Till Frömling

Enhanced lithium transference numbers in ionic liquid electrolytes.

Ion transport processes in mixtures of N-butyl- N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP-TFSI) and lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) were characterized by ac impedance spectroscopy and pulsed field gradient NMR. Molar ratios x = n Li-TFSI/( n Li-TFSI + n BMP-TFSI) up to 0.377 could be achieved without crystallization. From the bulk ionic conductivity and the individual diffusion coefficients of cations and anions we calculate the Haven ratio and the apparent lithium transference number. Although the Haven ratio exhibits typical values for ionic liquid electrolytes, the maximal apparent lithium transference number is higher than found in other recent studies on ionic liquid electrolytes containing lithium ions. On the basis of these results we discuss strategies for further improving the lithium transference number of such electrolytes.

Relationship between Cation Segregation and the Electrochemical Oxygen Reduction Kinetics of La0.6Sr0.4CoO3−δ Thin Film Electrodes

Pulsed laser deposited La 0.6 Sr 0.4 CoO 3―δ (LSC) thin film electrodes on yttria stabilized zirconia (YSZ) single crystals were investigated by impedance spectroscopy, time of flight secondary ion mass spectrometry (ToF-SIMS) and inductively coupled plasma optical emission spectrometry (ICP-OES). Effects caused by different film deposition temperatures, thermal annealing and chemical etching were studied. Correlations between changes in electrode polarization resistance of oxygen reduction and surface composition were found. At high deposition temperatures and after thermal annealing an inhomogeneous cation distribution was detected in the surface-near region, most manifest in a significant Sr enrichment at the surface. An activating effect of chemical etching of LSC is described, which can lower the polarization resistance by orders of magnitude. Chemistry behind this activation and thermal degradation was analyzed by ToF-SIMS and ICP-OES measurements of in-situ etched LSC films. The latter allow quantitative depth resolved compositional analysis with nominally sub nm resolution. High resolution scanning electron microscopy images illustrate the accompanying changes in surface morphology. All measurements suggest that stoichiometric LSC surfaces intrinsically exhibit very high activity towards oxygen reduction.

Oxygen tracer diffusion in donor doped barium titanate

Oxygen exchange with the ambient atmosphere and oxygen diffusion are assumed to play a decisive role in the re-oxidation process of positive temperature coefficient (PTC) resistors based on donor doped barium titanate. 18O tracer experiments with subsequent time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurements were thus carried out to investigate the oxygen diffusion properties of donor doped barium titanate. Fast grain boundary diffusion was found at temperatures between 750 °C and 900 °C. Moreover, evidence is given for a position dependent diffusion coefficient close to the surface. The secondary phase developing during the production process is shown to be Ti-rich and hardly any oxygen tracer exchange with this secondary phase could be observed. This suggests that grain boundary diffusion does not take place via such secondary phases. Rather, evidence of diffusion along an oxygen vacancy enriched space charge region is found.

Role of (Bi1/2K1/2)TiO3 in the dielectric relaxations of BiFeO3-(Bi1/2K1/2)TiO3 ceramics

Temperature-dependent dielectric relaxations of (1 − x)BiFeO3-x(Bi1/2K1/2)TiO3 (BF-BKT) lead-free piezoceramics (0.4 ≤ x ≤ 0.8) were investigated via impedance spectroscopic techniques. Regardless of the compositions, the dielectric maximum temperatures exhibit a frequency-dependent dispersion, originating from a Debye relaxation due to the presence of oxygen vacancies. It was also observed that there exist local dielectric maxima due to the relaxation of polar nanoregions as a shoulder on the lower temperature side. The onset temperature for the Debye-type relaxation decreased with decreasing BKT content, gradually overlapping with the low-temperature dielectric dispersion from the relaxation of polar nanoregions. It is proposed that the role of BKT in the BF-BKT system is to enhance the random fields that favor a relaxor state and to suppress the Debye-type relaxation of oxygen vacancy related dipoles.

Bulk ZnO as piezotronic pressure sensor

The impact of uniaxial compressive mechanical stress on the electrical properties of a ZnO varistor ceramic was studied with respect to a potential use in pressure sensor applications. Current-voltage measurements as a function of temperature are strongly affected by the applied stress. The modulation of charge transport properties with uniaxial stress causes large changes in resistance. Hence, a gauge factor of ∼800 is attained, which significantly exceeds the value of conventional sensors. The effect is attributed to the piezotronic effect, i.e., the altering of the potential barrier at grain boundaries due to the piezoelectricity of ZnO. This change in grain boundary potential barriers via mechanical deformation represents a promising physical concept for the development of better materials for sensor applications.

Varistor piezotronics: Mechanically tuned conductivity in varistors

The piezoelectric effect of ZnO has been investigated recently with the goal to modify metal/semiconductor Schottky-barriers and p-n-junctions by application of mechanical stress. This research area called “piezotronics” is so far focused on nano structured ZnO wires. At the same time, ZnO varistor materials are already widely utilized and may benefit from a piezotronic approach. In this instance, the grain boundary potential barriers in the ceramic can be tuned by mechanical stress. Polycrystalline varistors exhibit huge changes of resistivity upon applied electrical and mechanical fields and therefore offer descriptive model systems to study the piezotronic effect. If the influence of temperature is contemplated, our current mechanistic understanding can be interrogated and corroborated. In this paper, we present a physical model based on parallel conducting pathways. This affords qualitative and semi-quantitative rationalization of temperature dependent electrical properties. The investigations demonstrate that narrow conductive pathways contribute to the overall current, which becomes increasingly conductive with application of mechanical stress due to lowering of the barrier height. Rising temperature increases the thermionic current through the rest of the material with higher average potential barriers, which are hardly affected by the piezoelectric effect. Hence, relative changes in resistance due to application of stress are higher at low temperature.

Ionic conductivity of acceptor doped sodium bismuth titanate: influence of dopants, phase transitions and defect associates

We investigate both, experimentally and theoretically, the electrical conductivity of Mg- and Fe-doped polycrystalline Na0.5Bi0.5TiO3. Samples with up to 4% of acceptor dopants are studied by means of impedance spectroscopy, scanning electron microscopy, and X-ray diffraction, while an analytical defect chemical model is developed for describing the measured conductivities. Within the framework of defect chemistry, we demonstrate that the experimentally measured conductivities can only be reproduced, if the formation of dopant–vacancy defect complexes is considered and the phase transition from a rhombohedral to a tetragonal symmetry is taken into account, affecting the dissociation of the dopant–vacancy complex. By using migration energies from density functional theory calculations, we obtain a good agreement between the data obtained from the analytical model and the experimental results, if we assume that the association energy is strongly affected by the dopant concentration.

DC-bias dependent impedance spectroscopy of BaTiO3–Bi(Zn1/2Ti1/2)O3 ceramics

This report discusses the voltage-stability of the dielectric and transport properties of BaTiO3–Bi(Zn1/2Ti1/2)O3 (BT–BZT) ceramics which have shown excellent properties for emerging energy applications. For p-type BaTiO3, the ceramics deviated from Ohm’s law behavior at very low voltage levels along with a reversible drop in bulk resistivity by several orders of magnitude starting at bias fields as low as 0.1 kV cm^-1 (~8 V). In contrast, n-type BT–BZT ceramics exhibited a small (i.e. less than one order of magnitude) increase in resistivity on application of small field levels. These data indicate a hole-generation mechanism which becomes active at a low voltage threshold. The bulk capacitance values calculated using AC impedance spectroscopy, however, were relatively unaffected (<15% change) by this application of a DC bias (up to ~0.25 kV cm^-1). These findings provide important insights into the electric transport mechanisms in BT-based ceramics.

Synthesis of Novel Lithium Salts containing Pentafluorophenylamido-based Anions and Investigation of their Thermal and Electrochemical Properties

Abstract Three novel lithium salts, lithium bis(pentafluorophenyl)amide LiN(Pfp)2, lithium pentafluorphenyl(trifluormethylsulfonyl)imide LiN(Pfp)(Tf) and lithium pentafluorphenyl(nonafluorbutylsulfonyl)imide LiN(Pfp)(Nf) were synthesized and characterized with respect to their thermal and electrochemical properties. LiN(Pfp)2 decomposes at 108 ºC, whereas Li-N(Pfp)(Tf) and Li-N(Pfp)(Nf) show a much higher thermal stability of 307 ºC and 316 ºC, respectively. The ionic conductivity at 100 ºC measured by means of impedance spectroscopy decreases in the order LiN(Pfp)(Tf) > LiN(Tf)2> LiN(Pfp)(Nf). Both, the activation energy and entropy for ion conduction in the new salts are lower than in LiN(Tf)2 (LiTFSI), most likely due to the lower symmetry of the new anions. The electrochemical stability and ionic conductivity of LiN(Pfp)(Tf) and LiN(Pfp)(Nf) solutions (0.1 mol/l) in ethylene carbonate/dimethyl carbonate (1:3 w/w) are slightly lower than those of the LiTFSI solution, but still sufficient for application in lithium ion batteries. The high thermal stability of the novel salts and their stability towards hydrolysis makes them attractive candidates for overcoming the drawbacks of LiPF6-based electrolytes at elevated temperatures.

Designing properties of (Na1/2Bix)TiO3-based materials through A-site non-stoichiometry

Point defects largely determine the properties of functional oxides. So far, limited knowledge exists on the impact of cation vacancies on electroceramics, especially in (Na1/2Bi1/2)TiO3 (NBT)-based materials. Here, we report on the drastic effect of A-site non-stoichiometry on the cation diffusion and functional properties in the representative ferroelectric (Na1/2Bi1/2)TiO3–SrTiO3 (NBT–ST). Experiments on NBT/ST bilayers and NBT–ST with Bi non-stoichiometry reveal that Sr2+-diffusion is enhanced by up to six orders of magnitude along the grain boundaries in Bi-deficient material as compared to Bi-excess material with values of grain boundary diffusion ∼10−8 cm2 s−1 and ∼10−13 cm2 s−1 in the bulk. This also means a nine orders of magnitude higher diffusion coefficient compared to reports from other Sr-diffusion coefficients in ceramics. Bi-excess leads to the formation of a material with a core–shell microstructure. This results in 38% higher strain and one order of magnitude lower remanent polarization. In contrast, Bi-deficiency leads to a ceramic with a grain size six times larger than in the Bi-excess material and homogeneous distribution of compounds. Thus, the work sheds light on the rich opportunities that A-site stoichiometry offers to tailor NBT-based materials microstructure, transport properties, and electromechanical properties.