Exfoliated Graphene Oxide/MoO2 Composites as Anode Materials in Lithium-Ion Batteries: An Insight into Intercalation of Li and Conversion Mechanism of MoO2.

Exfoliated graphene oxide (EG)/MoO2 composites are synthesized by a simple solid-state graphenothermal reduction method. Graphene oxide (GO) is used as a reducing agent to reduce MoO3 and as a source for EG. The formation of different submicron sized morphologies such as spheres, rods, flowers, etc., of monoclinic MoO2 on EG surfaces is confirmed by complementary characterization techniques. As-synthesized EG/MoO2 composite with a higher weight percentage of EG performed excellently as an anode material in lithium-ion batteries. The galvanostatic cycling studies aided with postcycling cyclic voltammetry and galvanostatic intermittent titrations followed by ex situ structural studies clearly indicate that Li intercalation into MoO2 is transformed into conversion upon aging at low current densities while intercalation mechanism is preferably taking place at higher current rates. The intercalation mechanism is found to be promising for steady-state capacity throughout the cycling because of excess graphene and higher current density even in the operating voltage window of 0.005-3.0 V in which MoO2 undergoes conversion below 0.8 V.

[1]  S. Adams,et al.  Sustainable Graphenothermal Reduction Chemistry to Obtain MnO Nanonetwork Supported Exfoliated Graphene Oxide Composite and its Electrochemical Characteristics , 2015 .

[2]  B. Chowdari,et al.  Graphenothermal reduction synthesis of ‘exfoliated graphene oxide/iron (II) oxide’ composite for anode application in lithium ion batteries , 2015 .

[3]  Zhanhu Guo,et al.  Enhanced electrochemical performances of MoO2 nanoparticles composited with carbon nanotubes for lithium-ion battery anodes , 2015 .

[4]  B. Chowdari,et al.  Elucidation of few layered graphene-complex metal oxide (A2Mo3O8, A = Co, Mn and Zn) composites as robust anode materials in Li ion batteries , 2015 .

[5]  M. Prabu,et al.  Cobalt Sulfide Nanoparticles Grown on Nitrogen and Sulfur Codoped Graphene Oxide: An Efficient Electrocatalyst for Oxygen Reduction and Evolution Reactions , 2015 .

[6]  R. P. Rao,et al.  Evaluation of undoped and M-doped TiO2, where M = Sn, Fe, Ni/Nb, Zr, V, and Mn, for lithium-ion battery applications prepared by the molten-salt method , 2015 .

[7]  B. Chowdari,et al.  Mixed Oxides, (Ni1–xZnx)Fe2O4 (x = 0, 0.25, 0.5, 0.75, 1): Molten Salt Synthesis, Characterization and Its Lithium-Storage Performance for Lithium Ion Batteries , 2015 .

[8]  Lei Guo,et al.  Standing carbon-coated molybdenum dioxide nanosheets on graphene: morphology evolution and lithium ion storage properties , 2015 .

[9]  B. Chowdari,et al.  MgO-decorated few-layered graphene as an anode for li-ion batteries. , 2015, ACS applied materials & interfaces.

[10]  Jianqiang Wang,et al.  Facile fabrication of molybdenum dioxide/nitrogen-doped graphene hybrid as high performance anode material for lithium ion batteries , 2015 .

[11]  Omkar R. Lokare,et al.  Impact of the degree of functionalization of graphene oxide on the electrochemical charge storage property and metal ion adsorption , 2014 .

[12]  E. Uchaker,et al.  Facile and Green Preparation for the Formation of MoO2-GO Composites as Anode Material for Lithium-Ion Batteries , 2014 .

[13]  U. K. Sen,et al.  Intercalation anode material for lithium ion battery based on molybdenum dioxide. , 2014, ACS applied materials & interfaces.

[14]  B. Chowdari,et al.  Electrochemical studies of few-layered graphene as an anode material for Li ion batteries , 2014, Journal of Solid State Electrochemistry.

[15]  Aimin Li,et al.  Effects of the oxidation degree of graphene oxide on the adsorption of methylene blue. , 2014, Journal of hazardous materials.

[16]  Hai-sen Yang,et al.  Carbothermic Reduction of MoO3 for Direct Alloying Process , 2013 .

[17]  Kaixue Wang,et al.  Uniform hierarchical MoO2/carbon spheres with high cycling performance for lithium ion batteries , 2013 .

[18]  S. Liang,et al.  Synthesis of Mo2N nanolayer coated MoO2 hollow nanostructures as high-performance anode materials for lithium-ion batteries , 2013 .

[19]  H Zhao,et al.  Facile synthesis of yolk–shell MoO2 microspheres with excellent electrochemical performance as a Li-ion battery anode , 2013 .

[20]  B. Chowdari,et al.  Metal oxides and oxysalts as anode materials for Li ion batteries. , 2013, Chemical reviews.

[21]  Yi‐Ming Yan,et al.  Synthesis of MoS2 and MoO2 for their applications in H2 generation and lithium ion batteries: a review , 2013, Science and technology of advanced materials.

[22]  M. Deepa,et al.  Enhanced nanoscale conduction capability of a MoO2/Graphene composite for high performance anodes in lithium ion batteries , 2012 .

[23]  Zhongqiang Shan,et al.  MoO2–graphene nanocomposite as anode material for lithium-ion batteries , 2012 .

[24]  Kyu-Nam Jung,et al.  Synthesis of nitrided MoO2 and its application as anode materials for lithium-ion batteries , 2012 .

[25]  Zaiping Guo,et al.  Facile synthesis of graphene–molybdenum dioxide and its lithium storage properties , 2012 .

[26]  Lili Liu,et al.  Preparation of carbon coated MoO2 nanobelts and their high performance as anode materials for lithium ion batteries , 2012 .

[27]  Changwen Hu,et al.  Interconnected core–shell MoO2 microcapsules with nanorod-assembled shells as high-performance lithium-ion battery anodes , 2012 .

[28]  Jinlin Li,et al.  Template-free synthesis of hollow core–shell MoO2 microspheres with high lithium-ion storage capacity , 2012 .

[29]  Donghai Wang,et al.  High Capacity MoO2/Graphite Oxide Composite Anode for Lithium-Ion Batteries. , 2012, The journal of physical chemistry letters.

[30]  Wei Luo,et al.  Self-assembled hierarchical MoO2/graphene nanoarchitectures and their application as a high-performance anode material for lithium-ion batteries. , 2011, ACS nano.

[31]  Lixia Yuan,et al.  Morphosynthesis of a hierarchical MoO2 nanoarchitecture as a binder-free anode for lithium-ion batteries , 2011 .

[32]  G. Rao,et al.  Nano-phase tin hollandites, K2(M2Sn6)O16 (M = Co, In) as anodes for Li-ion batteries , 2011 .

[33]  Y. Chabal,et al.  Unusual infrared-absorption mechanism in thermally reduced graphene oxide. , 2010, Nature materials.

[34]  David O. Scanlon,et al.  Theoretical and Experimental Study of the Electronic Structures of MoO3 and MoO2 , 2010 .

[35]  Seung M. Oh,et al.  Thermoelectrochemically Activated MoO2 Powder Electrode for Lithium Secondary Batteries , 2009 .

[36]  Eun Sung Kim,et al.  Thermal stability of graphite oxide , 2009 .

[37]  R. Holze,et al.  MoO2 synthesized by reduction of MoO3 with ethanol vapor as an anode material with good rate capability for the lithium ion battery , 2008 .

[38]  J. Ding,et al.  Synthesis, Structure, and Magnetic Properties of [Li(H2O)M(N2H3CO2)3]·0.5H2O (M = Co,Ni) as Single Precursors to LiMO2 Battery Materials , 2006 .

[39]  Ju-tang Sun,et al.  Low temperature synthesis of a stable MoO2 as suitable anode materials for lithium batteries , 2005 .

[40]  K. Wetzig,et al.  Formation of COx species during the carbothermal reduction of oxides of Zr, Si, Ti, Cr, W, and Mo , 2000 .

[41]  S. Mukerjee,et al.  Kinetics and mechanism of carbothermic reduction of MoO3 to Mo2C , 1997 .

[42]  A. Ōya,et al.  Carbothermal Reduction of the Molybdenum Oxide/Phenanthroline Complex , 1991 .

[43]  B. Dunn,et al.  The Development of Pseudocapacitive Properties in Nanosized-MoO2 , 2015 .

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