Reversible superdense ordering of lithium between two graphene sheets.

Many carbon allotropes can act as host materials for reversible lithium uptake1,2, thereby laying the foundations for existing and future electrochemical energy storage. However, insight into how lithium is arranged within these hosts is difficult to obtain from a working system. For example, the use of in situ transmission electron microscopy3-5 to probe light elements (especially lithium)6,7 is severely hampered by their low scattering cross-section for impinging electrons and their susceptibility to knock-on damage8. Here we study the reversible intercalation of lithium into bilayer graphene by in situ low-voltage transmission electron microscopy, using both spherical and chromatic aberration correction9 to enhance contrast and resolution to the required levels. The microscopy is supported by electron energy-loss spectroscopy and density functional theory calculations. On their remote insertion from an electrochemical cell covering one end of the long but narrow bilayer, we observe lithium atoms to assume multi-layered close-packed order between the two carbon sheets. The lithium storage capacity associated with this superdense phase far exceeds that expected from formation of LiC6, which is the densest configuration known under normal conditions for lithium intercalation within bulk graphitic carbon10. Our findings thus point to the possible existence of distinct storage arrangements of ions in two-dimensional layered materials as compared to their bulk parent compounds.

The effects of n-type doping on lithium storage in TiO2.

In this report, we discuss the Li-storage performance of niobium-doped TiO2 nanostructures (Ti(1-y)Nb(y)O(2+δ)), with a special focus on the effects of ionic/electronic charge carrier concentration (defect chemistry) on Li storage and transport properties. By Nb-doping, Li storage kinetics of titania electrode material is significantly improved mainly due to the increased electronic charge carrier concentration (n-type doping). However, it was found that there is a maximum beyond which further doping is rather detrimental to Li diffusion kinetics. Defect chemical analysis indicates that this limited doping effect is due to the trapping of free lithium ions by the critical electron-ion association reactions at room temperature such as Li(i)(•) + e' ⇌ Li(i)(×) and Nb(Ti)(•) + e' ⇌ Nb(Ti)(×).

"Job-Sharing" Storage of Hydrogen in Ru/Li2O Nanocomposites.

A "job-sharing" hydrogen storage mechanism is proposed and experimentally investigated in Ru/Li2O nanocomposites in which H(+) is accommodated on the Li2O side, while H(-) or e(-) is stored on the side of Ru. Thermal desorption-mass spectroscopy results show that after loading with D2, Ru/Li2O exhibits an extra desorption peak, which is in contrast to Ru nanoparticles or ball-milled Li2O alone, indicating a synergistic hydrogen storage effect due to the presence of both phases. By varying the ratio of the two phases, it is shown that the effect increases monotonically with the area of the heterojunctions, indicating interface related hydrogen storage. X-ray diffraction, Fourier transform infrared spectroscopy, and nuclear magnetic resonance results show that a weak LiO···D bond is formed after loading in Ru/Li2O nanocomposites with D2. The storage-pressure curve seems to favor H(+)/H(-) over H(+)/e(-) mechanism.

Charge carrier accumulation in lithium fluoride thin films due to Li-ion absorption by titania (100) subsurface.

The thermodynamically required redistribution of ions at given interfaces is being paid increased attention. The present investigation of the contact LiF/TiO(2) offers a highly worthwhile example, as the redistribution processes can be predicted and verified. It consists in Li ion transfer from LiF into the space charge zones of TiO(2). We not only can measure the resulting increase of lithium vacancy conductivity in LiF, we also observe a transition from n- to p-type conductivity in TiO(2) in consistency with the generalized space charge model.

A chemically driven insulator-metal transition in non-stoichiometric and amorphous gallium oxide.

Insulator-metal transitions are well known in transition-metal oxides, but inducing an insulator-metal transition in the oxide of a main group element is a major challenge. Here, we report the observation of an insulator-metal transition, with a conductivity jump of seven orders of magnitude, in highly non-stoichiometric, amorphous gallium oxide of approximate composition GaO(1.2) at a temperature around 670 K. We demonstrate through experimental studies and density-functional-theory calculations that the conductivity jump takes place at a critical gallium concentration and is induced by crystallization of stoichiometric Ga(2)O(3) within the metastable oxide matrix-in chemical terms by a disproportionation. This novel mechanism--an insulator-metal transition driven by a heterogeneous solid-state reaction--opens up a new route to achieve metallic behaviour in oxides that are expected to exist only as classic insulators.

Phase evolution in single-crystalline LiFePO4 followed by in situ scanning X-ray microscopy of a micrometre-sized battery.

LiFePO4 is one of the most frequently studied positive electrode materials for lithium-ion batteries during the last years. Nevertheless, there is still an extensive debate on the mechanism of phase transformation. On the one hand this is due to the small energetic differences involved and hence the great sensitivity with respect to parameters such as size and morphology. On the other hand this is due to the lack of in situ observations with appreciable space and time resolution. Here we present scanning transmission X-ray microscopy measurements following in situ the phase boundary propagation within a LiFePO4 single crystal along the (010) orientation during electrochemical lithiation/delithiation. We follow, on a battery-relevant timescale, the evolution of a two-phase-front on a micrometre scale with a lateral resolution of 30 nm and with minutes of time resolution. The growth pattern is found to be dominated by elastic effects rather than being transport-controlled.

Heterogeneously catalysed partial oxidation of acrolein to acrylic acid--structure, function and dynamics of the V-Mo-W mixed oxides.

The major objective of this research project was to reach a microscopic understanding of the structure, function and dynamics of V-Mo-(W) mixed oxides for the partial oxidation of acrolein to acrylic acid. Different model catalysts (from binary and ternary vanadium molybdenum oxides up to quaternary oxides with additional tungsten) were prepared via a solid state preparation route and hydrochemical preparation of precursors by spray-drying or crystallisation with subsequent calcination. The phase composition was investigated ex situ by XRD and HR-TEM. Solid state prepared samples are characterised by crystalline phases associated to suitable phase diagrams. Samples prepared from crystallised and spray-dried precursors show crystalline phases which are not part of the phase diagram. Amorphous or nanocrystalline structures are only found in tungsten doped samples. The kinetics of the partial oxidation as well as the catalysts' structure have been studied in situ by XAS, XRD, temperature programmed reaction and reduction as well as by a transient isotopic tracing technique (SSITKA). The reduction and re-oxidation kinetics of the bulk phase have been evaluated by XAS. A direct influence not only of the catalysts' composition but also of the preparation route is shown. Altogether correlations are drawn between structure, oxygen dynamics and the catalytic performance in terms of activity, selectivity and long-term stability. A model for the solid state behaviour under reaction conditions has been developed. Furthermore, isotope exchange experiments provided a closer image of the mechanism of the selective acrolein oxidation. Based on the in situ characterisation in combination with micro kinetic modelling a detailed reaction model which describes the oxygen exchange and the processes at the catalyst more precisely is discussed.