with and without catechol

The stannous ion consumption in methane sulfonic acid (MSA) baths with and without catechol was quantitatively evaluated using platinum and IrO₂–Ta₂O₅/Ti anodes. The stannous ion is consumed at the same rate with both anodes, accompanied by the generation of tin sludge on the anode surfaces in the bath without catechol, while these undesirable phenomena are significantly suppressed in the bath containing catechol. Spectroscopic measurements indicate that stannous ion and catechol form a complex at the mole ratio of 1:2, thus preventing the oxidation of stannous ions. This complexation effect is independent of the anode material at low current density, but depends on the anode material at high current density. The stannous ion consumption at high current density is sufficiently inhibited only with the IrO₂–Ta₂O₅/Ti anode due to the low oxygen evolution potential. Voltammetric measurements also suggest that the continuous oxidation of stannous ion in the catechol-containing bath is simultaneous with oxygen evolution.     

溶胶-凝胶的制备及其在化学修饰电极中的应用

溶胶-凝胶技术的进一步改善和一些新材料的发现,为固定生物分子制备具有更好的响应性能的化学修饰电极提供了更多的机会和更大空间。追溯了溶胶-凝胶的起源,介绍了溶胶-凝胶制备的方法,综述了溶胶-凝胶在构筑化学修饰电极中的作用,展望了溶胶-凝胶技术应用的发展趋势。     

粘结剂对碳纳米管电极性能的影响

利用扫描电子显微镜．电极接触角和电极充放电等测试手段．研究了不同种类粘结剂和粘结剂含量对电极的影响．结果表明：采用酚醛树脂作为电极的粘结剂效果最好,当其质量占电极质量的15％时,电极的性能达到最佳。     

Mass transfer studies at rotating cylinder electrodes of expanded metal

Mass transfer has been studied at rotating cylinder electrodes of expanded metal using the reduction of ferricyanide as test reaction. The experimental data are well correlated by an empirical expression between the Sherwood number and the Reynolds number, both in terms of the hydraulic diameter as characteristic length, and including two additional dimensionless parameters in order to characterize the geometry of the expanded metal. Comparisons of the mass-transfer performance of the expanded metal electrodes with other three-dimensional structures are made.     

Impedance spectroscopy on porous materials: A general model and application to graphite electrodes of lithium-ion batteries

Electrochemical impedance spectroscopy (EIS) was applied to porous negative graphite electrodes for lithium-ion batteries in the EC:DMC, 1 M LiPF₆ electrolyte. The effect of porosity on the electrode response time was studied and a theoretical model was developed, based on free path of the current lines between subsequent reaction sites. The effect of porosity on the electrode response is evidenced by the impedance spectra in which the high frequency capacitive semicircle is distorted. Fresh electrodes (before the formation of the solid electrolyte interphase, SEI) and cycled electrodes have different shapes of the impedance spectra indicating a change of processes at the surface. In particular, the shape of the spectrum for a fresh electrode can be related to an adsorption process. Impedance spectra of fresh electrodes were fitted using a simple model that considers porosity and the assumed electrochemical processes, giving good agreement between model and data. A correlation was found between adsorption sites and irreversible charge capacity in the first cycle.     

Characterization of permselective coatings electrosynthesized on Pt-Ir from the three phenylenediamine isomers for biosensor applications

The permeability of polymers, electrosynthesized at neutral pH on Pt-Ir cylinders from each of the three isomers of phenylenediamine (oPD, mPD and pPD), to H₂O₂ (signal transduction molecule in many oxidase-based biosensors) and ascorbic acid (AA, archetypal interference species in biological applications of biosensors) was measured, and used to determine the permselectivity of the three polymers. PmPD was the coating with the greatest permselectivity for H₂O₂ over AA, for low concentrations of AA. For AA levels greater than 200 μM, however, poly-ortho-phenylenediamine (PoPD) was superior. Furthermore, stability studies indicated that the permselectivity of PmPD degraded rapidly, even after 1 day, supporting the choice of PoPD as the permselective membrane for biosensor implantation where AA levels are high, such as in brain monitoring. A variety of techniques were used to gain further insight into the PPD layers, specifically electrochemical quartz crystal microbalance, mass spectrometry and scanning electron microscopy. Together these studies indicate that PmPD forms the thickest layer (∼15 nm) and is the least soluble of the polymers, that the PoPD layer is ∼4 nm thick and may consist mostly of tetramers, while PpPD is the thinnest (∼3 nm) and appears to consist of trimers.     

SA-213T91/G102异种钢接头的焊材选用

对三种焊条焊接的SA－213T91与G102异种接头的组织与性能进行了对比性试验研究，认为对于电站锅炉中的这类接头焊接，采用R417作为焊材较为理想。     

锌空气电池空气电极催化材料的研究

采用将Li2CO3,电解二氧化锰(EMD)和Co(NO3)2·6H2O混合进行高温固熔反应的合成方法,制备了1种尖晶石型金属氧化物催化材料LiMn2-xCoxO4。通过电化学测试(极化曲线、放电曲线)、X射线衍射分析(XRD)以及扫描电镜(SEM)等方法对电极的微观结构和性能进行了研究。实验结果表明,以LiMn1.95Co0.05O4为催化材料的气体扩散电极具有最好的综合电化学性能。其0.9V极化电位时的最大电流密度可达210mA/cm2AA型(5号)样品电池以100mA电流恒流放电,容量可高达4439mAh。