熔盐电沉积硅的基础研究

在FLINAK-Na2SiF6熔盐体系中,以Pt为参比电极、硅钢片为工作电极、石墨为辅助电极,在750℃下,用循环伏安法和计时电位法对Si4+的电化学反应机理和扩散系数进行了研究。结果表明:该熔盐体系进行电沉积硅是可行的,该体系中硅离子的还原为扩散控制的可逆电极过程,且产物不可溶;整个还原过程为Si4++4e→Si0;该熔盐体系中阴极电位不应负于-2V,否则会有Na沉积出来,从而影响沉积层质量;Si4+的扩散系数为:D=5 42×10-11m2/s(C=2 58×103mol/m3)。     

LiCl-KCl熔盐La^3+在钨电极上的电化学还原机理

以LiCl-KCl为电解质体系,LaCl3为原料,利用循环伏安法、计时电位法和计时电流法研究773K时镧离子在钨电极上的电化学还原过程。结果表明,在773K、50%KCl-50%LiCl-2%LaCl3的熔盐体系中,镧离子在钨电极上还原是一步转移3个电子反应(La^3++3e→La),相对于Ag/AgCl电极析出电位为-2.05V;镧在钨电极析出过程中出现成核极化现象,且通过循环伏安和计时电流法可判断镧离子在钨电极上的析出还原过程为受扩散控制的准可逆反应,扩散系数D=6.36×10^-5 cm^2/s。     

KCl-NaCl-NaF-SiO_2熔盐体系中硅离子的还原机理研究

在KCl-NaCl-NaF-SiO2熔盐体系中,以铂丝为参比电极、研究电极,高纯石墨坩埚为辅助电极,采用循环伏安法和计时电位法对硅离子的还原机理进行了研究,结果表明此电化学反应为扩散控制的不可逆电极过程;求得硅离子在熔盐中的扩散系数D=1.33×10-3cm2/s(CSi4+=1.21×10-4mol/cm3,T=1 073 K)。     

LiF-SrF2-SrO熔盐体系中Sr2+电化学行为的研究

在电化学工作站AUTOLAB 上采用三电极体系以循环伏安法、计时电流法和计时电位法研究了LiF-SrF2-SrO熔盐体系于1253 K温度下锶在钨电极上的电化学还原过程及其控制步骤.研究结果表明：Sr2+在钨电极上的还原过程是一步得两个电子的准可逆反应,析出电位在-1.0 V 附近.阴极过程受离子的扩散步骤控制,计算得出扩散系数为6.07×10-5 cm2/s.     

LiF-CaF2-BaF2-ZrO2熔盐中Zr4+在钨电极上的电化学还原机理

以LiF-CaF₂-BaF₂为熔盐体系, ZrO₂为原料, 1 373 K条件温度下利用循环伏安法, 计时电位法, 计时电流法, 研究锆离子在钨电极上的电化学过程,对不同ZrO₂含量0.5 %,0.7 %,0.9 %的熔盐体系进行电化学分析,研究结果表明:Zr4+在钨电极上还原是通过两步得电子反应, 即Zr4++2e→Zr2+,Zr2++2e→Zr,相对参比电极铂还原峰分别为0.9 V和1.2 V,析出过程是受扩散控制的准可逆反应. 1 373 K时Zr4+在LiF-CaF₂-BaF₂-ZrO₂熔盐中的扩散系数D为6.7×10-6 cm2/s.      

NaCl-KCl-MgCl2熔盐Mg2+在钨电极上的 电化学还原机理

采用三电极在NaCl-KCl熔盐电解质体系,以MgCl₂为原料应用AUTOLAB电化学工作站分别通过循环伏安法、计时电流法、计时电位法研究了1 073 K时NaCl-KCl-MgCl₂熔盐体系中Mg2+在钨电极上的电化学还原过程.循环伏安测试结果表明:1 073 K时NaCl-KCl-MgCl₂熔盐体系中Mg2+在钨电极上的电化学还原是1步反应转移2个电子过程,电极反应受扩散控制,扩散系数为3.81×10-6 cm2/s,电极反应为Mg2++2e-→Mg.计时电位测试结果验证了循环伏安测试结果的正确性.计时电流测试数据拟合结果表明:1 073 K时NaCl-KCl-MgCl₂熔盐中Mg2+在钨电极上的电结晶是瞬时成核方式.      

CP熔盐电化学方法检测LiCl-KCl熔盐La（Ⅲ）浓度

在773 K氩气环境下,采用CP熔盐电化学方法对LiCl-KCl电解质体系中不同组分LaCl₃(0.98 %、2.0 %和3.3 %)进行La离子浓度检测.研究结果表明:La（Ⅲ）在钨电极上相对于银/氯化银参比电极的还原析出电位在-2.0~-2.2 V左右,通过阴极峰电流值、过渡时间与深度三者关系计算,773 K下La离子扩散系数在1.29×10-5~5.42×10-5 cm2/s之间.通过对比计时电位法（CP）和电感耦合等离子体原子发射光谱法（ICP）检测的La离子浓度结果,相对误差依次为1.25 %、1.11 %和1.72 %.LiCl-KCl熔盐中La电沉积的峰值电流和过渡时间平方根乘积与浓度呈良好线性关系,说明以CP熔盐电化学方法检测离子浓度可行性好.      

LiCl-LiF熔盐中Li_2CO_3在钨电极上的电化学行为

680℃、LiCl-LiF纯锂盐体系,以Li_2CO_3为原料熔盐电解法制备金属锂。采用电化学方法(循环伏安、计时电位法)分析了Li_2CO_3在钨丝工作电极上的电化学行为。金属锂在钨丝电极上的还原为一步得电子可逆反应过程,在氯气析出峰前的氧化峰为加入Li_2CO_3所致,Li_2CO_3在电场作用下分解成氧化锂和二氧化碳,氧离子在氯气析出峰前放电生成氧气。往LiCl-LiF熔盐体系加入1%Li_2CO_3使锂离子的扩散系数由1.98×10~(-8) cm~2/s减到0.82×10~(-8 )cm~2/s,最小还原电流密度由0.28A/cm~2增加到0.59A/cm~2,且锂离子在钨丝电极上的电化学还原过程由扩散环节控制。     

NaCl-KCl-CaCl_2熔盐体系中Mg~(2+)在Mo电极上的阴极过程

采用钼电极,在973K的温度下,研究了MgCl2在三元NaCl-KCl-CaCl2熔融氯化物混合物中的电化学行为。采用方波伏安法(SWV)、循环伏安法(CV)、计时电流法(CA)和计时电位法(CP)研究Mg~(2+)在钼电极上的反应过程。结果表明,Mg~(2+)在钼电极上发生一步还原反应(Mg~(2+)+2e=Mg),是由扩散控制的可逆反应,镁在钼电极上的成核过程是瞬时成核,这与半球核的形成和生长机制是一致的。通过CV、CP和CA在973K的不同方法计算的Mg~(2+)扩散系数分别为1.09×10-5、1.24×10-5和3.23×10-5 cm2/s。在给定电位下阴极沉积产物为金属镁。     

铜在LiCl-KCl熔盐中的电化学行为研究

采用循环伏安、方波伏安、计时电位及线性扫描伏安法研究了500℃时Cu(Ⅰ)在LiCl-KCl熔盐体系中石墨电极和钼电极上的电化学行为,并且研究了不同CuCl浓度下铜的沉积电位。结果显示,铜离子在熔盐中的还原过程分两步进行,分别在-1.05 V和-1.55 V处依次还原,即Cu(Ⅱ)→Cu(Ⅰ)和Cu(Ⅰ)→Cu(0)。通过循环伏安及计时电位测试,均得出Cu(Ⅰ)在LiCl-KCl熔盐中的阴极还原过程为受扩散控制的准可逆过程,扩散系数分别为1.79×10-5 cm2/s和1.26×10-5 cm2/s。     

Electrodeposition of magnesium-yttrium alloys by molten salt electrolysis

Electrodeposition of magnesium-yttrium alloys from molten salts was studied by electrochemical techniques.LiF-YF3 was electrolyte system with magnesium oxide and Yttrium oxide as raw materials.It was proved that Mg2+ and Y3+was deposited more prior than other ions during cyclic voltammetry and potential step measurement at 1050 °C.Voltammograms showed Mg2+ could be deposited at-0.5 V,and Y3+ could be deposited at-0.7 V on tungsten electrode compared with platinum electrode.The sedimentation of Mg2+ was more positive about 230 mV than that of other ions in electrolyte.The electrolytic codeposition of yttrium and magnesium was 0.58 V on condition that the weight ratio of Y2O3/MgO was 4:1.Chronopotentiogram indicated that the process of electrodeposition of magnesium-yttrium alloys on tungsten electrode was controlled by diffusion of ions from electrolyte to electrode interface.It was feasible to prepare Magnesium-Yttrium alloys by controlling content of ions in molten salt electrolyte.     

Fabrication of a novel Mg-RE(Nd,Ce) intermetallic compound coating by molten salt diffusion and its effect on corrosion resistance of magnesium alloys

A novel Mg-rare earth(Nd,Ce) coating containing intermetallic compound was fabricated on the surface of the AZ91D magnesium alloy by bathing the sample in a NaCl-KCl-LiCl-NdCl_3-CeCl_3 molten salt. The cross-sectional morphology, microstructure and phase composition of the coating were investigated by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and energy dispersive spectroscopy(EDS). The corrosion resistance was characterized by the potentiodynamic polarization curves. The SEM observation indicated that a continuous and compact diffusion coating was obtained on the surface of SMATed AZ91D magnesium alloy and the XRD and TEM investigations revealed that the new phases were Al_2Ce and Al_2Nd intermetallic. The potentiodynamic polarization curves showed that the Mg-RE coating improved the corrosion resistance of the AZ91D magnesium alloy, and the corrosion current density of the coated sample was about 1510 mA /cm~2 lower than the uncoated sample.     

Electrodeposition of magnesium-yttrium alloys by molten salt electrolysis

Electrodeposition of magnesium-yttrium alloys from molten salts was studied by electrochemical techniques. LiF-YF₃ was electrolyte system with magnesium oxide and Yttrium oxide as raw materials. It was proved that Mg²⁺ and Y³⁺was deposited more prior than other ions during cyclic voltammetry and potential step measurement at 1050 °C. Voltammograms showed Mg²⁺ could be deposited at ?0.5 V, and Y³⁺ could be deposited at ?0.7 V on tungsten electrode compared with platinum electrode. The sedimentation of Mg²⁺ was more positive about 230 mV than that of other ions in electrolyte. The electrolytic codeposition of yttrium and magnesium was 0.58 V on condition that the weight ratio of Y₂O₃/MgO was 4:1. Chronopotentiogram indicated that the process of electrodeposition of magnesium-yttrium alloys on tungsten electrode was controlled by diffusion of ions from electrolyte to electrode interface. It was feasible to prepare Magnesium-Yttrium alloys by controlling content of ions in molten salt electrolyte.     

Electrochemical behaviour of erbium and preparation of Mg-Li-Er alloys by codeposition

The electrodeposition of erbium on molybdenum electrodes and the formation of Mg-Li-Er alloys were investigated in LiCl-KCl molten salts. At a molybdenum electrode, the electroreduction of Er (III) proceeded in a one-step process involving three electrons. The diffu-sion coefficient of erbium ions in the melts was determined by cyclic voltammetry, chronopotentiometry and chronoamperometry respectively. Cyclic voltammograms (CVs) showed that the underpotential deposition (UPD) of lithium on pre-deposited Mg-Er alloy led to the formation of a Mg-Li-Er alloy. X-ray diffraction (XRD) indicated that Er5Mg24 phase was formed via potentiostatic electrolysis. Scanning electron microscopy (SEM) showed that Er atoms mainly concentrated at the grain boundaries while Mg element evenly located in the alloy.     

Nd(III)在NaF-KF熔盐钨电极上电化学行为

钕铁硼磁体中稀土元素钕占据较大比重,从钕铁硼废料回收稀土有重大意义。为进一步了解钕在高温下氟化物熔盐的行为,本文在1 063 K采用NaF-KF(摩尔比2:3)电解质体系,加入质量分数为1%的NdF₃,以Pt为参比电极,钨棒为对电极,用循环伏安法等电化学暂态测试研究了Nd(III)在惰性钨电极上的电化学过程,探究Nd(III)的还原机理。结果显示:Nd(III)于NaF-KF-NdF₃熔盐中在惰性钨电极上的电化学还原过程是受扩散控制的不可逆的一步反应:Nd(III)+3e-=Nd,1 063 K时循环伏安法得到Nd(III)的扩散系数为2.107×10-5 cm2/s,钕的成核机制为瞬时成核。      

Titanium powder production by TiCl4 gas injection into magnesium through molten salts

A process to produce titanium powder continuously is proposed and its applicability is examined experimentally. The method is based on the chemical reaction in the conventional Kroll reduction process; however, TiCl₄ gas is injected into molten salt on which a molten magnesium layer is floated as the reductant. Bubbles of gaseous TiCl₄ can be reacted at the lower surface of the liquid Mg layer, while TiCl₄ gas reacts on the upper surface in the Kroll process. The fine Ti particles produced in this study were well separated from magnesium and could be recovered from the bottom of the molten salts. The particles were small and fine enough for use in powder metallurgy, while congregated lumps of about 20 μm in size are obtained by the Kroll process. The composition of molten salts and an operation temperature above 1073 K did not affect the morphology of the Ti particles, if suitable material for the reaction vessel was chosen.     

Electrode process of La(Ⅲ) in molten LiCl-KCl

The electrode process of La(Ⅲ) at Mo electrode in the molten LiCl-KCl for temperatures ranging from 683 K to 773 K was studied by cyclic voltammetry and chronopotentiometry,respectively.The results showed that in the molten LiCl-KCl,reduction of La(Ⅲ) occurred in a step with a global exchange of three electrons.Cyclic voltammetry studies indicated that at a sweep rate lower than 0.2 V/s,the electroreduction of La(Ⅲ) to lanthanum metal was reversible and controlled by diffusion of La(Ⅲ).However,the process b...     

Electrochemical Preparation of La—Fe Alloy Films in Dimethylsulfoxide（DMSO）

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