all-solid-state fl exible micro-supercapacitor arrays with layer-by-layer assembled MWNT / MnO x nanocomposite electrodes †

In this study, we report on the fabrication of high performance planar-type flexible micro-supercapacitor (MSC) arrays using Au electrodes coated with a functionalized multi-walled carbon nanotube (MWNT) film and a layer of MWNT-COOH/MnOx nanoparticle (NP) composite on top. The MWNT thin film was formed via layer-by-layer (LbL) assembly of MWNTs functionalized with amine groups and MWNTs with carboxylic acid groups in water. The hydrothermally synthesized composite of MWNT-COOH/MnOx NPs was coated on top of the MWNT film (LbL-MWNT). The addition of MWNT-COOH/MnOx NP composite as a top layer enhanced the performance of the MSCs dramatically, resulting in a volumetric capacitance of 50 F cm(-3) at a scan rate of 10 mV s(-1) and a coulombic efficiency of ∼100%. By contrast, a volumetric capacitance of 3.6 F cm(-3) was obtained when using only the LbL-MWNT film. After repetitive operation up to ∼10(4) times, the capacitance remained at ∼88.3% of the original value. With a deliberate circuit design consisting of serially connected MSC arrays, various light-emitting diodes operating at different bias voltages could be lit. The MSC circuit fabricated on a polyethylene terephthalate (PET) film showed stable electrochemical properties upon 1000 cycles of bending deformation.

[1]  Fei Xiao,et al.  Flexible all-solid-state asymmetric supercapacitors based on free-standing carbon nanotube/graphene and Mn3O4 nanoparticle/graphene paper electrodes. , 2012, ACS applied materials & interfaces.

[2]  C. Lokhande,et al.  Mild chemical strategy to grow micro-roses and micro-woolen like arranged CuO nanosheets for high performance supercapacitors , 2013 .

[3]  Weiguo Song,et al.  Microwave-assisted gas/liquid interfacial synthesis of flowerlike NiO hollow nanosphere precursors and their application as supercapacitor electrodes , 2011 .

[4]  Chi-Chang Hu,et al.  Microwave-assisted hydrothermal synthesis of Mn3O4/reduced graphene oxide composites for high power supercapacitors , 2012 .

[5]  H. Kataura,et al.  Electrochemical behavior of metallic and semiconducting single-wall carbon nanotubes for electric double-layer capacitor , 2012 .

[6]  M. Jayachandran,et al.  XRD and XPS characterization of mixed valence Mn3O4 hausmannite thin films prepared by chemical spray pyrolysis technique , 2010 .

[7]  Zhiqiang Niu,et al.  All‐Solid‐State Flexible Ultrathin Micro‐Supercapacitors Based on Graphene , 2013, Advanced materials.

[8]  Xinhua Li,et al.  Flexible supercapacitor based on MnO2 nanoparticles via electrospinning , 2013 .

[9]  Yongsheng Hu,et al.  A repeated halving approach to fabricate ultrathin single-walled carbon nanotube films for transparent supercapacitors. , 2013, Small.

[10]  P. Taberna,et al.  Monolithic Carbide-Derived Carbon Films for Micro-Supercapacitors , 2010, Science.

[11]  Shuo Chen,et al.  Layer-by-layer assembly of all carbon nanotube ultrathin films for electrochemical applications. , 2009, Journal of the American Chemical Society.

[12]  P. Ajayan,et al.  Three-dimensional metal-graphene-nanotube multifunctional hybrid materials. , 2013, ACS nano.

[13]  Lei Su,et al.  Surfactant functionalization of carbon nanotubes (CNTs) for layer-by-layer assembling of CNT multi-layer films and fabrication of gold nanoparticle/CNT nanohybrid , 2006 .

[14]  G. An,et al.  Low-temperature synthesis of Mn3O4 nanoparticles loaded on multi-walled carbon nanotubes and their application in electrochemical capacitors , 2008, Nanotechnology.

[15]  Xiaodong Chen,et al.  Highly Stretchable, Integrated Supercapacitors Based on Single‐Walled Carbon Nanotube Films with Continuous Reticulate Architecture , 2013, Advanced materials.

[16]  T. Mallouk,et al.  A Facile and Template-Free Hydrothermal Synthesis of Mn3O4 Nanorods on Graphene Sheets for Supercapacitor Electrodes with Long Cycle Stability , 2012 .

[17]  M. El‐Kady,et al.  Scalable fabrication of high-power graphene micro-supercapacitors for flexible and on-chip energy storage , 2013, Nature Communications.

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

[19]  Jinlong Yang,et al.  Metallic few-layered VS2 ultrathin nanosheets: high two-dimensional conductivity for in-plane supercapacitors. , 2011, Journal of the American Chemical Society.

[20]  Husam N. Alshareef,et al.  Symmetrical MnO2-carbon nanotube-textile nanostructures for wearable pseudocapacitors with high mass loading. , 2011, ACS nano.

[21]  Zhong Lin Wang,et al.  Tungsten Oxide Nanowires Grown on Carbon Cloth as a Flexible Cold Cathode , 2010, Advanced materials.

[22]  Aifang Yu,et al.  An All‐Solid‐State Flexible Micro‐supercapacitor on a Chip , 2011 .

[23]  Peihua Huang,et al.  Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon. , 2010, Nature nanotechnology.

[24]  F. Meng,et al.  Sub‐Micrometer‐Thick All‐Solid‐State Supercapacitors with High Power and Energy Densities , 2011, Advanced materials.

[25]  Yong Ding,et al.  Hydrogenated ZnO core-shell nanocables for flexible supercapacitors and self-powered systems. , 2013, ACS nano.

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

[27]  Feng Li,et al.  Anchoring Hydrous RuO2 on Graphene Sheets for High‐Performance Electrochemical Capacitors , 2010 .

[28]  Yu‐Guo Guo,et al.  Highly Dispersed RuO2 Nanoparticles on Carbon Nanotubes: Facile Synthesis and Enhanced Supercapacitance Performance , 2010 .

[29]  Teng Zhai,et al.  Hydrogenated TiO2 nanotube arrays for supercapacitors. , 2012, Nano letters.

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

[31]  M. Chigane,et al.  Manganese Oxide Thin Film Preparation by Potentiostatic Electrolyses and Electrochromism , 2000 .

[32]  Xing Xie,et al.  High-performance nanostructured supercapacitors on a sponge. , 2011, Nano letters.

[33]  Chen Chen,et al.  Twisting Carbon Nanotube Fibers for Both Wire‐Shaped Micro‐Supercapacitor and Micro‐Battery , 2013, Advanced materials.

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

[35]  Gunchul Shin,et al.  Fabrication of a stretchable solid-state micro-supercapacitor array. , 2013, ACS nano.

[36]  Mathieu Toupin,et al.  Influence of Microstucture on the Charge Storage Properties of Chemically Synthesized Manganese Dioxide , 2002 .

[37]  Fei Wei,et al.  Building robust architectures of carbon and metal oxide nanocrystals toward high-performance anodes for lithium-ion batteries. , 2012, ACS nano.

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

[39]  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.

[40]  Katsuhiko Ariga,et al.  Layer-by-layer assembly as a versatile bottom-up nanofabrication technique for exploratory research and realistic application. , 2007, Physical chemistry chemical physics : PCCP.

[41]  Teng Zhai,et al.  H‐TiO2@MnO2//H‐TiO2@C Core–Shell Nanowires for High Performance and Flexible Asymmetric Supercapacitors , 2013, Advanced materials.

[42]  Gero Decher,et al.  Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites , 1997 .

[43]  Yury Gogotsi,et al.  Electrochemical performance of carbon onions, nanodiamonds, carbon black and multiwalled nanotubes in electrical double layer capacitors , 2007 .

[44]  Ran Liu,et al.  Highly flexible pseudocapacitor based on freestanding heterogeneous MnO2/conductive polymer nanowire arrays. , 2012, Physical chemistry chemical physics : PCCP.

[45]  B. Liu,et al.  Three‐Dimensional Hierarchical GeSe2 Nanostructures for High Performance Flexible All‐Solid‐State Supercapacitors , 2013, Advanced materials.

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

[47]  Bo-Yeong Kim,et al.  All-solid-state flexible supercapacitors fabricated with bacterial nanocellulose papers, carbon nanotubes, and triblock-copolymer ion gels. , 2012, ACS nano.

[48]  Yiqing Sun,et al.  Ultrahigh-rate supercapacitors based on eletrochemically reduced graphene oxide for ac line-filtering , 2012, Scientific Reports.

[49]  P. Taberna,et al.  Electrochemical Characteristics and Impedance Spectroscopy Studies of Carbon-Carbon Supercapacitors , 2003 .

[50]  Wenping Si,et al.  On chip, all solid-state and flexible micro-supercapacitors with high performance based on MnOx/Au multilayers , 2013 .

[51]  Norbert Fabre,et al.  Elaboration of a microstructured inkjet-printed carbon electrochemical capacitor , 2010 .

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

[53]  Yu-Lun Chueh,et al.  Fiber-based all-solid-state flexible supercapacitors for self-powered systems. , 2012, ACS nano.

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