Hollow SnO2 nanospheres with oxygen vacancies entrapped by a N-doped graphene network as robust anode materials for lithium-ion batteries.

The practical application of tin dioxide (SnO2) in lithium-ion batteries has been greatly hindered by its large volumetric expansion and low conductivity. Thus, a rational design of the size, geometry and the pore structure of SnO2-based nanomaterials is still a dire demand. To this end, herein we report an effective approach for engineering hollow-structured SnO2 nanospheres with adequate surface oxygen vacancies simultaneously wrapped by a nitrogen-doped graphene network (SnO2-x/N-rGO) through an electrostatic adsorption-induced self-assembly together with a thermal reduction process. The close electrostatic attraction achieved a tight and uniform combination of positively charged SnO2 nanospheres with negatively charged graphene oxide (GO), which can alleviate the aggregation and volume expansion of the entrapped SnO2 nanospheres. Subsequent thermal treatment not only ensures a significant reduction of the GO sheets accompanying nitrogen-doping, but also induces the generation of oxygen vacancies on the surface of the SnO2 hollow nanospheres, together building up a long-range and bicontinuous transfer channel for rapid electron and ion transport. Because of these structural merits, the as-built SnO2-x/N-rGO composite used as the anode material exhibits excellent robust cycling stability (∼912 mA h g-1 after 500 cycles at 0.5 A g-1 and 652 mA h g-1 after 200 cycles at 1 A g-1) and superior rate capability (309 mA h g-1 at 10 A g-1). This facile fabrication strategy may pave the way for the construction of high performance SnO2-based anode materials for potential application in advanced lithium-ion batteries.

[1]  Jiulin Wang,et al.  Nano/micro-structured Si/CNT/C composite from nano-SiO2 for high power lithium ion batteries. , 2014, Nanoscale.

[2]  Z. Wen,et al.  3D graphene network encapsulating SnO2 hollow spheres as a high-performance anode material for lithium-ion batteries , 2017 .

[3]  Zhichuan J. Xu,et al.  A Review on Design Strategies for Carbon Based Metal Oxides and Sulfides Nanocomposites for High Performance Li and Na Ion Battery Anodes , 2017 .

[4]  X. Wang,et al.  A Robust and Conductive Black Tin Oxide Nanostructure Makes Efficient Lithium‐Ion Batteries Possible , 2017, Advanced materials.

[5]  X. Sun,et al.  Ultrasmall MoS2 embedded in carbon nanosheets-coated Sn/SnOx as anode material for high-rate and long life Li-ion batteries , 2017 .

[6]  Chao Wang,et al.  High‐Density Microporous Li4Ti5O12 Microbars with Superior Rate Performance for Lithium‐Ion Batteries , 2017, Advanced science.

[7]  Yi Guo,et al.  Flakelike LiCoO2 with Exposed {010} Facets As a Stable Cathode Material for Highly Reversible Lithium Storage. , 2016, ACS applied materials & interfaces.

[8]  Li-zhen Fan,et al.  Hollow Core-Shell SnO2/C Fibers as Highly Stable Anodes for Lithium-Ion Batteries. , 2015, ACS applied materials & interfaces.

[9]  J. Niu,et al.  Sn Wears Super Skin: A New Design for Long Cycling Batteries. , 2018, Nano letters.

[10]  Yun Zhang,et al.  Nitrogen‐Doped Graphene Ribbon Assembled Core–Sheath MnO@Graphene Scrolls as Hierarchically Ordered 3D Porous Electrodes for Fast and Durable Lithium Storage , 2016 .

[11]  Yong Yang,et al.  Nitrogen-doped carbon coated Li4Ti5O12–TiO2/Sn nanowires and their enhanced electrochemical properties for lithium ion batteries , 2016 .

[12]  Yi-Rong Pei,et al.  Novel Carbon-Encapsulated Porous SnO2 Anode for Lithium-Ion Batteries with Much Improved Cyclic Stability. , 2016, Small.

[13]  Bin Wang,et al.  Sulfur quantum dots wrapped by conductive polymer shell with internal void spaces for high-performance lithium–sulfur batteries , 2015 .

[14]  Y. Gogotsi,et al.  Atomic layer deposition of SnO2 on MXene for Li-ion battery anodes , 2017 .

[15]  Chaojiang Niu,et al.  SnO2 Quantum Dots@Graphene Oxide as a High-Rate and Long-Life Anode Material for Lithium-Ion Batteries. , 2016, Small.

[16]  Di Zhang,et al.  Confined SnO2 quantum-dot clusters in graphene sheets as high-performance anodes for lithium-ion batteries , 2016, Scientific Reports.

[17]  Deren Yang,et al.  Large-Scale Synthesis of SnO2 Nanotube Arrays as High-Performance Anode Materials of Li-Ion Batteries , 2011 .

[18]  Ming Liu,et al.  Monodispersed SnO2 nanospheres embedded in framework of graphene and porous carbon as anode for lithium ion batteries , 2016 .

[19]  Xinlu Li,et al.  Graphene nanoribbons wrapping double nanoshells of SnO2@TiO2 for high lithium storage , 2016 .

[20]  Gengfeng Zheng,et al.  Nitrogen‐Doped Core‐Sheath Carbon Nanotube Array for Highly Stretchable Supercapacitor , 2017 .

[21]  Zhiyu Wang,et al.  A Top‐Down Strategy toward 3D Carbon Nanosheet Frameworks Decorated with Hollow Nanostructures for Superior Lithium Storage , 2016 .

[22]  G. Cao,et al.  Exploiting High‐Performance Anode through Tuning the Character of Chemical Bonds for Li‐Ion Batteries and Capacitors , 2017 .

[23]  Zaiping Guo,et al.  Li2TiSiO5: a low potential and large capacity Ti-based anode material for Li-ion batteries , 2017 .

[24]  Jianliang Cao,et al.  Solvothermal synthesis and characterization of ultrathin SnO nanosheets , 2014 .

[25]  Sen Xin,et al.  Biotemplated synthesis of three-dimensional porous MnO/C-N nanocomposites from renewable rapeseed pollen: An anode material for lithium-ion batteries , 2016, Nano Research.

[26]  Yongsong Luo,et al.  Nanosilicon anodes for high performance rechargeable batteries , 2017 .

[27]  H. Pan,et al.  Ultrafine SnO2 dispersed carbon matrix composites derived by a sol–gel method as anode materials for lithium ion batteries , 2010 .

[28]  Wei Luo,et al.  Reconstruction of Conformal Nanoscale MnO on Graphene as a High‐Capacity and Long‐Life Anode Material for Lithium Ion Batteries , 2013 .

[29]  Young Jun Hong,et al.  One‐Pot Facile Synthesis of Double‐Shelled SnO2 Yolk‐Shell‐Structured Powders by Continuous Process as Anode Materials for Li‐ion Batteries , 2013, Advanced materials.

[30]  H. Wu,et al.  Facile synthesis of one-dimensional LiNi0.8Co0.15Al0.05O2 microrods as advanced cathode materials for lithium ion batteries , 2015 .

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

[32]  Joonwon Lim,et al.  Nitrogen Dopants in Carbon Nanomaterials: Defects or a New Opportunity? , 2017 .

[33]  H. Wu,et al.  Restoration of Degraded Nickel‐Rich Cathode Materials for Long‐Life Lithium‐Ion Batteries , 2018 .

[34]  R. Hu,et al.  Inhibiting grain coarsening and inducing oxygen vacancies: the roles of Mn in achieving a highly reversible conversion reaction and a long life SnO2–Mn–graphite ternary anode , 2017 .

[35]  Yinzhu Jiang,et al.  Pseudocapacitance-Enhanced Li-Ion Microbatteries Derived by a TiN@TiO2 Nanowire Anode , 2017 .

[36]  Zongping Shao,et al.  Facile synthesis of nitrogen-doped carbon nanotubes encapsulating nickel cobalt alloys 3D networks for oxygen evolution reaction in an alkaline solution , 2017 .

[37]  X. Lou,et al.  SnO2 and TiO2 nanosheets for lithium-ion batteries , 2012 .

[38]  P. Ajayan,et al.  Pyridinic‐Nitrogen‐Dominated Graphene Aerogels with Fe–N–C Coordination for Highly Efficient Oxygen Reduction Reaction , 2016 .

[39]  Y. Tong,et al.  Oxygen vacancies enhancing capacitive properties of MnO2 nanorods for wearable asymmetric supercapacitors , 2014 .

[40]  C. Zhang,et al.  Pyridinic Nitrogen‐Enriched Carbon Nanogears with Thin Teeth for Superior Lithium Storage , 2016 .

[41]  Jun Chen,et al.  Stabilizing the Nanostructure of SnO2 Anodes by Transition Metals: A Route to Achieve High Initial Coulombic Efficiency and Stable Capacities for Lithium Storage , 2017, Advanced materials.

[42]  Shuangyin Wang,et al.  Creating coordinatively unsaturated metal sites in metal-organic-frameworks as efficient electrocatalysts for the oxygen evolution reaction: Insights into the active centers , 2017 .

[43]  Chengzhong Yu,et al.  A facile one-step solvothermal synthesis of SnO2/graphene nanocomposite and its application as an anode material for lithium-ion batteries. , 2011, Chemphyschem : a European journal of chemical physics and physical chemistry.

[44]  H. Wu,et al.  Template-Engaged Synthesis of 1D Hierarchical Chainlike LiCoO2 Cathode Materials with Enhanced High-Voltage Lithium Storage Capabilities. , 2016, ACS applied materials & interfaces.

[45]  Yan‐Bing He,et al.  Synthesis of Hierarchical Sisal-Like V2O5 with Exposed Stable {001} Facets as Long Life Cathode Materials for Advanced Lithium-Ion Batteries. , 2017, ACS applied materials & interfaces.

[46]  D. He,et al.  Facile synthesis of rGO/SnO2 composite anodes for lithium ion batteries , 2014 .

[47]  Xiaojing Wang,et al.  Synthesis, Properties, and Applications of Hollow Micro-/Nanostructures. , 2016, Chemical reviews.

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

[49]  Yu‐Guo Guo,et al.  Binding SnO2 Nanocrystals in Nitrogen‐Doped Graphene Sheets as Anode Materials for Lithium‐Ion Batteries , 2013, Advanced materials.

[50]  Q. Li,et al.  Graphene double protection strategy to improve the SnO2 electrode performance anodes for lithium-ion batteries , 2014 .

[51]  C. Jin,et al.  Silica-modified SnO 2 -graphene “slime” for self-enhanced li-ion battery anode , 2017 .

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

[53]  Gang Yang,et al.  Fast facile synthesis of SnO2/Graphene composite assisted by microwave as anode material for lithium-ion batteries , 2017 .

[54]  Fei Wang,et al.  Co3O4-carbon nanotube heterostructures with bead-on-string architecture for enhanced lithium storage performance. , 2013, Nanoscale.

[55]  Tianxi Liu,et al.  Flexible hierarchical membranes of WS2 nanosheets grown on graphene-wrapped electrospun carbon nanofibers as advanced anodes for highly reversible lithium storage. , 2016, Nanoscale.

[56]  Ning Li,et al.  Core–shell structured hollow SnO2–polypyrrole nanocomposite anodes with enhanced cyclic performance for lithium-ion batteries , 2014 .

[57]  Qingyu Li,et al.  Preparation of a Sn@SnO2@C@MoS2 composite as a high-performance anode material for lithium-ion batteries , 2016 .

[58]  Hua Zhang,et al.  Highly stable and reversible lithium storage in SnO2 nanowires surface coated with a uniform hollow shell by atomic layer deposition. , 2014, Nano letters.

[59]  Ning Li,et al.  Graphene/Fe2O3/SnO2 ternary nanocomposites as a high-performance anode for lithium ion batteries. , 2013, ACS applied materials & interfaces.