T. Šalkus

Electrical conductivity studies in (Ag3AsS3)x(As2S3)1−x superionic glasses and composites

Compositional, frequency, and temperature studies of impedance and electrical conductivity in (Ag3AsS3)x(As2S3)1−x superionic glasses and composites were performed. Frequency range from 10 Hz to 3 × 109 Hz and temperature interval 300–400 K were used for the measurements. Compositional dependences of electrical conductivity and activation energy are analyzed; the most substantial changes are observed with the transition from (Ag3AsS3)0.4(As2S3)0.6 glass to (Ag3AsS3)0.5(As2S3)0.5 composite. With increase of Ag3AsS3 content, the investigated materials are found to have crystalline inclusions and show the two-phase composite nature. Addition of Ag3AsS3 leads to the increase of electrical conductivity whereas the activation energy decreases.

Structural and electrical investigation of (Ag3AsS3)x(As2S3)1−x superionic glasses

Structural studies of (Ag3AsS3)x (As2S3)1−x chalcogenide superionic glasses in the compositional range x = 0.3–0.9 were performed by scanning electron microscopy. Temperature and compositional dependences of transmission coefficient, electrical conductivity, and activation energy were investigated

XRD, XPS, SEM/EDX and broadband impedance spectroscopy study of pyrophosphate (LiFeP2O7 and Li0.9Fe0.9Ti0.1P2O7) ceramics

LiFeP2O7 and Li0.9Fe0.9Ti0.1P2O7 were synthesised by solid-state reaction and ceramics were sintered. The structure of compounds was studied in the temperature range 300–700 K by X-ray diffraction. Ceramics’ surfaces were investigated by scanning electron microscope. Binding energies of Fe 2p, P 2p and O 1s core levels at ceramics’ surfaces have been determined by X-ray photoelectron spectroscopy and different valence states of Fe and P were detected. Elemental compositions of the compounds were studied by energy dispersive X-ray spectrometer. Impedance spectroscopy was performed in the frequency range 10 Hz–3 GHz and in the temperature interval 400–700 K. The changes of the activation energy of ionic conductivity at 528 and 550 K for LiFeP2O7 and Li0.9Fe0.9Ti0.1P2O7, respectively, were found. The phenomena can be related to disordering in the unit cells of the compounds.

Characterization of NASICON-type Na solid electrolyte ceramics by impedance spectroscopy

Na solid electrolytes are cheaper than the ones of Li and could be of interest to apply in secondary batteries and gas sensors. In the present work, the NASICON-type Na1.3Ti1.7Al0.3(PO4)3 compound has been synthesized by Pechini method and the phase purity of the compound was confirmed by XRD. Ceramics of the compound were prepared in several different sintering temperatures and the morphology of the samples was examined by SEM. The investigation of the electrical properties was performed in 10 Hz to 3 ⋅ 109 Hz and 300–500 K frequency and temperature ranges by means of impedance spectroscopy. The impedance spectra were analyzed and observed dispersions were related to microstructure of the ceramics.

SINTERING OF OXYGEN ION CONDUCTIVE CERAMICS AND THEIR ELECTRICAL PROPERTIES

Oxygen ion conducting ceramics (Sc2O3)0.1(ZrO2)0.9, (Sc2O3)0.1(CeO2)0.01(ZrO2)0.89 and Ce0.9Gd0.1O1.95 were sintered from powders with different specific surface areas. The produced ceramics were studied by scanning electron microscopy and impedance spectroscopy methods. Impedance spectroscopy measurements were performed in a wide frequency range of 10 Hz–3 GHz at temperatures up to 900 K in air. Temperature dependences of bulk and total ionic conductivities of ceramics were investigated. High bulk ionic conductivity of the order of 1 S/m at 900 K for 10ScSZ and 10Sc1CeSZ ceramics was achieved. Total ionic conductivity for both types of 10GDC ceramics was of the order of 0.1 S/m at 700 K.

Preparation and characterization of Li2.9Sc1.9−y Y y Zr0.1(PO4)3 (where y = 0, 0.1) solid electrolyte ceramics

The solid electrolyte Li2.9Sc1.9− y Y y Zr0.1(PO4)3 (where y = 0, 0.1) compounds belong to monoclinic symmetry (space group P21/n) at room temperature. The Zr 3d, Sc 2p, P 2p, Y 3d, O 1s, and Li 1s core level X-ray photoelectron spectra (XPS) were fitted. The Li ions in ceramics without Y occupy two different positions and in the ceramics with Y they occupy one position in the lattice. The deconvolutions of the Zr 3d, P 2p, Sc 2p, and Y 3d core level XPS are associated with different valence states on the surfaces of the investigated ceramics. Anomalies of enthalpy, change of activation energy of ionic conductivity, anomalies of dielectric permittivity in the temperature range 420–520 K of investigated compounds were found. The phenomena are related to diffuse structure phase transition in the compounds. At temperatures 600 and 900 K, the compounds belong to orthorhombic symmetry (space group Pbcn).

Preparation and Characterization of Solid Electrolytes Based on TiP2O7 Pyrophosphate

The Li4xTi1-xP2O7 (x = 0, 0.06, 0.1, 0.2) powders have been synthesized by the solid state reaction and their ceramics have been sintered. The Li4xTi1-xP2O7 (x = 0.06, 0.1, 0.2) compounds have cubic superstructure 3×3×3 (space group Pa-3), which is also typical for TiP2O7 pyrophosphate. The electrical properties of the ceramics were investigated in the frequency range of 10 to 3·109 Hz and temperature interval of 400–720 K by impedance spectroscopy. The relaxation dispersion region in the conductivity and dielectric permittivitty spectra of Li4xTi1-xP2O7 (x = 0, 0.06, 0.1, 0.2) ceramics was found.

Some aspects of charge transport in Li0.5-xNaxLa0.5TiO3 (x = 0, 0.25) ceramics

In this work, the influence of partial substitution of Li to Na in Li0.5La0.5TiO3 (LLTO) compound was investigated by broad frequency range impedance spectroscopy (IS). The equivalent circuit method was used to relate the electric modulus spectra with confinement of mobile Li ions by rigidly arranged Na in the lattice of LLTO.

Structure and Electrical Properties of Li3–xSc2–xZrx(PO4)3 (x = 0, 0.1, 0.2) Ceramics

At room temperature solid electrolyte Li3−xSc2−xZrx(PO4)3 (x = 0, 0.1) compounds belong to monoclinic symmetry (space group P21/n) and the compound with x = 0.2 belongs to orthorhombic symmetry (Pbcn). At 900 K all the investigated compounds belong to orthorhombic symmetry (space group Pbcn). Anomalies of enthalpy, change of activation energy of ionic conductivity, anomalies of dielectric permittivity in the temperature range 420 K–660 K of investigated compounds with x = 0 and 0.1 were found. The phenomena are related to structure phase transition in the compounds. The relaxation dispersion regions were found in conductivity spectra for the all investigated samples. The frequency dispersion regions are caused by the relaxation processes in grain, grain – boundaries and electrodes. The temperature dependencies of the bulk conductivity and relaxation frequency in the bulk are governed by the same activation energy. It is shown that major role in the temperature dependence of bulk conductivity is played by Li+ ion mobility, which increases as temperature increases.

Electrochemical Performance of Ni-CGO Nano-Grained Thin Film Anodes for Micro SOFCs

NiO-Ce0.8Gd0.2O1.9-x (CGO) thin film anodes with thicknesses around 400 nm were prepared by air blast spray pyrolysis. The film composition was 60/40 vol% Ni/CGO in the reduced state. The films were deposited on tape-cast YSZ electrolytes. The material was amorphous after deposition and was crystallized by sintering in air between 650 and 1200°C. The temperature treatment resulted in films with average grain sizes of the NiO and CGO grains between 5 and 250 nm. The area specific resistance of the thin film anodes was measured in a humidified 1:4 H2:N2 atmosphere as a function of grain size within the temperature interval of 400-600°C. The area specific resistance (ASR) was predominantly depending on the grain size of the films. At 550°C, an ASR of 0.5 Ωcm 2 was found for the 5 nm grain size anode. The value increased to 30 Ωcm 2 for the 250 nm grain size anode.