固相剪切磨盘碾磨法制备四氧化三铁/氮掺杂石墨烯复合材料及其在锂离子电池中的应用
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摘要
固相剪切磨盘碾磨法是一种基于全固相反应、不同于传统球磨方法制备微纳米基功能复合材料的新方法。本文以石墨和纳米四氧化三铁为原料,三聚氰胺为氮掺杂剂,采用固相剪切磨盘碾磨法,成功制备了四氧化三铁/氮掺杂石墨烯复合材料(Fe_3O_4/N-G)。通过X射线衍射(XRD)、拉曼光谱(RM)、透射电镜(TEM)、X射线光电子能谱(XPS)、比表面积(BET)测试和电化学测试对样品结构、形貌和电化学性能进行表征。测试结果显示:该方法能够在将石墨剥离成少数层石墨烯的同时,实现石墨烯的氮掺杂以及与Fe_3O_4的均匀复合,最终制得Fe_3O_4/N-G复合材料;将该复合材料作为锂离子电池负极材料,表现出优异的循环稳定性,在100mA·g-1的电流密度下经过100次循环后,Fe_3O_4/N-G可逆比容量保持在869 mAh·g-1,远高于纯Fe_3O_4的78mAh·g-1。该方法为制备石墨烯基复合电极材料提供了绿色环保、简便易行的新方法。
Different from traditional ball milling,solid-state shear pan-milling is an innovative approach that enables the synthesis of functional micro-and nano-composites.When graphite and nanometer scale Fe_3O_4 are applied as the raw material and melamine as the nitrogen doping agent,a composite of Fe_3O_4 and N-doped graphene(Fe_3O_4/N-G)could be successfully synthesized by employing the solid-state shearing pan-milling method.After characterization by X-ray diffraction(XRD),Raman spectroscopy(RM),transmission electronic microscopy(TEM),X-ray photoelectron spectroscopy(XPS),Brunauer,Emmett and Teller analysis(BET)and electrochemical measurements,it is found that graphite could be exfoliated into few-layered graphene while simultaneously doped by nitrogen and composited with Fe_3O_4 uniformly.When applied as an anode for lithium ion battery,an excellent cycling stability with a reversible capacity of 869 mAh·g-1 after 100 cycles at 100 mA·g-1 is delivered,which is far superior to pristine Fe_3O_4 with only 78 mAh·g-1 retained.The technique provides a green,and facile method for the preparation of graphene based composite electrode materials.
Different from traditional ball milling,solid-state shear pan-milling is an innovative approach that enables the synthesis of functional micro-and nano-composites.When graphite and nanometer scale Fe_3O_4 are applied as the raw material and melamine as the nitrogen doping agent,a composite of Fe_3O_4 and N-doped graphene(Fe_3O_4/N-G)could be successfully synthesized by employing the solid-state shearing pan-milling method.After characterization by X-ray diffraction(XRD),Raman spectroscopy(RM),transmission electronic microscopy(TEM),X-ray photoelectron spectroscopy(XPS),Brunauer,Emmett and Teller analysis(BET)and electrochemical measurements,it is found that graphite could be exfoliated into few-layered graphene while simultaneously doped by nitrogen and composited with Fe_3O_4 uniformly.When applied as an anode for lithium ion battery,an excellent cycling stability with a reversible capacity of 869 mAh·g-1 after 100 cycles at 100 mA·g-1 is delivered,which is far superior to pristine Fe_3O_4 with only 78 mAh·g-1 retained.The technique provides a green,and facile method for the preparation of graphene based composite electrode materials.
引文
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39 Jin S,Deng H,Long D,et al.Facile synthesis of hierarchically structured Fe3O4/carbon micro-flowers and their application to lithium-ion battery anodes[J].Journal of Power Sources,2011,196(8):3887.
40 Fu C,Zhao G,Zhang H,et al.A facile route to controllable synthesis of Fe3O4/graphene composites and their application in lithiumion batteries[J].International Journal of Electrochemical Science,2014,9(1):46.
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2 Hui W,Yi C.Designing nanostructured Si anodes for high energy lithium ion batteries[J].Nano Today,2012,7(5):414.
3 Lin K Z,Wang X L,Xu Y H.Recent development of tin-based materials as anode of the lithium ion battery[J].Chinese Journal of Power Sources,2005,1:019
4 Poizot P,Laruelle S,Grugeon S,et al.Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries[J].Nature,2001,32(3):496.
5 Zhang W M,Wu X L,Hu J S,et al.Carbon coated Fe3O4nanospindles as a superior anode material for lithium-ion batteries[J].Advanced Functional Materials,2010,18(24):3941.
6 Cui Z M,Jiang L Y,Song W G,et al.High-yield gas-liquid interfacial synthesis of highly dispersed Fe3O4nanocrystals and their application in lithium-ion batteries[J].Chemistry of Materials,2015,21(6):1162.
7 Guo C,Wang L,Zhu Y,et al.Fe3O4nanoflakes in an N-doped carbon matrix as high-performance anodes for lithium ion batteries[J].Nanoscale,2015,7(22):10123.
8 Muraliganth T,Murugan A V,Manthiram A.ChemInform abstract:Facile synthesis of carbon-decorated single-crystalline Fe3O4nanowires and their application as high performance anode in lithium ion batteries[J].Chemical Communications,2009,41(47):7360.
9 Liu H,Wang G,Wang J,et al.Magnetite/carbon core-shell nanorods as anode materials for lithium-ion batteries[J].Electrochemistry Communications,2008,10(12):1879.
10 Ma F X,Wu H B,Xu C Y,et al.Self-organized sheaf-like Fe3O4/C hierarchical microrods with superior lithium storage properties[J].Nanoscale,2015,7(10):4411.
11 Geim A K.Graphene:Status and prospects[J].Science,2009,324(5934):1530.
12 Zhou G,Wang D W,Li F,et al.Graphene-wrapped Fe3O4anode material with improved reversible capacity and cyclic stability for lithium ion batteries[J].Chemistry of Materials,2010,22(18):5306.
13 Li X,Huang X,Liu D,et al.Synthesis of 3Dhierarchical Fe3O4/graphene composites with high lithium storage capacity and for controlled drug delivery[J].Journal of Physical Chemistry C,2011,115(44):21567.
14 Su J,Cao M,Ren L,et al.Fe3O4-graphene nanocomposites with improved lithium storage and magnetism properties[J].Journal of Physical Chemistry C,2011,115(30):14469.
15 Wu Z S,Ren W,Xu L,et al.Doped graphene sheets as anode materials with superhigh rate and large capacity for lithium ion batteries[J].ACS Nano,2011,5(7):5463.
16 Liu C,Liu X G,Tan J,et al.Nitrogen-doped graphene by all-solidstate ball-milling graphite with urea as a high-power lithium ion battery anode[J].Journal of Power Sources,2017,342:157.
17 Liu Z W,Peng F,Wang H J,et al.Phosphorus-doped graphite layers with high electrocatalytic activity for the O2reduction in an alkaline medium[J].Angewandte Chemie International Edition,2011,50(14):3257.
18 Liu Y,Huang K,Luo H,et al.Nitrogen-doped graphene-Fe3O4architecture as anode material for improved Li-ion storage[J].RSC Advances,2014,4(34):17653.
19 Jiao J,Qiu W,Tang J,et al.Synthesis of well-defined Fe3O4,nanorods/N-doped graphene for lithium-ion batteries[J].Nano Research,2016,9(5):1.
20 Jiang Z J,Jiang Z.Fabrication of nitrogen-doped holey graphene hollow microspheres and their use as an active electrode material for lithium ion batteries[J].ACS Applied Materials&Interfaces,2014,6(21):19082.
21 Zhu H,Cao Y,Zhang J,et al.One-step preparation of graphene nanosheets via ball milling of graphite and the application in lithiumion batteries[J].Journal of Materials Science,2016,51(8):3675.
22 Wei P,Bai S.Fabrication of a high-density polyethylene/graphene composite with high exfoliation and high mechanical performance via solid-state shear milling[J].RSC Advances,2015,5(114):93697.
23 Li Z Q,Lu C J,Xia Z P,et al.X-ray diffraction patterns of graphite and turbostratic carbon[J].Carbon,2007,45(8):1686.
24 Jeon I Y,Choi H J,Ju M J,et al.Direct nitrogen fixation at the edges of graphene nanoplatelets as efficient electrocatalysts for energy conversion[J].Scientific Reports,2013,3(30):2260.
25 Zhang M,Liu L,He T,et al.Melamine assisted solid exfoliation approach for the synthesis of few-layered fluorinated graphene nanosheets[J].Materials Letters,2016,171:191.
26 Li L,Dou Y,Wang L,et al.One-step synthesis of high-quality Ndoped graphene/Fe3O4 hybrid nanocomposite and its improved supercapacitor performances[J].RSC Advances,2014,4(49):25658.
27 Chen S,Duan J,Ran J,et al.N-doped graphene film-confined nickel nanoparticles as a highly efficient three-dimensional oxygen evolution electrocatalyst[J].Energy&Environmental Science,2013,6(12):3693.
28 Lin Y C,Lin C Y,Chiu P W.Controllable graphene N-doping with ammonia plasma[J].Applied Physics Letters,2010,96(13):133110.
29 Lu W,Shen Y,Xie A,et al.Green synthesis and characterization of superparamagnetic Fe3O4,nanoparticles[J].Journal of Magnetism&Magnetic Materials,2010,322(13):1828.
30 Wal R L V,Tomasek A J,Pamphlet M I,et al.Analysis of HRTEM images for carbon nanostructure quantification[J].Journal of Nanoparticle Research,2004,6(6):555.
31 Zhang C,Fu L,Liu N,et al.Synthesis of nitrogen-doped graphene using embedded carbon and nitrogen sources[J].Advanced Materials,2011,23(8):1020.
32 Qin G,Fang Z,Wang C.Template free construction of a hollow Fe3O4architecture embedded in an N-doped graphene matrix for lithium storage[J].Dalton Transactions,2015,44(12):5735.
33 Liu Y,Yu L,Ong C N,et al.Nitrogen-doped graphene nanosheets as reactive water purification membranes[J].Nano Research,2016,9(7):1983.
34 Geng D,Yang S,Zhang Y,et al.Nitrogen doping effects on the structure of graphene[J].Applied Surface Science,2011,257(21):9193.
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