Electrochemical reduction of nitrates and nitrites in alkaline nuclear waste solutions

Sodium nitrate and nitrite are major components of alkaline nuclear waste streams and contribute to environmental release hazards. The electrochemical reduction of these materials to gaseous products has been studied in a synthetic waste mixture. The effects of electrode materials, cell design, and other experimental parameters have been investigated. Lead was found to be the best cathode material in terms of current efficiency for the reduction of nitrate and nitrite in the synthetic mix. The current efficiency for nitrite and nitrate removal is improved in divided cells due to the elimination of anodic oxidation of nitrite. Operation of the divided cells at high current densities (300–600 mA cm^–2) and high temperatures (80°C) provides more efficient reduction of nitrite and nitrate. Nearly complete reduction of nitrite and nitrate to nitrogen, ammonia, or nitrous oxide was demonstrated in 1000 h tests in a divided laboratory electrochemical flow cell using a lead cathode, Nafion® 417 cation exchange membrane, and oxygen evolving DSA® or platinum clad niobium anode at a current density of 500 mA cm^–2 and a temperature of 70° C. Greater than 99% of the nitrite and nitrate was removed from the synthetic waste mix batch in the 1000 h tests at an overall destruction efficiency of 55%. The process developed shows promise for treating large volumes of waste.     

A direct methanol fuel cell using acid-doped polybenzimidazole as polymer electrolyte

A direct methanol/oxygen solid polymer electrolyte fuel cell was demonstrated. This fuel cell employed a 4 mg cm^–2 Pt-Ru alloy electrode as an anode, a 4 mg cm^–2 Pt black electrode as a cathode and an acid-doped polybenzimidazole membrane as the solid polymer electrolyte. The fuel cell is designed to operate at elevated temperature (200°C) to enhance the reaction kinetics and depress the electrode poisoning, and reduce the methanol crossover. This fuel cell demonstrated a maximum power density about 0.1 W cm^–2 in the current density range of 275–500 mA cm^–2 at 200°C with atmospheric pressure feed of methanol/water mixture and oxygen. Generally, increasing operating temperature and water/methanol mole ratio improves cell performance mainly due to the decrease of the methanol crossover. Using air instead of the pure oxygen results in approximately 120 mV voltage loss within the current density range of 200–400 mA cm^–2 .     

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.     

Thermal battery cells utilizing molten nitrates as the electrolyte and oxidizer

The Ca/LiNO₃-LiCl-KCl (50-25-25 mol%) thermal battery cell can be activated at 160° C and operated over a temperature range of 250–450° C to produce 2.5–2.8 V at open-circuit and initial operating voltages above 2 V at 10 mA cm^–2. At operating temperatures between 250 and 350° C, this system shows promise for applications requiring a sixty-minute thermal battery. Cell lifetimes decrease at higher temperatures due to the accelerating reaction of calcium with the molten nitrate salt to form gaseous products. An experimental energy density value of 142 Whkg^–1 was obtained at 300° C during constant current discharge at 10 mAcm^–2. Effects of applied face pressure on cell discharge characteristics were small. At current densities above 20–30 mA cm^–2, the cell performance deteriorates due to polarization at the anode. This is probably caused by the precipitation of CaO which blocks the active sites at the anode.     

Experimental results on the direct electrochemical oxidation of methanol in PEM fuel cells

The cell performance of direct methanol fuel cells (DMFC) is 0.5 V at 0.5 A cm^–2 under high pressure oxygen operation (3 bar abs.) at 110 °C. However, high oxygen pressure operation at high temperatures is only useful in special market niches. Therefore, our work has now focused on air operation of a DMFC under low pressure (up to 1.5 bar abs.). At present, a power density of more than 100 mW cm^–2 can be achieved at 0.5 V on air operation at 110 °C. These measurements were carried out in single cells with an electrode area of 3 cm² and the air stoichiometry only amounted to 10. The effects of methanol concentration and temperature on the anode performance were studied by pseudo half cell measurements and the results are presented together with their impact on the cell voltage. A cell design with an electrode area of 550 cm², which is appropriate for assembling a DMFC stack, was tested. A three-celled stack based on this design revealed nearly the same power densities as in the small experimental cells at low air excess pressure and the voltage–current curves for the three cells were almost identical. At 110 °C a power output of 165 W at a stack voltage of 1.5 V can be obtained in the air mode.     

Performance and thermodynamic properties of Na-Sn and Na-Pb molten alloy electrodes for alkali metal thermoelectric converter (AMTEC)

An alkali metal thermoelectric converter (AMTEC) testing cell was set up, and run with molten sodium-tin (Na-Sn) and sodium-lead (Na-Pb) alloy cathodes. The Na activity, the partial molar enthalpy and partial molar entropy of sodium in molten Na-Sn and Na-Pb alloys have been determined, using a Na concentration cell: Na(1) I beta-alumina Na-Me(1), where Me= Sn or Pb. The thermodynamic results of these investigations agree with those of other authors. The electric performance of these Na-Me alloy electrodes of different Na concentration and temperatures is described, measuring current-voltage characteristics and a.c. impedance in the AMTEC test cell. The power density of the AMTEC cell with molten alloy cathodes decreases with increasing Na concentration, with the Na concentrations in molten alloys varying from 0.5 to 15 mol%. Maximum power densities of 0.21 to 0.15 W cm^–2 at 700°C for Na-Sn molten electrodes, and 0.30 to 0.15 W cm^–2 for Na-Pb molten electrodes have been obtained. The a.c. impedance data demonstrated that the molten alloy electrodes have a smaller cell resistance, 0.3–0.35 S2 cm^–2 at 700°C after 10–20 h. Comparison with the sputtered thin, porous film electrodes, showed that the contact resistance between electrode and surface of beta-alumina plays an important role on enhancing cell power density. At 700°C the power density of an AMTEC cell with the molten Na-Pb alloy electrode can be raised to values of about 0.2 W cm eat current densities of 0.8 A cm^–2, but at cell voltages not exceeding 0.2V. A model for the theoretical efficiency of the AMTEC cell with molten Na metal electrodes is also presented.     

New structures of thin air cathodes for zinc–air batteries

Thin composite cathodes for air reduction were manufactured using microfibre-based papermaking technology. The electrodes have a thin structural design, less than 0.15 mm in thickness. Composite cathode materials for oxygen reduction applications were fabricated by entrapping carbon particles in a sinter-locked network of 2–8 m diameter metal fibres. The thin structure not only results in electrodes that are 30–75% thinner than those commercially available, but also offers an opportunity for custom-built air cathodes optimized for high-rate pulse applications. Using a thin composite structure for the air cathode in a zinc–air battery that is part of a zinc–air/capacitor hybrid is likely to increase the pulse capability of the hybrid power system. The thin cathode structure provides a better, more efficient three-phase reaction zone. In a half-cell test, the ultrathin air cathode generated more than 1.0 V vs Zn/ZnO for a current of 200 mA cm^–2. Half-cell, full-cell and pulse-power tests revealed that thin composite cathodes have a better rate and pulse performance than the air cathodes commonly used.     

IrO2-deposited Pt electrocatalysts for unitized regenerative polymer electrolyte fuel cells

An IrO₂/Pt electrocatalyst for the polymer electrolyte-type unitized regenerative fuel cell (URFC) was prepared by deposition of iridium oxide (IrO₂) particles on Pt black via a colloidal iridium hydroxide hydrate precursor, and URFC performance was examined. After the iridium hydroxide hydrate deposited Pt was calcined at 400 °C in air for 1 h, rutile-structure IrO₂ particles (20–50 nm dia.) were formed on Pt particle clusters. TEM and pore volume distribution analysis revealed that the microstructure of the deposited IrO₂/Pt catalyst was different from the mixed IrO₂/Pt catalyst. The cell using the deposited IrO₂/Pt (20 at % Ir) catalyst showed similar fuel cell performance with the mixed IrO₂/Pt electrode of higher Pt content (10 at % Ir) while maintaining water electrolysis performance. Consequently, 51% round-trip energy conversion efficiency at a current density of 300 mA cm^–2 was attained.     

The effect of current density and temperature on the degradation of nickel cermet electrodes by carbon monoxide in solid oxide fuel cells

The oxidation of dry carbon monoxide (CO) in intermediate temperature solid oxide fuel cells (IT-SOFCs) has been studied using a three electrode assembly. Ni/CGO:CGO:LSCF/CGO three electrode pellet cells at 500, 550 and 600 °C were exposed to dry carbon monoxide for fixed periods of time, at open circuit and under load at 50 and 100 mA cm⁻², in an aggressive test designed to accelerate electrode degradation. It is shown that if the anode is kept under load during exposure to dry CO, degradation in anode performance can be minimised, and that under most conditions the anode showed significant irreversible degradation in performance after subsequent load cycling on dry H₂. Only at 500 °C and at 100 mA cm⁻² was the degradation in performance after operation on dry CO and subsequent load cycling on dry H₂ within the background degradation rates measured. Where anode performance was compromised, this appeared to be caused by a reduction in the exchange current density for hydrogen oxidation, and the relatively large degradation after load cycling on dry H₂ was primarily caused by an increase in the series resistance of the anode. It is suggested that this increase in series resistance is associated with the removal of carbon deposited in the non-electrochemically active region of the electrode during operation on dry CO, and that operation under load inhibits carbon deposition in the active region.     

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.     

Preparation and electrochemical characteristics of a new Li-Mn-V-O system formed from heat-treatment of a MnO2, NH4VO3 and LiNO3 mixture

New quarternary oxides (Li₂O) _x · MnO₂ · yV₂O₅ (x = 0.125 0.25, y = 0.125 0.25), formed by heating mixtures of MnO₂, NH₄VO₃ and LiNO₃ at various Li/Mn and V/Mn atomic ratios and at different temperatures (300 400 °C in air, have been characterized by X-ray diffraction, X-ray photoelectron spectroscopy (ESCA) and infrared spectroscopy. The quarternary oxide with x = 0.25 and y = 0.25 showed a discharge capacity of 220 A h (kg oxide)^–1 and an energy density of ca. 600 W h (kg oxide)^–1 at a current density of 0.20 mA cm^–1 in 1 m LiClO₄-propylene carbonate at 25 °C. When charge-discharge cycling with the (Li₂O) · MnO₂ · 0.25V₂O₅ electrode was performed at a constant capacity of 30 A h (kg oxide)^–1 and at a constant current density of 0.10 0.20 mA cm^–2, the electrode sustained over 100 cycles at a high mean discharge potential of ca. 3 V vs Li/Li⁺.This paper was originally presented at the 183rd meeting of the Electrochemical Society (Honolulu, Hawaii, 1993).     

Current efficiency during anodic dissolution of iron to ferrate(vi) in concentrated alkali hydroxide solutions

The dependence of the current efficiency for oxidation of an iron anode to ferrate(vi) ions in 14m NaOH was measured in the region of free convection. The highest current yield of 40% was obtained at a current density of 2.1 mA cm^–2 and temperature of 30°C. The iron anode was activated by cathodic prepolarization. The iron concentration in low oxidation states in solution was determined as 0.13 ± 0.1 and 0.29 ± 0.25 g Fe dm^–3 at 20 and 30°C, respectively. The steady state anodic polarization curves of iron in the transpassive potential region are shifted to lower potential values with increasing NaOH concentration from 11 to 171 m. At 40°C all the curves show a limiting current density around 660 mV vs Hg/HgO, namely 9 and 23 mA cm^–2 at NaOH concentrations of 11 and 17 m, respectively.     

Electrodeposition of Ni-W-B amorphous alloys

Partial polarization curves at the glassy carbon rotating disc electrode have been used to study the electrodeposition of Ni and Ni-W alloy from citrate-containing solution. For deposition of Ni-W alloys, the partial polarization curves indicate diffusion control for nickel reduction and stoichiometric limitation for tungsten deposition by the composition of the alloy. Plating experiments show that current efficiency of the electrodeposition and composition of the resulting alloy depend on the parameters of the electrolysis. The best conditions for electrodeposition of the alloy Ni-W-B are current density of 45–50 mA cm^–2, temperature of 60–70 °C, Ni(II) concentration of 20–25 mm, and pH 8.5. Pulsed galvanostatic plating at 1 Hz increased slightly the current efficiency. The concentration of Ni(II) in the solution can be self-regulated by using a nickel bipolar electrode in the cathode compartment.     

An oxygen electrode for air-consuming proton exchange membrane fuel cells for transportation applications

Electrodes for air-driven PEMFCs for transport applications have been developed. The structure of the electrodes has been specifically adapted to run with air as oxidant under near atmospheric pressure; such electrodes can be manufactured using conventional industrial methods and be easily scaled up. The technology has been demonstrated on a 50 cm² electrode area, assembled together with a Nafion® 117 membrane. Electrodes with different platinum loading, namely 0.4 and 0.2 mg Pt cm^–2, have been the subject of long duration tests which show a slow degradation of the cell performance. With air as oxidant at 180 kPa absolute pressure, 80°C as cell temperature and Nafion® 117 as membrane, a power density of 350 mW cm^–2 has been obtained.     

A Novel Type of Nanoporous Carbon Material Supporting High Dispersion of Rhodium Nanoparticles

Nanoporous carbon (NC) was prepared by the controlled pyrolysis of copolymer of vinylidene chloride and acrylonitrite. These organicinorganic hybrid polymers were synthesized by suspending polymerization. After gradually controlled pyrolysis at 180–300 °C under nitrogen stream, the resulting material was carbonized at 1000 °C for 3h under argon stream. In this way, nanoporous carbon was obtained, which has uniform pore size in the range of 0.8–1.6nm and specific surface area of 900–1000 m² g^-1. The surface morphology and chemical composition were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Rhodium particles kept in a highly dispersed state over it were prepared and characterized by XPS and transmission electron microscopy (TEM). The expected high catalytic activity of the final material for methanol carbonylation was observed experimentally.     

Partially immersed gas-diffusion electrodes

A new type of partially immersed carbon gas-diffusion electrode with a sandwich-like structure consisting of two active layers each side of the gas-supplying layer is described. The current collector grid is embedded into the electrically conductive gas-supplying layer. A theoretical model of the partially immersed electrodes is proposed and experimentally confirmed. The model can be used for the theoretical prediction of the steady state behaviour of partially immersed electrodes from experimental data obtained with non-immersed gas-diffusion electrodes. An experimental zinc-air battery of 1900 A h capacity with the new type of partially immersed carbon air gas-diffusion electrodes has shown a specific energy density of 250 W h kg^–1 and 420 W h 1^–1 at a current density of 0·5 mA cm^–2.     

The Effect of Aluminum Ions on the DC Etching of Aluminum Foil

A study has been made of the electrochemical etching of 99.99% aluminum foils at a current density of 50 mA cm^–2in AlCl₃–HCl solutions (1 m Cl^–) at 80 °C. The solutions were made by dissolving metallic aluminum into 1m HCl solution, to give a Cl^– concentration of 1 m. The number density of etch tunnels and the homogeneity of tunnel length decreased, and the mean pit size and its standard deviation increased with increasing Al³⁺ concentration. The results were discussed based on potential transients at a current density of 50 mA cm^–2, current–potential curves at a scan rate of 10 m Vs^–1 and electrochemical impedance spectra.     

Microbial fuel cells operated with iron-chelated air cathodes

The use of non-noble metal-based cathodes can enhance the sustainability of microbial fuel cells (MFCs). We demonstrated that an iron-chelated complex could effectively be used as an aerated catholyte or as an iron-chelated open air cathode to generate current with the use of MFCs. An aerated iron ethylenediaminetetraacetic acid (Fe-EDTA) catholyte generated a maximum current of 34.4 mA and a maximum power density of 22.9 W m⁻³ total anode compartment (TAC). Compared to a MFC with a hexacyanoferrate catholyte, the maximum current was similar but the maximum power was 50% lower. However, no replenishment of the Fe-EDTA catholyte was needed. The creation of an activated carbon cloth open air cathode with Fe-EDTA–polytetrafluoroethylene (PTFE) applied to it increased the maximum power density to 40.3 W m⁻³ TAC and generated a stable current of 12.9 mA (at 300 mV). It was observed that the ohmic loss of an open air cathode MFC was dependent on the type of membrane used. Moreover, increasing the anode electrode thickness of an open air cathode MFC from 1.5 to 7.5 cm, resulted in a lowering of the power and current density.     

Electrowinning of zinc from alkaline solutions

The objective of this work was to determine the best conditions for minimizing energy consumption in zinc electrowinning from alkaline solutions. The effects of several variables, i.e. hydroxide concentration (300–500 gl^–1), current density (50–1000 A m^–2), temperature (24–74°C), cathode material (magnesium, nickel, lead, stainless steels 304 and 316) and impurities (copper and arsenide) on current efficiency and cell voltage were investigated. The current efficiency was always 100% on magnesium except in the presence of arsenide (78% at 100 mg l^–1). With cathode materials such as stainless steels 304 and 316, nickel and lead, hydrogen evolution was observed at the beginning of electrolysis. Hydroxide concentration did not have a significant effect on cell voltage.Specific energy was low, even at 1000 A m^–2, and decreased with rising temperature, being only 2.17 kW h kg^–1 at 74°C. No redissolution of the deposit was observed. Decreasing distance between electrodes and using active anodes permitted a further reduction of specific energy to 1.75 kW h kg^–1. Decreasing space between electrodes was possible as no dendritic deposits were observed.     

DDQ cathodes for seawater cells

A positive electrode containing 2,3-dichloro-5,6-dicyano-p-quinone (DDQ) as the cathode active material was discharged in a magnesium seawater cell at room temperature. Analysis of the dissolved species of DDQ in water and potential sweep voltammetry studies were also carried out. The open circuit voltage of the DDQ-Mg cell was as high as 2.2 V and the single cell could be discharged at current densities greater than 50 mA cm^–2. However, the current efficiencies for the DDQ cathodes in a three-cell immersion-type battery were not high enough for high drain applications, probably due to a high leak current through the common electrolyte.