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Nanoscale. 2014 Oct 7;6(19):11411-8. doi: 10.1039/c4nr03395g.

Large-scale low temperature fabrication of SnO2 hollow/nanoporous nanostructures: the template-engaged replacement reaction mechanism and high-rate lithium storage.

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Max Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569, Stuttgart, Germany.


The morphology-controlled synthesis of SnO2 hollow/nanoporous nanostructures (nanotubes, urchin-like morphologies and nanospheres) was achieved via a template-engaged replacement reaction at a mild temperature (lower than 80 °C). The formation mechanism of hollow interior and nanoporous walls for the obtained SnO2 nanostructures (SnO2 nanotubes were used as an example) was investigated based on TEM and HRTEM observations during different reaction stages. It is found that bridge voids firstly form at the MnO2/SnO2 interface, followed by the inward development of voids before the MnO2 core is completely consumed. Two types of short-circuited galvanic cells, MnO2/Mn(2+)∣SnO2/Sn(2+) and concentration cell-SnO2/Sn(2+) (interior)∣SnO2/Sn(2+) (exterior), are probably responsible for the formation of SnO2 nanotubes and outward growth of SnO2 along MnO2. Moreover, the calculation result of the outer diameter of SnO2 nanotubes is in good agreement with the observation results by SEM and TEM. When evaluated as anodes for lithium ion batteries (LIBs), the three SnO2 nanostructures exhibit superior rate capability and cycling performance. Especially, SnO2 nanotubes present the best rate capability: specific capacities of above 800 mA h g(-1) at 200 mA g(-1) and about 500 mA h g(-1) at 4000 mA g(-1) were achieved, respectively. Importantly, the 1D morphology of SnO2 nanotubes can be well preserved after prolonged cycling at a relatively high current density, indicating good structural stability of the resulting nanotubes during the Li(+) insertion/extraction process. These results indicate that the obtained SnO2 hollow/nanoporous nanostructures would be promising anode materials for next-generation LIBs.

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