26August2019

Nano-Micro Letters

High Performance Solid-state Supercapacitors Fabricated by Pencil Drawing and Polypyrrole Depositing on Paper Substrate

Jiayou Tao1,2,†, Wenzhen Ma1,†, Nishuang Liu1, Xiaoliang Ren1,

Yuling Shi1, Jun Su1, Yihua Gao1,*

Abstract|Support Info
icon-htmlFull Text Html
icon-pdf-smPDF w/ Links
icon-citExport Citation
Figures
+Show more

Nano-Micro Letters, , Volume 7, Issue 3, pp 276-281

First online: 10 Apr 2015 (Article)

DOI: 10.1007/s40820-015-0039-3

*Corresponding author. E-mail: gaoyihua@hust.edu.cn

 

Abstract

 


a Schematic of fabrication process of the PPy-G-paper. b A SEM image of the G-paper. c A cross-sectional SEM image of the G-paper. d A SEM image of PPy-G-paper. e A cross- sectional SEM image of the PPy-G-paper. f XRD of the G-paper illustrating the graphite. g Raman spectra of the G-paper and PPy-G-paper.
A solid-state powerful supercapacitor is fabricated with a substrate of Xerox paper. Its current collector based on a foldable electronic circuit is developed by simply pencil drawing. Thin graphite sheets on paper provide effective channels for electrons transmission with a low resistance of 95 Ω sq-1. The conductive organic material of polypyrrole coated on thin graphite sheets acts as the electrode material of the device. The as-fabricated supercapacitor exhibits a high specific capacitance of 52.9 F cm-3 at a scan rate of 1 mV s-1. An energy storage unit fabricated by three full charged series supercapacitors can drive a commercial light-emitting diode robustly. This work demonstrated a simple, versatile and cost-effective method for paper-based devices.

 

Keywords

Supercapacitor;Paper; Pencil drawing; Polypyrrole

 

Full Text Html

 

1 Introduction


Supercapacitors (SCs), as the promising energy storage devices, have attracted tremendous attention for a set of features, such as high power density, fast rates of charge-discharge process, long cycling life and improved safety [1-3]. Particularly, SCs can provide much higher power density than batteries and higher energy density than conventional capacitors, which bridge the gap between those two kinds of typical energy storage devices [4-6]. According to the underlying energy storage mechanism, SCs can be classified two categories [4, 5]. One is electrochemical double layer capacitors (EDLCs) which stores electrical energy by electrostatic accumulation of charges between the surfaces of the electrode materials and electrolyte [4]. Though EDLCs exhibit ultrahigh power density and distinguished long-term cycling performance, the stored energy is limited by the finite electrical charge separation at the interface between electrolyte and electrode materials [3]. The other type of SC is so-called pseudocapacitor, which stores energy due to fast and reversible redox reactions occurring on the surface or near surface of the active electrode materials. Compared to EDLCs, pseudocapacitors have high energy density but low power density and short cycle life [6].

Paper is inexpensive, foldable, environmentally benign nature and widely used in our daily life. Commonly, paper is composed of cellulose fibers with a typical diameter of about 20 μm. In recent years, paper is becoming a promising flexible substrate for various electronics, such as solar cells [7], transistors [8], displays [9], and energy storage devices [10-12]. The realization of paper-based devices is highly desired not only for their wide range of applications, but also for their compatibility with printed electronics. Aimed at low cost, environmental benign nature and wide range of applications, paper was exploited for the substrate of our SCs. Carbon materials, as the most typical electrode materials for EDLCs, have been extensively studied in the past decades due to their good conductivity, robust mechanical character, and stable electrochemical behaviour [13-17]. Amongcarbon materials, graphene has some fascinating features, such as large surface area, high flexibility, excellent conductivity and good chemical/thermal stability [18, 19]. However, high temperature and vacuum are needed during the synthesis process of graphene [20-23]. Consequently, some unfavourable issues emerge such as high cost, elaborate or difficulty in large-scale fabrication. Herein, we got inspiration from ordinary writing manners and successfully drew arbitrary shapes of current collectors for our SCs using a pencil. Multilayered graphene (thin graphite sheets) was transferred onto the paper substrates during this simple process, which provided an effective transmission path for electrons. For the sake of enhancing the electrochemical performance of the devices, polypyrrole (PPy) was deposited on the pencil drawing paper, which was also used as the pseudocapacitive material in this research. Compared to other conductive polymers, PPy has greater density and a great degree of flexibility in electrochemical process [24, 25], which result in a high volumetric capacitance and high mechanical performance. After the depositing of PPy, two PPy-thin graphite sheets-paper electrodes were assembled with a gel electrolyte of H3PO4/polyvinyl alcohol (PVA). The as-fabricated solid-state SCs exhibited good flexibility and a high specific capacitance of 52.9 F cm-3 at a scan rate of 1 mV s-1, which is much higher of some SCs than in prior literatures [26, 27]. This technique represents a low cost, applied and versatile fabrication method for paper-based energy devices.

 

2 Experiment

 

To get paper-based SCs, the Xerox paper of a certain area (1.0 cm ×1.5 cm)was drawing by 4B pencil (86 % graphite and 14 % clay) until its sheet resistance reduced to about 95 Ω sq-1 (~150 times of scratching). After that, a layer of thin graphite sheets was deposited on the paper. Then, the graphite-paper composite (the area is about 1.0 cm × 1.0 cm) was immersed in a solution that contained 0.2 cm NaClO4 and 5 % (V:V) pyrrole monomer, and PPy was grown on the drawn paper via a electrochemical deposition process. Three-electrode configuration was used in this deposition process with Ag/AgCl as the reference electrode, platinum foil as the counter electrode, and the drawn paper as the working electrode. A constant voltage of 0.8 V was applied during the process. Then the as-grown sample was washed with deionized water and dried at room temperature. In order to seek for the dependence of SC performance on PPy deposition time, the deposition time of PPy on the drawn paper was different. Finally, two pieces of 1.0 cm × 1.5 cm functionalized paper were used as electrodes with the opposite area of 1.0cm × 1.0 cm. A gel composite H3PO4/PVA was used which acted as the separator and the electrolyte between the two electrodes. After the gel electrolyte dried completely, the quasi solid-state supercapacitor was prepared.

 

3 Results and Discussions

 

The fabrication process is illustrated in Fig. 1a. Scanning electron microscopy (SEM) images of the electrode show that the drawing on paper with 4B pencil produced multilayer graphene coating on the substrate (Fig. 1b). The cross-section SEM image shows that the thickness of the graphite film is about 3.0 µm (Fig. 1c), and the graphite has coated on the paper surface tightly. Fig. 1d shows that a layer of PPy has been polymerized and wrapped on the drawing paper. There are a certain amount of micro- or nanopores on the surface, which provides larger effective area for redox reaction during charge-discharge section (Fig. S1). The thickness of the active materials (graphite and PPy) also has been measured about 5.0 µm (after 5 min electrodeposition of PPy) and they tightly attach each other (Fig. 1e). X-ray diffraction (XRD) of graphite-paper (G-paper) was also carried out (Fig. 1f). The peaks at 26.67º and 54.83º fit well with graphite (111) and (222), respectively. It further confirmed that the film made by pencil drawing mainly contained graphite. To study the functional groups information, Raman spectra of both G-paper and PPy-G-paper were shown in Fig. 1g. The Raman spectrum of G-paper exhibits two prominent peaks. In detail, the peak at 1380 cm-1 is designated as the well-documented D band owing to the disorder-induced mode from Raman scattering at the graphene edges [28], and the peak at 1618 cm-1 is attributed to the doubly degenerate in-plane E2g vibration mode. In the Raman spectrum of the PPy-G-paper, three typical peaks arised from PPy can be indexed. The peak at 1582 cm-1 is assigned to C=C back-bone stretching attributed to the G band of graphene. The peak at 1336 cm−1 corresponds to the D band of graphene. The peak at 986 cm-1 is assigned to ring vibration of PPy [29], whereas bands 1046 and 1231 cm-1 are due to C-H stretching. The Raman spectra confirmed the presence of PPy and graphite in the composite film and forming a PPy-G-paper hybrid structure.

a Schematic of fabrication process of the PPy-G-paper. b A SEM image of the G-paper. c A cross-sectional SEM image of the G-paper. d A SEM image of PPy-G-paper. e A cross- sectional SEM image of the PPy-G-paper. f XRD of the G-paper illustrating the graphite. g Raman spectra of the G-paper and PPy-G-paper.

a Schematic of fabrication process of the PPy-G-paper. b A SEM image of the G-paper. c A cross-sectional SEM image of the G-paper. d A SEM image of PPy-G-paper. e A cross- sectional SEM image of the PPy-G-paper. f XRD of the G-paper illustrating the graphite. g Raman spectra of the G-paper and PPy-G-paper.

The electric resistance of G-paper was measured at different lengths (all the width of the measured G-paper is 0.5 cm). It reveals that there is a linear correlation between the length and distance (Fig. 2a). The results indicated that thin graphitic sheets coated on paper by pencil drawing have good conductivity, which provide a stable transmission channel for electrons during charge-discharge process. For convenient portability, some paper-based applications require electronic circuits could be folded irrespectively whether the folding angle is negative or positive. We have fabricated a simple foldable circuit which could drive a light-emitting diode (LED) under negative or positive folding angles (Fig. 2b, c). The small change of circuit resistance allows the paper-based circuit board to be folded with any angles. It illustrates that the graphite on paper provides a good conductivity. After the PPy deposition, the sheet resistance substantially reduced from 95 to 21.3Ω sq-1 with the PPy deposition time increased from 0 to 10 min (Fig. 2d). Obviously, the sheet resistances decreased slightly when the deposition times increased from 5 min to 10 min. This good conductivity also can be confirmed in the following Nyquist plot.

a The resistance measurement of the G-paper (width of the stripe is 0.5 cm) at different lengths. b The application of driving a LED with the G-paper circuit. c To drive a LED by the G-paper circuit under negative and positive angle folding. d The sheet resistance of PPy-G-paper with different PPy deposition time.

a The resistance measurement of the G-paper (width of the stripe is 0.5 cm) at different lengths. b The application of driving a LED with the G-paper circuit. c To drive a LED by the G-paper circuit under negative and positive angle folding. d The sheet resistance of PPy-G-paper with different PPy deposition time.

To explore the electrochemical performance of the PPy-G-paper SCs, a typical two electrode configuration has been employed in this work. All electrochemical measurements were carried out at room temperature. We performed the cyclic voltammogram (CV) scans of the G-paper electrodes at different scan rates from 1 to 200 mV s-1 (Fig. 3a and b). The CV curve kept in a near rectangular shape even at the scan rate of 100 mV s-1, indicating that the device has good capacitive performance. The CV curves during higher power process were shown in Fig. S2. The CV of PPy-G-paper with different PPy deposition time was also measured (as shown in Fig. 3c and Fig. S3). When the deposition time increased to 5 min, the capacitances of the PPy-G-paper SCs also had increased and there was a downward trend after 5 min PPy deposition. It indicates that the device with 5 min of PPy electrodeposition has better performance than that with 2 min and 10 min. So the optimized deposition time of PPy is 5 min. Figure 3d clearly showed that the excellent CV performance at different scan rates of the PPy-G-paper SCs with 5 min of PPy electrodeposition. The device has a high specific capacitance of 52.9 F cm-3 at 1 mV s-1, which is much higher than those reported in prior literatures [26, 27]. We supposed that the high specific capacitance value should be attributed to the synergetic effect of graphite and PPy conductive wrapping layer, which improved the electrical conductivity and acted as the pseudocapacitance materials simultaneously. To further evaluate the electrochemical performance of the SCs, the galvanostatic charge/discharge (GCD) characterization was performed with different current densities over the voltage window of 0-0.8 V (in Fig. 3e and 3f). The near linear voltage versus time profiles and the near symmetrical charge/discharge characteristics represent good capacitive characteristics of both G-paper SCs and PPy-G-paper SCs. Comparing Fig. 3e with Fig. 3f, it is clear to see that the capacitance of the PPy-G-paper SC is significantly improved than that of the G-paper SC.

CV curves of a G-paper SC with scan rate from 1 to 10 mV s-1 and b from 20 to 200 mV s-1; c The devices with different PPy deposition time at scan rate of 5 mV s-1; d The PPy-G-paper SC with scan rate from 1 to 10 mV s-1. GCD behaviour of e a G-paper based SC and f a PPy-G-paper based SC at different current density.

CV curves of a G-paper SC with scan rate from 1 to 10 mV s-1 and b from 20 to 200 mV s-1; c The devices with different PPy deposition time at scan rate of 5 mV s-1; d The PPy-G-paper SC with scan rate from 1 to 10 mV s-1. GCD behaviour of e a G-paper based SC and f a PPy-G-paper based SC at different current density.

Cycling life is an important parameter to determine the performances of SCs. In order to study the electrochemical stability, the cycling performance of the as-fabricated SCs was tested. Figure 4a shows that the SC based G-paper electrodes have excellent cycling performance with over 90 % retention of capacity after 3000 cycles. For the device based on PPy-G-paper, 80.5 % of the initial capacitance was retained after 3000 cycles (the inset of Fig. 4a). Figure 4b shows the Nyquist plots in the frequency range from 100 KHz to 0.01 Hz with the potential amplitude of 10 mV. The equivalent series resistance (ESR) of the G-paper and PPy-G-paper reduces from 536.6 to 280.8 Ω. It revealed that the conductivity was improved after PPy deposition.

In order to demonstrate the flexibility of our devices, the bent state was shown in Fig. 4c. We also test the CV performance at original/bent state, as shown in Fig. 4d, the CV curves of the device just have a little influence. An example for the application of the connected SCs is shown in Fig. 4e and the inset, where three arbitrary PPy-G-paper based SCs are connected in series. They can drive a commercial LED (Fig. 4e) as an energy source when it has been full charged. We picked two SCs (devices 1 and 2) and measured their capacitances, which is 16.1 and 11.3 mF at the current density of 20 A cm-3, respectively. As shown in Fig. 4f when they are connected in series, the capacitance of the whole device is calculated to be 7.6 mF, when in parallel, it is 32.8 mF. The results reveal that the capacitance of the connected SCs roughly obeys the basic rule of series and parallel connections of capacitors. So we can take various connections of our SCs to meet a wide variety of demands in practice.

a Capacity retention ratios of a G-paper based SC (the inset is of a PPy-G-paper based SC). b The Nyquist plot of the G-paper and PPy-G-paper based SCs. c The photography picture of bending state. d CV curves of the PPy-G-paper based SC at bending state. e Optical images of the three SCs in series driving a LED. f GCD curves of single SC and two SCs connected in series or in parallel.

a Capacity retention ratios of a G-paper based SC (the inset is of a PPy-G-paper based SC). b The Nyquist plot of the G-paper and PPy-G-paper based SCs. c The photography picture of bending state. d CV curves of the PPy-G-paper based SC at bending state. e Optical images of the three SCs in series driving a LED. f GCD curves of single SC and two SCs connected in series or in parallel.

 

4 Conclusions

 

In summary, we fabricated SCs on Xerox paper using pencil drawing and PPy deposition successfully. The thin graphite sheets drawn by pencil acted as a good EDLCs material and a good current collector. The SCs based on PPy-G-paper electrodes showed high specific capacitance of 52.9 F cm-3 at a scan rate of 1 mV s-1. In addition, three SCs connected in series can drive a commercial LED. This method of fabricating the energy storage devices is low cost and environment friendly,and thepaper SCs can potentially guide the development of paper electronics for its low cost and high compatibility.

 

Acknowledgements

 

This work was supported by the National Basic Research Program (2011CB933300) of China, the National Natural Science Foundation of China (11204093, 11374110), and ‘the Fundamental Research Funds for the Central Universities’, HUST: 2012QN114, 2013TS033.

 

References

 

 

[1] A.S. Arico, P. Bruce, B. Scrosati, J.M. Tarascon, W. Van Schalkwijk, Nanostructured materials for advanced energy conversion and storage devices. Nat. Mater. 4(5), 366-377 (2005). doi:10.1038/nmat1368

[2] P. Simon, Y. Gogotsi, Materials for electrochemical capacitors. Nat. Mater. 7(11), 845-854 (2008). doi:10.1038/nmat2297

[3] L.L. Zhang, X.S. Zhao, Carbon-based materials as supercapacitor electrodes. Chem. Soc. Rev. 38(9), 2520-2531 (2009). doi:10.1039/b813846j

[4] B.E. Conway, Electrochemical supercapacitor: scientific fundamentals and technological applications. New York Kluwer Academic/Plenum Publishers (1999). doi:10.1007/978-1-4757-3058-6

[5] M. Winter, R.J. Brodd, What are batteries, fuel cells, and supercapacitors? Chem. Rev. 104(10), 4245-4269 (2004). doi:10.1021/cr020730k

[6] W. Chen, R.B. Rakhi, L. Hu, X. Xie, Y. Cui, H.N. Alshareef, High-performance nanostructured supercapacitors on a sponge. Nano Lett. 11(12), 5165-5172 (2011). doi:10.1021/nl2023433

[7] M.C. Barr, J.A. Rowehl, R.R. Lunt, J. Xu, A. Wang, C.M. Boyce, S.G. Im, V. Bulovic, K.K. Gleason, Direct monolithic integration of organic photovoltaic circuits on unmodified paper. Adv. Mater. 23(31), 3499-3505 (2011). doi:10.1002/adma.201101263

[8] J. Kawahara, P.A. Ersman, K. Katoh, M. Berggren, Fast-switching printed organic electrochemical transistors including electronic vias through plastic and paper substrates. IEEE T. Electron Dev. 60(6), 2052-2056 (2013). doi:10.1109/TED.2013.2258923

[9] B. Yoon, D.Y. Ham, O. Yarimaga, H. An, C.W. Lee, J.M. Kim, Inkjet printing of conjugated polymer precursors on paper substrates for colorimetric sensing and flexible electrothermochromic display. Adv. Mater. 23(46), 5492-5497 (2011). doi:10.1002/adma.201103471

[10] G.Y. Zheng, L.B. Hu, H. Wu, X. Xie, Y. Cui, Paper supercapacitors by a solvent-free drawing method. Energy Environ. Sci. 4(9), 3368-3373 (2011). doi:10.1039/c1ee01853a

[11] L.B. Hu, J.W. Choi, Y. Yang, S. Jeong, F. La Mantia, L.F. Cui, Y. Cui, Highly conductive paper for energy-storage devices. PNAS 106(51), 21490-21494 (2009). doi:10.1073/pnas.0908858106

[12] L. Hu, H. Wu, F. La Mantia, Y. Yang, Y. Cui, Thin, flexible secondary Li-ion paper batteries. ACS Nano 4(10), 5843-5848 (2010). doi:10.1021/nn1018158

[13] Elzbieta Frackowiak François Béguin, Carbon materials for the electrochemical storage of energy in capacitors. Carbon 39(6), 937-950 (2001). doi:10.1016/S0008-6223(00)00183-4

[14] D.N. Futaba, K. Hata, T. Yamada, T. Hiraoka, Y. Hayamizu, Y. Kakudate, O. Tanaike, H. Hatori, M. Yumura, S. Iijima, Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes. Nat. Mater. 5(12), 987-994 (2006). doi:10.1038/nmat1782

[15] Kay Hyeok An, Won Seok Kim, Young Soo Park, Jeong-Mi Moon, Dong Jae Bae, Seong Chu Lim, Young Seak Lee, Young Hee Lee, Electrochemical properties of high-power supercapacitors using single-walled carbon nanotube electrodes. Adv. Funct. Mater. 11 (5), 387-392 (2001). doi:10.1002/1616-3028(200110)11:53.0.CO;2-G

[16] V.L. Pushparaj, M.M. Shaijumon, A. Kumar, S. Murugesan, L. Ci, R. Vajtai, R.J. Linhardt, O. Nalamasu, P.M. Ajayan, Flexible energy storage devices based on nanocomposite paper. PNAS 104(34), 13574-13577 (2007). doi:10.1073/pnas.0706508104

[17] M. Kaempgen, C.K. Chan, J. Ma, Y. Cui, G. Gruner, Printable thin film supercapacitors using single-walled carbon nanotubes. Nano Lett. 9(5), 1872-1876 (2009). doi:10.1021/nl8038579

[18] Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J.R. Potts, R.S. Ruoff, Graphene and graphene oxide: synthesis, properties, and applications. Adv. Mater. 22(35), 3906-3924 (2010). doi:10.1002/adma.201001068

[19] H.J. Choi, S.M. Jung, J.M. Seo, D.W. Chang, L.M. Dai, J.B. Baek, Graphene for energy conversion and storage in fuel cells and supercapacitors. Nano Energy 1(4), 534-551 (2012). doi:10.1016/j.nanoen.2012.05.001

[20] K. Zhang, L.L. Zhang, X.S. Zhao, J.S. Wu, Graphene/polyaniline nanoriber composites as supercapacitor electrodes. Chem. Mater. 22(4), 1392-1401 (2010). doi:10.1021/cm902876u

[21] Q. Wu, Y.X. Xu, Z.Y. Yao, A.R. Liu, G.Q. Shi, Supercapacitors based on flexible graphene/polyaniline nanofiber composite films. ACS Nano 4(4), 1963-1970 (2010). doi:10.1021/nn1000035

[22] D.W. Wang, F. Li, J.P. Zhao, W.C. Ren, Z.G. Chen, J. Tan, Z.S. Wu, I. Gentle, G.Q. Lu, H.M. Cheng, Fabrication of graphene/polyaniline composite paper via in situ anodic electropolymerization for high-performance flexible electrode. ACS Nano 3(7), 1745-1752 (2009). doi:10.1021/nn900297m

[23] Y. Wang, Z.Q. Shi, Y. Huang, Y.F. Ma, C.Y. Wang, M.M. Chen, Y.S. Chen, Supercapacitor devices based on graphene materials. J. Phys. C 113(30), 13103-13107 (2009). doi:10.1021/jp902214f

[24] Y. Huang, Y. Huang, W.J. Meng, M.S. Zhu, H.T. Xue, C. Lee, C.Y. Zhi, Enhanced tolerance to stretch-induced performance degradation of stretchable MnO2-based supercapacitors. ACS Appl. Mater. Inter. 7, 2569−2574 (2015). doi:10.1021/am507588p

[25] Y. Huang, J.Y. Tao, W.J. Meng, M.S. Zhu, Y. Huang, Y.Q. Fu, Y.H. Gao, C.Y. Zhi, Super-high rate stretchable polypyrrole-based supercapacitors with excellent cycling stability. Nano Energy 11, 518-525 (2015). doi:10.1016/j.nanoen.2014.10.031

[26] R.A. Davoglio, S.R. Biaggio, N. Bocchi, R.C. Rocha, Flexible and high surface area composites of carbon fiber, polypyrrole, and poly(dmct) for supercapacitor electrodes. Electrochim. Acta 93, 93-100 (2013). doi:10.1016/j.electacta.2013.01.062

[27] X.H. Lu, G.M. Wang, T. Zhai, M.H. Yu, S.L. Xie, Y.C. Ling, C.L. Liang, Y.X. Tong, Y. Li, Stabilized tin nanowire arrays for high-performance and flexible supercapacitors. Nano Lett. 12(10), 5376-5381 (2012). doi:10.1021/nl302761z

[28] A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri, S. Piscanec, D. Jiang, K.S. Novoselov, S. Roth, A.K. Geim, Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 97(18) (2006). doi:10.1103/PhysRevLett.97.187401

[29] L.Y. Yuan, B. Yao, B. Hu, K.F. Huo, W. Chen, J. Zhou, Polypyrrole-coated paper for flexible solid-state energy storage. Energy Environ. Sci.6(2), 470-476 (2013). doi:10.1039/c2ee23977a

 

 

References

[1] A.S. Arico, P. Bruce, B. Scrosati, J.M. Tarascon, W. Van Schalkwijk, Nanostructured materials for advanced energy conversion and storage devices. Nat. Mater. 4(5), 366-377 (2005). doi:10.1038/nmat1368

[2] P. Simon, Y. Gogotsi, Materials for electrochemical capacitors. Nat. Mater. 7(11), 845-854 (2008). doi:10.1038/nmat2297

[3] L.L. Zhang, X.S. Zhao, Carbon-based materials as supercapacitor electrodes. Chem. Soc. Rev. 38(9), 2520-2531 (2009). doi:10.1039/b813846j

[4] B.E. Conway, Electrochemical supercapacitor: scientific fundamentals andtechnological applications. New York Kluwer Academic/Plenum Publishers (1999). doi:10.1007/978-1-4757-3058-6

[5] M. Winter, R.J. Brodd, What are batteries, fuel cells, and supercapacitors? Chem. Rev. 104(10), 4245-4269 (2004). doi:10.1021/cr020730k

[6] W. Chen, R.B. Rakhi, L. Hu, X. Xie, Y. Cui, H.N. Alshareef, High-performance nanostructured supercapacitors on a sponge. Nano Lett. 11(12), 5165-5172 (2011). doi:10.1021/nl2023433

[7] M.C. Barr, J.A. Rowehl, R.R. Lunt, J. Xu, A. Wang, C.M. Boyce, S.G. Im, V. Bulovic, K.K. Gleason, Direct monolithic integration of organic photovoltaic circuits on unmodified paper. Adv. Mater. 23(31), 3499-3505 (2011). doi:10.1002/adma.201101263

[8] J. Kawahara, P.A. Ersman, K. Katoh, M. Berggren, Fast-switching printed organic electrochemical transistors including electronic vias through plastic and paper substrates. IEEE T. Electron Dev. 60(6), 2052-2056 (2013). doi:10.1109/TED.2013.2258923

[9] B. Yoon, D.Y. Ham, O. Yarimaga, H. An, C.W. Lee, J.M. Kim, Inkjet printing of conjugated polymer precursors on paper substrates for colorimetric sensing and flexible electrothermochromic display. Adv. Mater. 23(46), 5492-5497 (2011). doi:10.1002/adma.201103471

[10] G.Y. Zheng, L.B. Hu, H. Wu, X. Xie, Y. Cui, Paper supercapacitors by a solvent-free drawing method. Energy Environ. Sci. 4(9), 3368-3373 (2011). doi:10.1039/c1ee01853a

[11] L.B. Hu, J.W. Choi, Y. Yang, S. Jeong, F. La Mantia, L.F. Cui, Y. Cui, Highly conductive paper for energy-storage devices. PNAS 106(51), 21490-21494 (2009). doi:10.1073/pnas.0908858106

[12] L. Hu, H. Wu, F. La Mantia, Y. Yang, Y. Cui, Thin, flexible secondary Li-ion paper batteries. ACS Nano 4(10), 5843-5848 (2010). doi:10.1021/nn1018158

[13] Elzbieta Frackowiak François Béguin, Carbon materials for the electrochemical storage of energy in capacitors. Carbon 39(6), 937-950 (2001). doi:10.1016/S0008-6223(00)00183-4

[14] D.N. Futaba, K. Hata, T. Yamada, T. Hiraoka, Y. Hayamizu, Y. Kakudate, O. Tanaike, H. Hatori, M. Yumura, S. Iijima, Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes. Nat. Mater. 5(12), 987-994 (2006). doi:10.1038/nmat1782

[15] Kay Hyeok An, Won Seok Kim, Young Soo Park, Jeong-Mi Moon, Dong Jae Bae, Seong Chu Lim, Young Seak Lee, Young Hee Lee, Electrochemical properties of high-power supercapacitors using single-walled carbon nanotube electrodes. Adv. Funct. Mater. 11 (5), 387-392 (2001). doi:10.1002/1616-3028(200110)11:53.0.CO;2-G

[16] V.L. Pushparaj, M.M. Shaijumon, A. Kumar, S. Murugesan, L. Ci, R. Vajtai, R.J. Linhardt, O. Nalamasu, P.M. Ajayan, Flexible energy storage devices based on nanocomposite paper. PNAS 104(34), 13574-13577 (2007). doi:10.1073/pnas.0706508104

[17] M. Kaempgen, C.K. Chan, J. Ma, Y. Cui, G. Gruner, Printable thin film supercapacitors using single-walled carbon nanotubes. Nano Lett. 9(5), 1872-1876 (2009). doi:10.1021/nl8038579

[18] Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J.R. Potts, R.S. Ruoff, Graphene and graphene oxide: synthesis, properties, and applications. Adv. Mater. 22(35), 3906-3924 (2010). doi:10.1002/adma.201001068

[19] H.J. Choi, S.M. Jung, J.M. Seo, D.W. Chang, L.M. Dai, J.B. Baek, Graphene for energy conversion and storage in fuel cells and supercapacitors. Nano Energy 1(4), 534-551 (2012). doi:10.1016/j.nanoen.2012.05.001

[20] K. Zhang, L.L. Zhang, X.S. Zhao, J.S. Wu, Graphene/polyaniline nanoriber composites as supercapacitor electrodes. Chem. Mater. 22(4), 1392-1401 (2010). doi:10.1021/cm902876u

[21] Q. Wu, Y.X. Xu, Z.Y. Yao, A.R. Liu, G.Q. Shi, Supercapacitors based on flexible graphene/polyaniline nanofiber composite films. ACS Nano 4(4), 1963-1970 (2010). doi:10.1021/nn1000035

[22] D.W. Wang, F. Li, J.P. Zhao, W.C. Ren, Z.G. Chen, J. Tan, Z.S. Wu, I. Gentle, G.Q. Lu, H.M. Cheng, Fabrication of graphene/polyaniline composite paper via in situ anodic electropolymerization for high-performance flexible electrode. ACS Nano 3(7), 1745-1752 (2009). doi:10.1021/nn900297m

[23] Y. Wang, Z.Q. Shi, Y. Huang, Y.F. Ma, C.Y. Wang, M.M. Chen, Y.S. Chen, Supercapacitor devices based on graphene materials. J. Phys. C 113(30), 13103-13107 (2009). doi:10.1021/jp902214f

[24] Y. Huang, Y. Huang, W.J. Meng, M.S. Zhu, H.T. Xue, C. Lee, C.Y. Zhi, Enhanced tolerance to stretch-induced performance degradation of stretchable MnO2-based supercapacitors. ACS Appl. Mater. Inter. 7, 2569−2574 (2015). doi:10.1021/am507588p

[25] Y. Huang, J.Y. Tao, W.J. Meng, M.S. Zhu, Y. Huang, Y.Q. Fu, Y.H. Gao, C.Y. Zhi, Super-high rate stretchable polypyrrole-based supercapacitors with excellent cycling stability. Nano Energy 11, 518-525 (2015). doi:10.1016/j.nanoen.2014.10.031

[26] R.A. Davoglio, S.R. Biaggio, N. Bocchi, R.C. Rocha, Flexible and high surface area composites of carbon fiber, polypyrrole, and poly(dmct) for supercapacitor electrodes. Electrochim. Acta 93, 93-100 (2013). doi:10.1016/j.electacta.2013.01.062

[27] X.H. Lu, G.M. Wang, T. Zhai, M.H. Yu, S.L. Xie, Y.C. Ling, C.L. Liang, Y.X. Tong, Y. Li, Stabilized tin nanowire arrays for high-performance and flexible supercapacitors. Nano Lett. 12(10), 5376-5381 (2012). doi:10.1021/nl302761z

[28] A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri, S. Piscanec, D. Jiang, K.S. Novoselov, S. Roth, A.K. Geim, Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 97(18) (2006). doi:10.1103/PhysRevLett.97.187401

[29] L.Y. Yuan, B. Yao, B. Hu, K.F. Huo, W. Chen, J. Zhou, Polypyrrole-coated paper for flexible solid-state energy storage. Energy Environ. Sci. 6(2), 470-476 (2013). doi:10.1039/c2ee23977a

Citation Information

Jiayou Tao, Wenzhen Ma, Nishuang Liu, Xiaoliang Ren, Yuling Shi, Jun Su, Yihua Gao, High Performance Solid-state Supercapacitors Fabricated by Pencil Drawing and Polypyrrole Depositing on Paper Substrate. Nano-Micro Lett. 7(3), 276-281 (2015). http://dx.doi.org/10.1007/s40820-015-0039-3

History

Received: 10 January 2015 / Accepted: 5 March 2015

 


Additional Info

  • Type of Publishing: JOUR - Journal
  • Title:

    High Performance Solid-state Supercapacitors Fabricated by Pencil Drawing and Polypyrrole Depositing on Paper Substrate

  • Author: Jiayou Tao, Wenzhen Ma, Nishuang Liu, Xiaoliang Ren, Yuling Shi, Jun Su, Yihua Gao
  • Year: 2015
  • Volume: 7
  • Issue: 3
  • Journal Name: Nano-Micro Letters
  • Publisher: OPEN ACCESS HOUSE SCIENCE & TECHNOLOGY
  • ISSN: 2150-5551
  • URL: http://dx.doi.org/10.1007/s40820-015-0039-3
  • Abstract:

    A solid-state powerful supercapacitor is fabricated with a substrate of Xerox paper. Its current collector based on a foldable electronic circuit is developed by simply pencil drawing. Thin graphite sheets on paper provide effective channels for electrons transmission with a low resistance of 95 Ω sq-1. The conductive organic material of polypyrrole coated on thin graphite sheets acts as the electrode material of the device. The as-fabricated supercapacitor exhibits a high specific capacitance of 52.9 F cm-3 at a scan rate of 1 mV s-1. An energy storage unit fabricated by three full charged series supercapacitors can drive a commercial light-emitting diode robustly. This work demonstrated a simple, versatile and cost-effective method for paper-based devices.

  • Publish Date: Wednesday, 01 July 2015
  • Start Page: 276
  • Endpage: 281
  • DOI: 10.1007/s40820-015-0039-3