关贵清;李加新;黄志高;

• 1:宁德师范学院物理与电气工程系
• 2:福建师范大学物理与能源学院福建省量子调控与新能源材料重点实验室

摘要(Abstract)：

综述了Fe_3O_4、Fe_2O_3、NiO、Co_3O_4、CoO、CuO等多种金属氧化物通过水热、溶剂热、共沉淀、原子层沉积、溶胶凝胶及高温退火和微波辅热等多种合成策略和制备方法得到不同尺寸如纳米级和微米级,不同形貌如颗粒状、棒状、孔状、球状、层状、花状等不同维度金属氧化物以不同的方式如嵌入、卷入、植入修饰石墨烯,形成了层状结构、三明治结构、中空核壳状结构和混合结构等形式的金属氧化物/石墨烯复合物.并把它们应用于锂离子电池的负极材料,其电化学性能如容量、倍率、循环等性能相对于纯石墨烯和纯金属氧化物得到了提升.最后分析了金属氧化物/石墨烯复合物的制备材料、制备方法对最终产物的影响,讨论了金属氧化物和石墨烯的协同效应和复合机理以及石墨烯复合物性能的影响,展望了金属氧化物/石墨烯复合物作为锂离子电池电极材料的应用和开发前景.

关键词(KeyWords)： 锂离子电池;负极材料;金属氧化物;石墨烯

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金资助项目(61574037;21203025);; 福建省省属高校专项课题(JK2014055);; 宁德市科技计划项目(20140218;20150169)

作者(Authors): 关贵清;李加新;黄志高;

参考文献(References)：

• [1]POIZOT P,LARUELLE S,GRUGEON S,et al.Transition-metal oxides as negative-electrode materials for lithium-ion batteries[J].Nature,2000,407:496-499.
• [2]GEIM A K,NOVOSELOV K S.The rise of grapheme[J].Nature Materials,2007,6(3):183-191.
• [3]NOVOSELOV K S,GEIM A K,MOROZOV S V,et al.Electric field effect in atomically thin carbon films[J].Science,2004,306(5696):666-669.
• [4]SUZUKI T,HASEGAWA T,MUKAI S R,et al.A theoretical study on storage states of Li ions in carbon anodes of Li ion batteries using molecular orbital calculations[J].Carbon,2003,41(10):1933-1939.
• [5]YOO E J,KIM J,HOSONO E,et al.Large reversible Li storage of graphene nanosheet families for use in rechargeable lithiumion batteries[J].Nano Lett,2008,8(8):2277-2282.
• [6]WU Z S,ZHOU G M,YIN L C,et al.Graphene/metal oxide composite electrode materials for energy storage[J].Nano Energy,2012,1(1):107-131.
• [7]SUN W W,WANG Y.Graphene-base nanocomposite anodes for lithium-ion batteries[J].Nanoscale,2014,6(20):11528-11552.
• [8]SATHISH M,TOMAI T,HONMA I.Graphene anchored with Fe3O4nanoparticles as anode for enhanced Li-ion storage[J].Journal of Power Sources,2012,217(11):85-91.
• [9]LIU S K,CHEN Z X,XIE K,et al.A facile one-step hydrothermal synthesis of a Fe2O3nanoplates imbedded in graphene networks with high-rate lithium storage and long cycle life[J].J Mater Chem A,2014,2(34):13942-13948.
• [10]YE J,ZHANG J,WANG F X,et al.One-pot synthesis of Fe2O3/graphene and its lithium-storage performance[J].Electrochimica Acta,2013,113(4):212-217.
• [11]JIN B,LIU A H,LIU G Y,et al.Fe3O4-pyrolytic graphite oxide composite as an anode material for lithium secondary batteries[J].Electrochimica Acta,2013,90(5):426-432.
• [12]ZHOU G M,WANG D W,LI F,et al.Graphene-wrapped Fe3O4anode material with improved reversible capacity and cyclic stability for lithium ion batteries[J].Chem Mater,2010,22(18):5306-5313.
• [13]BEHERA S K.Enhanced rate performance and cyclic stability of Fe3O4-grapheme nanocomposites for Li ion battery anodes[J].Chemical Communications,2011,47(37):10371-10373.
• [14]MAI Y J,SHI S J,ZHANG D,et al.Ni O-graphene hybrid as an anode material for lithium ion batteries[J].Journal of Power Sources,2012,204(1):155-161.
• [15]JANG B C,CHAE O B,PARK S K,et al.Solventless synthesis of an iron-oxide/graphene nanocomposite and its application as an anode inhigh-rate Li-ion batteries[J]J Mater Chem A,2013,1(48):15442-15446.
• [16]WANG T Q,WANG X L,LU Y,et al.Self-assembly of hierarchical Fe3O4microsphere/graphene nanosheet composite:towards a promising high-performance anode for Li-ion batteries[J].RSC Adv,2014,4(1),322-330.
• [17]ZHANG F,ZHANG T F,CHEN Y S,et al.A high-performance supercapacitor-battery hybrid energy storage device based on graphene-enhanced electrode materials with ultrahigh energy density[J].Energy Environ Sci,2013,6(5):1623-1652.
• [18]BAEK S,YU S H,PARK S K,et al.A one-pot microwave-assisted non-aqueous sol-gel approach to metal oxide/graphene nanocomposites for Li-ion batteries[J].RSC Advances,2011,1(9):1687-1690.
• [19]ZHU X J,ZHU Y W,MURALI S,et al.Nanostructured reduced graphene oxide/Fe2O3composite as a high-performance anode material for lithium ion batteries[J].ACS Nano,2011,5(4):3333-3338.
• [20]CHEN S Q,WANG Y.Microwave-assisted synthesis of a Co3O4-graphene sheet-on-sheet nanocomposite as a superior anode material for Li-ion batteries[J].J Mater Chem,2010,20(43):9735-9739.
• [21]ZHANG M,QU B H,LEI D N,et al.A green and fast strategy for the scalable synthesis of Fe2O3/graphene with significantly enhanced Li-ion storage properties[J].J Mater Chem,2012,22(9):3868-3874.
• [22]ZHU X J,WU W Y,LIU Z,et al.A reduced graphene oxide-nanoporous magnetic oxide iron hybrid as an improved anode material for lithium ion batteries[J].Electrochimica Acta,2013,95(11):24-28.
• [23]YANG S B,CUI G L,PANG S P,et al.Fabrication of cobalt and cobalt oxide/graphene composites:towards high-performance anode materials for lithium ion batterie[J].Chem Sus Chem,2010,3(2):236-239.
• [24]ZHOU G W,WANG J L,GAO P F,et al.Facile spray drying route for the three-dimensional graphene encapsulated Fe2O3nanoparticles for lithium ion battery anodes[J].Chem Res,2012,52(3):1197-1204.
• [25]CHOI S H,KO Y N,LEE J K,et al.Rapid continuous synthesis of spherical reduced graphene ball-nickel oxide composite for lithium ion batteries[J].Scientific Reports,2014,4(4):5786-5786.
• [26]LUO J S,LIU J L,ZENG Z Y,et al.Three-dimensional graphene foam supported Fe3O4lithium battery anodes with long cycle life and high rate capability[J].Nano Lett,2013,13(12):6136-6143.
• [27]ZHU J X,SHARMA Y K,ZENG Z Y,et al.Cobalt xxide nanowall arrays on reduced graphene oxide sheets with controlled phase,grain size,and porosity for Li-ion battery electrodes[J].J Phys Chem C,2011,115(16):8400-8406.
• [28]LU L Q,WANG Y.Sheet-like and fusiform Cu O nanostructures grown on graphene by rapid microwave heating for high Li-ion storage capacities[J].J Mater Chem,2011,21(44):17916-17919.
• [29]ZOU Y Q,WANG Y,et al.Ni O nanosheets grown on graphene nanosheets as superior anode materialsfor Li-ion batteries[J].Nanoscale,2011,3(6):2615-2620.
• [30]DONG X M,LI L,ZHAO C J,et al.Controllable synthesis of RGO/FexOynanocomposites as high-performance anode materials for lithium ion batteries[J].J Mater Chem A,2014,2(25):9844-9850.
• [31]PAN L Y,ZHAO H B,SHEN W C,et al.Surfactant-assisted synthesis of a Co3O4/reduced graphene oxide composite as a superior anode material for Li-ion batteries[J].Chem A,2013,1(24):7159-7166.
• [32]CHEN D Z,WEI W,WANG R N,et al.A-Fe2O3nanoparticles anchored on graphene with 3D quasi-laminated architecture:in situ wet chemistry synthesisand enhanced electrochemical performance for lithium ion batteries[J].New J Chem,2012,36(8):1589-1595.
• [33]HSIEH C T,LIN J S,CHEN Y F,et al.Pulse microwave deposition of cobalt oxide nanoparticles on graphene nanosheets as anode materials for lithium ion batteries[J].J Phys Chem C,2012,116(29):15251-15258.
• [34]LU L Q,WANG Y.Facile synthesis of graphene-supported shuttle-and urchin-like Cu O for high and fast Li-ion storage[J].Electrochemistry Communications,2012,14(1):82-85.
• [35]KAN J,WANG Y.Large and fast reversible Li-ion storages in Fe2O3-graphene sheet-on-sheet sandwich-like nanocomposites[J].Scientific Reports,2013,3(12):1-10.
• [36]ZHANG X T,ZHOU J S,SONG H H,et al.“Butterfly effect”in Cu O/graphene composite nanosheets:a small interfacial adjustment triggers big changes in electronic structure and Li-ion storage performance[J].ACS Appl Mater Interfaces,2014,6(19):17236-17244.
• [37]ZHU X J,HU J,DAI H L,et al.Reduced graphene oxide and nanosheet-based nickel oxide microsphere composite as an anode material for lithium ion battery[J].Electrochimica Acta,2012,64(1):23-28.
• [38]XIE D,SU Q M,YUAN W W,et al.Synthesis of porous Ni O-wrapped graphene nanosheets and their improved lithium storage properties[J].J Phys Chem C,2013,117(46):24121-24128.
• [39]QIU D F,XU Z J,ZHENG M B,et al.Graphene anchored with mesoporous Ni O nanoplates as anode material for lithium-ion batteries[J].J Solid State Electrochem,2012,16(5):1889-1892.
• [40]ZAI J T,YU C,TAO L Q,et al.Synthesis of Ni-doped Ni O/RGONS nanocomposites with enhanced rate capabilities as anode materials for Li ion batteries[J].Cryst Eng Comm,2013,15(34):6663-6671.
• [41]HUANG Y,HUANG X L,LIAN J S,et al.Self-assembly of ultrathin porous Ni O nanosheets/graphene hierarchical structure for high-capacity and high-rate lithium storage[J]J Mater Chem,2012,22(7):2844-2847.
• [42]IRESHA R M,IDRIS N H,LU L,et al.Synthesis and characterization of graphene-nickel oxide nanostructures for fastcharge-discharge application[J].Electrochimica Acta,2011,56(16):5815-5822.
• [43]ZHU X,NING G Q,MA X L,et al.High density Co3O4nanoparticles confined in a porous graphene nanomesh network driven by an electrochemical process:ultra-high capacity and rate performance for lithium ion batteries[J].J Mater Chem A,2013,1(44):14023-14030.
• [44]LIU Y,WANG W,GU L,et al.Flexible Cu O nanosheets/reduced-graphene oxide composite paper:binder-free anode for high-performance lithium-ion batteries[J].ACS Appl Mater Interfaces,2013,5(19):9850-9855.
• [45]HSIEH C T,LIN J Y,MO C Y,et al.Improved storage capacity and rate capability of Fe3O4-graphene anodes for lithium-ion batteries[J].Electrochimica Acta,2011,58(1):119-124.
• [46]JIANG X,YANG X L,ZHU Y H,et al.Graphene/carbon-coated Fe3O4nanoparticle hybrids for enhanced lithium storage[J].J Mater Chem A,2015,3(5):2361-2369.
• [47]BHUVANESWARI S,PRATHEEKSHA P M,ANANDAN S,et al.Efficient reduced graphene oxide grafted porous Fe3O4composite as a high performance anode material for Li-ion ba material for Li-ion batteries[J].J Chem Phys,2014,16(11):5284-5294.