Juergen Janek

Mesoporous TiO2: Comparison of Classical Sol−Gel and Nanoparticle Based Photoelectrodes for the Water Splitting Reaction

This paper describes a systematic comparison of the photoelectrochemical properties of mesoporous TiO(2) films prepared by the two most prevalent templating methods: The use of preformed, crystalline nanoparticles is generally considered advantageous compared to the usage of molecular precursors such as TiCl(4), since the latter requires a separate heat treatment at elevated temperature to induce crystallization. However, our photoelectrochemical experiments clearly show that sol-gel derived mesoporous TiO(2) films cause an about 10 times higher efficiency for the water splitting reaction than their counterparts obtained from crystalline TiO(2) nanoparticles. This result indicates that for electrochemical applications the performance of nanoparticle-based metal oxide films might suffer from insufficient electronic connectivity.

From lithium to sodium: cell chemistry of room temperature sodium–air and sodium–sulfur batteries

Summary Research devoted to room temperature lithium–sulfur (Li/S8) and lithium–oxygen (Li/O2) batteries has significantly increased over the past ten years. The race to develop such cell systems is mainly motivated by the very high theoretical energy density and the abundance of sulfur and oxygen. The cell chemistry, however, is complex, and progress toward practical device development remains hampered by some fundamental key issues, which are currently being tackled by numerous approaches. Quite surprisingly, not much is known about the analogous sodium-based battery systems, although the already commercialized, high-temperature Na/S8 and Na/NiCl2 batteries suggest that a rechargeable battery based on sodium is feasible on a large scale. Moreover, the natural abundance of sodium is an attractive benefit for the development of batteries based on low cost components. This review provides a summary of the state-of-the-art knowledge on lithium–sulfur and lithium–oxygen batteries and a direct comparison with the analogous sodium systems. The general properties, major benefits and challenges, recent strategies for performance improvements and general guidelines for further development are summarized and critically discussed. In general, the substitution of lithium for sodium has a strong impact on the overall properties of the cell reaction and differences in ion transport, phase stability, electrode potential, energy density, etc. can be thus expected. Whether these differences will benefit a more reversible cell chemistry is still an open question, but some of the first reports on room temperature Na/S8 and Na/O2 cells already show some exciting differences as compared to the established Li/S8 and Li/O2 systems.

Defect chemistry of the cage compound, Ca12Al14O33−δ—understanding the route from a solid electrolyte to a semiconductor and electride

A crystallographic cage structure endows mayenite (Ca(12)Al(14)O(33) or 12CaO.7Al(2)O(3); C(12)A(7)) with remarkable properties, making it either an oxygen solid electrolyte or an inorganic electride upon reduction. In order to better understand the transport properties of C(12)A(7), we measured the equilibrium total conductivity as well as the electronic partial conductivity of single crystal mayenite as functions of activity of oxygen or water vapor at different temperatures in the range 1073 < or =T/K < or = 1273. A point defect model based on the assumption that the framework [Ca(12)Al(14)O(32)](2+) acts as a pseudo-donor describes well the isothermal conductivity vs. oxygen activity, enabling us to deconvolute the ionic and electronic partial conductivities. The ionic transference number evaluated therefrom clearly demonstrates how C(12)A(7) is converted from a solid electrolyte to an electride depending on the oxygen content. In addition, besides the well known degradation of ionic conductivity by water uptake, a short-term increase of conductivity upon abrupt hydration was recognized and interpreted as due to the transient increase in the concentration of oxygen interstitial along with proton in the initial stage of hydration. For the fully hydrated C(12)A(7), the conductivity relaxation curves upon switching of oxygen activity in a fixed water vapor pressure appear non-monotonic showing the extrema only in the plateau conductivity regime. A defect structure based hypothesis is proposed to explain the 2-fold re-equilibration kinetics.

Magnetoresistance in Ag2+δSe with high silver excess

In the present study, we investigated the galvanomagnetic transport properties of polycrystalline AgxSe thin films with silver excess in the range from x=1.5 to 18. The results prove that the silver excess controls the transition from linear magnetoresistance (MR) behavior to the quadratic ordinary MR and the temperature for the metal–semiconductor transition. Analyzing the MR effect by Kohler’s rule and comparing the results with the field-free resistivity we observe for 2<x<2.3 a steep rise of the product of mean free path and electron concentration (λ·n2∕3). We interpret this result as a consequence of the percolation of nanoscale silver networks within the semiconducting matrix, i.e., as a consequence of the two-phase character of the system.

Gas Evolution in Operating Lithium-Ion Batteries Studied In Situ by Neutron Imaging.

Gas generation as a result of electrolyte decomposition is one of the major issues of high-performance rechargeable batteries. Here, we report the direct observation of gassing in operating lithium-ion batteries using neutron imaging. This technique can be used to obtain qualitative as well as quantitative information by applying a new analysis approach. Special emphasis is placed on high voltage LiNi0.5Mn1.5O4/graphite pouch cells. Continuous gassing due to oxidation and reduction of electrolyte solvents is observed. To separate gas evolution reactions occurring on the anode from those associated with the cathode interface and to gain more insight into the gassing behavior of LiNi0.5Mn1.5O4/graphite cells, neutron experiments were also conducted systematically on other cathode/anode combinations, including LiFePO4/graphite, LiNi0.5Mn1.5O4/Li4Ti5O12 and LiFePO4/Li4Ti5O12. In addition, the data were supported by gas pressure measurements. The results suggest that metal dissolution in the electrolyte and decomposition products resulting from the high potentials adversely affect the gas generation, particularly in the first charge cycle (i.e., during graphite solid-electrolyte interface layer formation).

Applicability of ToF-SIMS for monitoring compositional changes in bone in a long-term animal model

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a well-established technique in material sciences but has not yet been widely explored for implementation in life sciences. Here, we demonstrate the applicability and advantages of ToF-SIMS analysis for the study of minerals and biomolecules in osseous tissue. The locally resolved analysis of fragment ions deriving from the sample surface enables imaging and differentiation of bone tissue and facilitates histology on non-stained cross sections. In a rat model, bilateral ovariectomy combined with either a multi-deficiency diet or steroid treatment was carried out to create osteoporotic conditions. We focused our study on the Ca content of the mineralized tissue and monitored its decline. Calcium mass images of cross sections show the progressive degenerative changes in the bone. We observed a decreased Ca concentration in the edge region of the trabeculae and a decline in the Ca/P ratio. Additionally, we focused on the non-mineralized matrix and identified fragment ions that are characteristic for the collagen matrix. We observed trabeculae with wide ranges of non-mineralized collagen for the diet group owing to an impaired mineralization process. Here, the advantage of coeval monitoring of collagen and minerals indicated an osteomalacic model rather than an osteoporotic one.

Sol–gel synthesis and room-temperature properties of α-LiZr2(PO4)3

The structural and electrical properties of α-LiZr2(PO4)3 are studied at room temperature for the first time. A room-temperature stable α-LiZr2(PO4)3 phase (Rc, a = 8.85196(4) A and c = 22.1510(1) A) is prepared by a modified sol–gel approach. The material exhibits a room-temperature (25 °C) total conductivity of 1.63 × 10−6 Scm−1 at a density of 76% of the theoretical density. A room-temperature bulk conductivity as high as 1.58 × 10−4 Scm−1 can be estimated from the impedance measurements. Conductivity measurements suggest that a nominal α → α′ phase transition occurs below room-temperature (at about 16–18 °C). The activation energies for the conductivity of the α and α′ phases are 0.39 and 0.99 eV, respectively (in the temperature range −20 to 100 °C).

Time of flight secondary ion mass spectrometry of bone—Impact of sample preparation and measurement conditions

Time of flight secondary ion mass spectrometry (ToF-SIMS) enables the simultaneous detection of organic and inorganic ions and fragments with high mass and spatial resolution. Due to recent technical developments, ToF-SIMS has been increasingly applied in the life sciences where sample preparation plays an eminent role for the quality of the analytical results. This paper focusses on sample preparation of bone tissue and its impact on ToF-SIMS analysis. The analysis of bone is important for the understanding of bone diseases and the development of replacement materials and new drugs for the cure of diseased bone. The main purpose of this paper is to find out which preparation process is best suited for ToF-SIMS analysis of bone tissue in order to obtain reliable and reproducible analytical results. The influence of the embedding process on the different components of bone is evaluated using principal component analysis. It is shown that epoxy resin as well as methacrylate based plastics (Epon and Technovit) as embedding materials do not infiltrate the mineralized tissue and that cut sections are better suited for the ToF-SIMS analysis than ground sections. In case of ground samples, a resin layer is smeared over the sample surface due to the polishing step and overlap of peaks is found. Beside some signals of fatty acids in the negative ion mode, the analysis of native, not embedded samples does not provide any advantage. The influence of bismuth bombardment and O2 flooding on the signal intensity of organic and inorganic fragments due to the variation of the ionization probability is additionally discussed. As C60 sputtering has to be applied to remove the smeared resin layer, its effect especially on the organic fragments of the bone is analyzed and described herein.

Influence of texture and grain misorientation on the ionic conduction in multilayered solid electrolytes – interface strain effects in competition with blocking grain boundaries

Interface strain and its influence on the ionic transport along hetero-interfaces has gained a lot of attention over the last decade and is controversially discussed. We investigate the relaxation of mismatch induced interfacial strain as a function of the degree of orientation/texture of the columnar crystallites and assess the impact on the oxygen ion conductivity in Er2O3/YSZ multilayer systems. Results from X-ray diffraction clearly show, that the width of the strained hetero-interface region increases with an increasing degree of orientation of the crystallites. The combined impact of film texture and strain at the hetero-interfaces of the film on the ionic conductivity however is not easily deduced from these measurements. The samples with the highest degree of orientation, i.e. with only one azimuthal variant, show strong anisotropic electrical properties. In samples with a lower degree of orientation, i.e. samples with a fiber texture, anisotropic properties cannot be detected, possibly due to a geometrical averaging of the electrical properties. The expected strain induced monotonic increase of the ionic conductivity with decreasing layer thickness and thus increasing interfacial influence could only be detected for samples with a fiber texture and a considerable degree of crystallite misorientation. This leads to the important conclusion that the texture and therefore the nature of the grain boundaries and their network influence the ionic conductivity of the multilayer thin films in the same order of magnitude as the misfit induced interface strain. Thus, the potential design of strain-controlled ionic conductors requires additionally the control of the microstructure in terms of grain orientation.

Next generation technologies

Rechargeable lithium-ion batteries have been continually developed since their introduction by Sony in 1991. Energy density is one of the key parameters for lithium-ion batteries. It was steadily increased by optimizing battery components such as electrode materials or electrolyte as well as by improving the cell construction technologies. The cell level progress during recent years is shown in Fig. 16.1. Both gravimetric (specific) and volumetric energy density were more than doubled.