Layered-MnO₂ Nanosheet Grown on Nitrogen-Doped Graphene Template as a Composite Cathode for Flexible Solid-State Asymmetric Supercapacitor.

Flexible solid-state supercapacitors provide a promising energy-storage alternative for the rapidly growing flexible and wearable electronic industry. Further improving device energy density and developing a cheap flexible current collector are two major challenges in pushing the technology forward. In this work, we synthesize a nitrogen-doped graphene/MnO2 nanosheet (NGMn) composite by a simple hydrothermal method. Nitrogen-doped graphene acts as a template to induce the growth of layered δ-MnO2 and improves the electronic conductivity of the composite. The NGMn composite exhibits a large specific capacitance of about 305 F g(-1) at a scan rate of 5 mV s(-1). We also create a cheap and highly conductive flexible current collector using Scotch tape. Flexible solid-state asymmetric supercapacitors are fabricated with NGMn cathode, activated carbon anode, and PVA-LiCl gel electrolyte. The device can achieve a high operation voltage of 1.8 V and exhibits a maximum energy density of 3.5 mWh cm(-3) at a power density of 0.019 W cm(-3). Moreover, it retains >90% of its initial capacitance after 1500 cycles. Because of its flexibility, high energy density, and good cycle life, NGMn-based flexible solid state asymmetric supercapacitors have great potential for application in next-generation portable and wearable electronics.

[1]  Wenjie Mai,et al.  Flexible solid-state electrochemical supercapacitors , 2014 .

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

[3]  P. Simon,et al.  Polythiophene-based supercapacitors , 1999 .

[4]  Rudolf Holze,et al.  Supercapacitors Based on Flexible Substrates: An Overview , 2014 .

[5]  Q. Xue,et al.  Free-standing three-dimensional graphene/manganese oxide hybrids as binder-free electrode materials for energy storage applications. , 2014, ACS applied materials & interfaces.

[6]  Bin Liu,et al.  NiCo2O4 nanowire arrays supported on Ni foam for high-performance flexible all-solid-state supercapacitors , 2013 .

[7]  S. Devaraj,et al.  Effect of Crystallographic Structure of MnO2 on Its Electrochemical Capacitance Properties , 2008 .

[8]  D. Bélanger,et al.  Electrochemical Characterization of Polyaniline in Nonaqueous Electrolyte and Its Evaluation as Electrode Material for Electrochemical Supercapacitors , 2001 .

[9]  W. Lu,et al.  Improved synthesis of graphene oxide. , 2010, ACS nano.

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

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

[12]  Huanli Dong,et al.  Synthesizing MnO2 nanosheets from graphene oxide templates for high performance pseudosupercapacitors , 2012 .

[13]  Hui Dou,et al.  Polypyrrole/carbon nanotube nanocomposite enhanced the electrochemical capacitance of flexible graphene film for supercapacitors , 2012 .

[14]  W. S. Hummers,et al.  Preparation of Graphitic Oxide , 1958 .

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

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

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

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

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

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

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

[23]  Xu Xiao,et al.  Paper-based supercapacitors for self-powered nanosystems. , 2012, Angewandte Chemie.

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

[25]  B. Conway Transition from “Supercapacitor” to “Battery” Behavior in Electrochemical Energy Storage , 1991 .

[26]  Seshu B. Desu,et al.  Pulse polymerized polypyrrole electrodes for high energy density electrochemical supercapacitor , 2006 .

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

[28]  Meryl D. Stoller,et al.  Review of Best Practice Methods for Determining an Electrode Material's Performance for Ultracapacitors , 2010 .

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

[30]  D. Bélanger,et al.  Nanostructured transition metal oxides for aqueous hybrid electrochemical supercapacitors , 2006 .

[31]  A. Hollenkamp,et al.  Carbon properties and their role in supercapacitors , 2006 .

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

[33]  Quan-hong Yang,et al.  A honeycomb-like porous carbon derived from pomelo peel for use in high-performance supercapacitors. , 2014, Nanoscale.

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

[35]  Songtao Lu,et al.  Flexible asymmetric supercapacitors with high energy and high power density in aqueous electrolytes. , 2013, Nanoscale.

[36]  Y. Gogotsi,et al.  True Performance Metrics in Electrochemical Energy Storage , 2011, Science.

[37]  Ning Pan,et al.  Supercapacitors using carbon nanotubes films by electrophoretic deposition , 2006 .

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

[39]  Po-Chiang Chen,et al.  Inkjet printing of single-walled carbon nanotube/RuO2 nanowire supercapacitors on cloth fabrics and flexible substrates , 2010 .

[40]  Chan‐Jin Park,et al.  Electrochemical characteristics of two-dimensional nano-structured MnO2 for symmetric supercapacitor , 2013 .

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

[42]  Teng Zhai,et al.  High energy density asymmetric quasi-solid-state supercapacitor based on porous vanadium nitride nanowire anode. , 2013, Nano letters.

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

[44]  Yu Huang,et al.  Flexible solid-state supercapacitors based on three-dimensional graphene hydrogel films. , 2013, ACS nano.

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

[46]  Zhenxing Zhang,et al.  Freestanding three-dimensional graphene/MnO2 composite networks as ultralight and flexible supercapacitor electrodes. , 2013, ACS nano.

[47]  D. He,et al.  Hydrothermal Self-assembly of Manganese Dioxide/Manganese Carbonate/Reduced Graphene Oxide Aerogel for Asymmetric Supercapacitors , 2015 .

[48]  Xu Xiao,et al.  WO3−x/MoO3−x Core/Shell Nanowires on Carbon Fabric as an Anode for All‐Solid‐State Asymmetric Supercapacitors , 2012 .

[49]  Lifeng Yan,et al.  Chemical Reduction of Graphene Oxide to Graphene by Sulfur-Containing Compounds , 2010 .

[50]  Pooi See Lee,et al.  Dodecyl sulfate-induced fast faradic process in nickel cobalt oxide–reduced graphite oxide composite material and its application for asymmetric supercapacitor device , 2012 .