Flexible free-standing hollow Fe3O4/graphene hybrid films for lithium-ion batteries

Flexible free-standing hollow Fe3O4/graphene (H-Fe3O4/GS) films were fabricated through vacuum filtration and thermal reduction processes, in which graphene formed a three-dimensional conductive network, with hollow and porous Fe3O4 spindles being captured and distributed homogeneously. Using the films as binder-free and free-standing electrodes for lithium-ion batteries, H-Fe3O4/GS with 39.6 wt% graphene exhibited a high specific capacity (1555 mA h g−1 at 100 mA g−1), enhanced rate capability and excellent cyclic stability (940 and 660 mA h g−1 at 200 and 500 mA g−1 after 50 cycles, respectively). The superior electrochemical performance of this novel material can be attributed to two factors. One is that the three dimensional (3D) graphene network formed is very helpful for keeping H-Fe3O4 in good electrical contact. Another is the short transport length for both lithium ions and electrons due to the porous nature which accommodates volume change and favors electrolyte penetration. It is believed that the strategy for preparing free-standing H-Fe3O4/GS films presented in this work will provide new insight into the design and synthesis of other metal oxide/GS electrodes for flexible energy storage devices.

[1]  X. Lou,et al.  Facile synthesis of metal oxide/reduced graphene oxide hybrids with high lithium storage capacity and stable cyclability. , 2011, Nanoscale.

[2]  Moon Jeong Park,et al.  Binder-free Ge nanoparticles-carbon hybrids for anode materials of advanced lithium batteries with high capacity and rate capability. , 2012, Chemical communications.

[3]  J. Tu,et al.  Self-supported nickel-coated NiO arrays for lithium-ion batteries with enhanced capacity and rate capability , 2012 .

[4]  Hua Zhang,et al.  Achieving high specific charge capacitances in Fe3O4/reduced graphene oxide nanocomposites , 2011 .

[5]  Qianhao Min,et al.  Synthesis of Fe3O4-graphene-TiO2 ternary composite networks for enhanced capture of phosphopeptides. , 2011, Chemical communications.

[6]  L. Archer,et al.  Double‐Walled SnO2 Nano‐Cocoons with Movable Magnetic Cores , 2007 .

[7]  Hui Xiong,et al.  Hollow iron oxide nanoparticles for application in lithium ion batteries. , 2012, Nano letters.

[8]  Jinping Liu,et al.  Synthesis of Fe3O4@SnO2 core-shell nanorod film and its application as a thin-film supercapacitor electrode. , 2012, Chemical communications.

[9]  J. Xue,et al.  One-step synthesis of hollow porous Fe3O4 beads–reduced graphene oxide composites with superior battery performance , 2012 .

[10]  Yong Hu,et al.  Assembling carbon-coated α-Fe2O3 hollow nanohorns on the CNT backbone for superior lithium storage capability , 2012 .

[11]  David Wexler,et al.  High-surface-area α-Fe2O3/carbon nanocomposite: one-step synthesis and its highly reversible and enhanced high-rate lithium storage properties , 2010 .

[12]  Yalin Lu,et al.  Synthesis of Hierarchical Hollow-Structured Single-Crystalline Magnetite (Fe3O4) Microspheres: The Highly Powerful Storage versus Lithium as an Anode for Lithium Ion Batteries , 2012 .

[13]  Yue Ma,et al.  Nitrogen-doped carbon-encapsulation of Fe3O4 for increased reversibility in Li+ storage by the conversion reaction , 2012 .

[14]  Hong-Yan Chen,et al.  Reduced Graphene Oxide-Hierarchical ZnO Hollow Sphere Composites with Enhanced Photocurrent and Photocatalytic Activity , 2012 .

[15]  Yanhuai Ding,et al.  A green approach to the synthesis of reduced graphene oxide nanosheets under UV irradiation , 2011, Nanotechnology.

[16]  R. Ruoff,et al.  Nanostructured reduced graphene oxide/Fe2O3 composite as a high-performance anode material for lithium ion batteries. , 2011, ACS nano.

[17]  Xin Zhao,et al.  Flexible holey graphene paper electrodes with enhanced rate capability for energy storage applications. , 2011, ACS nano.

[18]  Jin-Song Hu,et al.  Carbon Coated Fe3O4 Nanospindles as a Superior Anode Material for Lithium‐Ion Batteries , 2008 .

[19]  Chaohe Xu,et al.  Direct growth of monodisperse SnO2 nanorods on graphene as high capacity anode materials for lithium ion batteries , 2012 .

[20]  W. Marsden I and J , 2012 .

[21]  Fei Xiao,et al.  Growth of Metal–Metal Oxide Nanostructures on Freestanding Graphene Paper for Flexible Biosensors , 2012 .

[22]  C. Zhi,et al.  CoO octahedral nanocages for high-performance lithium ion batteries. , 2012, Chemical communications.

[23]  C. Hsieh,et al.  Improved storage capacity and rate capability of Fe3O4–graphene anodes for lithium-ion batteries , 2011 .

[24]  D. Wexler,et al.  Graphene-encapsulated Fe3O4 nanoparticles with 3D laminated structure as superior anode in lithium ion batteries. , 2011, Chemistry.

[25]  Harold H. Kung,et al.  In‐Plane Vacancy‐Enabled High‐Power Si–Graphene Composite Electrode for Lithium‐Ion Batteries , 2011 .

[26]  Guangmin Zhou,et al.  Graphene-Wrapped Fe(3)O(4) Anode Material with Improved Reversible Capacity and Cyclic Stability for Lithium Ion Batteries , 2010 .

[27]  Xiaoyi Liang,et al.  Facile synthesis of hierarchically structured Fe3O4/carbon micro-flowers and their application to lithium-ion battery anodes , 2011 .

[28]  E. Yoo,et al.  Enhanced cyclic performance and lithium storage capacity of SnO2/graphene nanoporous electrodes with three-dimensionally delaminated flexible structure. , 2009, Nano letters.

[29]  Hui‐Ming Cheng,et al.  The reduction of graphene oxide , 2012 .

[30]  T. Hyeon,et al.  Facile scalable synthesis of magnetite nanocrystals embedded in carbon matrix as superior anode materials for lithium-ion batteries. , 2010, Chemical communications.

[31]  M. Qu,et al.  l-Serine-Assisted Synthesis of Superparamagnetic Fe3O4 Nanocubes for Lithuium Ion Batteries , 2011 .

[32]  Liang Li,et al.  N‐Doped Graphene‐SnO2 Sandwich Paper for High‐Performance Lithium‐Ion Batteries , 2012 .

[33]  Keith J Stevenson,et al.  Silicon nanowire fabric as a lithium ion battery electrode material. , 2011, Journal of the American Chemical Society.

[34]  Xufeng Zhou,et al.  A magnetite nanocrystal/graphene composite as high performance anode for lithium-ion batteries , 2012 .

[35]  A. Manthiram,et al.  Facile synthesis of carbon-decorated single-crystalline Fe3O4 nanowires and their application as high performance anode in lithium ion batteries. , 2009, Chemical communications.

[36]  Xiaohong Liu,et al.  Flexible graphene/MnO2 composite papers for supercapacitor electrodes , 2011 .

[37]  Gi‐Heon Kim,et al.  Fe3O4 Nanoparticles Confined in Mesocellular Carbon Foam for High Performance Anode Materials for Lithium‐Ion Batteries , 2011 .

[38]  Y. Lai,et al.  Iron supported C@Fe3O4 nanotube array: a new type of 3D anode with low-cost for high performance lithium-ion batteries , 2012 .

[39]  John P. Sullivan,et al.  In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode , 2010, Science.

[40]  Jiaoyang Li,et al.  Flexible Hybrid Paper Made of Monolayer Co3O4 Microsphere Arrays on rGO/CNTs and Their Application in Electrochemical Capacitors , 2012 .

[41]  M. Cao,et al.  Porous Fe3O4/Carbon Core/Shell Nanorods: Synthesis and Electromagnetic Properties , 2009 .

[42]  K. Kang,et al.  Multicomponent Effects on the Crystal Structures and Electrochemical Properties of Spinel-Structured M3O4 (M = Fe, Mn, Co) Anodes in Lithium Rechargeable Batteries , 2012 .

[43]  Yan‐Bing He,et al.  A graphene-based nanostructure with expanded ion transport channels for high rate Li-ion batteries. , 2012, Chemical communications.

[44]  Dong-Hwa Seo,et al.  Flexible energy storage devices based on graphene paper , 2011 .

[45]  Y. Bando,et al.  Self-stacked Co3O4 nanosheets for high-performance lithium ion batteries. , 2011, Chemical communications.

[46]  Sirong Li,et al.  Self‐Assembly and Embedding of Nanoparticles by In Situ Reduced Graphene for Preparation of a 3D Graphene/Nanoparticle Aerogel , 2011, Advanced materials.

[47]  Qiang Zhang,et al.  High-performance flexible lithium-ion electrodes based on robust network architecture , 2012 .

[48]  H. Dai,et al.  LiMn(1-x)Fe(x)PO4 nanorods grown on graphene sheets for ultrahigh-rate-performance lithium ion batteries. , 2011, Angewandte Chemie.

[49]  Y. Bando,et al.  Coaxial Cu-Si@C array electrodes for high-performance lithium ion batteries. , 2011, Chemical communications.

[50]  T. Hyeon,et al.  Uniform hematite nanocapsules based on an anode material for lithium ion batteries , 2010 .

[51]  J. Xue,et al.  Synthesis of porous hollow Fe3O4 beads and their applications in lithium ion batteries , 2012 .

[52]  David Wexler,et al.  Free-standing single-walled carbon nanotube/SnO2 anode paper for flexible lithium-ion batteries , 2012 .