Freestanding flexible graphene foams@polypyrrole@MnO2 electrodes for high-performance supercapacitors

A new composite electrode design was successfully fabricated based on 3D flexible graphene foams (GF) with interconnected macropores as the freestanding substrate and a composite of MnO2 nanoparticles and polypyrrole (PPy) as an integrated electrode. Under assistance of PPy, the microscopic morphology of MnO2 changed from flower-like to nanoparticles, and correspondingly, a high specific capacity of 600 F g−1 at a current density of 1 A g−1 was obtained from the GF@PPy@MnO2 nanoparticles composite electrode. Moreover, over 92% of the initial capacity was retained after 5000 cycles at 30 A g−1. Also, the role of PPy in improving the electrochemical performance of the composite electrode was investigated. We also tested a full symmetric supercapacitor of GF@PPy@MnO2//GF@PPy@MnO2 obtaining the maximum energy density of 28 W h kg−1 at 508 W kg−1 and the maximum power density of 13 kW kg−1 at 14 W h kg−1. This well-designed nanostructured composite electrode could be a promising electrode material for high-performance supercapacitors.

[1]  Li Lu,et al.  Nanoflaky MnO2/carbon nanotube nanocomposites as anode materials for lithium-ion batteries , 2010 .

[2]  Rujia Zou,et al.  MnO2 ultralong nanowires with better electrical conductivity and enhanced supercapacitor performances , 2012 .

[3]  W. Shi,et al.  Characterisation of doped polypyrrole/manganese oxide nanocomposite for supercapacitor electrodes , 2011 .

[4]  Zichuan Ma,et al.  Effect of the KMnO4 concentration on the structure and electrochemical behavior of MnO2 , 2012, Journal of Materials Science.

[5]  Jinqiu Zhou,et al.  A new approach towards the synthesis of nitrogen-doped graphene/MnO2 hybrids for ultralong cycle-life lithium ion batteries , 2015 .

[6]  Li Lu,et al.  Incorporation of MnO2-coated carbon nanotubes between graphene sheets as supercapacitor electrode. , 2012, ACS applied materials & interfaces.

[7]  M. Chan-Park,et al.  Synthesis of a MnO2–graphene foam hybrid with controlled MnO2 particle shape and its use as a supercapacitor electrode , 2012 .

[8]  M. Dresselhaus,et al.  Importance of open, heteroatom-decorated edges in chemically doped-graphene for supercapacitor applications , 2014 .

[9]  Qiang Zhang,et al.  Advanced Asymmetric Supercapacitors Based on Ni(OH)2/Graphene and Porous Graphene Electrodes with High Energy Density , 2012 .

[10]  Jeng‐Kuei Chang,et al.  Material characterization and electrochemical performance of hydrous manganese oxide electrodes for use in electrochemical pseudocapacitors , 2003 .

[11]  Myeongjin Kim,et al.  Super-capacitive performance depending on different crystal structures of MnO2 in graphene/MnO2 composites for supercapacitors , 2013, Journal of Materials Science.

[12]  Wuzong Zhou,et al.  Nanoscale microelectrochemical cells on carbon nanotubes. , 2007, Small.

[13]  Yuanyuan Shang,et al.  Core-double-shell, carbon nanotube@polypyrrole@MnO₂ sponge as freestanding, compressible supercapacitor electrode. , 2014, ACS applied materials & interfaces.

[14]  Li Lu,et al.  Anisotropic Co3O4 porous nanocapsules toward high-capacity Li-ion batteries , 2010 .

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

[16]  C. Julien,et al.  Raman spectra of birnessite manganese dioxides , 2003 .

[17]  Alka Gupta,et al.  Synthesis and characterization of polypyrrole nanofibers with different dopants , 2010 .

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

[19]  Yi Xie,et al.  Ultrathin two-dimensional MnO2/graphene hybrid nanostructures for high-performance, flexible planar supercapacitors. , 2013, Nano letters.

[20]  F. Wei,et al.  Asymmetric Supercapacitors Based on Graphene/MnO2 and Activated Carbon Nanofiber Electrodes with High Power and Energy Density , 2011 .

[21]  Yong Ding,et al.  Low-cost high-performance solid-state asymmetric supercapacitors based on MnO2 nanowires and Fe2O3 nanotubes. , 2014, Nano letters.

[22]  Chang Liu,et al.  Advanced Materials for Energy Storage , 2010, Advanced materials.

[23]  Akihiko Hirata,et al.  Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors. , 2011, Nature nanotechnology.

[24]  Alka Gupta,et al.  Synthesis and characterization of poly (indene‐co‐pyrrole) nanofibers , 2010 .

[25]  A. Jorio,et al.  Influence of the atomic structure on the Raman spectra of graphite edges. , 2004, Physical review letters.

[26]  S. Bose,et al.  Carbon-based nanostructured materials and their composites as supercapacitor electrodes , 2012 .

[27]  Q. Yang,et al.  Self-assembled flower-like hierarchical spheres and nanobelts of manganese oxide by hydrothermal method and morphology control of them , 2007 .

[28]  W. Fei,et al.  In situ growth of manganese oxide on 3D graphene by a reverse microemulsion method for supercapacitors , 2016 .

[29]  Bingqing Wei,et al.  Nanostructured MnO2: Hydrothermal synthesis and electrochemical properties as a supercapacitor electrode material , 2006 .

[30]  J. Pereira‐Ramos,et al.  Doping effects on structure and electrode performance of K-birnessite-type manganese dioxides for rechargeable lithium battery , 2008 .

[31]  Hongcai Gao,et al.  High-performance asymmetric supercapacitor based on graphene hydrogel and nanostructured MnO2. , 2012, ACS applied materials & interfaces.

[32]  J. Liu,et al.  Graphene/MnO2 composite prepared by a simple method for high performance supercapacitor , 2016 .

[33]  R. Holze,et al.  A new cheap asymmetric aqueous supercapacitor: Activated carbon//NaMnO2 , 2009 .

[34]  Rujia Zou,et al.  Effect of temperature on the performance of ultrafine MnO2 nanobelt supercapacitors , 2014 .

[35]  F. Kang,et al.  Engineering of MnO2-based nanocomposites for high-performance supercapacitors , 2015 .

[36]  Ning Pan,et al.  Supercapacitors Performance Evaluation , 2015 .

[37]  Junhong Chen,et al.  Crumpled Nitrogen‐Doped Graphene Nanosheets with Ultrahigh Pore Volume for High‐Performance Supercapacitor , 2012, Advanced materials.

[38]  Songtao Lu,et al.  Synergistic effects from graphene and carbon nanotubes enable flexible and robust electrodes for high-performance supercapacitors. , 2012, Nano letters.

[39]  Yihua Gao,et al.  Solid-State High Performance Flexible Supercapacitors Based on Polypyrrole-MnO2-Carbon Fiber Hybrid Structure , 2013, Scientific Reports.

[40]  E. Xie,et al.  An overview of carbon materials for flexible electrochemical capacitors. , 2013, Nanoscale.

[41]  Zhong Lin Wang,et al.  Hierarchical network architectures of carbon fiber paper supported cobalt oxide nanonet for high-capacity pseudocapacitors. , 2012, Nano letters.

[42]  Norio Shinya,et al.  Graphene and nanostructured MnO2 composite electrodes for supercapacitors , 2011 .

[43]  Tianxi Liu,et al.  One-step synthesis of graphene nanoribbon-MnO₂ hybrids and their all-solid-state asymmetric supercapacitors. , 2014, Nanoscale.

[44]  Lifeng Yan,et al.  In situ self-assembly of mild chemical reduction graphene for three-dimensional architectures. , 2011, Nanoscale.

[45]  H. R. Ghenaatian,et al.  High performance hybrid supercapacitor based on two nanostructured conducting polymers: Self-doped polyaniline and polypyrrole nanofibers , 2012 .

[46]  Shuhong Yu,et al.  Flexible graphene–polyaniline composite paper for high-performance supercapacitor , 2013 .

[47]  X. Duan,et al.  Solution Processable Holey Graphene Oxide and Its Derived Macrostructures for High-Performance Supercapacitors. , 2015, Nano letters.

[48]  E. Xie,et al.  Importance of polypyrrole in constructing 3D hierarchical carbon nanotube@MnO2 perfect core-shell nanostructures for high-performance flexible supercapacitors. , 2015, Nanoscale.

[49]  R. Li,et al.  Facile controlled synthesis and growth mechanisms of flower-like and tubular MnO2 nanostructures by microwave-assisted hydrothermal method. , 2012, Journal of colloid and interface science.