RESUMO
Li-Se battery is a promising energy storage candidate owing to its high theoretical volumetric capacity and safe operating condition. In this work, for the first time, we report using the whole organic Melamine-based porous polymer networks (MPNs) as a precursor to synthesize a N, O, S co-doped hierarchically porous carbon nanobelts (HPCNBs) for both Li-ion and Li-Se battery. The N, O, S co-doping resulting in the defect-rich HPCNBs provides fast transport channels for electrolyte, electrons and ions, but also effectively relieve volume change. When used for Li-ion battery, it exhibits an advanced lithium storage performance with a capacity of 345 mAh g-1 at 500 mA g-1 after 150 cycles and a superior rate capacity of 281 mAh g-1 even at 2000 mA g-1. Further density function theory calculations reveal that the carbon atoms adjacent to the doping sites are electron-rich and more effective to anchor active species in Li-Se battery. With the hierarchically porous channels and the strong dual physical-chemical confinement for Li2Se, the Se@ HPCNBs composite delivers an ultra-stable cycle performance even at 2 C after 1000 cycles. Our work here suggests that introduce of heteroatoms and defects in graphite-like anodes is an effective way to improve the electrochemical performance.
RESUMO
Active crystal facets can generate special properties for various applications. Herein, we report a (001) faceted nanosheet-constructed hierarchically porous TiO2/rGO hybrid architecture with unprecedented and highly stable lithium storage performance. Density functional theory calculations show that the (001) faceted TiO2 nanosheets enable enhanced reaction kinetics by reinforcing their contact with the electrolyte and shortening the path length of Li+ diffusion and insertion-extraction. The reduced graphene oxide (rGO) nanosheets in this TiO2/rGO hybrid largely improve charge transport, while the porous hierarchy at different length scales favors continuous electrolyte permeation and accommodates volume change. This hierarchically porous TiO2/rGO hybrid anode material demonstrates an excellent reversible capacity of 250 mAh g-1 at 1 C (1 C = 335 mA g-1) at a voltage window of 1.0-3.0 V. Even after 1000 cycles at 5 C and 500 cycles at 10 C, the anode retains exceptional and stable capacities of 176 and 160 mAh g-1, respectively. Moreover, the formed Li2Ti2O4 nanodots facilitate reversed Li+ insertion-extraction during the cycling process. The above results indicate the best performance of TiO2-based materials as anodes for lithium-ion batteries reported in the literature.
RESUMO
The lithium-selenium (Li-Se) battery has attracted growing interest recently due to its high energy density and theoretical capacity. However, the shuttle effect and volume change during cycling severely hinder its further application. In this work, we report a metal-organic framework (MOF)-derived nitrogen-doped core-shell hierarchical porous carbon (N-CSHPC) with interconnected meso/micropores to effectively confine Se for high-performance Li-Se batteries. The micropores were located at the ZIF-8-derived core and the ZIF-67-derived shell, while mesopores appeared at the core-shell interface after the pyrolysis of the core-shell ZIF-8@ZIF-67 precursor. Such a special hierarchical porous structure effectively confined selenium and polyselenides to prevent their dissolution from the pores and also alleviated the volume change. In particular, in situ nitrogen doping, which afforded N-CSHPC, not only improved the electrical conductivity of Se but also provided strong chemical adsorption on Li2Se, as confirmed by density functional theory calculations. On the basis of dual-physical confinement and strong chemisorption, Se/N-CSHPC-II (molar ratio of Co source to Zn source of 1.0 in the core-shell ZIF-8@ZIF-67 precursor) exhibited reversible capacities of up to 555 mA h g-1 after 150 cycles at 0.2 C and 462 mA h g-1 after 200 cycles at 0.5 C and even a discharge capacity of 432 mA h g-1 after 200 cycles at 1 C. Our demonstration here suggests that the carefully designed Se/C composite can improve the reversible capacity and cycling stability of Se cathodes for Li-Se batteries.
RESUMO
Photocatalytic hydrogen (H2) production based on semiconductors is important to utilize solar light for clean energy and environment. Herein, we report a visible light responsive heterostructure, designed and constructed by molybdenum disulfide quantum dots (MoS2-QDs) in-situ seeds-directing growth and self-assemble of zinc indium sulfide (ZnIn2S4) nanosheet to ensure their full contact through a simple one-step solvothermal method for highly improved visible light H2 production. The MoS2-QDs in-situ seeds-directing ZnIn2S4 heterostructure not only builds heterojunctions between MoS2 and ZnIn2S4 to spatially separate the photogenerated electrons and holes, but also serves as the active sites trapping photogenerated electrons to facilitate H2 evolution. As a result, MoS2-QDs/ZnIn2S4 exhibits high photocatalytic activity for H2 production, and the optimized 2â¯wt% MoS2-QDs/ZnIn2S4 (2MoS2-QDs/ZnIn2S4) heterostructure exhibits the highest H2 evolution rate of 7152 umol·h-1·g-1 under visible light, â¼9 times of pure ZnIn2S4. Our strategy here could shed some lights on developing noble-metal free heterostructures for highly efficient photocatalytic H2 production.