Li₀.₆[Li₀.₂Sn₀.₈S₂] – a layered lithium superionic conductor

One of the key challenges of energy research is finding solid electrolytes with high lithium conductivities comparable to those of liquid electrolytes. In this context, developing new structural families of potential Li+ ion conductors and identifying structural descriptors for fast Li+ ion conduction to occur is key to expand the scope of viable Li+ ion conductors. Here, we report that the layered material Li0.6[Li0.2Sn0.8S2] shows a Li+ ion conductivity comparable to the currently best lithium superionic conductors (LISICONs). Li0.6[Li0.2Sn0.8S2] is composed of layers comprising edge-sharing Li/SnS6 octahedra, interleaved with both tetrahedrally and octahedrally coordinated Li+ ions. Pulsed field gradient (PFG) NMR studies on powder samples show intragrain (bulk) diffusion coefficients DNMR on the order of 10−11 m2 s−1 at room temperature, which corresponds to a conductivity σNMR of 9.3 × 10−3 S cm−1 assuming the Nernst–Einstein equation, thus putting Li0.6[Li0.2Sn0.8S2] en par with the best Li solid electrolytes reported to date. This is in agreement with impedance spectroscopy on powder pellets, showing a conductivity of 1.5 × 10−2 S cm−1. Direct current galvanostatic polarization/depolarization measurements on such samples show negligible electronic contributions (less than 10−9 S cm−1) but indicate significant contact resistance (d.c. conductivity in a reversible cell is 1.2 × 10−4 S cm−1 at 298 K). Our results suggest that the partial occupation of interlayer Li+ positions in this layered material is beneficial for its transport properties, which together with tetrahedrally coordinated Li sites provides facile Li+ ion diffusion pathways in the intergallery space between the covalent Sn(Li)S2 layers. This work therefore points to a generic design principle for new layered Li+ ion conductors based on the controlled depletion of Li+ ions in the interlayer space

Modal Logics of Topological Relations

Logical formalisms for reasoning about relations between spatial regions play a fundamental role in geographical information systems, spatial and constraint databases, and spatial reasoning in AI. In analogy with Halpern and Shoham's modal logic of time intervals based on the Allen relations, we introduce a family of modal logics equipped with eight modal operators that are interpreted by the Egenhofer-Franzosa (or RCC8) relations between regions in topological spaces such as the real plane. We investigate the expressive power and computational complexity of logics obtained in this way. It turns out that our modal logics have the same expressive power as the two-variable fragment of first-order logic, but are exponentially less succinct. The complexity ranges from (undecidable and) recursively enumerable to highly undecidable, where the recursively enumerable logics are obtained by considering substructures of structures induced by topological spaces. As our undecidability results also capture logics based on the real line, they improve upon undecidability results for interval temporal logics by Halpern and Shoham. We also analyze modal logics based on the five RCC5 relations, with similar results regarding the expressive power, but weaker results regarding the complexity

Surface floating 2D bands in layered nonsymmorphic semimetals : ZrSiS and related compounds

Work at Argonne National Laboratory is supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357; additional support by National Science Foundation under Grant No. DMR-0703406. This work was partially supported by the DFG, proposal no. SCHO 1730/1-1.In this work, we present a model of the surface states of nonsymmorphic semimetals. These are derived from surface mass terms that lift the high degeneracy imposed on the band structure by the nonsymmorphic bulk symmetries. Reflecting the reduced symmetry at the surface, the bulk bands are strongly modified. This leads to the creation of two-dimensional floating or unpinned bands, which are distinct from Shockley states, quantum well states, or topologically protected surface states. We focus on the layered semimetal ZrSiS to clarify the origin of its surface states. We demonstrate an excellent agreement between density functional theory calculations and angle-resolved photoemission spectroscopy measurements and present an effective four-band model in which similar surface bands appear. Finally, we emphasize the role of the surface chemical potential by comparing the surface density of states in samples with and without potassium coating. Our findings can be extended to related compounds and generalized to other crystals with nonsymmorphic symmetries.Publisher PDFPeer reviewe

Topological insulator in a Bi-Bi2_2Se3_3 infinitely adaptive superlattice phase

We report spin- and angle-resolved photoemission studies of a topological insulator from the infinitely adaptive series between elemental Bi and Bi$_2$Se$_3$. The compound, based on Bi$_4$Se$_3$, is a 1:1 natural superlattice of alternating Bi$_2$ layers and Bi$_2$Se$_3$ layers; the inclusion of S allows the growth of large crystals, with the formula Bi$_4$Se$_{2.6}$S$_{0.4}$. The crystals cleave along the interfaces between the Bi$_2$ and Bi$_2$Se$_3$ layers, with the surfaces obtained having alternating Bi or Se termination. The resulting terraces, observed by photoemission electron microscopy, create avenues suitable for the study of one-dimensional topological physics. The electronic structure, determined by spin- and angle- resolved photoemission spectroscopy, shows the existence of a surface state that forms a large, hexagonally shaped Fermi surface around the $\Gamma$ point of the surface Brillouin zone, with the spin structure indicating that this material is a topological insulator.Comment: published version, 5 pages, 4 figure

IrOOH nanosheets as acid stable electrocatalysts for the oxygen evolution reaction

In solids, heterogeneous catalysis is inherently bound to reactions on the surface. Yet, atomically efficient preparation of specific surfaces and the characterization of their properties are impeding its applications towards a clean energy future. Here, we present the synthesis of single layered IrOOH nanosheets and investigations of their structure as well as their electrochemical properties towards oxygen evolution under aqueous acidic conditions. The nanosheets are synthesized by treating bulk IrOOH with a tetrabutylammonium hydroxide solution and subsequent washing. Electron diffraction shows that the triangular arrangement of the edge sharing Ir(O,OH)(6) octahedra found in the layers of bulk IrOOH is retained after exfoliation into single layers. When incorporated as an active component in Ti electrodes, the nanosheets exhibit a Tafel slope of 58(3) mV dec(-1) and an overpotential of eta(-2)(10 mA cm) = 344(7) mV in 0.1 M HClO4, while retaining the trivalent oxidation state of iridium. They outperform bulk rutile-IrO2 and bulk IrOOH as electrocatalytic water oxidation catalysts under the same conditions. The results of this study on the structure-property relationships of low valence IrOOH nanosheets offer new pathways for the development of atom efficient, robust and highly active oxygen evolution catalysts