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.     

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.     

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.     

铅基稀土合金作为正极板栅的阳极膜性能

采用交流阻抗（EIS)、交流伏安（ACV）、循环伏安(CV)、腐蚀失重实验等方法研究了铅-钙-锡-铝-银合金中添加混合镧铈稀土在硫酸溶液中的阳极行为。 实验结果表明,混合镧铈稀土的添加能有效抑制阳极Pb(Ⅱ)膜的生长,降低Pb电极表面生成的Pb(Ⅱ)膜氧化膜电化学反应阻抗,改善阳极膜的导电性。 增强合金的耐腐蚀性能,并且增加析氧的过电位,抑制氧气的析出,降低电池的早期容量损失。 混合镧铈稀土的添加有利于提高电池的深循环寿命。 当镧铈混合稀土质量分数为0.5％时,各方面综合性能更优,效果更好。     

电沉积Al/Pb-Ag阳极在硫酸中的电化学性能

采用阳极极化曲线、循环伏安法、交流阻抗法、XRD和SEM等技术手段研究了银含量对铝基铅银合金电化学性能的影响。结果表明,在硫酸电解液中,随着银含量的增加,合金的耐腐蚀性逐渐提高,腐蚀膜的阻抗和析氧过电位逐渐降低。     

AZ91镁合金表面稀土转化膜的制备及耐蚀性能研究

采用在镁合金表面形成无毒、无污染的稀土铈转化膜的方法解决AZ91镁合金表面的腐蚀问题。确定了最佳成膜工艺参数，讨论了处理液的浓度、成膜温度和成膜时间等因素对转化膜耐蚀性的影响。利用湿热实验、阳极极化曲线的测定等实验方法评价了转化膜对镁合金表面的防护作用。结果表明，在潮湿温热条件下稀土铈转化膜试样仍能保持膜层的完整性并具有较高的覆盖度，腐蚀现象不明显。腐蚀电势升高，出现钝化现象，腐蚀电流密度下降，稀土铈转化膜可以提高AZ91镁合金的耐蚀性能。用扫描电镜观察了膜的微观形貌，稀土铈转化膜是由基膜和附着的细小颗粒组成，最佳工艺形成的铈转化膜无破碎现象，对AZ91镁合金表面的腐蚀过程的发生有明显的抑制作用。     

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.     

混合稀土对6063合金耐蚀性能的影响

采用金属覆盖层-铜加速醋酸盐雾实验(CASS)、阳极氧化膜连续性实验、腐蚀失重及扫描电镜观察(SEM)等方法,对比研究了6063合金和6063RE合金耐蚀性能的变化趋势。结果表明,适量的混合稀土(0.15wt％～0.24wt%)能提高6063合金在盐雾介质中以及在HCl、NaOH、NaCl、Na_2CO_3稀溶液中的耐蚀性能,且以在HCl稀溶液中的效果最明显。     

稀土盐对铝合金阳极化过程的影响

在阳极化溶液中添加稀土盐得到的铝合金氧化膜在腐蚀试验中表现出优良的耐蚀性能,现场椭圆法对阳极氧化过程的研究结果表明,稀土盐的加入,对椭圆编振参数的振荡方式没有显著影响,但却使振荡的周期和振幅发生了一些变化,由此可以推知,稀土盐的加入并未改变氧化膜的组成,但却在一定程度上影响了成膜过程,使膜的结构发生了变化。对椭圆数据进行定量分析的结果进一步表明：加入稀土盐后,氧化膜多孔层生长速率加快,阻挡层厚度增加,多孔部分变得更加致密,这种结构上的变化是阳极化膜耐蚀性能得以提高的主要原因,EDAX和TEM分析结果也证实了椭圆法研究的结果。     

几种稀土盐封闭的铝阳极氧化试样的腐蚀行为

为提高铝硫酸阳极氧化膜的抗污染和防腐蚀性能，分别采用环境友好的铈盐、钇盐和镧盐溶液对阳极氧化膜进行了封闭处理。采用动电位极化法比较了不同稀土盐封闭的铝阳极氧化试样在弱酸性NaCl腐蚀介质中的电化学行为，采用扫描电子显微镜（SEM）和能量色散谱（EDS）对封闭试样腐蚀前后的表面形貌、组成进行了表征。结果表明：在腐蚀介质的侵蚀及强电化学极化条件下，铈盐和镧盐封闭的阳极氧化膜对铝基体具有较好的保护作用，而钇盐封闭膜的保护作用则较差。这种差别的主要原因是不同稀土盐封闭过程中封闭产物的析出倾向及速率不同。     

Effects of casting temperature of Pb-Sb-Sn grid alloy on the polarization potential of oxygen evolution of lead acid batteries

The electrochemical polarization potential of oxygen evolution at the surface of lead-antimony-tin alloy is varied in different casting temperature of electrode production, which is used in the most of battery manufacturer. Effect of the casting temperature on the polarization potential of oxygen evolution and electrochemical behavior of lead-antimony-tin alloy in low antimony grid (1.7%) of lead acid battery is studied by using cyclic voltammetry and linear sweep voltammetry in aqueous sulfuric acid solution. The grid morphology is studied by using scanning electron microscopy and optical microscopy at the different casting temperatures. Cyclic voltammograms of the Pb-Sb-Sn and lead-antimony electrodes are similar, and both alloys show the anodic excursion peak under the same experimental conditions. The oxidation of tin is done at the formation potential of PbO. The results show the polarization potential for oxygen gas evolution to vary with casting temperature for production of lead-antimony electrodes. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 4, pp. 401–405. The text was submitted by the author in English.     

提高AB_5型贮氢电极合金低温电化学性能研究

采用优化稀土成分并添加适量的硼改善AB5型贮氢合金的低温性能 .实验表明 ,含富Ce稀土及添加适量硼的AB5型合金 ,其低温电化学性能优良 ,能满足Ni/MH电池在低至 - 35℃小倍率电流密度放电的要求 .贮氢合金低温性能的改善与合金的微结构、热力学和动力学性能相一致     

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。     

Effect of Sn content on the properties of passive film on PbSn alloy in sulfuric acid solution

The effect of Sn content on properties of anodic film formed on PbSn alloys in sulfuric acid solution was investigated using linear sweeping voltage (LSV), cyclic voltammetry (CV), and a.c. voltammetry (ACV), based on the Mott-Schottky analysis. The results revealed that the addition of Sn into lead alloys can promote the corrosion resistance property and could decrease the impedance of anodic film; these results were more remarkable with enhancing the Sn content. The over potential of oxygen evolution on lead alloys enhanced with the increase of Sn content. The Mott-Schottky analysis indicated that the passive film appeared an n-type semiconductor, and the donor density of passive film increased with increasing Sn content. The increased vacancies in the passive film with Sn content increasing could illustrate this trend.     

Effects of tetrabutylammonium hydrogen sulfate as an electrolyte additive on the electrochemical behavior of lead acid battery

Tetrabutyl ammonium hydrogen sulfate is an ion-paring reagent that has similar properties with ionic liquid. Ionic liquids belong to new branch of salts with unique properties that have ever increasing applications in electrochemical systems especially lithium-ion batteries. For the first time, the effects of tetrabutylammonium hydrogen sulfate (TBAHS) as an electrolyte additive in battery’s electrolyte was studied on the hydrogen and oxygen evolution overpotential and anodic layer formation on lead–antimony–tin grid alloy of lead acid battery by using cyclic voltammetry and linear sweep voltammetry in aqueous sulfuric acid solution. The grid surface morphology after cyclic redox reaction was studied by using scanning electron microscopy. The results show that, by increasing TBAHS concentration in the electrolyte, hydrogen and oxygen overpotential were increased, and so the crystalline structure of PbSO₄ layer changed. Also, cyclic voltammogram on carbon–PbO paste electrode shows that with presence of TBAHS in the electrolyte, oxidation and reduction peak current intensively increased and peak potential for oxidation and reduction of PbO were dependent on TBAHS concentration.     

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 .