This work deciphers the modulation essence of p bands on Li-S chemistry by systematically studying the kinetic behaviors of Li-S chemistry on Co-based compounds with fixed metal cation and varied non-metal anions. The p bands originated from the non-metal anions can benefit the interfacial charge interaction by tuning the electron energy of the valence band, endowing S@rGO/CoP with unprecedented rate performance for Li-S batteries. It offers a new vision to rationally design highly efficient materials for Li-S batteries.
Molybdenum disulfide is naturally inert for alkaline hydrogen evolution catalysis, due to its unfavorable water adsorption and dissociation feature originated from the unsuitable orbital orientation. Herein, we successfully endow molybdenum disulfide with exceptional alkaline hydrogen evolution capability by carbon-induced orbital modulation. The prepared carbon doped molybdenum disulfide displays an unprecedented overpotential of 45 mV at 10 mA cm−2, which is substantially lower than 228 mV of the molybdenum disulfide and also represents the best alkaline hydrogen evolution catalytic activity among the ever-reported molybdenum disulfide catalysts. Fine structural analysis indicates the electronic and coordination structures of molybdenum disulfide have been significantly changed with carbon incorporation. Moreover, theoretical calculation further reveals carbon doping could create empty 2p orbitals perpendicular to the basal plane, enabling energetically favorable water adsorption and dissociation. The concept of orbital modulation could offer a unique approach for the rational design of hydrogen evolution catalysts and beyond.
Metal sulfides for hydrogen evolution catalysis typically suffer from unfavorable hydrogen desorption properties due to the strong interaction between the adsorbed H and the intensely electronegative sulfur. Here, we demonstrate a general strategy to improve the hydrogen evolution catalysis of metal sulfides by modulating the surface electron densities. The N modulated NiCo2S4 nanowire arrays exhibit an overpotential of 41 mV at 10 mA cm−2 and a Tafel slope of 37 mV dec−1, which are very close to the performance of the benchmark Pt/C in alkaline condition. X-ray photoelectron spectroscopy, synchrotron-based X-ray absorption spectroscopy, and density functional theory studies consistently confirm the surface electron densities of NiCo2S4 have been effectively manipulated by N doping. The capability to modulate the electron densities of the catalytic sites could provide valuable insights for the rational design of highly efficient catalysts for hydrogen evolution and beyond.
Large-volume-expansion-induced material pulverization severely limits the electrochemical performance of red phosphorous (P) for energy-storage applications. Hollow nanospheres with porous shells are recognized as an ideal structure to resolve these issues. However, a chemical synthetic approach for preparing nanostructured red P is always of great challenge and hollow nanosphere structures of red P have not yet been fabricated. Herein, a wet solvothermal method to successfully fabricate hollow P nanospheres (HPNs) with porous shells via a gas-bubble-directed formation mechanism is developed. More importantly, due to the merits of the porous and hollow structures, these HPNs reveal the highest capacities (based on the weight of electrode materials) of 1285.7 mA h g for lithium-ion batteries and 1364.7 mA h g for sodium-ion batteries at 0.2 C, and excellent long-cycling performance.
A molten salt system is developed for low-temperature metallothermic reduction of various silicates or silica to crystalline Si nanoparticles as high-performance anode materials.
The low capacity and unsatisfactory rate capability of hard carbon still restricts its practical application for Li/K‐ion batteries. Herein, a low‐cost and large‐scale method is developed to fabricate phosphorus‐doped hard carbon (PHC‐700) by crosslinking phosphoric acid and epoxy resin and followed by annealing at 700 °C. H3PO4 acts not only as a crosslinker to solidify epoxy resin for promoting the degree of graphitization and lowering the specific surface area, but also as phosphorus source for forming PC and PO bonds, thus providing more active sites for Li/K storage. As a result, the PHC‐700 electrode delivers a highly reversible capacity of 1294.8 mA h g−1 at 0.1 A g−1 and a capacity of 214 mA h g−1 after 10 000 cycles at 10 A g−1. As for potassium‐ion batteries, PHC‐700 exhibits a reversible capacity of 381.9 mA h g−1 at 0.1 A g−1 and a capacity of 260 mA h g−1 after 1000 cycles at 0.2 A g−1. In situ Raman and in situ NMR measurements reveal that the P‐containing bonds can enhance the adsorption to alkali metal ions, and the PC bond can participate in electrochemical redox reaction by forming Lix
PCy
. Additionally, P‐doped hard carbon shows better structural/interfacial stability for improved long‐term cycling stability.
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