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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

US 4,183,794 - Electrowinning zinc from a zinc sulfate solution produced by leaching zinc ore with sulfuric acid. The leach liquor is subjected to electrolysis in a first cell having an insoluble anode to deposit primary zinc on the common electrode. The coated electrode is transferred to a second cell having an alkaline electrolyte, and electrolysis is effected in the second cell to transfer zinc from the common electrode to the second cell cathode in a spongelike form which is readily stripped. R.H.C.L. Ross. Jan 15, 1980. 10 pp. (204-119). Filed: 12-22-77 (863,190). Same: Canadian 1,051,820, dated Apr. 3, 1979.

Jan 1, 1982

By P More

US 4,132,621-In the electrowinning of aluminum, the cells are aligned in a lengthwise direction so as to lessen the harmful influence of the induced magnetic fields Each cell is supplied with current from the preceding cell both via the head arid at least one side riser The output of the cathode bars is divided into two separate groups, the upstream group supplying the head of the subsequent cell arid the downstream group supplying the side risers of the subsequent cell This produces a substantial improvement in cell efficiency arid a greater regularity P Morel, J P Dugois, arid B Langon, assigned to Aluminium Pechiney. Jan 2, 1979 12 pp. (204¬243M) Filed 1-12-78 (868,861) Priority: France, 1-19-77 (77/2,213) US 4,134,806-Cells, anodes, arid methods for use in the electrowinning of nickel, cobalt, copper, zinc, or other metals from an acid ore leach solution or the like The cell is provided with vertically immersed stationary cathodes and stationary rod anodes which are noncorrodible by the electrolyte arid are electrocatalytic to the anode reaction. The spaced parallel anode rods are connected to electric current supply bars The anode rods have an electroconductive core made of a metal alloy arid a surface coating of an oxide of platinum or a platinum group metal The ratio of active cathode surface area to active anode surface area is preferably at least 3 0. De Nora arid C Traini, assigned to Diamond Shamrock Tech¬nologies, SA Jan 16, 1979 13 pp. (204-105R) Filed 9-15-77 (833,661) Priority Italy, 1-29-73 (19738 A/73). Same British 1,434,334-5, dated May 5, 1976 US 4,135,994-In the electrowinning of aluminum at a high current efficiency, the electrolytic bath is a mixed molten salt consisting of 2-15% by weight of aluminum trichloride, 15-83% of sodium chloride, 15-70% of combined calcium chloride arid magnesium chloride but riot more than 40% of calcium chloride, arid optionally up to 10% of barium chloride Preferably, plate-shaped graphite electrodes used for both cathodes and anodes are arranged in parallel inclined relation so that the axis in the lengthwise direction makes an angle of from 10° to 45° to the horizontal. T Ishikawa arid H Ichikawa, assigned to Nippon Light Metal Co Ltd Jan 23, 1979 4 pp (204-67) Filed 11-15-77(851,632) Same British 1,550,502, dated Aug 15, 1979

Jan 1, 1980

By Jin C, Shi X

The electrochemistry of leaching gold with thiosulphate has been studied systematically by using electrochemical techniques. Results show that the current peak of anodic dissolution of gold occurs at about 50 mV(SCE) and there is passivation in the polarisation curve in the thiosulphate solution in the absence of ammonia. Ammonia markedly improves the anodic dissolution rate of gold and reduces the passivation as well as making the current peak shift negatively. Results also show that there is no current peak for a cathodic process in the range of 0 -900 mV(SCE) in the thiosulphate solution in the presence of oxygen but absence of cupric ions and ammonia. In the solution containing 0. 1 mol/L cupric-ammonia ions, the peak occurs at about -400 mV (SCE) and the cathodic process is characteristic of a catalytic reaction. Oxygen presents a predominate effect on the cathodic process. Based on the electrochemical investigation, the following mechanism of leaching gold with ammoniacal thiosulphate has been proposed. Ammonia reacts primarily with gold ions on th anodic surface of gold and the formed A (NH3)2+ rea~s then with S2O 3 in solution to form the stabler Au(S203) 2 . Cu (NHS) 4 gains electrons on the cathodic surface and is reduced to CU(N) ? which is then oxidised by oxygen and regenerated into Cu(NH3) 4 after entering the solution.

Jan 1, 1993

By Fathi Habashi, Ahmet Deniz Bas

"The mechanism of leaching of semiconducting minerals such as PbS, ZnS, UO2, etc., has been the subject of intensive speculation by hydrometallurgy researchers in the early 1950s who assumed the formation of intermediate surface complexes that could be neither separated nor identified by physicochemical techniques. The electrochemical theory of leaching introduced in the late 1960s resolved this problem by comparing the leaching process to a corrosion phenomenon similar to the corrosion of metals. Few years later, experimental evidence showed that anodic and cathodic zones are formed on the dissolving mineral although no electric current is imposed on the mineral during dissolution. A discussion of these findings is outlined.INTRODUCTIONIn the early 1950s researchers realized that kinetic studies for leaching ores are as important as thermodynamic calculations. It was also during this period that the concept of species adsorption on mineral surfaces has dominated the interpretation of the mechanisms of most reactions. This may have been due to the fact that many researchers of this period came from the mineral dressing sector and were influenced by flotation theories. However, when the knowledge of lattice defects and the semiconductivity of minerals became known and their importance in extractive metallurgy was realized, there was a need to explain the leaching reactions in light of these modern theories (Habashi, 1969, 1970). Semiconducting minerals of importance in metallurgy are two categories: the sulfides such as those of copper, lead, zinc, and the oxides such as those of uranium."

Jan 1, 2016

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 J. D. Miller, P. J. McDonough, H. Q. Portillo

Previous investigations have demonstrated the catalytic effect of silver additions in the ferric sulfate leaching of chalcopyrite [ ] The enhanced rate of leaching was found to be due to the formation of an intermediate Ag S film which forms on the Cures2 surface by an exchange reaction Under these conditions, unlike the uncatalysed ferric sulfate leach, the elemental sulfur forms a nonprotective reaction product on the Ag S crystallites As a result, the rate appears to become limited by an intermediate electrochemical reaction in {he Ag2S film rather than by transport through the elemental sulfur reaction product [ ] The reaction rate was found to have a complex dependence on the Ag+, Fe++ and Fe+3 concentrations, but independent of the Cu concentration Electrochemical measurements with a Ag,S-coated chalcopyrite electrode provide further information regarding the nature of the reaction mechanism The kinetics of the rate limiting, intermediate electrochemical reaction are analyzed in terms of the Butler-Volmer equation

Jan 1, 1981

Electrochemistry Measurement, Using Chena Analyser, to Investigate Selective Separation of Pentlandite and Pyrrhotite

Sep 13, 2010

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 J. R. Levin, E. J. Schelter

"We present some of our recent efforts in the development of predictive, directed oxidation chemistry of cerium(III) complexes under non-aqueous conditions. The electrochemistry of cerium(III)- alkali metal heterobimetallic aryloxide complexes is reported and compared with cerium aryloxide complexes that are kinetically stabilized by hydrogen bonding cations that span between the complexed aryloxide ligands. Comparative electrochemical measurements reveal differences between the heterobimetallic complexes and the hydrogen-bonded complexes.INTRODUCTIONThe rare earth elements comprise the lanthanides, La–Lu, and the element yttrium (Aspinall, 2001). Rare earth ores such as monazite, LnPO4, and bastnäsite, LnFCO3, typically bear mixtures of light rare earths: La–Sm while monazite, LnPO4, contains mixtures of heavy rare earths (Eu–Lu) (Cotton, 2006). Pure rare earth elements typically are isolated using a liquid-liquid separations process.(Bautista, 1995) The hydrometallurgy of these elements is a difficult problem because the separation factors between neighboring rare earths, which are predicated on the small differences in the sizes of the trivalent ions, are quite small (Cox, 1992). The element cerium, with its 4f1 electronic configuration in the trivalent state, is unique among the rare earth elements due to a relatively accessible 4f0 electronic configuration. The accessibility of the 4f0 configuration underlies the chemistry of cerium(IV), the only rare earth ion with molecular chemistry in the tetravalent oxidation state (Cotton, 2006). Cerium is trivially separated from mixtures of light rare earths by making use of its unique oxidation chemistry. In an effort to extend separations chemistry by oxidation reactions to other rare earth elements such as terbium and praseodymium, the solution electrochemistry of well-defined cerium complexes is of interest."

Jan 1, 2012

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 F. M. Doyle, Jun Li, Milton E. Wadsworth, Ximeng Zhu, E. Peters

The electrochemical behavior of pyrite in borate/sulfate solutions was investigated using cyclic voltammetry. Three anodic peaks at approximately -0.8 V, -0.1 V and +0.5 V (SCE) were detected along with their corresponding reduction peaks. The first two peaks correspond to the oxidation of surface products. The third peak corresponds to the direct oxidation of pyrite with reaction products FeO oxides. sulfate ion and partially oxidized sulfur intermediates present as a surface film of polysulfides and So. The Few oxides and sulfur intermediates were reduced to ferrous hydroxide and HS during the negative-going scan. The HS interacted preferentially with Fe(OH), on the surface to form FeS. Excess fenous hydroxide continued to reduce to metallic iron. During the return positive-going scan, metallic iron was oxidized to ferrous hydroxide and FeS was oxidized to pyrite. These reactions are characterized by a unique double peak observed in the region -0.8 to -0.65 V. The growth kinetics of the surface sulfur film formed during anodic oxidation were studied using chronoarnperomeay. Potentiostatic measurements were well correlated by a paralinear rate equation, suggesting the formation of an intermediate passive film, associated with the simultaneous dissolution of the outer layer of the film. The reaction rates were affected by applied potential, solution pH and temperature, but were independent of electrode rotation speed. A reaction kinetics model which fitted well with experimental results, was developed.

Jan 1, 1993

By H. Majima

In spite of the importance of the presence of pyrite in the flotation of sulphide ores, not many studies have been made from the electrochemical point of view. It is generally recognized that the oxidation of sulphide minerals is one of the most Important factors among those which affect the floatability of sulphide minerals. The concept that the presence of oxygen is essential to the flotation of sulphide minerals is supported by numerous experimental results (1). The presence of oxygen in sulphide minerals- aqueous solution systems would affect the electrochemical behaviour of sulphide minerals and subsequently lead to more complicated reactions on the surface of sulphides. Actually some of the phenomena observed in sulphide flotation are deemed to be more appropriately explained from the electrochemical point of view. The author and co-workers have studied extensively the electrode reactions of pyrite and its significance in sulphide flotation. The results have been partly published elsewhere (2-7). In this paper, the author discusses the electrochemical nature of pyrite, and the three different phenomena observed in pyrite flotation: (1) Xanthate¬dixanthogen system on pyrite, (2) Flotation of complex sulphide ores containing pyrite and (3) Depressive mechanisms of pyrite with cyanide. The phenomenon which has been known as an iron contamination effect due to steel grinding media on sulphide flotation is also explained from the electrochemical aspect. However, this problem is not directly concerned with pyrite, and it will be discussed elsewhere (8).

Jan 1, 1971

By V. E. Vigdergauz

The work presented shows results of electrochemical study of pyrite hydrophobicity evaluated by air bubble induction time (IT) measurements. On the basis of measured IT?s an average thickness of the thin liquid film prior to its rupture has been evaluated, which confirms long-range character of the interactions between air bubbles and hydrophobic surfaces. Obtained data are discussed in the frame of recent studies of structures of solid-liquid interface based on molecular dynamics simulations and results of surface force measurements.

Jan 1, 2014

By R. Woods

INTRODUCTION Gaudin (1), considered that "the mechanism of mineral collection is the central problem of flotation theory". From their work on adsorption phenomena in flotation for more than fifty years (2), Gaudin and his co-workers have made major contributions to the elucidation of this mechanism, a fact acknowledged by their contemporaries in the field (e.g. (3)). Their investigations in a number of areas, e. g. demonstrating that submonolayer quantities of adsorbed collector species can induce flotation, or identifying the influence of substances which can activate or depress (1), have helped to provide the basis for and the development of a theory to account for the interaction between mineral and collector. It was established in the late fifties (4) that the presence of oxygen is a prerequisite for the flotation of metal sulfides with thiol collectors. This fact rendered inadequate the concept of simple ion adsorption being responsible for rendering these minerals hydrophobic. The requirement for oxygen has been explained (1) in terms of this species being a component in chemical reactions between the sulfide surface and the collector. Gaudin has been instrumental in identifying the products of chemical reactions at sulfide minerals (1, 5), a line of work which has been continued particularly by Finkelstein and co-workers in South Africa (6). In presenting a detailed mechanism of the mineral-collector- oxygen interaction, it has often been considered that the mineral surface [must] first be oxidized to a metal oxy-sulfur species which

Jan 1, 1976

By R. Woods

INTRODUCTION Gaudin (1), considered that "the mechanism of mineral collection is the central problem of flotation theory". From their work on adsorption phenomena in flotation for more than fifty years (2), Gaudin and his co-workers have made major contributions to the elucidation of this mechanism, a fact acknowledged by their contemporaries in the field (e.g. (3)). Their investigations in a number of areas, e.g. demonstrating that submonolayer quantities of adsorbed collector species can induce flotation, or identifying the influence of substances which can activate or depress (1), have helped to provide the basis for and the development of a theory to account for the interaction between mineral and collector. It was established in the late fifties (4) that the presence of oxygen is a prerequisite for the flotation of metal sulfides with thiol collectors. This fact rendered inadequate the concept of simple ion adsorption being responsible for rendering these minerals hydrophobic. The requirement for oxygen has been explained (1) in terms of this species being a component in chemical reactions between the sulfide surface and the collector. Gaudin has been instrumental in identifying the products of chemical reactions at sulfide minerals (1.5), a line of work which has been continued particularly by Finkelstein and co-workers in South Africa (6). In presenting a detailed mechanism of the mineral-collector- oxygen interaction, it has often been considered that the mineral surface - must first be oxidized to a metal oxy-sulfur species which

Jan 1, 1976

The interaction of flotation collectors with sulfide minerals takes place at the solid - solution interface. The electrochemistry of the processes which affect this interface are discussed. The interaction of xanthates with sulfides is an electrochemical process, xanthates being electro-oxidised to chemisorbed xanthate and dixanthogen. The role of oxygen is to provide a cathodic process to allow the anodic oxidation to occur. The hydrophobic condition of the mineral surface is brought about by the presence of the oxidised xanthate species. The action of reagents which can activate or depress the flotation of sulfides is discussed briefly.

Jan 1, 1971