Bounded diffusion in solid solution electrode powder compacts. Part I. The interfacial impedance of a solid solution electrode (MxSSE) in contact with a m+-ion conducting electrolyte

The transient and ac electrical response of electrochemical systems containing a solid solution electrode is derived using Laplace transform methods. First, the operational impedance of the electrolyte/solid solution electrode interface is derived, for both asymmetrical and symmetrical cell systems. From the operational impedance the current, voltage and ac impedance response is calculated. By combination of semi-infinite and bounded diffusive behaviour, both the chemical diffusion coefficient of the inserted ions and the thermodynamic factor (? ln a/? ln c) can be obtained from kinetic data only.     

The thermoelectric power in AgxTiS2 and AgxNiPS3. Part II. The ionic component of the thermoelectric power

The EMF of the isothermal cells: Ag/AgI/Ag_xTiS₂: 0<x<1, T=150–200°C/Ag_xNiPS₃: 0<x<3, T=150–350°C has been measured. From the EMF-x curves the existence ranges of the 2-phase (stage I and II) regions ?0.16<x<0.32 for the Ag/Ag_xTiS₂ system at 190°C; 0.20 < x < 0.50 and 1 < x < 2 for the Ag/Ag_xNiPS₃ system at 400°C - have been determined. The results are sustained by X-ray diffraction and electrical conductivity measurements. From the EMF-T curves the partial enthalpy (ΔH?_Ag) and entropy (ΔS?_Ag) of dissolution of silver in the Ag_xSSE (solid solution electrode) materials were obtained. In the case of Ag_xTiS₂, ΔH?_Ag has a low absolute value, while ΔS?_Ag is distinctly positive. The EMF of the Ag/Ag_xNiPS₃ system also has a positive temperature coefficient. Furthermore, the ionic component of the thermoelectric power, ΔE/ΔT, of the thermogalvanic cells: Ag/AgI/Ag_xSSE/AgI/Ag Ag_xTiS₂: 0 < x < 1, T = 150–200°C( T ) (T+ΔT) Ag_xNiPS₃: 0 < x < 1, T= 150–350°C has been measured. The kinetically important heat of transport of silver ions in the Ag_xSSE materials has been determined in two ways: first from the dependence of the ionic Seebeck coefficient (?_Ag+) on reciprocal temperature; and second from direct calculation, using the data for ?_Ag+ and ΔS?_Ag. The heat of transport is much smaller than the activation enthalpy for Ag⁺-conduction, indicating a high ionic polaron binding energy in these materials.     

Electric field gradient,anisotropic shift,tetrahedral site occupation,and atomic motion in LixTiS2

New measurements of NMR lineshape parameters and relaxation rates have been made to characterize a carefully prepared set of samples of Li_xTiS₂, with x spanning the composition range from one-tenth to one. Electric quadrupole coupling constants are in general agreement with previous measurements, but display differences at the high end of the composition range and an unpredicted upturn as x tends toward zero. An anisotropic shift of the line has been discovered and its possible origins are discussed. An unexpected discontinuity in the linewidth-composition relation may be due to lithium occupation of tetrahedral sites at the level of a few percent. Lithium hopping rates derived from continuous wave NMR and pulsed NMR measurements are found to agree quite well with one another.     

Physicochemical properties of NaxCoO2 as a cathode for solid state sodium battery

An intercalation compound with composition Na_0.7CoO₂ has been synthesized through different preparative techniques such as solid state reaction, ball milling and sol gel techniques. The investigation reveals that the cathode material with an average particle size of about 500 nm of uniform morphology can be synthesized through sol gel technique. Further, this synthesis technique improves the stoichiometry of the sodium content significantly. The electrical resistivity of these cathode materials is found to be in the range of 4 to 12 mΩ-cm at 300 K. It has been observed that, the resistivity of the cathode material increases with increase in sodium content. The electrochemical cells with the configuration Na | [wt.% 0.3 PEO-0.7 PEG]₆:NaPO₃ |composite cathode material, have shown an open circuit voltage (OCV) value of 2.7 V. The (OCV) of the cells with the cathode prepared by sol-gel and ball milling route has shown a plateau region of about 40 h, when compared to the plateau region of 10 h for the battery with the cathode prepared by solid state reaction. The reduction in the particle size of the cathode material has improved the stability of the electrode electrolyte interface and thereby discharges characteristics.     

Tight-binding calculation of the optical conductivity in NaxCoO2

Optical conductivity in Na_xCoO₂ is calculated with tight binding approximation. The calculated gross features agree with the experimental findings. Interband transitions between nearly degenerate t_2g bands bring about absorption in the mid-infrared and near infrared regions. Structures observed at higher energies are also quite well reproduced with the present calculation. Possible effects of electron correlation are also briefly discussed.     

Structural and magnetic properties in the powder form of Sn1−xCrxO2 solid solution

Structural and magnetic properties were studied in powder form of Sn_1−xCr_xO₂ with x=0.01, 0.02, 0.03, 0.04 and 0.05 in nominal composition. The structural parameters were obtained at room temperature by the Rietveld refinement of the x-ray powder diffraction profiles. Samples of x=0 to 0.04 are tetragonal phase with a space group P4₂/mnm. The lattice parameters indicate three-step changes with increasing Cr content. The distortion of the metal-oxygen octahedral unit occurs. The substitution of Cr ions on the Sn sites shortens the lattice parameters and the octahedral unit becomes elongated with a displacement of an apical oxygen from x=0 to x=0.02. The incorporation of Cr over x=0.02 leads to the recovery of the length of lattice parameters together with a relaxation of the octahedral unit. This result indicates a possible interstitial occupation of Cr ions from x=0.03 to x=0.04. The Cr doping reaches a saturation limit at x=0.05 with a trace of the excess Cr oxides in the x-ray study. A room temperature ferromagnetism appears in the sample with x=0.01 and becomes remarkable in one with x=0.02. The magnetization decreases with increasing the Cr doping with the amount x>0.02. Thus, the appearance of ferromagnetism highly correlated with the oxygen displacements at the apical position of the octahedral in the Sn_1−xCr_xO₂ system at room temperature. The critical oxygen displacement in the elongated octahedral at around x=0.02 may encourage the vacancy of the apical oxygen and eventually leads to appearance of a ferromagnetism based on an F-center exchange with a micro- and/or nano-structural transition. The observed ferromagnetism is highly correlated with the averaged structural change appeared in the x-ray powder diffraction.     

Preparation of LixCa1−xTiO3 solid electrolytes by the sol-gel method

Solid electrolytes based on lithium doped CaTiO_3,Li_xCa_1−xTiO₃ (x=0-0.5) were prepared by the sol-gel method in an ethanol and water mixture medium. Phase identification and morphology observation of the products were carried out by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that the Li_xCa_1−xTiO₃ powders sintered above 700 ^°C are of cubic perovskite structure and the mean size of Li_xCa_1−xTiO₃ powders is about 80 nm. A study of ionic conductivity by AC impedance implies that the conductivity of Li_xCa_1−xTiO₃ increases with the increase of substituted Li⁺ ions and reaches a maximum value of 4.53×10⁻⁴ S cm⁻¹ at x=0.1, and then decreases for x>0.1.     

Neutron powder diffraction study of the Nd(Ba1−xNdx)2Cu3O7+δ solid solution

The Nd(Ba_1−xNd_x)₂Cu₃O_7+δ solid solution, Nd123ss, has been investigated by neutron powder diffraction and Rietveld analysis. It is confirmed that the crystal structure of its Nd-rich limit, Nd(Ba_0.55Nd_0.45)₂Cu₃O_7.33, is satisfactorily described in the space group Bmmm (a=7.7679(3), b=3.8542(1), and c=22.9590(9) Å). The fourfold superstructure with respect to the orthorhombic cell of YBCO is due to ordering between Ba and Nd atoms in the bridging layer. Differences with previous works concern exclusively the distribution of O atoms in the ‘chain’ layer. Our results give strong indications that ordering also occurs for lower Nd contents.     

Investigations on magnetically-dilute CoxZn1−x Rh2O4 spinel solid solution

Magnetic measurements have been performed on polycrystalline solid solutions Co_xZn_1?xRh₂O₄ with a spinel structure. The samples with 0.50? x ? 1.00 are antiferromagnets. The samples with x?0.40 do not show a magnetic order, and their magnetic behavior can be explained taking into account the presence of finite clusters of Co²⁺ ions and paramagnetic isolated ions.     

Epr study of CoxZn1−xRh2O4 spinel solid solution

The EPR powder spectra of Co_xZn_1?xRh₂O₄ spinel solid solutions have been studied in the temperature range, 6–300 K for x ? 0.10. The principal features of the spectrum have been examined as a function of the temperature and of the composition. Evidence is presented that the solid solutions are antiferromagnetically ordered for x ? 0.40.     

Structural characterization for the chemically Li ion extracted LiyCoO2, LiyCo0.95Ga0.05O2, and LiyCo0.9Ga0.1O2 compounds

Chemical Li ion extraction processes have been carried out for pristine LiCoO₂, LiCo_0.95Ga_0.05O₂, and LiCo_0.9Ga_0.1O₂ compounds by swirling them in 0.35 M H₂SO₄ solution. It is confirmed from XRD patterns that the compounds maintain the two-dimensional framework with pristine-type structure even after the acid treatment up to 12 h. The Ga-substituted compounds keep Li ions for longer time on the acid treatment rather than the LiCoO₂. The average oxidation state of Co ions increases with the Li⁺ ion extraction time up to 3.45+. The local structure refinements for the chemically Li⁺ ion extracted compounds have been investigated by Co K-edge X-ray absorption spectroscopy. The extraction causes the increase of Debye-Waller (DW) factor or static disorder around the Co ion. The DW factor of the Co-Co bond pair less increases with the extraction time for the Li_yCo_0.95Ga_0.05O₂, and Li_yCo_0.9Ga_0.1O₂ compounds than that for the LiCoO₂. The Ga-substituted compounds are more stable against acid treatments than the LiCoO₂, since more basic Ga³⁺ ion retards the structural distortion of the CoO₆ octahedra against the Li ion extraction.     

Thermochemistry of the high and ambient temperature lithium vanadium bronze phases LixV2O5

The enthalpies of formation of a series of high and low temperature phases in the ternary oxide system Li_xV₂O₅ have been determined by solution calorimetry. Samples of the former, α-Li_0.04V₂O₅, β-Li_0.30V₂O₅, β'-Li_0.48V₂O₅ and γ-LiV₂O₅, were prepared by solid state reaction at 650°C. The ambient temperature materials Li_0.1V₂O₅(I), Li_0.45V₂O₅(II) and Li_1.03V₂O₅(III) were prepared by n-butyl lithiation in hexane. The thermochemistries of the two classes of material were examined and related to structural features and to the observed behaviour of V₂O₅ as a battery cathode material in lithium cells.     

Structure, microstructure and ionic conductivity of the solid solution LiTi2−xSnx(PO4)3

The Nasicon compounds with the composition LiTi_2−xSn_x(PO₄)₃ (x=0-1.8) were synthesised by the solid state reaction. Their structures were determined from X-ray powder diffraction using Rietveld analysis. All the compositions present the space group R-3c. The refinements show that the Ti and Sn cations are statistically distributed over the same position while the Li ones are exclusively located on the M1 site. The lattice constants a and c exhibit linear variation over the whole composition range. The bond lengths are in accordance with those of other Nasicon structures. The SEM micrographs of the samples show relative porous microstructures. The ionic conductivity is about 10⁻⁴-10⁻⁵ S cm⁻¹; for the activation energy, a typical value of 0.32 eV is obtained for x=0.6 composition whereas significant deviation from linearity in the temperature dependence of the dc conductivity, is observed for the Sn-rich ones. This tendency is discussed along with the structural features.     

X-ray and spectroscopic investigations on polycrystalline CoxZn1−xIn2S4 solid solution

The system Co_xZn_1?xIn₂S₄ is investigated by means of X-ray diffraction, optical and EFR spectra. The ZnIn₂S₄-type structure exists up to x = 0.60, and spectroscopic investigations suggest that the cobalt ions are distributed among the tetrahedral as well as octahedral sites of the lattice.     

Theoretical investigations on the elastic and thermodynamic properties of Ti2AlC0.5N0.5 solid solution

We have performed theoretical studies on the elastic and thermodynamic properties of the solid solution: Ti₂AlC_0.5N_0.5. The lattice parameters, elastic constants, bulk, shear, Young's moduli, Poisson's ratio and Debye temperature were calculated and compared with those of the end members, Ti₂AlC and Ti₂AlN. The temperature dependence of the bulk moduli, thermal expansion coefficient and specific heats of Ti₂AlC_0.5N_0.5 were obtained from the quasi-harmonic Debye model. The calculated elastic and thermodynamic properties were compared with experimental data.     

Electronic structural properties and formation energy of Sn1−xPbxO2 solid solutions electrode

First-principles calculations based on density functional theory within the generalized gradient approximation have been performed for the Sn_1−xPb_xO₂ solid solution. The doped formation energies and electronic structures are also analyzed. Results show that the Sn_0.9375Pb_0.0625O₂ solid solution has the highest stability because of its minimum formation energy value of 0.04589 eV at a doping ratio of 0.0625. The SnO₂ lattice constants expand in a distorted rutile structure after Pb doping. The band structure and density of states calculations indicate that the band gap of SnO₂ narrowed due to the presence of the Pb impurity energy levels in the forbidden band, namely, Pb 6s energy band overlaps with the conductivity band in the F–Q direction. In addition, the number of electrons filled at the bottom of the conduction band increases from 0.13 to 3.96 after doping, resulting in the strengthening of the conductivity of the solid solution after doping of plumbum. The results provide a theoretical basis for the development and application of the Sn_1−xPb_xO₂ solid solution electrode.     

Effect of Li substitution on the magnetic properties of LixMg0.40Ni0.60−2xFe2+xO4 ferrites

Structural and magnetic properties of a series of polycrystalline spinel type ferrites with the nominal chemical composition Li_xMg_0.40Ni_0.60−2xFe_2+xO₄, where x=0.0-0.3 in steps of 0.05, were investigated thoroughly. The formation of spinel structure was confirmed by X-ray diffraction analysis. Lattice constants and average grain diameters increased with increase in Li content. The real part of the initial permeability (μ^/_i) is found to increase not only with increase in Li content up to x=0.25 but also with the increase in sintering temperature up to 1100 °C. However, it decreases for further increase in sintering temperature except for x=0 and 0.05 compositions. The grain size dependent μ^/_i is also observed clearly in this research. From the magnetization as a function of applied magnetic field plots, it is clear that all samples exhibit ferrimagnetic state at room temperature and have a low saturation field. The magnetization obtained is explained with the help of redistribution of cations in the tetrahedral and octahedral sites and spin canting due to weakening of exchange interaction.     

Lattice dynamics study of the solid solution (Bi1−xLax) FeO3 by i.r. spectroscopy

By i.r. absorption spectral measurements, (Bi_1?xLa_x) FeO₃ solid solution is shown to have phase transitions near x = 0.20; 0.40; 0.75, the range $\text{0.20?x?0.40}$ being of an intermediate nature.     

Raman spectra of Ba6−3xSm8+2xTi18O54 solid solution

Raman spectra of Ba_6−3xSm_8+2xTi₁₈O₅₄ solid solution were investigated as the function of x and sintering time. Reasonable explanations were provided about the Raman shifts and their intensities at 1013, 590, 751, 280, 232 cm⁻¹. 1013 cm⁻¹ demonstrates the existence of BaCO₃ phase in solid solution, 590 cm⁻¹ is the symmetric stretching mode of the basal oxygens of the octahedral; 280 and 232 cm⁻¹ are the symmetric stretching modes resulted from the tilt of octahedral when large cation sites are Sm³⁺ and Ba²⁺. The shoulder peak appearing around 302 cm⁻¹ is related to the vacancy produced by the unequal valence of Sm³⁺ and Ba²⁺.     

Aerosol-assisted flow synthesis of WxTi1−xO2 solid solution spheres with enhanced photocatalytic activity

In this paper, W_xTi_1−xO₂ solid solutions (x = 0.000, 0.005, 0.010, 0.015, and 0.020) microspheres were synthesized with an aerosol-assisted flow synthesis method. The resulting samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption, UV-vis diffuse reflectance spectrum (DRS) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the as-prepared catalysts were measured by the degradation of rhodamine B (RhB) under visible light irradiation (λ ≥ 420 nm). All the solid solutions exhibited higher photocatalytic activities than pure TiO₂ and the W_0.015Ti_0.985O₂ solid solution possessed the highest photocatalytic activity. The degradation constant of RhB on W_0.015Ti_0.985O₂ solid solution catalyst was about 15 times of that of the pure TiO₂ and 25 times of that of Degussa P25, respectively. This study provides an effective method to prepare visible light photocatalysts on a large scale.