Synergistic effects in 3D honeycomb-like hematite nanoflakes/branched polypyrrole nanoleaves heterostructures as high-performance negative electrodes for asymmetric supercapacitors

Abstract Rational assembly of unique branched heterostructures is one of the facile techniques to improve the electrochemical figure of merit of materials. By taking advantages of hydrogen bubbles dynamic template, hydrothermal method and electrochemical polymerization, branched polypyrrole (PPy) nanoleaves decorated honeycomb-like hematite nanoflakes (core-branch Fe2O3@PPy) are fabricated. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM, and scanning transmission electron microscopy in high angle annular dark field mode with electron energy loss spectroscopy were combined to elucidate the mechanisms underlying formation and morphogenesis evolution of core-branch Fe2O3@PPy heterostructures. Benefiting from the stability of honeycomb-like hematite nanoflakes and the high conductivity of PPy nanoleaves, the resultant core-branch Fe2O3@PPy exhibits an ultrahigh capacitance of 1167.8 F g−1 at 1 A g−1 in 0.5 M Na2SO4 aqueous solution. Moreover, the assembled bi-metal oxides asymmetric supercapacitor (Fe2O3@PPy//MnO2) gives rise to a maximum energy density of 42.4 W h kg−1 and a maximum power density of 19.14 kW kg−1 with an excellent cycling performance of 97.1% retention after 3000 cycles at 3 A g−1. These performance features are superior than previous reported iron oxide/hydroxides based supercapacitors, offering an important guideline for future design of advanced next-generation supercapacitors.

[1]  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.

[2]  James M Tour,et al.  Three-dimensional thin film for lithium-ion batteries and supercapacitors. , 2014, ACS nano.

[3]  G. Cao,et al.  Mesoporous Hydrous Manganese Dioxide Nanowall Arrays with Large Lithium Ion Energy Storage Capacities , 2009 .

[4]  Shuhong Yu,et al.  In situ hydrothermal growth of ferric oxides on carbon cloth for low-cost and scalable high-energy-density supercapacitors ☆ , 2014 .

[5]  Xinliang Feng,et al.  2D Sandwich‐like Sheets of Iron Oxide Grown on Graphene as High Energy Anode Material for Supercapacitors , 2011, Advanced materials.

[6]  Stephen A. Morin,et al.  Rational solution growth of α-FeOOH nanowires driven by screw dislocations and their conversion to α-Fe2O3 nanowires. , 2011, Journal of the American Chemical Society.

[7]  C. Tai,et al.  Formation of nitrogen-doped graphene nanoscrolls by adsorption of magnetic γ-Fe2O3 nanoparticles , 2013, Nature Communications.

[8]  Junwu Zhu,et al.  Bioinspired Effective Prevention of Restacking in Multilayered Graphene Films: Towards the Next Generation of High‐Performance Supercapacitors , 2011, Advanced materials.

[9]  Li Zhang,et al.  Hierarchical Co3O4@PPy@MnO2 core–shell–shell nanowire arrays for enhanced electrochemical energy storage , 2014 .

[10]  Wen‐Cui Li,et al.  Ionic Liquid‐Assisted Synthesis of Microporous Carbon Nanosheets for Use in High Rate and Long Cycle Life Supercapacitors , 2014, Advanced materials.

[11]  Hua Zhang,et al.  Iron oxide-decorated carbon for supercapacitor anodes with ultrahigh energy density and outstanding cycling stability. , 2015, ACS nano.

[12]  Jun Yan,et al.  Supercapacitors based on graphene-supported iron nanosheets as negative electrode materials. , 2013, ACS nano.

[13]  H. Dai,et al.  Advanced asymmetrical supercapacitors based on graphene hybrid materials , 2011, 1104.3379.

[14]  Min Wei,et al.  Flexible CoAl LDH@PEDOT core/shell nanoplatelet array for high-performance energy storage. , 2013, Small.

[15]  Z. Bao,et al.  A review of fabrication and applications of carbon nanotube film-based flexible electronics. , 2013, Nanoscale.

[16]  Genevieve Dion,et al.  Natural Fiber Welded Electrode Yarns for Knittable Textile Supercapacitors , 2015 .

[17]  S. Xie,et al.  Asymmetric Supercapacitors Based on Graphene/MnO2 Nanospheres and Graphene/MoO3 Nanosheets with High Energy Density , 2013 .

[18]  Fei Wei,et al.  Design and Synthesis of Hierarchical Nanowire Composites for Electrochemical Energy Storage , 2009 .

[19]  J. Morante,et al.  Polarity-driven polytypic branching in cu-based quaternary chalcogenide nanostructures. , 2014, ACS nano.

[20]  Y. Tong,et al.  Design and synthesis of MnO₂/Mn/MnO₂ sandwich-structured nanotube arrays with high supercapacitive performance for electrochemical energy storage. , 2012, Nano letters.

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

[22]  M. El‐Kady,et al.  Laser Scribing of High-Performance and Flexible Graphene-Based Electrochemical Capacitors , 2012, Science.

[23]  G. Gary Wang,et al.  Flexible solid-state supercapacitors: design, fabrication and applications , 2014 .

[24]  Kunfeng Chen,et al.  Composition Design Upon Iron Element Toward Supercapacitor Electrode Materials , 2015 .

[25]  G. Cao,et al.  Hydrous Manganese Dioxide Nanowall Arrays Growth and Their Li+ Ions Intercalation Electrochemical Properties , 2008 .

[26]  Wenhui Shi,et al.  High-power and high-energy-density flexible pseudocapacitor electrodes made from porous CuO nanobelts and single-walled carbon nanotubes. , 2011, ACS nano.

[27]  H. Fan,et al.  Branched nanowires: Synthesis and energy applications , 2012 .

[28]  B. Wei,et al.  In situ synthesis of SWNTs@MnO2/polypyrrole hybrid film as binder-free supercapacitor electrode , 2014 .

[29]  Hua Zhang,et al.  Controllable growth of conducting polymers shell for constructing high-quality organic/inorganic core/shell nanostructures and their optical-electrochemical properties. , 2013, Nano letters.

[30]  Andrew C. Chu,et al.  Comparison of commercial supercapacitors and high-power lithium-ion batteries for power-assist applications in hybrid electric vehicles , 2002 .

[31]  B. Dunn,et al.  High‐Performance Supercapacitors Based on Intertwined CNT/V2O5 Nanowire Nanocomposites , 2011, Advanced materials.

[32]  L. Manna,et al.  Colloidal branched semiconductor nanocrystals: state of the art and perspectives. , 2013, Accounts of chemical research.

[33]  H. Hng,et al.  Epitaxial Growth of Branched α‐Fe2O3/SnO2 Nano‐Heterostructures with Improved Lithium‐Ion Battery Performance , 2011 .

[34]  Zhanhu Guo,et al.  One-step preparation of single-crystalline Fe2O3 particles/graphene composite hydrogels as high performance anode materials for supercapacitors , 2014 .

[35]  Jun Zhou,et al.  Flexible solid-state supercapacitors based on carbon nanoparticles/MnO2 nanorods hybrid structure. , 2012, ACS nano.

[36]  Y. Tong,et al.  An Electrochemical Capacitor with Applicable Energy Density of 7.4 Wh/kg at Average Power Density of 3000 W/kg. , 2015, Nano letters.

[37]  Yuanyuan Li,et al.  Construction of high-capacitance 3D CoO@polypyrrole nanowire array electrode for aqueous asymmetric supercapacitor. , 2013, Nano letters.

[38]  Jean Gamby,et al.  Studies and characterisations of various activated carbons used for carbon/carbon supercapacitors , 2001 .

[39]  Minghao Yu,et al.  Advanced Ti‐Doped Fe2O3@PEDOT Core/Shell Anode for High‐Energy Asymmetric Supercapacitors , 2015 .

[40]  Lei Zhang,et al.  A review of electrode materials for electrochemical supercapacitors. , 2012, Chemical Society reviews.

[41]  Feng Li,et al.  High-energy MnO2 nanowire/graphene and graphene asymmetric electrochemical capacitors. , 2010, ACS nano.

[42]  Zhiyong Tang,et al.  Growth of Polypyrrole Ultrathin Films on MoS2 Monolayers as High‐Performance Supercapacitor Electrodes , 2015, Advanced materials.

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

[44]  Yunqi Liu,et al.  Facile Synthesis of 3D MnO2–Graphene and Carbon Nanotube–Graphene Composite Networks for High‐Performance, Flexible, All‐Solid‐State Asymmetric Supercapacitors , 2014 .

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

[46]  R. Ruoff,et al.  Carbon-Based Supercapacitors Produced by Activation of Graphene , 2011, Science.

[47]  A. Fakhry,et al.  Templateless electrogeneration of polypyrrole nanostructures: impact of the anionic composition and pH of the monomer solution , 2014 .

[48]  J. Xu,et al.  Flexible asymmetric supercapacitors based upon Co9S8 nanorod//Co3O4@RuO2 nanosheet arrays on carbon cloth. , 2013, ACS nano.

[49]  A. Fakhry,et al.  Mechanism of formation of templateless electrogenerated polypyrrole nanostructures , 2015 .

[50]  N. Munichandraiah,et al.  Synthesis and characterization of porous flowerlike alpha-Fe2O3 nanostructures for supercapacitor application , 2013 .

[51]  S. Yen,et al.  Novel iron oxyhydroxide lepidocrocite nanosheet as ultrahigh power density anode material for asymmetric supercapacitors. , 2014, Small.

[52]  R. Ruoff,et al.  Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage , 2015, Science.

[53]  Xinzhi Yu,et al.  Super Long‐Life Supercapacitors Based on the Construction of Nanohoneycomb‐Like Strongly Coupled CoMoO4–3D Graphene Hybrid Electrodes , 2014, Advanced materials.