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Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

CN 11-5985/TB

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Front. Mater. Sci.    2019, Vol. 13 Issue (2) : 145-155    https://doi.org/10.1007/s11706-019-0455-2
RESEARCH ARTICLE
Preparation of sulfur-doped graphene fibers and their application in flexible fibriform micro-supercapacitors
Bin CAI1, Changxiang SHAO2, Liangti QU2, Yuning MENG1(), Lin JIN3()
1. School of Chemistry and Chemical Engineering, Zhoukou Normal University, Zhoukou 466001, China
2. Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Key Laboratory of Cluster Science (Ministry of Education), School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China
3. The Key Laboratory of Rare Earth Functional Materials and Applications, Zhoukou Normal University, Zhoukou 466001, China
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Abstract

A novel type of sulfur-doped graphene fibers (S-GFs) were prepared by the hydrothermal strategy, the in situ interfacial polymerization method and the annealing method. Two S-GFs were assembled into an all-solid-state fibriform micro-supercapacitor (micro-SC) that is flexible and has a high specific capacitance (4.55 mF·cm−2) with the current density of 25.47 μA·cm−2. The cyclic voltammetry (CV) curve of this micro-SC kept the rectangular shape well even when the scan rate reached 2 V·s−1. There is a great potential for this type of S-GFs used in flexible wearable electronics.
Keywords graphene fiber      sulfur doping      wearable electronics      flexible supercapacitor      micro-supercapacitor     
Corresponding Author(s): Yuning MENG,Lin JIN   
Online First Date: 11 June 2019    Issue Date: 19 June 2019
 Cite this article:   
Bin CAI,Changxiang SHAO,Liangti QU, et al. Preparation of sulfur-doped graphene fibers and their application in flexible fibriform micro-supercapacitors[J]. Front. Mater. Sci., 2019, 13(2): 145-155.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-019-0455-2
https://academic.hep.com.cn/foms/EN/Y2019/V13/I2/145
Fig.1  Schematic of the preparation of S-GFs.
Fig.2  SEM images of (a)(b)(c) an S-GF and (d)(e)(f) a pure GF at different scales.
Fig.3  (a) The EDS result of S-GFs. (b) XPS survey spectra of GFs and S-GFs. (c) The S 2p spectrum of S-GFs.
Fig.4  CV curves: (a) S-GFs and (b) pure GFs at different scan rates; (c) at the scan rate of 800 mV·s−1 for S-GFs and pure GFs. All the CV curves were got in a three-electrode system with the electrolyte of 1 mol·L−1 LiClO4 aqueous solution. The lengths of all samples were 1.2 cm.
Fig.5  Photographs of an S-GF micro-SC (a) in the straight status and (b) in the bending status with the functioning length of 1.2 cm. SEM images of (c) the fiber micro-SC and (d) its cross-section view.
Fig.6  Electrochemical characterization of a fiber micro-SC with the length of 1 cm in a two-electrode system: (a) CV curves with the scan rate ranging from 0.01 to 1 V·s−1. (b) GCD curves (current density: 25.47?890 μA·cm−2). (c) Areal specific capacitances corresponding to different current densities. (d) Cycle testing at the current density of 282 μA·cm−2 and the voltage of 1 V (the inset: GCD curves after 500 cycles).
Fig.7  (a) Photographs of the fiber micro-SCs with the active length of 1.2 cm during a straight?bending?straight cycle. (b) CV curves and (c) GCD curves of the fiber micro-SC during a straight?bending?straight cycle. (d) The stable specific capacitance during 300 straight?bending?straight cycles.
  Fig. S1 Typical stress?strain curves of a single pristine GF before and after doping with the sulfur element. The tensile stress was calculated on the basis of the diameter of the GF.
  Fig. S2(a)(b) SEM images of an S-GF. Corresponding EDS mappings of (c) the C element, (e) the O element and (f) the S element. (d) Element percents of C, O and S.
  Fig. S3 The C 1s spectrum of S-GFs.
  Fig. S4 Raman spectra of GFs and S-GFs.
  Fig. S5 CV curves of an S-GF with the length of 1.2 cm tested in a three-electrode system with the electrolyte of the 1 mol·L−1 LiClO4 aqueous solution.
  Fig. S6 Electrochemical characterization of a fiber micro-SC with the length of 1 cm in a two-electrode system: (a) CV curves with the scan rate from 0.3 to 2.0 V·s−1; (b) GCD curves at different current densities (25.47?114.64 μA·cm−2). The fiber micro-SC was assembled by intertwining two S-GFs with the PVA?H2SO4 gel electrolyte.
  Fig. S7 A Ragone plot of the S-GF fibriform micro-SC. The GCD current density is in the range of 25.47?282 μA·cm−2.
  Fig. S8(a) Photographs showing an S-GF fibriform micro-SC with the length of 1 cm at different bending angles. (b) Schematic showing how to measure the bending angle. (c)(d) GCD curves (I = 3 μA) and normalized capacitance of the supercapacitor at different bending angles corresponding to (a).
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