The crystallographic shear planes of the non-stoichiometric molybdenum oxides as revealed by RHEED: Investigation from the Mo18O52(100) surface

Large Mo₁₈O₅₂ crystals are obtained by an appropriate crystallization method. The examination of their well developed surfaces by the use of reflection high energy electron diffraction (RHEED) proves that these are (100) surfaces stepped along [010] directions. It is concluded that this oxide surface conformation can be connected to the particular Mo₁₈O₅₂ structure which is built up of MoO₃ slabs of finite width mutually joined by crystallographic shear planes (CS planes). Transmission electron microscopy (TEM) analysis from Mo₁₈O₅₂ crystal flakes confirms that these are single crystals without disorder in the periodicity of the CS planes.     

Magnetic and structural studies of Cr2O5 and Cr3O8

The infrared spectra, indexed X-ray powder diffraction patterns, magnetic susceptibilities between 80 and 300 K, and electron paramagnetic resonance spectra at 80 and 300 K are reported for Cr₂O₅ and Cr₃O₈. The results indicate that both oxides are Cr³⁺/Cr⁶⁺ mixed-valence compounds which contain CrO₆ octahedra and CrO₄ tetrahedra in different ratios. The valence formula for Cr₂O₅ is Cr³⁺₂Cr⁶⁺₄O₁₅ and that of Cr₃O₈ is Cr³⁺₂Cr⁶⁺₇O₂₄. The X-ray powder data for Cr₂O₅ and Cr₃O₈ could be indexed on the basis of a monoclinic unit cell $\text{(a = 12.01(2), b = 8.52(1), c = 9.39(1)}\text{A}\text{?}\text{β = 92.0(1)°)}$ and an orthorhombic unit cell $\text{(a = 12.01(7), b = 36.60(7) and c = 3.82(1)}\text{A}\text{?}\text{)}$, respectively.     

A comparative study of lithium and sodium insertion into HfMo2O8 and two polymorphs of ZrMo2O8

Lithium and sodium insertion into RMo₂O₈ (R = Zr,Hf) has been studied by galvanostatic chronopotentiometry, cyclic voltammetry (CV) and quantitative XRD phase analysis as well as by flame photometry after treatment with n-butyllithium or sodium naphtalide solutions. Low-temperature modification of ZrMo₂O₈ with monoclinic framework structure accommodates two lithiums, in agreement with the topological analysis based on the Voronoi tessellation, at a constant open-circuit voltage of 2.4 V and discharge voltage of ca. 2.1 V. According to CV, the process is partially reversible, but lithium extraction is kinetically hindered, presumably due to the low electronic conductivity of the oxidized phase. Further lithium insertion results in complete amorphization at 4Li per formula unit. This value is limiting also for the isostructural trigonal layered phases, HfMo₂O₈ and high-temperature ZrMo₂O₈; in those cases, however, amorphization starts from the beginning of reduction. Sodium insertion (both electrochemical and chemical) in the three phases is sterically hindered and could only be detected by CV.     

Synthesis and characterization of lithium manganese oxides with core-shell Li4Mn5O12@Li2MnO3 structure as lithium battery electrode materials

By a facile LiNO₃ flux method, lithium manganese oxide composites (xLi₄Mn₅O₁₂? yLi₂MnO₃) were synthesized using a hierarchical organization precursor of manganese dioxide. Li₄Mn₅O₁₂ and Li₂MnO₃ have spinel and rocksalt structures, respectively. The lithiation and structural transformation from the precursor to the composites occurred topotactically from exterior toward interior in the precursor particle with the increase of reaction time, and the composites had core-shell spinel@rocksalt structures in addition to the original hierarchical core-shell organization. The electrochemical measurements at 50 °C after 50 cycles confirmed that a typical spinel@rocksalt cathode had higher capacity retention (87.1%) than that with the composition close to the stoichiometric spinel (64.6%), indicating the Li₂MnO₃ shell can improve cycling stability for the composite electrode at elevated temperature.     

First-principles calculations of structural and thermodynamic properties of Y 3Al5O12

The pseudo-potential plane-wave method using the generalized gradient approximation (GGA) within the framework of the density functional theory is applied to study the structural and thermodynamic properties of Y ₃Al₅O₁₂. The lattice constants and bulk modulus are calculated. They keep in good agreement with other theoretical data and experimental results. The quasi-harmonic Debye model, in which the phononic effects are considered, is applied to the study of the thermodynamic properties. The temperature effect on the structural parameters, bulk modulus, thermal expansion coefficient, specific heats and Debye temperatures in the whole range from 0 to 20 GPa and temperature range from 0 to 1500 K.     

Organic acid assisted solid-state synthesis of Li1.2Ni0.16Co0.08Mn0.56O2 nanoparticles as lithium ion battery cathodes

Lithium-rich layered oxide Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ can be referred as a crystalline mixture of Li₂MnO₃ and LiNi_0.4Co_0.2Mn_0.4O₂ at equal molar ratio. In the paper, the solid state reaction of M(AC)₂·4H₂O (M = Mn, Co and Ni) and LiOH·H₂O has been performed to obtain nanocrystalline Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ using a small molecular organic acid (i.e., oxalic acid (OA), citric acid (CA) or tartaric acid (TA)) as additive. The introduction of organic acids can help to improve the layered structure and inhibit the particle growth of Li_1.2Ni_0.16Co_0.08Mn_0.56O₂, and the different organic acids exert distinct influences on the structural and electrochemical properties of Li_1.2Ni_0.16Co_0.08Mn_0.56O₂. In detail, the nanoparticles obtained in the presence of OA have the smallest average size of 50–150 nm, which correspondingly exhibit the highest initial discharge capacity of 267.52 mAh g⁻¹ at 0.1C and the best high-rate capability (e.g., 152.22 mAh g⁻¹, 5C) when applied as a lithium ion battery cathode. Furthermore, the active substance obtained from TA shows the best cycling stability and a discharge capacity of 202.42 mAh g⁻¹ can be retained after 50 cycles at 0.5C.     

Solid solutions Li1+xV3O8 as cathodes for high rate secondary Li batteries

Following a preliminary investigation, Li/Li_1+xV₃O₈ cells have been examined. Using samples of low x content, up to 3 eq Li⁺ could be accepted both chemically and electrochemically by one mole of active material. Li⁺ is accomodated in the tetrahedral sites existing between the (V₃O₈)^(1+x)- layers. Li⁺ jumping from site to site is fast and permits high rate capabilities: at 10 mA/cm², 1.1 eq Li⁺ per mole could still be inserted. The structure does not show irreversible alterations upon extended lithiation, allowing long cycle lives to be achieved. Kinetic constraints limit the recovery of the full capacity of the first discharge at medium-high rates, but the second-discharge capacity declines slowly with cycle number.     

Electrochemical behaviour of sputtered c-V2O5 and LiCoO2 thin films for solid state lithium microbatteries

Here are reported for the first time electrochemical data on all-solid-state lithium microbatteries using crystalline sputtered V₂O₅ thin films as cathode materials and LiPON as solid electrolyte. The stable specific capacity of 30 µAh/cm² found with a 2.4 µm thick film competes very well with the best values obtained for solid state microbatteries using amorphous films. With the challenge of decreasing the temperature of heat treatment for sputtered LiCoO₂ thin films, we show that a temperature of 500 °C combined with an optimized bias sputtering (-50 V) allows to get highly crystalline deposits, to minimize the presence of Co₃O₄ and to suppress any trace of the cubic phase. At the same time the theoretical specific capacity is reached in the 4.2 V-3 V range and a good cycling behaviour is achieved with a high capacity of 50 µAh/cm²/µm after 140 cycles at 10 µA.cm².     

Magnetic behavior and structural feature of quasi-one-dimensional BaCu2V2O8 crystal

Magnetic properties of BaCu₂V₂O₈ single crystals obtained by the spontaneous nucleation method using V₂O₅ as a self-flux are investigated. Singlet ground states with spin gaps of 215 and 223 K are observed along the directions parallel and perpendicular to the c-axis of the crystal, respectively, being in good agreement with powder sample measurements. Reinvestigation of the crystal structure reveals that the whole structural framework of BaCu₂V₂O₈ crystal can be described as an assembly of alternating chains, which are built by edge-sharing pairs of CuO₄ square-plaquettes and VO₄ tetrahedra along the c-axis. The magnetic nature of BaCu₂V₂O₈ is well understood based on this structural interpretation.     

Correlation between P chemical shift tensor and local structure in lithium cyclohexaphosphates Li6P6O18·3H2O and Li6P6O18

To understand the surprising behavior between the variations of the P′–P–P″ angles and the correlated variations of the O′–P–O″ ones, two lithium cyclohexaphosphate compounds Li₆P₆O₁₈·3H₂O and Li₆P₆O₁₈ are studied by solid state nuclear magnetic resonance (NMR) spectroscopy. The two compounds exhibit the same [P₆O₁₈]⁶⁻ ring anions but with 3m or internal symmetry, respectively. Such symmetries induce local distortions that are exhibited by NMR spectroscopy. One-dimensional (1D) NMR gives information on structural sites of ⁷Li and ³¹P ions and the crystallographic non-equivalencies are observed. Nevertheless, in the anhydrous compound, X-ray diffraction and NMR results do not completely agree and some discrepancy exists between the number of sites observed with the first technique and the number of lines exhibited in the NMR spectra either for ⁷Li or ³¹P nuclei. This problem is elucidated by using 2D double quantum NMR spectroscopy coupled with theoretical considerations. We find that the ³¹P chemical shift tensor is dependent on the deviations of the O–P–O angles from those in the regular tetrahedron. Within the same empirical model, we suggest that the surprising behavior between the variations of the P′–P–P″ and the ones of the O′–P–O″ is related to the overall charge on the PO₄ group. We also find the positions of the isotropic lines for ⁷Li essentially depend on the site co-ordination of this nuclei.     

Recent development and application of Li4Ti5O12 as anode material of lithium ion battery

Lithium-ion batteries with both high power and high energy density are one of the promising power sources for electric devices, especially for electric vehicles (EV) and other portable electric devices. One of the challenges is to improve the safety and electrochemical performance of lithium ion batteries anode materials. Li₄Ti₅O₁₂ has been accepted as a novel anode material of power lithium ion battery instead of carbon because it can release lithium ions repeatedly for recharging and quickly for high current. However, Li₄Ti₅O₁₂ has an insulating character due to the electronic structure characterized by empty Ti 3d-states, and this might result in the insufficient applications of LTO at high current discharge rate before any materials modifications. This review focuses first on the present status of Li₄Ti₅O₁₂ including the synthesized method, doping, surface modification, application and theoretical calculation, then on its near future development.     

Nd5Fe18B18 (Nd1.11Fe4B4), a new nowotny-like phase. structural and magnetic properties

The crystal structure of a ternary compound, whose chemical composition is Nd₅Fe₁₈B₁₈, has been determined. Nd atoms on the one hand, Fe and B atoms on the other hand, form 2 different substructures, both of tetragonal symmetry. In a previous investigation¹ only incommensurate or very long period ordering along the $\overrightarrow{c}$ directions between the 2 substructures was proposed, with non-definite composition. The whole structure is now described in the Pccn orthorhombic space group (a=b=7.117Å ; c = 35.07Å). This compound appears then as a new Nowotny-like phase. Fe atoms are essentially non magnetic. Ferromagnetic order between Nd atoms occurs only below 14 K. 2^nd order Crystalline Electric Fiel (CEF) terms are deduced from the anisotropy of the paramagnetic susceptibility. Higher order CEF terms must also be considered.     

The structural, optical, and dielectric spectroscopy studies of novel ZnO–As2O3 glass system with Sb2O3 as additive

ZnO–As₂O₃–Sb₂O₃ glasses of varying concentrations of Sb₂O₃ with ZnO (ranging from 5 to 45 mol%) are prepared. A number of studies, including differential thermal analysis, and study of spectroscopic properties (viz., optical absorption and IR spectra) and dielectric properties (constant ε′, loss tan δ and ac conductivity σ_ac) over a wide range of frequency and temperature of these glasses are carried out. Analyses of the results of these investigations have indicated that the glasses containing higher concentrations of Sb₂O₃ are more suitable for non-linear optical (NLO) applications.     

Electrical and structural properties of epitaxially grown Y1Ba2Cu3O7 − x and Y2Ba4Cu8O16 − x thin films using the BaF2 method

Thin films of Cu, Y and BaF₂ are co-condensed in ultrahigh vacuum onto SrTiO₃ (1 0 0)-substrates at room temperature without any additional oxygen supply. It is found that the temperature of the ex situ fluorine-oxygen exchange reaction in flowing wet oxygen essentially determines whether the Y₁Ba₂Cu₃O_{7 − x}-phase (T_ex = 850°C) or the Y₂Ba₄Cu₈O_{16 − x}-phase (T_ex = 800°C) forms or any mixture of both phases in between. Small-angle X-ray diffraction verifies the strictly epitaxial growth of the superconducting phases. The variation of the composition around the ideal 1,2,3-stoichiometry affects only the superconducting and normal conducting properties which are measured using the four-probe Montgomery method. The values of the normal state resistivity and its temperature dependence are discussed in combination with a reduced cross section of the conduction paths in the films.     

Annealing effects on the optical and structural properties of Al2O3/SiO2 films as UV antireflection coatings on 4H-SiC substrates

Al₂O₃/SiO₂ films have been prepared by electron-beam evaporation as ultraviolet (UV) antireflection coatings on 4H-SiC substrates and annealed at different temperatures. The films were characterized by reflection spectra, ellipsometer system, atomic force microscopy (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. As the annealing temperature increased, the minimum reflectance of the films moved to the shorter wavelength for the variation of refractive indices and the reduction of film thicknesses. The surface grains appeared to get larger in size and the root mean square (RMS) roughness of the annealed films increased with the annealing temperature but was less than that of the as-deposited. The Al₂O₃/SiO₂ films maintained amorphous in microstructure with the increase of the temperature. Meanwhile, the transition and diffusion in film component were found in XPS measurement. These results provided the important references for Al₂O₃/SiO₂ films annealed at reasonable temperatures and prepared as fine antireflection coatings on 4H-SiC-based UV optoelectronic devices.     

A revisit of photoluminescence property for vanadate oxides AVO3 (A:K, Rb and Cs) and M3V2O8 (M:Mg and Zn)

We revisited the vanadium oxide phosphors, AVO₃ (A:K, Rb, and Cs) and M₃V₂O₈ (A:Mg and Zn) for a revaluation of possibility of these compounds for lighting applications, and the internal quantum efficiency (η) and luminescent colour properties for AVO₃ (A:K, Rb, and Cs) and M₃V₂O₈ (A:Mg, and Zn) have been presented. The AVO₃ showed the broadband emission from 380 to 800 nm, and the η for the KVO₃, RbVO₃ and CsVO₃ were 4%, 79% and 87%, respectively. The CIE colour coordinates are located at white region on the chromaticity diagram. The M₃V₂O₈ (A:Mg and Zn) also exhibited a quite broadband emission between 410 and 900 nm, indicating yellow luminescent colour. The Zn₃V₂O₈ showed high η value, 52%, compared to that of the Mg₃V₂O₈ (η=6%). This enhancement of η in the Zn₃V₂O₈ could be due to the increasing exciton diffusion assisted by the hybridizations of Zn 3d and O 2p orbitals for the valence band, and Zn 4s and Ti 3d orbitals for the conduction band.     

Heat capacity and thermodynamic properties of α-Fe2O3 in the region 300–1050 K. antiferromagnetic transition

The heat capacity of synthetic α-Fe₂O₃ has been measured in the range 300–1050K by adiabatic shield calorimetry with intermittent energy inputs and temperature equilibration in between. A λ-type transition, related to the change from antiferro- to paramagnetism in the compound, is delineated and a maximum heat capacity of about 195 JK^?1 mole^?1 is observed over a 3 K interval around 955 K. Values of thermodynamic functions have been derived and C_P (1000K), [H⁰(1000K)-H⁰(0)], and [S⁰(1000K)-S⁰(0)] are 149.0JK^?1 mole^?1, 115.72 kJ mole^?1, and 252.27 JK^?1 mole^?1, respectively, after inclusion of earlier low-temperature results [X⁰ (298.15K)-X⁰(0)]. The non-magnetic heat capacity is estimated and the thermodynamic properties of the magnetic transition evaluated. The results are compared with spin-wave calculations in the random phase approximation below the Néel temperature and the Oguchi pair model above. An upper estimate of the total magnetic entropy gives 32.4JK^?1 mole^?1, which compares favorably with that calculated for randomization of five unpaired electron spins on each iron, ΔS = 2R ln 6 = 29.79 JK^?1 mole^?1 for α-Fe₂O₃. The critical exponent α in the equation $\text{C}{}_{\mathrm{m}}\text{= (}\text{A}\text{α}\text{) [(|T}{}_{\mathrm{<mtext>n</mtext>}}\text{?T|/T}{}_{\mathrm{<mtext>n</mtext>}}\text{)?1]}{}^{\mathrm{?\alpha }}\text{+ B}$ is ?(0.50±0.10) below the maximum and 0.15±0.10 above, for T_n = 955.0K. The high temperature tail is discussed in terms of short range order.     

High temperature corrosion behaviour of some Fe-, Co- and Ni-base superalloys in the presence of Y2O3 as inhibitor

High temperature corrosion is accelerated degradation of materials at higher temperatures of operation caused by the presence of a deposit of salt or ash. Inhibitors and fuel additives have been investigated with varying success to control this type of corrosion. In this work, effect of an oxide additive namely Y₂O₃ on the hot corrosion behaviour of some superalloys viz Superfer 800H (alloy A), Superco 605 (alloy B) and Superni 75 (alloy C) has been investigated in an Na₂SO₄-60%V₂O₅ environment at 900 °C for 50 cycles. Each cycle consisted of 1 h heating in a Silicon Carbide Tube Furnace followed by 20 min cooling in ambient air. Weight data were taken by an electronic balance having an accuracy of 0.01 mg after each cycle. Subsequently, the exposed alloys were characterized by XRD, SEM and EPMA analyses to evaluate the role of the oxide additive. In the Na₂SO₄-60%V₂O₅ environment, the corrosion rate for the Co-base alloy was found to be highest, whereas that for the Ni-base Superni 75 the lowest. Superficially applied Y₂O₃ was observed to be useful in reducing the high temperature corrosion of the alloys. It was found to be most effective for the alloy A for which the oxide scale was continuous and rich in protective Cr. Alloy B showed the formation of medium size scale rich in Cr and Co. The oxide scale for the alloy C contained mainly Cr and Ni.     

X-ray single-crystal structural characterization of MgCr2O4, a post-spinel phase synthesized at 23 GPa and 1600 °C

The crystal structure and chemical composition of a crystal of MgCr₂O₄ post-spinel phase synthesized in the model system Mg₃Cr₂Si₃O₁₂–Mg₄Si₄O₁₂ at 23 GPa and 1600 °C have been investigated. Electron microprobe analysis confirmed the MgCr₂O₄ stochiometry of the studied phase. The compound was found to crystallize with the orthorhombic calcium-titanate (CaTi₂O₄) structure type, space group Bbmm, with lattice parameters a=9.468(1), b=9.670(1), c=2.845(1) Å, V=260.5(1) Å³, and Z=4. The structure was refined to R1=0.046 using 286 independent reflections. Magnesium was found to fully occupy the eightfold-coordinated A site (with a mean bond distance of 2.289 Å) and Cr the octahedral B site (mean: 1.986 Å). The successful synthesis of MgCr₂O₄ with (CaTi₂O₄)-type structure and its structural characterization demonstrate the stability of the new post-spinel phase. The absence of MgCr₂O₄ compounds with spinel structure coexisting with the post-spinel phase in the investigated run is discussed.     

Growth and decay of the Pd(1 1 1)-Pd5O4 surface oxide: Pressure-dependent kinetics and structural aspects

Growth and decomposition of the Pd₅O₄ surface oxide on Pd(1 1 1) were studied at sample temperatures between 573 and 683 K and O₂ gas pressures between 10⁻⁷ and 6 × 10⁻⁵ mbar, by means of an effusive O₂ beam from a capillary array doser, scanning tunnelling microscopy (STM) and thermal desorption spectrometry (TDS). Exposures beyond the p(2 × 2)O adlayer (saturation coverage 0.25) at 683 K (near thermodynamic equilibrium with respect to Pd₅O₄ surface oxide formation) lead to incorporation of additional oxygen into the surface. To initiate the incorporation, a critical pressure beyond the thermodynamic stability limit of the surface oxide is required. This thermodynamic stability limit is near 8.9 × 10⁻⁶ mbar at 683 K, in good agreement with calculations by density functional theory. A controlled kinetic study was feasible by generating nuclei by only a short O₂ pressure pulse and then following further growth kinetics in the lower (10⁻⁶ mbar) pressure range.Growth of the surface oxide layer at a lower temperature (573 K) studied by STM is characterized by a high degree of heterogeneity. Among various metastable local structures, a seam of disordered oxide formed at the step edges is a common structural feature characteristic of initial oxide growth. Further oxide nucleation appears to be favoured along the interface between the p(2 × 2)O structure and these disordered seams. Among the intermediate phases one specifically stable phase was detected both during growth and decomposition of the Pd₅O₄ layer. It is hexagonal with a distance of about 0.62 nm between the protrusions. Its well-ordered form is a superstructure.Isothermal decay of the Pd₅O₄ oxide layer at 693 K involves at first a rearrangement into the structure, indicating its high-temperature stability. This structure can break up into small clusters of uniform size and leaves a free metal surface area covered by a p(2 × 2)O adlayer. The rate of desorption increases autocatalytically with increasing phase boundary metal-oxide. We propose that at close-to-equilibrium conditions (693 K) surface oxide growth and decay occur via this intermediate structure.