A simple and controllable nanostructure comprising non-conductive poly(vinylidene fluoride) and graphene nanosheets for supercapacitor

doi:10.1007/s11706-012-0163-7

Front Mater Sci

2012, Vol. 6

Issue (2) : 149-159 https://doi.org/10.1007/s11706-012-0163-7

RESEARCH ARTICLE

A simple and controllable nanostructure comprising non-conductive poly(vinylidene fluoride) and graphene nanosheets for supercapacitor

Jing SUN¹, Ling-Hao HE¹, Qiao-Ling ZHAO², Li-Fang CAI¹, Rui SONG^1,3(

), Yong-Mei HAO³, Zhi MA², Wei HUANG⁴

1. Key Lab of Surface and Interface Sciences of Henan Provincial, Zhengzhou University of Light Industry, Zhengzhou 450002, China; 2. Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China; 3. College of Chemistry and Chemical Engineering, Graduate University of Chinese Academy of Sciences, Beijing 100049, China; 4. Laboratory of Advanced Polymer Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China

Download: PDF(868 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

An?effective?method?was?used?to produce stable and homogeneous colloidal suspensions of highly reduced graphene oxide (RGO) in N,N-dimethylformamide (DMF) without the assistance of dispersing agents. According to the results of general characterization, relatively pure graphene sheets with the morphology of single layer or few-layer structure were obtained. Then nanocomposite powders of RGO and poly(vinylidene fluoride) (PVDF) were prepared by vacuum filtration of the mixed dispersions of both components. The nanocomposites exhibit a high-frequency capacitative response with small equivalent series resistance (ESR) at 0.4 Ω, a nearly rectangular cyclic voltammogram and possess a rapid current response as electrodes for supercapacitor in 5 mol/L KOH electrolyte. Furthermore, after 600 galvanostatic charge/discharge cycles, the supercapacitor still performs a very high stability and efficiency of capacitance.

Keywords reduced graphene oxide (RGO) poly(vinylidene fluoride) (PVDF) nanocomposite supercapacitor

Corresponding Author(s): SONG Rui,Email:rsong@gucas.ac.cn

Issue Date: 05 June 2012

Cite this article:

Jing SUN,Ling-Hao HE,Qiao-Ling ZHAO, et al. A simple and controllable nanostructure comprising non-conductive poly(vinylidene fluoride) and graphene nanosheets for supercapacitor[J]. Front Mater Sci, 2012, 6(2): 149-159.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-012-0163-7
https://academic.hep.com.cn/foms/EN/Y2012/V6/I2/149

Fig.1 Schematic diagrams of the fabrication of homogeneous colloidal suspensions of RGO sheets and PG nanocomposites. Optical photographs of GO/HO/DMF (left), and RGO/HO/DMF before (middle)/after (right) sonication. TEM image of PG composites. Optical photographs of PG-0.11% (left), PG-0.037% (middle) and PVDF (right) in DMF.

Fig.2 FTIR spectra of GO and RGO, the insets show the high-resolution XPS C 1s spectra. XPS images of GO and RGO, the inset of (d) shows the high-resolution XPS N 1s spectrum.

Fig.3 Raman spectra and XRD patterns of GO and RGO powders obtained by filtration from their suspensions, the inset of (b) shows the XRD pattern of graphite.

Fig.4 TEM images of GO, RGO (the insert shows the SAED pattern), and PG-0.11%. The model of PVDF chains absorbed on the RGO sheet. SEM images of PVDF, PG-0.037%, and PG-0.11%, the insets show their optical photographs.

Fig.5 XRD patterns and FTIR spectra of PG nanocomposites used for electrode materials.

Fig.6 Schematic illustration of a supercapacitor cell.

Fig.7 Supercapacitor performances: CV curves at the scan rate of 0.1 V/s; specific capacitance as a function of scan rate of PG nanocomposites; CV curves of PG-0.11% at different scan rates; frequency response analysis in 5 mol/L KOH electrolyte (the inset shows the magnified view in the high frequency range).

Fig.8 Galvanostatic charge/discharge cycling curves of neat PVDF and PG nanocomposite electrodes at the current density of 0.03 A/g. Cyclic stability of supercapacitor device with PG-0.11% nanocomposite electrode in 5 mol/L KOH electrolyte at different current densities, the inset shows its first 2 charge/discharge cycles.

Tab.1 The specific capacitances of PVDF and PG nanocomposites at different current loadings based on discharge branch in 5 mol/L KOH electrolyte

1	Pandolfo A G, Hollenkamp A F. Carbon properties and their role in supercapacitors. Journal of Power Sources , 2006, 157(1): 11-27
2	Miller J R, Simon P. Electrochemical capacitors for energy management. Science , 2008, 321(5889): 651-652
3	Wang Y, Shi Z Q, Huang Y, . Supercapacitor devices based on graphene materials. The Journal of Physical Chemistry C , 2009, 113(30): 13103-13107
4	Stoller M D, Park S J, Zhu Y W, . Graphene-based ultracapacitors. Nano Letters , 2008, 8(10): 3498-3502
5	Si Y C, Samulski E T. Exfoliated graphene separated by platinum nanoparticles. Chemistry of Materials , 2008, 20(21): 6792-6797
6	Yoo E J, Kim J, Hosono E, . Large reversible Li storage of graphene nanosheet families for use in rechargeable lithium ion batteries. Nano Letters , 2008, 8(8): 2277-2282
7	Xu C, Wang X, Zhu J W. Graphene - metal particle nanocomposites. The Journal of Physical Chemistry C , 2008, 112(50): 19841-19845
8	Wang D H, Kou R, Choi D, . Ternary self-assembly of ordered metal oxide-graphene nanocomposites for electrochemical energy storage. ACS Nano , 2010, 4(3): 1587-1595
9	Zhang K, Zhang L L, Zhao X S, . Graphene/polyaniline nanofiber composites as supercapacitor electrodes. Chemistry of Materials , 2010, 22(4): 1392-1401
10	Zhang D C, Zhang X, Chen Y, . Enhanced capacitance and rate capability of graphene/polypyrrole composite as electrode material for supercapacitors. Journal of Power Sources , 2011, 196(14): 5990-5996
11	Vignali M, Edwards R A H, Serantoni M, . Electropolymerized polythiophene layer extracted from the interface between two immiscible electrolyte solutions: Current–time analysis. Journal of Electroanalytical Chemistry , 2006, 591(1): 59-68
12	Jang J. Conducting polymer nanomaterials and their applications. Advances in Polymer Science , 2006, 199: 189-260
13	Zhou Y K, He B L, Zhou W J, . Preparation and electrochemistry of SWNT/PANI composite films for electrochemical capacitors. Journal of the Electrochemical Society , 2004, 151(7): A1052-A1057
14	Hu C-C, Chu C-H. Electrochemical and textural characterization of iridium-doped polyaniline films for electrochemical capacitors. Materials Chemistry and Physics , 2000, 65(3): 329-338
15	Ryu K S, Kim K M, Park N G, . Symmetric redox supercapacitor with conducting polyaniline electrodes. Journal of Power Sources , 2002, 103(2): 305-309
16	Khomenko V, Frackowiak E, Béguin F. Determination of the specific capacitance of conducting polymer/nanotubes composite electrodes using different cell configurations. Electrochimica Acta , 2005, 50(12): 2499-2506
17	Li L X, Song H H, Zhang Q C, . Effect of compounding process on the structure and electrochemical properties of ordered mesoporous carbon/polyaniline composites as electrodes for supercapacitors. Power Source , 2009, 187(1): 268-274
18	Benz M, Euler W B, Gregory O J. The role of solution phase water on the deposition of thin films of poly(vinylidene fluoride). Macromolecules , 2002, 35(7): 2682-2688
19	Lin D-J, Chang H-H, Beltsios K, . Effect of postcasting heat-treatment on the structure and properties of semicrystalline phase-inversion poly(vinylidene fluoride) membranes. Journal of Polymer Science Part B: Polymer Physics , 2009, 47(19): 1880-1893
20	Hummers W S Jr, Offeman R E. Preparation of graphitic oxide. Journal of the American Chemical Society , 1958, 80(6): 1339
21	Park S J, An J, Jung I, . Colloidal suspensions of highly reduced graphene oxide in a wide variety of organic solvents. Nano Letters , 2009, 9(4): 1593-1597
22	Conway B E. Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications. New York: Kluwer Academic/Plenum Press, 1999
23	Titelman G I, Gelman V, Bron S, . Characteristics and microstructure of aqueous colloidal dispersions of graphite oxide. Carbon , 2005, 43(3): 641-649
24	Wu Z S, Ren W C, Gao L B, . Synthesis of high-quality graphene with a pre-determined number of layers. Carbon , 2009, 47(2): 493-499
25	Stankovich S, Dikin D A, Piner R D, . Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon , 2007, 45(7): 1558-1565
26	Becerril H A, Mao J, Liu Z, . Evaluation of solution-processed reduced graphene oxide films as transparent conductors. ACS Nano , 2008, 2(3): 463-470
27	Wang H L, Robinson J T, Li X L, . Solvothermal reduction of chemically exfoliated graphene sheets. Journal of the American Chemical Society , 2009, 131(29): 9910-9911
28	Sun Z Z, Yan Z, Yao J, . Growth of graphene from solid carbon sources. Nature , 2010, 468(7323): 549-552
29	Wang C, Li D, Too C O, . Electrochemical properties of graphene paper electrodes used in lithium batteries. Chemistry of Materials , 2009, 21(13): 2604-2606
30	Liao K H, Mittal A, Bose S, . Aqueous only route toward graphene from graphite oxide. ACS Nano , 2011, 5(2): 1253-1258
31	Chen S, Zhu J W, Wu X D, . Graphene oxide–MnO₂ nanocomposites for supercapacitors. ACS Nano , 2010, 4(5): 2822-2830
32	Zhang J, Lee J-K, Wu Y, . Photoluminescence and electronic interaction of anthracene derivatives adsorbed on sidewalls of single-walled carbon nanotubes. Nano Letters , 2003, 3(3): 403-407
33	Byl O, Kondratyuk P, Forth S T, . Adsorption of CF₄ on the internal and external surfaces of opened single-walled carbon nanotubes: a vibrational spectroscopy study. Journal of the American Chemical Society , 2003, 125(19): 5889-5896
34	Li H P, Zhou B, Lin Y, . Selective interactions of porphyrins with semiconducting single-walled carbon nanotubes. Journal of the American Chemical Society , 2004, 126(4): 1014-1015
35	Zhao J J, Lu J P, Han J, . Noncovalent functionalization of carbon nanotubes by aromatic organic molecules. Applied Physics Letters , 2003, 82(21): 3746-3748
36	Guo C X, Li C M. A self-assembled hierarchical nanostructure comprising carbon spheres and graphene nanosheets for enhanced supercapacitor performance. Energy & Environmental Science , 2011, 4(11): 4504-4507
37	Guo C X, Yang H B, Sheng Z M, . Layered graphene/quantum dots for photovoltaic devices. Angewandte Chemie International Edition , 2010, 49(17): 3014-3017
38	Gregorio R Jr. Determination of the α, β, and γ crystalline phases of poly(vinylidene fluoride) films prepared at different conditions. Journal of Applied Polymer Science , 2006, 100(4): 3272-3279
39	Conway B E, Pell W G. Double-layer and pseudocapacitance types of electrochemical capacitors and their applications to the development of hybrid devices. Journal of Solid State Electrochemistry , 2003, 7(9): 637-644
40	Simon P, Gogotsi Y. Materials for electrochemical capacitors. Nature Materials , 2008, 7(11): 845-854
41	Li F H, Song J F, Yang H F, . One-step synthesis of graphene/SnO₂ nanocomposites and its application in electrochemical supercapacitors. Nanotechnology , 2009, 20(45): 455602 (6 pages)
42	Sugimoto W, Iwata H, Yokoshima K, . Proton and electron conductivity in hydrous ruthenium oxides evaluated by electrochemical impedance spectroscopy: the origin of large capacitance. The Journal of Physical Chemistry B , 2005, 109(15): 7330-7338
43	Park S, An J, Piner R D, . Aqueous suspension and characterization of chemically modified graphene sheets. Chemistry of Materials , 2008, 20(21): 6592-6594
44	Zhang K, Mao L, Zhang L L, . Surfactant-intercalated, chemically reduced graphene oxide for high performance supercapacitor electrodes. Journal of Materials Chemistry , 2011, 21(20): 7302-7307
45	Biswas S, Drzal L T. Multilayered nano-architecture of variable sized graphene nanosheets for enhanced supercapacitor electrode performance. ACS Applied Materials & Interfaces , 2010, 2(8): 2293-2300

[1]	Dandan HAN, Jinhe WEI, Shanshan WANG, Yifan PAN, Junli XUE, Yen WEI. Feather-like NiCo₂O₄ self-assemble from porous nanowires as binder-free electrodes for low charge transfer resistance[J]. Front. Mater. Sci., 2020, 14(4): 450-458.
[2]	Yun ZHAO, Linan YANG, Canliang MA. One-step gas-phase construction of carbon-coated Fe₃O₄ nanoparticle/carbon nanotube composite with enhanced electrochemical energy storage[J]. Front. Mater. Sci., 2020, 14(2): 145-154.
[3]	Meenaketan SETHI, U. Sandhya SHENOY, Selvakumar MUTHU, D. Krishna BHAT. Facile solvothermal synthesis of NiFe₂O₄ nanoparticles for high-performance supercapacitor applications[J]. Front. Mater. Sci., 2020, 14(2): 120-132.
[4]	Danhua ZHU, Qianjie ZHOU, Aiqin LIANG, Weiqiang ZHOU, Yanan CHANG, Danqin LI, Jing WU, Guo YE, Jingkun XU, Yong REN. Two-step preparation of carbon nanotubes/RuO₂/polyindole ternary nanocomposites and their application as high-performance supercapacitors[J]. Front. Mater. Sci., 2020, 14(2): 109-119.
[5]	Yanlin JIA, Zhiyuan MA, Zhicheng LI, Zhenli HE, Junming SHAO, Hong ZHANG. Electrochemical performances of NiO/Ni₂N nanocomposite thin film as anode material for lithium ion batteries[J]. Front. Mater. Sci., 2019, 13(4): 367-374.
[6]	Liuxin YANG, Zhou CHEN, Jian ZHANG, Chang-An WANG. SrTiO₃/TiO₂ heterostructure nanowires with enhanced electron--hole separation for efficient photocatalytic activity[J]. Front. Mater. Sci., 2019, 13(4): 342-351.
[7]	Chengzhi LUO, Guanghui LIU, Min ZHANG. Electric-field-induced microstructure modulation of carbon nanotubes for high-performance supercapacitors[J]. Front. Mater. Sci., 2019, 13(3): 270-276.
[8]	Bin CAI, Changxiang SHAO, Liangti QU, Yuning MENG, Lin JIN. Preparation of sulfur-doped graphene fibers and their application in flexible fibriform micro-supercapacitors[J]. Front. Mater. Sci., 2019, 13(2): 145-155.
[9]	Meng LIU, Lei LIU, Yifeng YU, Haijun LV, Aibing CHEN, Senlin HOU. Synthesis of nitrogen-doped carbon spheres using the modified Stöber method for supercapacitors[J]. Front. Mater. Sci., 2019, 13(2): 156-164.
[10]	Haiyan LI, Yucheng ZHAO, Chang-An WANG. MoS₂/CoS₂ composites composed of CoS₂ octahedrons and MoS₂ nano-flowers for supercapacitor electrode materials[J]. Front. Mater. Sci., 2018, 12(4): 354-360.
[11]	Wei LI, Lizhong ZHAO, Zhongwu LIU. Micromagnetic simulation on magnetic properties of Nd₂Fe₁₄B/α-Fe nanocomposites with Fe nanowires as the soft phase[J]. Front. Mater. Sci., 2018, 12(4): 348-353.
[12]	M. Mohamed Jaffer SADIQ, U. Sandhya SHENOY, D. Krishna BHAT. Synthesis of BaWO₄/NRGO‒g-C₃N₄ nanocomposites with excellent multifunctional catalytic performance via microwave approach[J]. Front. Mater. Sci., 2018, 12(3): 247-263.
[13]	Wang YANG, Wu YANG, Lina KONG, Shuanlong DI, Xiujuan QIN. Nitrogen--oxygen co-doped corrugation-like porous carbon for high performance supercapacitor[J]. Front. Mater. Sci., 2018, 12(3): 283-291.
[14]	Ke ZHAN, Tong YIN, Yuan XUE, Yinwen TAN, Yihao ZHOU, Ya YAN, Bin ZHAO. A two-step approach to synthesis of Co(OH)₂/γ-NiOOH/reduced graphene oxide nanocomposite for high performance supercapacitors[J]. Front. Mater. Sci., 2018, 12(3): 273-282.
[15]	Jiangli XUE, Maosong MO, Zhuming LIU, Dapeng YE, Zhihua CHENG, Tong XU, Liangti QU. A general synthesis strategy for the multifunctional 3D polypyrrole foam of thin 2D nanosheets[J]. Front. Mater. Sci., 2018, 12(2): 105-117.

Viewed

Full text

Abstract

Cited

Shared

Discussed