Structural and electrochemical characterization of mechanochemically synthesized calcium zincate as rechargeable anodic materials

Hydrated calcium zincate was synthesized by mechanical ball milling of ZnO and Ca(OH)₂ in water at room temperature. The structural and electrochemical properties of this material used as rechargeable anodic material were examined by microelectrode voltammetry, charge–discharge measurements and structural analysis. The results showed that during mechanical milling, ZnO, Ca(OH)₂ and H₂O reacted rapidly to form Ca[Zn(OH)₃]₂ · 2H₂O which was subsequently transformed to a stable structure CaZn₂(OH)₆ · 2H₂O. Since this composite oxide has lower solubility in KOH solution (<35 wt %) and better electrochemical reversibility than ZnO-based negative materials, the zinc anodes using this material can overcome the problems of shape changes and dendritc formation, and therefore exhibit improved cycling life.     

Oxidation of methanol on nickel—zinc catalysts

The activity of nickel—zinc and smooth nickel electrodes for methanol oxidation is investigated in KOH 1 M + CH₃OH 1 M at 60°C. Nickel—zinc alloys of different composition are easily obtained from electrodeposition. After their attack in KOH 1 M, the electrodes contain about 50% of zinc and they have the βNiZn alloy structure. The I(V) curves are compared. On smooth nickel the oxidation of methanol is strongly inhibited by the superficial oxides whereas on nickel—zinc electrodes superficial oxides are easier to reduce. The effect of adsorbed hydrogen and of mixed oxides is discussed.     

Degradation mechanisms of nickel oxide electrodes in zinc/nickel oxide cells with low-zinc-solubility electrolytes

Nickel oxide electrodes that suffered capacity degradation during extended cycling in zinc/nickel oxide cells were examined by a variety of chemical and physical techniques. Nickel hydroxyzincates, which have been speculated to cause such capacity degradation, were also examined. Powder X-ray diffraction experiments indicated that the intersheet distance between layers of turbostratic nickel hydroxide increased when zinc was incorporated. Photoelectron spectra (XPS) showed that this material is probably a mixture of NiOH)₂ and ZnO or Zn(OH)₂. Raman spectroscopy data also supported this conclusion. XPS indicated that the form of zinc in degraded nickel oxide electrodes is probably ZnO or Zn(OH)₂. Significant increases in resistivity were found in cycled nickel oxide electrodes, and optical microscopy provided visible evidence of mechanical damage during cycling. These results suggest that the observed capacity degradation was largely mechanical in nature, and not due to the formation of nickel-zinc double hydroxides, as had been reported by others. Cell-cycling experiments indicated that the mechanical degradation is largely irreversible.     

ZINC ELECTRODE CYCLE-LIFE PERFORMANCE IN ALKALINE ELECTROLYTES HAVING REDUCED ZINC SPECIES SOLUBILITY

Electrolytes having 3.5 M hydroxide-ion concentration were tested in 1.35 Ah Zn/NiOOH cells to evaluate their ability to reduce the extent of zinc species migration and slow the rate of cell capacity decline. Alkaline-fluoride and alkaline-borate electrolytes, in which ZnO solubility is approximately 25° of that in standard 7.4 M KOH electrolyte, exhibited 0.09-0.14^°/cycle zinc-electrode area loss, which may be compared to a value of 0.46^°/cycle observed in standard electrolyte, In addition, no zinc penetration of the separator occurred in cells that employed alkaline-fluoride and alkaline-borate electrolytes, even when zinc-electrode overpotcntials reached 290 mV at the end of charge. Less than 2^° of the zinc remaining after cycling was electrochemically inactive.     

Aspects of nickel-cadmium cells in single cycle applications. III. Effects of electrolyte additives on cadmium hydroxide crystal growth in sintered nickel negative electrodes during discharged storage

The single duty cycle application requires nickel-cadmium cells to be stored for long periods in a discharged, short-circuited state. Under these conditions Cd(OH)₂ active material in the negative electrode is subject to crystal growth processes which result in reduced charge efficiency when cycled after storage. Of equal importance, however, is the observed gross redistribution of Cd(OH)₂ active material, whereby crystals penetrate into the separator, sometimes as far as the positive electrode. This must be considered undesirable and could lead to internal short-circuiting of the cell. This paper examines the effects of various surfactant electrolyte additives on Cd(OH)₂ crystal growth and capacity of sintered, negative electrode material, stored in excess 6 M KOH, at various temperatures between +30 and +60°C. Results show that, under the test conditions, low concentrations (0.1%) of the anionic surfactants sodium lauryl sulphate and turkey red oil strongly suppress Cd(OH)₂ growth and result in markedly higher aged electrode capacities compared to control electrodes stored in the absence of these additives.     

Cyclic voltammetric study of zinc and zinc oxide electrodes in 5.3 M KOH

The behaviour of zinc and zinc oxide in 5.3 M KOH in the presence of alkaline earth oxides, SnO, Ni(OH)₂ and Co(OH)₂ was examined by cyclic voltammetry. The influence of the alkaline earth oxides was compared with additives of established effects (Bi₂O₃, LiOH, Na₂CO₃ and CdO). The alkaline earth oxide each exhibits a distinct behaviour towards zincate. Whereas, a single process of interaction with zincate was shown by CaO; two modes of reaction were obtained with SrO and BaO. Solid solution formation was noticed with BeO and MgO. The other additives forming solid solution with ZnO were CdO, SnO. The ionic sizes of Ni(OH)₂ and Co(OH)₂ allow solid solution formation with Zn(OH)₂. Both Bi₂O₃ and Na₂CO₃ enter into complexation with zincate. LiOH forms two distinct zincates, of which one is an oxo zincate leaching the `hydroxyl' functionality. Cyclic voltammetry revealed the deposition of the oxide/hydroxide additives as metal prior to the onset of zinc deposition and the potential range for this additive metal deposition is almost the same for different additives (SnO, CdO, Ni(OH)₂). The beneficial action of these additives to zinc alkaline cells is associated with a substrate effect. The implication of this electrocatalytic deposition of metals on a zinc oxide electrode is also discussed.     

Cathodic reduction of the anodically formed zinc species as a contribution to the study of the potentiodynamic passivation of zinc in alkaline media

The cathodic part of the potentiodynamic curves obtained for upward-facing horizontal 99.9% zinc electrodes in KOH solutions 0.4, 1.0, 2.0 and 3.0 M and sweep rates in the range 1–100 mV s⁻¹ have been systematically analyzed in order to assign the possible species formed and contribute to the study of the potentiodynamic passivation of Zn in alkaline media. The anodic limit of the potentiodynamic cycles was changed and set for significant points of the total curve (between hydrogen and oxygen evolution). Also, the anodic sweep was interrupted at the potentials corresponding to the anodic limit and the cathodic sweep applied immediately from a potential near that of zero current of the cathodic half-cycle. Only two cathodic peaks have been found for the non-interrupted cycles. The assignation of peaks according to the equilibrium potentials of the reduction of the possible species implied, ie Zn(OH)²⁻₄, Zn(OH)₂ and ZnO, is not possible because local pH changes are expected and the zincate concentration near the electrode is unknown. The peak placed at more positive potentials for KOH concentrations 0.4 and 1.0 M is assigned to zincate and that at more negative potentials, to the reduction of the film. Just the opposite assignation has been found for 2.0 and 3.0 M KOH solutions. The experimental results can be interpreted assuming that the product formed at the passivation potential consists of the same chemical species as those corresponding to the first anodic peak, probably Zn(OH)₂ or hydrated ZnO. From calculating the maximum film thickness according to the charge passed and taking into account the recent theoretical analysis made by Chang and Prentice, it is concluded that the direct formation of ZnO on the electrode at the passivation potential as a consequence of local pH changes is not probable.     

Voltage decay at passivated zinc anodes

A study has been made of the passivating process at a zinc electrode in KOH solutions. Zinc electrodes were passivated at a constant overpotential and the current response during passivation was measured. The potential response after the passivating potential was removed was also measured.The current during passivation soon reached a semi-steady-state value which increased with increasing overpotential but varied only slightly with changing KOH concentrations.When electrodes were passivated at overpotentials >325 mV, the open circuit voltage decay showed an arrest, the duration of which decreased with increasing KOH concentration. This duration increased when ZnO was dissolved in the electrolyte, when the temperature was decreased, and when the passivating overpotential was increased.The results are interpreted by assuming that passivation is due to the formation of a film, possibly Zn(OH)₂, which can dissolve in the electrolyte. The potential of the electrode is a mixed potential.     

Supercritical hydrothermal synthesis of nano-ZnO: Effects of key parameters and reaction mechanism

In this paper, ZnO particles with the particle size as low as 23 nm were successfully prepared by supercritical hydrothermal synthesis technique. The particle size of nano-ZnO decreased with the increase of temperature and pressure. Nano-ZnO particles in ZnSO₄ system were spherical with smaller particle size. The discrepancy in nano-ZnO produced by different precursor of Zn(NO₃)₂, Zn(CH₃COO)₂ or ZnSO₄ is attributed to the anion effects and supersaturation. The particles in the KOH system (29 nm) were smaller than those in the NaOH system (44 nm). For precursor concentration, intermediate Zn(OH)₂ was generated at lower concentration, while Zn₄SO₄(OH)₆·4H₂O was produced at higher concentration. For alkali concentration, as the gradual increase of KOH concentration, Zn(OH)₂ began to decrease and gradually transformed into Zn(OH)₃^– and [Zn(OH)₄]²⁻. When the KOH concentration reached a certain value, [Zn(OH)₄]²⁻ occupied the dominance in the mixed solution.     

ZINC ELECTRODE CYCLE-LIFE PERFORMANCE IN ALKALINE ELECTROLYTES HAVING REDUCED ZINC SPECIES SOLUBILITY

Electrolytes having 3.5 M hydroxide-ion concentration were tested in 1.35 Ah Zn/NiOOH cells to evaluate their ability to reduce the extent of zinc species migration and slow the rate of cell capacity decline. Alkaline-fluoride and alkaline-borate electrolytes, in which ZnO solubility is approximately 25% of that in standard 7.4 M KOH electrolyte, exhibited 0.09-0.14%/cycle zinc-electrode area loss, which may be compared to a value of 0.46%/cycle observed in standard electrolyte. In addition, no zinc penetration of the separator occurred in cells that employed alkaline-fluoride and alkaline-borate electrolytes, even when zinc-electrode overpotentials reached 290 mV at the end of charge. Less than 2% of the zinc remaining after cycling was electrochemically inactive.     

ZINC ELECTRODE CYCLE-LIFE PERFORMANCE IN ALKALINE ELECTROLYTES HAVING REDUCED ZINC SPECIES SOLUBILITY

Electrolytes having 3.5 M hydroxide-ion concentration were tested in 1.35 Ah Zn/NiOOH cells to evaluate their ability to reduce the extent of zinc species migration and slow the rate of cell capacity decline. Alkaline-fluoride and alkaline-borate electrolytes, in which ZnO solubility is approximately 25% of that in standard 7.4 M KOH electrolyte, exhibited 0.09-0.14%/cycle zinc-electrode area loss, which may be compared to a value of 0.46%/cycle observed in standard electrolyte. In addition, no zinc penetration of the separator occurred in cells that employed alkaline-fluoride and alkaline-borate electrolytes, even when zinc-electrode overpotentials reached 290 mV at the end of charge. Less than 2% of the zinc remaining after cycling was electrochemically inactive.     

Bond strength between C3S paste and iron,copper or zinc wire and microstructure of interface

Bond strength between C₃S paste and iron, copper or zinc wire and microstructure of the interfacial region were examined by pull-out test and scanning electron microscope respectively. The bond strength between C₃S paste and iron wire at 28-day curing is larger than that between C₃S paste and copper or zinc wire. In the case of iron and copper wires, CSH and Ca(OH)₂ are formed in the paste at the interface. On the other hand, Ca[Zn(OH)₃·H₂O]₂, CSH and Ca(OH)₂ are formed in between C₃S paste and zinc wire. The relation between the development of bond strength and curing time is characteristic according to the kind of metal wires.     

Effects of charge rate and cycling on the morphology of Cd and Cd(OH)2 in sintered plate electrodes

Optical and scanning electron microscopy have been used to study the growth and redistribution of Cd and Cd(OH)₂ in sintered plate electrodes as a function of charge rate and cycle number. As expected, the growth of both components was found to increase with increasing cycle number and decreasing charge rate. Because the deposits, particularly after extended cycling, always contained appreciable quantities of Cd metal in both the charged and discharged state, the sizes of Cd(OH)₂ crystallites were difficult to quantify. High charge and discharge rates promoted greater aggregation and redistribution of active material towards the electrode edge. This resulted in a considerable decrease in the available pore volume per unit mass of active material and in extreme cases to localized pore blockage. The trapping of Cd metal by highly crystalline, unchargeable hexagonal platelets of (-Cd(OH)₂ resulted in about 50% of the active material becoming obsolete after 100 cycles at high charge and discharge rates. At this stage only the finely divided Cd metal in the electrode interior continued to function. Low charge rates gave deposits of more uniform size and distribution but these contained a high percentage of large Cd particles which discharged less efficiently than those produced at the high charge rate.     

The zinc-chlorine battery: half-cell overpotential measurements

The voltaic performance of the zinc-chlorine battery was investigated by measuring the individual potentials of the Zn and Cl₂ electrodes versus a reference electrode. The overpotential at the Zn electrode is very small for both the charging and the discharging processes, and the use of a flow-through porous Cl₂ electrode is advantageous. Energy efficiency in the region of 65% has been achieved for a complete cycle. Tafel polarization data for both the zinc and the Cl₂/graphite electrodes was obtained using rotating zinc hemisphere and graphite disc electrodes. Exchange current densities and Tafel slopes are reported.     

Impedance study of hydrogen evolution on Ni/Zn and Ni–Co/Zn stainless steel based electrodeposits

A study on the electrocatalytic performance of Ni/Zn and Ni–Co/Zn alloys for hydrogen evolution reaction (HER) in alkaline media (30 wt.% KOH solution) has been carried out. After preparing by electrodeposition on stainless steel supports, the alloys were leached of to remove part of the zinc and generate a porous layer. For the developed electrodes, the surface roughness factor, R_f, was evaluated by electrochemical impedance spectroscopy (EIS). The HER on these electrodes was evaluated by means of steady-state polarization curves and EIS. The obtained electrodes were characterized by large R_f for HER, and very low overpotentials at the current density of 250 mA cm⁻², η₂₅₀ ∼ 0.138 V at 30 °C. The high electrode activity was mainly attributed to the high surface area of the developed electrodes.     

Synthesis and characterization of nano-sized calcium zincate powder and its application to Ni–Zn batteries

Nano-sized calcium zincate powders used as active materials for a secondary Zn electrode were prepared by a chemical co-precipitation method. The properties were studied by thermal gravimetric analysis (TGA), micro-Raman spectroscopy and nitrogen adsorption–desorption experiments. The secondary Zn electrodes using chemical co-precipitation calcium zincate powders (CP-ZnCa) and ball-milled calcium zincate powders (BM-ZnCa), were examined and compared. The electrochemical performance of the secondary Zn electrodes was systematically investigated by cyclic voltammetry and galvanostatic charge/discharge measurements. It was demonstrated that the electrochemical properties of the secondary Zn-pasted electrode using CP-ZnCa powders were greatly improved, as compared with conventional secondary ZnO electrodes. The results indicated that secondary Ni-Zn batteries using CP-ZnCa powders exhibited a better charge/discharge property and a longer life-cycle performance, compared with those based on ball-milled ZnO + Ca(OH)₂ (BM-ZnCa) powders.     

Effect of cations and anions on properties of zinc oxide particles synthesized in supercritical water

Hydrothermal synthesis of zinc oxide fine particles from zinc salt (Zn(CH₃COO)₂, ZnSO₄, Zn(NO₃)₂) and alkali metal hydroxide (LiOH, KOH) aqueous solution was carried out with a Ti alloy batch reactor in supercritical water. Particle size synthesized in LiOH solution was relatively smaller than that in KOH. Emission spectra of the particle produced from ZnSO₄ and LiOH aqueous solution shows the highest intensity among these systems. Hydrothermal synthesis of zinc oxide fine particles from Zn(NO₃)₂ and LiOH solution was also carried out with a flow-through apparatus for continuous production and rapid heating of the starting solution to supercritical states. Nanoparticles having an average particle diameter of 16 nm was produced at 659 K and 30 MPa.     

Modeling of an electrically rechargeable alkaline Zn-air battery

The charging and discharge behavior of an electrically rechargeable alkaline Zn-air battery consisting of a porous Zn/ZnO electrode on the negative side and a porous O₂ electrode on the positive side has been investigated. Galvanostatic experiments have been performed and a one-dimensional numerical model has been developed to analyze these experimental data. The cell voltages, the Zn electrode potentials versus Zn reference, and the O₂ electrode potentials versus Zn reference calculated with this model are in fairly good agreement with the corresponding experimental values. The unwanted redistribution of Zn per cycle is predicted to decrease with increasing cycle number. The numerical model is expected to be useful when optimizing zinc cell designs for specific applications.     

Etch rate studies of base catalyzed hydrolysis of polyimide film. II

The influence of a potassium carbonate (K₂CO₃) additive on the base catalyzed hydrolysis of polyimide (Kapton?) film in aqueous potassium hydroxide (KOH) was determined experimentally. The etch rate is significantly greater for KOH/K₂CO₃ solutions compared with solutions composed of KOH only. The experimental order of the reaction with respect to the KOH concentration was found to be 1.5. In addition, the rate was found to increase linearly with respect to the K₂CO₃ concentration at a fixed KOH concentration. Visual observations of a thinner gel layer on the surface of the film, combined with increased solubility of the etch by-products in KOH/K₂CO₃ relative to KOH, help to explain the difference in etch rate. It appears the ability of K₂CO₃ to enhance the solubility of the hydrolyzed polyimide (polyamic acid salt) results in faster etch rates.     

Dehydration,Water Vapor Adsorption and Desorption Behavior of Zn[B3O3(OH)5] · H2O and Zn[B3O4(OH)3]

The dehydration behaviors of two different hydrated zinc borate species, Zn[B₃O₃(OH)₅] · H₂O and Zn[B₃O₄(OH)₃], which are industrially important flame retardants, were studied by thermal gravimetric(TG) analysis and in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. Dehydration onset temperatures of Zn[B₃O₃(OH)₅] · H₂O and Zn[B₃O₄(OH)₃] were 129 and 320°C, respectively, at a 10°C/min ramp rate. A very small amount of boric acid was volatilized in addition to water vapor when both samples were heated at 250°C. A significant amount of water vapor was adsorbed by Zn[B₃O₃(OH)₅] · H₂O from air at 25°C. However, Zn[B₃O₄(OH)₃] adsorbed a very small amount of water under the same conditions. Both zinc borates did not have a tendency to cake during storage.