Electrides are characteristic of anionic electrons trapped at the structural voids in the host lattice. Electrides are potentially useful in various technological applications; however, electrides, particularly their inorganic subgroup, have been discovered only in limited material systems, notably zero-dimensional [Ca24Al28O64](4+):4e(-) and two-dimensional [Ca2N](+):e(-) and [Y2C](1.8+):1.8e(-). Here, on the basis of density functional theory calculations, we report the first one-dimensional (1D) electride with a [La8Sr2(SiO4)6](4+):4e(-) configuration, in which the four anionic electrons are confined in the channel spaces of the host material. According to this theoretical prediction, an insulator-semiconductor transition originating from electron confinement in the crystallographic channel sites was demonstrated experimentally, where 10.5% of the channel oxygen was removed by reacting an oxygen stoichiometric La8Sr2(SiO4)6O2 precursor with Ti metal at a high temperature. This study not only adds an unprecedented role to silicate apatite as a parent phase to a new 1D electride, but also, and more importantly, demonstrates an effective approach for developing new electrides with the assistance of computational design.
Electrides are unique in the sense that they contain localized anionic electrons in the interstitial regions. Yet they exist with a diversity of chemical compositions, especially under extreme conditions, implying generalized underlying principles for their existence. What is rarely observed is the combination of electride state and superconductivity within the same material, but such behavior would open up a new category of superconductors. Here, we report a hexagonal Nb 5 Ir 3 phase of Mn 5 Si 3 -type structure that falls into this category and extends the electride concept into intermetallics. The confined electrons in the one-dimensional cavities are reflected by the characteristic channel bands in the electronic structure. Filling these free spaces with foreign oxygen atoms serves to engineer the band topology and increase the superconducting transition temperature to 10.5 K in Nb 5 Ir 3 O. Specific heat analysis indicates the appearance of low-lying phonons and two-gap s-wave superconductivity. Strong electron-phonon coupling is revealed to be the pairing glue with an anomalously large ratio between the superconducting gap Δ 0 and T c , 2Δ 0 /k B T c = 6.12. The general rule governing the formation of electrides concerns the structural stability against the cation filling/extraction in the channel site.
Sodium-ion batteries (SIBs) have attracted much interest as a low-cost and environmentally benign energy storage system, but more attention is justifiably required to address the major technical issues relating to the anode materials to deliver high reversible capacity, superior rate capability, and stable cyclability. A SnSe/reduced graphene oxide (RGO) nanocomposite has been prepared by a facile ball-milling method, and its structural, morphological, and electrochemical properties have been characterized and compared with those of the bare SnSe material. Although the redox behavior of SnSe remains nearly unchanged upon the incorporation of RGO, its electrochemical performance is significantly enhanced, as reflected by a high specific capacity of 590 mA h g(-1) at 0.050 A g(-1) , a rate capability of 260 mA h g(-1) at 10 A g(-1) , and long-term stability over 120 cycles. This improvement may be attributed to the high electronic conductivity of RGO, which also serves as a matrix to buffer changes in volume and maintain the mechanical integrity of the electrode during (de)sodiation processes. In view of its excellent Na(+) storage performance, this SnSe/RGO nanocomposite has potential as an anode material for SIBs.
Cu3 V2 O8 nanoparticles with particle sizes of 40-50 nm have been prepared by the co-precipitation method. The Cu3 V2 O8 electrode delivers a discharge capacity of 462 mA h g(-1) for the first 10 cycles and then the specific capacity, surprisingly, increases to 773 mA h g(-1) after 50 cycles, possibly as a result of extra lithium interfacial storage through the reversible formation/decomposition of a solid electrolyte interface (SEI) film. In addition, the electrode shows good rate capability with discharge capacities of 218 mA h g(-1) under current densities of 1000 mA g(-1) . Moreover, the lithium storage mechanism for Cu3 V2 O8 nanoparticles is explained on the basis of ex situ X-ray diffraction data and high-resolution transmission electron microscopy analyses at different charge/discharge depths. It was evidenced that Cu3 V2 O8 decomposes into copper metal and Li3 VO4 on being initially discharged to 0.01 V, and the Li3 VO4 is then likely to act as the host for lithium ions in subsequent cycles by means of the intercalation mechanism. Such an "in situ" compositing phenomenon during the electrochemical processes is novel and provides a very useful insight into the design of new anode materials for application in lithium-ion batteries.
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