Flexible Zn2SnO4/MnO2 core/shell nanocable-carbon microfiber hybrid composites for high-performance supercapacitor electrodes.

We demonstrate the design and fabrication of a novel flexible nanoarchitecture by facile coating ultrathin (several nanometers thick) films of MnO2 to highly electrical conductive Zn2SnO4 (ZTO) nanowires grown radially on carbon microfibers (CMFs) to achieve high specific capacitance, high-energy density, high-power density, and long-term life for supercapacitor electrode applications. The crystalline ZTO nanowires grown on CMFs were uniquely served as highly conductive cores to support a highly electrolytic accessible surface area of redox active MnO2 shells and also provide reliable electrical connections to the MnO2 shells. The maximum specific capacitances of 621.6 F/g (based on pristine MnO2) by cyclic voltammetry (CV) at a scan rate of 2 mV/s and 642.4 F/g by chronopotentiometry at a current density of 1 A/g were achieved in 1 M Na2SO4 aqueous solution. The hybrid MnO2/ZTO/CMF hybrid composite also exhibited excellent rate capability with specific energy of 36.8 Wh/kg and specific power of 32 kW/kg at current density of 40 A/g, respectively, and good long-term cycling stability (only 1.2% loss of its initial specific capacitance after 1000 cycles). These results suggest that such MnO2/ZTO/CF hybrid composite architecture is very promising for next generation high-performance supercapacitors.

[1]  Kwang Man Kim,et al.  Poly(ethylenedioxythiophene) (PEDOT) as polymer electrode in redox supercapacitor , 2004 .

[2]  M. Winter,et al.  What are batteries, fuel cells, and supercapacitors? , 2004, Chemical reviews.

[3]  Li-Zhen Fan,et al.  High-performance polypyrrole electrode materials for redox supercapacitors , 2006 .

[4]  R. Kötz,et al.  Principles and applications of electrochemical capacitors , 2000 .

[5]  O. Inganäs,et al.  Poly(3,4‐ethylenedioxythiophene) as Electrode Material in Electrochemical Capacitors , 1997 .

[6]  A. Burke.  R&D considerations for the performance and application of electrochemical capacitors , 2007 .

[7]  H. Teng,et al.  Influence of Carbon Nanotube Grafting on the Impedance Behavior of Activated Carbon Capacitors , 2008 .

[8]  Ye Hou,et al.  Design and synthesis of hierarchical MnO2 nanospheres/carbon nanotubes/conducting polymer ternary composite for high performance electrochemical electrodes. , 2010, Nano letters.

[9]  Zhongwei Chen,et al.  Ultrathin, transparent, and flexible graphene films for supercapacitor application , 2010 .

[10]  Junhua Jiang,et al.  Electrochemical supercapacitor material based on manganese oxide: preparation and characterization , 2002 .

[11]  R. Piner,et al.  Transfer of large-area graphene films for high-performance transparent conductive electrodes. , 2009, Nano letters.

[12]  Peidong Yang,et al.  Solution-grown zinc oxide nanowires. , 2006, Inorganic chemistry.

[13]  Candace K. Chan,et al.  Printable thin film supercapacitors using single-walled carbon nanotubes. , 2009, Nano letters.

[14]  Y. Gogotsi,et al.  Materials for electrochemical capacitors. , 2008, Nature materials.

[15]  Feng Li,et al.  Electrochemical interfacial capacitance in multilayer graphene sheets: Dependence on number of stacking layers , 2009 .

[16]  Mathieu Toupin,et al.  Charge Storage Mechanism of MnO2 Electrode Used in Aqueous Electrochemical Capacitor , 2004 .

[17]  Yi Shi,et al.  Preparation and characterization of flexible asymmetric supercapacitors based on transition-metal-oxide nanowire/single-walled carbon nanotube hybrid thin-film electrodes. , 2010, ACS nano.

[18]  Lili Zhang,et al.  Graphene-based materials as supercapacitor electrodes , 2010 .

[19]  Chi-Chang Hu,et al.  Design and tailoring of the nanotubular arrayed architecture of hydrous RuO2 for next generation supercapacitors. , 2006, Nano letters.

[20]  J. S. Lee,et al.  Fabrication of ZnO/CdS core/shell nanowire arrays for efficient solar energy conversion , 2009 .

[21]  Zhennan Gu,et al.  Growth of manganese oxide nanoflowers on vertically-aligned carbon nanotube arrays for high-rate electrochemical capacitive energy storage. , 2008, Nano letters.

[22]  Yi Cui,et al.  Stretchable, porous, and conductive energy textiles. , 2010, Nano letters.

[23]  G. Chen,et al.  Carbon nanotube and conducting polymer composites for supercapacitors , 2008 .

[24]  Mao-Sung Wu.  Electrochemical capacitance from manganese oxide nanowire structure synthesized by cyclic voltammetric electrodeposition , 2005 .

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

[26]  G. Lu,et al.  Fabrication of Graphene/Polyaniline Composite Paper via In Situ Anodic Electropolymerization for High-Performance Flexible Electrode. , 2009, ACS nano.

[27]  Hiroyuki Nishide,et al.  Toward Flexible Batteries , 2008, Science.

[28]  Ran Liu,et al.  MnO2/poly(3,4-ethylenedioxythiophene) coaxial nanowires by one-step coelectrodeposition for electrochemical energy storage. , 2008, Journal of the American Chemical Society.

[29]  Y. Shao-horn,et al.  Carbon nanotube/manganese oxide ultrathin film electrodes for electrochemical capacitors. , 2010, ACS nano.

[30]  Eunsung Lee,et al.  Synthesis and characterization of manganese dioxide spontaneously coated on carbon nanotubes , 2007 .

[31]  Yi Cui,et al.  Highly conductive paper for energy-storage devices , 2009, Proceedings of the National Academy of Sciences.

[32]  John R. Miller,et al.  Electrochemical Capacitors for Energy Management , 2008, Science.

[33]  Zhong Lin Wang,et al.  Fiber supercapacitors made of nanowire-fiber hybrid structures for wearable/flexible energy storage. , 2011, Angewandte Chemie.

[34]  Robert F. Nelson,et al.  Power requirements for batteries in hybrid electric vehicles , 2000 .

[35]  Anran Liu,et al.  Supercapacitors based on flexible graphene/polyaniline nanofiber composite films. , 2010, ACS nano.

[36]  Jun Li,et al.  Hybrid Supercapacitor Based on Coaxially Coated Manganese Oxide on Vertically Aligned Carbon Nanofiber Arrays , 2010 .

[37]  H. Teng,et al.  Structural Feature and Double-Layer Capacitive Performance of Porous Carbon Powder Derived from Polyacrylonitrile-Based Carbon Fiber , 2007 .

[38]  Xiaodong Wu,et al.  Graphene oxide--MnO2 nanocomposites for supercapacitors. , 2010, ACS nano.

[39]  H.Q. Li,et al.  Ordered Whiskerlike Polyaniline Grown on the Surface of Mesoporous Carbon and Its Electrochemical Capacitance Performance , 2006 .

[40]  Kai Zhang,et al.  Graphene/Polyaniline Nanofiber Composites as Supercapacitor Electrodes , 2010 .

[41]  Pooi See Lee,et al.  Facile coating of manganese oxide on tin oxide nanowires with high-performance capacitive behavior. , 2010, ACS Nano.

[42]  B. C. Kim,et al.  Performance evaluation of CNT/polypyrrole/MnO2 composite electrodes for electrochemical capacitors , 2007 .

[43]  Norio Miura,et al.  Effects of electrochemical-deposition method and microstructure on the capacitive characteristics of nano-sized manganese oxide , 2006 .

[44]  M. B. Bever,et al.  Concise encyclopedia of composite materials , 1989 .

[45]  F. Wei,et al.  Fast and reversible surface redox reaction of graphene–MnO2 composites as supercapacitor electrodes , 2010 .

[46]  G. Lu,et al.  3D aperiodic hierarchical porous graphitic carbon material for high-rate electrochemical capacitive energy storage. , 2008, Angewandte Chemie.

[47]  D. Bélanger,et al.  Direct Redox Deposition of Manganese Oxide on Multiscaled Carbon Nanotube/Microfiber Carbon Electrode for Electrochemical Capacitor , 2009 .

[48]  Ran Liu,et al.  Redox exchange induced MnO2 nanoparticle enrichment in poly(3,4-ethylenedioxythiophene) nanowires for electrochemical energy storage. , 2010, ACS nano.

[49]  Yongsheng Chen,et al.  SUPERCAPACITOR DEVICES BASED ON GRAPHENE MATERIALS , 2009 .