Structural Characterization of LaSrCoO Thin Films Grown on (100)-, (110)-, and (111)-Oriented LaSrGaMgO.

In this study, a detailed structural characterization of epitaxial La0.6Sr0.4CoO3-δ (LSC) films grown in (100), (110), and (111) orientations was conducted.

Engineering surface dipoles on mixed conducting oxides with ultra-thin oxide decoration layers.

Improving materials for energy conversion and storage devices is deeply connected with an optimization of their surfaces and surface modification is a promising strategy on the way to enhance modern energy technologies. This study shows that surface modification with ultra-thin oxide layers allows for a systematic tailoring of the surface dipole and the work function of mixed ionic and electronic conducting oxides, and it introduces the ionic potential of surface cations as a readily accessible descriptor for these effects. The combination of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) illustrates that basic oxides with a lower ionic potential than the host material induce a positive surface charge and reduce the work function of the host material and vice versa.

Defect Chemistry of Spinel Cathode Materials-A Case Study of Epitaxial LiMnO Thin Films.

Spinels of the general formula LiMO are an essential class of cathode materials for Li-ion batteries, and their optimization in terms of electrode potential, accessible capacity, and charge/discharge kinetics relies on an accurate understanding of the underlying solid-state mass and charge transport processes. In this work, we report a comprehensive impedance study of sputter-deposited epitaxial LiMnO thin films as a function of state-of-charge for almost the entire tetrahedral-site regime (1 ≤ δ ≤ 1.9) and provide a complete set of electrochemical properties, consisting of the charge-transfer resistance, ionic conductivity, volume-specific chemical capacitance, and chemical diffusivity.

Crystal-Orientation-Dependent Oxygen Exchange Kinetics on Mixed Conducting Thin-Film Surfaces Investigated by Studies.

The oxygen exchange kinetics and the surface chemistry of epitaxially grown, dense LaSrCoO (LSC) thin films in three different orientations, (001), (110), and (111), were investigated by means of impedance spectroscopy during pulsed laser deposition (i-PLD) and near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS). i-PLD measurements showed that pristine LSC surfaces exhibit very fast surface exchange kinetics but revealed no significant differences between the specific orientations. However, as soon as the surfaces were in contact with acidic, gaseous impurities, such as S-containing compounds in nominally pure measurement atmospheres, NAP-XPS measurements revealed that the (001) orientation is substantially more susceptible to the formation of sulfate adsorbates and a concomitant performance decrease.

Improving and degrading the oxygen exchange kinetics of LaSrCoO by Sr decoration.

Minimizing the overpotential at the air electrode of solid oxide fuel cells (SOFC) is one of the key challenges regarding a broad applicability of this technology. Next to novel materials and geometry optimization, surface modification is a promising and flexible method to alter the oxygen exchange kinetics at SOFC cathode surfaces. Despite extensive research, the mechanism behind the effect of surface decorations is still under debate.

Surface Decorations on Mixed Ionic and Electronic Conductors: Effects on Surface Potential, Defects, and the Oxygen Exchange Kinetics.

The oxygen exchange kinetics of epitaxial PrCeO electrodes was modified by decoration with submonolayer amounts of different basic (SrO, CaO) and acidic (SnO, TiO) binary oxides. The oxygen exchange reaction (OER) rate and the total conductivity were measured by PLD impedance spectroscopy (-PLD), which allows to directly track changes of electrochemical properties after each deposited pulse of surface decoration. The surface chemistry of the electrodes was investigated by near-ambient pressure XPS measurements (NAP-XPS) at elevated temperatures and by low-energy ion scattering (LEIS).

Electronic and ionic effects of sulphur and other acidic adsorbates on the surface of an SOFC cathode material.

The effects of sulphur adsorbates and other typical solid oxide fuel cell (SOFC) poisons on the electronic and ionic properties of an SrO-terminated (La,Sr)CoO (LSC) surface and on its oxygen exchange kinetics have been investigated experimentally with near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), low energy ion scattering (LEIS) and impedance spectroscopy as well as computationally with density functional theory (DFT). The experiment shows that trace amounts of sulphur in measurement atmospheres form SO adsorbates and strongly deactivate a pristine LSC surface. They induce a work function increase, indicating a changing surface potential and a surface dipole.

Closed-Pore Formation in Oxygen Electrodes for Solid Oxide Electrolysis Cells Investigated by Impedance Spectroscopy.

Electrochemical impedance spectroscopy was used to investigate the chemical capacitance of LaSrCoO (LSC) thin-film electrodes under anodic polarization (i.e., in the electrolysis mode).

Exo- and endophytic fungi enable rapid transfer of nutrients from ant waste to orchid tissue.

The epiphytic orchid Caularthron bilamellatum sacrifices its water storage tissue for nutrients from the waste of ants lodging inside its hollow pseudobulb. Here, we investigate whether fungi are involved in the rapid translocation of nutrients. Uptake was analysed with a N labelling experiment, subsequent isotope ratio mass spectrometry (IRMS) and secondary ion mass spectrometry (ToF-SIMS and NanoSIMS).

electrochemical observation of anisotropic lattice contraction of LaSrFeO electrodes during pulsed laser deposition.

LaSrFeO (LSF) electrodes were grown on different electrolyte substrates by pulsed laser deposition (PLD) and their oxygen exchange reaction (OER) resistance was tracked in real-time by PLD impedance spectroscopy (i-PLD) inside the PLD chamber. This enables measurements on pristine surfaces free from any contaminations and the direct observation of thickness dependent properties. As substrates, yttria-stabilized zirconia single crystals (YSZ) were used for polycrystalline LSF growth and LaSrGaMgO (LSGM) single crystals or YSZ single crystals with a 5 nm buffer-layer of GdCeO for epitaxial LSF film growth.

techniques reveal the true capabilities of SOFC cathode materials and their sudden degradation due to omnipresent sulfur trace impurities.

In this study, five different mixed conducting cathode materials were grown as dense thin films by pulsed laser deposition (PLD) and characterized impedance spectroscopy directly after growth inside the PLD chamber (i-PLD). This technique enables quantification of the oxygen reduction kinetics on pristine and contaminant-free mixed conducting surfaces. The measurements reveal excellent catalytic performance of all pristine materials with polarization resistances being up to two orders of magnitude lower than those previously reported in the literature.

Formation and Detection of High-Pressure Oxygen in Closed Pores of LaSrCoO Solid Oxide Electrolysis Anodes.

The chemical capacitance of LaSrCoO (LSC) thin film microelectrodes with different microstructures was investigated upon varying anodic DC voltages. Dense and porous electrodes (open porosity) were prepared by using different parameters during pulsed laser deposition (PLD). Furthermore, electrodes with closed porosity were fabricated by depositing a dense capping layer on a porous film.

How UV light lowers the conductivity of SrTiO by photochemical water splitting at elevated temperature.

Nominally undoped SrTiO single crystals were illuminated by UV light at 350 °C in oxidizing as well as reducing atmospheres. In N/O atmospheres, UV irradiation enhances the conductivity of SrTiO by several orders of magnitude. In dry H atmosphere UV exposure leads to the opposite conductivity effect, , above band gap energy illumination surprisingly lowers the conductivity.

Performance modulation through selective, homogenous surface doping of lanthanum strontium ferrite electrodes revealed by PLD impedance measurements.

Accelerating the oxygen reduction kinetics of solid oxide fuel cell (SOFC) cathodes is crucial to improve their efficiency and thus to provide the basis for an economically feasible application of intermediate temperature SOFCs. In this work, minor amounts of Pt were doped into lanthanum strontium ferrite (LSF) thin film electrodes to modulate the material's oxygen exchange performance. Surprisingly, Pt was found to be incorporated on the B-site of the perovskite electrode as non metallic Pt.

Investigating oxygen reduction pathways on pristine SOFC cathode surfaces by PLD impedance spectroscopy.

The oxygen exchange reaction mechanism on truly pristine surfaces of SOFC cathode materials (LaSrCoO = LSC, LaSrFeO = LSF, (LaSr)PtFeO = Pt:LSF, SrTiFeO = STF, PrCeO = PCO and LaSrMnO = LSM) was investigated employing impedance spectroscopy during pulsed laser deposition (i-PLD) over a wide temperature and (O) range. Besides demonstrating the often astonishing catalytic capabilities of the materials, it is possible to discuss the oxygen exchange reaction mechanism based on experiments on clean surfaces unaltered by external degradation processes. All investigated materials with at least moderate ionic conductivity ( all except LSM) exhibit polarization resistances with very similar (O)- and -dependences, mostly differing only in absolute value.

Photoinduced electronic and ionic effects in strontium titanate.

The interaction of light with solids has been of ever-growing interest for centuries, even more so since the quest for sustainable utilization and storage of solar energy became a major task for industry and research. With SrTiO being a model material for an extensive exploration of the defect chemistry of mixed conducting perovskite oxides, it has also been a vanguard in advancing the understanding of the interaction between light and the electronic and ionic structure of solids. In the course of these efforts, many phenomena occurring during or subsequent to the illumination of SrTiO have been investigated.

Cation non-stoichiometry in Fe:SrTiO thin films and its effect on the electrical conductivity.

The interplay of structure, composition and electrical conductivity was investigated for Fe-doped SrTiO thin films prepared by pulsed laser deposition. Structural information was obtained by reciprocal space mapping while solution-based inductively-coupled plasma optical emission spectroscopy and positron annihilation lifetime spectroscopy were employed to reveal the cation composition and the predominant point defects of the thin films, respectively. A severe cation non-stoichiometry with Sr vacancies was found in films deposited from stoichiometric targets.

Mercury content in fish from drinking-water reservoirs in the Morava River Basin (Czech Republic).

This study focused on the total mercury content in fish from seven drinking-water reservoirs located in the Morava River Basin: Bojkovice, Boskovice, Hubenov, Karolinka, Landstejn, Ludkovice and Nova Rise in the Czech Republic. A total of 308 fish were collected for the analysis. The content of total mercury was measured in the muscle tissue of bream, roach and perch using atomic absorption spectrometry and varied from 0.

Investigating the electrochemical stability of LiLaZrO solid electrolytes using field stress experiments.

Cubic LiLaZrO (LLZO) garnets are among the most promising solid electrolytes for solid-state batteries with the potential to exceed conventional battery concepts in terms of energy density and safety. The electrochemical stability of LLZO is crucial for its application, however, controversial reports in the literature show that it is still an unsettled matter. Here, we investigate the electrochemical stability of LLZO single crystals by applying electric field stress macro- and microscopic ionically blocking Au electrodes in ambient air.

Study of metabolism and identification of productive regions in filamentous fungi via spatially resolved time-of-flight secondary ion mass spectrometry.

Filamentous fungi are well-established production hosts that feature a strong interconnection between morphology, physiology, and productivity. For penicillin production in Penicillium chrysogenum, industrial processes frequently favor a pellet morphology comprising compact hyphal agglomerates. Inherently these tightly packed entanglements lead to inactive, degrading sections within the pellet's core because of limitations.

In Situ Impedance Analysis of Oxygen Exchange on Growing LaSrCoO Thin Films.

The further development of solid oxide fuel and electrolysis cells (SOFC/SOEC) strongly relies on research activities dealing with electrode materials. Recent studies showed that under operating conditions many perovskite-type oxide electrodes are prone to changes of their surface composition, leading to severe changes of their electrochemical performance. This results in a large scatter of data in literature and complicates comparison of materials.

Influence of surface atomic structure demonstrated on oxygen incorporation mechanism at a model perovskite oxide.

Perovskite oxide surfaces catalyze oxygen exchange reactions that are crucial for fuel cells, electrolyzers, and thermochemical fuel synthesis. Here, by bridging the gap between surface analysis with atomic resolution and oxygen exchange kinetics measurements, we demonstrate how the exact surface atomic structure can determine the reactivity for oxygen exchange reactions on a model perovskite oxide. Two precisely controlled surface reconstructions with (4 × 1) and (2 × 5) symmetry on 0.

Resistive states in strontium titanate thin films: Bias effects and mechanisms at high and low temperature.

A study on charge transport properties of thin film Fe-doped SrTiO epitaxially grown on Nb-doped SrTiO is reported. Electric measurements between 350 °C and 750 °C show a transition from predominant ionic to electronic conduction and lower conductivity of the thin films compared to the bulk of polycrystalline samples. Defect chemical changes at elevated temperature were investigated by applying a bias voltage.