Structural position and charge state of nickel in SrTiO3

The properties of nickel-doped strontium titanate are studied using X-ray diffraction and XAFS spectroscopy. It is shown that, independently of preparation conditions, the most stable phases in the samples are single-phase SrTi_{1 ? x} Ni _x O₃ solid solution and NiTiO₃ which can coexist. According to the EXAFS data, in the single-phase SrTi_0.97Ni_0.03O₃ sample the nickel atoms substitute the titanium atoms and are on-center ones. In this case, no distortions of the oxygen octahedron which would appear in the presence of oxygen vacancies in the nickel environment were detected. An analysis of the XANES spectra shows that the nickel charge state in NiTiO₃ is 2+, whereas in the SrTi_{1 ? x} Ni _x O₃ solid solution it is close to 4+. It is shown that the strongest light absorption in doped samples is associated with the presence of tetravalent Ni in the SrTi_{1 ? x} Ni _x O₃ solid solution. This doping seems to be the most promising for solar energy converters based on the bulk photovoltaic effect.     

Ball-milled Ni-Mn-Zn hydroxide for alkaline secondary battery

In our previous study, Mn-substituted nickel hydroxide (Ni_0.8Mn_0.2(OH)₂) was prepared by a simple ball milling method to reduce the cost of nickel hydroxide for alkaline secondary battery, but compared to the Ni(OH)₂ electrode, the Ni_0.8Mn_0.2(OH)₂ one showed an obvious decrease in its discharge potential. In this paper, Zn and Mn co-substituted nickel hydroxide (Ni_0.8Mn_0.2???x Zn _x (OH)₂, x?=?0–0.075) is prepared by ball milling. The results of the cyclic voltammetry (CV) tests illustrate that the co-reduction of Mn(IV) to Mn(III) and NiOOH is observed on the Ni_0.8Mn_0.2???x Zn _x (OH)₂ electrodes, and it has a lower reduction potential than NiOOH. The co-substitution of Zn can effectively increase the co-reduction potential. The ball-milled Ni_0.8Mn_0.15Zn_0.05(OH)₂ electrode has a similar capacity (about 270 mAh g^?1 at a 0.2C rate) and cycling durability to the commercial Ni(OH)₂ with ball milling treatment, but the former has better high-power performance.     

Mixed conductive electrode materials for sensors and SOFC

Modified active electrode materials based upon rare earth manganites were developed for different solid electrolyte electrochemical cells. The preparation, structure, thermal expansion, the state of oxygen on the surface, the electronic and ionic conductivity of the perovskites Ln_1−xCa(Sr)_xMn_1−y(Co, Ni)_yO_3−δ with various compositions and electrode kinetics on the manganite electrode/solid electrolyte interfaces were investigated. The value of the bulk conductivity was larger than 150 S/cm (at 1100 K) and increased significantly with increasing contents of Ni or Co. The thermal expansion coefficients of rare earth manganites were close to those of ZrO₂ based solid electrolytes. The expansion coefficients of Co or Ni subsituted lanthanum manganites increase with Co or Ni substitution and are over 12•10⁻⁶K⁻¹. The ionic conductivities were determined using encapsulated zirconia microelectrodes based on a Hebb-Wagner analysis of the currentvoltage curves. The relatively high oxide ion conductivity of 10⁻⁵ S/cm at 900...1000 K was found by Ni or Co doped manganites. Studies of the electrode kinetics using complex impedance spectroscopy show that Co and Ni doped manganites have advantages if used as electrodes as compared with these for noble metals. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11–18 Sept. 1994     

On the nature of differences in the Ni charge states in barium and strontium titanates

XAFS studies of nickel-doped solid solution Ba_1–xSr_xTiO₃ show that the Ni charge state changes from 4 in SrTiO₃ to ~2.5 in BaTiO₃ as x is varied. First-principles electronic structure calculations show that nickel creates an impurity band in the forbidden gap of BaTiO₃ and SrTiO₃. Calculations of the formation energy of the oxygen vacancies explain the difference between the Ni charge states in these compounds by the different formation energies of these vacancies.     

Comparative study of NiSb2 and FeSb2 as negative electrodes for Li-ion batteries

Crystalline FeSb₂ powder prepared by ceramic route is examined as negative electrodes for lithium-ion batteries. The complete reaction mechanism of FeSb₂ is investigated by ¹²¹Sb and ⁵⁷Fe Mössbauer spectroscopy as well as magnetic measurements and the results are correlated with a previous in situ XRD characterization. On the first discharge the reaction with Li proceeds through a biphasic process transforming FeSb₂ into a new Li_xFe_ySb₂ phase, and this ternary phase is then converted into fcc Li₃Sb and metallic Fe nanoparticles. The combination of Mössbauer spectroscopy and magnetic analyses leads i) to a better understanding of the FeSb₂ → ternary phase reaction and concomitantly allowed ii) to specify the stoichiometry of the new ternary phase. On charge, the extrusion of lithium includes the back conversion of the Li₃Sb/Fe mixture into both Li₄Fe_0.5Sb₂ and metallic Sb, which are the main active species for the following cycles, responsible for the poor cycling life of the FeSb₂ electrode. The nature of these resulting products is quite different from that previously observed for the isotype NiSb₂ electrode which is characterized by a highly reversible mechanism.     

Magnetic properties and electronic structure of the LaGaO3 perovskite doped with nickel

Solid solutions of the composition LaGa_{1 ? x} Ni _x O₃ (0.01 ≤ x ≤ 0.10) are synthesized, and their magnetic and electrical properties are investigated. It is established that the ground state of the Ni(III) atoms is the low-spin state ² E _g ; however, in the temperature range under investigation, there occurs the ² E _g ? ⁴ T _1g spin equilibrium. An increase in the nickel concentration leads to an increase in the electron conduction of the solid solutions. The band structure of the LaGa_0.5Ni_0.5O₃ model compound is calculated using the ab initio full-potential linearized augmented-plane-wave method within the generalized gradient approximation (FLAPWGGA). It is shown that the dominant role in the variations observed in the magnetic and electrical properties of the nonmagnetic semiconductor LaGaO₃ upon doping with nickel is played by the Ni 3d(e _g ↑, ↓) states.     

Evidence for fcc-like short range order in Fe-Ni-B metallic glasses

Soft X-ray appearance potential spectra have been measured for iron and nickel in (Fe_0.5Ni_0.5)_100?xB_x metallic glasses with x = 16, 18, 20, 22, 24, 26. For x = 16 both iron and nickel spectra exhibit structural features characteristic for the electronic structure of fcc transition metals. It is concluded that in the amorphous state Ni and Fe are arranged in fcc-like geometry beyond nearest neighbours.     

Dielectric-breakdown-like forming process in the unipolar resistance switching of Ta2O5−x thin films

We report unipolar resistance switching (URS) in Ta₂O_5−x thin films. The current increased suddenly when we applied voltages up to 5-7 V to the pristine state of Pt/Ta₂O_5−x/Pt, Ni/Ta₂O_5−x/Pt, and Ti/Ta₂O_5−x/Pt cells. Just after this forming process, we observed a repetitive URS occurring independently of the electrodes. We found that the required voltages for the forming process did not depend on the top electrode type, but on the film thickness. These results suggest that the forming process is driven by a dielectric-breakdown-like phenomenon, and that URS occurs due to the formation and rupture of conducting channels inside the Ta₂O_5−x thin film.     

Effect of Ni/Mn ratio on the performance of LiNi x Mn2 − x O4 cathode material for lithium-ion battery

Lithium nickel manganate is recognized as a type of promising cathode material for lithium-ion battery, due to its advantages such as high voltage, high power density, and relative lower cost. In this paper, a series of LiNi _x Mn_2???x O₄ cathode materials with various molar ratio of Ni/Mn have been prepared with a co-precipitation method, followed by a solid state reaction, and the effect of the molar ratio of Ni/Mn on the structure and properties of materials are intensively investigated by means of X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR), scanning electron microscopy (SEM), and performance measurements, etc. It is revealed that all the samples with x from 0 to 0.5 have well-defined spinel structure and fit well to Fd-3 m space group. With the increase of the molar ratio of Ni/Mn, the diffraction peaks shift to higher angle slightly and the lattice parameter decreases gradually by the XRD results. Furthermore, it is found that the capacity at the 4.0 V plateau decreases while the capacity at 4.7 V plateau increases with the increase of the ratio of Ni/Mn, and the total discharge capacity shows growth trend with the increase of Ni content. It is important that all the samples with various molar ratio of Ni/Mn exhibit good cyclic stability. Based on the experimental results, we suggest that the Ni may incorporate into the lattice of LiMn₂O₄ substituting of Mn. The plateau at 4.7 V is related to the Ni ions and the plateau at 4.0 V is related to the Mn ions in the materials.     

FMR and EPR in Ni@C nanocomposites: Size and concentration effects

One-domain Ni@C nanoparticles encapsulated in carbon coating have been investigated depending on the size and concentration of Ni in carbon. The nanoparticles of nickel were prepared with the average diameters changing in a broad range of 4–45 nm, and the concentration of Ni in C varies in 2–12 wt%. To prepare the Ni@C nanocomposites the solid solutions of nickel phthalocyanine–metal-free phthalocyanine (NiPc) _x (H₂Pc)_1–x , 0 ≤ x ≤ 1 were synthesized and the solidphase pyrolysis of these compounds was performed. In the case of ultradispersive Ni nanoparticles (the interval of quantum dots is 1–10 nm), a considerable shift of the resonance field and broadening of resonance absorption field were revealed in the spectra of FMR at room temperature. The data were interpreted taking into account the essential contribution of the surface magnetic anisotropy, the magnetic field of which far exceeds the magnetic field of volume anisotropy.     

Reactivity and XAFS study on (1−x)CeO2-xNiO (x=0.025-0.3) system in the two-step water-splitting reaction for solar H2 production

The redox reaction of Ce⁴⁺-Ce³⁺ promoted by the catalytic function of nickel ions in a (1−x)CeO₂-xNiO solid solution was investigated for solar H₂ production by the two-step water-splitting reaction. By irradiation using an infrared imaging lamp as a solar simulator, the O₂-releasing reaction with (1−x)CeO₂-xNiO solid solution proceeded at 1673-1873 K, and its reduced form was produced. The amounts of H₂ gas evolved by the reduced form were 1.2-2.5 cm³/g and the evolved gases amounts ratio of H₂/O₂ was nearly 2, which is equal to the stoichiometric value of the water-splitting reaction (H₂O=H₂+1/2O₂). The maximum amounts of evolved H₂ and O₂ gases were obtained at the Ce:Ni mole ratio of 0.95:0.05 (x=0.05) in the (1−x)CeO₂-xNiO system. The X-ray absorption fine structure (XAFS) measurement showed that the O₂-releasing and H₂-generation reactions with (1−x)CeO₂-xNiO solid solution were repeatable with the redox system of Ce⁴⁺-Ce³⁺, which was enhanced by the catalytic function of Ni²⁺-Ni⁰.     

Conductivity and sintering property of LaNi1 − xFexO3 ceramics prepared by Pechini method

Preparation of LaNi_1 − xFe_xO₃, which is one of the candidate materials of solid oxide fuel cell cathode, current collecting layer and interconnect coating was examined with Pechini method and solid state reaction method. Single phase LaNi_1 − xFe_xO₃ with large Ni content has successfully been prepared by low temperature sintering as 750 °C with Pechini method, whereas large amount of raw materials has remained with solid state reaction method by sintering at the same temperature. It can be ascribed to more homogenous cation distribution in raw powder material prior to sintering with Pechini method. It has also been revealed that LaNi_1 − xFe_xO₃ with x lower than 0.3 is thermodynamically unstable in air above 1000 °C. LaNi_0.6Fe_0.4O₃ showed superior property as cathode material with high electrical conductivity, thermodynamic stability and appropriate sintering property.     

Tailoring resistive switching characteristics in WOx films using different metal electrodes

We have investigated the role of the metal/oxide junction interface on the resistive switching (RS) characteristics in WO_3+x films. The WO_x films are fabricated on Pt substrates by magnetron sputtering at room temperature. Top metal contact (Au or Al) is fabricated by using thermal evaporator. The thicknesses of WO_x films and top electrodes are 1 μm and 200 nm, respectively. It has been found that the bi-polar RS direction is dependent on the choice of top metal electrode, Au or Al. The sample with a Au top electrode shows clockwise (CW) RS mode whilst the sample with a Al top electrode shows counter-clockwise (CCW) RS mode. The on/off ratio is 10 times for Au/WO_x/Pt and 100 times for Al/WO_x/Pt. The bi-polar RS modes are modeled in terms of the difference in the electronegativity of the top and bottom electrodes.     

Spinel-type solid solutions involving Mn and Ti:Crystal chemistry, magnetic and electrochemical properties

This study reports the structural and magnetic properties of spinel systems Li₄Mn_5−xTi_xO₁₂ (“4-5-12” series) and LiNi_0.5Mn_1.5−xTi_xO₄ (“LNMTO” series), both based on Mn⁴⁺ substitution by Ti⁴⁺. Intermediate compositions covering the whole range of compositions (0≤x≤5 and 0≤x≤1.5, respectively) were prepared by solid state reaction. The 4-5-12 system forms a continuous spinel solid solution, whereas the spinel phase range in LNMTO stops before the end member “LiNi_0.5Ti_1.5O₄”, which is multi-phased with a major hexagonal phase component. Cell parameters and (Mn,Ti)-O distances increase monotonically with titanium content in both series. In the LNMTO series, the end member LiNi_0.5Mn_1.5O₄ is known to form a superstructure with Ni/Mn cation ordering. Neutron diffraction and Raman spectroscopy show that this order is lost when Ti is substituted, even at low level (x=0.15). The LNMTO crystal chemistry is also complicated by the presence of partial cation inversion, and the presence of a secondary rocksalt-type phase that modifies the spinel stoichiometry. Magnetic properties are characterized by a competition between ferromagnetic and antiferromagnetic interactions; no magnetic ordering is achieved, in agreement with B-site cation frustration and disorder. Electrochemical measurements show that the Ti^3+/4+ and Mn^3+/4+ redox couples behave independently in the 4-5-12 series, and that titanium decreases the high-potential electrochemical redox activity of LNMTO because of its blocking character for electron transfer to and from the nickel sites in the spinel structure.     

Improving the electrochemistry and microstructure of nickel electrode by deposition on anodized titanium substrate for the electrocatalytic oxidation of methanol and ethanol

The electrodeposition process of nickel and the substrate used for the electrodeposition can be improved to obtain an effective catalyst for methanol oxidation. Thus, nanoparticles of nickel have been uniformly electrodeposited on the surface of previously anodized titanium at 5 V during 1 h. The optimized microstructure has been studied by using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The XPS and argon-ion etching experiments have revealed the composition profile of the titanium/titania/nickel thin film electrode. Metallic Ni is detected by XRD. The nickel particles dispersed in a porous TiO₂ substrate have great catalytic activity for methanol oxidation in basic solution and through the redox couple NiO(OH)/Ni(OH)₂. The optimized titania substrate yields to electrodes (crystalline titanium/amorphous titania/nanocrystalline nickel) with higher catalytic activity than non-anodized metallic titanium (titanium/nickel). However, further oxidation and thickening of the titania film drives to poorer electrochemical behavior. The SEM and EDS results show that the nickel particles exhibit certain tendency to agglomerate and to form spherical particles of around 2 μm. This electrode material also is active to oxidize ethanol, but this activity is poorer.     

Magnetic properties of Ni0.8Cu0.2−xGex solid solutions

The results of magnetic measurements performed on Ni_0.8Cu_0.2-xGe_x solid solutions, with x ? 0.10 are reported. The saturation magnetization, Curie temperature and effective nickel moments decrease nearly linear when substituting Cu by Ge. The ferromagnetic resonance measurements show that the g values are not dependent on composition. Finally, the magnetic behaviour of nickel in these solid solutions is analysed.     

Structural and magnetic properties of Ce(Cu,Ni)2 pseudobinary phases

The stability of the pseudobinary phases obtained by partial substitution of Ni with Cu, Ag or Au in the cubic Laves phase CeNi₂, or by partial substitution of Cu with Ni in the orthorhombic compound CeCu₂ has been investigated. No solid solubility of Cu, Ag and Au in the CeNi₂ cubic lattice could be detected. In contrast, pseudobinary orthorhombic phases, corresponding to the formula CeCus_2?xNi_x, exist over the range x = 0 to 1. For these phases, crystal structures and magnetic properties have been determined. In every case, the electronic configuration of cerium appears to be unaffected to the Ni content, and corresponds to the trivalent state. The Ni atoms are in a non-magnetic state. The magnetic susceptibility of CeCu₂ in the region from 530 to 900 K shows anomalous behaviour, which should be due to a metamagnetic transition.     

Magnetism in quasibinary systems based on the valence-unstable compound CeNi

Magnetic ordering in solid solutions of Ce _x (Gd,Pr,Nd,La)_1-x Ni is studied by measuring the DC magnetization and the AC susceptibility in the temperature range of 1.8–300 K. The valence state of ceriumions in Ce _x (Gd,Pr,Nd,La)_1-x Ni quasibinary systems is studied based on X-ray absorption spectra measured at synchrotron-radiation sources in the temperature range of 5–300 K. It is shown that chemical pressure and lowering the temperature help heighten the degree of delocalization of the 4f electrons of cerium in Cex(Gd, Nd, Pr)_1-x Ni systems. It is found that the substitution of magnetic ions (Gd, Pr, and Nd) with cerium results in significantly weaker magnetic-ordering suppression than the substitution of these ions with lanthanum at equal concentrations. The obtained data reveal the strong influence of cerium electrons on localized magnetism in the studied compounds. This effect is most probably associated with the contribution of partially delocalized 4f electrons of cerium to the exchange interaction.     

Mechanism of magnetic ordering in Dy<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>-Ni bilayer films

A mechanism for the magnetic ordering of dysprosium in Dy_1?x Ni _x -Ni bilayer films is proposed. This ordering was discovered earlier by the authors when studying magnetic circular dichroism. For x exceeding a threshold value (～0.05), the contribution from the Dy_1?x Ni _x layer in a bilayer film to the magnetic circular dichroism over the temperature range 80–300 K is approximately equal in magnitude to the magnetic circular dichroism observed in a single-layer Dy film at temperatures below the ferromagnetic phase transition temperature of Dy (～100 K). Since magnetic circular dichroism is an effect linear in magnetization, the observed effect is associated with magnetic ordering of the Dy_1?x Ni _x layer in bilayer films due to the simultaneous influence of two factors: the incorporation of Ni into the Dy layer and the influence of the continuous Ni sublayer. The ferromagnetic ordering of a dysprosium layer doped with nickel (under conditions of an atomic contact with a continuous nickel layer) was confirmed by the field dependences of the polar and longitudinal Kerr effects. It was shown that both layers in the bilayer structure are magnetized in the same direction and characterized by an anisotropy of the easy-plane type. The magnetic ordering is assumed to be due to the change in the density of states of the Dy_1?x Ni _x alloy caused by hybridization with the narrow peaks near the Fermi level characteristic of nickel.     

Formation of nickel magnetic nanoparticles and modification of nickel phthalocyanine matrix by sodium doping

Data for the vapor-phase doping (300°C) of nickel phthalocyanine (NiPc) by sodium taken in different concentrations (x), as well as structural analysis data for Na _{x = 0.2}NiPc, Na _{x = 1}NiPc, and Na _{x = 3}NiPc samples, have been reported. The structure of the samples and their atomic configuration versus the doping level have been studied by transmission electron microscopy, Raman scattering, X-ray diffraction, X-ray absorption spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The structural parameters of Ni–N, Ni–C, and Ni–Ni bonds have been determined, and it has been found that, at a low level of doping by sodium, local structural distortions are observed in some molecules of the NiPc matrix near nickel atoms. The fraction of these molecules grows as the doping level rises from x = 0.2 to x = 1.0. It has been shown that doping changes the oscillation mode of light atoms, which indicates a rise in the electron concentration on five- and six-membered rings. At a high level of sodium doping (x = 3.0), nickel nanoparticles with a mean size of 20 nm and molecule decomposition products have been observed in the NiPc matrix. It has been found that the fraction of nickel atoms in the Na _{x = 3}NiPc nanoparticles as estimated from EXAFS data is sufficient for the room-temperature magnetic properties of the samples to persist for a long time.