稀土铅钙合金与传统铅钙合金在硫酸溶液中的阳极行为研究

应用交流阻抗,交流伏安和循环伏安等方法研究了Pb-Ca-Sn-Re合金和Pb-Ca-Sn合金在1.28 V(vs.SCE)和4.5 mol/L硫酸溶液中的阳极行为.结果表明:稀土铅钙合金提高了合金的耐腐蚀性能,同时抑制其阳极膜中Pb(Ⅱ)化合物的生长,从而降低阳极膜的阻抗,提高膜的导电性能,这对改善电池的深循环性能十分有利.     

铅镧和铅钐合金在硫酸溶液中生长的阳极膜性质的研究

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     

一种新型铅钐锡正极板栅合金

目前,铅钙锡合金已广泛用作阀控式铅酸蓄电池(VRLAB)的板栅材料.由于钙的存在,使铅钙锡合金阳极氧化时易形成高阻抗的阳极腐蚀层,并出现晶间腐蚀,电池循环充放电能力仍不理想.为克服铅钙锡合金作为正极板栅材料的不利因素.     

铈对铅钙锡合金在硫酸溶液中阳极行为的影响

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 .     

Sm-La二元稀土对铅基板栅材料显微结构和电化学性能的影响

为提高铅酸蓄电池板栅材料的性能,在Pb-Ca-Sn-Al合金中添加了Sm-La二元稀土元素,研究其含量对显微结构和电化学性能的影响。利用金相和循环伏安、线性扫描、阻抗-电位、电化学阻抗谱等电化学测试方法对板栅性能进行了表征。结果表明:Sm-La稀土元素的加入促进合金晶粒细化,随其含量的增加,析出物颗粒变小并弥散分布。与添加Sm的合金相比,复合添加Sm-La的材料具有更低的析氢电位,改善了深放电时铅合金上所形成的阳极Pb(II)膜的阻抗特性,表现出良好的性能。     

添加铈对铅钙合金在硫酸溶液中电化学性能的影响

为了改善铅钙合金的耐腐蚀性能和提高铅蓄电池的循环寿命, 应用交流阻抗, 阳极极化曲线, 交流伏安, 恒流腐蚀等方法研究了在铅钙锡铝合金中添加铈对合金电化学性能的影响. 研究结果表明: 铈能提高合金的耐腐蚀能力, 添加铈使合金腐蚀膜的阻抗明显降低, 有利于缓解早期容量损失(PCL-1)现象, 实验电池的循环寿命也明显延长. 因此掺铈铅钙合金是一种性能优良的阀控式铅酸电池正极板栅合金材料.     

铅(Ⅱ)离子印迹复合膜的制备及其性能研究

以聚丙烯微孔膜(MPPM)为支撑,采用共价表面修饰和离子印迹技术,制备了Pb(Ⅱ)离子印迹复合膜.首先通过紫外光引发丙烯酸接枝聚合,在MPPM表面引入羧基;然后基于羧基和氨基的反应,将壳聚糖共价接枝到MPPM表面;再以Pb(Ⅱ)为模板离子、环氧氯丙烷为交联剂,通过配位键作用形成离子印迹位点.制备过程通过ATR-FTIR和XPS分析得到了证实.利用扫描电子显微镜(SEM)-能量色散X射线光谱仪(EDX)对膜表面及截面的形貌及元素分布进行了分析.静态水接触角和纯水通量实验结果显示,印迹复合膜具有良好的表面亲水性和渗透性,在离子印迹聚合物接枝率为174.4μg/cm2时,水通量高达2659±58 L/(m2.h).印迹复合膜对Pb(Ⅱ)离子的吸附亲和性和渗透选择性分别通过平衡结合实验和竞争渗透实验进行评价.与非印迹复合膜相比,印迹复合膜对Pb(Ⅱ)离子展现出更强的吸附亲和性,更快的吸附速率及更好的渗透选择性,以Cu(Ⅱ)和Zn(Ⅱ)作为竞争离子,其渗透选择性因子分别为3.43和3.93.     

温度对铅阳极膜电化学性能的影响

利用线性电位扫描法、交流伏安法、电化学阻抗谱(EIS)及Mott-Schottky方程, 研究了温度对纯铅在4.5 mol/L H₂SO₄溶液中形成的阳极腐蚀膜电性能的影响. 结果表明: 温度对膜电化学性能具有显著的影响, 随着温度的升高, 膜的电阻增加, 孔隙率增加, 传递电阻减小. EIS结果表明膜的生长遵循固相机理, Mott-Schottky曲线显示腐蚀膜呈现n型半导体特性, 随着溶液温度升高, 膜内的施主密度减小.     

VA族元素对阳极铅(II)氧化物膜半导体性质的影响(I)

用交流阻抗法研究了铅、铅砷、铅锑和铅铋金在4.5 mol·L~(-1) H_2SO_4溶液(20 ℃)中，以0.9 V(vs．Hg/Hg_2SO_4)极化2 h而形成的阳极膜的半导体性质．根据Mott-Schottky图，此种膜为n型半导体．pb，pb-lat％As，Pb-lat％Sb和Sb-lat％Bi上膜的平带电位分别为-0.95，-1.1, -1.0，-1.1 V(vs. Hg/Hg_2SO_4)；相应的施主密度分别为0.82×10~(16)，2.6×10~(16)，1.2×10~(17)和0.71×10~(16) cm~(-3).     

VA族元素对阳极铅(II)氧化物膜半导体性质的影响(II)

用光电化学电流法研究了铅、铅砷、铅锑和铅铋合金在4.5 mol·L~(-1) H_2SO_4溶液(22 ℃)中，以0.9 V(vs．Hg/Hg_2SO_4)极化7 h而形成的阳极膜中的氧化铅的半导体性质，合金添加剂砷、锑和铋对t-PbO(四方氧化铝)和o-PbO(斜方氧化铝)的禁带宽度没有影响，从量子效率和电位的关系可求Pb，Pb-lat％As(at％表示原子百分比，全文同)，Pb-lat％Sb和Sb－lat％Bi上膜中t－Pbo的施主密度(N_D)分别为9.3×10~(15)，1.0×10~(16)，3.1×10~(16)和1.3×10~(17) cm~(-3)，平带位分别为-0.20，－0.22，－0.28和-0.08 V(vs．Hg/Hg_2SO_4)．比较VA元素砷、锑和铋对上述膜中t-PbO的N_D(从而自由电子密度)和膜中t-PbO的生长速率的影响，可认为法添加剂砷、锑和铋对阳极膜中t-PbO的作用符合Hauffe规则．     

铅铈和铅钙锡合金阳极腐蚀膜的性能研究

利用叠加交流伏安法、线性电位扫描法、交流阻抗技术和XPS研究了铅铈合金和铅钙锡合金在阳极1.28 V, 4.5 mol/L的硫酸溶液中所形成的阳极腐蚀膜. 结果表明: 稀土铈能抑制阳极膜中高阻抗的Pb(II)化合物的生长, 降低腐蚀膜的阻抗, 并增加膜的孔隙率. 同时可以提高合金的析氢过电位, 有利于电池免维护性能的提高.     

Effect of Sb on the properties of anodic Pb(Ⅱ) oxide film formed in alkaline solution

The composition and properties of the anodic films formed on Pb and Pb-3at.%Sb alloy at -0.10 V (vs. Hg/HgO) for 2.5 h in 0.1 mol.dm-3 NaOH solution (25℃) were investigated by cyclic voltammetry, linear sweep voltammetry, open circuit decay curve, photocurrent technique, X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that the anodic film formed oh Pb mainly consists of t-PbO, while that on Pb-3at.%Sb consists of o-PbO, t-PbO and a small amount of orthorhombic Sb2O3. The dominant component of the film anodically grown on Pb-3at.%Sb for less than 5 min is o-PbO, however, t-PbO is the major component of the anodic film formed for 1 h or longer. It is established that Sb suppresses the growth of t-PbO. The anodic film formed on Pb-3at.%Sb is less porous than that on Pb. The bandgap energies of t-PbO and o-PbO in the films were determined by photocurrent measurements to be 1.83-1.84 eV and 2.60 eV, respectively.     

Effects of Samarium on the Properties of the Anodic Pb（Ⅱ） Oxides Film Formed on Pb in Sulfuric Acid Solution

The effects of samarium on the properties of the anodic Pb(II) oxides films formed on lead at 0.9 V (vs. Hg/Hg₂SO₄) in 4.5 mol/L H₂SO₄ solution were studied using linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and scanning electron micrographs (SEM). The experimental results show that adding Sm to lead metal can inhibit the growth of the Pb(II) oxides film effectively, and reduce the resistance of the PbO oxides film obviously. The addition of Sm increases the porosity of the anodic film, which may cause the increase of the ionic conductance produced by the interstitial liquid among the PbO particles in the film and lead to the decrease of the resistance of the anodic film.     

Effects of Samarium on the Properties of the Anodic Pb(II) Oxides Film Formed on Pb in Sulfuric Acid Solution

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Nanostructure Analysis of Anodic Films Formed on Aluminum-Focusing on the Effects of Electric Field Strength and Electrolyte Anions

In this review, the research conducted by the authors on anodic oxide films on aluminum is described, paying particular attention to how the electric field strength, as a factor other than voltage, controls the nanostructures and properties of the films. It will also be indicated what factors contribute to the formation of defects, which, in contrast to the ideal or model film structure, contains a significant number of defects in the film. In addition to electrochemical measurements, the films were examined with a variety of advanced instruments, including electron microscopes, to confirm the “reality of film nanostructure” from a slightly different angle than the conventional view. The following topics on anodic films formed in four types of major anodizing electrolytes are discussed: pore initiation process, steady-state porous structure, sealing mechanism, the relationship between cell parameters and voltage/electric field strength, amount and depth of anion incorporation, electrolyte types, radial branching of pores, atypical pore structures, defect formation mechanism, self-ordering, Al coordination number, and the creation of α-alumina membranes.     

Electronic Properties of Passive Films Formed on G3 and G30 Nickel-based Alloys in Bicarbonate/Carbonate Buffer Solution

The electronic properties of passive films formed on G3 and G30 alloys in bicarbonate/carbonate buffer solution were comparatively studied by electrochemical impedance spectra(EIS) and Mott-Schottky analysis, the chemical composition of the passive film formed on G3 alloy was detected by X-ray photoelectron spectroscopy (XPS). The results show that passive film on G3 alloy had better protection than that on G30 alloy. The transfer resistance, film resistance and diffusion resistance of the passive films on ...     

Mercury Films on Commercial Carbon Screen‐Printed Devices for the Analysis of Heavy Metal Ions: a Critical Evaluation

The suitability of mercury films on commercial screen‐printed electrodes for the analysis of heavy metal ions is critically tested for the particular case of Pb(II)‐ions. Although determination is possible by anodic stripping voltammetry with a reasonable detection limit (8.9 µg L^?1), important drawbacks are noticed as a consequence of the heterogeneous deposition of mercury on the rough surface of screen‐printed devices.