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By Jingwei Lou, Bing Li, Suzhen Li, Miao Shen, Jianguo Yu

"As a main impurity in primary lithium metal, magnesium is difficult to remove because of the very close relative volatility of the two metals. Electrochemical refining provides a possibility to completely remove Mg in the LiCl-KCl melt prior to Li reduction. MgCl2 reduction processes in LiCl-KCl- MgCl2 melt were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry and chronopotentiometry. Then potentiostatic electrolysis was carried out and Mg (II) ion was reduced onto a liquid lead cathode from the LiCl-KCl-MgCl2 melt at the Mg deposition potential. The results show that Mg ( II ) is reduced in one step with two-electron transfer. The reduction potential of Mg ( II ) was well defined. The reduction of Mg( II) results in Li ( I ) underpotential deposition at 0.2V more negative potential than that of Mg( II) reduction. Therefore, in order to prevent Li ( I ) from codeposition with Mg, accurately controlling Mg ( II) reduction potential during the potentiostatic electrolysis was necessary. Ninety three to 99 % removal rate of MgCl2 was achieved after 8-12 h electrolysis when liquid lead was used as cathode.IntroductionMetallic Li has been widely used in batteries, light weight alloys and in fusion reactors because of its excellent properties. Currently, the only way in industry to produce metallic Li is by electrowinning from molten LiCl-KCl at about 450 °C [l-5]. LiCl-KCl is the only electrolyte used, because they presents a lower eutectic temperature and KCl shows a slightly higher theoretical decomposition voltage than LiCl, as shown in Table l .The produced metallic Li generally contains 1-2 wt% impurities including Na, K, Al, Ca, Mg, Si, etc. [6l, which are derived from the corresponding metal chloride compounds or metal oxide compounds existing in the LiCl and/or KCl raw materials. These impurities have to be removed by subsequent vacuum distillation at high temperatures to meet the requirements for metal Li purity in the final products. Separation of Mg from Li by vacuum distillation is difficult because their relative volatilities are very close, as shown in Table 2."

Jan 1, 2011

By Kazuya Koyama

We are studying the hydrometallurgical recycling process of indium from an Indium-Tin-Oxide(ITO) target. For this process, it is necessary to remove Sn(IV) ions from the aqueous hydrochloric acid solutions containing In(III). In this study, the removal of Sn(IV) ions by a potentiostatic electrolysis method was examined. The polarization measurements and potentiostatic electrolyses were carried out under a nitrogen atmosphere. In the Sn(IV) solution, current begins to rise at the cathode potential of -0.26 V vs. SHE, and increases with a reduction in the cathode potential. In the In(III) solution, current begins to rise at a cathode potential of -0.43 V vs. SHE. Metallic tin was electrodeposited without indium electrodeposition at the cathode potentials of -0.30 and -0.40V vs. SHE. More than 98% of the Sn(IV) was removed at the cathode potential of -0.40 V after the electrolysis for 3hrs. Both tin and indium were electrodeposited at the cathode potential of -0.50V vs. SHE.

Jan 1, 2006

By Q. G. Liu

New solid-state electrochemical sensors 1;.1sing Li2SO4-Ag2SO4 electrolytes have been developed to measure SO2 and/or SO3 in gas mixtures. Silver embedded in part of the electrolyte is used as the reference electrode. Although single-phase electrolyte sensors yield accurate results for one to two days, a two-phase electrolyte cell exhibits excellent long-term chemical stability. For example, stable and accurate potent iometric responses have been obtained over a six mo.nth period. The. advantages of the two-phase electrolyte ( 23 mol% Ay 2SO4 ) cell include excellent mechanical strength on temperature cycling and an insensitivity to compositional variations in the electrolyte and to temperature fluctuations. Experimental tests have shown excell.ent results in SO2-air. mixtures with the SO2 concentration ranging from 3 to 10,000 ppm (vol). However, the SO2 concentration range was limited by a lack of standard gas mixtures, and our sensor cells can be used to measure S02 concentrations significantly less than or larger than our experimental range. Results also indicate that the presence of significant concentrations of CO2 and H2O in the gas mixture has no effect on the sensor response. Thus the two-phase electrolyte ( 23 mol% Ag2S04) sensor has exceptional selectivity, reliability and long-term chemical and mechanical stability.

Jan 1, 1985

By Toshiyuki Nohira, Eiichi Takeuchi, Tetsuo Oishi, Hideki Ono, Hirokazu Konishi

The Dy-Nd-Pr-Ni alloy sample was prepared by cathodic potentiostatic electrolysis at 0.65 V (vs. Li+/Li) for 1 h using a Ni plate in a molten LiCl-KCl-DyCl3-NdCl3-PrCl3 system at 723 K. The highest mass ratio (Dy/Nd+Pr) in the alloy sample was observed to be 50 at 0.65 V. Anodic potentiostatic electrolysis at 2.20 V for 12 h was conducted using the Nd-Fe-B magnet electrode in a molten LiCl-KCl system. All elements were almost dissolved from the magnet, and the original form of the magnet disintegrated. After anodic potentiostatic electrolysis at 2.20 V, cathodic potentiostatic electrolysis was conducted at 1.00 V for 5 h using a Mo plate in order to remove the dissolved Fe from the bath. Finally, cathodic potentiostatic electrolysis was conducted at 0.65 V for 12 h using a Ni plate. The mass ratio of Dy/Nd in the alloy sample was determined to be about 18.

Jan 1, 2015

The present work is mainly focused on developing intermetallic inert anodes for aluminum electrolysis. The anode alloy based on Al-Ti-Cu system was prepared by casting, followed by the application of a protective coating. Behaviour of corrosion and the passivation under anodic condition was characterized using the electrochemical and microscopic techniques. The results obtained clearly demonstrate that the oxide coating can provide good corrosion resistance via surface passivation of alloy anodes, rendering them inert in cryolite melt.

Jan 1, 2006

By Tomás Vargas

The catalytic influence of a pure strain of Thiobacillus ferrooxidans (ATCC 19859) on the dissolution of natural pyrite crystals was studied using electrochemical techniques. The results showed that this microorganism catalyze the leaching of pyrite by both, oxidizing ferrous iron in solution and depolarizing the reduction of ferric ion on this sulfide. In addition, studies of bacterial corrosion under applied potential showed that pitting on the pyrite surface centers on weak sites of the sulfide structure in which bacteria has attached, but occurs only when the ferric iron in solution induces an adequate level of anodic polarization on the mineral.

Jan 1, 1992

By H. K. Lin

Pyrite oxidation in chloride solutions was investigated with cyclic voltammetry, ac impedance and potential step techniques. The pyrite oxidation in quiescent electrolytes is irreversible and controlled by diffusion. Depression of the semi-circle in the complex plane plot has been explained mathematically based on the concept of the equivalent circuit. When the semi-circle is depressed, the mathematical formula indicates that the reaction resistance should be obtained from the intersection of the semi-circle with Z-axis instead of the semi- circle diameter. The peak charging current densities at 1.10 and 0.90 V vs. SHE obtained from the equivalent circuit coupled with the ac impedance measurements match the peak current densities obtained with the potential step measurements.

Jan 1, 1997

By Sheng-hai Yang

The electrochemical synthesis was conducted in anhydrous ethanol solvent mixed with conductive reagent when tantalum plate was used as anode and stainless steel plate as cathode. The effects of different conductive reagents (such as NH4Br, (CH3)4NCl, (C4H9)4NCl), conductive reagent concentration and the space on the cell voltage and the current density were investigated. The current efficiency of electrosynthesis was more than 95%. The electrolyte, a mixed solution was then undergone air distillation and vacuum distillation to get the final product which was characterized by Fourier Transform Infrared(FTIR) spectroscopy, Raman spectra, 1H-Neclear Magnetic Resonance(1H-NMR) spectroscopy. Carbon and hydrogen contents in the product were determined by elemental analysis instrument. Results consistently show that the product was tantalum penta-ethoxide.

Jan 1, 2006

By Xiao Y. Yan

A fused salt electrochemical process was investigated for the synthesis of non-oxide ceramic powders directly from metal oxides, boric oxide, and carbon powders by electro-deoxidation. Sintered pellets of the mixed powders were designed to act as a composite cathode in the electrolytic cell. Electrolysis was carried out in molten CaCl2-NaCl eutectic at 3.1 V and at 600-900 ºC under argon. The favoured cathodic reaction was the removal of the oxygen from the oxides to produce metal atoms that reacted with either the reduced boron atoms, forming a metal boride, or the carbon initially present in the sintered pellets to produce a metal carbide. The technical viability of the process was demonstrated by the electro-deoxidation of sintered pellets of TiO2/B2O3 and TiO2/C to produce TiB2 and TiC, respectively. Compared to existing carbothermic reduction process, this new electrochemical process may be less energy intensive and may lead to lower production costs. I

Jan 1, 2008

Sodium is added to aluminum-silicon eutectic alloys to modify the structure. The ideal amount is about 100 ppm but due to the fact that sodium is lighter than aluminum and can float to the surface where it bums, oxidizes ad volatilizes, a far greater amount is usually added. Furthermore, as the sodium is continually lost from the alloy the optimum amount is only present for a limited time. The net result is a process which is hard to control, produces fumes and a considerable amount of dross. It is shown that by electrochemically titrating sodium through a tube of sodium beta alumina electrolyte that the sodium can be added continuously in a controlled way. As the sodium is added to the bulk of the aluminum, there is no sodium on the surface of the alloy so that little surface oxidation occurs, and no fumes and dross are produced. This leads to an improved product and working conditions.

Jan 1, 1995

By I. Gaballah

The chalcopyrite ore's anodic and cathodic electrodissolution are studied using a Porous Pulsed Percolated Electrode (3PE) reactor. Stationary solid electrode experiments are also performed to explore the mechanism of electrochemical dissolution of chalcopyrite. Experiments with a low - grade natural ore have been carried out at 25 "C in solutions containing 1 M NaCl and 1 M HCl. Galvanostatic and potentiostatic conditions are employed. The influences of current and potential on selectivity of the chalcopyrite ore dissolution are assessed. Anodic oxidation of this ore leads to a preferential dissolution of iron bearing minerals, whereas cathodic reduction is more selective with respect to chalcopyrite. However, in both cases the electrochemical dissolution is incomplete and the current efficiency is low. Design of the actual reactor has to be modified to increase the bed conductivity and to allow continuous experimentations.

Jan 1, 1994

By T. Mason, R. Macko

Electroless nickel (EN) coatings are widely used in the manufacture of automotive parts, providing uniform coating, corrosion protection, wear resistance and lubrication. In contrast to EN plating benefits, the disposal and treatment of waste solutions can cause many difficulties. The use of electrochemical treatment technology greatly improves _the operation of the main wastewater treatment process and reduces operation costs. A new, state-of-the-art job shop in the Chicago area, which provides EN plating for the automotive industry, has installed a large separated electrolytic cell for the treatment of spent EN solution (from dumps and wastewater). The waste/wastewater is handled by the separated electrolytic cell, batch treatment system, filter press and neutralization station. The implementation of modem electrolytic technology and auxilliary equipment provides an effective waste treatment process that meets environmental compliance criteria.

Jan 1, 2000

By Uday B. Pal

In the electrochemical vapor deposition (EVD) process, gaseous cation precursors are passed over one side of a porous substrate, and oxygen is passed on the other side of the substrate. The gases diffuse and react within the porous substrate, and the pores get filled with the desired solid oxide. Subsequent solid state electrochemical transport through the solid oxide in the pores continues the reaction, and the film grows over the porous substrate. The EVD process has been used to deposit lanthanum chromite interconnection films and yttria stabilized zirconia electrolyte films over porous air electrodes. The EVD growth of these solid oxide films is found to be parabolic in nature, which indicates that the solid state transport (diffusion) of ions through the film controls the growth. This solid state transport can be analyzed using Wagner's treatment of the electrochemical transport. Conductivity measurements and the information on the defect structure of the oxide can be combined with the EVD growth rate measurements to calculate the solid state transport properties (transport numbers and partial conductivities) of the rate-controlling minority species in the oxide. Using this approach, the EVD growth of other electronic, mixed conducting and ionic solid oxide films can also be analyzed.

Jan 1, 1992

By K. S. Han, M. Yoshimuura, H. Fujita, Y. Sato, S. W. Song

"Film of LlCoO2 as cathode material for rechargeable lithium microbatteries has been fabricated on the platinum metal substrate by electrochemical-hydrothermal method in concentrated LiOH solution at 200 °C as Soft Solution-Processing. The film fabrication has been understood in terms of dissolution of cobalt metal powders and subsequent oxidative deposition on the substrate. The film structure was characterized using scanning electron microscope, X-ray diffraction analysis; X-ray photoelectron spectroscopy and micro-Raman spectroscopy.IntroductionRapid growth of wireless communications and emerging integrated optoelectronic circuits caused the miniaturization· cif electronic devices, thus the demand for high energy density microbatteries as a power source for the microelectronics increases. In this regard, all solid-state lithium microbatteries including LiCoO2 and LlMn2O 4 [l-4], the most promising intercalation cathode material, have been developed. However, major difficulty of .fabrication of a lithium microbattery arose from the preparation of cathode film, according to a· recent report on Rare Metal News [5]. Although many attempts have been made to deposit the cathode films, all those methods are mostly chemical vapor deposiiton (CVD), various evaporation, sputtering techniques and spray pyrolysis. These methods require preparation of bulk cathode materials cir its precursor, then deposition with complicated instruments including high· vacuum system, and even postsynthesis annealing to obtain desire electrochemical 'properties. It is clear that all of these techniques are neither economic nor environmentally friendly. Compared to those methods, film form.ation from an aqueous solution is thought to be simpler and more economical, and requires much· less energy consumption. Our .group has demonstrated the utility of Soft SolutionProcessing [6,7], which is defined as environmentally friendly processing using (aqueous) solutions, to produce films of a variety of functional solid materials. According to the Pourvaix's diagram [8], some metal can be dissolved in an alkaline solution and consequently combined with hydroxyl group or oxygen anion forming metalate or metalite. Cobalt also seemed to form cobaltite, HCoOi in strong alkaline solution in the Pourvaix's pH-potential diagram. Based on this information, it was expected that LiCoO2 could be prepared using the cobalt metal in Li OH solution by Soft Solution-Processing. Recently, we reported the successful single step fabrication of electrochemically active LlCoO2 films on the cobalt metal substrate by hydrothermal methods without any post-synthesis annealing as Soft SolutionProcessing [9,10]. Film formation mechanism could be elucidated by the following evidences. . As expected from Pourvaix's diagram, cobalt metal was dissolved in concentrated LiOH solution forming dissolved cobalt species which was detected by an observation of absorption band in UV-VIS absorption spectrum [10]. Thus the reaction was assumed to be started from dissolution. Time dependent potential of Co electrode exhibited only one-step evolution with 0.6 eV from Co metal to LiCoO2 [10]. Another strong evidence was the finding of LiCoO2 powder precipitates at the bottom of tetlon beaker after the reaction [11]. Based on those experimental findings, it was understood that film is formed by dissolution-precipitation mechanism [9-11]."

Jan 1, 2000

By Shizhe Liu, Bing Li, Heng Wang, Zuxin Zhao

In this paper, cyclic voltammetry and chronoamperometry have been applied to investigate the effects of Nd2O3 concentration on the anode effects, critical potential for the anode effects and Nd2O3 reduction in LiF-NdF3-Nd2O3 melts at 950℃. The results show that the oxidation peaks in the potential of about 2.7V are attributed to the oxygen ions oxidation and the peak current density increases with Nd2O3 concentration increase from 0 to 0.5wt%. The critical potential caused the anode effects shifts to 0.3V more positive value as Nd2O3 content in the melts decreases from 0.01wt% to 0.5wt%. The cyclic votammograms on W electrodes in the LiF-NdF3-Nd2O3 melts present two pairs of reduction and oxidation peaks, indicating that the reduction of Nd ions in the LiF-NdF3-Nd2O3 melts in two steps rather than one step.

Jan 1, 2014

By Xuan Cheng

The electrochemistry of sulfide mineral flotation is reviewed with particular emphasis on galvanic interaction among minerals and grinding media, and its relevance to flotation of complex sulfide ores is discussed. Surface alteration due to galvanic interactions among chalcopyrite, pyrrhotite and mild steel is analyzed in terms of voltammetric and chronoamperometric studies on individual minerals and through galvanic current measurements in 2- and 3- electrode combinations. The results are related to laboratory flotation behaviors of chalcopyrite-pyrrhotite mixtures simulating copper-nickel bearing Duluth gabbro.

Jan 1, 1993

By Miguel N. Herrera

The electrochemistry of coal pyrite is relevant to coal desulfurization by chemical or bacterial leaching, flotation and oil agglomeration. The electrochemical behavior of polished and etched Upper Freeport and Pittsburgh coal pyrite samples was investigated from pH 1.0 to 10.5. The open-circuit potentials decreased with increasing pH, as expected, but were well above the thermodynamic stability region of pyrite, and decreased with time. Cyclic voltammetry revealed behavior highly sensitive to pH and scan rate (2.0 and 20.0 mV/s). The behavior on the first cycle was always substantially different from that on subsequent cycles. The anodic and cathodic reactions were correlated with the Eh-pH diagram for the Fe-S-H20 system to identify the reactions occurring at different pH values. There was also evidence that the buffers used to maintain basic pH values are themselves electrochemically active, which should be considered in interpreting many earlier electrochemical studies of sulfide minerals.

Jan 1, 1994

By G Hope, C Young, R. N. Gow

"The presence of enargite (Cu3AsS4) is problematic in gold processing as it is refractory, increasing cyanide and oxygen consumption, and enviromnentally hazardous. Selective leaching and treatment of the arsenic would prove advantageous to conventional gold leaching methods. The reactivity of enargite samples from Montana, US and Quiruvilca, Peru were studied under alkaline conditions, pH range of 8-13, using a cyclic voltammetry corrosion cell setup. Raman spectra of the surface were taken during and after cycling to compare surface species against theoretical predominance diagrams. Under slightly oxidizing conditions, covellite (CuS) peaks were found on the surface in a short matter of time, above - 200m V vs SHE for pH 9-13, suggesting arsenic leaching, but for longer conditioning times, elemental sulfur peaks were also found, which created a passivating surface layer. By operating above pH 12, under reducing conditions, ~-500mV vs SHE, arsenic can be leached as a thioarsenate (AsS4-xOx3-), without sulfur formation.IntroductionEnviromnental limitations on pyrometallurgical processing of arsenic has pushed the desire to process enargite-, Cu3AsS4, bearing concentrates towards a hydrometallurgical solution. Attempts to process can be broken down into two categories - the co-dissolution of arsenic and copper under acidic conditions or the selective leaching of arsenic under basic conditions. The selective leaching of arsenic would preferably leave behind a chalcocite, Cu2S, or covellite, CuS, phase that would be more amenable to conventional processing methods of the copper and gold industries. These methods employ bi- or poly-sulfides to leach arsenic as Assl· [1-4], hypochlorite leaching [5-7], ammoniacal leaching [8] or fine grinding to mechanically activate the enargite surface and increase normally slow reaction kinetics[9]. This study looked into the surface formations of an enargite electrode under alkaline conditions, in a pH range from 8-13, as it cycled from -1000 mV to 1000 mV vs SHE. The understanding of the formations and under what conditions they form will be helpful in further development of any of the aforementioned processes."

Jan 1, 2012

By Shulan Wang, Xuan Liu, Li Li

"Electrochemistry of Fe(III) in 69CaCl2-12CaF2-19KF and 81CaCl2-19KF (mole percentage, %) was investigated at 827 oC on molybdenum electrode by cyclic voltammetry, chronoamperometry and galvanostatic electrolysis using Fe2O3 as the Fe(III) source. The reduction of Fe(III) to Fe was conducted in one step and controlled by diffusion process. Fe(III) shown greater reduction rate and diffusion coefficient in molten 81CaCl2-19KF than in 69CaCl2- 12CaF2-19KF. Galvanostic electrolysis of Fe was performed in both molten salts with a cylindrical cathode rotating at 200 r/min and dendritic iron deposit was obtained.Keywords: iron; electrolysis; electrochemistry; molten saltIntroductionThe production of iron and steel causes huge emissions of CO2. Iron electrowinning in molten salts with dissolved Fe2O3 using an inert oxygen evolving anode is an alternative process to reduce or eliminate the formation of CO2. Research on novel process of producing metal has been reported recently [1-2] by using CaCl2 as the main electrolyte and dissolving CaO in CaCl2 due to the high solubility of CaO in the melt. This process has been used in preparing many active metals and alloys [3-14]. In the present work, the electrochemical behavior of iron in CaCl2-KF was studied and transport property of iron ion in the melt was discussed.ExperimentalCaCl2,CaF2 and KF (in analytical purity) were dried in air for 48 h. Mixed salts used in experiments were placed in a graphite crucible (??58 mm inner diameter). The graphite crucible together with the salts was heated at 473 K for 12 h in a furnace with flowing Ar (99.99%) before further heating. Temperature inside the furnace was measured by an S type thermocouple. Electrochemical measurements, such as cyclic voltammetry and chronocoulometry, were performed in a three electrode cell by EG&G PAR273A potentiostat/galvanostatand. Galvanostatic electrodepositon of iron was conducted in a two electrode cell. Molybdenum (??2 mm) and iron (??5 mm) were used as the working electrode (WE) and the reference electrode, respectively. A graphite crucible and a magnetite rod (??25 mm ) consisted of 100% magnetite and sintered at 950 oC in argon atmosphere for 2 h with electrical conductivity of 366 O-1m-1 at room temperature were used as the counter electrodes in the galvanostatic electrolysis experiment. Carbon (??10 mm) was used as the counter electrode in electrochemical measurement. The deposits were washed in distilled water bubbled with argon and dried in air before being characterized by X-ray diffraction (PW3040/60 diffractometer) and scanning electron microscope (SEM, SSX-550)."

Jan 1, 2014

By Batric Pesic

The interactions of mineral-pyrite with T. ferrooxidans were studied by using a cyclic voltametry technique. The interactions with bacteria were carefully examined during the entire growth stage of bacteria (fermentation). Several very important discoveries were made. For example, the pyrite surface invariably drastically changed its properties at the second day of fermentation. Beyond two days of fermentation, the cyclic voltamograms were insensitive to convective diffusion produced by stirring. The SEM study revealed that bacteria populated the pyrite surface at an extremely high density levels. The high density of bacteria, and the solid reaction products formed on the pyrite surface created conditions for pore diffusion which explained why the CVs became insensitive to convective diffusion in solution (stirring).

Jan 1, 1990