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A ternary nanocomposite of reduced grapheneoxide, Ag nanoparticle and Polythiophene used forsupercapacitors

Murat Ates, Sinan Caliskan & Esin Ozten

To cite this article: Murat Ates, Sinan Caliskan & Esin Ozten (2018) A ternary nanocomposite ofreduced graphene oxide, Ag nanoparticle and Polythiophene used for supercapacitors, Fullerenes,Nanotubes and Carbon Nanostructures, 26:6, 360-369, DOI: 10.1080/1536383X.2018.1438414

To link to this article: https://doi.org/10.1080/1536383X.2018.1438414

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A ternary nanocomposite of reduced graphene oxide, Ag nanoparticleand Polythiophene used for supercapacitors

Murat Ates , Sinan Caliskan, and Esin Ozten

Department of Chemistry, Faculty of Arts and Sciences, Namik Kemal University, Degirmenalti Campus, Tekirdag, Turkey

ARTICLE HISTORYReceived 23 January 2018Accepted 5 February 2018

ABSTRACTThe ternary nanocomposites of reduced graphene oxide (rGO), Ag nanoparticles, and polythiophene (PTh),(rGO/Ag/PTh) with different initial feed ratios of [GO]o/[Th]o D 0.2, 0.3 and 0.4 were used in a symmetricsupercapacitor device formation. rGO/Ag/PTh nanocomposite has been prepared by in-situpolymerization and chemical reduction of graphene oxide. Fourier transform infrared spectroscopy–Attenuated total reflectance (FTIR-ATR) and scanning electron microscopy (SEM) were employed in orderto characterize the composition of the resulting nanocomposites and morphology. The electrochemicalbehavior of these nanocomposites were studied by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), electrochemical impedance spectroscopic (EIS) measurements in 1.0 M H2SO4 solution.As an electroactive material, rGO/Ag/PTh nanocomposite shows good capacitive performance in acidicelectrolyte solution, a high specific capacitance (up to Csp D 953.13 F/g at a scan rate of 4 mV/s) at[GO]o/[Th]o D 0.2. Moreover, the rGO/Ag/PTh nanocomposites at [GO]o/[Th]o D 0.2 show high stabilitywith 91.88% specific capacitance saved after 1000 charge/discharge processes. Furthermore, larger energydensity (up to E D 28.8 Wh/kg at a scan rate of 5 mV/s and a power density of P D 2843.3 W/kg at a scanrate of 1000 mV/s) of the nanocomposites at [GO]o/[Th]o D 0.2 is obtained in 1 M H2SO4 aqueouselectrolyte for two-electrode device formation. This study has revealed that the rGO/Ag/PThnanocomposite electrode materials may lead to a stable supercapacitor for portable electronicapplications.

GRAPHICAL ABSTRACT

KEYWORDSSupercapacitor;nanocomposite; reducedgraphene oxide;polythiophene; Agnanoparticle

Research Highlights

1- Synthesis of rGO, rGO/Ag/PTh nanocomposites in the ini-tial feed ratio of [GO]o/[Th]o D 0.2, 0.3 and 0.4.2- Supercapacitor device formation of rGO, and rGO/Ag/PThnanocomposites in different feed ratios.3- Energy and power density and capacitance measurements ofrGO, and rGO/Ag/PTh nanocomposites.

1. Introduction

Supercapacitors can be used in many practical applications, suchas cell phones, electric vehicles, flash camera, etc.[1] They are themost popular candidate for energy storage devices of 21 century,which has the ability to protect the environment from pollutionas well as to satisfy the roboust demand of energy.[2] Graphenebased electroactive materials have high surface area, high

CONTACT Murat Ates mates@nku.edu.tr Department of Chemistry, Faculty of Arts and Sciences, Namik Kemal University, Degirmenalti Campus, 59030,Tekirdag, Turkey.

Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lfnn.Website: www.atespolymer.org© 2018 Taylor & Francis Group, LLC

FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES2018, VOL. 26, NO. 6, 360–369https://doi.org/10.1080/1536383X.2018.1438414

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conductivity and high capacitance values compared to othermaterials. Supercapacitors are classified as electric double layercapacitance (EDLCs) and pseudocapacitors. Pseudocapacitorshave 10 to 100 times higher capacitance values than EDLCs.[3]

Pseudocapacitors can be obtained from conducting polymers,such as polythiophene,[4,5] polyaniline[6,7] or polypyrrole[8,9] andmetal nanoparticles such as Ag nanoparticles. Pseudocapacitorshave longer stability problems. To solve this problem, we used aternary composite system, which includes rGO, Ag nanoparticleand polythiophene. Conducting polymers (CPs) have been usedfor applications such as electronics, energy storage / conversion,biosensors, biotechnology, nanotechnology and environmentalmonitoring.[10-12] Conducting polymers have many advanta-geous, such as low cost, high charge/discharge capability[13] andgood electrical conductivity.[14,15]

Polythiophenes with heteroatoms in the polymer main chainare used among the most important classes of heterocyclic pol-ymers with extended p-conjugation.[16-18] Polythiophenes wasfirst synthesized in the early 1980 s via metal-catalyzed poly-condensation polymerization of 2,5-dibromothiophene or theoxidative polymerization of thiophene.[19,20] They have highthermal stability, electrical conductivity, and environmentalstability.[21] Polythiophene have been synthesized and appliedin many areas due to their intrinsic, electronic, optical andredox properties.[22,23] In literature, graphene / 3-hexylthio-phene was synthesized by dip-coating method to obtain a spe-cific capacitance of Csp D 1.22 F/cm2 at 2 mA/cm2.[24] PTh thinfilms have been prepared by chemical bath deposition methodat room temperature.[25] Its specific capacitance was obtainedas Csp D 300 F/g at 5mV/s in 0.1 M LiClO4/PC electrolyte.

Carbon based nanocomposites including activated carbon,mesoporous carbon, carbon nanotube, graphene have beenused for electric double layer capacitors (EDLCs) due to theirhigh surface area,[26] electronic conductivity, easy availabilityand environmental friendliness.[27,28] Graphene has beenreported with remarkable properties, such as excellent elec-tronic transport properties, high thermal conductivity, andsuperior mechanical properties.[29,30]

The use of nanomaterials and composites of reduced gra-phene oxide, conducting polymers, metal nanoparticles hasproven to produce significant progress.[31] To improve thecapacitive performance of PTh, nanocomposite materials havebeen obtained in literature.[32,33] Bora et al[34] have reportedpreparation of PTh/graphene composite by interfacialpolymerization and its use as a counter electrode (CE) for dye-sensitized solar cells (DSSCs). PTh/GO composites were syn-thesized by interfacial polymerization at the interface of twoimmiscible solvents, i.e. n-hexane containing thiophene andnitromethane containing GO and an initiator. The specificcapacitance of the composites was obtained as Csp D 99 F/g byCV method.[35]

Herein, rGO/Ag/PTh nanocomposite has been synthesizedby in-situ polymerization and chemical reduction of GO. Theinitial feed ratio of [GO]o/[Th]o was used 0.2, 0.3 and 0.4 toobtain the optimum conditions for synthesis. Their character-izations were performed by FTIR-ATR, SEM-EDX, CV, galva-nostatic charge/discharge and EIS analysis. To the best of ourknowledge the catalytic properties of rGO/Ag/PTh nanocom-posite have not been investigated in literature.

2. Experimental

2.1. Materials

Graphite, sodium nitrate (NaNO3), potassium permanganate(KMnO4,> 98%), hydrogen peroxide (H2O2, 30%), hydro-chloric acid (HCl), Zinc (II) chloride (ZnCl2) and sulfuricacid (H2SO4, 95–97%) were purchased from Merck (Darm-stadt, Germany). Thiophene (Th, > 99%), iron (III) chloride(FeCl3), chloroform, ethanol (99.8%), ammonia, acetonitrile(99.8%) hydrazine hydrate, cellulose ester membrane and Agnanoparticles (

filtered solid matter was added into 50 ml, 1 MHCl stirring for 1h at room temperature. The mixture was filtered again andwashed with DI water. We used 1 M HCl to purify of PTh.According to the above purification method, the PTh solid pow-ders were treated for 3–4 times until the color of filtrate to color-less. And then, the PTh solid powders were washed by DI waterand filtrared until the pH D 7. Finally, the PTh powders weredried under vacuum atmosphere at 60oC for 24 h.[40]

3.3. Preparation of graphene

1.0 g graphite powders and 0.5 g NaNO3 were added into 23 ml18 M H2SO4 solution stirring for 15 min. at 0

oC. After that, 3.0g KMnO4 was added into this solution stirring for 1 h at 5

oC.The mixture was stirring for 30 min. at 35oC. After that, underthe ice-bath, the mixture was diluted by 50 ml DI water. Then,10 ml, 30% H2O2 was added into this mixture. The color of themixture turned bright yellow. The supernatant of the mixturewas removed. And the rest was dispersed into 100 ml ethanolultrasounding for 30 min. In addition, 50 ml ammonia, 50 mlhydrazine hydrate were added into this solution ultrasoundingfor 10 min. Then the mixture solution was refluxed at 90oC for1 h. And then, the mixture was filtered and washed by ethanoland DI water, respectively. Finally, graphene was formed bydrying under vacuum atmosphere at 60oC for 12 h.

3.4. Preparation of rGO/Ag/PTh nanocomposite

0.2 g graphene was added into 50 ml chloroform ultrasoundingfor 1 h. 8 g FeCl3 and 0.012 g Ag nanoparticles were added intothe mixture solution stirring for 30 min. 1.0 g Th monomer wasadded into the solution stirring for 6 h at 5oC. After that, the solu-tion was filtered by the DI water circulating multi-purpose vac-uum pump. The filtered solid matter was purified. After that, the

solid powders were washed by DI water until the pHD 7. Finally,rGO/Ag/PTh nanocomposites powders were dried under vac-uum at 60oC for 24 h. By changing of [GO]o/[Th]oD 0.2, 0.3 and0.4 ratio, the nanocomposite was obtained. The preparation ofrGO/Ag/PTh nanocomposite was presented in Figure 1.

3.3. FTIR-ATR measurements

The FTIR-ATR spectra of rGO, and rGO/Ag/PTh nanocompo-sites are shown in Figure 2. The peak at 3224 cm¡1 refers to O-Hstretching vibrations for rGO. It is significantly evidence for deox-ygenation process.[41] The absorption peak at 1630 cm¡1 wasattributed to the skeletal vibrations of C D C.[42] The band at1181 cm¡1 can be assigned to the C-O stretching vibration.[43,44]

The FTIR-ATR spectrum of PTh are well-known inliterature.[45,46] FTIR-ATR spectrums of rGO/Ag/PTh nano-composites at different initial feed ratios of [GO]o/[Th]o D 0.2,0.3 and 0.4 were given in Figure 3. Some peaks assigned to PThare slightly shifted such as C-C vibrations at 1203 cm¡1, theC-H in plane bending bond at 1074 cm¡1 [47] and the C-Sstretching in the thiophene ring at 686 cm¡1. These signal dis-placements show that the rGO is intercalating in some waywith PTh. The peaks at 3003 and 1597 cm¡1 belong to C-Hstretching and C-C stretching vibrations for rGO/Ag/PThnanocomposite.[48] The band at 844 cm¡1 belongs to the C-Hout of plane vibration of the 2,5-substituted thiophene mono-mer,[49] while the peaks at 586, 582 and 447 cm¡1 are related toC-S stretching in the thiophene ring[50-53] and the C-S-C ringdeformation,[54] respectively.

3.4. SEM-EDX analysis

The surface morphologies of the GO, rGO, and rGO/Ag/PThwith different initial feed ratios of [GO]o/[Th]o D 0.2, 0.3 and

Figure 1. Schematic illustration of preparation rGO/Ag/PTh nanocomposite.

362 M. ATES ET AL.

0.4 were given in Figure 4 & 5. The SEM image of rGO haslight-weight, wrinkled, crumpled structure. However, for rGO/Ag/PTh nanocomposite, rGO nanosheets embedded into PThmatrix. Therefore, there is an image difference between rGOand rGO/Ag/PTh nanocomposites as shown in Figure 4. TheGO shows a multi-layered sheet structure. However, rGO/Ag/PTh nanocomposites have the uniform morphology of PTh

disappears and a mixture of coarse and flaky structure. Wheninitial feed ratio of [GO]o/[Th]o increases, in other words, theamount of PTh in the composite decreases, the structure showsa greater number of layers as shown in Figure 5, related to thehigher amount of rGO in the nanocomposite structure.

The percentage amounts of carbon ©, oxygen (O), sulfur (S),and silver (Ag) nanoparticles are summarized from EDX

Figure 2. FTIR-ATR specta of rGO and rGO/Ag/PTh nanocomposite films at [GO]o/[Th]o D 0.2.

Figure 3. FTIR-ATR specta of rGO/Ag/PTh nanocomposite with different initial feed ratios of [GO]o/[Th]o D 0.2, 0.3, 0.4.

Figure 4. SEM images of a) GO, b) rGO, c) rGO/Ag/PTh nanocomposite.

FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES 363

spectrum as shown in Table 1. The weight percent of S and Agnanoparticles were existed in 0.79% and 39.90% in nanocom-posite at [GO]o/[Th]o D 0.2. It is strongly evidence of rGO for-mation due to the absent of O and S elements in EDXspectrum.

3.5. Cyclic voltammetric (CV) measurements

Specific capacitances (Csp) were obtained from cyclic vol-tammetry (CV) experiments. It was calculated by means of

the following equation (1) [55]:

Csp DZ

.I£dV=D#£m£DV/ (1)

where I £ dV is the integral area of the cyclic voltammogramloop, Csp is the specific capacitance based on the mass of electro-active materials (F/g), I is the response current (A), DV is thepotential window (V), Δ# is the scan rate (V/s), and m(g) is thetotal mass of the active materials (Figure 6). If the CV plot hasrectangular box shape, it can be named as ideal supercapacitor.However, most of the CV plots deviate from rectangular boxshape due to the redox reactions of electroactive materials.[56]

The interaction of PTh and Ag nanoparticles on GOnanosheets shows a synergic effect to increase specificcapacitance.[57] In most cases, electrochemical capacitors con-taining a PTh component have suffered from relatively largeinternal resistance. However, Ag nanoparticles, which couldsupply a good conducting, network.

The Csp values of rGO and rGO/Ag/PTh nanocompositeswith different feed ratios ([GO]o/[Th]o D 0.2, 0.3, and 0.4)

Figure 5. SEM images of rGO/Ag/PTh nanocomposite with different initial feed ratios of [GO]o/[Th]o D 0.2, 0.3, and 0.4.

Table 1. EDX analysis of GO, rGO, and rGO/Ag/PTh nanocomposites in the initialfeed ratio of [GO]o/]Th]o D 0.2.

Weight percent / %

Elements GO rGO rGO/Ag/PTh [GO]o/[Th]o D 0.2C 22.05 52.64 30.11N 3.38 47.36 —O 73.65 — 29.80S 0.93 — 0.79Ag — — 39.30

Figure 6. CVs of chemically synthesized materials of rGO/Ag/PTh nanocomposites at different initial feed ratios of a) [GO]o/[Th]o D 0.2, b) [GO]o/[Th]o D 0.3, and c) [GO]o/[Th]o D 0.4 in 1M H2SO4 solution for a potential window of 0.0 and C0.8 V at a scan rate of 10, 20, 40, 60, 80 and 100 mV/s.

364 M. ATES ET AL.

were calculated in 1 M H2SO4 aqueous electrolyte solution fordifferent scan rates from 10 mV/s to 100 mV/s by CV method(Figure 7). The integrated area of the rGO/Ag/PTh nanocom-posite at [GO]o/[Th]o D 0.2. CV curve is much larger com-pared to [GO]o/[Th]o D 0.3 and 0.4 and this leads to higherareal capacitance values.

The highest Csp value of rGO/Ag/PTh nanocomposite at[GO]o/[Th]o D 0.2 was obtained as Csp D 953.13 F/g byCV method. Csp values were also obtained as 93.16 and45.16 F/g for rGO and GO nanosheets, respectively. Thespecific capacitance was increased 10.23 times for the

comparison of rGO/Ag/PTh nanocomposite and rGOnanosheets.

The highest specific capacitances were obtained as Csp D120.83 F/g and 161.91 F/g for rGO/Ag/PTh nanocompositeat [GO]o/[Th]o D 0.3 and 0.4, respectively. The total weightof electrode is very important to prepare the SS electrode asactive electrode materials. After electrochemical measure-ments of device performances (CV, galvanostatic charge/dis-charge, and EIS), we have scraped the active materials fromSS electrode, dried under vacuum atmosphere and thenweighted in specific capacitance calculations. We have mea-sured the weight of pellets as 17.2, 23, 30, 5 and 20 mg forGO, rGO, rGO/Ag/PTh nanocomposite at [GO]o/[Th]o D0.2, 0.3 and 0.4, respectively.

The highest energy density (E) and power density (P)were obtained as E D 28.68 Wh/kg at a scan rate of 4 mV/sfor nanocomposite at [GO]o/[Th]o D 0.2 and P D 11304.5W/kg for nanocomposite at [GO]o/[Th]o D 0.2, as given inFigure 8.

3.6. Galvanostatic charge/discharge measurements

The galvanostatic charge/discharge (GCD) measurements weretaken at a constant current density of 1 A/g as shown inFigure 9. The Csp values were obtained by applying the follow-ing Eq (2):[58,59]

Csp D i£Dt = m£DV (2)

where i (A) is the discharge current, and Dt (s) is the dischargetime, m (g) is the mass of the electrode active material and DV(V) is the potential window.

The highest specific capacitance of GCD measurementswas obtained as Csp D 904 F/g for rGO/Ag/PTh nanocom-posite at [GO]o/[Th]o D 0.3. The other highest Csp valueswere obtained as Csp D 163.33 and 214.5 F/g at [GO]o/[Th]o D 0.2 and 0.4 at 10 mA. There is a resistance namedas electrical serial resistance (ESR), which was obtainedfrom Eq (3):

ESRD Vdrop= 2£iapp (3)

In this formula, Vdrop is the potential drop in Eq 3. Itoccurs ESR of the capacitor. ESR is the equivalent series

Figure 7. Specific capacitance of rGO, and rGO/Ag/PTh nanocomposites in differ-ent initial feed ratios of [GO]o/[Th]o D 0.2, 0.3 and 0.4 with scan rates, as deter-mined by CV measurements.

Figure 8. Energy density vs Power density obtained in 1 M H2SO4 solution from CVmeasurements for rGO, and rGO/Ag/PTh nanocomposites with different initial feedratios, [GO]o/[Th]o D 0.2, 0.3 and 0.4.

Figure 9. Galvanostatic charge/discharge (GCD) measurements of rGO/Ag/PTh nanocomposites in different initial feed ratios of a) [GO]o/[Th]o D 0.2, b) [GO]o/[Th]o D 0.3and c) [GO]o/[Th]o D 0.4 with constant current of 0.1, 0.2, 0.5, 1, 2, 5, and 10 mA.

FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES 365

resistance of the supercapacitors in ohms, iapp is the dis-charge current in Amperes. The ESR values were obtainedas 0.057 V, 0.093 V and 0.090 V for rGO/Ag/PTh nano-composite at [GO]o/[Th]o D 0.2, 0.3 and 0.4, respectively.GCD plots show only small ohmic drops at high currentsrelated to the resistivity of the cells. The capacitance valuesmeasured in H2SO4 electrolyte solution is almost higherthan measured in Na2SO4 electrolyte solution. The electro-lyte type and material type are affected the electrochemicalresults.[60,61]

3.7. Electrochemical impedance spectroscopicmeasurements

Electrochemical impedance spectroscopy (EIS) measure-ments of rGO and rGO/Ag/PTh nanocomposite at [GO]o/[Th]o D 0.2, 0.3 and 0.4 were carried out in the frequencyrange from 100 kHz to 0.01 Hz and is showed by Nyquistplot, as shown in Fig. 10a. At higher frequencies, a verticalline was obtained as a good capacitive behavior of the elec-trode (Figure 10b). At lower frequencies, a semicircle wasshown due to the charge transfer resistance at the contactinterface between electrode and electrolyte solution.[62] Thespecific capacitance was obtained from Nyquist plot as thefollowing Eq. (4):

Csp D ¡ 1= 2£p£f£Z}� �

(4)

where p D 3.14, f is frequency in Hz, and Z" is the imagi-nary part of the impedance values.[63] The highest specificcapacitance was obtained as Csp D 9.15 F/g for rGO/Ag/PTh nanocomposite at [GO]o/[Th]o D 0.2 obtained fromNyquist plot. Moreover, the other Csp values were obtained

as 0.635, 0.312, and 0.305 F/g for [GO]o/[Th]o D 0.4, 0.3and rGO, respectively.

Double layer capacitance (Cdl) was calculated from Bode-magnitude plot by extrapolating the linear section to a value ofw D 1 (log(w D 0) and using the following Eq. (5):[64]

Cdl D 1=IZI (5)

The highest double layer capacitance (Cdl) was obtainedas Cdl D 1.82 F/g for rGO/Ag/PTh nanocomposite at[GO]o/[Th]o D 0.3 (Figure 10c). In addition, the other Cdlvalues were obtained as Cdl D 0.088, 0.071 and 0.066 F/gfor rGO, rGO/Ag/PTh nanocomposite at [GO]o/[Th]o D 0.4and 0.2, respectively. The phase angles (u) were only about-86o at the frequency of 9.57 Hz (Figure 10d).

3.8. Cycle life of device

Long charge/discharge properties of less amount of capacitanceloss are important for supercapacitors. rGO and rGO/Ag/PThwith different initial feed ratios of [GO]o/[Th]o D 0.2, 0.3 and0.4 was performed by repeating the 1000 charge/dischargecycles in the potential between 0.0 and 0.8 V at 100 mV/s(Figure 11). The specific capacitance loss were obtained as8.12%, 15% and 26% for [GO]o/[Th]o D 0.2, 0.4 and rGO mate-rials. It proves the good stability performance of the devices.The decrease in the capacitance for rGO, nanocomposite at[GO]o/[Th]o D 0.2 and 0.4 in the capacitance with repetition ofcycles is due to the loss of active electrode materials during cal-ation and intercalation of the ions.[65] However, The initial spe-cific capacitance of nanocomposite was increased 50.8% for[GO]o/[Th]o D 0.3 due to the more accessible surface area ofrGO.[66,67]

Figure 10. EIS analysis of rGO, and rGO/Ag/PTh nanocomposites in different initial feed ratios of [GO]o/[Th]o D 0.2, 0.3 and 0.4, a) Nyquist plot at frequency from 10 mHzto 100 kHz, b) Nyquist plot at high frequencies from 1580 Hz to 100 kHz, c) Bode-magnitude plot, d) Bode-phase plot. EIS measurements were taken at frequenciesbetween 10 mHz and 100 kHz with a sinusoidal signal amplitude of 10 mV in 1 M H2SO4.

366 M. ATES ET AL.

4. Conclusion

In this study, rGO/Ag/PTh nanocomposite at [GO]o/[Th]oD 0.2, 0.3 and 0.4 were chemically synthesized by in-situpolymerization method. The nanocomposites were charac-terized by FTIR-ATR, SEM-EDX, CV, GCD and EIS analy-sis. The highest specific capacitance was obtained as Csp D904 F/g at a constant current of 10 mA for galvanostaticcharge/discharge measurements of rGO/Ag/PTh nanocom-posite at [GO]o/[Th]o D 0.3. The lowest ohmic drop wasalso obtained as ESR D 0.093 V for rGO/Ag/PTh nanocom-posite at [GO]o/[Th]o D 0.3. The high specific capacitanceof the rGO/Ag/PTh nanocomposite electrode material hasenhanced conductivity, low interfacial resistance, and thesynergetic effects of both rGO, Ag nanoparticles and poly-thiophene as a ternary nanocomposite. As a result, rGO/Ag/PTh nanocomposite electrode active material is promis-ing for high-energy supercapacitor applications.

Acknowledgments

The financial support of Namik Kemal University, Tekirdag, Turkey, proj-ect number: NKUBAP.01.GA.16.076 is gratefully acknowledged. Authorsalso thank to Expert Muhammet Aydın (Namik Kemal Uni., NABILTEM,Tekirdag, Turkey) for recording SEM-EDX and FTIR-ATR measurements.

Author contributions

The manuscript was written through the contributions of all authors. Allauthors have given approval to the final version of the manuscript.

Conflict of interest

The authors declared none.

Funding

Scientific Research Project of Namik Kemal University, Tekirdag, Turkey,NKUBAP.01.GA.16.076.

ORCID

Murat Ates http://orcid.org/0000-0002-1806-0330

References

[1] Li, G. R.; Feng, Z. P.; Zhang, J. H.; Wang, Z. L.; Tong, Y. X. Electro-chemical Synthesis of Polyaniline Nanobelts with Predominant Elec-trochemical Performances.Macromolecules 2010, 43, 2178–2183.

[2] Alabadi, A.; Razzaque, S.; Dong, Z.; Wang, W.; Tan, B. GrapheneOxide-Polythiophene Derivative Hybrid Nanosheet for Enhanc-ing Performance of Supercapacitor. J. Power Sources 2016, 306,241–247.

[3] Ramirez, F. C. R.; Ramakrishnan, P.; Flores-Payag, Z. P.; Shanmugan,S.; Binag, C. A. Polyaniline and Carbon Nanotube Coated Pineapple-Polyester Blended Fabric Composites as Electrodes for Supercapaci-tors. Synth. Met. 2017, 230, 65–72.

[4] Lu, Q.; Zhou, Y. K. Synthesis of Mesoporous Polythiophene MnO(O)Nanocomposite and its Enhanced Pseudocapacitive Properties. J.Power Sources 2011, 196, 4088–4094.

[5] Gnanakan, S. R. P.; Rajasekhar, M.; Subramania, A. Synthesis of Pol-ythiophene Nanoparticles by Surfactant-Assisted Dilute Polymeriza-tion Method for High-Performance Redox Supercapacitors. Int. J.Electrochem. Sci. 2009, 4, 1289–1301.

[6] Tan, Y. T.; Zhang, Y. F.; Kong, L. B.; Ran, F. Nano-Au@PANI Core-Shell Nanoparticles via In-Situ Polymerization as Electrode forSupercapacitor. J. Alloys Compds. 2017, 722, 1–7.

[7] Hu, J.; Jia, F. F., Song, Y. F. Engineering High-Performance Polyoxo-metalate/PANI/MWNTs Nanocomposite Anode Materials for Lith-ium Ion Batteries. Chem. Eng. J. 2017, 326, 273–280.

[8] Zhang, J.; Liu, Y.; Guan, H. J.; Zhao, Y. F.; Zhang, B. Decoration ofNickel Hydroxide Nanoparticles onto Polypyrrole Nanotubes withEnhanced Electrochemical Performance for Supercapacitors. J. AlloysCompds. 2017, 721, 731–740.

[9] Wang, C.; Liu, H.; Jiang, M.; Wang, Y. D.; Liu, R. N.; Luo, Z. P.; Liu,X. Q.; Xu, W. L.; Xiong, C. X.; Fang, D. Ammonium vanadate@poly-pyrrole@manganese Dioxide Nanowire Arrays with EnhancedReversible Lithium Storage. Appl. Surf. Sci. 2017, 416, 402–410.

[10] Matindoust, S.; Farzi, A.; Nejad, M. B.; Abadi, M. H. S.; Zou, Z.;Zheng, L. R. Ammonia Gas Sensor Based on Flexible PolyanilineFilms for Rapid Detection of Spoilage in Protein-Rich Foods. J.Mater. Sci. Mater. Electron. 2017, 28(11), 7760–7768.

[11] Devi, R.; Relhan, S.; Pundir, C. S. Construction of a Chitosan/Polya-niline/Graphene Oxide Nanoparticles/Polypyrrole/Au Electrode forAmperometric Determination of Urinary/Plasma Oxalate. Sens.Actuators B. Chem. 2013, 186, 17–26.

[12] Marsh, R. A.; Hodgkiss, J. M.; Friend, R. H. Direct Measurements ofElectric Field-Assisted Charge Separation in Polymer, Fullerene Pho-tovoltaic Diodes. Adv. Mater. 2010, 22(33), 3672-C.

[13] Belanger, D.; Ren, X.; Davey, J.; Uribe, F.; Gottesfeld, S. Characteriza-tion and Long-Term Performance of Polyaniline Based Electrochem-ical Capacitors. J. Electrochem. Soc. 2000, 147(8), 2923–2929.

[14] Aradilla, D.; Estrany, F.; Aleman, C. Symmetric SupercapacitorsBased on Multilayers of Conducting Polymers. J. Phys. Chem. C.2011, 115, 8430–8438.

[15] Ramya, R.; Sivasubramanian, R.; Sangaranarayanan, M. V. Conduct-ing Polymers-Based Electrochemical Supercapacitors-Progress andProspects. Electrochim. Acta 2013, 101, 109–129.

[16] Osaka, I.; Sauve, G.; Zhang, R.; Kowalewski, T.; McCullough, R. D.Novel Thiophene-Thiazolothiazole Copolymers for Organic Field-Effect Transistors. Adv. Mater. 2007, 19, 4160–4165.

[17] Cheng, Y. J.; Yang, S. H.; Hsu, C. S. Synthesis of Conjugated Poly-mers for Organic Solar Cell Applications. Chem. Rev. 2009, 109,5868–5923.

[18] Braunger, M. L.; Barros, A.; Ferreira, M.; Olivati, C. A. Electrical andElectrochemical Measurements in Nanostructured Films of Polythio-phene Derivatives. Electrochim. Acta 2015, 165, 1–6.

[19] Yamamoto, T.; Sanechika, K.; Yamamoto, A. Preparation of Thermo-stable and Electric-Conducting Poly(2-5thienylene). J. Polym. Sci.Polym. Lett. Ed. 1980, 18, 9–12.

[20] Lin, J. W. P.; Dudek, L. P. Synthesis and Properties of poly(2,5-thie-nylene). J. Polym. Sci. Polym. Chem. Ed. 1980, 18, 2869–2873.

[21] McCullough, R. D. The Chemistry of Conducting Polythiophenes.Adv. Mater. 1998, 10, 93–116.

Figure 11. Stability of rGO, and rGO/Ag/PTh nanocomposites in different initialfeed ratios of [GO]o/ [Th]o D 0.2, 0.3 and 0.4 tested by CVs. Scan rate was measuredas 100 mV/s for 1000 cycles.

FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES 367

http://orcid.org/0000-0002-1806-0330

[22] Garnier, F.; Horowitz, G.; Fichou, D. Conjugated Polymers andOligomers as Active Material for Electronic Devices. Synth. Met.1989, 28, 705–714.

[23] Clement, J. A.; Mohanakrishnan, A. K. Synthesis and Characteriza-tion of Naphthannelated Thiophene Analogs. Tetrahedron 2010, 66,2340–2350.

[24] Momodu, D.; Bello, A.; Dangbegnon, J.; Barzeger, F.; Fabiane, M.;Manyala, N. P3HT, PCBM/Nickel-Aluminum Layered DoubleHydroxide-Graphene Foam Composites for Supercapacitor Electro-des. J. Solid Electrochem. 2015, 19(2), 445–452.

[25] Patil, B. H.; Patil, S. J.; Lokhande, C. D. Electrochemical Characteri-zation of Chemically Synthesized Polythiophene Thin Films, Perfor-mance of Asymmetric Supercapacitor Device. Electroanalysis 2014,26, 2023–2032.

[26] Melo, J. P.; Schulz, E. N.; Morales-Verdejo, C.; Horswell, S. L.;Camarada, M. B. Synthesis and Characterization of Graphene/Poly-thiophene (GR/PT) Nanocomposites, Evaluation as High-Perfor-mance Supercapacitor Electrodes. Int. J. Electrochem. Sci. 2017, 12,2933–2948.

[27] Hao, L.; Li, X. L.; Zhi, L. J. Carbonaceous Electrode Materials forSupercapacitors. Adv. Mater. 2013, 25(28), 3899–3904.

[28] Fang, Y.; Luo, B.; Jia, Y. Y.; Li, X. L.; Wang, B.; Song, Q.; Kang, F. Y.;Zhi, L. J. Renewing Functionalized Graphene as Electrodes for High-Performance Supercapacitors, Adv. Mater. 2012, 24(47), 6348–6355.

[29] Dreyer, R. D.; Park, S.; Bielawski, C. W.; Ruoff, R. S. The Chemistryof Graphene Oxide. Chem. Soc. Rev. 2010, 39, 228–240.

[30] Wang, G.; Shen, X.; Wang, B.; Yao, J.; Park, J. Synthesis and Charac-terization of Hydrophilic and Organo-Philic Graphene Nanosheets.Carbon 2009, 47, 1359–1364.

[31] Wang, G. P.; Zhang, L.; Zhang, J. J. A Review of Electrode Materials forElectrochemical Supercapacitors. Chem. Soc. Rev. 2012, 41, 797–828.

[32] Selvakumar, M.; Bhat, D. K. Activated Carbon Polyethylenedioxy-thiophene Composite Electrodes for Symmetrical Supercapacitors. J.Appl. Polym. Sci. 2008, 107(4), 2165–2170.

[33] Lota, K.; Khomenko, V.; Frackowiak, E. Capacitance Properties ofpoly(3,4-ethylenedioxythiophene)/Carbon Nanotubes Composites. J.Phys. Chem. Solids 2004, 65, 295–301.

[34] Bora, C.; Sarkar, C.; Mohan, K. J.; Dolui, S. Polythiophene/GrapheneComposite as a Highly Efficient Platinum-Free Counter Electrode inDye-Sensitized Solar Cells. Electrochim. Acta 2015, 157, 225–231.

[35] Bora, C.; Pegu, R.; Saikia, B. J.; Dolui, S. K. Synthesis of Polythio-phene/Graphene Oxide Composites by Interfacial Polymerizationand Evaluation of Their Electrical and Electrochemical Properties.Polym. Int. 2014, 63, 2061–2067.

[36] Miraftab, R.; Ramezanzadeh, B.; Bahlakeh, G.; Mahdavian, M. AnAdvanced Approach for Fabrication a Reduced Graphene Oxide-AZO Dye/Polyurethane Composite with Enhanced Ultraviolet (UV)Shielding Properties, Experimental and First-Principles QM Model-ing. Chemical Engineering Journal 2017, 321, 159–174.

[37] Chen, C. M.; Yang, Q. H.; Yang, Y. G.; Lv, W.; Wen, Y. F.; Hou, P. X.;Wang, M. Z.; Cheng, H. M. Self-Assembled Free-Standing GraphiteOxide Membrane. Adv. Mater. 2009, 21, 3007–3011.

[38] Liu, X.; Pan, L.; Lv, T.; Zhu, G.; Lu, T.; Sun, Z.; Sun, C. Q. MicrowaveAssisted Synthesis of TiO2 Reduced Graphene Oxide Composites orthe Photocatalytic Reduction of Cr(VI). RSC Adv. 2011, 1, 1245–1249.

[39] Stylianakis, M. M.; Stratakis, E.; Koudoumas, E.; Kymakis, E.; Anas-tasiadis, S. H. Organic Bulk Heterojunction Photovoltaic DevicesBased on Polythiophene-Graphene Composites. ACS Appl. Mater. &Interfaces 2012, 4 (9), 4864–4870.

[40] Zhao, J.; Xie, Y.; Le, Z. G.; Yu, J.; Gao, Y. H.; Zhong, R.; Qin, Y. C.;Huang, Y. Preparation and Characterization of an ElectromagneticMaterial, The Graphene Nanosheet/Polythiophene Composite.Synth. Met. 2013, 181, 110–116.

[41] Li, D.; Muller, M. B.; Gilje, S.; Kaner, R. B.; Wallace, G. G. Process-able Aqueous Dispersions of Graphene Nanosheets. Nat. Nanotech.2008, 3(2), 101–105.

[42] Khanra, P.; Lee, C. N.; Kuila, T.; Kim, N. H.; Park, M. J.; Lee, J. H.7,7,8,8-Tetracyanoquinodimethane-Assisted One-Step Electrochemi-cal Exfoliation of Graphite and its Performance as an ElectrodeMaterial. Nanoscale 2014, 6(9), 4864–4873.

[43] Tang, Z. H.; Zhang, L. Q.; Zeng, C. F.; Lin, T. F.; Guo, B. C. GeneralRoute to Graphene with Liquid-Like Behavior by Non-CovalentModification. Soft Matter. 2012, 8(35), 9214–9220.

[44] Li, Y.; Chen, Q.; Xu, K.; Kaneko, T.; Hatakeyama, R. Synthesis ofGraphene Nanosheets from Petroleum Asphalt by Pulsed Arc Dis-charge in Water. Chem. Eng. J. 2013, 215, 45–49.

[45] Patil, B.; Jagadale, A.; Lokhande, C. Synthesis of Polythiophene ThinFilms by Simple Successive Ionic Layer Absorption and Reaction(SILAR) Method for Supercapacitor Application. Synth. Met. 2012,162 (15-16), 1400–1405.

[46] Tahmasebi, E.; Yamimi, Y.; Moradi, M.; Esrafili, A. Polythiophene-Coated Fe3O4 Superparamagnetic Nanocomposite, Synthesis andApplication as a New Sorbent for Solid-Phase Extraction. Anal.Chim. Acta 2013, 770, 68–74.

[47] Zabihi, O.; Khodabandeh, A.; Mostafavi, S. M. Preparation, Optimi-zation and Thermal Characterization of a Novel Conductive Ther-moset Nanocomposite Containing Polythiophene NanoparticlesUsing Dynamic Thermal Analysis. Polym. Degrad. Stab. 2012, 97(1),3–13.

[48] Kalyani, R.; Grurunathan, K. PTh-rGO-TiO2 Nanocomposite forPhotocatalytic Hydrogen Production and Dye Degradation. J. Photo-chemistry and Photobiology A, Chemistry 2016, 329, 105–112.

[49] Guo, X. Z.; Kang, Y. F.; Yang, T. L.; Wang, S. R. Low-temperatureNO2 Sensors Based on Polythiophene/WO3 Organic-InorganicHybrids. Transactions of Nonferrous Metals Society of China, Non-ferr T.,Metal Soc. 2012, 22(2), 380–385.

[50] Karim, M. R.; Lee, C. J.; Lee, M. S. Synthesis and Characterization ofConducting Polythiophene/Carbon Nanotubes Composites. J. Polym.Sci. Part A, Polym. Chem. 2006, 44(18), 5283–5290.

[51] Zhu, Y. F.; Xu, S. B.; Jiang, L.; Pan, K. L.; Dan, Y. Synthesis and Char-acterization of Polythiophene/Titanium Dioxide Composites. React.Funct. Polym. 2008, 68(10), 1492–1498.

[52] Karim, M. R.; Lim, K. T.; Lee, C. J.; Lee, M. S. A facile Synthesis ofPolythiophene Nanowires. Synth. Met. 2007, 157(22-23), 1008–1012.

[53] Han, M. G.; Foulger, S. H. Crystalline Colloidal Arrays Com-posed of Poly(3,4-ethylenedioxythiophene)-Coated PolystyreneParticles with a Stop Band in the Visible Regime. Adv. Mater.2004, 16(3), 231-C.

[54] Gnanakan, S. R. P.; Rajasekhar, M.; Subramania, A. Synthesis of Pol-ythiophene Nanoparticles by Surfactant-Assisted Dilute Polymeriza-tion Method for High Performance Redox Supercapacitors. Int. J.Electrochem. Sci. 2009, 4(9), 1289–1301.

[55] Yue, B. B.; Wang, C. Y.; Wagner, P.; Yang, Y.; Ding, X.; Officer, D. L.;Wallace, G. G. Electrodeposition of Pyrrole and 3-(4-tert-Butyl Phe-nyl) Thiophene Copolymer for Supercapacitor Applications. Synth.Met. 2012, 162(24), 2216–2221.

[56] Meng, Q.; Cai, K.; Chen, Y.; Chen, L. Research Progress on Conduct-ing Polymer Based Supercapacitor Electrode Materials. Nano Energy2017, 36, 268–285.

[57] Bae, J.; Park, J. Y.; Kwon, O. S.; Lee, C. S. Energy Efficient CapacitorsBased on Graphene/Conducting Polymer Hybrids. Journal of Indus-trial and Engineering Chemistry 2017, 51, 1–11.

[58] Zhang, J.; Ma, J.; Zhang, L. L.; Guo, P.; Jiang, J.; Zhao, X. S. TemplateSynthesis of Tubular Ruthenium Oxides for Supercapacitor Applica-tions. J. Phys. Chem.C. 2010, 114(32), 13608–13613.

[59] Zhang, J. T.; Jiang, Y. W.; Zhao, X. S. Synthesis and Capacitive Prop-erties of Manganese Oxide Nanosheets Dispersed on FunctionalizedGraphene Sheets. J. Phys. Chem. C. 2011, 115(14), 6448–6454.

[60] Seredych, M.; Koscinski, M.; Sliwinska-Bartkowiak, M.; Bandosz, T.J. Active Pore Space Utilization in Nanoporous Carbon Based Super-capacitors, Effects of Conductivity and Pore Accessibility. J. PowerSources 2012, 220, 243–252.

[61] Nian, Y. R.; H. Teng, H. Nitric Acid Modification of Activated Car-bon Electrodes for Improvement of Electrochemical Capacitance. J.Electrochem. Soc. 2002, 149(8), A1008–A1014.

[62] Prabaharan, S. R. S.; Vimala, R.; Zainal, Z. Nanostructured mesopo-rous carbon as electrodes for supercapacitors 2006, 161(1), 730–736.

[63] Miller, J. R.; Outlaw, R. A.; Holloway, B. C. Graphene Electric DoubleLayer Capacitor with Ultra-High Power Performance. Electrochim.Acta 2011, 56, 10443–10449.

368 M. ATES ET AL.

[64] Ates, M.; Serin, M. A.; Ekmen, I.; Ertas, Y. N. Supercapacitor Behav-iors of Polyaniline/CuO, Polypyrrole/CuO and PEDOT/CuO Nano-composites. Polym. Bull. 2015, 72(10), 2573–2589.

[65] Kulkarni, S. B.; Jagadale, A. D.; Kumbhar, V. S.; Bulakhe, R. N.; Joshi,S. S.; Lokhande, C. D. Potentiodynamic Deposition of CompositionInfluenced Co1-xNixLDHs Thin Film Electrode for Redox Superca-pacitors. Int. J. Hydrogen Energy 2013, 38(10), 4046–4053.

[66] Peng, Z. W.; Ye, R. Q.; Mann, J. A.; Zakhidov, D.; Li, Y. L.; Smalley, P.R.; Lin, J. Flexible Boron-Doped Laser Induced Graphene Microsu-percapacitors. ACS Nano 2015, 9, 5868–5875.

[67] Mao, X.; Yang,W.; He, X.; Chen, Y.; Zhao, Y.; Yang, Y.; Xu, J. The Prepa-ration and Characteristic of poly(3,4-ethylenedioxythiophene)/ReducedGraphene Oxide Nanocomposite and its Application for SupercapacitorElectrode.Materials Science and Engineering B 2017. 216, 16–22.

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AbstractResearch Highlights1. Introduction2. Experimental2.1. Materials2.2. Instrumentations2.3. Preparation of supercapacitor device

3. Results and discussion3.1. Preparation of graphene oxide (GO)3.2. Synthesis of polythiophene3.3. Preparation of graphene3.4. Preparation of rGO/Ag/PTh nanocomposite3.3. FTIR-ATR measurements3.4. SEM-EDX analysis3.5. Cyclic voltammetric (CV) measurements3.6. Galvanostatic charge/discharge measurements3.7. Electrochemical impedance spectroscopic measurements3.8. Cycle life of device

4. ConclusionAcknowledgmentsAuthor contributionsConflict of interestFundingReferences学霸图书馆link:学霸图书馆