5,5-二甲基乙内酰脲配位体系中银的电沉积行为研究

选用5,5-二甲基乙内酰脲(DMH)作为配位剂进行电镀银，通过计时电位曲线、阴极极化曲线、电化学阻抗谱等分析了碱性DMH镀银体系中银的阴极还原过程，采用循环伏安曲线、计时电流法研究了银的成核/生长机制，综合探讨了碱性DMH镀银体系中银的电沉积行为。结果表明，碱性DMH镀银体系中，银配离子的主要存在形式为[Ag(C₅H₇N₂O₂)₂]-，并且通过前置转化反应生成[Ag(C₅H₇N₂O₂)]在阴极上直接放电。该体系中银的电沉积过程是由扩散控制的不可逆电极反应，且经历了晶核形成过程，并遵循三维瞬时成核生长机理。     

Sb(Ⅲ)在碱性木糖醇溶液中的阴极电沉积(英文)

运用循环伏安法、线性电位扫描法研究木糖醇在碱性溶液(含锑)中的电化学稳定性及锑在木糖醇碱性溶液中的沉积动力学参数;采用计时电流法研究锑在不锈钢阴极上的电化学成核机理。循环伏安测试结果表明,木糖醇在碱性溶液中的稳定性较好,在-1.20V～+0.60V(vsHg/HgO)范围内无氧化还原反应发生,在电位负于-1.70V(vs.Hg/HgO)时木糖醇在锑电极上可能发生分解。在该体系中,锑在阴极上的沉积经历了不可逆电结晶过程。根据线性电势扫描结果,锑沉积的活化能、表观传递系数、交换电流密度等动力学参数分别为46.33kJ/mol、0.64和4.40×10-6A/m2。计时电流法实验结果表明,锑在碱性木糖醇溶液中的成核机理符合扩散控制下的三维连续成核模型,外加电位对晶体生长速率和恒定电位下的饱和晶核密度有显著影响。通过分析恒电位阶跃曲线,求出锑离子在该体系中的扩散系数为1.53×10-6cm2/s。     

在LiCl-KCl熔盐体系中Zr(Ⅳ)的电化学还原

利用电化学暂态技术如循环伏安法、计时电位法和计时电流法研究了K2ZrF6-LiCl-KCl熔盐体系中,温度为923K时Zr(Ⅵ)在钼电极上的电还原过程.结果表明,Zr(Ⅵ)在钼电极上的电还原是通过两步电子转移反应完成的.其电化学反应历程为:Zr(Ⅵ)+2e=Zr(Ⅱ),Zr(Ⅱ)+2e=zr.其中间产物经X射线衍射分析为ZrCl2.计时电流曲线研究表明,锆在析出时存在成核极化现象,成核过程为瞬间成核过程.     

氨络合物体系电积锌的阴极过程

采用CHI650电化学工作站测定了在锌氨络合物体系中锌电沉积的稳态阴极极化曲线及电流-时间暂态曲线.结果表明:锌的阴极电结晶过程是以瞬时成核方式进行的,随外加电位负移,晶体的向外生长速率增大;添加剂的加入不会改变锌阴极电沉积的成核方式,但将大大减小晶体的向外生长速率.通过对不同NH3浓度下测得的阴极极化曲线的分析,可获得各条件下的平衡电位,以及阴极过程动力学参数(交换电流密度J°、传递系数α),进而推导出溶液中存在的主要离子为Zn(NH3)2 4,在阴极直接放电的络离子为Zn(NH3)22 .     

Q235钢在模拟海水环境混凝土孔隙液中阴极氧还原反应的动力学研究

通过用循环伏安和旋转圆盘电极伏安等电化学方法研究了Q235钢在模拟海水环境下的混凝土孔隙液中阴极氧还原反应行为及动力学参数.结果表明：在0.02 mol/L Ca(OH)2溶液中氧还原反应在阴极反应电位范围内,最初为混合过程控制的二电子反应即O2还原为HO-2,电位较负时为扩散过程控制的四电子反应,反应的最终产物为OH-.0.02 mol/L Ca(OH)2+3.5% NaCl溶液中氧还原反应半波电位与无氯离子溶液体系相比发生正移,氧还原反应以四电子反应为主,反应的最终产物为OH-.     

MnO_2@graphene复合材料的制备及其对微生物燃料电池阴极氧还原反应的催化活性EI北大核心CSCD

以高锰酸钾、草酸锰、石墨烯为原料,采用化学共沉淀法制备MnO_2@graphene复合材料,用X射线衍射、红外光谱、拉曼光谱、扫描电镜、比表面测定等对其进行表征。以MnO_2@graphene为MFC阴极氧还原反应催化剂,采用循环伏安法和电化学阻抗法研究MnO_2@graphene催化电极对氧还原反应的催化活性。结果表明:粒度为400 nm左右的MnO_2颗粒通过静电相互作用均匀而牢固地分散在纸片状graphene表面,形成MnO_2@graphene复合材料。循环伏安测试结果表明:当扫描速率为5 m V/s时,虽然MnO_2@graphene催化电极在p H为7.0的磷酸盐缓冲体系(PBS)的氧还原反应起峰电位比Pt/C催化电极负0.048V,但其峰电位(-0.440 V)与Pt/C催化电极的起峰电位(-0.434 V)接近。随着循环次数的增加,MnO_2@graphene催化电极的起峰电位稍有下降,但峰电流密度下降很小,表明MnO_2@graphene催化剂具有更好的氧还原催化活性和更优秀的循环稳定性。电化学阻抗实验发现:MnO_2@graphene催化电极的电荷转移阻抗为12.6?,比同条件下Pt/C催化电极和MnO_2催化电极的低,表明由于graphene增加MnO_2的导电性,降低催化电极电荷转移阻抗,加快电子的转移速率,促进阴极氧还原反应。     

钼在KF-B_2O_3-K_2MoO_4熔体中的电还原

本文用线性电位扫描,循环伏安和计时电位等方法研究了钼在KF-B_2O_3-K_2MoO_4熔体中的电还原机理.发现电还原反应分两步进行:第一步为准可逆反应,第二步为可逆反应.在815℃时用循环伏安法测得的MO~(6+)扩散系数为1.99×10~(-5)cm~2/s,用计时电位法测得的为2.25×10~(-5)cm~2/s.     

MnO_2@graphene复合材料的制备及其对微生物燃料电池阴极氧还原反应的催化活性

以高锰酸钾、草酸锰、石墨烯为原料,采用化学共沉淀法制备MnO_2@graphene复合材料,用X射线衍射、红外光谱、拉曼光谱、扫描电镜、比表面测定等对其进行表征。以MnO_2@graphene为MFC阴极氧还原反应催化剂,采用循环伏安法和电化学阻抗法研究MnO_2@graphene催化电极对氧还原反应的催化活性。结果表明:粒度为400 nm左右的MnO_2颗粒通过静电相互作用均匀而牢固地分散在纸片状graphene表面,形成MnO_2@graphene复合材料。循环伏安测试结果表明:当扫描速率为5 m V/s时,虽然MnO_2@graphene催化电极在p H为7.0的磷酸盐缓冲体系(PBS)的氧还原反应起峰电位比Pt/C催化电极负0.048V,但其峰电位(-0.440 V)与Pt/C催化电极的起峰电位(-0.434 V)接近。随着循环次数的增加,MnO_2@graphene催化电极的起峰电位稍有下降,但峰电流密度下降很小,表明MnO_2@graphene催化剂具有更好的氧还原催化活性和更优秀的循环稳定性。电化学阻抗实验发现:MnO_2@graphene催化电极的电荷转移阻抗为12.6?,比同条件下Pt/C催化电极和MnO_2催化电极的低,表明由于graphene增加MnO_2的导电性,降低催化电极电荷转移阻抗,加快电子的转移速率,促进阴极氧还原反应。     

在Na_2S-NaOH浸出液中电沉积Sb时的电化学行为

本文是湿法炼Sb的物理化学研究中的一部分。当用Na_2S-NaOH溶液浸出复杂的Pb-Sb精矿时,Sb以SbS_3~(3-)离子形态进入溶液。精矿中的Sn和As部分溶解,而Pb则留在残渣中与Sb分离,SbS_3~(3-)离子与空气接触时,部分氧化成SbS_4~(3-)离子。用稳态法测定了极化曲线,确定了在硫化碱溶液中Sb(Ⅲ).Sn(Ⅳ),As(Ⅲ),Sb(Ⅴ)和H~ 离子的放电电位。其相应数值如下:-0.92,-1.04,-0.81,-0.68和-1.12V。这些数值分别用纯化学试剂配制的溶液和工业电解液进行了比较测定,并用热力学计算结果进行核对。Sb(Ⅴ)的放电电位还通过计时电位法核对。将所得极化曲线进行浓差极化修正后获得了Tafel直线,由此计算出有关的电极动力学参数。应用计时电位法,探讨了SbS_3~(3-)和SbS_4~(3-)离子的阴极放电机理。结果表明:SbS_3~(3-)离子放电前经历一个前置转化步骤,即: SbS_3~(3)→SbS~ 2S~(2-) (1)生成的中间产物SbS~ 按下列反应SbS~ 3e→Sb S~(2-) (2)还原为金属Sb。SbS_4~(3-)离子在阴极上放电过程分两步进行,首先,SbS_4~(3-)离子按下式还原为SbS_3~(3-)离子, SbS_4~(3-) 2e→SbS_3~(3-) S~(2-) (3)生成的中间产物SbS_3~(3-)离子再按反应(1)和(2)式还原为金属Sb。     

THE ELECTROCHEMICAL BEHAVIOUR OF Sb ELECTROWINNING IN Na_2S-NaOH SOLUTION

本文是湿法炼Sb的物理化学研究中的一部分。 当用Na_2S-NaOH溶液浸出复杂的Pb-Sb精矿时,Sb以SbS_3~(3-)离子形态进入溶液。精矿中的Sn和As部分溶解,而Pb则留在残渣中与Sb分离,SbS_3~(3-)离子与空气接触时,部分氧化成SbS_4~(3-)离子。 用稳态法测定了极化曲线,确定了在硫化碱溶液中Sb(Ⅲ).Sn(Ⅳ),As(Ⅲ),Sb(Ⅴ)和H~+离子的放电电位。其相应数值如下:-0.92,-1.04,-0.81,-0.68和-1.12V。这些数值分别用纯化学试剂配制的溶液和工业电解液进行了比较测定,并用热力学计算结果进行核对。Sb(Ⅴ)的放电电位还通过计时电位法核对。 将所得极化曲线进行浓差极化修正后获得了Tafel直线,由此计算出有关的电极动力学参数。 应用计时电位法,探讨了SbS_3~(3-)和SbS_4~(3-)离子的阴极放电机理。结果表明:SbS_3~(3-)离子放电前经历一个前置转化步骤,即: SbS_3~(3)→SbS~++2S~(2-) (1)生成的中间产物SbS~+按下列反应 SbS~++3e→Sb+S~(2-) (2)还原为金属Sb。 SbS_4~(3-)离子在阴极上放电过程分两步进行,首先,SbS_4~(3-)离子按下式还原为SbS_3~(3-)离子, SbS_4~(3-)+2e→SbS_3~(3-)+S~(2-) (3)生成的中间产物SbS_3~(3-)离子再按反应(1)和(2)式还原为金属Sb。     

Nature of the potential of nonpolarized zinc electrode in zincate solutions

The effect of components of alkaline zincate solution and surface compounds, which form on metal zinc in the alkaline solutions, on the nature of nonpolarized electrode potential (E) is studied. It is proposed to determine the nature of E by taking into account more rigorously the activities of all solution components. It is found that in the zincate solutions, the potential of nonpolarized metal zinc is the potential of Zn/Zn(OH)₂, OH⁻ electrode of the second kind. Original Russian Text ? V. Rezaite, L. Deresh, 2006, published in Zashchita Metallov, 2006, Vol. 42, No. 4, pp. 368–372.     

Anodic Behaviour of Zinc in Potassium Hydroxide Solution: II.* Horizontal Anodes in Electrolytes Containing Zn(II)

Abstract

Equilibrium solubility data for ZnO in KOH are reported for KOH concentraiions up to 14M.

Results of passivation time determination for horizontally orientated zinc anodes In alkaline zincate electrolytes are reported. These results are correlated in the form: (i–i₁) t_p½ = k, where k and i₁ depend on [Zn(II)], [OH_?] and temperature. Passivation occurs when the [Zn(II)] at the anode is equivalent to the [OH?] of the electrolyte.

Overpotential–current density relationships indicate that the charge-transfer reactIon is complicated.     

糖苷对碱性溶液中钢筋表面钝化膜性能的影响

利用动电位极化和表面形貌观察技术,结合电容-电位曲线测量和Mott-Schottky分析,探讨了糖苷化合物对钢筋在含3.5%NaCl的Ca(OH)₂饱和溶液中的缓蚀行为和表面钝化膜性能的影响。结果表明,糖苷阻锈剂的加入可有效减缓钢筋的腐蚀,促进钢筋表面的钝化,提高钢筋耐Cl^-侵蚀能力;阻锈剂虽未改变钢筋表面钝化膜的半导体性能,但钝化膜内载流子密度却显著下降;钝化膜致密性分析表明,随糖苷浓度增大,钢筋表面钝化膜稳定性和致密性逐渐增强,耐蚀性提高。     

碱性锌酸盐体系电镀Zn—Ce合金工艺研究

研究碱性锌酸盐体系电镀Zn-Ce合金工艺.对镀液中不同Ce~(3+)含量所获得镀层的耐蚀性作了研究,并以X-射线衍射对Zn-Ce镀层和纯Zn层的结构作了对比分析.     

添加剂对Zn/KOH/AgO电池性能的影响

本文以电沉积锌为负极,过氧化银为正极,KOH溶液为电解质,组装成Zn/KOH/ AgO模拟电池.研究不同浓度的KOH电解质溶液对Zn/KOH/AgO电池比容量的影响,探索电解质溶液中不同添加剂对电池放电过程中锌电极钝化的影响,并考察了放电倍率对电池性能的影响.结果表明:KOH电解质溶液的最佳浓度为5 mol/L,电解质...     

α-Ni(OH)2 electrodeposition from NiCl2 solution

α-Ni(OH)₂ was synthesized from a NiCl₂ solution by electrodeposition method. In order to conduct a systematic study on the effects of experimental parameters, a series of electrolyte initial pH values, current densities, electrodeposition temperatures, and electrodeposition time were used. Cyclic voltammetry results demonstrated a side reaction of Ni²⁺+2e→Ni. The X-ray diffraction analysis, Fourier-transform infrared spectrum, and the color of the product showed that pure α-Ni(OH)₂ could be obtained in the initial pH value range of 2–5.86, current density range of 10–25 mA/cm² electrodeposition temperature range of 25–35 °C, and electrodeposition time range of 1.0–3.0 h. When electrodeposition temperature increased to 45 °C, a mixture of α-Ni(OH)₂ and metallic Ni was obtained. A current density higher than 30 mA/cm² resulted in the sample with features of β-Ni(OH)₂. A small amount of metallic Ni existed in the as-prepared sample when current density decreased to 5 mA/cm². A slight increase of electrolyte pH was observed with increasing initial solution pH and current density. Electrodeposition mass revealed a slight decrease with initial pH decreasing and showed an almost linear increase with current density increasing. The slope of the curve for electrodeposition mass versus electrodeposition time remained stable in the first 2.0 h and then decreased.     

A study on open circuit voltage reduction as a main drawback of Zn–polyaniline rechargeable batteries

The factors influencing the reduced open circuit voltage (OCV) of a Zn–polyaniline (PANI) rechargeable battery were investigated. The reduced OCV of battery at various number of charge/discharge cycles was measured and its relevance to the zinc anode and polymeric cathode was investigated. The results revealed that the battery OCV is reduced with the number of charge/discharge cycles. The composition of cathode surface and nature of electrolyte solution were evaluated by using scanning electron microscope (SEM) and spectrofluorimetric measurements, respectively. The decreased OCV was found cause by the cathode electrode. Although the SEM analysis showed that some zinc particles are adsorbed on the polymeric cathode electrode, this factor was not a major factor contribution to the OCV reduction. The spectrofluorimetric analysis of electrolyte solution revealed its increased hydroquinone (HQ) content with increasing charge/discharge cycles, as a result of the electrochemical degradation of the charged polyaniline. Consequently, the OCV of Zn–PANI rechargeable battery is reduced by chemical redox reaction of charged PANI with HQ.     

Electrochemical performance of tris(2-chloroethyl) phosphate as a flame-retarding additive for lithium-ion batteries

We studied tris(2-chloroethyl) phosphate (TCEP) as a potential flame-retarding additive and its effect on the electrochemical cell performance of lithium-ion battery electrolytes. The electrochemical cell performance of additive-containing electrolytes in combination with a cell comprised of a LiCoO₂ cathode and a mesocarbon microbeads anode was tested in coin cells. The cyclic voltammetry results show that the oxidation potential of TCEP-containing electrolyte is about 5.1 V (vs. Li/Li⁺). A cell with TCEP has a better electrochemical cell performance than a cell without TCEP in an initial charge and discharge test. In a cycling test, a cell containing a TCEP-containing electrolyte has a greater discharge capacity and better capacity retention than a TCEP-free electrolyte after cycling. The results confirm the promising potential of TCEP as a flame-retarding additive and as a means of improving the electrochemical cell performance of lithium-ion batteries.     

Current efficiency of Ga electrodeposition under different anions concentrations

The gallium electrodeposition from alkaline solution has a very low current efficiency,the reason for which is still not quite understood.The effects of electrode materials used for gallium electrodeposition,as well as the effects of Na OH concentration and the anions concentrations in the solution,including SO_4~(2-),SiO_3~(2-),CO_3~(2-),AlO_2~-,F~-,and Cl~-,on the deposition were analyzed in this study.The suitable materials of SUS316–SUS316 were suggested for the gallium electrodeposition.Based on the electrode couples,the Na OH concentration of 4 mol L~(-1)for gallium electrodeposition exhibits the greatest current efficiency.Moreover,the current efficiency would decrease in the electrolyte along with the increasing concentration of the anions,except that,0.2 mol L~(-1)Cl-in the solution slightly improves the current efficiency of gallium electrodeposition.Moreover,the gallium deposited on the cathode from the solution with 0.6 mol L~(-1)SiO_3~(2-)appears tiny black in color and coarse.Meanwhile,SUS304 is shown to be not suitable to be used as cathode for the gallium electrodeposition from the alkaline solution.     

NH4HF2对铁电沉积过程的影响

目的研究稳定剂NH4HF2对铁电结晶过程的影响。方法采用线性电位扫描伏安法、单电位阶跃计时电流法、电化学交流阻抗谱等技术,研究含不同浓度NH4HF2的镀铁溶液中,铁在玻碳电极上的电沉积行为。结果随着NH4HF2浓度的增加,铁沉积的阴极极化变小。在-1.225~-1.300 V阶跃电位范围内,铁在玻碳电极上的电结晶都遵循三维瞬时成核理论,稳定剂浓度的变化不会改变其成核机理。随着NH4HF2浓度的增加,晶核垂直生长速率和双电层电容明显增大,溶液/电极界面电荷传递电阻显著降低,而溶液电阻呈小幅度降低。结论稳定剂NH4HF2的加入可促进Fe2+的电沉积,并提高晶核的垂直生长速率。