Nanostructured metal oxide-based materials as advanced anodes for lithium-ion batteries.

The search for new electrode materials for lithium-ion batteries (LIBs) has been an important way to satisfy the ever-growing demands for better performance with higher energy/power densities, improved safety and longer cycle life. Nanostructured metal oxides exhibit good electrochemical properties, and they are regarded as promising anode materials for high-performance LIBs. In this feature article, we will focus on three different categories of metal oxides with distinct lithium storage mechanisms: tin dioxide (SnO(2)), which utilizes alloying/dealloying processes to reversibly store/release lithium ions during charge/discharge; titanium dioxide (TiO(2)), where lithium ions are inserted/deinserted into/out of the TiO(2) crystal framework; and transition metal oxides including iron oxide and cobalt oxide, which react with lithium ions via an unusual conversion reaction. For all three systems, we will emphasize that creating nanomaterials with unique structures could effectively improve the lithium storage properties of these metal oxides. We will also highlight that the lithium storage capability can be further enhanced through designing advanced nanocomposite materials containing metal oxides and other carbonaceous supports. By providing such a rather systematic survey, we aim to stress the importance of proper nanostructuring and advanced compositing that would result in improved physicochemical properties of metal oxides, thus making them promising negative electrodes for next-generation LIBs.

[1]  R. J. Neat,et al.  Performance of titanium dioxide-based cathodes in a lithium polymer electrolyte cell , 1992 .

[2]  Tsutomu Miyasaka,et al.  Tin-Based Amorphous Oxide: A High-Capacity Lithium-Ion-Storage Material , 1997 .

[3]  T. Abe,et al.  Transmission electron microscopy (TEM) analysis of two-phase reaction in electrochemical lithium insertion within α-MoO3 , 2000 .

[4]  Younan Xia,et al.  Preparation of Mesoscale Hollow Spheres of TiO2 and SnO2 by Templating Against Crystalline Arrays of Polystyrene Beads , 2000 .

[5]  L. Kavan,et al.  Orientation Dependence of Charge‐Transfer Processes on TiO2 (Anatase) Single Crystals , 2000 .

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

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

[8]  Jane F. Bertone,et al.  A lost-wax approach to monodisperse colloids and their crystals. , 2001, Science.

[9]  Younan Xia,et al.  Preparation and Characterization of Micrometer-Sized “Egg Shells” , 2001 .

[10]  J. Tarascon,et al.  The Electrochemical Reduction of Co3 O 4 in a Lithium Cell , 2002 .

[11]  H. Zeng,et al.  Hydrothermal Synthesis of α-MoO3 Nanorods via Acidification of Ammonium Heptamolybdate Tetrahydrate. , 2002 .

[12]  Younan Xia,et al.  Template-Engaged Replacement Reaction: A One-Step Approach to the Large-Scale Synthesis of Metal Nanostructures with Hollow Interiors , 2002 .

[13]  M. Wagemaker,et al.  Equilibrium lithium transport between nanocrystalline phases in intercalated TiO2 anatase , 2002, Nature.

[14]  X. Lou,et al.  Complex α-MoO3 Nanostructures with External Bonding Capacity for Self-Assembly , 2003 .

[15]  S. W. Leeuw,et al.  Diffusion of Li-ions in rutile. An ab initio study , 2003 .

[16]  Y. Qian,et al.  One-Dimensional Arrays of Co3O4 Nanoparticles: Synthesis, Characterization, and Optical and Electrochemical Properties , 2004 .

[17]  L. Kavan,et al.  Lithium Storage in Nanostructured TiO2 Made by Hydrothermal Growth , 2004 .

[18]  H. Yang,et al.  Creation of intestine-like interior space for metal-oxide nanostructures with a quasi-reverse emulsion. , 2004, Angewandte Chemie.

[19]  Gabor A. Somorjai,et al.  Formation of Hollow Nanocrystals Through the Nanoscale Kirkendall Effect , 2004, Science.

[20]  Byung Chul Jang,et al.  Simple Synthesis of Hollow Tin Dioxide Microspheres and Their Application to Lithium‐Ion Battery Anodes , 2005 .

[21]  Yong Wang,et al.  Polycrystalline SnO2 Nanotubes Prepared via Infiltration Casting of Nanocrystallites and Their Electrochemical Application , 2005 .

[22]  Li-Jun Wan,et al.  Self-assembled vanadium pentoxide (V2O5) hollow microspheres from nanorods and their application in lithium-ion batteries. , 2005, Angewandte Chemie.

[23]  Lei Xu,et al.  Co3O4 Nanomaterials in Lithium‐Ion Batteries and Gas Sensors , 2005 .

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

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

[26]  Peter G. Bruce,et al.  Lithium‐Ion Intercalation into TiO2‐B Nanowires , 2005 .

[27]  Yong‐Mook Kang,et al.  A study on the charge-discharge mechanism of Co3O4 as an anode for the Li ion secondary battery , 2005 .

[28]  Y. Liu,et al.  Beaded Cobalt Oxide Nanoparticles along Carbon Nanotubes: Towards More Highly Integrated Electronic Devices , 2005 .

[29]  C. Feng,et al.  Low-temperature synthesis of alpha-MnO2 hollow urchins and their application in rechargeable Li+ batteries. , 2006, Inorganic chemistry.

[30]  Li Wan,et al.  Self‐Assembled 3D Flowerlike Iron Oxide Nanostructures and Their Application in Water Treatment , 2006 .

[31]  P. Bruce,et al.  TiO2(B) Nanowires as an Improved Anode Material for Lithium‐Ion Batteries Containing LiFePO4 or LiNi0.5Mn1.5O4 Cathodes and a Polymer Electrolyte , 2006 .

[32]  Yi Xie,et al.  Synthesis of hematite (alpha-Fe2O3) nanorods: diameter-size and shape effects on their applications in magnetism, lithium ion battery, and gas sensors. , 2006, The journal of physical chemistry. B.

[33]  J. Nelson,et al.  Defect chemistry, surface structures, and lithium insertion in anatase TiO2. , 2006, The journal of physical chemistry. B.

[34]  Luwei Chen,et al.  Controlled synthesis, characterization, and catalytic properties of Mn(2)O(3) and Mn(3)O(4) nanoparticles supported on mesoporous silica SBA-15. , 2006, The journal of physical chemistry. B.

[35]  J. Maier,et al.  High Lithium Electroactivity of Nanometer‐Sized Rutile TiO2 , 2006 .

[36]  L. Wan,et al.  Hierarchically structured cobalt oxide (Co3O4): the morphology control and its potential in sensors. , 2006, The journal of physical chemistry. B.

[37]  Yong Wang,et al.  Template‐Free Synthesis of SnO2 Hollow Nanostructures with High Lithium Storage Capacity , 2006 .

[38]  Guoxiu Wang,et al.  Electrochemical Performance of Co3O4–C Composite Anode Materials , 2006 .

[39]  Y. Chiang,et al.  Virus-Enabled Synthesis and Assembly of Nanowires for Lithium Ion Battery Electrodes , 2006, Science.

[40]  Luwei Chen,et al.  Preparation of nanosized Mn3O4/SBA-15 catalyst for complete oxidation of low concentration EtOH in aqueous solution with H2O2 , 2007 .

[41]  W. S. Choi,et al.  Templated Synthesis of Porous Capsules with a Controllable Surface Morphology and their Application as Gas Sensors , 2007 .

[42]  Kristina Edström,et al.  Recent findings and prospects in the field of pure metals as negative electrodes for Li-ion batteries , 2007 .

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

[44]  L. Archer,et al.  Shell-by-shell synthesis of tin oxide hollow colloids with nanoarchitectured walls: cavity size tuning and functionalization. , 2007, Small.

[45]  Qiang Wang,et al.  In Situ Growth of Mesoporous SnO2 on Multiwalled Carbon Nanotubes: A Novel Composite with Porous‐Tube Structure as Anode for Lithium Batteries , 2007 .

[46]  Yong-Mook Kang,et al.  Preparation and electrochemical properties of SnO2 nanowires for application in lithium-ion batteries. , 2007, Angewandte Chemie.

[47]  P. Bruce,et al.  Mesoporous and nanowire Co3O4 as negative electrodes for rechargeable lithium batteries. , 2007, Physical chemistry chemical physics : PCCP.

[48]  M. Wagemaker,et al.  Large impact of particle size on insertion reactions. A case for anatase Li(x)TiO2. , 2007, Journal of the American Chemical Society.

[49]  L. Mai,et al.  Lithiated MoO3 Nanobelts with Greatly Improved Performance for Lithium Batteries , 2007 .

[50]  Xiaobo Chen,et al.  Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. , 2007, Chemical reviews.

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

[52]  R. Schlögl,et al.  Superior storage performance of a Si@SiOx/C nanocomposite as anode material for lithium-ion batteries. , 2008, Angewandte Chemie.

[53]  P. He,et al.  A Polyaniline‐Intercalated Layered Manganese Oxide Nanocomposite Prepared by an Inorganic/Organic Interface Reaction and Its High Electrochemical Performance for Li Storage , 2008 .

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

[55]  D. Deng,et al.  Hollow Core–Shell Mesospheres of Crystalline SnO2 Nanoparticle Aggregates for High Capacity Li+ Ion Storage , 2008 .

[56]  Jin Zou,et al.  Anatase TiO2 single crystals with a large percentage of reactive facets , 2008, Nature.

[57]  M. Antonietti,et al.  Facile One-Pot Synthesis of Mesoporous SnO2 Microspheres via Nanoparticles Assembly and Lithium Storage Properties , 2008 .

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

[59]  Candace K. Chan,et al.  High-performance lithium battery anodes using silicon nanowires. , 2008, Nature nanotechnology.

[60]  Peter G Bruce,et al.  Alpha-MnO2 nanowires: a catalyst for the O2 electrode in rechargeable lithium batteries. , 2008, Angewandte Chemie.

[61]  Anne C. Dillon,et al.  Reversible Lithium‐Ion Insertion in Molybdenum Oxide Nanoparticles , 2008 .

[62]  Zaiping Guo,et al.  Shape Evolution of α-Fe2O3 and Its Size-Dependent Electrochemical Properties for Lithium-Ion Batteries , 2008 .

[63]  L. Archer,et al.  Thermal formation of mesoporous single-crystal Co3O4 nano-needles and their lithium storage properties , 2008 .

[64]  P. Bruce,et al.  Nanomaterials for rechargeable lithium batteries. , 2008, Angewandte Chemie.

[65]  Jiaguo Yu,et al.  Electrochemical properties of TiO2 hollow microspheres from a template-free and green wet-chemical route , 2008 .

[66]  L. Archer,et al.  Preparation of SnO2/carbon composite hollow spheres and their lithium storage properties , 2008 .

[67]  L. Archer,et al.  A General Route to Nonspherical Anatase TiO2 Hollow Colloids and Magnetic Multifunctional Particles , 2008 .

[68]  P. Marcus,et al.  Li-Ion Intercalation in Thermal Oxide Thin Films of MoO3 as Studied by XPS, RBS, and NRA , 2008 .

[69]  Yuping Wu,et al.  Tremella-like molybdenum dioxide consisting of nanosheets as an anode material for lithium ion battery , 2008 .

[70]  Jing Liang,et al.  Template-Directed Materials for Rechargeable Lithium-Ion Batteries† , 2008 .

[71]  N. Zheng,et al.  Nonaqueous production of nanostructured anatase with high-energy facets. , 2008, Journal of the American Chemical Society.

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

[73]  Younan Xia,et al.  Gold nanocages: synthesis, properties, and applications. , 2008, Accounts of chemical research.

[74]  Chang Ming Li,et al.  One-pot formation of SnO2 hollow nanospheres and alpha-Fe2O3@SnO2 nanorattles with large void space and their lithium storage properties. , 2009, Nanoscale.

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

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

[77]  X. Lou,et al.  Anatase TiO2 nanosheet : an ideal host structure for fast and efficient lithium insertion/extraction , 2009 .

[78]  D. He,et al.  Synthesis of α-Fe2O3 dendrites by a hydrothermal approach and their application in lithium-ion batteries , 2009 .

[79]  Sean C. Smith,et al.  Solvothermal synthesis and photoreactivity of anatase TiO(2) nanosheets with dominant {001} facets. , 2009, Journal of the American Chemical Society.

[80]  Jun Song Chen,et al.  SnO2 Nanoparticles with Controlled Carbon Nanocoating as High-Capacity Anode Materials for Lithium-Ion Batteries , 2009 .

[81]  Wenjie Shen,et al.  Low-temperature oxidation of CO catalysed by Co3O4 nanorods , 2009, Nature.

[82]  Jimmy C. Yu,et al.  A micrometer-size TiO2 single-crystal photocatalyst with remarkable 80% level of reactive facets. , 2009, Chemical communications.

[83]  Ying Bai,et al.  Preparation and electrochemical properties of TiO2 hollow spheres as an anode material for lithium-ion batteries , 2009 .

[84]  L. Archer,et al.  One-Pot Synthesis of Carbon-Coated SnO2 Nanocolloids with Improved Reversible Lithium Storage Properties , 2009 .

[85]  Zhaoxiong Xie,et al.  Synthesis of titania nanosheets with a high percentage of exposed (001) facets and related photocatalytic properties. , 2009, Journal of the American Chemical Society.

[86]  Ji‐Guang Zhang,et al.  Self-assembled TiO2-graphene hybrid nanostructures for enhanced Li-ion insertion. , 2009, ACS nano.

[87]  J. Zou,et al.  α-MoO3 Nanobelts: A High Performance Cathode Material for Lithium Ion Batteries , 2010 .

[88]  Li-Jun Wan,et al.  Symbiotic Coaxial Nanocables: Facile Synthesis and an Efficient and Elegant Morphological Solution to the Lithium Storage Problem , 2010 .

[89]  J. Goodenough Challenges for Rechargeable Li Batteries , 2010 .

[90]  C. M. Li,et al.  Synthesis, Characterization, and Lithium Storage Capability of AMoO4 (A = Ni, Co) Nanorods† , 2010 .

[91]  X. Lou,et al.  Shape-controlled synthesis of MnO2 nanostructures with enhanced electrocatalytic activity for oxygen reduction , 2010 .

[92]  X. Lou,et al.  Shape-controlled synthesis of porous Co3O4 nanostructures for application in supercapacitors , 2010 .

[93]  Michael H. Huang,et al.  Fabrication of truncated rhombic dodecahedral Cu2O nanocages and nanoframes , 2008, 2010 3rd International Nanoelectronics Conference (INEC).

[94]  X. Lou,et al.  The superior lithium storage capabilities of ultra-fine rutile TiO2 nanoparticles , 2010 .

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

[96]  Zhan Lin,et al.  Assembly of carbon-SnO2 core-sheath composite nanofibers for superior lithium storage. , 2010, Chemistry.

[97]  Jun Song Chen,et al.  Top-down fabrication of α-Fe2O3 single-crystal nanodiscs and microparticles with tunable porosity for largely improved lithium storage properties. , 2010, Journal of the American Chemical Society.

[98]  Xiao Hua Yang,et al.  Higher charge/discharge rates of lithium-ions across engineered TiO2 surfaces leads to enhanced battery performance. , 2010, Chemical communications.

[99]  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.

[100]  Zhiyu Wang,et al.  Engineering nonspherical hollow structures with complex interiors by template-engaged redox etching. , 2010, Journal of the American Chemical Society.

[101]  Mingyuan Ge,et al.  Large-scale synthesis of SnO2 nanosheets with high lithium storage capacity. , 2010, Journal of the American Chemical Society.

[102]  P. Bruce,et al.  Influence of size on the rate of mesoporous electrodes for lithium batteries. , 2010, Journal of the American Chemical Society.

[103]  G. Graff,et al.  Ternary self-assembly of ordered metal oxide-graphene nanocomposites for electrochemical energy storage. , 2010, ACS nano.

[104]  X. Lou,et al.  One-pot synthesis of uniform carbon-coated MoO(2) nanospheres for high-rate reversible lithium storage. , 2010, Chemical communications.

[105]  J. Cabana,et al.  Beyond Intercalation‐Based Li‐Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions , 2010, Advanced materials.

[106]  Jun Song Chen,et al.  Fast Synthesis of α-MoO3 Nanorods with Controlled Aspect Ratios and Their Enhanced Lithium Storage Capabilities , 2010 .

[107]  X. Lou,et al.  Shape-controlled synthesis of cobalt-based nanocubes, nanodiscs, and nanoflowers and their comparative lithium-storage properties. , 2010, ACS applied materials & interfaces.

[108]  X. Lou,et al.  Porous Spheres Assembled from Polythiophene (PTh)-Coated Ultrathin MnO2 Nanosheets with Enhanced Lithium Storage Capabilities , 2010 .

[109]  Dongsheng Xu,et al.  Tetragonal faceted-nanorods of anatase TiO2 single crystals with a large percentage of active {100} facets. , 2010, Chemical communications.

[110]  Jae-Hun Kim,et al.  Li-alloy based anode materials for Li secondary batteries. , 2010, Chemical Society reviews.

[111]  X. Lou,et al.  Fast formation of SnO2 nanoboxes with enhanced lithium storage capability. , 2011, Journal of the American Chemical Society.

[112]  W. Xu,et al.  Chrysanthemum-like α-FeOOH microspheres produced by a simple green method and their outstanding ability in heavy metal ion removal , 2011 .

[113]  X. Lou,et al.  TiO2 hollow spheres with large amount of exposed (001) facets for fast reversible lithium storage , 2011 .

[114]  X. Lou,et al.  Interconnected MoO2 nanocrystals with carbon nanocoating as high-capacity anode materials for lithium-ion batteries. , 2011, ACS applied materials & interfaces.

[115]  G. Chen,et al.  Interfacial synthesis: amphiphilic monomers assisted ultrarefining of mesoporous manganese oxide nanoparticles and the electrochemical implications. , 2011, ACS applied materials & interfaces.

[116]  X. Lou,et al.  Graphene-wrapped TiO2 hollow structures with enhanced lithium storage capabilities. , 2011, Nanoscale.

[117]  X. Lou,et al.  Carbon-supported ultra-thin anatase TiO2 nanosheets for fast reversible lithium storage , 2011 .

[118]  L. Archer,et al.  Formation of SnO2 hollow nanospheres inside mesoporous silica nanoreactors. , 2011, Journal of the American Chemical Society.

[119]  L. Archer,et al.  SnO2 hollow structures and TiO2 nanosheets for lithium-ion batteries , 2011 .

[120]  X. Lou,et al.  Synthesis of octahedral Mn3O4 crystals and their derived Mn3O4–MnO2 heterostructures via oriented growth , 2011 .

[121]  X. Lou,et al.  One-pot synthesis of uniform Fe₃O₄ nanospheres with carbon matrix support for improved lithium storage capabilities. , 2011, ACS applied materials & interfaces.

[122]  X. Lou,et al.  A Hierarchically Nanostructured Composite of MnO2/Conjugated Polymer/Graphene for High‐Performance Lithium Ion Batteries , 2011 .

[123]  Xiong Wen (David) Lou,et al.  SnO₂ nanosheet hollow spheres with improved lithium storage capabilities. , 2011, Nanoscale.

[124]  X. Lou,et al.  Unusual rutileTiO2 nanosheets with exposed (001) facets , 2011 .

[125]  G. Lu,et al.  Synthesis of anatase TiO2 rods with dominant reactive {010} facets for the photoreduction of CO2 to CH4 and use in dye-sensitized solar cells. , 2011, Chemical communications.

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

[127]  X. Lou,et al.  Sandwich‐Like, Stacked Ultrathin Titanate Nanosheets for Ultrafast Lithium Storage , 2011, Advanced materials.

[128]  X. Lou,et al.  CNTs@SnO2@carbon coaxial nanocables with high mass fraction of SnO2 for improved lithium storage. , 2011, Chemistry, an Asian journal.

[129]  Deyan Luan,et al.  α-Fe2O3 nanotubes with superior lithium storage capability. , 2011, Chemical communications.

[130]  X. Lou,et al.  Graphene-supported anatase TiO2 nanosheets for fast lithium storage. , 2011, Chemical communications.

[131]  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 .

[132]  X. Lou,et al.  Formation of large 2D nanosheets via PVP-assisted assembly of anatase TiO2 nanomosaics. , 2011, Chemical communications.

[133]  J. Chen,et al.  One‐Dimensional Hierarchical Structures Composed of Novel Metal Oxide Nanosheets on a Carbon Nanotube Backbone and Their Lithium‐Storage Properties , 2011 .

[134]  X. Lou,et al.  SnO2 nanosheets grown on graphene sheets with enhanced lithium storage properties. , 2011, Chemical communications.

[135]  X. Lou,et al.  SBA-15 derived carbon-supported SnO2 nanowire arrays with improved lithium storage capabilities , 2011 .

[136]  X. Lou,et al.  Synthesis of SnO2 Hierarchical Structures Assembled from Nanosheets and Their Lithium Storage Properties , 2011 .

[137]  Yu Zhang,et al.  Superior electrode performance of mesoporous hollow TiO2 microspheres through efficient hierarchical nanostructures , 2011 .

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