The lithium-sulfur battery is receiving intense interest because its theoretical energy density exceeds that of lithium-ion batteries at much lower cost, but practical applications are still hindered by capacity decay caused by the polysulfide shuttle. Here we report a strategy to entrap polysulfides in the cathode that relies on a chemical process, whereby a host--manganese dioxide nanosheets serve as the prototype--reacts with initially formed lithium polysulfides to form surface-bound intermediates. These function as a redox shuttle to catenate and bind 'higher' polysulfides, and convert them on reduction to insoluble lithium sulfide via disproportionation. The sulfur/manganese dioxide nanosheet composite with 75 wt% sulfur exhibits a reversible capacity of 1,300 mA h g(-1) at moderate rates and a fade rate over 2,000 cycles of 0.036%/cycle, among the best reported to date. We furthermore show that this mechanism extends to graphene oxide and suggest it can be employed more widely.

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A highly efficient polysulfide mediator for lithium-sulfur batteries.

Localized surface plasmon resonances (LSPRs) typically arise in nanostructures of noble metals resulting in enhanced and geometrically tunable absorption and scattering resonances. LSPRs, however, are not limited to nanostructures of metals and can also be achieved in semiconductor nanocrystals with appreciable free carrier concentrations. Here, we describe well-defined LSPRs arising from p-type carriers in vacancy-doped semiconductor quantum dots (QDs). Achievement of LSPRs by free carrier doping of a semiconductor nanocrystal would allow active on-chip control of LSPR responses. Plasmonic sensing and manipulation of solid-state processes in single nanocrystals constitutes another interesting possibility. We also demonstrate that doped semiconductor QDs allow realization of LSPRs and quantum-confined excitons within the same nanostructure, opening up the possibility of strong coupling of photonic and electronic modes, with implications for light harvesting, nonlinear optics, and quantum information processing.

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Localized surface plasmon resonances arising from free carriers in doped quantum dots

Quantum confinement of electronic wavefunctions in semiconductor quantum dots (QDs) yields discrete atom-like and tunable electronic levels, thereby allowing the engineering of excitation and emission spectra. Metal nanoparticles, on the other hand, display strong resonant interactions with light from localized surface plasmon resonance (LSPR) oscillations of free carriers, resulting in enhanced and geometrically tunable absorption and scattering resonances. The complementary attributes of these nanostructures lends strong interest toward integration into hybrid nanostructures to explore enhanced properties or the emergence of unique attributes arising from their interaction. However, the physicochemical interface between the two components can be limiting for energy transfer and synergistic coupling within such a hybrid nanostructure. Therefore, it is advantageous to realize both attributes, i.e., LSPRs and quantum confinement within the same nanostructure. Here, we describe well-defined LSPRs arising from p-type carriers in vacancy-doped semiconductor quantum dots. This opens up possibilities for light harvesting, non-linear optics, optical sensing and manipulation of solid-state processes in single nanocrystals.

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Near-Infrared Localized Surface Plasmon Resonances Arising from Free Carriers in Doped Quantum Dots

Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

Metodija Najdoski

Papers

Optical and Electrical Properties of Copper Sulfide Films of Variable Composition

Raman spectra of thin solid films of some metal sulfides

A solution growth route to nanocrystalline nickel oxide thin films

Fabrication and characterization of nanocrystalline cobalt oxide thin films

Chemical bath deposition of nanocrystalline (111) textured Ag2Se thin films