【作者】 赵夕；

【导师】 徐强；

【作者基本信息】 天津大学 ， 应用化学， 2010， 硕士

【摘要】 镁是一种很有发展前景的高能量密度电池的负极材料,因此在有机溶液体系中进行金属镁电沉积的研究,对于高效新型镁一次和二次电池的开发,具有十分重要的意义。在本论文中,首先比较了三种市售格氏试剂电解液乙基溴化镁/四氢呋喃溶液（EtMgBr/THF）、乙基氯化镁/四氢呋喃溶液（EtMgCl/THF）和苯基氯化镁/四氢呋喃溶液（PhMgCl/THF）在三种不同阴极材料（平板纯铜基体,镀铜平板镍基体和镀铜泡沫镍基体）上镁的电沉积行为。发现在平板基体上都能得到均匀致密的镁镀层,但泡沫基体内部的镁沉积量很少。表明这三种格氏试剂溶液的深镀能力均较差。然后利用直角阴极法研究了加入支持电解质四丁基氯化铵（NBu₄Cl）对于格氏试剂电解液EtMgBr/THF深镀能力的影响。实验发现,L形铜片电极表面的镁电沉积面积和镁含量随着NBu₄Cl浓度的增大而不断增大,NBu₄Cl在EtMgBr/THF中的最佳浓度为0.6M。将0.6M NBu₄Cl加入EtMgBr/THF溶液中进行电沉积镁,实验发现,泡沫基体电沉积镁后的表面和内层均被镁镀层所覆盖,并且内层的镁含量提高到了60%左右。表明加入支持电解质NBu₄Cl可以有效改善EtMgBr/THF的深镀能力。最后利用直角阴极法研究了脉冲电沉积方法对于格氏试剂电解液EtMgBr/THF的深镀能力的影响,优选出最佳的脉冲电沉积参数,在泡沫基体上进行镁电沉积实验。实验发现,在平均电流密度0.0500A/cm²,占空比80%,脉冲频率5Hz的脉冲电沉积实验条件下,泡沫基体的表面和内层均被镁镀层所覆盖,并且内层的镁含量提高到了60%左右。表明脉冲电沉积方法可以有效改善EtMgBr/THF的深镀能力。更多还原

【Abstract】 Magnesium is a promising high energy density battery anode material, so it is of great significance to research the electrodeposition of metal magnesium in organic solution systems for the development of new efficient primary and secondary magnesium batterys.In this paper, firstly, three commercially available Grignard reagent electrolyte magnesium bromide / tetrahydrofuran solution （EtMgBr / THF）, ethyl magnesium chloride / tetrahydrofuran solution （EtMgCl / THF） and phenyl magnesium chloride / tetrahydrofuran solution （PhMgCl / THF） was used to compare the electrodeposition behavior of magnesium on three differet cathode materials（planar pure copper substrate, planar plated-copper nickel substrate and foamed plated-copper nickel substrate）.It is found that, on the planar substrate, uniform and compact magnesium coating can be get; but inside the planar substrate, the magnesium deposition is very few. It reveals that the deepening plating ability of these three Grignard reagent solutions is low.Secondly, rectangular cathode method was used to study the impact of supporting electrolyte tetrabutylammonium chloride （NBu₄Cl） to the deepening plating ability of Grignard reagent electrolyte EtMgBr / THF. It is found that the area and the component of magnesium electrodeposition on the L-shaped copper electrode surface increased with the concentration of the NBu₄Cl.The best concentration of NBu₄Cl was 0.6M. Then 0.6M NBu₄Cl was added to the EtMgBr / THF solution and the magnesium electrodeposition experiment was done on the formed substrate. The result shows that after the magnesium electrodeposition, the magnesium coating covered outside and inside the foamed substrate, and the component of the magnesium is increased to 60% inside the foamed substrate. It reveals that the deepening plating ability of EtMgBr / THF can be improved by adding NBu₄Cl supporting electrolyte to the solution.Finally, Rectangular cathode method was used to study the impact of pulse electrodeposition method to the deepening plating ability of Grignard reagent electrolyte EtMgBr / THF, and the best pulse electrodeposition parameters were optimized. Then the magnesium electrodeposition experiment was done on the formed substrate. The result shows that, under 0.0500 A/cm² average current density, 80% dutyfactor, 5Hz pulse frequency pulse electrodeposition conditions, the magnesium coating covered outside and inside the foamed substrate, and the component of the magnesium is increased to 60% inside the foamed substrate. It reveals that the deepening plating ability of EtMgBr / THF can be improved by pulsed electrodeposition method.更多还原