Behaviour of tungsten carbide hydrogen-diffusion electrodes in chloride etching solutions

Studies were performed of tungsten carbide hydrogen-diffusion electrodes operating as anodes in electrolytic baths for regeneration of etching solutions of CuCl₂ and FeCl₃. Under conditions of electrolytic regeneration of copper chloride solutions (i = 40 mA cm^–2, 40° C) after 1500 h operation the electrode polarization increased by about 200 mV. Maximum current efficiency of 60–65% was obtained at I _k = 80 mA cm^–2. It is demonstrated that the replacement of the standard carbon anodes with tungsten carbide hydrogen-diffusion electrodes and the elimination of the ion exchange membrane separating the anodic from the cathodic space leads to a 2–4 V decrease of the electrolytic bath voltage. The regenerated solutions of CuCl₂ and FeCl₃ can be reused as etching agents after adding 7–10 ml 30% solution of hydrogen peroxide per litre.     

Effect of CsF-concentration on electrolytic conductivity, viscosity and anodic reaction of nickel electrode in (CH3)3N-CsF–HF system at room temperature

In order to increase the formation ratio of perfluorotrimethylamine, (CF₃)₃N, to overall anode gas in electrolytic production using Ni anode, mixed melts of (CH₃)₃N·mHF + CsF·2.3HF were used as electrolytes at room temperature. The ionic conductivity of the mixed melts decreased with an increase in the CsF concentration, whereas the viscosity of the mixed melts increased with increasing the CsF concentration. AC impedance and XRD analysis revealed that the presence of CsNi₂F₆ in the oxidized layer formed on the Ni anode after electrolysis. The gas evolved at the Ni anode was composed of (CF₃)₃N, (CF₃)₂CHF₂N, CF₃(CHF₂)₂N, (CHF₂)₃N, CF₄, NF₃, CHF₃, C₂HF₅, and C₂F₆. The best ratio of (CF₃)₃N to the overall anode gas (52.11%) was obtained in the electrolyte of (CH₃)₃N·5.0HF + 50 wt% CsF·2.3HF mixed melt at 20 mA cm⁻².     

Electrolysis of mixed melt of (CH3)4NF·mHF+x wt.% CsF·2.0HF with nickel anode

A new process for electrolytic synthesis of a perfluorinated compound using mixed melts of (CH₃)₄NF·4.0HF+x wt.% CsF·2.0HF as electrolytes and Ni sheet anode at room temperature was developed. The addition of CsF·2.0HF reduced the overvoltage of the Ni anode. The surface film on the anode formed in the presence of CsF·2.0HF consisted of inorganic compounds of NiF₂, CsNi₂F₆, and an organic compound of (CH₃)₄NF. The presence of CsNi₂F₆, which is a highly oxidized nickel compound, gave a high electronic conductivity to the film and decreased the anode overvoltage. The gas evolved on the anode was composed of (CF₃)₃N and CF₄ as main products with small amounts of NF₃, C₂F₆, CHF₃, C₂HF₅, CF₃N(CF₂H)₂, and (CF₃)₂NCHF₂. The addition of 20 wt.% CsF·2.0HF gave the highest ratio of (CF₃)₃N of 40.5% when the electrolysis was carried out at 5 mA cm⁻² at room temperature.     

The influence of oxygen additions to hydrogen in their electrode reactions at Pt/Nafion interface

The influence of oxygen gas added to hydrogen in their electrode reactions at the Pt/Nafion interface was investigated using ac impedance method. The electrochemical cell was arranged in either electrolytic (hydrogen enrichment) or galvanic (fuel cell) mode. The impedance spectra of the electrode reaction of a H₂/O₂ gas mixture were taken in each mode as a function of the gas composition, electrode surface roughness and the cell potential. The spectrum taken for the anodic reaction of electrolytic arrangement confirmed the anodic oxygen reduction reaction (AOR, the local consumption of hydrogen by the added oxygen) by showing an independent arc distinguishable from that for hydrogen oxidation. But the independent arc was not revealed in the spectrum taken on a smooth (low surface area) electrode or on a Pt/C anode of the galvanic cell. At any cell current density, the electrolytic mode showed its anodic overpotential much higher (nearly three times higher at the current density of 100 mA cm⁻²) than the potential registered in galvanic mode implying that the oxygen gas in the mixture engages more active and independent AOR at the anode of the electrolytic cell.     

A comparison of La0.75Sr0.25Cr0.5Mn0.5O3−δ and Ni impregnated porous YSZ anodes fabricated in two different ways for SOFCs

In this paper, La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCrM) and Ni impregnated porous yttria-stabilized zirconia (YSZ) anodes have been fabricated in two different ways. The testing results demonstrated the excellent performance of the anode made by infiltrating a mixture of LSCrM and Ni(NO₃)₂ solutions into porous YSZ matrix. After reduction of the anode with hydrogen, an inner nano-network structure with mixed ionic-electronic conducting path has been formed within and between these added particles. A single cell with the anode at 800 °C exhibited the maximum power densities of 1151 and 704 mW cm⁻² when dry H₂ and CH₄ were used as the fuels, respectively; under the same conditions, the cell performances for LSCrM and Ni impregnated YSZ anode separately were 810 and 508 mW cm⁻². A cavity model was proposed to simulate the impregnating process and the loading was calculated. No carbon deposition was detected in the anode, even with the presence of Ni, after operation in dry CH₄ for about 6 h under open-circuit condition.     

Effect of fluoride additive on the mechanical properties of hydroxyapatite/alumina composites

The effect of fluoride additives on the mechanical properties of hydroxyapatite/alumina composites was investigated. When MgF₂ (5 vol%) was added to hydroxyapatite/alumina composites, the decomposition of hydroxyapatite was suppressed due to the substitution of F⁻ for OH⁻ in the crystal structure. Comparing two additives, such as MgF₂ and CaF₂, MgF₂ showed much more effective for the suppression of phase decomposition in the hydroxyapatite/alumina composites due to the enhanced substitution of F⁻ for OH⁻. In the case of MgF₂ addition, a relatively high-mechanical properties (flexural strength: ∼170 MPa; Vickers hardness: ∼7 GPa) was obtained compared to MgF₂-free composites.     

Material properties and processing in the production of fuel cell components: I. Hydrogen anodes from Raney nickel for lightweight alkaline fuel cells

The production steps of Raney nickel based, PTFE bonded hydrogen anodes for alkaline fuel cells are examined. The Raney nickel catalyst has been made by leaching the nickel aluminium alloy and additional stabilization. The electrode is fabricated by mixing the catalyst with copper oxide for enhancing electronic conductivity and aqueous PTFE emulsion as a hydrophobic binder. Each process step, starting from the nickel aluminium alloy is described and the physical properties of catalyst and electrode are evaluated. At an overpotential of 100 mV the optimized hydrogen anode exhibits at negligable excess hydrogen pressure (1·02bars) a current density of nearly 400 mA cm^–2 at 80°C in 30 wt% KOH. Long term performance test shows that electrode overpotential of more than 60 mV should be avoided. A life time of 5000 hrs at 50°C and a current density of 100 mA cm^–2 has been proven.     

Electrochemistry of metals and semiconductors in fluoride media

The electrochemical surface transformations and diverse applications of a variety of metals and semiconductors in a wide range of fluoride media such as aqueous, non-aqueous media, liquid HF media, room temperature fluoride melts and molten fluoride media with a melting range covering 50–1000°C are reviewed. Nickel shows excellent corrosion resistance in the absence of water. The anodic performance of this metal in electrochemical perfluorination and NF₃ production is discussed. Compact carbon materials serve as anodes in fluorine generators. In high temperature melts, they perform as consumable anodes. Graphitic carbon undergoes intercalation/de-intercalation process and related battery applications. Cu/CuF₂ couple is a good reference electrode. Pt and vitreous carbon materials are the inert electrodes of choice for electro analytical applications. Electrodeposition of Lithium as a non-dendritic uniform phase is important in Lithium metal based secondary batteries. High temperature fluoride melts are used in electro-deposition of valve metals such as Nb, Ta, and Ti. The stability and decomposition of fluoride complexes in these media are of interest.     

Electrochemical oxidation of boron containing compounds on titanium carbide and its implications to direct fuel cells

Electrochemical oxidation of sodium borohydride (NaBH₄) and ammonia borane (NH₃BH₃) (AB) have been studied on titanium carbide electrode. The oxidation is followed by using cyclic voltammetry, chronoamperometry and polarization measurements. A fuel cell with TiC as anode and 40 wt% Pt/C as cathode is constructed and the polarization behaviour is studied with NaBH₄ as anodic fuel and hydrogen peroxide as catholyte. A maximum power density of 65 mW cm⁻² at a load current density of 83 mA cm⁻² is obtained at 343 K in the case of borhydride-based fuel cell and a value of 85 mW cm⁻² at 105 mA cm⁻² is obtained in the case of AB-based fuel cell at 353 K.     

Platinum-modified titanium anodes for the electrolytic destruction of nitric acid

Three sets of electrodes, namely Pt electroplated Ti (PET) and diffusion annealed PET (DAPET) of plating thickness 3, 5, 7 and 10 μm and thermochemically glazed mixed oxide coated titanium anode (MOCTA-G) were evaluated for their performance, with a view to optimizing the current density conditions for maximum efficiency during the electrolytic destruction of nitric acid. In the acid killing by electro-reduction process, concentration of nitric acid in the high level waste (HLW) from the spent nuclear fuel reprocessing plant was brought down from about 4 to 0.5 M in order to reduce the amount of HLW by subsequent evaporation and to minimise the corrosion in waste tanks during storage of the concentrated waste solution. The electrochemical reduction of 4 and 8 M nitric acid to near neutral conditions was carried out with the above-said anodes and Ti cathode at various cathodic current densities ranging from 10 to 80 mA cm⁻². At current densities below 15 mA cm⁻² MOCTA-G electrode worked satisfactorily, whereas PET and DAPET electrodes could withstand and function well at much higher cathodic current densities (up to 80 mA cm⁻²). The life assessment of a 3 μm thick PET electrode at a cathodic current density of 60 mA cm⁻² in 8 M HNO₃ for a period of 110 h showed no failure. Phase identification of the plated electrodes was done by XRD measurements and their surface morphology was investigated by SEM.     

A new magnesium — air cell for long-life applications

A novel type of magnesium-air primary cell has been evolved which employs non-polluting and abundantly available materials. The cell is based on the scheme Mg/Mg(NO₃)₂, NaNO₂, H₂O/O₂(C). The magnesium anode utilization is about 90% at a current density of 20 mA cm^–2. The anode has been shown to exhibit a low open-circuit corrosion, a relatively uniform pattern of corrosion and a low negative difference effect in the electrolyte developed above as compared to the conventional halide or perchlorate electrolytes. In the usual air-depolarized mode of operation, the cell has been found to be capable of continuous discharge over several months at a constant cell voltage of about 1 V and a current density of 1 mA cm^–2 at the cathode. The long service-life capability arises from the formation of a protective film on the porous carbon cathode and fast sedimentation of the anodic product (magnesium hydroxide) in the electrolyte. The cell has a shelf-life in the activated state of about a year due to the low open-circuit corrosion of the anode. These favourable features suggest the practical feasibility of developing economical, long-life, non-reserve magnesium-air cells for diverse applications using magnesium anodes with a high surface area and porous carbon-air electrodes.     

A new rechargeable lithium-ion battery with a xLi2MnO3·(1 − x) LiMn0.4Ni0.4Co0.2O2 cathode and a hard carbon anode

We reported a new type of rechargeable lithium-ion battery consisting of a structurally integrated 0.4Li₂MnO₃·0.6LiMnNi_0.4Co_0.2O₂ cathode and a hard carbon anode. The drawback of the high irreversible capacity loss of both electrodes, occurring at the first charge/discharge process, can be counterbalanced each other. The battery shows good reversibility with a sloping voltage from 1.5 V to 4.5 V and delivers a capacity of 105 mA h g⁻¹ and a specific energy of 315 W h kg⁻¹ based on the total weight of the both active electrode materials.     

Electrosynthesis of iminodiacetic acid from nitrilotriacetic acid

The electrosynthesis of iminodiacetic acid by electrooxidation of nitrilotriacetic acid in undivided cells has been studied using Zn, Cu, PbO₂, DSA^®O₂, DSA^®Cl₂, C, Ni and porous carbon as anodes. Results show that the synthesis is possible in both acid and basic mediums. The best results were obtained in aqueous 40% w/w sulphuric acid with porous carbon RVC-4000 as anode and SUS 316 as cathode, at 60 °C, 400 mA cm^-2 and charge 95% of theoretical. Under these conditions, nitrilotriacetic acid conversion was 92%, current efficiency 80% and selectivity 85%. Loss of selectivity was due to chemical side reaction between iminodiacetic acid and HCHO electrogenerated in the electrolysis.     

Highly reversible Co3O4/graphene hybrid anode for lithium rechargeable batteries

A Co₃O₄/graphene hybrid material was fabricated using a simple in situ reduction process and demonstrated as a highly reversible anode for lithium rechargeable batteries. The hybrid is composed of 5 nm size Co₃O₄ particles uniformly dispersed on graphene, as observed by transmission electron microscopy, atomic force microscopy, Raman spectroscopy and X-ray diffraction analysis. The Co₃O₄/graphene anode can deliver a capacity of more than 800 mA h g⁻¹ reversibly at a 200 mA g⁻¹ rate in the voltage range between 3.0 and 0.001 V. The high reversible capacity is retained at elevated current densities. At a current rate as high as 1000 mA g⁻¹, the Co₃O₄/graphene anode can deliver more than 550 mA h g ⁻¹, which is significantly higher than the capacity of current commercial graphite anodes. The superior electrochemical performance of the Co₃O₄/graphene is attributed to its unique nanostructure, which intimately combines the conductive graphene network with uniformly dispersed nano Co₃O₄ particles.     

Electrochemical Performance of MnO2‐based Air Cathodes for Zinc‐air Batteries

This paper compares the oxygen reduction on four MnO₂‐based air cathodes assembled in home‐made electrochemical cells, with some particular observations on α‐MnO₂ cathode. The results show that the catalytic activity decreases in the following order: electrolytic MnO₂ (EMD) > natural MnO₂ (NMD) > β‐MnO₂ > α‐MnO₂. The maximum power density of the zinc‐air battery with EMD as the catalyst reaches up to 141.8 mW cm⁻² at the current density of 222.5 mA cm⁻², which is about 60%, 20% and 10% higher than that of α‐MnO₂ (90.0 mW cm⁻² at 120.3 mA cm⁻²), β‐MnO₂ (121.5 mW cm⁻² at 150.4 mA cm⁻²) and NMD (128.2 mW cm⁻² at 207.8 mA cm⁻²), respectively. It is believed that its unique crystal structure and biggest BET surface area make EMD have the smallest charge transfer resistance (R_ct), thus EMD has the highest activity.     

The electrochemical behaviour of a molten CF3COOK-CF3COONa eutectic

Electrolysis with platinum electrodes of a molten CF₃COOK-CF₃COONa mixture yields at the anode mainly CO₂ and C₂F₆; CF₄, C₃F₈ and C₂F₄ are also present in low quantities. At the cathode, only sodium is formed. The useful potential range of this molten electrolyte is 4·9 V at a current density of 1 mA cm^–2.     

Fluoroacidity evaluation in molten salts

The fluoroacidity of several alkaline fluoride media was studied by monitoring the concentration of electroactive species which is decreasing vs. time due to a gas species release, such as silicon fluorides, as indicated by the reaction: SiF_{4 + x}^x− = SiF_4(g) + xF⁻. This article relates the Si(IV) reaction study to define a relative fluoroacidity scale by studying the silicon ions stability in different melts. Electrochemical techniques allow the measurement of SiF_{4 + x}^x− concentration evolution and thus the reaction rate constant to be calculated at different temperatures and for several fluoride media. The article shows that the free F⁻ content depends on the fluoride mixture and that the rate values are correlated with the fluoroacidity allowing a qualitative estimation. Then a fluoride solvents fluoroacidity scale was proposed, scaling the different eutectic melts from basic melt to acidic one: NaF–KF < LiF–KF < NaF–MgF₂ < NaF–CaF₂ < LiF–NaF < LiF < LiF–CaF₂.     

Effects of manganese substitution at the B-site of lanthanum-rich strontium titanate anodes on fuel cell performance and catalytic activity

Sr_0.4La_0.6Ti_1−xMn_xO_3−δ with rhombohedral structure has been investigated in terms of their electrochemical performance, redox stability, and electro-catalytic properties for solid oxide fuel cell anodes. The performance of Sr_0.4La_0.6Ti_1−xMn_xO_3−δ anodes for solid oxide fuel cells strongly depends on the Mn substitution at the B-site of the perovskites. Electrical conductivity of Sr_0.4La_0.6Ti_1−xMn_xO_3−δ increases with increasing Mn content. X-ray photoelectron spectroscopy analysis reveals that the amount of Mn³⁺ and Ti³⁺, which is an electronic charge carrier, increases with Mn doping. The reduced anode powders with high Mn/Ti ratio show oxygen storage capability and a low carbon deposition rate. Linear thermal expansion coefficients of Sr_0.4La_0.6Ti_1−xMn_xO_3−δ anodes range from 9.46×10⁻⁶ K⁻¹ to 11.3×10⁻⁶ K⁻¹. The maximum power densities of the single cell with the Sr_0.4La_0.6Ti_0.2Mn_0.8O_3−δ anode in humidified H₂ and CH₄ at 800 °C are 0.29 W cm⁻² and 0.24 W cm⁻², respectively.     

Electrochemical degradation of Ibuprofen on Ti/Pt/PbO2 and Si/BDD electrodes

The electrochemical oxidation of Ibuprofen (Ibu) was performed using a Ti/Pt/PbO₂ electrode as the anode, prepared according to literature, and a boron doped diamond (BDD) electrode, commercially available at Adamant Technologies. Tests were performed with model solutions of Ibu, with concentrations ranging from 0.22 to 1.75 mM for the Ti/Pt/PbO₂ electrode and 1.75 mM for the BDD electrode, using 0.035 M Na₂SO₄ as the electrolyte, in a batch cell, at different current densities (10, 20 and 30 mA cm⁻²). Absorbance measurements, Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC) tests were conducted for all samples. The results have shown a very good degradation of Ibu, with COD removals between 60 and 95% and TOC removals varying from 48 to 92%, in 6 h experiments, with higher values obtained with the BDD electrode. General Current Efficiency and Mineralization Current Efficiency, determined for both electrodes, show a similar behaviour for 20 mA cm⁻² but a very different one at 30 mA cm⁻². The combustion efficiency was also determined for both anodes, and found to be slightly higher with BDD at lower current density and equal to 100% for both anodes at 30 mA cm⁻².     

CO tolerance of PdPt/C and PdPtRu/C anodes for PEMFC

The performance of H₂/O₂ proton exchange membrane fuel cells (PEMFCs) fed with CO-contaminated hydrogen was investigated for anodes with PdPt/C and PdPtRu/C electrocatalysts. The physicochemical properties of the catalysts were characterized by energy dispersive X-ray (EDX) analyses, X-ray diffraction (XRD) and “in situ” X-ray absorption near edge structure (XANES). Experiments were conducted in electrochemical half and single cells by cyclic voltammetry (CV) and I-V polarization measurements, while DEMS was employed to verify the formation of CO₂ at the PEMFC anode outlet. A quite high performance was achieved for the PEMFC fed with H₂ + 100 ppm CO with the PdPt/C and PdPtRu/C anodes containing 0.4 mg metal cm⁻², with the cell presenting potential losses below 200 mV at 1 A cm⁻², with respect to the system fed with pure H₂. For the PdPt/C catalysts no CO₂ formation was seen at the PEMFC anode outlet, indicating that the CO tolerance is improved due to the existence of more free surface sites for H₂ electrooxidation, probably due to a lower Pd-CO interaction compared to pure Pd or Pt. For PdPtRu/C the CO tolerance may also have a contribution from the bifunctional mechanism, as shown by the presence of CO₂ in the PEMFC anode outlet.