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Abstract Sodium–oxygen (Na–O2) batteries are considered a promising energy storage alternative to current state‐of‐the‐art technologies owing to their high theoretical energy density, along with the natural abundance and low price of Na metal. The chemistry of these batteries depends on sodium superoxide (NaO2) or peroxide (Na2O2) being formed/decomposed. Most Na–O2batteries form NaO2, but reversibility is usually quite limited due to side reactions at interfaces. By using new materials, including a highly active catalyst based on vanadium phosphide (VP) nanoparticles, an ether/ionic liquid‐based electrolyte, and an effective sodium bromide (NaBr) anode protection layer, the sources of interface reactivity can be reduced to achieve a Na–O2battery cell that is rechargeable for 1070 cycles with a high energy efficiency of more than 83%. Density functional theory calculations, along with experimental characterization confirm the three factors leading to the long cycle life, including the effectiveness of the NaBr protective layer on the anode, a tetraglyme/EMIM‐BF4based electrolyte that prevents oxidation of the VP cathode catalyst surface, and the EMIM‐BF4ionic liquid aiding in avoiding electrolyte decomposition on NaO2.more » « less
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Abstract It is shown that structural disorder—in the form of anisotropic, picoscale atomic displacements—modulates the refractive index tensor and results in the giant optical anisotropy observed in BaTiS3, a quasi‐1D hexagonal chalcogenide. Single‐crystal X‐ray diffraction studies reveal the presence of antipolar displacements of Ti atoms within adjacent TiS6chains along thec‐axis, and threefold degenerate Ti displacements in thea–bplane.47/49Ti solid‐state NMR provides additional evidence for those Ti displacements in the form of a three‐horned NMR lineshape resulting from a low symmetry local environment around Ti atoms. Scanning transmission electron microscopy is used to directly observe the globally disordered Tia–bplane displacements and find them to be ordered locally over a few unit cells. First‐principles calculations show that the Tia–bplane displacements selectively reduce the refractive index along theab‐plane, while having minimal impact on the refractive index along the chain direction, thus resulting in a giant enhancement in the optical anisotropy. By showing a strong connection between structural disorder with picoscale displacements and the optical response in BaTiS3, this study opens a pathway for designing optical materials with high refractive index and functionalities such as large optical anisotropy and nonlinearity.more » « less
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Abstract Materials with large birefringence (Δn, wherenis the refractive index) are sought after for polarization control (e.g., in wave plates, polarizing beam splitters, etc.), nonlinear optics, micromanipulation, and as a platform for unconventional light–matter coupling, such as hyperbolic phonon polaritons. Layered 2D materials can feature some of the largest optical anisotropy; however, their use in most optical systems is limited because their optical axis is out of the plane of the layers and the layers are weakly attached. This work demonstrates that a bulk crystal with subtle periodic modulations in its structure—Sr9/8TiS3—is transparent and positive‐uniaxial, with extraordinary indexne= 4.5 and ordinary indexno= 2.4 in the mid‐ to far‐infrared. The excess Sr, compared to stoichiometric SrTiS3, results in the formation of TiS6trigonal‐prismatic units that break the chains of face‐sharing TiS6octahedra in SrTiS3into periodic blocks of five TiS6octahedral units. The additional electrons introduced by the excess Sr form highly oriented electron clouds, which selectively boost the extraordinary indexneand result in record birefringence (Δn> 2.1 with low loss). The connection between subtle structural modulations and large changes in refractive index suggests new categories of anisotropic materials and also tunable optical materials with large refractive‐index modulation.more » « less
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