【作者】 黄亮；

【导师】 陈范才； 刘忠海；

【作者基本信息】 湖南大学 ， 化学工程， 2012， 硕士

【摘要】 氢能具有清洁、高效及可再生等许多突出的优点受到了世界各国的普遍重视。电解水制氢是实现大规模、廉价生产氢的重要手段，为了降低阴极过电位以降低能耗，制备低析氢过电位、高催化活性的阴极材料具有重要的意义。本文以具有高比表面积的聚氨酯泡沫为模板，通过电沉积方法制备高析氢性能的泡沫镍钼合金材料，并为生产800×800mm2工业电解用析氢电极的小型电镀中试车间进行设计。聚氨酯泡沫模板必须先导电化，然后电镀加厚，再热解去除模板，最后还原得到泡沫合金。本文采用化学镀镍使模板导电化，针对聚氨酯泡沫的特性，研究制定了聚氨酯的前处理工艺，并系统研究了化学镀液中硫酸镍浓度、次亚磷酸钠浓度、镀液pH值和温度对化学镀沉积速度及导电镀层质量的影响。设计制定了碱性化学镀镍和电镀镍钼合金工艺及工艺流程。采用碘量法测量镀液中次亚磷酸根、亚磷酸根的含量；采用分光光度法测量镀液中镍、钼离子的含量，并研究了分光光度法测定镍、钼离子含量时各种因素对测试结果的影响，设计制定了分光光度法测定镀液中镍、钼离子含量的检测方案和步骤。在实验室小试的基础上，考虑相关的放大效应，合理设计出了制备800×800mm2泡沫镍钼合金材料的小型电镀中试车间，确定了车间主要设备的选型，绘制了电镀挂具、电镀槽、双联水洗槽、其它辅助槽的设计图以及车间的平面布置图，并完成了中试车间的建设及中试调试。通过该中试车间制备了70块800×800mm2的泡沫镍钼合金电极材料并对其进行了面密度、极化曲线及小型电解槽装槽实验测试。测试发现，约90%的产品达到了生产要求，其析氢过电位η200介于260mV到300mV之间，远远低于泡沫镍电极的析氢过电位(η200=496mV)，其交换电流密度i0为(8.000±4)×10-3A cm-2，远远大于泡沫镍电极的交换电流密度(i0=2.7×10-5A cm-2)；经小型电解槽间歇电解50h后，阴极为泡沫镍钼合金电极的平均小室槽压增大了约30mV；拆槽后检验发现泡沫镍钼合金电极的析氢过电位η200增加了约35mV；SEM与EDS测试发现，经电解槽间歇电解后，镍钼合金镀层有少许脱落，钼元素的质量百分比下降了约6.86%，原子百分比下降了约2.41%，从而使得镍钼合金镀层的析氢活性下降。更多还原

【Abstract】 Hydrogen energy is generally appreciated all around the world for its prominentmerits, such as cleanability, high efficiency, renewable ability and so on. It is waterelectrolysis that is the important way to get the vast and inexpensive hydrogen energy.In order to decrease cathode overpotential for reducing energy consumption, it’s ofmomentous significance to research new cathode electrode materials which have lowerhydrogen evolution overpotential and high catalytic activity. This thesis researched thepreparation of foamed nickel molybdenum alloy material of high hydrogen evolutionactivity with a template of polyurethane foam with high specific surface area byelectrodeposition, and designed a small electroplating pilot plant to produce hydrogenevolution electrode material of800×800mm2which was used for industrial electrolysis.The template of polyurethane foam must be made to conduct electricity at first,then thickened by electrodeposition, and then pyrolyzed to remove the template,finally deoxidized to get the foam alloy. The template of polyurethane foam was madeto conduct electricity by chemical nickel plating in this paper. According to thecharacteristics of polyurethane foam, the pretreatment process of polyurethane foamwas studied and determined, and the influence of concentration of NiSO46H2O andNaH2PO2H2O, the pH and temperature of chemical plating solution on the chemicaldeposition rate and quality of clad layer was systematacially studied. The technologyand process of alkaline chemical nickel plating and electroplating nickel molybdenumalloy were also designed and determined.The content of H2PO2-and HPO32-was measured by iodometric method. Thecontent of nickel ions and molybdenum ions was measured by spectrophotometry,and the influence of various factors on the test results was studied whenspectrophotometry was used to measure the content of nickel ions and molybdenumions, and the measuring scheme and steps of spectrophotometry were designed anddetermined.On the basis of laboratory experiments, considering some amplification effects,the small electroplating pilot plant of preparation of foamed nickel molybdenum alloymaterial of800×800mm2was designed. The selection of main equipment wasdetermined, and the design drawings of plating hangers, electroplating tank, doublewash tank, other auxiliary tank and the floor plan of the pilot plant were drawn. Andthe construction of the pilot plant and its pilot debugging were completed. In this pilot plant, seventy pieces of foamed nickel molybdenum alloy electrodematerials were prepared and their properties were studied with areal density,polarization curve and electrolyzer experiment. The experimental results showed thatabout90%of the products achieved the production requirements, and hydrogenevolution overpotential η200of the products was between260mV and300mV whichwas far below the one of foamed nickel electrode(η200=496mV), and exchange currentdensity i0of the products was (8.000±4)×10-3A cm-2which was far beyond the one offoamed nickel electrode(i0=2.7×10-5A cm-2). After intermittent electrolysis of50h byelectrolyzer, average cell voltage of foamed nickel molybdenum alloy electrodeincreased about30mV. After the electrolyzer was dismantled, the hydrogen evolutionoverpotential η200of the foamed nickel molybdenum alloy electrode increased about35mV by the test of polarization curve. The test of SEM and EDS showed that theNi-Mo alloy cladding droped off a little after intermittent electrolysis by electrolyzer,and the mass percentage and atom percentage of Mo decreased by about6.86%and2.41%respectively, which made the hydrogen evolution activity of nickel molybdenumalloy electrode decrease.更多还原