δ-MnO2/holey graphene hybrid fiber for all-solid-state supercapacitor

δ-MnO2/holey reduced graphene oxide (HRGO) fiber electrodes with good flexibility and enhanced electrochemical performance were prepared by depositing δ-MnO2 on the surface of the holey reduced graphene oxide fibers. HRGO-650 was obtained by soaking graphene oxide in a 0.5 M H3PO4 solution for 12 h followed by calcining it at 650 °C for 2 h in N2. The loose curling manganese oxide nanosheets are reassembled on the surface of the HRGO-650 fiber freely, causing the close contact between the manganese oxide nanosheets and the graphene nanosheets. The prepared δ-MnO2(4.0)/HRGO fiber electrode shows a larger specific capacitance (245 F g−1) at a current density of 1 A g−1 in the 1 M Na2SO4 electrolyte. An all-solid-state fiber supercapacitor was assembled by two intertwined δ-MnO2(4.0)/HRGO fiber electrodes, both of which are solidified in a H3PO4–polyvinyl alcohol (PVA) gel electrolyte. This all-solid-state δ-MnO2(4.0)/HRGO fiber supercapacitor not only shows good flexibility, but also gives enhanced capacitive performance. The optimal all-solid-state δ-MnO2(4.0)/HRGO fiber supercapacitor obtains a high area-specific capacitance (16.3–16.7 mF cm−2) at a current density of 0.05 mA cm−2, enhanced rate capability (64% capacitance retention from 0.05–0.6 mA cm−2), and relative good stability (80% of initial capacitance values after 1000 cycles). This method is expected to improve the conductivity and capacitance for all-solid-state carbon-based fiber supercapacitor with good flexibility and light weight.

[1]  Hua Bai,et al.  Size fractionation of graphene oxide sheets by pH-assisted selective sedimentation. , 2011, Journal of the American Chemical Society.

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

[3]  L. Qu,et al.  All‐Graphene Core‐Sheath Microfibers for All‐Solid‐State, Stretchable Fibriform Supercapacitors and Wearable Electronic Textiles , 2013, Advanced materials.

[4]  Xiaomiao Feng,et al.  The synthesis of shape-controlled MnO2/graphene composites via a facile one-step hydrothermal method and their application in supercapacitors , 2013 .

[5]  Shing‐Jong Huang,et al.  Supplementary Information for , 2013 .

[6]  Andreas Winter,et al.  Three‐Dimensional Nitrogen and Boron Co‐doped Graphene for High‐Performance All‐Solid‐State Supercapacitors , 2012, Advanced materials.

[7]  Z. Lei,et al.  Creation of nanopores on graphene planes with MgO template for preparing high-performance supercapacitor electrodes. , 2014, Nanoscale.

[8]  Konstantin Konstantinov,et al.  High-performance multifunctional graphene yarns: toward wearable all-carbon energy storage textiles. , 2014, ACS nano.

[9]  Zhong Lin Wang,et al.  Fiber supercapacitors made of nanowire-fiber hybrid structures for wearable/flexible energy storage. , 2011, Angewandte Chemie.

[10]  Jinqing Wang,et al.  Synthesis of hydrothermally reduced graphene/MnO2 composites and their electrochemical properties as supercapacitors , 2011 .

[11]  Yanwen Ma,et al.  Conductive graphene fibers for wire-shaped supercapacitors strengthened by unfunctionalized few-walled carbon nanotubes. , 2015, ACS nano.

[12]  Ping Wang,et al.  Wet-spinning assembly of continuous, neat, and macroscopic graphene fibers , 2012, Scientific Reports.

[13]  Yuanyuan Shang,et al.  Macroscopic, flexible, high-performance graphene ribbons. , 2013, ACS nano.

[14]  Chao Gao,et al.  Ultrastrong Fibers Assembled from Giant Graphene Oxide Sheets , 2013, Advanced materials.

[15]  G. Barbastathis,et al.  Origami fabrication of nanostructured, three-dimensional devices: Electrochemical capacitors with carbon electrodes , 2006 .

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

[17]  Lan Jiang,et al.  Facile Fabrication of Light, Flexible and Multifunctional Graphene Fibers , 2012, Advanced materials.

[18]  G. Shi,et al.  A high-performance flexible fibre-shaped electrochemical capacitor based on electrochemically reduced graphene oxide. , 2013, Chemical communications.

[19]  B. Popov,et al.  Electrochemical synthesis of birnessite-type layered manganese oxides for rechargeable lithium batteries , 2008 .

[20]  Huisheng Peng,et al.  Elastic and wearable wire-shaped lithium-ion battery with high electrochemical performance. , 2014, Angewandte Chemie.

[21]  Jun Chen,et al.  Highly Compressible and All‐Solid‐State Supercapacitors Based on Nanostructured Composite Sponge , 2015, Advanced materials.

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

[23]  Hao Sun,et al.  Novel Graphene/Carbon Nanotube Composite Fibers for Efficient Wire‐Shaped Miniature Energy Devices , 2014, Advanced materials.

[24]  Zhe Yan,et al.  Mesoporous-assembled MnO2 with large specific surface area , 2015 .

[25]  Yu Huang,et al.  Holey graphene frameworks for highly efficient capacitive energy storage , 2014, Nature Communications.

[26]  Huisheng Peng,et al.  Flexible and stretchable lithium-ion batteries and supercapacitors based on electrically conducting carbon nanotube fiber springs. , 2014, Angewandte Chemie.

[27]  Li Lu,et al.  Hydrothermal synthesis of MnO2/CNT nanocomposite with a CNT core/porous MnO2 sheath hierarchy architecture for supercapacitors , 2012, Nanoscale Research Letters.

[28]  Huisheng Peng,et al.  Superelastic Supercapacitors with High Performances during Stretching , 2015, Advanced materials.

[29]  Lili Zhang,et al.  Graphene-based materials as supercapacitor electrodes , 2010 .

[30]  L. Qu,et al.  MnO 2 -modified hierarchical graphene fiber electrochemical supercapacitor , 2014 .

[31]  Yanjie Hu,et al.  Nanostructured Ternary Nanocomposite of rGO/CNTs/MnO2 for High-Rate Supercapacitors , 2014 .

[32]  Xiaoyan Yang,et al.  Synthesis of a graphene/polyaniline/MCM-41 nanocomposite and its application as a supercapacitor , 2013 .

[33]  P. Cheng,et al.  Activation of graphene aerogel with phosphoric acid for enhanced electrocapacitive performance , 2015 .

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

[35]  Zhe Yan,et al.  High performance graphene/manganese oxide hybrid electrode with flexible holey structure , 2014 .

[36]  Xuemei Sun,et al.  Electrochromic Fiber‐Shaped Supercapacitors , 2014, Advanced materials.

[37]  Peng Zhang,et al.  Facile synthesis of nitrogen-doped graphene-ultrathin MnO2 sheet composites and their electrochemical performances. , 2013, ACS applied materials & interfaces.

[38]  Huisheng Peng,et al.  Aligned carbon nanotube/polymer composite films with robust flexibility, high transparency, and excellent conductivity. , 2008, Journal of the American Chemical Society.

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

[40]  Seong Chu Lim,et al.  Supercapacitors Using Single‐Walled Carbon Nanotube Electrodes , 2001 .

[41]  Minbaek Lee,et al.  Single‐Fiber‐Based Hybridization of Energy Converters and Storage Units Using Graphene as Electrodes , 2011, Advanced materials.

[42]  Chao Gao,et al.  Flexible high performance wet-spun graphene fiber supercapacitors , 2013 .

[43]  R. Ma,et al.  Synthesis and exfoliation of Co2+-Fe3+ layered double hydroxides: an innovative topochemical approach. , 2007, Journal of the American Chemical Society.

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

[45]  Qingming Shen,et al.  The self-assembly of shape controlled functionalized graphene–MnO2 composites for application as supercapacitors , 2014 .

[46]  F. Kang,et al.  Directly drawing self-assembled, porous, and monolithic graphene fiber from chemical vapor deposition grown graphene film and its electrochemical properties. , 2011, Langmuir : the ACS journal of surfaces and colloids.