Experimental evidence for the relaxation coupling of all longitudinal 7Li magnetization orders in the superionic conductor Li10GeP2S12.

This contribution addresses the experimental proof of the relaxation coupling of the 7Li (I = 3/2) longitudinal magnetization orders in the solid-state electrolyte Li10GeP2S12 (LGPS). This effect was theoretically described by Korb and Petit in 1988 but has not yet been shown experimentally. In a 2D-T1/spin-alignment echo (SAE) experiment, the inverse Laplace transformation of the spectral component over two time dimensions revealed the asymmetric course of the spin-lattice relaxation following from the coupling of all longitudinal orders. These observations were supported by Multi-quantum-filter experiments and by simulations of the 2D-T1/SAE experiment with a lithium spin system. Since the asymmetric relaxation effects are directly dependent on the velocities and degrees of freedom of ion motion they could be used especially in fast Li-ion conductors as a separation tool for environments with different mobility processes.

Defibrillation of soft porous metal-organic frameworks with electric fields.

Gas transport through metal-organic framework membranes (MOFs) was switched in situ by applying an external electric field (E-field). The switching of gas permeation upon E-field polarization could be explained by the structural transformation of the zeolitic imidazolate framework ZIF-8 into polymorphs with more rigid lattices. Permeation measurements under a direct-current E-field poling of 500 volts per millimeter showed reversibly controlled switching of the ZIF-8 into polar polymorphs, which was confirmed by x-ray diffraction and ab initio calculations. The stiffening of the lattice causes a reduction in gas transport through the membrane and sharpens the molecular sieving capability. Dielectric spectroscopy, polarization, and deuterium nuclear magnetic resonance studies revealed low-frequency resonances of ZIF-8 that we attribute to lattice flexibility and linker movement. Upon E-field polarization, we observed a defibrillation of the different lattice motions.

The mechanically induced structural disorder in barium hexaferrite, BaFe12O19, and its impact on magnetism.

The response of the structure of the M-type barium hexaferrite (BaFe12O19) to mechanical action through high-energy milling and its impact on the magnetic behaviour of the ferrite are investigated. Due to the ability of the (57)Fe Mössbauer spectroscopic technique to probe the environment of the Fe nuclei, a valuable insight on a local atomic scale into the mechanically induced changes in the hexagonal structure of the material is obtained. It is revealed that the milling of BaFe12O19 results in the deformation of its constituent polyhedra (FeO6 octahedra, FeO4 tetrahedra and FeO5 triangular bi-pyramids) as well as in the mechanically triggered transition of the Fe(3+) cations from the regular 12k octahedral sites into the interstitial positions provided by the magnetoplumbite structure. The response of the hexaferrite to the mechanical treatment is found to be accompanied by the formation of a non-uniform nanostructure consisting of an ordered crystallite surrounded/separated by a structurally disordered surface shell/interface region. The distorted polyhedra and the non-equilibrium cation distribution are found to be confined to the amorphous near-surface layers of the ferrite nanoparticles with the thickness extending up to about 2 nm. The information on the mechanically induced short-range structural disorder in BaFe12O19 is complemented by an investigation of its magnetic behaviour on a macroscopic scale. It is demonstrated that the milled ferrite nanoparticles exhibit a pure superparamagnetism at room temperature. As a consequence of the far-from-equilibrium structural disorder in the surface shell of the nanoparticles, the mechanically treated BaFe12O19 exhibits a reduced magnetization and an enhanced coercivity.

Lithium diffusion in congruent LiNbO3 single crystals at low temperatures probed by neutron reflectometry.

The self-diffusion of lithium in congruent LiNbO3 single crystals was investigated at low temperatures between 379 and 523 K by neutron reflectometry. From measurements on (6)LiNbO3 (amorphous film)/(nat)LiNbO3 (single crystal) samples, Li self-diffusivities were determined in single crystals down to extremely low values of 1 × 10(-25) m(2) s(-1) on small length scales of 1-10 nm. The measured diffusivities are in excellent agreement with (extrapolated) literature data obtained by experiments based on Secondary Ion Mass Spectrometry and Impedance Spectroscopy. The tracer diffusivities can be described by a single Arrhenius line over ten orders of magnitude with an activation enthalpy of 1.33 eV, which corresponds to the migration energy of a single Li vacancy. A deviation from the Arrhenius behaviour at low temperatures, e.g., due to defect cluster formation is not observed.

NMR relaxometry as a versatile tool to study Li ion dynamics in potential battery materials.

NMR spin relaxometry is known to be a powerful tool for the investigation of Li(+) dynamics in (non-paramagnetic) crystalline and amorphous solids. As long as significant structural changes are absent in a relatively wide temperature range, with NMR spin-lattice (as well as spin-spin) relaxation measurements information on Li self-diffusion parameters such as jump rates and activation energies are accessible. Diffusion-induced NMR relaxation rates are governed by a motional correlation function describing the ion dynamics present. Besides the mean correlation rate of the dynamic process, the motional correlation function (i) reflects deviations from random motion (so-called correlation effects) and (ii) gives insights into the dimensionality of the hopping process. In favorable cases, i.e., when temperature- and frequency-dependent NMR relaxation rates are available over a large dynamic range, NMR spin relaxometry is able to provide a comprehensive picture of the relevant Li dynamic processes. In the present contribution, we exemplarily present two recent variable-temperature (7)Li NMR spin-lattice relaxation studies focussing on Li(+) dynamics in crystalline ion conductors which are of relevance for battery applications, viz. Li(7) La(3)Zr(2)O(12) and Li(12)Si(7).

Li self-diffusion in lithium niobate single crystals at low temperatures.

Li self-diffusion in Li(2)O-deficient LiNbO(3) single crystals is investigated in the temperature range between 423 and 773 K (150-500 °C) by secondary ion mass spectrometry. A thin layer of ion-beam sputtered isotope enriched (6)LiNbO(3) was used as a tracer source, which allows one to study pure isotope interdiffusion. The diffusivities can be described by the Arrhenius law with an activation enthalpy of (1.33 ± 0.03) eV, which is in acceptable agreement with the migration energy of a single Li vacancy as determined by ab initio calculations given in the literature. Charge diffusivities as derived from impedance spectroscopy measurements on the same type of samples are identical to the tracer diffusivities within error limits. No indication of the formation of defect-complexes at low temperatures could be found in the diffusion behaviour.

Self-diffusion of lithium in LiAlSi2O6 glasses studied using mass spectrometry.

In order to improve our understanding of the transport mechanisms of lithium in glasses, we have performed diffusion and ionic conductivity studies on spodumene composition (LiAlSi(2)O(6)) glasses. In diffusion couple experiments pairs of chemically identical glasses with different lithium isotopy (natural Li vs pure (7)Li) were processed at temperatures between 482 and 732 K. Profiles of lithium isotopes were measured after the diffusion runs innovatively applying femtosecond UV laser ablation combined with inductively coupled plasma mass spectrometry (LA ICP-MS). Self-diffusion coefficients of lithium in the glasses were determined by fitting the isotope profiles. During some of the diffusion experiments the electrical conductivity of the samples was intermittently measured by impedance spectrometry. Combining ionic conductivity and self-diffusivity yields a temperature-independent correlation factor of ~0.50, indicating that motions of Li ions are strongly correlated in this type of glasses. Lithium self-diffusivity in LiAlSi(2)O(6) glass was found to be very similar to that in lithium silicate glasses although Raman spectroscopy demonstrates structural differences between these glasses; that is, the aluminosilicate is completely polymerized while the lithium silicate glasses contain large fractions of nonbridging oxygen.

High anion conductivity in a ternary non-equilibrium phase of BaF(2) and CaF(2) with mixed cations.

A highly conductive ternary fluoride with mixed cations is prepared by joint high-energy ball milling of cubic BaF(2) and CaF(2) in the ratio 0.4 : 0.6. The sample produced at room temperature consists of a nanocrystalline, defect-rich mixed (Ba,Ca)F(2) phase with retained cubic symmetry as well as of single-phase CaF(2) particles. The anion conductivity of the mixed phase, which decomposes at higher temperature (770 K) into BaF(2) and CaF(2), exceeds that of single-phase nanocrystalline BaF(2) by two and that of CaF(2) by four orders of magnitude. In turn, these conductivities are each greater by about two orders than those of the respective microcrystalline counterparts. Structural features of the samples are characterized by X-ray diffraction, TEM and (19)F MAS NMR spectroscopy. Static (19)F NMR spectra confirm the unexpectedly high anion conductivity probed by impedance spectroscopy.

From ultraslow to fast lithium diffusion in the 2D ion conductor Li0.7TiS2 probed directly by stimulated-echo NMR and nuclear magnetic relaxation.

7Li stimulated-echo NMR and classical relaxation NMR techniques are jointly used for the first time for a comprehensive investigation of Li diffusion in layer-structured Li0.7TiS2. One single 2D Li diffusion process was probed over a dynamic range of almost 10 orders of magnitude. So far, this is the largest dynamic range being measured by 7Li NMR spectroscopy directly, i.e., without the help of a specific theoretical model. The jump rates obey a strict Arrhenius law, determined by an activation energy of 0.41(1) eV and a preexponential factor of 6.3(1)x10(12) s-1, and range between 1x10(-1) s-1 and 7.8x10(8) s-1 (148-510 K). Ultraslow Li jumps in the kHz to sub-Hz range were measured directly by recording 7Li spin-alignment correlation functions. The temperature and, in particular, the frequency dependence of the relaxation rates fully agree with results expected for 2D diffusion.

Influence of gas atmosphere and temperature on the conductivity and the photoconductivity of a TiO2 single crystal in the surface region.

The electrical photoconductivity and conductivity at (and near) the surface of a TiO(2) single crystal (rutile) was studied in a range of temperatures between 300 and 573 K and under different ambient gases (oxygen and nitrogen) by means of impedance spectroscopy. The long times required (many hours) to reach steady state photoconductivity can be explained by the reduction of the material upon illumination. At about 475 K a maximum is observed in the equilibrium photoconductivity and a minimum in the rate constants of the rise and decay after switching on and off, respectively, the light. After switching off the light a fast decay takes place during the first milliseconds followed by a slow exponential decay. The first one is related to recombination through defects, while the latter is due to re-oxidation processes of the material. The results are correlated with measurements of photocatalytic activity.

Nanocrystalline versus microcrystalline Li(2)O:B(2)O3 composites: anomalous ionic conductivities and percolation theory

We study ionic transport in nano- and microcrystalline (1-x)Li(2)O:xB(2)O3 composites using standard impedance spectroscopy. In the nanocrystalline samples (average grain size of about 20 nm), the ionic conductivity sigma(dc) increases with increasing content x of B2O3 up to a maximum at x approximately 0.5. Above x approximately 0.92, sigma(dc) vanishes. By contrast, in the microcrystalline samples (grain size about 10 &mgr;m), sigma(dc) decreases monotonically with x and vanishes above x approximately 0. 55. We can explain this strikingly different behavior by a percolation model that assumes an enhanced conductivity at the interfaces between insulating and conducting phases in both materials and explicitly takes into account the different grain sizes.