General recyclable redox-metallothermic reaction route to hierarchically porous carbon/metal composites

Publication Type:
Journal Article
Citation:
Chemistry of Materials, 2016, 28 (12), pp. 4403 - 4408
Issue Date:
2016-06-01
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© 2016 American Chemical Society. Herein, we develop a general synthetic route to obtain composites of porous carbon and electrochemically active metal particles such as Ge, In, Bi, and Sn. The thermolysis of a Zn-based metal-organic framework (MOF) produces hierarchically porous carbon (HPC) and metallic Zn at high temperatures, which can act as a reducing agent of metal oxides. In the reaction system of a Zn-based MOF with GeO 2 , in situ evolved Zn reduces GeO 2 , producing Ge and ZnO. Interestingly, ZnO is automatically reduced to Zn via a carbothermic reduction during the conversion process, which returns reducing agent to the reaction. Thus, the repeated occurrence of the zincothermic and carbothermic reduction reactions promotes a recyclable redox-metallothermic reaction. After complete reduction of GeO 2 , Zn metal is spontaneously vaporized to yield Ge/HPC composites. This facile method can be successfully extended to other metal oxides including In 2 O 3 , Bi 2 O 3 , and SnO. The as-synthesized Ge/HPC is tested as a rechargeable battery anode material, which exhibits a reversible capacity as high as 600 mA h g -1 after 300 cycles at a rate of 0.5 C and a low electrode volume expansion (less than 30%).
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