Electrocatalysis of oxygen reduction on a carbon supported platinum-vanadium alloy in polymer electrolyte fuel cells

The electrocatalysis of the oxygen reduction reaction (ORR) on carbon supported Pt:V 1:1 catalyst in polymer electrolyte fuel cells (PEFC) was investigated. At an oxygen pressure of 1 atm results indicate a lower electrocatalytic activity for the ORR in the presence of vanadium. However, at an O₂ pressure ≥2 atm an enhanced electrocatalytic property of PtV/C compared with Pt/C is revealed. This result indicates the occurrence of a different electrocatalytic mechanism for the ORR on Pt/C and PtV/C. An increase of mass transport overpotentials is observed for the PtV/C catalyst, and this was related to the presence of vanadium oxide. Indeed, XRD analysis revealed that only about 30% of V present in the catalyst is alloyed with Pt, forming a face centred cubic (fcc) Pt₃V solid solution. A thermal treatment at 850 °C under reducing atmosphere leads to the formation of an ordered fcc Pt₂V phase. After this, the ORR activity of PtV/C at O₂ pressure 1 atm is higher than that of Pt/C.     

Ionic liquid mediated nano-composite polymer gel electrolyte for rechargeable battery application

ABSTRACT

Nano-composite polymer gel electrolytes (NPGEs) based on polymer poly(vinylidene fluoride-co-hexafluoropropylene) PVdF-HFP, ionic liquid, 1-butyl-3- methylimidazolium bis(trifluoromethanesulfonyl)imide BMIMTFSI, Li-salt along with the addition of SiO₂ nanoparticles have been synthesized and characterized by various techniques. Prepared NPGEs show high room temperature ionic conductivity (~10^?3 S/cm) and have a wide electrochemical window (ECW) (~3.3–3.5 V). The galvanostatic charge/discharge profile was studied by sandwiching best performing NPGEs between a LiFePO₄ cathode and lithium metal anode. The specific discharge capacity of the cell (Li/NPGE/LiFePO₄) room temperature at 0.1C rate is found to be 138 mAh/g.     

Embedding poly(styrene sulfonic acid) into PVDF matrix—a new type of proton electrolyte membrane

Hydrophilic polymer segments, consisting of styrene sulfonic acid (SSA) units, were uniformly embedded into hydrophobic poly(vinylidene fluoride) (PVDF) matrix through the mediation of poly(methyl methacrylate) (PMMA) segments, with which SSA segments form a copolymer. Discrete domains (∼100 nm) assembled by the SSA segments have been identified throughout the matrix of the membrane, which was prepared through blending of the copolymer P(MMA-SSA) and the PVDF. The thermal stability of the SSA was largely boosted in such hydrophobic environment. This unique matrix structure offers proton conductivity of as high as 10⁻³ S/cm at a low SSA equivalent (0.6 mmol -SO₃H/g of membrane), which is accompanied with a low level of water uptake (26%) at ambient temperature. Using this type of polymer membrane as electrolyte, the electrochemical cell possesses obvious capacitive resistance when the membrane is in the anhydride form according to the impedance analysis. However, the capacitive character vanishes when the membrane is hydrated; this response is attributed to the existence of highly dispersed SSA domains in the membrane. This work also analyzes the impedance spectra of the membranes at different hydrated states or with different SSA contents by using an equivalent electrical circuit.     

Electrical double layer characteristics of nanoporous carbon derived from titanium carbide

Electrochemical parameters of the nanoporous carbide-derived carbon|organic electrolyte have been studied by cyclic voltammetry and electrochemical impedance spectroscopy. The gas adsorption measurements have been used for evaluating the specific surface area, pore size distribution and porosity as the essential parameters influencing the double layer performance of carbon. The region of ideal polarizability, values of series and parallel resistance, capacitance and other important electrical double layer parameters were established. It was shown that specific capacitance of typical nanoporous carbon derived from titanium carbide is in the range of 70-90 F cm⁻³ or 100-130 F g⁻¹ and it depends on the synthesis conditions. The influence of the electrolyte solvent to the capacitance was insignificant, although acetonitrile was advantageous with respect of smaller viscosity.     

铝电解电容器用新型宽温高压工作电解液

采用异癸二酸铵为主溶质,乙二醇和γ-丁内酯为复合溶剂,制备新型宽温(-40~105℃)、高压(400 V)铝电解电容器工作电解液,并检测了该电解液和用该电解液生产的电解电容器的性能。测试结果表明,该工作电解液25℃时电导率达到1.6 mS/cm,闪火电压为480 V,-40℃下未见晶体析出;CD 110/400 V铝电解电容器试样的漏电流≤10μA,损耗0.03,容量变化率只有-3%。经过105℃高温贮存250 h后各项电气性能不仅优于国家标准,而且能达到严格的企业标准。     

非水电解质浓溶液的热力学研究(Ⅰ)——用缔合模型关联、推算298.15K时HCL甲醇浓溶液的活度系数

利用HCl在甲醇中稀溶液的活度系数,通过Pitzer的缔合模型,关联出298.15K HCl在甲醇中的缔合常数Kx=1.7×10~2,然后利用HCl在甲醇中浓溶液的活度系数关联出近程作用单参数,进而推算溶剂甲醇的活度系数及溶液总压,均得到满意的结果,说明HCl甲醇浓溶液的热力学关联必须考虑HCl的部分离解效应。     

锂离子电池固态聚合物电解质研究进展

电解质是制备高功率密度和高能量密度、长循环寿命的锂离子电池的重要材料之一,而聚合物电解质是实现全固态锂离子电池的关键技术.总结近几年来为提高聚合物电解质电导率所作研究的新进展,并提出了今后的研究方向.     

Cycling of lithium/metal oxide cells using composite electrolytes containing fumed silicas

The effect on cycle capacity is reported of cathode material (metal oxide, carbon, and current collector) in lithium/metal oxide cells cycled with fumed silica-based composite electrolytes. Three types of electrolytes are compared: filler-free electrolyte consisting of methyl-terminated poly(ethylene glycol) oligomer (PEGdm, M_w=250)+lithium bis(trifluromethylsufonyl)imide (LiTFSI) (Li:O=1:20), and two composite systems of the above baseline liquid electrolyte containing 10-wt% A200 (hydrophilic fumed silica) or R805 (hydrophobic fumed silica with octyl surface group). The composite electrolytes are solid-like gels. Three cathode active materials (LiCoO₂, V₆O₁₃, and Li_xMnO₂), four conducting carbons (graphite Timrex® SFG 15, SFG 44, carbon black Vulcan XC72R, and Ketjenblack EC-600JD), and three current collector materials (Al, Ni, and carbon fiber) were studied. Cells with composite electrolytes show higher capacity, reduced capacity fade, and less cell polarization than those with filler-free electrolyte. Among the three active materials studied, V₆O₁₃ cathodes deliver the highest capacity and Li_xMnO₂ cathodes render the best capacity retention. Discharge capacity of Li/LiCoO₂ cells is affected greatly by cathode carbon type, and the capacity decreases in the order of Ketjenblack>SFG 15>SFG 44>Vulcan. Current collector material also plays a significant role in cell cycling performance. Lithium/vanadium oxide (V₆O₁₃) cells deliver increased capacity using Ni foil and carbon fiber current collectors in comparison to an Al foil current collector.     

Oxygen reduction on platinum electrodes in base: Theoretical study

Electrode-potential-dependent activation energies for electron transfer have been calculated using a local reaction center model and constrained variation theory for the oxygen reduction reaction on platinum in base. Results for four one-electron transfer steps are presented. For the first, O₂(ads) is predicted to be reduced to adsorbed superoxide, O₂⁻(ads), which dissociates with a low activation barrier to O(ads) + O⁻(ads). Then a proton transfer form H₂O(ads) to O⁻(ads) takes place, forming OH(ads) + OH⁻(aq). The second electron transfer reacts O(ads) with H₂O(aq) to form a second OH(ads) + OH⁻(aq). The third and fourth electron transfers react the two OH(ads) with two H₂O(aq) to form two H₂O(ads) + two OH⁻(aq). All three different surface reduction reactions are predicted to have reversible potentials in the −0.24 V(SHE) to −0.29 V(SHE) range for 0.1 M base and activation energies for the superoxide formation step are close to the experimentally observed range in 0.1 M base for the overall four-electron to water over the three low index (1 1 0) (1 0 0) and (1 1 1) surfaces: 0.38-0.49 eV at 0.35 eV respectively at 0.88 V(RHE). Predicted reversible potentials for forming O₂⁻(ads) are compared with estimates from the experimental literature. The difference between the acid mechanism, where the peroxyl radical, OOH(ads) is the first reduction intermediate, and the base mechanism, where superoxide, O₂⁻(ads) is the first reduction intermediate, is discussed.     

交流示波极谱滴定法测定电镀液中的微量铅

提出了用交流示波极谱法测定电镀液中的微量铅，并研究了各项试验条件。铅在0．100～10.0mg／mL范围内，标准偏差在0．200％～0．220%之间，相对标准偏差为4．29‰～4．73‰。该法可用于硫酸盐镀锌技术的电镀液中微量铅的分析测定，其加标回收率在98．0％～103％之间，操作简便，测定快速，分析可靠。