To enhance the long stability of sulfur cathode for a high energy lithium-sulfur battery system, a sulfur-carbon sphere composite was prepared by encapsulating sulfur into micropores of carbon spheres by thermal treatment of a mixture of sublimed sulfur and carbon spheres. The elemental sulfur exists as a highly dispersed state inside the micropores of carbon spheres with a large surface area and a narrow pore distribution, based on the analyses of the X-ray powder diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), thermogravimetry (TG) and local element line-scanning. It is demonstrated from galvanostatic discharge-charge process, cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) that the sulfur-carbon sphere composite has a large reversible capacity and an excellent high rate discharge capability as cathode materials. In particular, the sulfur-carbon sphere composite with 42 wt% sulfur presents a long electrochemical stability up to 500 cycles, based on the constrained electrochemical reaction inside the narrow micropores of carbon spheres due to strong adsorption. Therefore, the electrochemical reaction constrained inside the micropores proposed here would be the dominant factor for the enhanced long stability of the sulfur cathode. The knowledge acquired in this study is important not only for the design of efficient new electrode materials, but also for understanding the effect of the micropores on the electrochemical cycle stability.

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Titanate nanofibers of various sizes and layered structure were prepared from inorganic titanium compounds by hydrothermal reactions. These fibers are different from "refractory" mineral substances because of their dimension, morphology, and significant large ratio of surface to volume, and, surprisingly, they are highly reactive. We found, for the first time, that phase transitions from the titanate nanostructures to TiO(2) polymorphs take place readily in simple wet-chemical processes at temperatures close to ambient temperature. In acidic aqueous dispersions, the fibers transform to anatase and rutile nanoparticles, respectively, but via different mechanisms. The titanate fibers prepared at lower hydrothermal temperatures transform to TiO(2) polymorphs at correspondingly lower temperatures because they are thinner, possess a larger surface area and more defects, and possess a less rigid crystal structure, resulting in lower stability. The transformations are reversible: in this case, the obtained TiO(2) nanocrystals reacted with concentrate NaOH solution, yielding hollow titanate nanotubes. Consequently, there are reversible transformation pathways for transitions between the titanates and the titanium dioxide polymorphs, via wet-chemical reactions at moderate temperatures. The significance of these findings arises because such transitions can be engineered to produce numerous delicate nanostructures under moderate conditions. To demonstrate the commercial application potential of these processes, we also report titanate and TiO(2) nanostructures synthesized directly from rutile minerals and industrial-grade rutiles by a new scheme of hydrometallurgical reactions.

Polyaniline-coated sulfur/conductive-carbon-black (PANI@S/C) composites with different contents of sulfur are prepared via two facile processes including ball-milling and thermal treatment of the conductive carbon black and sublimed sulfur, followed by an in situ chemical oxidative polymerization of the aniline monomer in the presence of the S/C composite and ammonium persulfate. The microstructure and electrochemical performance of the asprepared composites are investigated systematically. It is demonstrated that the polyaniline, with a thickness of ≈ 5-10 nm, is coated uniformly onto the surface of the S/C composite forming a core/shell structure. The PANI@S/C composite with 43.7 wt% sulfur presents the optimum electrochemical performance, including a large reversible capacity, a good coulombic efficiency, and a high active-sulfur utilization. The formation of the unique core/ shell structure in the PANI@S/C composites is responsible for the improvement of the electrochemical performance. In particular, the high-rate charge/ discharge capability of the PANI@S/C composites is excellent due to a synergistic effect on the high electrical conductivity from both the conductive carbon black in the matrix and the PANI on the surface. Even at an ultrahigh rate (10C), a maximum discharge capacity of 635.5 mA h per g of sulfur is still retained for the PANI@S/C composite after activation, and the discharge capacity retention is over 60% after 200 cycles.