Intercalation of Sodium Ions into Hollow Iron Oxide Nanoparticles

Cation vacancies in hollow γ-Fe2O3 nanoparticles are utilized for efficient sodium ion transport. As a result, fast rechargeable cathodes can be assembled from Earth-abundant elements such as iron oxide and sodium. We monitored in situ structural and electronic transformations of hollow iron oxide nanoparticles by synchrotron X-ray adsorption and diffraction techniques. Our results revealed that the cation vacancies in hollow γ-Fe2O3 nanoparticles can serve as hosts for sodium ions in high voltage range (4.0–1.1 V), allowing utilization of γ-Fe2O3 nanoparticles as a cathode material with high capacity (up to 189 mAh/g), excellent Coulombic efficiency (99.0%), good capacity retention, and superior rate performance (up to 99 mAh/g at 3000 mA/g (50 C)). The appearance of the capacity at high voltage in iron oxide that is a typical anode and the fact that this capacity is comparable with the capacities observed in typical cathodes emphasize the importance of the proper understanding of the structure–propertie...

[1]  D. Wexler,et al.  Magnetite/carbon core-shell nanorods as anode materials for lithium-ion batteries , 2008 .

[2]  Jiayan Luo,et al.  LiMn2O4 Nanorods, Nanothorn Microspheres, and Hollow Nanospheres as Enhanced Cathode Materials of Lithium Ion Battery , 2008 .

[3]  J. Tarascon,et al.  High rate capabilities Fe3O4-based Cu nano-architectured electrodes for lithium-ion battery applications , 2006, Nature materials.

[4]  L. Archer,et al.  Hollow Micro‐/Nanostructures: Synthesis and Applications , 2008 .

[5]  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.

[6]  Yan Yu,et al.  Electrospinning synthesis of C/Fe3O4 composite nanofibers and their application for high performance lithium-ion batteries , 2008 .

[7]  Huilin Pan,et al.  Carbon coated Na3V2(PO4)3 as novel electrode material for sodium ion batteries , 2012 .

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

[9]  J. Tarascon,et al.  Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries , 2000, Nature.

[10]  Ling Zhang,et al.  Hierarchically Nanostructured Magnetic Hollow Spheres of Fe3O4 and γ-Fe2O3: Preparation and Potential Application in Drug Delivery , 2008 .

[11]  Jean-Marie Tarascon,et al.  Synthesis, Structure, and Electrochemical Properties of the Layered Sodium Insertion Cathode Material: NaNi1/3Mn1/3Co1/3O2 , 2012 .

[12]  Christopher S. Johnson,et al.  Self-Improving Anode for Lithium-Ion Batteries Based on Amorphous to Cubic Phase Transition in TiO2 Nanotubes , 2012 .

[13]  Shinichi Komaba,et al.  P2-type Na(x)[Fe(1/2)Mn(1/2)]O2 made from earth-abundant elements for rechargeable Na batteries. , 2012, Nature materials.

[14]  Changwen Hu,et al.  Fe3O4–Graphene Nanocomposites with Improved Lithium Storage and Magnetism Properties , 2011 .

[15]  Zhenguo Yang,et al.  Reversible Sodium Ion Insertion in Single Crystalline Manganese Oxide Nanowires with Long Cycle Life , 2011, Advanced materials.

[16]  S. Kuwabata,et al.  Ligand-free platinum nanoparticles encapsulated in a hollow porous carbon shell as a highly active heterogeneous hydrogenation catalyst. , 2006, Angewandte Chemie.

[17]  S. Donne,et al.  Enhanced manganese dioxide supercapacitor electrodes produced by electrodeposition , 2011 .

[18]  X. Lou,et al.  LiNi(0.5)Mn(1.5)O4 hollow structures as high-performance cathodes for lithium-ion batteries. , 2012, Angewandte Chemie.

[19]  A. Mansour,et al.  Electrochemical Li-ion storage in defect spinel iron oxides: the critical role of cation vacancies , 2011 .

[20]  Kang Xu,et al.  Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. , 2004, Chemical reviews.

[21]  M Newville,et al.  ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. , 2005, Journal of synchrotron radiation.

[22]  Vidvuds Ozolins,et al.  Ab Initio Study of the Charge-Storage Mechanisms in RuO2-Based Electrochemical Ultracapacitors , 2012 .

[23]  Chunmei Ban,et al.  Nanostructured Fe3O4/SWNT Electrode: Binder‐Free and High‐Rate Li‐Ion Anode , 2010, Advanced materials.

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

[25]  L. Archer,et al.  Self‐Supported Formation of Needlelike Co3O4 Nanotubes and Their Application as Lithium‐Ion Battery Electrodes , 2008 .

[26]  S. Han,et al.  Simple Solid‐Phase Synthesis of Hollow Graphitic Nanoparticles and their Application to Direct Methanol Fuel Cell Electrodes , 2003 .

[27]  Jun Liu,et al.  Hollow Nanostructured Anode Materials for Li-Ion Batteries , 2010, Nanoscale research letters.

[28]  K. Kanamura,et al.  Electrochemical oxidation of propylene carbonate (containing various salts) on aluminium electrodes , 1995 .

[29]  H. Kwon,et al.  Gram‐Scale Synthesis of Cu2O Nanocubes and Subsequent Oxidation to CuO Hollow Nanostructures for Lithium‐Ion Battery Anode Materials , 2009 .

[30]  Martin Winter,et al.  Filming mechanism of lithium-carbon anodes in organic and inorganic electrolytes , 1995 .

[31]  Lei Li,et al.  A Facile Preparation of Hollow Palladium Nanosphere Catalysts for Direct Formic Acid Fuel Cell , 2009 .

[32]  Hui Xiong,et al.  Amorphous TiO2 Nanotube Anode for Rechargeable Sodium Ion Batteries , 2011 .

[33]  Ling Huang,et al.  Structure and electrochemical performance of nanostructured Fe3O4/carbon nanotube composites as anodes for lithium ion batteries , 2010 .

[34]  P. Bruce,et al.  The lithium intercalation process in the low-voltage lithium battery anode Li(1+x)V(1-x)O2. , 2011, Nature materials.

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

[36]  Dong-Hwa Seo,et al.  New iron-based mixed-polyanion cathodes for lithium and sodium rechargeable batteries: combined first principles calculations and experimental study. , 2012, Journal of the American Chemical Society.

[37]  Lynden A. Archer,et al.  Designed Synthesis of Coaxial SnO2@carbon Hollow Nanospheres for Highly Reversible Lithium Storage , 2009 .

[38]  D. Rolison,et al.  Something from nothing: enhancing electrochemical charge storage with cation vacancies. , 2013, Accounts of chemical research.

[39]  Donghan Kim,et al.  Sodium‐Ion Batteries , 2013 .

[40]  C. Love,et al.  Improved lithium capacity of defective V2O5 materials , 2002 .

[41]  Teófilo Rojo,et al.  Na-ion batteries, recent advances and present challenges to become low cost energy storage systems , 2012 .

[42]  J. Tarascon,et al.  Li Metal‐Free Rechargeable LiMn2 O 4 / Carbon Cells: Their Understanding and Optimization , 1992 .

[43]  Gerbrand Ceder,et al.  Electrode Materials for Rechargeable Sodium‐Ion Batteries: Potential Alternatives to Current Lithium‐Ion Batteries , 2012 .

[44]  Zhiyu Wang,et al.  Metal Oxide Hollow Nanostructures for Lithium‐ion Batteries , 2012, Advances in Materials.

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

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

[47]  M Newville,et al.  IFEFFIT: interactive XAFS analysis and FEFF fitting. , 2001, Journal of synchrotron radiation.

[48]  Donghan Kim,et al.  Enabling Sodium Batteries Using Lithium‐Substituted Sodium Layered Transition Metal Oxide Cathodes , 2011 .

[49]  Y. Bando,et al.  Multishelled Co3O4-Fe3O4 hollow spheres with even magnetic phase distribution: Synthesis, magnetic properties and their application in water treatment , 2011 .

[50]  Philippe Guyot-Sionnest,et al.  n-type colloidal semiconductor nanocrystals , 2000, Nature.

[51]  Wantai Yang,et al.  Carbon-Encapsulated Metal Oxide Hollow Nanoparticles and Metal Oxide Hollow Nanoparticles: A General Synthesis Strategy and Its Application to Lithium-Ion Batteries , 2009 .

[52]  Shinichi Komaba,et al.  Synthesis and electrode performance of carbon coated Na2FePO4F for rechargeable Na batteries , 2011 .

[53]  Jean-Marie Tarascon,et al.  Effect of Particle Size on Lithium Intercalation into α ­ Fe2 O 3 , 2003 .

[54]  Jiujun Zhang,et al.  Facile Synthesis of Co−Pt Hollow Sphere Electrocatalyst , 2007 .

[55]  Jian Jiang,et al.  Iron Oxide-Based Nanotube Arrays Derived from Sacrificial Template-Accelerated Hydrolysis: Large-Area Design and Reversible Lithium Storage , 2010 .

[56]  Hui Xiong,et al.  Nanostructured bilayered vanadium oxide electrodes for rechargeable sodium-ion batteries. , 2012, ACS nano.

[57]  Haihui Wang,et al.  Enhanced cycling performance of Fe3O4–graphene nanocomposite as an anode material for lithium-ion batteries , 2010 .

[58]  Dong-Hwa Seo,et al.  A comparative study on Na2MnPO4F and Li2MnPO4F for rechargeable battery cathodes. , 2012, Physical chemistry chemical physics : PCCP.

[59]  Yong-Min Huh,et al.  Hollow silica nanocontainers as drug delivery vehicles. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[60]  Dan Wang,et al.  General synthesis and gas-sensing properties of multiple-shell metal oxide hollow microspheres. , 2011, Angewandte Chemie.

[61]  Chang Ming Li,et al.  TiO2 and SnO2@TiO2 hollow spheres assembled from anatase TiO2 nanosheets with enhanced lithium storage properties. , 2010, Chemical communications.

[62]  In Su Lee,et al.  Hollow manganese oxide nanoparticles as multifunctional agents for magnetic resonance imaging and drug delivery. , 2009, Angewandte Chemie.

[63]  T. Hyeon,et al.  Fabrication of hollow palladium spheres and their successful application to the recyclable heterogeneous catalyst for suzuki coupling reactions. , 2002, Journal of the American Chemical Society.

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

[65]  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.

[66]  Chaoquan Hu,et al.  Hematite Hollow Spheres with Excellent Catalytic Performance for Removal of Carbon Monoxide , 2006 .