疏松多孔CoFe_2O_4-还原石墨烯电极复合材料的制备与性能
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摘要
采用原位溶剂热法,以氧化石墨烯(GO)与Co2+、Fe3+为原料制备疏松多孔的纳米CoFe_2O_4-还原氧化石墨烯(CoFe_2O_4-rGO)复合材料。采用XRD、Raman、SEM和HRTEM测试表征了纳米CoFe_2O_4-rGO复合材料的结构与形貌。测试结果表明,纳米CoFe_2O_4-rGO复合材料具有三维结构。自组装的多孔CoFe_2O_4纳米球粒径约为200nm,在rGO上均匀分散,解决了CoFe_2O_4易团聚的问题。电化学测试结果表明,纳米CoFe_2O_4-rGO复合材料具有较高的比容量及优异的循环和倍率性能,在100mA·g-1的电流密度下其比容量为1 262mAh·g-1,50次循环后比容量仍能保持在642mAh·g-1;并在2 000mA·g-1的大电流密度下仍具有221mAh·g-1的比容量。纳米CoFe_2O_4-rGO复合材料拥有更优异的电化学性能的原因在于CoFe_2O_4纳米球在rGO上均匀分布。三维结构增加了Li+储存的活性位点,有效缓解了电极的体积收缩/膨胀效应,提高了纳米CoFe_2O_4-rGO复合材料的导电性。
Loose and porous nano CoFe_2O_4-reduced graphene oxide(CoFe_2O_4-rGO)composites were prepared via in situ solvothermal method,using graphene oxide(GO),Co2+and Fe3+as the raw materials.XRD,Raman,SEM and HRTEM were employed to characterize the structure and morphology of nano CoFe_2O_4-rGO composites.The results show that nano CoFe_2O_4-rGO composites exhibit 3 Dstructure.The self-assembled porous nanospheres with a diameter of about 200 nm are uniformly dispersed on rGO,which solves the agglomeration of CoFe_2O_4.The electrochemical test results show that nano CoFe_2O_4-rGO composites deliver a comparatively high specific capacity and excellent cycle and rate performance.The specific capacity reaches 1 262 mAh·g-1 at a current density of100 mA·g-1,which can still maintain at 642 mAh·g-1 after 50 cycles.The specific capacity reaches 221 mAh·g-1 at a high current density of 2 000 mA·g-1.The enhanced electrochemical performance of nano CoFe_2O_4-rGO composites results from the homogenous distribution of CoFe_2O_4 nanospheres on rGO.The 3 Dstructure provides more active sites of Li+storage,and thus effectively relieve the volume shrinkage/expansion of the electrodes,which in return improve the conductivity of nano CoFe_2O_4-rGO composites.
Loose and porous nano CoFe_2O_4-reduced graphene oxide(CoFe_2O_4-rGO)composites were prepared via in situ solvothermal method,using graphene oxide(GO),Co2+and Fe3+as the raw materials.XRD,Raman,SEM and HRTEM were employed to characterize the structure and morphology of nano CoFe_2O_4-rGO composites.The results show that nano CoFe_2O_4-rGO composites exhibit 3 Dstructure.The self-assembled porous nanospheres with a diameter of about 200 nm are uniformly dispersed on rGO,which solves the agglomeration of CoFe_2O_4.The electrochemical test results show that nano CoFe_2O_4-rGO composites deliver a comparatively high specific capacity and excellent cycle and rate performance.The specific capacity reaches 1 262 mAh·g-1 at a current density of100 mA·g-1,which can still maintain at 642 mAh·g-1 after 50 cycles.The specific capacity reaches 221 mAh·g-1 at a high current density of 2 000 mA·g-1.The enhanced electrochemical performance of nano CoFe_2O_4-rGO composites results from the homogenous distribution of CoFe_2O_4 nanospheres on rGO.The 3 Dstructure provides more active sites of Li+storage,and thus effectively relieve the volume shrinkage/expansion of the electrodes,which in return improve the conductivity of nano CoFe_2O_4-rGO composites.
引文
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[2]ETACHERI V,MAROM R,ELAZARI R,et al.Challenges in the development of advanced Li-ion batteries:A review[J].Energy&Environmental Science,2011,4(9):3243-3262.
[3]CHEN D,MEI X,JI G,et al.Reversible lithium-ion storage in silver-treated nanoscale hollow porous silicon particles[J].Angewandte Chemie International Edition,2012,51(10):2409-2413
[4]杨绍斌,张琴,沈丁,等.钠离子电池TiO2/还原氧化石墨烯负极材料的制备及储钠性能[J].复合材料学报,2016,33(12):2905-2910.YANG S B,ZHANG Q,SHEN D,et al.Preparation and storage sodium properties of TiO2/reduced graphene oxide anode materials for sodium-ion batteries[J].Acta Materiae Compositae Sinica,2016,33(12):2905-2910(in Chinese)
[5]李旭,孙晓刚,陈玮,等.多孔碳纳米管纸负载中空硅微球作为阳极的高容量锂硅电池[J].复合材料学报,2018,35(11):3219-3226.LI X,SUN X G,CHEN W,et al.High capacity lithium Si battery with hollow silicon microspheres loaded with porous carbon nanotubes as anode[J].Acta Materiae Compositae Sinica,2018,35(11):3219-3226(in Chinese).
[6]WANG Z,LUAN D,MADHAVI S,et al.Assembling carbon-coatedα-Fe2O3hollow nanohorns on the CNT backbone for superior lithium storage capability[J].Energy&Environmental Science,2012,5(1):5252-5256.
[7]HASSAN M F,GUO Z,CHEN Z,et al.α-Fe2O3 as an anode material with capacity rise and high rate capability for lithium-ion batteries[J].Materials Research Bulletin,2011,46(6):858-864.
[8]HUANG Y,HUANG X,LIAN J,et al.Self-assembly of ultrathin porous NiO nanosheets/graphene hierarchical structure for high-capacity and high-rate lithium storage[J].Journal of Materials Chemistry,2012,22(7):2844-2847.
[9]ZHAO Y,LI J,DING Y,et al.Single-walled carbon nanohorns coated with Fe2O3as a superior anode material for lithium ion batteries[J].Chemical Communications,2011,47(26):7416-7418.
[10]LIU Y,ZHAO X,LI F,et al.Facile synthesis of MnO/Canode materials for lithium-ion batteries[J].Electrochimica Acta,2011,56(18):6448-6452.
[11]KANG J G,KO Y D,PARK J G,et al.Origin of capacity fading in nano-sized Co3O4electrodes:electrochemical impedance spectroscopy study[J].Nanoscale Research Letters,2008,3(10):390-394.
[12]CHERIAN C T,REDDY M V,RAO G V S,et al.Li-cycling properties of nano-crystalline(Ni1-xZnx)Fe2O4(0≤x≤1)[J].Journal of Solid State Electrochemistry,2012,16(5):1823-1832.
[13]LI Z H,ZHAO T P,ZHAN X Y,et al.High capacity threedimensional ordered macroporous CoFe2O4as anode material for lithium ion batteries[J].Electrochimica Acta,2010,55(15):4594-4598.
[14]WANG Y,SU D,UNG A,et al.Hollow CoFe2O4nanospheres as a high capacity anode material for lithium ion batteries[J].Nanotechnology,2012,23(5):055402.
[15]JIN Y H,SEO S D,SHIM H W,et al.Synthesis of core/shell spinel ferrite/carbon nanoparticles with enhanced cycling stability for lithium ion battery anodes[J].Nanotechnology,2012,23(12):125402.
[16]LI M,YIN Y X,LI C,et al.Well-dispersed bi-componentactive CoO/CoFe2O4 nanocomposites with tunable performances as anode materials for lithium-ion batteries[J].Chemical Communications,2012,48(3):410-412.
[17]ZHAO Y,LI J,DING Y,et al.Enhancing the lithium storage performance of iron oxide composites through partial substitution with Ni 2+or Co2+[J].Journal of Materials Chemistry,2011,21(47):19101-19105.
[18]LIU S,XIE J,FANG C,et al.Self-assembly of a CoFe2O4/graphene sandwich by a controllable and general route:Towards a high-performance anode for Li-ion batteries[J].Journal of Materials Chemistry,2012,22(37):19738-19743.
[19]XIAO Y,LI X,ZAI J,et al.CoFe2O4-graphene nanocomposites synthesized through an ultrasonic method with enhanced performances as anode materials for Li-ion batteries[J].Nano-Micro Letters,2014,6(4):307-315.
[20]LIU Y,CHEN Z,ZHANG Y,et al.Broadband and lightweight microwave absorber constructed by in-situ growth of hierarchical CoFe2O4/rGOporous nanocomposites[J].ACSapplied materials&interfaces,2018,10(16):13860-13868
[21]LV H,GUO Y,WU G,et al.Interface polarization strategy to solve electromagnetic wave interference issue[J].ACS Applied Materials&Interfaces,2017,9(6):5660-5668.
[22]LI Z H,ZHAO T P,ZHAN X Y,et al.High capacity threedimensional ordered macroporous CoFe2O4as anode material for lithium ion batteries[J].Electrochimica Acta,2010,55(15):4594-4598.
[23]VIDAL-ABARCA C,LAVELA P,TIRADO J L.A 57Fe M9ssbauer spectroscopy study of cobalt ferrite conversion electrodes for Li-ion batteries[J].Journal of Power Sources,2011,196(16):6978-6981.
[24]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):5306-5313.
[25]WEI W,YANG S,ZHOU H,et al.3D graphene foams cross-linked with pre-encapsulated Fe3O4nanospheres for enhanced lithium storage[J].Advanced Materials,2013,25(21):2909-2914.
[26]付永胜.石墨烯-磁性尖晶石型铁氧体多功能异质结的控制合成及其性质研究[D].南京:南京理工大学,2013.FU Y S.Controlled synthesis and properties study of graphene-magnetic spinel ferrite multifunctional heteroarchitecture[D].Nanjing:Nanjing University of Science&Technology,2013(in Chinese).
[27]XUE D J,XIN S,YAN Y,et al.Improving the electrode performance of Ge through Ge@C core-shell nanoparticles and graphene networks[J].Journal of the American Chemical Society,2012,134(5):2512-2515.
[28]邓凌峰,余开明,严忠,等.Co2+掺杂石墨烯/LiFePO4锂离子电池复合正极材料的制备与表征[J].复合材料学报,2015,32(5):1390-1398.DENG L F,YU K M,YAN Z,et al.Preparation and characterization of Co2+doped graphene/LiFePO4composite cathode materials for lithium battery[J].Acta Materiae Compositae Sinica,2015,32(5):1390-1398(in Chinese).