Electrical conductivity of binary sulphates of lithium sulphate

To engineer lithium sulphate based material with high ionic conductivity at lowest possible temperature, the electrical conductivity of binary sulphates of Li₂SO₄ with Na₂SO₄, K₂SO₄, MgSO₄, ZnSO₄ and Ag₂SO₄ has been measured in the temperature range from 513 K to 773 K. The results are interpreted on the basis of different phases present therein. Li₂SO₄:Ag₂SO₄(40:60) mol % has high ionic conductivity = 2.17×10^-3(ohm cm)^-1 at 606 K which could be utilized in power sources.     

Enhancing the electrical conductivity and thermoelectric figure of merit of the p-type delafossite CuAlO2 by Ag2O addition

(CuAlO₂)_1-x(Ag₂O)_x specimens with 0 ≤ x ≤ 0.06 were prepared through the sintering of mixtures of CuO, Al₂O₃ and Ag₂O powders at 1373 K. Hall effect, Seebeck coefficient and electrical conductivity measurements were subsequently employed to assess the electrical transport properties. The electrical conductivity of the as-sintered samples was found to increase with Ag₂O addition as a result of increases in the carrier density. Over the temperature range of 323–623 K, the transport properties can be attributed to thermally activated transitions from the acceptor state to the valence band. In contrast, the variable range hopping theory is applicable over the temperature range of 623–873 K. Ag₂O addition evidently reduces the defect binding energy in the electronic structure of the CuAlO₂. The addition of this compound also obstructs the formation of both a spinel phase and CuO, such that the oxygen off-stoichiometry value and the carrier density are increased with increasing Ag₂O levels. The presence of Ag metal has the main effect on thermal conductivity below 400 K, while above 400 K increases in the phonon concentration affect the conductivity. The highest value obtained for the figure of merit was 0.0044 at 573 K, from a sample containing 0.2 at.% Ag₂O.     

Ionic and electronic conduction in β-PbF2

β-PbF₂ is an extrinsic n-type semiconductor at temperatures below 300 K. The contribution of lattice defects to the electrical conductivity increases rapidly above room temperature. Polarization studies using a Wagner-cell indicate that above 350 K ionic conductivity becomes predominant in undoped β-PbF₂ crystals.     

Electrical conductivity of magnesium oxide single crystal below 1200 K

Using 2-, 3- and 4-electrodes configurations the direct current conductivity of MgO single crystals of nominally highest purity (with respect to cation impurities), grown by arc-fusion, was studied in argon or oxygen between 500–1200 K with special reference to both hysteresis effects during heating and cooling cycles and conductivity phenomena which occur underneath the surface in a thin subsurface zone. The samples contained 250–2500 at.-ppm carbon and typically 800 at.-ppm hydrogen.Below 1000 K the low temperature (LT) conductivity mechanism is characterized by an activation energy of 1.1 ± 0.2eV, distinctly lower than that of the high temperature region (HT) approximately 2.4 eV. By annealing at 300 K the LT mechanism progressively builds up and causes a very pronounced conductivity increase between 700–900 K, unaffected or even enhanced by O₂. Above 900 K, O₂ decreases the conductivity.The LT mechanism is proposed to be due to defect electrons on anion sites corresponding to O^? in the O^2? structure which are a consequence of the presence of carbon and hydrogen dissolved in the MgO and formally derived from the dissolution of traces of CO₂ and H₂O [J. Chem. Phys. Solids43, 129 (1982)].The dissolved carbon is known to segregate into the elastically relaxed subsurface zone (J. Chem. Phys. Solids43, 59 1982). The conductivity data suggest that between 700–900 K, defect species of C + 2O^?, the dipolar CO^?₂, which become strongly enriched in the subsurface zone upon annealing at 300 K, dissociate according to the equation CO₂^2?→CO^? + O^?, thus generating the defect electrons responsible for the LT mechanism.     

Anomalous conductivity effects in (Na,K) mixed crystals of the β-Al2O3 type

Anomalous behavior has been observed in the ionic conductivity of (Na,K) mixed crystals of the alkali gallates and aluminate of the β-Al₂O₃ type fast ion conductors. The conductivity goes through a minimum at some intermediate composition as a consequence of a maximum in the activation energy, and is most pronounced in the (Na,K)-β-gallate, followed by (Na,K)-β-Al₂O₃ and (Na,K)-β“-gallate. The effect is similar to the well-known “mixed alkali effect” in glasses. A second anomaly consisting of a pronounced increase in conductivity over about a 70° temperature range, without any permanent change in activation energy, was observed for some compositions of (Na,K)-β“-gallate.     

Unusual thermal conductivity of the negative thermal expansion material, ZrW2O8

In order to investigate the relationship between negative thermal expansion and other thermal properties, the thermal conductivity of the α-phase of ZrW₂O₈ has been determined from 1.9 to 390 K. In addition, the heat capacity was measured from 1.9 to 300 K. The thermal conductivity of ZrW₂O₈ is low, glass-like and close to its theoretical minimum value. The phonon-phonon coupling of the highly anharmonic low-frequency modes which are responsible for negative thermal expansion in ZrW₂O₈ appears to be highly efficient, leading to short phonon mean free paths and exceptionally low thermal conductivity.     

Ionic conductivity of Li2NaK(SO4)2

A DSC study of Li₂NaK(SO₄)₂ in the range 300∽925 K has revealed that the compound undergoes phase transitions at 654, 682, 778 and 866 K, before melting congruently at 900 K. The five phase which are observed are designated I, II, III, IV and V with increasing order of temperature. A comparison of the enthalpy of melting with the transition enthalpies suggests that the phases IV and V are plastic phases. The ionic conductivity was measured in the range 584∽895 K by an ac impedance technique. The phase IV showed the smallest activation energy as determined from the temperature dependence of the conductivity (E_a=0.82 eV). The highest conductivity (1.0 Ω⁻¹ cm⁻¹) was observed in phase V at 895 K.     

Thermal conductivity and electrical resistivity of the high-Tc superconductor YBa2Cu3O9−Δ

Thermal conductivity and electrical resistivity of single-phase YBa₂Cu₂O_9−Δ compound were measured in the superconducting (T_c=89.5 K) and normal states, in the temperature range 5–320 K. The electronic component of the total thermal conductivity was estimated to be 20%. The electrical resistivity changed linearly in the normal state up to highest measured temperature.     

TiO2/ZnO纳米薄膜界面热导率的分子动力学模拟

采用平衡分子动力学方法及Buckingham势研究了金红石型TiO₂薄膜与闪锌矿型ZnO薄膜构筑的纳米薄膜界面沿晶面[0001](z轴方向)的热导率.通过优化分子模拟初始条件中的截断半径r_c和时间步后,计算并分析了平衡温度、薄膜厚度、薄膜截面大小对热导率的影响.研究表明,薄膜热导率受薄膜温度和厚度的影响很大,当温度由300 K升高600 K时,薄膜的热导率逐渐减小;当薄膜厚度由1.8 nm增大到5 nm时,热导率会逐渐增大;并在此基础 关键词： 热导率 分子动力学 2/ZnO纳米薄膜界面')" href="#">TiO₂/ZnO纳米薄膜界面 数值模拟     

Study of trapping and recombination centres in Tl2InGaTe4 chain crystals by dark electrical conductivity and photoconductivity measurements

Dark electrical conductivity and photoconductivity of Tl₂InGaTe₄ single crystals have been measured and analyzed in the temperature region 100–300 K. The dark electrical conductivity measurements revealed an intrinsic- or extrinsic-type of conductivity above or below 210 K, respectively. From intrinsic conductivity data analysis, the energy band gap of Tl₂InGaTe₄ crystals was determined as 0.85 eV. In the extrinsic region, the dark conductivity arises from a donor energy level located at 0.30 eV below the conduction band. The photocurrent increases with increasing illumination intensity. The recombination mechanism in the crystal changes as temperature decreases due to the effect of exponential trapping centres. Two trapping and/or recombination centres located at 89 and 27 meV were determined from the temperature dependence of the photocurrent, which decreased or increased with increasing temperature in the regions above or below 180 K, respectively.     

Thermal,Electrical and Optical Studies of Phase Transitions in Ag2CdI4 Solid Electrolyte

The article deals with the preparation method of bulk Ag₂CdI₄ superionic material and with investigations of structural phase transitions (PT) which take place in the 100÷450 K temperature range. The phase transitions were studied by thermal, electrical and luminescence methods. The temperature dependencies of thermal expansion, heat capacity, thermal conductivity, electric conductivity and excitation luminescence spectra show that in the temperature range 100 ÷ 450 K Ag₂CdI₄ possesses a sequence of structural changes at 180 ÷190 K, 320 ÷ 330 K, 350 ÷ 370 K and at T>400K. The nature and mechanisms of the observed structural changes are discussed.     

Metallic conductivity of quasi-one-dimensional conductor copper vanadium bronze

The d.c electrical conductivity of oxygen deficient β-phase copper vanadium bronze was measured over the range 1.5 k<T<300 K. At the limit of the large oxygen deficiency and the large copper content (Cu_0.50V₂O_4.80) the bronze retained metallic conductivity down to 1.5 K.     

Thermal conductivity of Na<Subscript>2</Subscript>W<Subscript>2</Subscript>O<Subscript>7</Subscript> crystal

The thermal conductivity of Na₂W₂O₇ single crystal has been studied along the main crystallographic directions at temperatures of 50–573 K. A low thermal conductivity is found to correlate with a significant difference in the cation weight.     

Factors affecting ionic conductivity in the lithium conducting glassy solid electrolytes

The electrical conductivity results of lithium borosilicate glasses with addition of Li₂SO₄ and LiCl have been critically analyzed. In general, it is observed that the factors viz. lithium fraction, f_Li and the number of non-bridging oxygens (NBOs) govern the ionic conductivity in the lithium conducting glasses. For the same f_Li, the presence of mixed formers in the glass gives higher conductivity compared to that of the glass with only one former. Thus the competitive network of glass in mixed former systems provides higher mobilities for lithium ions and hence high ionic conductivity. The addition of Li₂SO₄ and LiCl in the lithium borosilicate glasses gave enhancement in the conductivity. However, the mechanism of enhancement in conductivity is different in the two glass systems. The comparison of the result of binary, ternary and quaternary glass systems suggests that in general, the decrease in activation energy, increase in f_Li and increase in NBOs gives rise to enhancement in conductivity. For the same value of f_Li the higher conductivity is exhibited by glasses with lower value of K (K=SiO₂/B₂O₃). Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Anisotropy of the electrical conductivity of lithium heptagermanate crystals

The electrical conductivity σ of single crystals of lithium heptagermanate Li₂Ge₇O₁₅ is studied in an electric field in the frequency range 0.5–100 kHz at temperatures ranging from 300 to 700 K. Heating the crystal above 500 K gives rise to a pronounced anisotropy in the electrical conductivity, which differs in magnitude by one to two orders of magnitude for different directions of the measurement field along the crystallographic axes. It is shown that an increase in the electrical conductivity σ with increasing temperature originates from charge transfer with an activation energy U = 1.04 eV. It is assumed that the thermally activated contribution to the electrical conductivity is governed by transport of lithium interstitial ions along channels in the structure of the Li₂Ge₇O₁₅ compound.     

Growth and dc conductivity studies of tripotassium sodium dichromate single crystal

DC electrical conductivity studies were carried out along the three crystallographic axes for tripotassium sodium dichromate (K₃Na(CrO₄)₂ or KNCr). Earlier studies of phase transition in this crystal show successive phase transitions at 239 K and 853 K. In this paper we report the dc electrical conductivity measurements in the temperature region 303–430 K along the crystallographic axes. An anomaly in conductivity was obtained around 326 K along both the axes. This may be attributed as due to a newly observed phase transition in the crystal. DSC taken for the sample also shows exothermic peak supporting the occurrence of newly observed phase transition.     

Electric and electrochemical properties of solid CdBr2·4H2O in the stage of dehydration

The electric conductivity of solid crystallohydrate CdBr₂·4H₂O was measured at temperatures ranging from room temperature up to 673 K. By means of thermal analysis, infrared spectroscopy and electrochemical methods the conductivity mechanism in certain temperature ranges was assumed. The relatively low conductivity before the beginning of dehydration (≈10^?4 S/m, with activation energy of 38.2 kJ/mol)_originates from the movement of H⁺ ions. With a rise in temperature, the structural changes, due to dehydration, cause a change in the nature of the charge carrier and the conductivity mechanism. Gradual dehydration which starts at ≈310 K activates new charge carriers and causes a sudden increase in the conductivity which remains relatively high (≈1 S/m) up to ≈383 K, until the liberated water, evaporating, leaves the sample. The conductivity of the dehydrated sample is very low (≈10^?6 S/m).     

Electrical conduction in undoped and yttrium-doped Na2SO4

The electrical conductivity of undoped and yttrium-doped Na₂SO₄ has been measured by the ac two-terminal method at temperatures between 540 and 1075 K in air or in SO₂O₂SO₃ atmospheres. At high temperatures such as 1075 K, doping of 1.7 at% yttrium (Y) decreases the conductivity, which indicates that the Frenkel defect of sodium ions is pre-dominant in Na₂SO₄ and that the mobility of the interstitial ions is higher than that of the vacancies. However, the vacancy concentration is high enough to increase the conductivity in the samples doped with 2.0–3.8 at% Y. A further addition of yttrium decreases the electrical conductivity again, suggesting the appeareance of defect interactions such as ordering or clustering of the defects. The electrical conductivity of the undoped and the 4 at% Y-doped Na₂SO₄ is independent of the SO₃ partial pressure. The complex impedance analysis shows that the grain boundary resistance increases with sintering time. This is probably caused by a decrease in the contact area between grains during sintering.     

Thermal conductivity and expansion of PbF2 single crystals

In order to check a phenomenon of the negative correlation between ionic and thermal conductivities of solid substances, we studied the thermal conductivity and expansion of cubic PbF₂ single crystals at 50–300 and 5.6–317 K, respectively. We found that lead difluoride had a thermal expansion coefficient α that was equal to (28.5 ± 0.3)10⁻⁶ K⁻¹ at 300 K, and a thermal conductivity coefficient k(T) was equal to 1.40 ± 0.07 W/(m K) at the same temperature. Thus, the thermal conductivity for PbF₂ is the lowest among fluorite-type MF₂ (M = Ca, Sr, Ba, Cd, Pb) thermal conductivities, whereas its fluoride-ion conductivity is the highest one among MF₂ (M = Ca, Sr, Ba, Cd, Pb) ionic conductors.

     

Semiconducting properties of CoO thin films

This paper reports electrical properties of CoO thin films of different thickness in the range 0.375 – 7.95 μm. Both electrical conductivity and thermopower were measured at elevated temperatures (1223 – 1423 K) and under controlled oxygen partial pressure (5 − 2.1x10⁴ Pa). It was found that at low p(O₂) the electrical conductivity decreases with film thickness. The activation energy of the electrical conductivity (E_a) in air decreases with the oxide thickness from 0.56 eV at 0.375 μm to 0.52 eV for massive CoO while at low p(O₂)=5 Pa the E_a is independent of the thickness (E_a = 0.46 eV). The reciprocal of the p(O₂) exponent of the electrical conductivity (n_δ) in the range 1223 K – 1373 K is close to four for the 7,95 μm film and is about 3.5–3.7 for the 0.375 μm film. The electrical properties of the CoO thin films are considered assuming different defect structures in the bulk phase and the surface layer.