Rationally Designed Hierarchical TiO2@Fe2O3 Hollow Nanostructures for Improved Lithium Ion Storage

Hollow and hierarchical nanostructures have received wide attention in new-generation, high-performance, lithium ion battery (LIB) applications. Both TiO2 and Fe2O3 are under current investigation because of their high structural stability (TiO2) and high capacity (Fe2O3), and their low cost. Here, we demonstrate a simple strategy for the fabrication of hierarchical hollow TiO2@Fe2O3 nanostructures for the application as LIB anodes. Using atomic layer deposition (ALD) and sacrificial template-assisted hydrolysis, the resulting nanostructure combines a large surface area with a hollow interior and robust structure. As a result, such rationally designed LIB anodes exhibit a high reversible capacity (initial value 840 mAh g−1), improved cycle stability (530 mAh g−1 after 200 cycles at the current density of 200 mA g−1), as well as outstanding rate capability. This ALD-assisted fabrication strategy can be extended to other hierarchical hollow metal oxide nanostructures for favorable applications in electrochemical and optoelectronic devices.

[1]  Xin-bo Zhang,et al.  General and Controllable Synthesis Strategy of Metal Oxide/TiO2 Hierarchical Heterostructures with Improved Lithium-Ion Battery Performance , 2012, Scientific Reports.

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

[3]  Bing Tan,et al.  Mesoporous Co3O4 nanowire arrays for lithium ion batteries with high capacity and rate capability. , 2008, Nano letters.

[4]  Klaus Müllen,et al.  Porous Iron Oxide Ribbons Grown on Graphene for High-Performance Lithium Storage , 2012, Scientific Reports.

[5]  Min Gyu Kim,et al.  Green energy storage materials: Nanostructured TiO2 and Sn-based anodes for lithium-ion batteries , 2009 .

[6]  P. Bruce,et al.  Nanostructured materials for advanced energy conversion and storage devices , 2005, Nature materials.

[7]  Dan Wang,et al.  Recent advances in micro-/nano-structured hollow spheres for energy applications: From simple to complex systems , 2012 .

[8]  G. Kearley,et al.  Multiple Li positions inside oxygen octahedra in lithiated TiO2 anatase. , 2003, Journal of the American Chemical Society.

[9]  Philippe Poizot,et al.  Clean energy new deal for a sustainable world: from non-CO2 generating energy sources to greener electrochemical storage devices , 2011 .

[10]  L. Personnaz,et al.  Combined XRD, EXAFS, and Mössbauer Studies of the Reduction by Lithium of α ­ Fe2 O 3 with Various Particle Sizes , 2003 .

[11]  C. Sow,et al.  α‐Fe2O3 Nanoflakes as an Anode Material for Li‐Ion Batteries , 2007 .

[12]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

[13]  X. Lou,et al.  Glucose-Assisted One-Pot Synthesis of FeOOH Nanorods and Their Transformation to Fe3O4@Carbon Nanorods for Application in Lithium Ion Batteries , 2011 .

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

[15]  J. Tarascon,et al.  On the Origin of the Extra Electrochemical Capacity Displayed by MO/Li Cells at Low Potential , 2002 .

[16]  A. Heller,et al.  α-Fe2O3 Nanorods as Anode Material for Lithium Ion Batteries , 2011 .

[17]  Haoshen Zhou,et al.  Nanomaterials for lithium ion batteries , 2006 .

[18]  G. Yushin,et al.  High-performance lithium-ion anodes using a hierarchical bottom-up approach. , 2010, Nature materials.

[19]  Y. Ni,et al.  Microwave-hydrothermal synthesis, characterization and properties of rice-like α-Fe2O3 nanorods , 2012 .

[20]  P. Bruce,et al.  Nanoparticulate TiO2(B): an anode for lithium-ion batteries. , 2012, Angewandte Chemie.

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

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

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

[24]  Jian Jiang,et al.  Carbon/ZnO Nanorod Array Electrode with Significantly Improved Lithium Storage Capability. , 2009 .

[25]  Jian Jiang,et al.  Seed-assisted synthesis of highly ordered TiO2@α-Fe2O3 core/shell arrays on carbon textiles for lithium-ion battery applications , 2012 .

[26]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[27]  Ji won Lee,et al.  Fabrication of highly ordered and vertically oriented TiO2 nanotube arrays for ordered heterojunction polymer/inorganic hybrid solar cell , 2011 .

[28]  Chen Feng,et al.  Cross‐Stacked Carbon Nanotube Sheets Uniformly Loaded with SnO2 Nanoparticles: A Novel Binder‐Free and High‐Capacity Anode Material for Lithium‐Ion Batteries , 2009 .

[29]  Jian Jiang,et al.  Recent Advances in Metal Oxide‐based Electrode Architecture Design for Electrochemical Energy Storage , 2012, Advanced materials.

[30]  Xiuli Wang,et al.  High-quality metal oxide core/shell nanowire arrays on conductive substrates for electrochemical energy storage. , 2012, ACS nano.

[31]  N. S. McIntyre,et al.  Investigation of multiplet splitting of Fe 2p XPS spectra and bonding in iron compounds , 2004 .

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

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

[34]  Chang Sheh Lit,et al.  Fabrication of NiO Nanowall Electrodes for High Performance Lithium Ion Battery , 2008 .

[35]  Jun Chen,et al.  α‐Fe2O3 Nanotubes in Gas Sensor and Lithium‐Ion Battery Applications , 2005 .

[36]  Xianghong Liu,et al.  Single crystal α-Fe2O3 with exposed {104} facets for high performance gas sensor applications , 2012 .

[37]  A. Tok,et al.  Atomic layer deposition for nanofabrication and interface engineering. , 2012, Nanoscale.

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

[39]  Mijung Noh,et al.  Critical Size of a Nano SnO2 Electrode for Li-Secondary Battery , 2005 .

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

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

[42]  X. Lou,et al.  Quasiemulsion-templated formation of α-Fe2O3 hollow spheres with enhanced lithium storage properties. , 2011, Journal of the American Chemical Society.

[43]  M. Armand,et al.  Building better batteries , 2008, Nature.

[44]  C. M. Li,et al.  Constructing hierarchical spheres from large ultrathin anatase TiO2 nanosheets with nearly 100% exposed (001) facets for fast reversible lithium storage. , 2010, Journal of the American Chemical Society.

[45]  Jingshan Luo,et al.  Homogeneous Photosensitization of Complex TiO2 Nanostructures for Efficient Solar Energy Conversion , 2012, Scientific Reports.

[46]  Paul V. Braun,et al.  Three-dimensional bicontinuous ultrafast-charge and -discharge bulk battery electrodes. , 2011, Nature nanotechnology.