模板法构建ZnMn2O4/石油沥青基多孔石墨烯复合材料及其锂电性能研究

Energy and environment are currently hot issues, and environmental friendly material for energy storage is key project of the 12th Five Year Developmental Project of New Materials. Lithium ion secondly batteries (LIBs) with high energy density attract more and more attention. The low power density and charge/discharge speed limit the further application of LIBs. Herein, porous graphene with controlled pores can be prepared by template method from petroleum asphalt. ZnMn2O4/petroleum asphalt based porous graphene (ZMO/PAPG) can be obtained by heat treatment of petroleum asphalt based porous graphene mixed with zinc nitrate and manganous nitrate. Mechanisms on lithium storage on porous graphene and ZMO and the interaction in carbon/ZMO interface are needed to be investigated. The effects of mass ratio, structure parameters of the template and temperature of heat treatment on the formation and lithium storage of ZMO/PAPG are discussed, and the relationship between the chemical structure and electrochemical performance is also investigated. The aim of this work is to integrate the advantages of porous graphene, i.e. high electrical conductivity and little resistance for ion entering and going out, with the high power density of metal oxide. Thus, LIBs with both high energy density and high power density can be obtained. This work opens a new application field for petroleum asphalt and provides theory for the preparation of LIBs with high electrical performance.

当今社会能源与环保问题日益突出，《新材料产业“十二五”发展规划》里将环保储能材料列为重点攻关项目。具有高能量密度的锂离子二次电池（LIBs）受到越来越多的关注。LIBs小的功率密度和慢的充放电速度限制了其进一步发展。本课题以富含芳烃的石油炼化副产物-石油沥青为原料，通过模板法构建孔径可控的多孔石墨烯，再与锌、锰盐混合，经高温处理合成ZnMn2O4/石油沥青基多孔石墨烯复合材料（ZMO/PAPG）；研究ZMO/PAPG各组元电化学储锂机理及碳/非碳界面之间的相互作用；解析复合材料中ZnO，MnO2与多孔石墨烯的含量、模板结构参数、热处理温度等对ZMO/PAPG结构及储锂性能的内在影响机制。本课题旨在通过多孔石墨烯的导电、孔隙输运和活性组分的高容量的优势集成，提升LIBs的比电容。课题成果有望为石油沥青的高附加值利用开辟一条新途径，同时为高性能LIBs的开发奠定理论基础。

具有高能量密度的锂离子二次电池（LIBs）受到越来越多的关注，但LIBs 小的功率密度和慢的充放电速度限制了其进一步发展。本课题以富含芳烃的石油炼化副产物石油沥青为原料，通过模板法构建孔径可控的多孔石墨烯，再与锌、锰盐混合，经高温处理合 成ZnMn2O4/石油沥青基多孔石墨烯复合材料（ZMO/PAPG）；研究了ZMO/PAPG各组元电化学储锂机 理及碳/非碳界面之间的相互作用，解析了复合材料中ZnO，MnO2与多孔石墨烯的含量、模板结构参数、热处理温度等对ZMO/PAPG结构及储锂性能的内在影响机制，通过多孔石墨烯 的导电、孔隙输运和活性组分的高容量的优势集成，显著提升了LIBs的比电容， 1 A g-1的大电流下，550次长循环后容量仍能保持在420 mAh g-1，具有广阔的应用前景。课题成果为石油沥青的高附加值利用开辟一条新途径，同时为高性能LIBs的开发奠定理论基础。