【作者】 张胜涛；

【导师】 徐楚韶；

【作者基本信息】 重庆大学 ， 钢铁冶金， 2003， 博士

【摘要】 从人类1800年发明简易电池装置始，至今逾200年。在这200年人类文明发展过程中，电池技术得到了突飞猛进的发展，电池的种类各式各样，已与人类的生活结下了不解之缘。电池的应用领域无处不在，大到航天飞行器，小到电动玩具，到处可见到电池的身影。可以说，电池技术的发展促进了人类科技的发展。电池为人类璀璨的生活增加了光彩。然而，正是在这人们常见常用看似极普通的电池相关的领域中，仍然存在许多的问题需要深究和解决。在大多数电池中使用的电极都包括金属电极。铅酸电池的寿命受到金属极板腐蚀的限制，镍电池的容量难以提高，充电与放电时氧气或氢气析出会导致电池整体损坏，锌电极腐蚀既损失了锌电池的容量也缩短了电池有效存放期限或使用期限，空气电池中的金属电极同样需要进行性能的改进或品质的提高。这些问题的解决无疑都和金属表面性质的认识和改良有关，也是冶金学和其它学科结合研究的前沿课题。本论文针对上述问题，应用离子注入技术将几种金属元素注入到铅与铅-4%锑合金的表面，并以电化学研究方法和现代表面分析技术对上述两个体系展开深入研究，意在提高铅与铅-4%锑合金在蓄电池用硫酸中的抗腐蚀能力，延长铅酸电池的使用寿命；其中重点针对钛离子注入提高铅酸蓄电池极板抗腐蚀能力的原因进行分析，探讨钛离子注入影响铅及其合金表面腐蚀性能的机理，从工艺上优化钛离子注入的条件。论文通过实验，研究了钛离子注入剂量、钛离子加速能量改变对铅以及铅-4%锑合金腐蚀性能的影响，明确给出了应用钛离子注入技术改良铅与铅-4%锑合金在5 mol.L-1 H2SO4中的控制工艺条件：离子注入剂量在5x1016 atom.cm-2附近，离子加速能量约为60keV时可以获得较理想的防腐蚀效果。论文中还根据对钛元素注入之后在试样表面层中分布情况的实验研究对提出的控制工艺条件作出了理论分析和解释。本论文还应用椭圆偏振技术原位考察了铅在硫酸中的电化学振荡过程。离子注入过程中试样表面温度的升降对电极性能改良的效果有重要影响。本论文将传质学中的一些理论和处理方法应用于传热学，从理论上得到了离子注入过程中，基材表面温度与注入时间等因素之间的定量关系，并将这些理论结果应用于指导铅和铅-4%锑合金的离子注入实验，为离子注入技术的广泛应用提供了温度控制依据。在反射式椭圆偏振方法的基础上，本论文结合化学电源部件进行了改性的具体研究,率先提出了椭圆偏振方法的掠射测量方式，并且从理论上对掠射式椭圆偏振参数的物理意义给出了解释。掠射式椭圆偏振方法是本论文提出的一种全新的研究方法，为验证这种现场研究方法的可行性，本论文选择了几个用其它方法研究较为成熟的电化学体系并结合本论文研究的化学电源体系，以掠射式椭圆偏振技术进行研究，提出了改良镍电极、锌电极、铝电极和铜电极性能的具体措施或者理解这些电极表面性质和涉及它们的电极过程的实验依据，为使用这些电极的化学电源性能的提高奠定了基础。配合离子注入技术的应用，对钴元素注入提高镍电极充电效率的机理进行了探索，证明钴离子注入能够缓解充电过程中镍电极表面氧气的析出，从而使Ni(OH)2到NiOOH转化率提高大约10%。通过掠射式椭圆偏振方法的研究，不仅肯定了这种新方法在表面化学反应或表面变化过程现场<WP=5>研究中特有的优势，而且也证明这种方法能够适应于研究反应物和产物都可以溶解的界面化学反应体系，如K4[Fe(CN)6]/ K3[Fe(CN)6]电对之间在固体电极表面的氧化还原反应。以镍电池为应用背景，本论文还研究了钴离子注入对镍电极性能的影响，并分析了产生这种影响的原因，为离子注入技术改良含镍电极的化学电源的性能奠定了基础。锌—空气电池和铝—空气电池作为新颖的化学电源正在迅速发展，本论文通过实验研究了钛离子注入对铝电极点蚀性能的影响，还应用掠射式椭圆偏振技术研究了碱性锌电池涉及到的一些部件或组分的电化学性质，结合电化学性质的改进或分析以及电解质的影响对锌电极和一些电解液体系在化学电源中的作用进行了研究，为金属—空气电池的技术完善提供了依据，并开辟了改良金属—空气电池性能的新技术途径。更多还原

【Abstract】 It has been over 200 years since simple battery was invented in 1800. During the human civilized development course, battery technique is improved advance rapidly. There are many kinds of batteries. And they have banded human life cheek by jowl. Application area of battery is immanent. Battery’s silhouette can be seen everywhere from electric toy to space probe. It is identifiable that development of the battery technique accelerates development of human science and technology. Battery has increased sheen for human bright life. But a lot of questions do still need to be solved in the most ubiquitous battery field.Metal electrodes exist in many batteries. Life of lead-acid battery is limited by corrosion of the metal electrode frame. It is difficulty to increase capacity of nickel electrode. Destruction of all batteries can be brought on because oxygen and hydrogen are given out when the batteries are charged or discharged. Capacity of zinc battery is decreased and effective store time or use time is shortened due to corrosion of zinc electrode. To improve properties and enhance quality for metal electrode in metal-air battery are still needed. To solve these questions is relational with grasp and improvement of metal surface properties. Also the questions are front matters of combination of metallurgy and other sciences.To aim at above-mentioned questions, study is carried through. To improve inhibit ability to corrosion of lead and lead-4% antimony alloy in sulfuric acid and to prolong life of lead-acid battery, a several of metal elements are imported into surfaces of lead and lead-4% antimony alloy with ion implantation. Then electrochemical methods and advanced surface analytical techniques are applied to study the two systems. Reasons and mechanisms of inhibiting lead and lead-4% antimony alloy corrosion with titanium ion implantation have been discussed emphatically. Technical conditions of titanium ion implantation for above-mention two systems have been optimized. Effects of the dosages and energies of titanium on lead and lead-4% antimony alloy corrosion properties have also been studied through experiments. To obtain good inhibiting results, the ideal conditions are about 5x1016 atom.cm-2 dosage of titanium and 60 keV titanium ion energy for lead and lead-4% antimony alloy. Relationship between distribution of titanium on lead and lead-4% antimony alloy and technical conditions have been experimentally studied and theoretically explained. Electrochemical oscillation of lead electrode in sulfuric acid has been explored with in-situ ellipsometry.Effects of improvement of electrodes properties are affected by increase or decrease of surface temperature of the samples badly during ion implantation. Some theories and methods on substance diffusion transfer have been applied to calorifics to obtain mathematical relation between the surface temperature on the samples and operation time during ion implantation. And the mathematical relation has been applied to direction experiments of ion implantation for lead and lead-4% antimony alloy. The mathematical relation provides to foundation for controlling temperature during ion implantation. Basing on reflection ellipsometry and combining property improvement of parts in chemical<WP=7>power sources, graze ellipsometry is brought forward primarily. Physical meanings of graze ellipsometrical parameters are given out theoretically. To examine feasibility of the new graze ellipsometry, which is suggested at first in this thesis, a few of matured investigation electrochemical systems and chemical power sources have been studied with the graze ellipsometry. Then effective measures to improve properties of nickel, zinc, aluminum and copper electrodes and experimental data to understand electrode processes on the electrodes surfaces have been put forward.Mechanism to increase charge efficiency of the alkaline nickel electrode with cobalt ion implantation has been investigated. The results indicate that cobalt ion implantation can slow formation of oxygen d更多还原