Radiolysis of mixed KI + RbI and KI + CsI powders

Abstract

Pure and mixed powders of KI + RbI and KI + CsI are irradiated by X-rays at room temperature. V-type defects are identified by means of Raman scattering experiments. Raman spectra show that similar defects are obtained in pure powders or crystals. Iodine molecules are stabilized in KI in the form of large clusters (I₂)_n while I³ _- ions are obtained in RbI and CsI.     

Influence of pyrazole on the photovoltaic performance of dye-sensitized solar cell with polyvinylidene fluoride polymer electrolytes

We investigate the influence of the pyrazole content on the polyvinylidene fluoride (PVDF)/KI/I₂ electrolytes for dye-sensitized solar cells (DSSCs). The solid polymer electrolyte films consisting of different weight percentage ratios (0 20, 30, 40, and 50 %) of pyrazole doped with PVDF/KI/I₂ have been prepared by solution casting technique using N,N-dimethyl formamide (DMF) as a solvent. The as-prepared polymer electrolyte films were characterized by various techniques such as Fourier transform infrared spectroscopy (FT-IR spectroscopy), differential scanning calorimetry (DSC), X-ray diffractometer (XRD), alternate current (AC)-impedance analysis, and scanning electron microscopy (SEM). The 40 wt% pyrazole-PVDF/KI/I₂ electrolyte exhibited the highest ionic conductivity value of 9.52?×?10^?5 Scm^?1 at room temperature. This may be due to the lower crystallinity of PVDF and higher ionic mobility of iodide ions in the electrolyte. The DSSC fabricated using this highest ion conducting electrolyte showed an enhanced power conversion efficiency of 3.30 % under an illumination of 60 mW/cm² than that of pure PVDF/KI/I₂ electrolyte (1.42 %).     

Ionic conductivity in tysonite-type solid solutions La1−xBaxF3−x

The ionic conductivity of single crystals of tysonite-type solid solutions La_1?xBa_xF_3?x(0?x?0.095) has been studied parallel and perpendicular to the crystallographic c axis in the temperature range 293–1300 K. Three regions can be discerned in the compositional dependence of the ionic conductivity: (i) the “pure” crystal, in which at room temperature no exchange occurs between different types of anion sites in the tysonite structure; (ii) an intermediate region(0 < x < 7 × 10^-2) which reveals changes in both the conductivity activation enthalpy and the magnitude of the conductivity; (iii) a concentrated solid-solution region (x > 7 × 10^-2), where fluoride ions interchange easily among the different anion sublattices. Diffusion coefficients calculated from ionic conductivity results, are in good agreement with those calculated from ¹⁹F NMR measurements. Using the present data, along with ¹⁹F NMR data, dielectric relaxation data and structural considerations, mechanisms governing the ionic conductivity are proposed.     

Conductivity enhancement in fluorite-structured Ba1−xLaxF2+x solid solutions

The ionic conductivity of single crystals of the fluorite-structured solid solutions Ba_1?xLa_xF_2+x(10^?3 <×<0.45) has been studied as a function of temperature and composition in the range 300–900 K. Three regions can be discerned in the concentration dependence of the ionic conductivity: a dilute concentration region (x<10^?3), where classic relations between solute content and ionic conductivity hold; an intermediate concentration region (10^?3<x?5×10^?2), where large changes occur in the conductivity activation enthalpy and the magnitude of the conductivity; and a concentrated solid solution region (x?5×10^?2) characterized by enhanced ionic motion. In the dilute region the migration enthalpy for interstitial fluoride ions is determined to be 0.714 eV, while a value of 0.39 eV is found for the (La_BaF_i)^X association enthalpy. The defect chemistry in the intermediate concentration region is shown to be controlled by a superlinear increase of the concentration of mobile defects, while in the concentrated solid solution region a composition-independent amount of ≈1 mole% of interstitial fluoride ions with enhanced mobility, carry the current.     

Effects of compositions on properties of PEO–KI–I2 salts polymer electrolytes for DSSC

The effects of compositions on properties of PEO/KI/I₂ salts polymer electrolytes were investigated to optimize the photovoltaic performance of solid state DSSCs. XRD pattern for the mole ratio 12:1 of [EO:KI] was showed the formation of complete amorphous complex. DSC results also confirmed the amorphous nature of the polymer electrolyte. The highest value of ionic conductivity is 8.36 × 10^− 5 S/cm at 303 K (ambient temperature) and 2.32 × 10^− 4 S/cm at 333 K (moderate temperature) for the mole ratio 12:1 of EO:KI complex. The effect of contribution of [I⁻] and [I₃⁻] concentration with conductivity were also evaluated. FTIR spectrum reveals that the alkali metal cations were co-ordinated to ether oxygen of PEO. The formation of polyiodide ions, such as symmetric I₃⁻ (114 cm^− 1) and I₅⁻ (145 cm^− 1) caused by the addition of iodine was confirmed by FT Raman spectroscopic measurements. The optimum composition of PEO–KI–I₂ polymer electrolyte system for higher conductivity at ambient and moderate temperatures was reported. A linear Arrhenius type behaviour was observed for all the PEO–KI polymer complexes. Transport number measurements were carried out for several polymer electrolyte compositions. Dye-sensitized solar cells were fabricated by using higher conductivity polymer electrolyte compositions and its photoelectrochemical performance was investigated. The fill factor, short-circuit current, photovoltage and energy conversion efficiency of the DSSC assembled with optimized electrolyte composition were calculated to be 0.563, 6.124 mA/cm², 593 mV and 2.044% respectively.     

Solid state reactions and transport properties in the quasibinary system AgI/RbI

The reactions between AgI and Rb₂AgI₃, RbI and RbAg₄I₅ and AgI and RbI have been investigated by measurements of reaction layer thickness and by experiments with inert markers. A theoretical derivation of the growth kinetics for reactions with double layers is given. The Rb⁺-diffusion coefficients, which are needed to apply these relations to the reaction between AgI and RbI, have been obtained from an investigation of the other two reactions which form only a single product layer. The diffusion coefficient of Ag⁺in Rb₂AgI₃ was also determined from conductivity measurements on Rb₂AgI₃.     

The influence of chromium on the defect structure and their mobility in nonstoichiometric cobaltous oxide

Defect structure and the mobility of point defects in pure metal deficient cobalt oxide (Co_1−yO) and in Co_1−yO-Cr₂O₃ solid solutions have been studied as a function of temperature (1223-1573 K) and oxygen pressure (10-10⁵ Pa) using microthermogravimetric techniques. It has been shown that the predominant defects in pure and Cr-doped cobaltous oxide are singly ionized cation vacancies, and 3% at of dopant is high enough to fix the concentration of predominant defects in such solid solutions on a constant level being much higher than in pure Co_1−yO. Re-equilibration rate measurements have demonstrated that the chemical diffusion coefficient and thereby the mobility of point defects in pure Co_1−yO is concentration independent, strongly suggesting that in spite of rather high their concentration no interactions and clustering of defects is to be expected. On the other hand, in Cr-doped cobaltous oxide, re-equilibration rate measurements have shown, that in this case the defect structure is more complicated, although singly ionized cation vacancies seem to be still predominant defects.     

Phase relations, ionic transport and diffusion in the alloys of Cu2S-Ag2S mixed conductors

Results are reported of the phase relations in the (Ag_x-δ/2Cu_1-x)₂ system, ionic conductivity, self-diffusion and chemical diffusion coefficients for the solid solutions as a function of the composition x, degree of non-stoichiometry δ, and temperature in the range 473 – 673 K. The extensions of the homogeneity regions for single-phases are determined. Total and partial ionic conductivity values are given for copper and silver ions for the solid solutions. Measurements of the self-diffusion coefficient and the correlation factors are reported. It is shown that for solid solutions that the chemical diffusion is well described in terms of the phenomenological theory of ionic transport in mixed ionic electronic conductors.     

Kinetic properties of p-Mg2SixSn1 ? x solid solutions for x < 0.4

The results of a study of Mg₂Si _x Sn_{1 − x} solid solutions (x = 0.25, 0.3, 0.35, 0.4) are reported. The measurements performed cover the Seebeck coefficient, electrical conductivity and the Hall coefficient over broad ranges of temperatures (80–700 K) and carrier concentrations (10¹⁸ to 6 × 10²⁰ cm⁻³). These measurements were used to derive the band structure parameters (band gap, hole mobility, hole effective mass). The effective mass of holes was found to grow strongly with an increase in their concentration.     

Microhardness of crystals of KBr-KI solid solutions with Sr2+ and OH− impurities

The microhardness, conductivity, and dielectric-loss angle have been studied in KBr and KI single crystals and in their solid solutions with Sr²⁺ and OH^– impurities. It is shown that the Sr²⁺ impurity dissolves only slightly in KI crystals and in KBr-KI solid solutions having a large KI content. Addition of the anionic OH^– impurity to the molten salts reduces the micro-hardness of KBr but it does not affect that of KI crystals or KBr-KI solid solutions having a large KI content. The composition dependence of the microhardness for KBr-KI solid solutions is constructed on the basis of the microhardness values for the corresponding crystals purified of cationic impurities of different valence.Translated from Izvestiya VUZ. Fizika, No. 10, pp. 18–21, October, 1969.     

The effect of composition,electron irradiation and quenching on ionic conductivity in a new solid polymer electrolyte: (PEG)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>NH<Subscript>4</Subscript>I

We have prepared, characterized and investigated a new PEG-2000 based solid polymer electrolyte (PEG) _x NH₄I. Ionic conductivity measurements have been made as a function of salt concentration as well as temperature in the range 265–330 K. Selected compositions of the electrolyte were exposed to a beam of 8 MeV electrons to an accumulated dose of 10 kGy to study the effect on ionic conductivity. The electrolyte samples were also quenched at liquid nitrogen temperature and conductivity measurements were made. The ionic conductivity at room temperature exhibits a characteristic double peak for the composition x = 20 and 70. Both electron beam irradiation and quenching at low temperature have resulted in an increase in conductivity by 1–2 orders of magnitude. The enhancement of conductivity upon irradiation and quenching is interpreted as due to an increase in amorphous region and decrease in crystallinity of the electrolyte. DSC and proton NMR measurements also support this conclusion.      

Organic-inorganic nanocomposite materials prepared by the sol-gel route as new ionic conductors in quasi solid state electrolytes

Nanocomposite organic/inorganic materials made through sol-gel method exhibit high values of ionic conductivity when they were impregnated with the redox couple I ₃ ⁻ /I⁻ Two different kinds of nanocomposite materials, depending on the different interactions between silica and poly(ethylene)oxide or poly(propylene)oxide blends, were prepared by the sol-gel technique in room temperature. Gels, for both nanocomposite materials, were obtained by acetic acid catalyzed solvolysis and were regulated by formation of intermediate products, such as silicon ester and -Si-O-Si-oligomers. Time-resolved fluorescence techniques and conductivity measurements were performed in order to define the parameters which allow maximum probe mobility and minimum confinement conditions with the aim to apply these materials in quasi solid state electrolytes. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Organic dopant added polyvinylidene fluoride based solid polymer electrolytes for dye-sensitized solar cells

The effect of phenothiazine (PTZ) as dopant on PVDF/KI/I₂ electrolyte was studied for the fabrication of efficient dye-sensitized solar cell (DSSC). The different weight percentage (wt%) ratios (0, 20, 30, 40 and 50%) of PTZ doped PVDF/KI/I₂ electrolyte films were prepared by solution casting method using DMF as a solvent. The following techniques such as Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray diffractometer (XRD) and AC-impedance analysis have been employed to characterize the prepared polymer electrolyte films. The FT-IR studies revealed the complex formation between PVDF/KI/I₂ and PTZ. The crystalline and amorphous nature of polymer electrolytes were confirmed by DSC and XRD analysis respectively. The ionic conductivities of polymer electrolyte films were calculated from the AC-impedance analysis. The undoped PVDF/KI/I₂ electrolyte exhibited the ionic conductivity of 4.68×10⁻⁶ S cm⁻¹ and this value was increased to 7.43×10⁻⁵ S cm⁻¹ when PTZ was added to PVDF/KI/I₂ electrolyte. On comparison with different wt% ratios, the maximum ionic conductivity was observed for 20% PTZ-PVDF/KI/I₂ electrolyte. A DSSC assembled with the optimized wt % of PTZ doped PVDF/KI/I₂ electrolyte exhibited a power conversion efficiency of 2.92%, than the undoped PVDF/KI/I₂ electrolyte (1.41%) at similar conditions. Hence, the 20% PTZ-PVDF/KI/I₂ electrolyte was found to be optimal for DSSC applications.     

Bi<Subscript>13-x</Subscript>Me<Subscript>x</Subscript>Mo<Subscript>5</Subscript>O<Subscript>34±δ</Subscript> (Me = Mg,Ca, Sr,Ba) solid solutions: synthesis and properties

A series of complex oxides Bi_13-xMe_xMo₅O_34±δ, Me = Mg, Ca, Sr, Ba were synthesized and studied. The solid solutions ranges and polymorphic modifications limits were determined. High temperature X-ray powder diffraction measurements showed the deviation of unit cell parameters dependence versus temperature from the linear function. Processes of forming of ceramic samples based on the synthesized powders were analyzed, and dense ceramic samples were obtained. Impedance spectroscopy displayed the changes of slope of Arrhenius plots which correspond with the HT-XPRD measurements. The presence of two different forms of monoclinic modification was supposed. The studied materials are promising ionic conductors, with the highest conductivity values about 6?×?10^?3 S cm^?1 at 973 K and 1.4?×?10^?4 S cm^?1 at 623 K.     

The effect of sulfide substitution in the mixed conductor Cu7PSe6

Cu₇PSe₆ is a mixed conductor exhibiting structural phase transitions above and below room temperature that are accompanied by step-like changes in electrical conductivity. The substitution of S²⁻ for Se²⁻ in Cu₇PSe₆ significantly enhances electrical conductivity at room temperature compared to that observed for the pure compound. In the case of Cu₇P(Se_0.80S_0.20)₆, a nearly temperature-independent electrical conductivity exceeds 1 S/cm with no evidence of any phase transitions throughout the temperature interval 200-400 K. However, the ionic contribution accounts for just 2% of the total electrical conductivity in this solid solution at room temperature.     

Electronic conductivity in La1−xBaxF3−x crystals

The electronic conductivities of solid solutions La_1?xBa_xF_3?x (0 ? x ? 0.0952) were investigated up to 533 K using the Hebb-Wagner dc polarization technique. The electrochemical cell (-)La|La_1?xBa_xF_3?x|Pt(+) has been utilized with Pt as the ion-blocking electrode. Under steady-state conditions the La_1?xBa_xF_3?x solid solutions exhibit electronic conductivity. The electronic conductivity vanishes in pure LaF₃. Together with ac conductivity measurements it appears that the ionic transference number for La_1?xBa_xF_3?x (0 ? x ? 0.0952) is essentially unity over the temperature range studied.     

Electrical properties of solid iodo mercurates resulting from the reaction of HgI2 with alcaline iodides

Potassium iodide solutions are currently used during the fabrication process of mercuric iodide based nuclear radiation detectors. However, KI treatment leaves the HgI₂ surface covered with a residual compound (namely the potassium tri-iodo mercurate) which has a significant influence on the surface properties and stability of mercuric iodide devices and therefore on the detectors characteristics. Looking for other solutions to etch mercuric iodide, we found it interesting to investigate the electrical properties of the compounds which may form when etching HgI₂ in NH₄I, NaI, and RbI. For this purpose, solid iodo mercurates with the cations ammonium, sodium, and rubidium, have been prepared by reacting HgI₂ with the solutions of interest. Study of the electrical properties of these samples and comparison with those of potassium tri-iodo mercurate ones, especially with respect to humidity, indicates noticeable stability differences in presence of water vapour. This could have interesting consequences on the surface cleaning of mercuric iodide. PACS 81.65.Cf; 81.10.Dn; 72.90.+y     

Ion-electron transfer in solid solutions Rb2 ? 2xFe2 ? xPxO4

The rubidium monoferrite RbFeO₂-based solid solutions with the composition Rb_{2 − 2x} Fe_{2 − x} P _x O₄ have been synthesized, and their crystal structure and the temperature and concentration dependences of the total and electron conductivities have been studied. The introduction of P⁵⁺ ions has been found to sharply decrease the electron conductivity that prevails in pure rubidium monoferrite and, at the same time, to increase the ionic conductivity. The latter becomes dominant as the phosphorus concentration increases. The maximum rubidium-cation conductivity of the materials under study is ∼3 × 10⁻² S/cm at 300°C and ∼3 × 10⁻¹ S/cm at 700°C. The results have been compared with the previously obtained data for similar solid solutions based on rubidium monogallate and monoaluminate.     

Etching of mercuric iodide in cation iodide solutions

The surface properties of mercuric iodide after etching in various cation iodide solutions have been investigated in terms of dissolution rate, morphology, electrical properties and reaction with water vapour. No significant differences have been observed in the etching rates. However, dissolution of HgI₂ in NH₄I, NaI, KI or RbI leaves the surface more or less covered with a residual iodo mercurate compound whose electrical properties and stability with regard to humidity may noticeably influence the behaviour of mercuric iodide devices. The smallest effect has been observed for etching in NaI.     

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.