Search Documents

By Henrik Gudbrandsen, Geir Martin Haarberg, Ana Maria Martinez, Karen S. Osen, Sverre Rolseth

"The Several approaches were tried for developing an electrochemical route for producing high purity silicon from molten salts. K2SiF6 and metallurgical grade silicon were used as the source of silicon. Molten LiF-KF and pure KF with additions of K2SiF6 were used as electrolytes at temperatures from 550 - 900 oC. Silicon was cathodically deposited and anodically dissolved in the fluoride electrolytes. High electrorefining efficiency was obtained for many elements after electrolysis experiments at constant potential or constant current. The main challenge was to reduce the contents of boron and phosphorus. Another difficulty was to remove inclusions of solidified electrolyte. The lowest energy consumption was estimated to be ~ 3 kWh/kg Si, while the best current efficiency for Si deposition was found to be ~ 95 %.IntroductionSilicon is the most important material for photovoltaic power generation devices because of high feasible efficiency, low ecological impact and slow degradation. Development of a new and less expensive route for producing silicon of the desired quality is necessary in order to make solar cells competitive. Electrochemical routes may be an alternative possibility, and many laboratory studies have been reported over the past few decades. Most of the studies have been performed in molten salts, chloride or fluoride, at moderate temperatures so that solid silicon was deposited at the cathode. The production of high purity silicon has shown an annual increase of about 25 %, due to the increasing demand of solar grade silicon (SoG-Si). For future increased use of solar energy it is important to develop alternative, more energy efficient and cheaper processes for SoG-Si production compared to the Siemens process.Common silicon sources have been SiO2 and K2SiF6 for electrowinning and MG-Si in the case of electrorefining. A serious challenge is to find an oxygen evolving anode for electrolytes containing dissolved oxides. Especially at moderate to high temperatures and in molten fluoride electrolytes this is a difficult task.Many experimental results have been reported in molten chloride electrolytes. Nohira et al. [1-3] and Chen et al. [4] cathodically deposited silicon by electrodeoxidation of solid SiO2 in molten CaCl2 by potentiostatic electrolysis. An alternatice approach is to use electrorefining of low-cost metallurgical grade silicon (MGSi) to produce SOG-Si. In previous studies [5], an MG-Si anode was used, and silicon was successfully electrodeposited on a molybdenum wire in a CaCl2 based melt. It was found that the anode was strongly passivated due to the precipitation of silicon. Also, some deposits detached from the molybdenum wire because of the poor adherence to the cathode.Considering the Cu-Si alloy which has a good segregation effect for some impurities, and should not passivate, could be a good candidate anode for electrorefining. [6]."

Jan 1, 2014

By I. Gaballah

The electrochemical behavior of a chalcopyrite concentrate having a high pyrite content was studied in HC1 by potentiodynamic, potentiostatic and galvanostatic experiments using a cell having separate anodic and cathodic compartments. Anodic oxidation of chalcopyrite particles was realized both by their contact with the cunent feeder and by reaction with ferric and cupric ions. An increase of current leads to a more selective dissolution of chalcopyrite. Surface passivation was observed after an electrolysis time related to the cell current. Cathodic reduction of chalcopyrite concentrate seems to be more promising. Almost complete conversion of chalcopyrite to a copper sulfide (Cui.8.S) is observed, whereas no reaction of the pyrite was detected. This confirms the possible selective dissolution of copper from the chalcopyrite concentrate. Copper sulfide obtained by cathodic reduction was leached using a cupric chloride solution.

Jan 1, 1994

By Thomas J. Keefe, O&apos

The effects of cobalt, B-naphthol, glue and antimony on the polarization behavior of zinc sulfate electrolyte were investigated. It was found that B-naphthol was beneficial in reducing the detrimental effects of cobalt while antimony and excess glue were each harmful. Since the nu cl eat ion over potential was insensiti1ve to coba1t, other regions of the polarization curve were used to indicate electrolyte balance. The low? current density area occurring in the reverse or anodic sweep direction was? often an indicator when an ?unstable condition existed. The two parameters evaluated were the degree of inflection in the polarization curve in the low current density region during scanning and the rate of current rise observed when the sample was potentiostated at -0.781 Volts (SHE). Using this technique, a two-additive system was shown to be desirable to control cobalt and antimony containing electrolytes. The structure of the deposits was examined using scanning electron microscope techniques.

Jan 1, 1985

By Melvin H. Miles

"Considerable research has been conducted on the anodic oxidation of methanol in fuel cells. The electrochemical reduction of carbon dioxide in aqueous solutions to form methanol is the same reaction in reverse, i.e. CO2 + 6 H+ + 6 e- ? CH3OH + H2O. The same catalysts and conditions may operate for both reaction directions. This carbon dioxide reduction reaction, however, must be able to compete with the electrochemical reduction of water to form hydrogen gas. Thermodynamically, the reduction of CO2 to form CH3OH is slightly more favorable than the reduction of water. The use of nearly neutral electrolytes rather than acidic electrolytes makes the reduction of CO2 kinetically more favorable. The thermodynamics of various reaction steps are presented. Similarities exist with the electrochemical reduction of CO2 and the green-plant photosynthesis process that converts CO2 to carbohydrates.IntroductionVirtually all of the oxygen in the earth’s atmosphere is of biological origin having been generated by green-plant photosynthesis from water and carbon dioxide [1]. The net reaction can be represented byCO2 + H2O ? O2 + [CH2O] (carbohydrates, etc.) (1)Chlorophyll and enzymes promote this reaction, and the energy required comes from sunlight. The actual photosynthesis process is a complex multistage reaction and requires 469 kJ mol-1 of energy supplied by the sun. Isotope tracer experiments using 18O have shown that both the oxygen atoms in the O2 molecule originate from H2O, whereas oxygen atoms in the carbohydrates come from CO2 [1]. The total amount of water on the earth is split by photosynthesis and reconstituted by respiration and combustion once every 2 million years or so. The photosynthetically generated oxygen gas temporarily enters the atmosphere and is recycled about once every 2000 years [1]. The carbon dioxide is partly recycled in the atmosphere and oceans after an average residence time of 300 years and is partly fixed by precipitation of CaCO3 and other carbonate minerals [1]."

Jan 1, 2008

By J. Howarth

Two electrochemical processing methodologies have been used to electrogenerate bromine-laden solutions for gold-leaching purposes. In the first process, a laboratory-scale cell in which the anode and cathode compartments were separated by a cation-exchange membrane was employed. The bromine produced by electrolysis of a 4% bromide solution was used to leach gold from a low-grade ore. The pregnant leach solution was then returned to the cell to recommence the cycle. High current efficiencies (90-93%) were maintained over six cycles. In the second process, an undivided hypochlorite generating cell (Chloropac"') was used to generate bromine from a simulated leach solution. Electrolyses were performed on a pilot-scale (100-150 gallons) with solutions containing different levels of bromide ion. The current efficiencies were also high (80-90%) and unaffected by the bromide concentration (over the range 2.5-5%) provided the electrolysis was run to low conversion « 15%). The Chloropac module was capable of delivering 0.6 kg bromine per hour at a power cost of $0.09 per kg. Using these figures, a detailed economic assessment for a 1000 metric tonnes (MT) per day gold ore processing plant was made. Electrolytic regeneration of bromine in a gold leach/recovery circuit dramatically improves the process economics over cyanidation.

Jan 1, 1991

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 A Frydrychewicz, J. Mirza, J. Lipkowski

The objective of this work was to understand the mechanisms of action of additives, such as thiourea, that enhance gold leaching in thiosulfate solution. The leaching reaction and surface passivation were investigated using linear sweep voltammetry. Leaching currents were determined using analysis of current-potential curves and the mixed potential theory. The gold-electrolyte interface was further characterized with surface enhanced Raman spectroscopy. The results show how thiourea prevents formation of oxysulfur compounds, which passivate the gold surface. Other molecules such as 3- m ercaptopropionic acid and L-cysteine were also studied as possible additives to prevent passive layer formation.

Jan 1, 2011

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 Kevin Lofftus

The rest potentials of molybdenite electrodes are measured as a function of pH in absence and presence of flotation reagents. The chemicals used include sodium ethyl xanthate, kerosene, dextrin,sodium hydrosulfide, hydrated sodium molybdate, sodium sulfate, and hydrated sodium thiosulfate. The effect of dissolved oxygen is also noted. The obtained data are correlated with the results of micro-flotation tests obtained under similar chemical conditions.

Jan 1, 1984

By Batric Pesic

The interactions of mineral-pyrite with T. ferrooxidans were studied by using a cyclic voltametry technique. The interactions with bacteria were examined during the entire growth stage of bacteria (fermentation), 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 product layer was examined by SEM,. X-ray diffraction and chemical analysis. 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). The x-r:ay diffraction study confirmed jarosite as a product layer. A mechanism of T. ferrooxidans cells serving as nucleation sites for jiarosite formation is proposed.

Jan 1, 1991

By P. K. Sahoo, C. R. Ray, S. S. Rao

Good operation of Soderberg electrodes is dependent upon high quality electrode paste coupled with better electrode management procedures. Without having a good electrode operation, it is not possible to obtain the best outcome from the furnace. In other words that is a good way to say how important the proper electrode operation is. Good electrode performance depends on the slipping rate and current levels, which decides the shape of the baking curve at the level of just below the contact clamps. Negative curvature of baking zone in the central part is considered dangerous because shrinkage takes place outwardly creating abnormal stresses in the electrode. Soft breakages occur when the baking zone comes below the clamps and the casing cannot take the current. This paper deals with various factors affecting baking characteristics leading to soft breakages and also presents case studies in a closed 48MVA furnace with smelting for charge chrome. In case studies in a closed furnace, it has happened that the energy for baking at the low current operation before breakage has been lower than the actual slipping has demanded. At low current there should not be problem, but a problem can occur when the current for some period is raised above the current carrying capacity of the casing. So data for electrode operation in actual period was studied and presented in this paper.

Jan 1, 2007

By B. Larsen

The Søderberg electrode was invented about 95 years ago by the company Elektrokjemisk, later known as ELKEM. It is still the most commonly used electrode system in submerged-arc furnaces for ferroalloys, platinum smelting, and slag cleaning operations. The size of the furnaces and electrodes has increased over the years and electrode diameters up to 2000 mm are today in use. Such large electrodes can be challenging to manage, and large electrodes are also more demanding when it comes to the electrode paste used in the electrodes. Although electrode sizes and equipment around the electrodes have changed, the main principles of the Søderberg electrode processes are the same. To assists in proper understanding of the electrode processes and to optimize electrode management, Elkem has developed several mathematical tools covering various aspect of the process. Both temperatures and thermal stresses can be calculated during dynamic conditions. The paper demonstrates, with examples, how the tools are used in both education and as practical input to improved electrode performance.

Jan 1, 2012

By E. Ghali, N. Sorour, G. Houlachi

"The binary Fe53Mo47 and ternary Fe54Mo30P16 coatings have been electrodeposited from citrate-based electrolyte on mild steel (MS) substrates. The electrodeposition has been conducted for 6 hours at 20 mA cm-2 and 30°C. The electrochemical tests were carried out in chlorate solutions containing 300 g L-1 NaCl and 4 g L-1 K2Cr2O7 at pH 6.4 and 80°C. A number of surface characterization techniques such as SEM-EDS, XRD and EMP were used to study the microstructure of the alloys. The electrocatalytic activity of these coatings was investigated using steady-state polarization and galvanostatic technique. This study revealed that the Fe-Mo-P coating could be considered as a promising cathode material for the hydrogen evolution reaction (HER). The results showed an important decrease of hydrogen overpotential for Fe-Mo-P alloy as compared to that of Fe-Mo and especially MS which is a traditional cathode in chlorate industry. The HER overpotential for Fe54Mo30P16 at current density of 250 mA cm-2 was decreased by 30% in comparison to that of MS (1029 mV), and by 16.5% to that of Fe53Mo47 coating (857 mV).INTRODUCTIONSodium chlorate is used for manufacturing of several daily consumption products. This chemical is mainly employed for the production of chlorine dioxide (ClO2) that is a bleaching agent used in the pulp and paper industry. The ClO2 is also consumed for generation of perchlorates, chlorites and other chlorates, as an herbicide and in uranium processing (Cornell, 2002). Sodium chlorate is produced industrially via following overall formula in un-divided electrochemical cell (Nylén & Cornell, 2009):"

Jan 1, 2016

By P. Louis

Although cobalt is known and used for its hardness and wear resistance, ductile cobalt can be obtained by electrolysis in chloride solutions, under the following conditions : pH : 1.5 - 2, Co++ : 30 - 60 g/l, current density : 100 - 500 A/m2, temperature 40 - 70°C. No explanation was found for the ductility of the deposit under these conditions. Indeed the ductile P (FCC) cobalt and the hydrogen contents in the cobalt deposits are nearly the same as those obtained in a sulfate media, which gives brittle depo¬sits under equivalent electrolysis conditions. Malleable cobalt sheets can be easily obtained under the proposed conditions which could lead to new applications for cobalt.

Jan 1, 1988

By Zhongning Shi, Ramana G. Reddy

"By cyclic voltammetry and potentiostat electrodeposition using Potentiostat/Galvanstat, electrochemical behavior on Ag electrode in electrolyte 0.2M NaOH+0.01MPb(NO3)2-0.01M TeO2 -0.01M TlNO3 solution were also carried out at 298K. The processes of electrodeposition of Tl2Te3 and PbTl4Te3, a thermoelectric material, are reported along with analysis of the composition of the obtained deposits. The results showed that two different underlying processes are occurring depending on deposition potential. One process involves the reduction of TeO3 2- and Tl+ to Tl2Te3 in a potential interval of -0.70V < E < - 0.89V (vs. Hg/HgO). A second process at more negative reduction potentials involves reduction of TeO3 2-, Pb2+ and Tl+ to PbTl4Te3 in a potential interval of -1.02V < E < - 1.19V. The crystalline Tl2Te3 and PbTl2Te3 were deposited electrochemically on Ag substrates at -0.84V and -1.10V respectively. Thermoelectric (TE) material can form a temperature gradient across the material to make electric voltage, which is popular in waste heat utilization and recovery industry. Lead telluride, PbTe, is a small band gap semiconductor of 0.32eV at 300K. PbTe can change its n-type semiconductors with Pb-rich to p-type semiconductors with Te-rich[1]. And it is one of the best TE materials used in thermoelectric generators working between 500K and 600K, or even at a higher temperature of 800K.Three facto,rs play a role in the performance of a thermoelectric material: electrical conductivity (s), thermal conductivity(?), and the Seebeck coefficient (S). These can be combined with absolute temperature (T) to give a figure of merit (ZT) for the material, ZT = s2sT/?. By increasing the electrical conductivity and decreasing the thermal conductivity, which can enhance the ZT value, many efforts, such as alloying with other elements and making the materials nano-sized, have been done to improve its properties recently. Hsu et al. reported that the ZT value of Cubic AgPbmSbTe2+m is increased to 2.2 by doping Ag-Sb to PbTe.[2]."

Jan 1, 2011

By Ramana. G. Reddy, Haoxing Yang

The electrodeposition of zinc from zinc oxide using urea and choline chloride mixture in a molar ratio 2:1 is investigated in different experimental variables, namely, the concentration of added [BMIM]HSO4, temperature, and applied cell voltage. The additive, [BMIM]HSO4, was determined to have beneficial effect on the current efficiency, energy consumed in the process and surface morphology of the deposits. The highest current efficiency (92.6%) and lowest energy consumption (2.92kWh/kg) was obtained for solution with 20mg/mL [BMIM]HSO4. The morphology showed the formation of absorbed additive layer on the cathode at higher concentration of additives. Experiments were conducted at different temperatures between 343K and 388K and at various applied cell voltages between 2.7V to 3.6V to determine the best experimental conditions. By varying temperature, highest current efficiency (91.3%) and lowest energy consumption (2.69 kWh/kg) was obtained at 373K. The electrodeposition process is enhanced between the applied voltage 3.0-3.3V by achieving lower energy consumption (2.75~3.06kWh/kg) and higher current efficiency (88.4~89.7%). SEM images showed grain size is significantly increased in higher applied voltages. While at higher temperatures, it seemed to generate particle growth as clusters at the outer deposit layer.

Jan 1, 2014

By Andreas Zielonka

To meet the increasing demands of the quality and long term stability of technical systems also the applied materials have to full fill higher standards. This is of special importance where the function of a whole system depends on the reliability of the used materials for example for connector systems in automotive, computer and other electronic equipment?s. In most cases for connector systems electro deposited top layers are applied. To improve the quality of the applied layers new electro deposited systems are developed. One important field of research are the development of composite materials as dispersion coatings and multilayer systems. Multilayers are systems with a high number of single inter-layers of different metals or alloys with the wide chance of the alloy composition. As gold is one of the most important contact material for high quality connector systems it is used as basis for the development of multilayer systems. For the electrodeposition of multilayers two different methods can be applied, the single and the dual plating process. As in the dual plating process two different electrolytes are used, the single plating process allows the formation of multilayers from one electrolyte. In the presented research results cobalt and nickel are used besides gold for the formation of the multilayers. The properties of the layers can be influenced in a wide range by the change of electrolyte composition and the process parameters as current density, current waveform, temperature, hydro-dynamic conditions at the electrode surface and by the number and thickness of the inter layers of the deposited materials. The paper describes the fundamentals of the electro deposition of multilayer systems. For the investigation of the properties of the multilayers different techniques are applied. One of the most important parameter are the thickness of the total layer and of the applied sublayers. The thickness of the sublayers can be varied between a few nanometers up to micrometers. The wear resistance, the contact resistance and the plug-in forces are measured as these parameters are important for the technical application of such layers. For the description of the structure composition and surface properties the sample where also investigated by scanning electron microscopy (SEM), energy dispersive x-ray-analyses (EDX) and glow discharge optical spectroscopy (GDOS). The paper shows that the deposition of gold based multilayers is possible and that the properties of such systems can be varied in a wide range what opens new fields of applications of such materials.

Oct 1, 2003

By Raj K. Rajamani, James R. Nagel, York R. Smith

In this work, we examine the efficacy of Electrodynamic Eddy Current Separation (EECS) to recover valuable materials from end-of-life solar panels. Traditional rotary-based eddy current separators are capable of excitation frequencies of 1 kHz or less and struggle to economically separate particles smaller than 1 cm. A new design of eddy current separators has been developed at the University of Utah which has no mechanically moving parts. The design is capable of excitation frequencies up to 50 kHz, allowing sorting of particles as small as 1.0 mm. Recently, we have been successful in separating mixtures of Si/Al and CdTe/Al particles (1–3 mm) with recovery and grades greater than 85%, an energy demand of 68 kWh/short ton of sorted material, and throughput of roughly 10 kg/h. Current and future challenges utilizing this method for valuable material recovery from end-of-life solar panels are discussed.

Mar 1, 2017

By Guo Xueyi

The electrochemical couple behavior of manganese dioxide with ferrous/ferric ions in acidic chloride medium was investigated, It was proven that the dissolution of Mn01 is due to the electrochemical couple reaction between MnO2/Mn2+ and Fe2+/lFe3+ in the solution, The driving force for the process originates from the rest potential difference of the two couples. The reduction of Mn02 is controlled by clectrochemical kinetics, whereas the conversion of F e2+ to Fe3+ is limited by diffusion, The factors such as the Mn2+, Fe2+, Fe3+, Cl concentration, pH of the solution and the temperature, have much influence on the kinetics of the couple process, This study will be useful to elucidate the mechanism for the leaching of manganese nodule from the deep ocean as well as manganese dioxide ores in land,

Jan 1, 2003

By David Wright, Colin Burns

Successful leaching of gold depends on appropriate chemical conditions; contact between leach solution and the gold particles; separation of the leach solution from the solids and extraction of the valuable ion from the solution. Irrespective of the leaching method employed the chemical conditions required are similar as is the dependence of solu­tion/gold contact on liberation. The various leaching methods available vary in the means by which gold/solution contact and solid/liquid separation are achieved. The essential difference between heap or vat leaching techniques and those involving agitation of a slurry is dependence on percolation for effective gold/solution contact. The most significant factor preventing uniform percolation is the presence of fines or clays. The quantity and character of the fines fraction is ore type dependent and may result from crushing, degradation during stacking or leaching, or the natural size distribution of the ore. The problems associated with fines can be aggravated during stacking and preparation of the heap. Segregation during stacking can result in concentration of fine particles at the centre of heaps. Further concentration of fines may also occur during irrigation by the movement of the fine particles with the solution. The end result is that the areas in which fines are concentrated become areas of low permeability. The contact between leach solution and the ore in such areas is, at best, slowed down dramatically and, in some cases, prevented altogether. The consequences of this phenomena are slow leaching and a reduction in recovery. The conventional solution to this problem is well known. Agglomeration of ore prior to heap leaching is practised widely. The effect of agglomeration is to immobilise the fines by causing them to adhere either to each other or to larger ore particles. The net effect is that the ore behaves as if no fines were present. The use of agglomeration is limited only by its cost, the most significant components of which are the cost of binding agent, commonly cement, and the capital cost of the agglomerating equipment.

Jan 1, 1995