Mathematical modeling of hysteresis in porous electrodes

We study the mathematical model of the Li+ ions’ intercalation from the electrolyte into the porous graphite surface of the negatively charged electrode and further Li diffusion inside the electrode particle. For proper approximation of experimental data we use the cubic polynomial. We prove the multiplicity of the steady state solutions in a certain range of the electrode potential values. This multiplicity may be explained by the simultaneous existence of several phases at the graphite electrode surface. Numerical investigation allows us to demonstrate the experimentally observed hysteresis. After including the diffusion of Li into the model we compare the charging time for various electrode structures.     

碱性介质中多孔纳米结构镍/钯-镍电极上甲醇电氧化反应(英文)

A nanostructured Ni/Pd-Ni catalyst with high activity for methanol oxidation in alkaline solution was prepared by electrodeposition followed by galvanic replacement, that is, electrodeposition of Ni-Zn on a Ni coating with subsequent replacement of the Zn by Pd at the open circuit potential in a Pd-containing alkaline solution. The surface morphology and composition of the coatings were examined by energy dispersive X-ray spectroscopy and scanning electron microscopy. The Ni/Pd-Ni coatings were porous and were composed of discrete Pd nanoparticles of about 58 nm. The electrocatalytic activity of the Ni/Pd-Ni electrodes for the oxidation of methanol was examined by cyclic voltammetry and electrochemical impedance spectroscopy. The onset potentials for methanol oxidation on Ni/Pd-Ni were 0.077 V and 0.884 V, which were lower than those for flat Pd and smooth Ni electrodes, respectively. The anodic peak current densities of these electrodes were 4.33 and 8.34 times higher than those of flat Pd (58.4 mA/cm2 vs 13.47 mA/cm2) and smooth Ni (58.4 mA/cm2 vs 7 mA/cm2). The nanostructured Ni/Pd-Ni electrode is a promising catalyst for methanol oxidation in alkaline media for fuel cell application.     

Electro-oxidation of methanol catalysed by porous nanostructured Fe/Pd-Fe electrode in alkaline medium

Nanostructured Fe/Pd-Fe catalysts are prepared first by the deposition of Fe-Zn onto the Fe electrode surface, followed by replacement of the Zn by Pd at open circuit potential in a Pd-containing alkaline solution. The surface morphology and composition of coatings are determined by scanning electron microscopy and energy dispersive X-ray techniques. The results show that the Fe/Pd-Fe coatings are porous structure and the average particle size of Pd-Fe is low, in the range of 30–80 nm. The electrocatalytic activity and stability of Fe/Pd-Fe electrodes for oxidation of methanol are examined by cyclic voltammetry and chronoamperometry techniques. The new Fe/Pd-Fe catalyst has higher electrocatalytic activity and better stability for the electro-oxidation of methanol in an alkaline media than flat Pd and smooth Fe catalysts. The onset potential and peak potential on Fe/Pd-Fe catalysts are more negative than that on flat Pd and smooth Fe electrodes for methanol electro-oxidation. All results show that the nanostructured Fe/Pd-Fe electrode is a promising catalyst towards methanol oxidation in alkaline media for fuel cell applications.     

Electrocatalytic activity of porous nanostructured Fe/Pt-Fe electrode for methanol electrooxidation in alkaline media

An electrochemical approach to fabricate a nanostructured Fe/Pt-Fe catalyst through electrodepo-sition followed by galvanic replacement is presented. An Fe/Pt-Fe nanostructured electrode was prepared by deposition of Fe-Zn onto a Fe electrode surface, followed by replacement of the Zn by Pt at open-circuit potential in a Pt-containing alkaline solution. Scanning electron microscopy and energy-dispersive X-ray techniques reveal that the Fe/Pt-Fe electrode is porous and contains Pt. The electrocatalytic activity of the Fe/Pt-Fe electrode for oxidation of methanol was examined by cyclic voltammetry and chronoamperometry. The electrooxidation current on the Fe/Pt-Fe catalyst is much higher than that on flat Pt and smooth Fe catalysts. The onset potential and peak potential on the Fe/Pt-Fe catalyst are more negative than those on flat Pt and smooth Fe electrodes for methanol electrooxidation. All results show that this nanostructured Fe/Pt-Fe electrode is very attractive for integrated fuel cell applications in alkaline media.     

Mathematical modeling of overpotentials of direct glucose alkaline fuel cell and experimental validation

Development of a mathematical model for batch-type direct glucose fuel cell (DGFC) and validation of the model with experimental results in terms of i-V characteristics is attempted. The DGFC model equation is derived to predict the cell voltage at a given current density considering overall ohmic overpotential and activation and concentration overpotentials at anode. The activation overpotential is modeled by taking into account the reaction mechanism of glucose electro-oxidation available in literature and a semi-empirical equation is used to estimate the concentration overpotential. The charge transfer coefficient used in estimation of activation overpotential for different anode catalysts, namely, PtAu/C, PtPdAu/C, and PtBi/C, is determined from cyclic voltammetry analyses. The ohmic resistance is calculated from specific conductance of KOH solution found from non-linear regression analysis given in literature. Two different parameters, m and k are used in estimation of concentration overpotentials. While k signifies departure from ideal i-V characteristics and its value used is 1, m is area-specific resistance for mass transport and its value is 0.2 kΩ cm² for PtAu/C and PtPdAu/C and 0.12 kΩ cm² for PtBi/C. The trend of current–voltage characteristics at different operating conditions, such as anode catalysts, anode loadings, glucose, and KOH concentrations, is predicted reasonably by the proposed model.     

Flow-injection potentiometric determination of free cadmium ions with a cadmium ion-selective electrode

The determination of free cadmium ions with solid-state cadmium ion-selective electrode can be performed in non-flow measurements in non-buffered solutions in a wide concentration range down to pCd 10. In cadmium ion buffered solutions linear Nernstian response was obtained even down to pCd 12, which is lower, that expected based on calculation of cadmium solubility from the conditional solubility product. Interferences of trace amounts of Fe(III), Cu(II) and Pb(II) commonly present in natural waters in larger concentrations than Cd(II) can be eliminated by reduction with hydroxylamine, complexation with Neocuproine and ion-exchange on anion-exchange resin in sulphate form, respectively. The developed procedure might be suitable for the determination of activity of free cadmium ions in natural water. A preliminary study on this subject is demonstrated for river water sample using stopped-flow flow-injection system.     

Lithium intercalation with phase transitions in model systems of electrode materials for lithium power sources

A comparison was made for Li⁺ chemical diffusion coefficients (D _Li) in graphite as calculated by mathematical models of Li⁺ intercalation under constant potential into semirestricted and restricted kinetic systems with mobile phase boundary and into a single-phase system. Close D _Li values were calculated by means of double-phase models. The double-phase model produces 6–7-fold D _Li coefficient as compared to the values of the single-phase model.     

Highly active porous nickel-film electrode via polystyrene microsphere template-assisted composite electrodeposition for hydrogen-evolution reaction in alkaline medium

A highly porous nickel-film electrode with satisfactory mechanical strength was prepared by a facile vertical template-assisted composite electrodeposition method using polystyrene(PS) microspheres templates, with the aim of improving the electrocatalytic activity for the hydrogen-evolution reaction(HER). During the composite electrodeposition process, the hydrophobic PS microspheres were highly dispersed in the electrolyte with the help of a surfactant, and then co-deposited with Ni to form the film electrode. After removing the PS templates by annealing, a porous Ni film containing large amount of uniformly dispersed pores with narrow size distribution was obtained, and then applied as the electrode for the HER in an alkaline medium. As evidenced by the electrochemical analysis, the porous Ni film electrode exhibits higher catalytic activity as compared to a dense Ni film electrode and is superior to a Ni/Ru O2/Ce O2 commercial electrode. The effect of temperature on the catalytic properties of the porous Ni film electrode was also investigated; the activation energy was calculated as 17.26 k J/mol. The enhanced activity toward the HER was attributed to the improved electrochemical surface area and mass transportation facilitated by the high porosity of the synthesized Ni film electrode.     

Flow-injection determination of phosphate with a cadmium ion-selective electrode

A flow-injection method is described, in which phosphate standards are introduced into a reagent stream containing Cd(2+) ,resulting in the formation of Cd(3)(PO(4))(2). The associated reduction in free metal concentration is sensed by a cadmium-selective electrode. With the exception of major interference from iodide and moderate interference from bromide and thiocyanate, the system exhibits excellent response to phosphate and selectivity over several common anions in solutions buffered at pH 8.4. A maximum sampling rate of 160/hr is possible for phosphate standards in the concentration range 10(-1)-10(-1)M with a 10(-4)M Cd(2+) reagent stream at a total flow-rate (carrier and reagent stream combined) of 8.4 ml/min.     

Analytical study of a cadmium ion-selective ceramic membrane electrode

Summary A cadmium ion-selective membrane electrode has been developed by applying a hot-pressing method. The membrane contains cadmium sulphide, silver sulphide, and copper(I)-sulphide.The best response was obtained with a membrane containing less than 30% of copper(I) sulphide and more than 5% of cadmium sulphide. The Nernstian slope was secured over an activity range of 10^–1 to 10^–6 M, and potentiometric analysis could be carried out over a concentration range of 10^–1-10^–7 M. The potentials were maintained at constant values over more than 6 months. Also, the potentials satisfied the Nernst's factor 2.303 RT/2F at the temperature range between 0 and 95°C. Among the common ions, silver, copper(II), iron(III), mercury(II), sulphide, and iodide ions interfered seriously. However, about 10–100 times of lead and bromide ions and more than 1000 times of alkali metal, alkaline earth metal, zinc, aluminium, nickel, cobalt, manganese(II), perchlorate, and nitrate ions did not interfere at all.

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Analytische Untersuchung einer cadmiumionenselektiven keramischen Membranelektrode

Zusammenfassung Die Membran wurde durch Pressen von Cd-, Ag und Cu(I)-sulfid bei 200–500°C und 3–7 t/cm² hergestellt. Die beste Ansprechempfindlichkeit ergab sich bei einem Gehalt von <30% Cu₂S und >5% CdS. Die Nernstsche Gleichung war gültig im Bereich von 10^–1–10^–6 M, der analytische Bereich war 10^–1–10^–7 M. Die Potentiale konnten mehr als 6 Monate auf einem konstanten Wert gehalten werden. Sie entsprachen dem Nernstschen Faktor, 2,303·R·T/2 F, im Temperaturbereich von 0–95°C. Erhebliche Störungen werden durch Ag⁺-, Cu²⁺-, Fe³⁺-, Hg²⁺-, S^2– und J^–-Ionen verursacht. Jedoch verursachen etwa 10–100fache Mengen von Pb²⁺- und Br^–-Ionen sowie mehr als 1000fache Mengen von Alkali-, Erdalkali-, Zn²⁺-, Al³⁺-, Ni²⁺-, Co²⁺-, Mn²⁺-, ClO₄ ^–- und NO₃ ^–-Ionen keine Störungen.

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The authors thank Dr. S. Kisaka, Dr. K. Sugihara, Dr. S. Hayakawa and Dr. S. Mori for their encouragement in this work.     

Electrochemical reduction of oxygen at a porous flow-through electrode

The electrochemical reduction of oxygen at a porous flow-through electrode is described with emphasis on the effects of concentration, flow speed and surface area. On a packed bed copper electrode in sulfuric acid, it was found that oxygen undergoes a two electron reduction process giving rise to H₂O₂.     

Determination of cadmium in Bentonite clay mineral using a carbon paste electrode

Sodium activated Bentonite, a sodium modified Montmorillonite, was submitted to cadmium sorption from nitrate solutions in order to simulate a cadmium polluted clay mineral. The remaining cadmium concentration in solution was analyzed at equilibrium by means of Differential Pulse Polarography (DPP) in order to calculate the cadmium concentration sorbed by the clay. The cadmium distribution between clay mineral and solution was observed for different concentrations, showing a Freundlich sorption profile. The clay mineral, previously submitted to the cadmium sorption procedure, was included in a carbon paste in order to investigate the cadmium content by voltammetric determination. For cadmium detection in Bentonite, a linear response of the carbon paste electrode (CPE) was observed in the 5 · 10^–5– 1.8 · 10^–4 mol/g range with good reproducibility. Received: 23 July 1998 / Revised: 19 November 1998 / Accepted: 26 November 1998     

Determination of cadmium in Bentonite clay mineral using a carbon paste electrode

Sodium activated Bentonite, a sodium modified Montmorillonite, was submitted to cadmium sorption from nitrate solutions in order to simulate a cadmium polluted clay mineral. The remaining cadmium concentration in solution was analyzed at equilibrium by means of Differential Pulse Polarography (DPP) in order to calculate the cadmium concentration sorbed by the clay. The cadmium distribution between clay mineral and solution was observed for different concentrations, showing a Freundlich sorption profile. The clay mineral, previously submitted to the cadmium sorption procedure, was included in a carbon paste in order to investigate the cadmium content by voltammetric determination. For cadmium detection in Bentonite, a linear response of the carbon paste electrode (CPE) was observed in the 5 · 10^–5– 1.8 · 10^–4 mol/g range with good reproducibility. Received: 23 July 1998 / Revised: 19 November 1998 / Accepted: 26 November 1998     

Electrogenerated chemiluminescence of lucigenin in aqueous alkaline solutions at a platinum electrode

Lucigenin is shown to emit light during electrolysis in aqueous alkaline solutions at a platinum electrode. In the mechanism proposed, lucigenin is initially reduced at —0.30 V vs. Ag/AgCl and subsequently the reaction product reacts either with oxygen or a reduction product of oxygen. Previous evidence on this phenomenon is contradictory.     

用旋转圆盘电极制备碲化镉光电极

有关电沉积法制备碲化镉薄膜的报道中,碲化镉薄膜大多在静止的金属片上沉积.最近,我们用旋转圆盘电极(RDE)研究了电沉积碲化镉过程的动力学,发现在RDE上沉积的碲化镉具有更好的光电化学性能. 我们设计了一种可换盘的RDE.沉积基片为一镍盘(直径6mm,厚0.2mm),用导电银