General Recyclable Redox-Metallothermic Reaction Route to Hierarchically Porous Carbon/Metal Composites
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Chemistry of Materials, ISSN: 0897-4756, Vol: 28, Issue: 12, Page: 4403-4408
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- Chemistry; Chemical Engineering; Materials Science; METAL-ORGANIC FRAMEWORK; LITHIUM-ION BATTERIES; HIGH-SURFACE-AREA; NANOPOROUS CARBON; COORDINATION-POLYMER; DIRECT CARBONIZATION; ANODE MATERIAL; DOPED CARBON; PERFORMANCE; GERMANIUM
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, in situ evolved Zn reduces GeO, 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, Zn metal is spontaneously vaporized to yield Ge/HPC composites. This facile method can be successfully extended to other metal oxides including InO, BiO, 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 gafter 300 cycles at a rate of 0.5 C and a low electrode volume expansion (less than 30%).