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DOI: 10.1039/C5CC03981A

Graphene Quantum Dots doped Polyaniline Nanofiber as High Performance Supercapacitor Electrode Materials

Published on 04 June 2015. Downloaded by North Dakota State University on 04/06/2015 16:38:21.

Cite this: DOI: 10.1039/x0xx00000x

Sanjoy Mondal, Utpal Rana and Sudip Malik* Received 00th January 2012, Accepted 00th January 2012 DOI: 10.1039/x0xx00000x www.rsc.org/

Graphene quantum dot-doped polyaniline composites have been prepared by the chemical oxidation of aniline. Synthesized novel fibrous composites are showing excellent specific capacitance value ~1044 F/g at current density of 1 A/g as well as moderate cyclic stability with retention of life time 80.1% after 3000 cycles. Supercapacitors or electrochemical capacitors have received great attention in recent years due to strong demand in lightweight and flexible portable energy storage devices.1-5 Supercapacitors are quite different from traditional capacitors. They combine the advantages of dielectric capacitor and rechargeable batteries to get high power density, long durability, fast charge-discharge rate and operational safety. A good supercapacitor material should exhibit the high power density, long cycle life, fast charge/discharge capability. During last decade, different materials like metal oxide,6 carbon materials (CNT or graphene),7, 8 conducting polymers,9 composite materials10 are reported as supercapacitor electrode materials. Among different conducting polymers, polyaniline (PANI) is the most important and popular polymer due to easy synthesis, low cost of starting or raw materials, good environmental and thermal stability, multi-redox state and high range electrical conductivity etc.11 Because of these advantages, bulk PANI are also applied in supercapacitor electrode substances.9, 10, 12, 13, 14 Recent developments of facile as well as effective method of synthesis of PANI nanotube with high aspect ratio and increased surface area have generated tremendous interest as capacitors. Owing to the exciting properties such as high electrical conductivity, high surface area, tunable photoluminescence and excellent dispersion in various solvent, graphene quantum dots (GQDs) have emerged as promising material for energy storage devices, bioimaging devices and

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fuel cells.15 Excellent properties of GQDs and the advantages of PANI have received more attention for preparation of high performance supercapacitor electrode materials.8b-c,16 Recently, there are some reports of supercapacitor based on polyaniline nanostructure made either by electro-spinning17 or by electro chemical deposition of PANI on ZnO template.18 In this context, our aim is to prepare of high performance supercapacitor electrode materials exploiting the possible synergy of GQD and PANI.

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GQDs were prepared from graphene oxide according to reported procedure.19 Synthesized GQDs were unambiguously characterized with the help of available techniques. In UV-vis study (Fig.S1), peak at 198 nm was for - * transition of C=C within the GQD structure. The fluorescence emission peaks of the GQDs showed the bathochromic shift with increasing the excitation wavelength and maximum fluorescence intensity was observed at excited wavelength 420 nm (Fig.1a).19 Water-dispersed GQDs solution produced sky-blue fluorescence (inset image of Fig.1a) under UV lamp (365 nm). Dynamic light scattering study provided the narrow lateral size distribution of GQDs ranging from 4.0~8.0 nm (Fig.1b). AFM (Fig.1c) and TEM images (Fig.1d) exhibited homogenous GQDs having size ~6.0 nm and the narrow height distribution from 0.6 to 3.1 nm (1.4 nm

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All GQDP composites reveal one dimensional (1D) nanofibers of different diameters and several micrometers in length, except GQDP0 View Article Online and GQDP20 (Fig.2). The diameter of the PANI nanofibers increases DOI: 10.1039/C5CC03981A with the increase of wt% GQD from GQDP5 to GQDP10 and it decreases from GQDP15 to GQDP20 (Table 1). In case of GQDP20 agglomerated structures are formed and homogeneous polymerization does not possibly take place at higher concentration of GQDs. Interestingly, high aspect ratio nanofibers with uniform diameter are observed for GQDP10. Nanofibers with rougher surfaces are formed in all cases and it will enhance the accessible surface area and speed up the ion diffusion process, indicating the suitability of GQDP as supercapacitor electrode materials. In the HRTEM image (Fig.3), all composites show fibrous like morphology with different aspect ratio depending on GQD to aniline w/w ratio. In GQDP20 composite, small or damaged fibers are formed. A closer look at the HRTEM images of GQDPs (inset image of Fig.3)

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The calculated specific capacitance value of GQDP0, GQDP5, GQDP10, GQDP15 and GQDP20 composites are 206, 333, 1044, 776 and 319 F/g respectively. The maximum specific capacitance (1044 F/g) is achieved

Table 1: Diameter and specific capacitance of GQDP composites Composites

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for GQDP10 composite because higher surface area in nanotube morphology provides better conductive paths for fast electron transport. All GCD curves show typical nonlinear behaviour that confirms pseudo-capacitive nature.28 The specific capacitance value decreases with increasing current density (Fig.5c-d). The specific capacitance of GQDP10 observed at the current density 1, 2, 3,5 and 10 A/g are 1044, 802, 752 and 635 F/g, respectively. Maximum energy density (E) and power density (P) estimated for GQDP10 composite are 117.45 Wh /kg and 448.8 W/ kg, respectively. The cyclic stability is also an imperative parameter from the application point of view. Long term cyclic life stability has been tested

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In conclusion, we have successfully synthesized ~6.0 nm size graphene quantum dots from graphene oxide flakes. Synthesized GQDP composites are nanofibrous or nanotube in nature. The inner diameter of GQDP nanotubes varies with the ratio (w/w) of GQD to aniline. Synthesized GQDP composite shows highest specific capacitance value ~1044 F/g at current density 1 A/g with 80.1% retention of capacitance property after 3000 cycles.

Notes and references 1 2 3 4 5 6 7

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M. D. Stoller, S. Park, Y. Zhu, J. An and R. S. Ruoff, Nano Lett, 2008, 8, 3498. M. Winter and R. J. Brodd, Chem. Rev., 2004, 104, 4245. C. Liu, F. Li, L. P. Ma and H. M. Cheng, Adv Mater, 2010, 22, E28. X. Huang, X. Qi, F. Boey and H. Zhang, Chem. Soc. Rev., 2012, 41, 666. H. P. Cong, X. C. Ren, P. Wang and S. H. Yu, Energy Environ. Sci., 2013, 6, 1185. J. Jiang , Y. Li, J. Liu, X. Huang, C. Yuan and X. W. Lou, Adv. Mater., 2012, 24, 5166. (a) L. L. Zhang and X. S. Zhao, Chem. Soc. Rev., 2009, 38, 2520; (b) M. Kaempgen, C. K. Chan, J. Ma, Y. Cui and G. Gruner, Nano Lett., 2009, 9, 1872. (a) D. N. Futaba, K. Hata, T. Yamada, T. Hiraoka1, Y. Hayamizu, Y. Kakudate, O. Tanaike, H. Hatori, M. Yumura and S. Iijima, Nature Materials, 2006, 5, 987; (b) X. Zang, X. Li, M. Zhu, X. Li, Z. Zhen, Y. He, K. Wang, J. Wei, F. Kang and H. Zhu, Nanoscale, 2015, 7, 7318; (c) X. Zang, M. Zhu, X. Li, X. Li, Z. Zhen, J. Lao, K. Wang, F. Kang, B. Wei, H. Zhu, Nano Energy, 2015, 15, 83. (a) Y. Miao, W. Fan, D. Chen, and T. Liu, ACS Appl. Mater. Interfaces, 2013, 5, 4423; (b) X. Li, L. Yang, Y. Lei, L. Gu and D. Xiao, ACS Appl. Mater. Interfaces, 2014, 6, 19978.

10 (a) L. Wang, X. Lu, S. Lei and Y. Song, J. Mater. Chem. A, 2014, 2, 4491; (b) Q. Zhou, Y. Li, L. Huang, C. Li and G. Shi, J. Mater. View Article Online Chem. A, 2014, 2, 17489. DOI: 10.1039/C5CC03981A 11 (a) U. Rana and S. Malik, Chem. Commun., 2012, 48, 10862, (b) U. Rana, K. Chakrabarti and S. Malik, J. Mater. Chem., 2012, 22, 15665; (c) S. Mondal, U. Rana, and S. Malik, ACS Appl. Mater. Interfaces, 2015, 7, 10457. 12 (a) S. H. Domingues, R. V. Salvatierra, M. M. Oliveira and A. J. G. Zarbin, Chem. Commun., 2011, 47, 2592; (b) X. Yan, Z. Tai, J. Chen and Q. Xue, Nanoscale, 2011, 3, 212. 13 W. Chen, R. B. Rakhi and H. N. Alshareef, Nanoscale, 2013, 5, 4134. 14 Z. Lei, Z. Chen and X. S. Zhao, J. Phys. Chem. C, 2010, 114, 19867. 15 M. Bacon, S. J. Bradley and T. Nann, Part. Part. Syst. Charact, 2014, 31, 415. 16 W. Liu, X. Yan, J. Chen Y. Feng and Q. Xue, Nanoscale, 2013, 5, 6053. 17 Y. E. Miao, W. Fan, D. Chen and T. Liu, ACS Appl. Mater. Interfaces, 2013, 5, 4423. 18 Z. L. Wang, R. Guo, G. R. Li, H. L. Lu, Z. Q. Liu, F. M. Xiao and M. Zhang, Y. X. Tong, J. Mater. Chem., 2012, 22, 2401. 19 F. Jiang, D. Chen, R. Li, Y. Wang, G. Zhang, S. Li, J. Zheng, N. Huang, Y. Gu, C. Wang and C. Shu, Nanoscale, 2013, 5, 1137. 20 B. A. Deore, I. Yu and M. S. Freund, J. Am. Chem. Soc., 2004, 126, 52. 21 K. Lee, S. Cho, S. H. Park, A. J. Heeger, C. W. Lee and S. H. Lee, Nature, 2006, 441, 65. 22 N. Wu, X. She, D. Yang, X. Wu, F. Su and Y. Chen, J. Mater. Chem., 2012, 22, 17254. 23 G. Wang, X. Shen, B. Wang, J. Yao and J. Park, Carbon, 2009, 47, 1359. 24 L. Shi, R. Liang and J. Qiu, J. Mater. Chem., 2012, 22, 17196. 25 H. Wang, Q. Hao, X. Yang, L. Lu and X. Wang, Nanoscale, 2010, 2, 2164. 26 D. Ghosh, S. Giri and C. K. Das, Nanoscale, 2013, 5, 10428. 27 X. Yan, Z. Tai, J. Chen and Q. Xue, Nanoscale, 2011, 3, 212. 28 X. Ma, Y. Li, Z. Wen, F. Gao, C. Liang and R. Che, ACS Appl. Mater. Interfaces, 2015, 7, 974.

ChemComm Accepted Manuscript

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Potential (V)

Sp capacitance (F/g)

Published on 04 June 2015. Downloaded by North Dakota State University on 04/06/2015 16:38:21.

by 3000 continuous GCD for GQDP10 composite. After 3000th number of cycle, the 19.9% of total specific capacitance loss (i,e ~80.1% retention of specific capacitance) at current density 1 A/g in 0.5 M H2SO4 electrolyte solution (Fig.6) has been observed. This decrease of specific capacitance after 3000th cycles may be explained by the loss of active material in the current collector (due to swelling or contraction) which causes partial blockage of the regular structure.

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Graphene quantum dot-doped polyaniline nanofiber as high performance supercapacitor electrode materials.

Graphene quantum dot-doped polyaniline composites have been prepared by the chemical oxidation of aniline. Synthesized novel fibrous composites show a...
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