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[摘要]：Mesoporous thin films (MTFs) appear as an interesting architecture for positive electrodes in Li-ion energy storage systems because they offer high specific area and interconnected porosity presenting homogeneous pore size and wall thickness. However, it must be ascertained that the mesostructure survives template removal or/and crystallization and is retained on electrochemical cycling. In order to investigate the potentialities and limits of the soft-templating approach in the case of complex transition metal oxide networks, we deliberately selected a "difficult" compound: NbVO(5) was chosen because it combines a challenging synthesis with reported severe structural distortions during the first lithium insertion in the bulk material. In this work, NbVO(5) MTFs with different pore sizes were synthesized using the evaporation induced micelles packing (EIMP) method. PS-b-PEO diblock copolymers of different molar weights were used as structure directing agent in order to obtain wormlike porous networks with pore size and wall thickness ranging from 15 to 100 nm. Thermal ellipsometry analysis, used to track surfactant removal and crystallization of the layer, reveals that partial crystallization is possible while retaining the mesoporous architecture. Electron tomography complements result from environmental ellipsometric porosimetry, atomic force microscopy, and transmission electron microscopy to provide a comprehensive description of the structure. A multilayer process is also proposed to build crack-free thick mesoporous films. The mechanical stability of MTFs presenting three different pore sizes is tested by inserting Li(+) in amorphous NbVO(5) MTFs using cyclic voltammetry. Capacity retention data show that the mechanical stresses associated with Li(+) insertion are better accommodated by MTFs compared to nonporous films, and this ability is enhanced as the pore size decreases. |
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