Progress on the study of anodic Pb(Ⅱ) Film on Pb in H_2SO_4 solution

讨论了铅在硫酸溶液中生长的阳极Pb(Ⅱ)膜的物相组成、膜的生长与相转化过程及其光电化学性质等方面的研究进展.The phase composition, the mechanism of phase Formation and growth, the process of phase transFormation, and the photoelectrochemistry of the anodic Film Formed on Pb in Pb/ Pb( II ) potential region in sulFuric acid solution were reviewed

Problems on the Study of Anodic Films on Pb in Sulfuric Acid Solution(Ⅰ)

基于铅酸电池的实际应用以及对铅本身电化学行为的兴趣，人们对铅及其合金在硫酸溶液中形成的阳极膜，已做了大量的研究￣［１～４］。其三大进展为：Ｆｌｅｉｓｃｈｍａｎｎ与Ｔｈｉｒｓｋ￣［５］提出成核与生长机理来解释β－ＰｂＯ＿２的形成；Ｐａｖｌｏｖ￣［６］采用光电化学方法研究ＰｂＯ电位区的固相反应；Ｒｕｅｔｓｃｈｉ￣［７］提出阳极膜最外层ＰｂＳＯ＿４为半透膜，保证膜内部的碱性环境。然而总的来说，各个研究者对铅阳极膜缺乏统一的认识。其主要原因是铅阳极膜相组成复杂，至今尚未完全确定。有鉴于此，我们将陆续介绍本小组对于硫酸溶液中铅阳极膜研究的几个问题所持的观点。The identification of the phase composition of the anodic film on Pb formed inH_2SO_4 solution in PbO potential region has long been argued,together with the explanation of thecathodic peak at about -0.9V(Hg/Hg_2SO_4)in the linear sweep voltammogram for a Pb-H_2SO_4system. In this article, a review of our recent investigations was presented on the above problems.作者联系地址：复旦大学化学系Author's Address: Department of Chemistry,Fudan University,Shanghai 20043

Problems of the Study of Anodic Films on Pb in Sulfuric Acid Solution(Ⅲ)

硫酸溶液中铅阳极膜研究的几个问题（三）①柳厚田＊王群洲周伟舫（复旦大学化学系上海２００４３３）蔡文斌（固体表面物理化学国家重点实验室厦门大学化系系厦门３６１００５）１阳极硫酸铅膜阴极还原为金属铅的液膜机理［１］奇怪的是，对铅蓄电池充电时的基本过程的机...The interstitial liquid among the particles in anodic Pb(Ⅱ) films could be the major passage for ion transportation. This is discussed with the mechanism of the cathodic reduction of anodic PbSO 4 film and the effect of Sb on the growth of anodic Pb(Ⅱ) oxides film.作者联系地址：复旦大学化学系Author's Address: Dept. of chem., Fudan Univ., shanghai 200433 Cai Wenbin State Key Lab. for Phys. Chem. of Solid Surf., Dept. of chem., Xiamen Univ., Xaimen 36100

Problems on the Study of Anodic Films on Pb in Sulfuric Acid Solution(Ⅱ)

硫酸溶液中铅阳极膜研究的几个问题（二）①柳厚田＊王群洲万咏勤周伟舫（复旦大学化学系，上海２００４３３）蔡文斌（厦门大学化学系，厦门３６１００５）在硫酸溶液中开始生长阳极Ｐｂ（Ⅱ）膜后不久，表面即形成ＰｂＳＯ４半透膜，该膜仅Ｈ＋、ＯＨ－和Ｈ２Ｏ可通过，...The conditions for the growth of the different phases in the anodic Pb(Ⅱ) film on Pb in sulfuric acid solution were discussed.作者联系地址：复旦大学化学系,厦门大学化学系Author's Address: Department of Chemistry, Fudan University, Shanghai 200433 Cai Wenbin Department of Chemistry, Xiamen University, Xiamen 36100

Studies on the Properties of the Anodic Films Formed on Lead- Lanthanum and Lead-Samarium Alloys in Sulfuric Acid Solution

应用交流伏安法和线性电位扫描法研究了Pb ,Pb 1.0at%La和Pb 1.0at%Sm电极在硫酸溶液中以 0 .9V(vs .Hg/Hg2 SO4 )生长的阳极Pb(Ⅱ )膜增长率和膜的阻抗实部变化 ,并采用循环伏安法研究了它们在 0 .6～ 1.6V(vs.Hg/Hg2 SO4 )间的循环伏安特性 ,结果表明 :在铅中添加Sm有利于抑制铅的阳极腐蚀和降低阳极Pb(Ⅱ )膜的阻抗 ,La亦可降低阳极Pb(Ⅱ )膜的阻抗 ,但其作用不如Sm明显AC voltammetry,linear sweep voltammetry,and cyclic voltammetry were applied to study the anodic corrosion of Pb,Pb 1.0at%La and Pb 1.0at%Sm electrodes in 4.5 mol·dm -3 H 2SO 4 solution (25 ℃).The experiment results show that samarium can inhibit the anodic corrosion of lead and decrease the impedance of anodic Pb(Ⅱ) film. Lanthanum can also decrease the impedance of the anodic Pb(Ⅱ)film, but the effect is smaller.作者联系地址：复旦大学化学系,复旦大学化学系,复旦大学化学系,复旦大学化学系,复旦大学化学系 上海200433 ,上海200433 ,上海200433 ,上海200433 ,上海200433Author's Address: Dept. of Chem., Fudan Univ., Shanghai 200433, Chin

The Effect of Cerium on the Anodic Behavior of Pb-Ca-Sn Alloy in Sulfuric Acid Solution

应用循环伏安法研究了Pb - 0 .5at %Ca - 1 .5at %Sn和含Ce的Pb - 0 .5at%Ca - 1 .5at%Sn合金电极在 4.5mol·dm- 3H2 SO4溶液中和 0 .6～ 1 .4V(vs .Hg/Hg2 SO4电极 )电位范围内的电化学特性 ,并采用线性电位扫描法和交流伏安法分别研究了上述合金在相同溶液中以 0 .9V(vs .Hg/Hg2 SO4电极 )生长的阳极Pb(Ⅱ )膜增长率和膜的阻抗实数部分 (Z’)变化 .结果表明 ,在铅合金中添加Ce对阳极Pb(Ⅱ )膜的生长有显著的抑制作用并降低铅阳极膜的Z’ .以上述两种合金作为正极板栅制作的铅蓄电池 ,含Ce的Pb Ca Sn合金的深充放循环性能明显优于Pb Ca Sn合金 .The cyclic voltammograms for Pb - 0.5 at% Ca - 1.5 at% Sn and Pb - 0.5 at% Ca - 1.5 at% Sn containing a certain amount of cerium in 4.5 mol·dm -3 H 2SO 4 at 20℃ were measured between 0.6 V and 1.4 V(vs. Hg/Hg 2SO 4). The growth rate of the anodic Pb(Ⅱ) films formed on the mentioned alloy electrodes at 0.9 V in the same sulfuric acid medium was investigated using the Linear Sweep Voltammetry. The variation with electrode potential of the real part of the impedence (Z’) for the anodic Pb(Ⅱ) films was measured using the A.C. Voltammetry. The experiment results show that the cerium added to Pb Ca Sn alloys may inhibit the growth of the anodic Pb(Ⅱ) film and reduce the resistivity of the anodic Pb(Ⅱ) film. The capacity losses at deep charge/discharge cycles for the lead acid batteries with the positive grids manufactured using the mentioned lead alloys were measured. The results show that the performance of the deep charge/discharge cycles for the grid made of Pb Ca Sn Ce alloy is better than that of Pb Ca Sn alloy.作者联系地址：复旦大学化学系!上海200433,复旦大学化学系!上海200433,复旦大学化学系!上海200433,复旦大学化学系!上海200433,复旦大学化学系!上海200433Author's Address: Dept.of Chem., Fudan Univ., Shanghai 200433, Chin