High performance flexible solid-state asymmetric supercapacitors from MnO2/ZnO core–shell nanorods//specially reduced graphene oxide

With a view to developing flexible solid-state asymmetric supercapacitors, we have specially designed and nanoscopically engineered two types of electrodes: a MnO2/ZnO core–shell nanorod array and a HI-reduced graphene oxide assembly, both deposited in situ on a carbon cloth. These materials were thoroughly characterized by structural and spectroscopic techniques. The flexible solid-state asymmetric supercapacitors with cathodes and anodes made of these materials have demonstrated superior performance characteristics. They can be cycled in a wide potential window of 0–1.8 V for 5000 cycles with only 1.5% capacitance loss. The demonstrated volumetric energy density of 0.234 mW h cm−3 and volumetric power density of 0.133 W cm−3 are much higher than those of similar devices reported previously in the literature.

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

[2]  Yongyao Xia,et al.  A new concept hybrid electrochemical surpercapacitor: Carbon/LiMn2O4 aqueous system , 2005 .

[3]  Peng Diao,et al.  Hydrothermal growth of well-aligned ZnO nanorod arrays: Dependence of morphology and alignment ordering upon preparing conditions , 2005 .

[4]  François Béguin,et al.  Optimisation of an asymmetric manganese oxide/activated carbon capacitor working at 2 V in aqueous medium , 2006 .

[5]  Jingwei Sun,et al.  Hybrid supercapacitor based on MnO2 and columned FeOOH using Li2SO4 electrolyte solution , 2008 .

[6]  Thierry Brousse,et al.  Variation of the MnO2 Birnessite Structure upon Charge/Discharge in an Electrochemical Supercapacitor Electrode in Aqueous Na2SO4 Electrolyte , 2008 .

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

[8]  Xiao‐Qing Yang,et al.  Electrodeposited manganese oxides on three-dimensional carbon nanotube substrate: Supercapacitive behaviour in aqueous and organic electrolytes , 2009 .

[9]  Bin Wang,et al.  Electrochemical Performance of MnO2 Nanorods in Neutral Aqueous Electrolytes as a Cathode for Asymmetric Supercapacitors , 2009 .

[10]  R. Holze,et al.  V2O5·0.6H2O nanoribbons as cathode material for asymmetric supercapacitor in K2SO4 solution , 2009 .

[11]  R. Ruoff,et al.  Reduced graphene oxide by chemical graphitization. , 2010, Nature communications.

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

[13]  Luzhuo Chen,et al.  Highly flexible and all-solid-state paperlike polymer supercapacitors. , 2010, Nano letters.

[14]  A. Lewandowski,et al.  Performance of carbon–carbon supercapacitors based on organic, aqueous and ionic liquid electrolytes , 2010 .

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

[16]  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.

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

[18]  Teng Zhai,et al.  Facile synthesis of large-area manganese oxide nanorod arrays as a high-performance electrochemical supercapacitor , 2011 .

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

[20]  H. Gong,et al.  Co3O4 Nanowire@MnO2 Ultrathin Nanosheet Core/Shell Arrays: A New Class of High‐Performance Pseudocapacitive Materials , 2011, Advanced materials.

[21]  Y. Tong,et al.  Single-crystal ZnO nanorod/amorphous and nanoporous metal oxide shell composites: Controllable electrochemical synthesis and enhanced supercapacitor performances , 2011 .

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

[23]  Shihe Yang,et al.  Sequential crystallization of sea urchin-like bimetallic (Ni, Co) carbonate hydroxide and its morphology conserved conversion to porous NiCo2O4 spinel for pseudocapacitors , 2011 .

[24]  Yexiang Tong,et al.  ZnO@MoO3 core/shell nanocables: facile electrochemical synthesis and enhanced supercapacitor performances , 2011 .

[25]  Shihe Yang,et al.  Bio-inspired synthesis: understanding and exploitation of the crystallization process from amorphous precursors. , 2012, Nanoscale.

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

[27]  Wei Chen,et al.  High energy density supercapacitors using macroporous kitchen sponges , 2012 .

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

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

[30]  X. Zhao,et al.  Ultrathin MnO2 nanofibers grown on graphitic carbon spheres as high-performance asymmetric supercapacitor electrodes , 2012 .

[31]  Shihe Yang,et al.  Bio-inspired synthesis of NaCl-type CoxNi1−xO (0 ≤ x < 1) nanorods on reduced graphene oxide sheets and screening for asymmetric electrochemical capacitors , 2012 .

[32]  Yexiang Tong,et al.  Polyaniline nanotube arrays as high-performance flexible electrodes for electrochemical energy storage devices , 2012 .

[33]  Teng Zhai,et al.  LiCl/PVA gel electrolyte stabilizes vanadium oxide nanowire electrodes for pseudocapacitors. , 2012, ACS nano.

[34]  Chi-Hwan Han,et al.  All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes , 2012, Nanotechnology.

[35]  Teng Zhai,et al.  WO3–x@Au@MnO2 Core–Shell Nanowires on Carbon Fabric for High‐Performance Flexible Supercapacitors , 2012, Advanced materials.

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

[37]  Yun Suk Huh,et al.  High performance of a solid-state flexible asymmetric supercapacitor based on graphene films. , 2012, Nanoscale.

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

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

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

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