Structural modifications induced by the second discharge process in the Ni(OH)2/NiOOH redox system

Electrochemical behavior and related structural modifications of the nickel hydroxide/oxyhydroxide electrode are investigated as a function of the reduction state achieved on discharge. Reduction proceeds at two successive potential steps, with recovering of the initial structural properties only after the second discharge process. Active material cycled in the positive potential range (vs. Hg/HgO), including only the first discharge step, is non-stoichiometric and characterized by high lattice defect content. Whatever the oxidation state, the presence of Ni³⁺ defects and protonic delocalization are observed. The 2nd discharge process restores O-H covalent bonds and a better defined Ni(II) state, similar to the precursor nickel hydroxide chemically obtained. Electrochemical cycling in the positive potential range is characterized by the retention of the same nanocrystallite dimension and a high fragmented morphology, while the 2nd discharge induces crystallite agglomeration. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Structural aspects of undoped and doped nickel hydroxides

Nickel hydroxide is widely used as an active material in Ni-Cd and Ni-MeH batteries. The electrochemical properties such as charge acceptance, electronic conductivity etc. can be dramatically influenced by doping β-Ni(OH)₂ with small amounts of Co, Cd or Zn. Stabilizing of α-Ni(OH)₂ offers the possibility to obtain nickel electrodes with enhanced capacity. The stabilizing of α-Ni(OH)₂ is achieved by replacing at least 20% of the nickel by a trivalent metal ion. The structural features of the undoped and doped nickel hydroxides and the resulting electrochemical properties are discussd and reviewed. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Effect of synthesis temperature on the phase structure and electrochemical performance of nickel hydroxide

Nickel hydroxide powder is prepared by chemical precipitation method, and the effect of synthesis temperature on the phase structure and electrochemical performances of nickel hydroxide is investigated. The phase structure is characterized by X-ray diffraction (XRD), and the electrochemical performances are characterized by cyclic voltammetry, electrochemical impedance spectroscopy, and charge/discharge tests. The XRD results show that low temperatures (0–20 °C) induce the precipitation of badly crystallized nickel hydroxide while at high temperatures (40–60 °C) crystallized β-nickel hydroxide is formed. Electrochemical performance tests show that the nickel hydroxide synthesized at low temperature has better electrochemical reversibility, lower electrochemical reaction impedance, and higher discharge capacity than that of the nickel hydroxide synthesized at high temperature.     

Structural and electrochemical characterization of nickel hydroxide obtained by the new synthesis route of electrodialysis. a comparison with spherical β-Ni(OH)2

Both structural and electrochemical properties of non-doped nickel hydroxide produced by a new synthesis route of electrodialysis are investigated. A comparison with two spherical β-type Ni(OH)₂ is made. Structural characterization is carried out by X-ray diffraction, vibrational spectroscopy and thermal analysis. Electrochemical properties are studied by cyclic voltammetric and chronoamperometric experiments. The material obtained by electrodialysis is found to have a highly defective structure, which corresponds to a complex electrochemical behavior. More particlarly, it is shown that this new nickel hydroxide is more stable regarding the β → γ transformation. Project financed by the E.U. under the Brite Euram program (#BRPR-CT97-0515) Paper presented at the 6th Euroconference on Solid State Ionics, Sept. 12–19, 1999, Cetraro, Calabria, Italy     

Electrochromic and electrochemical properties of amorphous porous nickel hydroxide thin films

Nickel hydroxide films were prepared using the chemical bath deposition (CBD) technique. The amorphous nature of the films was confirmed by X-ray diffraction measurements. X-ray photoelectron spectroscopy (XPS) measurements showed that the films exhibited nickel hydroxide nature. The porosity of the films was studied using optical measurements. The electrochromic properties of the porous nickel hydroxide layers were investigated, using cyclic voltammetry, chronoamperometry, in situ transmittance, UV-vis spectroscopy, and impedance spectroscopy. The change in the optical density (ΔOD) was found to be 0.79 for the as-deposited nickel hydroxide films, whereas it is 0.53 and 0.50 for the films annealed at 150 °C and 200 °C, respectively. The in situ transmittance and chronoamperometry curves revealed that the annealed films had a very fast colouration (t_c < 290 ms) and decolouration (t_b < 130 ms). The measured colouration efficiencies range between 30 and 40 cm²/C. The impedance measurements revealed the faster colouration and good electrochromic properties for the annealed nickel hydroxide films.     

Synthesis and electrochemical performance of amorphous nickel hydroxide codoped with Fe<Superscript>3+</Superscript> and CO<Stack><Subscript>3</Subscript><Superscript>2−</Superscript></Stack>

Amorphous nickel hydroxide codoped with Fe³⁺ and CO₃²⁻ was synthesized by micro-emulsion precipitation method combined with rapid freezing technique. The microstructure and composition of the sample were characterized by X-ray diffraction and IR analysis. The electrochemical performance of the sample was analyzed by cyclic voltammetry, electrochemical impedance spectroscopy, and charge–discharge tests. The results showed that the Fe³⁺ and CO₃²⁻ codoping enhances the amorphous feature of the prepared nickel hydroxide. Moreover, the Fe³⁺ and CO₃²⁻ codoping could increase the specific capacity and improve the electrochemical reversibility of the amorphous nickel hydroxide electrode.     

Optical properties and electronic structure of YNi<Subscript>5 − <Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> intermetallic compounds

The optical properties of hexagonal intermetallic compounds YNi_{5 − x} Cu _x (x = 0, 1, 2) have been investigated by ellipsometry in the spectral range of 0.22–15 μm. It is shown that the replacement of nickel atoms by copper atoms leads to local changes in the optical-conductivity spectra. A new absorption band is found at 3.5–4.5 eV; its intensity depends on the copper content. The plasma and relaxation frequencies of conduction electrons are determined. The electronic structure and interband optical conductivity of these compounds are calculated within the electron density functional theory using the pseudopotential method. The main parameters of the band structure and the total and partial densities of electronic states are determined. Qualitative agreement is obtained between the experimental and theoretical frequency dependences of the optical conductivity.     

Properties of NiO thin films deposited by chemical spray pyrolysis using different precursor solutions

NiO thin films have been deposited by chemical spray pyrolysis using a perfume atomizer to grow the aerosol. The influence of the precursor, nickel chloride hexahydrate (NiCl₂·6H₂O), nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O), nickel hydroxide hexahydrate (Ni(OH)₂·6H₂O), nickel sulfate tetrahydrate (NiSO₄·4H₂O), on the thin films properties has been studied. In the experimental conditions used (substrate temperature 350 °C, precursor concentration 0.2-0.3 M, etc.), pure NiO thin films crystallized in the cubic phase can be achieved only with NiCl₂ and Ni(NO₃)₂ precursors. These films have been post-annealed at 425 °C for 3 h either in room atmosphere or under vacuum. If all the films are p-type, it is shown that the NiO films conductivity and optical transmittance depend on annealing process. The properties of the NiO thin films annealed under room atmosphere are not significantly modified, which is attributed to the fact that the temperature and the environment of this annealing is not very different from the experimental conditions during spray deposition. The annealing under vacuum is more efficient. This annealing being proceeded in a vacuum no better than 10⁻² Pa, it is supposed that the modifications of the NiO thin film properties, mainly the conductivity and optical transmission, are related to some interaction between residual oxygen and the films.     

Ni-MH battery based on plasticized alkaline solid polymer electrolytes

Solid-state nickel metal hydride cells were fabricated using plasticized alkaline solid polymer electrolytes (ASPE) prepared from polyvinyl alcohol (PVA), potassium hydroxide (KOH), alumina (α-Al₂O₃), and propylene carbonate (PC). The ASPE film with PVA/KOH/α-Al₂O₃/PC/H₂O weight ratio of 1.00:0.67:0.09:2.64:1.32 and conductivity of (6.6 ± 1.7) × 10⁻⁴ S cm⁻¹ was used in fabrication of the electrochemical cells. To investigate the electrochemical properties of the plasticized ASPE, cells with the configuration Mg₂Ni/plasticized ASPE/Ni(OH)₂ were fabricated. At the eighth cycle with a current drain of 0.1 mA and plateau voltage of ∼1.1 V, the discharge lasted for 14 h before the cell was considered to have failed. The failure mode of the cell was due to the formation of thin Mg(OH)₂ insulating layers.     

Comparative study of transport properties relevant to a textured sol-gel PZT coating on Ni substrate

In this work, the preparation of PbZr_0.52Ti_0.48O₃ (PZT) thin films for piezoelectric applications on untextured and (200) textured nickel foil substrates is reported. Transport properties of the nickel substrate relevant to the sintering of PZT and their interaction with PZT are also reported in this paper. Sols of PZT were prepared and used to deposit films of thickness between 150–1000 nm by dip coating. PZT could be sintered to full density at <750 °C in air. Catastrophic oxidation of the Ni substrate could be avoided either by pre-oxidising a textured Ni foil or by the use of un-oxidised textured Ni foil. The PZT film obtained was also textured while the amount of nickel oxide formed was negligible and could not be detected by field emission electron microscopy, and barely detectable by X-ray diffraction. The films thus produced show a step forward in developing piezoelectric devices using more economic routes. Paper presented at the Patras Conference on Solid State Ionics - Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Optical and magneto-optical properties of Fe/Cu multilayered films: Influence of the modulation period and the bcc-fcc phase transition in iron

The optical and magneto-optical properties of multilayered film samples of the Fe/Cu system prepared by high-frequency sputtering on an Si(100) substrate are studied by ellipsometry and by measuring the equatorial Kerr effect (the δ _p effect) in the spectral range 0.25–7 μm. The optical characteristics, the plasma frequency ω _p and the relaxation frequency γ ₀ of the conduction electrons, and the δ _p effect are found as functions of the modulation period D=12.5–100 Å. Anomalous behavior of the optical and magneto-optical characteristics is discovered in short-period Fe/Cu structures. The results are discussed within a phenomenological theory of optical and magneto-optical properties for layered structures. Several factors, such as the indirect exchange interaction between the iron layers, the presence of a transition layer on the internal boundaries, the possible “magnetizing” of copper, and the formation of an fcc iron phase in the thin layers, are taken into account in the analysis of the experimental data. Zh. éksp. Teor. Fiz. 112, 1694–1709 (November 1997)     

Two-color photoionization spectroscopy of uranium in a U–Ne hollow cathode discharge tube

A U–Ne hollow cathode discharge tube is used as a source of uranium atomic vapors as well as a photoelectron/photoion detector for carrying out two-color three-photon photoionization spectroscopy of uranium. Using the uranium excitation transition 0 cm⁻¹ (⁵L ₆ ⁰ ) → 16 900.38 cm⁻¹ (⁷M₇) at 591.5-nm laser wavelength as a first step transition and scanning the wavelength of a second laser from 558 to 568 nm, high-lying odd-parity atomic levels of uranium are studied in the energy region 34 500–34 813 cm⁻¹. All the expected 21 odd-parity atomic levels identified by various researchers in this region are observed in a single spectrum, demonstrating the high sensitivity achieved therein. In addition to this, we have identified eight autoionization resonances of uranium starting from its odd-parity atomic level at 33 801.06 cm⁻¹ pumped by two-photon excitation. Four out of these eight autoionization resonances are observed for the first time.     

Optical properties of BiB3O6 with different phase matching orientations

Basic optical properties of the new nonlinear crystal BiB₃O₆ (BIBO) are measured for second harmonic generation (SHG) of 1064 nm radiation. These properties include the effective nonlinearities for different phase matching orientations, the corresponding acceptance bandwidths and the optical losses. Effective nonlinearities of up to 3.2 pm/V (ϕ=90°, θ=-11°) and losses of less than 0.1 %/cm at 1064 nm indicate that BIBO is a promising new nonlinear crystal for SHG of 1064 nm radiation. A two-dimensional measurement with high spatial resolution of the SHG efficiency and the optical homogeneity, clearly demonstrate the high optical quality of BIBO crystals now available. PACS 42.65.Ky; 42.70.Mp     

A three-step laser stabilization scheme for excitation to Rydberg levels in <Superscript>85</Superscript>Rb

We demonstrate a three-step laser stabilization scheme for excitation to nP and nF Rydberg states in ⁸⁵Rb, with all three lasers stabilized using active feedback to independent Rb vapor cells. The setup allows stabilization to the Rydberg states 36P_3/2–70P_3/2 and 33F_7/2–90F_7/2, with the only limiting factor being the available third step laser power. We study the scheme by monitoring the three laser frequencies simultaneously against a self-referenced optical frequency comb. The third step laser, locked to the Rydberg transition, displays an Allan deviation of 30 kHz over 1 second and <80 kHz over 1 hour. The scheme is very robust and affordable, and it would be ideal for carrying out a range of quantum information experiments.     

Optical characteristics of nickel and boron carbonitride films in Si(100)/Ni/BC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> structures

The optical characteristics of nickel films deposited on Si(100) substrates by vacuum thermal evaporation have been studied. The thickness and optical constants of the films are determined using monochromatic zero ellipsometry, while the inverse problems are solved within the three-layer optical model of the samples. It is shown that thermal annealing leads to a change in the optical constants of nickel films in the heating-temperature range of 500–900°C. Boron carbonitride layers deposited on silicon substrates with a nickel sublayer are analyzed within multilayer optical models, which make it possible to determine the refractive index and absorption coefficient distributions along the thickness of the synthesized Si(100)/Ni/BC _x N _y structure.     

Transverse discharge with prebreakdown ionization multiplication of electrons in the working media of N2- and HF-lasers

Results of an investigation of the characteristics of a transverse discharge with prebreakdown ionization multiplication of electrons in the working media of N₂(C-B)-and SF₆/H₂ chemical HF-lasers are reported. The conditions of initiation of a stable volume discharge in the discharge gap with low homogeneity of the electrical-field distribution are investigated. A quasisteady plasma based on N₂ molecules with a radiation duration of ≤0.5 μsec at transitions of the 2⁺-system and a homogeneous discharge in a SF₆/H₂=(3–7)/(1–2) kPa mixture, which is of interest for preionization of the working medium of an HF-laser by the predischarge method, are obtained. Uzhgorod State University, 46, Pidgirna Str., Uzhgorod, 294000, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 412–415, May–June, 1999.     

Structure and lithium storage performances of nickel hydroxides synthesized with different nickel salts

Nickel hydroxides with hierarchical micro-nano structures are prepared by a facile homogeneous precipitation method with different nickel salts (Ni(NO₃)₂·6H₂O, NiCl₂·6H₂O, and NiSO₄·6H₂O) as raw materials. The effect of nickel sources on the microstructure and lithium storage performance of the nickel hydroxides is studied. It is found that all the three prepared samples are α-nickel hydroxide. The nickel hydroxides synthesized with Ni(NO₃)₂·6H₂ or NiCl₂·6H₂O show a similar particle size of 20–30 μm and are composed of very thin nano-sheets, while the nickel hydroxide synthesized with Ni(SO₄)₂·6H₂O shows a larger particle size (30–50 μm) and consists of very thin nano-walls. When applied as anode materials for lithium-ion batteries (LIBs), the nickel hydroxide synthesized with NiSO₄·6H₂O exhibits the highest discharge capacity, but its cyclic stability is very poor. The nickel hydroxides synthesized with NiCl₂·6H₂O exhibit higher discharge capacity than the nickel hydroxides synthesized with Ni(NO₃)₂·6H₂O, and both of them show much improved cyclic stability and rate capability as compared to the nickel hydroxide synthesized with Ni(SO₄)₂·6H₂O. Moreover, pseudocapacitive behavior makes a great contribution to the electrochemical energy storage of the three samples. The discrepancies of lithium storage performance of the three samples are analyzed by ex-situ XRD, FT-IR, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) tests.     

Tailoring the microwave permittivity and permeability of composite materials

The microwave permittivity (ɛ_r) and permeability (μ_r) of composite materials are tailored by adding various loading agents to a host plastic and are subsequently modeled using the Maxwell Garnett theory and second order polynomials. With the addition of manganese zinc ferrite, strontium ferrite, nickel zinc ferrite, barium tetratitanate and graphite powders, materials with values of ɛ′, e″, μ′, μ″ as high as 22, 5, 2.5 and 1.7 have been obtained. Permittivity and permeability data are calculated at 2.0245 GHz from reflection and transmission measurements performed in a 7 mm coaxial test line. The Maxwell Garnett (MG) theory successfully models ɛ_r if the filling factor is less than 0.30 and ratio |ɛ₁| (host)/ |ɛ₂| (powder) is greater than 0.04. As this ratio decreases, the MG theory is shown to be independent of ɛ₂ and second order polynomials are used to effectively model the dielectric constant. Polynomials are also used for the ferrite composites because it was determined that the MG theory was unable to model μ_r. This deficiency is attributed to the difference of domain structures that exist in powdered and sintered ferrites.     

Stepwise synthesis of fine crystalline Ce-doped yttrium aluminum garnet in water medium in subcritical and supercritical conditions

In this paper the continuous stepwise method of a production of fine crystalline yttrium aluminum garnet doped with cerium (YAG: Ce³⁺) in supercritical water fluid (SCWF) are represented. The synthesis was carried out in water medium in two stages: first in subcritical conditions and then in an atmosphere of supercritical water fluid. The stoichiometric mixture of yttrium oxide and aluminum hydroxide in a water solution of cerium nitrate was maintained the certain time at 280°C and under vapor water pressure 6.3 MPa. Then temperature and pressure were risen up to a supercritical condition (T = 392–400°C, P_{H2 O}P_{H_2 O} = 22 MPa). The concentration of cerium ions in reaction medium was changed in the interval 0.012–0.706 wt %. The products, obtained on various stages of synthesis, were investigated by physical-chemical methods. During the first stage, the crystals of boehmite and yttrium hydroxide under hydrothermal conditions were arising, and eventually poorly formed YAG: Ce³⁺ were appearing. At this stage, the diffusion of cerium ions into intermediate products takes place. Because of this, at the second step of synthesis, in supercritical conditions, YAG: Ce³⁺, phosphor with high luminescence intensity at 530 nm, was obtained. In supercritical conditions well-faceted crystals of 0.5–3.0 μm with rhombododecahedral habitus were produced.     

Structural and electrochemical properties of LiNi0.4Co0.4−xAl0.2+xO2 cathode materials for lithium-ion batteries

Three Al doped lithium nickel cobalt oxide (LiNi_0.4Co_0.4−xAl_0.2+xO₂) cathode materials for lithium ion batteries were synthesized by solid state reaction method at a temperature of 800 °C for 18 hours. The samples were crystalline as revealed by powder X-Ray diffraction (XRD). The ratios of the elements were determined by Energy Dispersive Analysis of X-rays (EDAX). The electrochemical properties obtained by charge/discharge cycling showed that the average discharge capacity for LiNi_0.4Co_0.4Al_0.2O₂ was 117 mAh/g. A good capacity retention was also shown by the material upon cycling. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.