Chloride spinels: A new group of solid lithium electrolytes

The chloride spinels Li₂MCl₄ with M = Mg, Mn, Fe and Cd show very high lithium ionic conductivity in the solid state. The ionic conductivity in the compounds under investigation was established with the help of emf measurements. The specific conductivities measured by both frequency response analysis and the four probe ac method are 1.3 Ω^?1 · cm^?1 for Li₂CdCl₄, and about 0.9Ω^?1 · cm^?1 for Li₂MnCl₄, Li₂MgCl₄, and Li₂FeCl₄ at 773 K. There are several indications that the ternary chlorides become highly disordered at elevated temperatures. Thus the Arrhenius plots, i.e. In σ · T vs 1/T-curves, exhibit significant bends, the slopes below the transition temperature being considerably higher than those above.     

Complex impedance study of annealing effects on polycrystalline KDP conductivity

Annealing effects on the conductivity of KDP (KH₂PO₄) samples prepared either by melting under slight pressure (5.7 kgf/cm²) or by powder compression (1.3 × 10³kgf/cm²) were studied in air by complex impedance spectroscopy. In both cases, annealing at 423 K reduces the conductivities to constant values: from 6.2 × 10 ⁻⁶ to 1.6 × 10⁻⁷ Ω⁻¹ cm⁻¹ for samples prepared by melting and from 1.9 × 10^∼7 to 6.1 × 10^∼8 Ω⁻¹ cm⁻¹ for samples prepared by compression. Heating KDP at about 500 K significantly modifies its electric properties. Two relaxation processes are observed after this treatment. One of them is associated with a fairly strong dielectric polarizability. A small conductivity jump is observed close to 440 K.     

Transport properties of PbSnI4

PbSnI₄ has been prepared from equimolar amounts of PbI₂ and SnI₂. X-ray and DSC measurements show the material to be uniphase in the temperature range 30 to 400°C; it has a tetragonal structure and melts at 379°C. The electrical conductivity is mainly ionic with an ionic transport number greater than 0.99 at 200°C. Conductivity at room temperature is 2.56 × 10⁻⁸ Ω⁻¹ cm⁻¹ while the value at 200°C is 1.25 × 10⁻⁶ Ω⁻¹ cm⁻¹.     

Ionic conductivity of lithium nitride doped with hydrogen

Lithium ionic conductivity of Li₃N single crystals is reported for temperatures from 120 K to 350 K. The intrinsic ionic conductivity is rather small (< 10^?6 Ω^?1 cm^?1 at 300 K) and shows no strong anisotropy. The activation energy is near 0,6 eV. It is shown that hydrogen is the critical impurity in the crystals grown and studied at this laboratory. The relative impurity concentration is determined from infrared transmission measurements near 3130 cm^?1. An estimate for absolute values is obtained from dielectric studies. Increases in ionic conductivity with hydrogen doping by a factor 5000 are reported for E⊥c but no significant effects are found for E6c. The proposed defect is an impurity-vacancy complex consisting of an NH^?? and a lithium vacancy.     

Experimental measurement of the electrical conductivity of pyroxenite at high temperature and high pressure under different oxygen fugacities

Electrical conductivities of pyroxenite were measured between frequencies of 10^?1 and 10⁶ Hz in a multi-anvil pressure apparatus using different solid buffers (Ni+NiO, Fe+Fe₃O₄, Fe+FeO and Mo+MoO₂) to stabilize the partial pressure of oxygen. The temperature ranged from 1073 to 1423 K (800 to 1200 °C) and the pressure from 1.0 to 4.0 GPa. We observe that: (1) the electrical conductivity (σ) of pyroxenite depends on frequency; (2) σ tends to increase with rising temperature (T), and Log σ and 1/T obey a linear Arrhenius relationship; (3) under control of the buffer Fe+Fe₃O₄, σ tends to decrease with rising pressure, nevertheless the activation enthalpy tends to increase. For the first time we have obtained values for the activation energy and activation bulk volume of the main charge carriers, which are (1.60±0.07) eV and (0.05±0.03) cm³/mol, respectively; (4) for a given pressure and temperature, σ tends to rise with increased oxygen fugacity, whereas the activation enthalpy and preexponential factor tend to decrease; and (5) the behaviour of the electrical conductivity at high temperature and high pressure can be reasonably interpreted by assuming that small polarons provide the dominant conduction mechanism in the pyroxenite samples.     

Spectroscopic study of thulium-activated double sodium yttrium fluoride Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript>:Tm<Superscript>3+</Superscript> crystals: I. Intensity of spectra and luminescence kinetics

Na_0.4Y_0.6F_2.2:Tm³⁺ crystals with a thulium content from 1 to 100 at % have been grown by the Stockbarger-Bridgman method. The optical spectra of Na_0.4Y_0.6F_2.2:Tm³⁺ crystals were investigated in detail at room and low (10 K) temperatures, and the luminescence kinetics was analyzed using different excitation methods. The structure of the Stark splitting of thulium levels as “quasi-centers,” characterized by inhomogeneous broadening of the Stark components, is determined from analysis of the absorption spectrum at 10 K. The oscillator strengths of the transitions from the ground state to excited multiplets are determined from the absorption cross-section spectra at 300 K for ten transitions in the range 5000–38 500 cm^?1 and seven transitions in the range 5000–28 500 cm^?1. The transition intensity parameters Ω _t , obtained by the Judd-Ofelt method from the spectra due to the transitions to ten and seven excited levels, were found to be, respectively, (i) Ω₂ = 1.89 × 10^?20, Ω₄ = 2.16 × 10^?20, and Ω₆ = 1.40 × 10^?20 cm² and (ii) Ω₂ = 2.04 × 10^?20, Ω₄ = 2.01 × 10^?20, and Ω₆ = 1.44 × 10^?20 cm². These values of the intensity parameters were used to calculate the radiative transition probabilities and branching ratios and to estimate the multiphonon nonradiative transition probabilities for NYF:Tm. The luminescence decay kinetics from thulium radiative levels upon their selective excitation by nanosecond laser pulses has been studied and the lifetimes of thulium radiative levels in NYF crystals have been found.     

Photoinduced submillimeter-wave amplitude diffraction grating in a semiconducting CdF<Subscript>2</Subscript>:Ga crystal

It is shown that exposure of an additively colored CdF₂:Ga crystal with bistable DX centers that is slowly cooled to 150 K to blue-green light through a slotted mask produces a submillimeter-wave diffraction grating, which persists for a long time at temperatures of 160–240 K. It is also shown that the diffraction grating induced in a sample is an amplitude grating. The absorption of submillimeter waves in illuminated regions of the sample is associated with the conductivity due to the transition of impurity centers to a metastable donor state. In the n-i-n-i-type conducting structure obtained, the conductivity of n-type regions at 225 K amounts to σ ′ ≈ 0.24 Ω^?1 cm^?1.     

Calibration of the R ruby fluorescence lines in the pressure range [0-1 GPa] and the temperature range [250-300 K]

Abstract

The pressure range [&1 GPa] and the temperature range [250–300 K] are commonly used in many science fields like biology, agro-chemistry, pharmacology, or geology. In this paper, the calibration of the ruby R lines of fluorescence is performed in these pressure and temperature ranges, using the melting curve of pure water. The linear shifts of ruby peaks are equal to ?0.140cm^?1/K and ?0.768cm^?1/kbar with R₁, and to ?0.137cm^?1/K and ?0.779 cm^?1/kbar with R₂. The accuracy of pressure measurements can be as good as ± 10MPa if the temperature is known with ±0.5 K. Such a precision is achieved if: (1) the position of each peak is determined using an inversion method; (2) daily shifts of the spectrometer are corrected before each acquisition; (3) peak positions of each ruby are known at ambient pressure and temperature.     

Anomalous electrical conductivity of the potassium deficient linear chain platinum compound: K1.75Pt(CN)4·1.5H2O

Four probe single crystal dc conductivity, σ, has been measured for K_1.75Pt (CN)₄·1.5H₂O for temperature 360K > T > 30K on crystals prepared via electrochemical growth, with σ (295K)

25–50 Ω^?1cm^?1. An anomalous behavior in σ (T) is reported with σ (T) nearly constant for T > 300K and 160K > T > 80K, and rapidly decreasing σ (T) observed for 300K > T > 160K and T < 80K. The data for 200K < T < 308K are analyzed in terms of a three-dimensional second order phase transition occurring at T_c = 308K. These results contrast sharply with those of the well studied K₂Pt(CN)₄X_0.3·3H₂0 (X=Cl,Br).     

Low temperature metallic conductivity in bis(tetrathiotetracene) triiodide,a new organic metal

The d.c. electrical conductivity of bis(tetrathiotetracene)triiodide,a new organic metal, has been measured for 3.3K?T?300K. The room temperature conductivity is ～ 1000 Ω^-1 cm^-1. The conductivity exhibits a broad maximum of about 3000 Ω^-1 cm^-1 in the temperature range 40–80 K followed by a gradual decrease in conductivity with decreasing temperature. No sharp metal-insulator transition is observed down to 3.3 K. The conductivity at 4 K is ～ 100 Ω^-1 cm^-1.     

Possibility of Anderson transition in liquid Se and As in the region of high temperatures and pressures

Conductivity of selenium and arsenic at high temperatures, 2000°C, and supercritical pressures has been measured. With the density decrease the conductivity was found to drop rapidly from the ～ 10² Ω^?1 cm^?1 level corresponding to the minimal conductivity estimated by Mott. This is accounted for by the Anderson localization of electrons and confirmed by the calculations presented.     

Semiconductor-metal transition in selenium under shock compression

Phase transitions in selenium are studied by time-resolved measurements of the electrical conductivity under shock compression at a pressure of up to 32 GPa. The pressure dependence of the electrical conductivity (σ(P)) has two portions: a sharp increase at P < 21 GPa and a plateau at P > 21 GPa. The experimental data and the temperature estimates indicate that, at P < 21 GPa, selenium is in the semiconductor state. The energy gap of semiconducting selenium decreases substantially under compression. At P > 21 GPa, the electrical conductivity saturates at ～10⁴ Ω^?1 cm^?1. Such a high value of the electrical conductivity shows the effective semiconductor-metal transition taking place in shock-compressed selenium. Experiments with samples having different initial densities demonstrate the effect of temperature on the phase transition. For example, powdered selenium experiences the transition at a lower shock pressure than solid selenium. Comparison of the temperature estimates with the phase diagram of selenium shows that powdered selenium metallizes in a shock wave as a result of melting. The most plausible mechanism behind the shock-induced semiconductor-metal transition in solid selenium is melting or the transition in the solid phase. Under shock compression, the metallic phase arises without a noticeable time delay. After relief, the metallic phase persists for a time, delaying the reverse transition.     

Superionic phase transition in (NH4)2SeO4·2NH4HSeO4 single crystal at 378 K

Abstract

DTA, structural and electric conductivity investigations were made for (NH₄)₄H₂(SeO₄)₃ single crystals. A high-temperature phase transition at 378 K to a superionic phase was found. The phase is characterized by a high electrical conductivity (～4.10^?3 Ω^?1 cm^?1) and a low activation energy (0.11 eV).     

Minimum metallic conductivity in a thin crystal

Electrical conductivities of thin crystals of Bi₂(Te,S)₃ measured from 4.2°K to 300°K fall into four regions: 1) σ < 1.3×10^?5 S with positive temperature coefficient of conductivity; 2) 1.3×10^?5 S < σ < 1.4×10^?5 S with temperature independent conductivity; 3) 1.4×10^?5 S σ < 4×10^?5 S with negative temperature coefficient of conductivity, and 4) σ > 4×10^?5 S with hardly any temperature dependence. A disproportionately high fraction of samples falls into the second range; 1.3×10^?5 S < σ < 1.4×10^?5 S.     

Anomalous ionic conduction in AgBrAgI mixed crystals and multiphase systems

Ionic conductivity, σ, of the AgBrAgI system has been studied as a function of composition and temperature. The maximum conductivity of $\text{3 × 10}{}^{-4}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$ at 25°C is obtained for a AgI-20 mole% AgBr two-phase mixture which is $\text{\$}\text{?}$3 orders of magnitude larger than that predicted by the classical theories of Lord Rayleigh and Maxwell. On the other hand, the substitution of so-called homovalent ions, e.g. Br^? in AgI and I^? in AgBr one phase solid solutions leads to anomalously large increase in the ionic conductivity that cannot be explained in terms of the charge compensation (doping) mechanism, and is attributed to purely elastic displacements (lattice distortion) due to the very “wrong” size of the substituted ions. A quadratic dependence of conductivity on the concentration of substituents is substantiated. An important consequence of the latter anomaly is that AgBr + 30 mole% AgI exhibits σ $\text{\$}\text{?}$7 Ω^?1 cm^?1 at 380°C which is $\text{\$}\text{?}$170% higher than that of α-AgI, the best known superionic conductor, at its melting point (557°C).     

Volume properties and compressibility of the graphite-potassium-mercury compounds

Abstract

The volume properties of graphite intercalation compounds (GIGS) C4KHg and of the initial intermetallic compounds KHg and KHg₂ have been investigated in the piston-cylinder apparatus, using the direct volumetric technique, under pressures up to 25 kbar. The compounds, average compressibility K₊, was determined to be 3.8×10^?3 kbar^?1 for C₄KHg, 3.0×10^?3 kbar-^?1 for C₈KHg, 4.8×10^?1 kbar^?1 for KHg, and 4.0 ×10^?1 kbar^?1 for KHg₂ at pressures of 0-20 kbar. The compressibility of the “two-dimensional” KHg layer in the GIC under various pressure conditions has been estimated. These estimates permit comparison of KHg properties in the “three dimensional” and “quasi-two dimensional” states. It was concluded that the influence of the graphite matrix on the intercalant is insignificant for this type ternary GIC.     

Conductivity of β″ and ion rich β alumina.I.H.+(H2O)n compounds

The conductivity and thermal stability of H⁺(H₂O)_n β″ and ion rich β alumina single crystals have been measured by the complex impedance method in the 25–700°C temperature range. Two mechanisms of conductivity were assumed: proton transfer at lower temperatures and H₃O⁺ diffusion in the high-temperature range. Both structures have similar properties, but ion rich β alumina possesses the best stability and the lowest activation energy (β: 0.15 eV, β″: 0.20 eV below 400 and 300°C respectively). The room-temperature conductivity is ≈5×10^?6 Ω^?1 cm^?1. The conducting properties and mechanisms are discussed and compared to other protonic or ionic conductors.     

Hopping conductivity of carbynes modified under high pressures and temperatures: Galvanomagnetic and thermoelectric properties

The conductivity, thermopower, and magnetoresistance of carbynes structurally modified by heating under a high pressure are investigated in the temperature range 1.8–300 K in a magnetic field up to 70 kOe. It is shown that an increase in the synthesis temperature under pressure leads to a transition from 1D hopping conductivity to 2D and then to 3D hopping conductivity. An analysis of transport data at T ≤ 40 K makes it possible to determine the localization radius a ～ (56?140) Å of the wave function and to estimate the density of localized states _g(E _F) for various dimensions d of space: _g(E _F) ≈ 5.8 × 10⁷ eV^?1 cm^?1 (d=1), _g(E _F) ≈5×10¹⁴ eV^?1 cm ^?2 (d=2), and _g(E _F)≈1.1×10²¹ eV^?1 cm_?3 (d=3). A model for hopping conductivity and structure of carbynes is proposed on the basis of clusterization of sp ² bonds in the carbyne matrix on the nanometer scale.     

Electrical transport properties of polyacetylene tetrachloroferrate - [CH(FeCl4)y]x]

Conductivity and thermopower measurements of polyacetylene doped with FeCl₄ are reported. The conductivity changes over 10 orders of magnitude and reaches the maximum value of 200 Ω^-1 cm^-1 at y = 0.07. The thermopower reveals the semiconductor to metal transition at y ? 0.002, with high and temperature independent Seebeck coefficient in the dilute limit and a metallic dependence in the heavily doped samples.     

DX-Like behavior of Se-impurity centers in gasb under hydrostatic pressure

Abstract

Hall coefficient (R_H) and electrical resistivity measurements have been performed as a function of temperature (between 77 K and 300 K) and under hydrostatic pressures (up to 15 kbar) on a set of Se-doped GaSb samples with impurity concentrations in the range 8×10¹⁷ cm^?3 - 1×10¹⁸ cm^?3. With increasing pressure at 300 K, the electrons are strongly trapped into a resonant impurity level. The pressure induced occupation of this level leads to time-dependent effects at T<120 K. The activated thermal electron emission over a potential barrier E<sb>B = 300×30 meV gives clear evidence for a large lattice relaxation around the impurity centers characteristic for DX-like behavior.