功能化石墨烯的制备及其在锂硫电池中的应用
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摘要
采用改进的Hummer's法制备了氧化石墨(GO),对GO进行氨基接枝和还原,以氨基为桥梁制备了氨基功能化石墨烯(EFG)/聚苯胺(PANI)复合材料,并采用化学沉积法制备了EFG/PANI/硫(S)复合材料,将其用作锂硫电池正极。通过傅立叶变换红外光谱仪、X射线衍射仪、扫描电子显微镜、比表面积分析仪对复合材料的微观结构、形貌和比表面积等进行了表征,采用恒流充放电测试和交流阻抗测试对复合材料的电化学性能进行了研究。结果表明,制备的EFG/PANI富含孔隙结构,能够为锂硫电池的电化学反应提供充足的空间;该材料中富含的氮能够与多硫化物中的Li+以化学键的方式结合,有效缓解锂硫电池的"穿梭效应"。
The graphite oxide(GO) was prepared by modified Hummer's method,and amino grafting and reduction of GO were performed. Then,amino-functionalized graphene(EFG)/polyaniline(PANI) composites was obtained by chemical deposition method and used as the cathode material for lithium-sulfur(Li-S) batteries. The microstructure,morphology and specific surface area of the EFG/PANI composites were characterized by FTIR,XRD,SEM,and BET,respectively. Electrochemical performance of the composites was determined by galvanostatic charge-discharge test and impedance spectroscopy. Results showed that the EFG/PANI was rich in the pore structure,providing enough space to accommodate the active materials for Li-S batteries,and alleviating the shuttle effect effectively with the chemical bond combination between abundant N and Li+ in polysulfides to improve the electrochemical performance of Li-S batteries.
The graphite oxide(GO) was prepared by modified Hummer's method,and amino grafting and reduction of GO were performed. Then,amino-functionalized graphene(EFG)/polyaniline(PANI) composites was obtained by chemical deposition method and used as the cathode material for lithium-sulfur(Li-S) batteries. The microstructure,morphology and specific surface area of the EFG/PANI composites were characterized by FTIR,XRD,SEM,and BET,respectively. Electrochemical performance of the composites was determined by galvanostatic charge-discharge test and impedance spectroscopy. Results showed that the EFG/PANI was rich in the pore structure,providing enough space to accommodate the active materials for Li-S batteries,and alleviating the shuttle effect effectively with the chemical bond combination between abundant N and Li+ in polysulfides to improve the electrochemical performance of Li-S batteries.
引文
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[2]Son Y,Lee J,Son Y,et al.Recent advances in lithium-sulfide cathode materials and their use in lithium-sulfur batteries[J].Advanced Energy Materials,2015,5(16):1-14.
[3]付海涛,黄英,杨毅文,等.石墨烯在锂硫电池中的应用[J].工程塑料应用,2015,43(6):122-127.Fu Haitao,Huang Ying,Yang Yiwen,et al.Application of graphene in Lithium sulfur batteries[J].Engineering Plastics Application,2015,43(06):122-127.
[4]肖淑娟,于守武,谭小耀.石墨烯类材料的应用及研究进展[J].化工进展,2015,34(5):1 345-1 348.Xiao Shujuan,Yu Shouwu,Tan Xiaoyao.Research progress of graphene-based composite electrodes in asymmetric supercapacitors[J].Chemical Industry and Engineering Progress,2015,34(5):1 345-1 348.
[5]杨蓉,李兰,王黎晴,等.微波法制备还原氧化石墨及其在锂硫电池中的应用[J].化工学报,2017,68(11):4 333-4 340.Yang Rong,Li Lan,Wang Liqing,et al.Preparation of reduced graphene oxide by microwave method and its application in lithiumsulfur batteries[J].CIESC Journal,2017,68(11):4 333-4 340.
[6]Komlev A A,Makarova T L,Lahderanta E,et al.Magnetism of aniline modified graphene-based materials[J].Journal of Magnetism&Magnetic Materials,2016,415:45-50.
[7]Li Y,Jian Z,Lang M,et al.Covalently functionalized graphene by radical polymers for graphene-based high-performance cathode materials[J].Acs Applied Materials&Interfaces,2016,8(27):17 352-17 379.
[8]Wang H,Yang Y,Liang Y,et al.Graphene-wrapped sulfur particles as a rechargeable lithium-sulfur battery cathode material with high capacity and cycling stability[J].Nano Letters,2011,11(7):2 644-2 647.
[9]Georgakilas V,Otyepka M,Bourlinos A B,et al.Functionalization of graphene:Covalent and non-covalent approaches,derivatives and applications[J].Chemical Reviews,2012,112(11):6 156-6 214.
[10]Wang A,Wang Y,Huang Z,et al.Covalent functionalization of reduced graphene oxide with porphyrin by means of diazonium chemistry for nonlinear optical performance[J].Scientific Reports,2016,6:23 325-23 337.
[11]刘伟伟.聚合物/石墨烯复合材料研究进展[J].工程塑料应用,2017,45(1):133-136.Liu Weiwei.Research progress in polymer/aligned graphene composites[J].Engineering Plastics Application,2017,45(1):133-136.
[12]William S,Hummers J,Richard E.Preparation of graphitic oxide[J].Journal of the American Chemical Society,1958,80(6):1 339-1 339.
[13]Chen R.Graphene based three-dimensional hierarchical sandwichtype architecture for high-performance Li/S batteries[J].Nano Letters,2013,13:4 642-4 649.
[14]龚水水.功能化石墨烯-聚苯胺纳米杂化材料的制备及其性能研究[D].上海:东华大学,2016.Gong Shuishui.Frabrication and properties of functionlized graphere-polyaniline nanohybrid materials[D].Shanghai:Donghua University,2016.
[15]Zhao Q,Chen J,Luo F,et al.Vertically oriented polyanilinegraphene nanocomposite based on functionalized graphene for supercapacitor electrode[J].Journal of Applied Polymer Science,2017,134(19):115-121.
[16]Hou T Z,Peng H J,Huang J Q,et al.The formation of strongcouple interactions between nitrogen-doped graphene and sulfur/lithium(poly)sulfides in lithium-sulfur batteries[J].2D Materials,2015,2(1):014 001.
[17]Zhou W,Yu Y,Hao C,et al.Yolk-shell structure of polyanilinecoated sulfur for lithium-sulfur batteries[J].Journal of the American Chemical Society,2013,135(44):16 736-16 743.
[18]Mikhaylik Y V,Akeidge J R.Polysulfide shuttle study in the Li/S battery system[J].Journal of the Electrochemical Society,2004,151(151):A1 969-A1 976.
[19]Li L,Zhou G M,Yin L C,et al.Stabilizing sulfur cathodes using nitrogen-doped graphene as a chemical immobilizer for Li-Sbatteries[J].Carbon,2016,108:120-126.
[20]Deng Z,Zhang Z,Lai Y,et al.Electrochemical impedance spectroscopy study of a lithium/sulfur battery:modeling and analysis of capacity fading[J].Journal of the Electrochemical Society,2013,160(4):A553-A558.
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