Accepted Manuscript

Coaxial silver nanowire/polypyrrole nanocomposite supercapacitors

Recep Yuksel, Ece Alpugan, Husnu Emrah Unalan

PII: S1566-1199(17)30502-5
DOI: 10.1016/j.orgel.2017.10.012
Reference: ORGELE 4345

To appear in: Organic Electronics

Received Date: 1 June 2017

Revised Date: 26 August 2017
Accepted Date: 10 October 2017

Please cite this article as: R. Yuksel, E. Alpugan, H.E. Unalan, Coaxial silver nanowire/polypyrrole
nanocomposite supercapacitors, Organic Electronics (2017), doi: 10.1016/j.orgel.2017.10.012.

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT
Coaxial Silver Nanowire / Polypyrrole Nanocomposite Supercapacitors

Recep Yuksel1, 2*, Ece Alpugan3 and Husnu Emrah Unalan1, 2, 3

1
Department of Micro and Nanotechnology, METU, Ankara 06800, Turkey
2
Energy Storage Materials and Devices Research Center (ENDAM), METU, Ankara, 06800,

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Turkey

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Department of Metallurgical and Materials Engineering, METU, Ankara 06800, Turkey

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Abstract

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Three-dimensional (3D) core-shell silver nanowire (Ag NW) - polypyrrole (PPy)
nanocomposites are used for the fabrication of supercapacitors. In-situ chemical
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polymerization of PPy onto Ag NWs results in the formation of diameter tunable, coaxial and
3D nanocomposites. Inner Ag NW core facilitates the charge transfer and PPy shell shows a
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remarkably high pseudocapacitance. Fabricated Ag NW/PPy nanocomposite has a specific

capacitance of 509 F g-1 at a current density of 0.31 A g-1, while the energy and power
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densities are found to be 4.27 Wh kg-1, 60.7 W kg-1, respectively. For these devices a capacity
retention of more than 90 % is obtained following 10000 cycles. It is envisaged that the 3D
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core-shell nanocomposite architecture investigated here can be extended to other conducting

polymer and metal nanowire systems.
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*Corresponding author. Phone: +90 (312) 2105939. E-mail: reyuksel@gmail.com

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Keywords: silver nanowires, polypyrrole, nanocomposite, pseudocapacitor, electrode,

supercapacitors.

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Introduction

There is an increasing demand for energy storage devices with higher efficiency.
Supercapacitors with high power density, long cycle life and fast charge-discharge
characteristics are among these energy storage devices. They are utilized in many fields
spanning from public transportation to wearable and portable consumer electronics [1-4]. But
still, the charge storage capacity and energy density of the supercapacitors need to be

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improved. Hierarchically structured nanomaterials are highly promising for improving the
energy storage properties of the supercapacitors [5, 6]. Therefore, recent research efforts are

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focused on the development of alternative electrode active materials. Novel electrode
materials should have high charge accumulation and enhanced charge transfer to improve the

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electrochemical performance of the supercapacitor devices [7]. This is only possible through
the utilization of structurally engineered nanomaterial electrodes. Nanomaterials with a core-

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shell (conductor-capacitive) structure may provide a solution to improve energy storage
characteristics of supercapacitor devices [7, 8]. Core-shell architecture can also eliminate the
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need for heavy current collectors and allowe all active electrode materials to be in close
contact. One-dimensional nanomaterials are highly promising as conductive cores within
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coaxial electrode materials [9-11]. Carbon nanotubes, for instance, have already been
investigated for this purpose but still have some drawbacks such as high cost and intricate
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fabrication processes [12, 13]. Metal nanowires that are synthesized through solution-based
methods can be used as alternative conductive core materials. In fact, the use of silver
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nanowires (Ag NWs) with high aspect ratio and superior conductivity have already been
demonstrated for energy storage applications [14-20]. Active surfaces of Ag NWs allow the
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deposition of capacitive materials for the realization of a core-shell morphology. These

nanostructures with an Ag NW core and a capacitive shell advances charge transport and
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decreases the overall resistance, which seriously enhances the electrochemical performance of
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the supercapacitor devices. In recent years, supercapacitor devices utilizing Ag NWs have
been reported. In these, Ag NWs were used in conjunction with graphene [16, 21], indium tin
oxide (ITO) [22] and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)
[14]. However, in these studies, Ag NWs were utilized with additional current collectors and
active electrode materials were deposited as a thin film onto these charge collectors.
Therefore, Ag NWs might have had a limited contribution to the charge transfer. On the other
hand, in a core-shell architecture, nanocomposites with Ag NWs are highly promising for

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supercapacitor electrodes, where the internal resistance of the electrodes is highly reduced
[17, 18].

Pseudocapacitive materials such as metal oxides and CPs have fast and reversible
redox reactions on the electrode surface and have higher charge storage capacity than the
electric double layer capacitors (EDLCs). However, these materials commonly suffer from
their poorly conductive nature and dense morphology, limiting their pseudocapacitance.

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Therefore, conductive additives or supports during electrode fabrication were utilized to
highlight their pseudocapacitive properties. CPs are intrinsically electronic conductors and

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their conductivity changes depending on the doping level. Moreover, CPs are promising
materials due to their low cost, high conductivity (in doped state), easy processability and

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environmental compatibility [23-25]. Most commonly used CPs are polyaniline (PANI),
poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy) and their derivatives. Bulk or

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dense CP films decelerate the electrolyte ion diffusion and result in poor charge storage in
supercapacitors. Volume changes during ion intercalation/deintercalation enhance the
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mechanical deformation of the CPs [24, 25]. PPy have significant advantages compared to
other CPs such as biocompatibility, appreciable mechanical properties, fast redox activity and
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high conductivity [6, 23]. The use of PPy in many electronic devices such as batteries,
supercapacitors, fuel cells [26], solar cells [27], photoelectrochromics, corrosion protection
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[28] and sensors [29] has already been demonstrated. The main drawback of PPy is the short
cycle life, similar to many other CPs. The main reason for the poor cyclability of PPy is the
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instabilities in the polymer backbone. Atoms in the reaction media can occupy active redox
sites in the polymer backbone, and this may result in the polymer degradation. To enhance the
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capacitance and improve the structural stability of the PPy, it is used in nanocomposite form
in the supercapacitor devices. Fabrication of PPy nanocomposites with single-walled carbon
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nanotubes [30], multi-walled carbon nanotubes [31-33], carbon fibers [34], carbon foam [35],
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activated carbon [36], reduced graphene oxide [37], graphene [38], molybdenum sulfide [24],
titanium carbide [39] and silver [40] have been reported to improve the structural stability of
the PPy as well as enhancing its electrochemical properties.

An alternative solution to overcome the mentioned drawbacks is the in-situ growth of

CPs on the surface of one-dimensional materials [41, 42]. The core-shell morphology can
offer a uniform architecture and fast charge transfer from outer shell layer to the inner
metallic core. In addition to this, the hierarchical 3D structure of the fabricated
nanocomposites has large openings, which allows easy electrolyte ion movement. Therefore,

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3D core-shell structured nanocomposites have the potential to show high power and energy
densities compared to bulk or thin film supercapacitor materials. Moreover, metal nanowires
are sensitive to air and moisture, which would adversely affect the device performance. A
polymer shell at this stage may be very useful and protect metal nanowires from oxidation and
corrosion. This polymer shell can be deposited through solution based routes. These routes
have numerous advantages. First of all, they are template-free methods that are easy to scale

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up. In addition, the deposition can take place at atmospheric conditions without the need for
expensive lithographical techniques [43]. It is a challenging process to prepare 3D structures

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with high porosity, flexibility, robustness and conductivity [38]. Therefore, in-situ chemical
polymerization of PPy directly on the surface of Ag NWs in solution holds great potential to

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meet all the requirements and the fabricated core shell structures can be used in many devices.
During polymerization, it is also possible to control the thickness of the nanocomposite.
Chemical polymerization of the Py is typically conducted using Py monomer with the

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addition of equimolar iron (III) chloride (FeCl3). Silver nitrate (AgNO3) can be used instead
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of FeCl3, since its standard reduction potential is close to that of FeCl3 and AgNO3 can in-situ
polymerize Py monomer to PPy [43]. It is also an advantage that the unwanted complex
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chemical reactions and impurities are eliminated in this method using AgNO3 instead of
FeCl3.
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In this study, core Ag NW and shell PPy nanocomposites were fabricated via in-situ
chemical oxidation route. Highly conductive Ag NWs formed internal structure of the
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nanocomposites and PPy with a tunable thickness was deposited atop. This core-shell
structure of Ag NW/PPy was then used in energy storage devices without the need for current
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collectors for the first time. Symmetric supercapacitor devices were fabricated with these
nanocomposites and their electrochemical properties were determined.
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Experimental

Pyrrole monomer (% 98), polytetrafluoroethylene (PTFE, 60 wt % dispersion in

water), potassium chloride (KCl, ≥ 99 %), potassium hydroxide (KOH, ≥ 85 %), potassium
iodide (KI, ≥ 99 %) and lithium sulfate (Li2SO4, ≥ 98 %) were purchased from Sigma-
Aldrich. Super P carbon black (conductive, 99 % (metals basis)) was obtained from Timcal
and silver nitrate (AgNO3, ≥ 99 %) was purchased from Merck. All these reagents were used
without further purification.

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Ag NWs were synthesized according to the polyol method and purified as reported
elsewhere [10]. Purified Ag NWs were dispersed in ethanol and used in the fabrication of the
nanocomposites. An Ag NW concentration of 0.68 mg/ml was used for this purpose.

Ag NW/PPy nanocomposites were prepared using a chemical polymerization route

[40]. Briefly, Ag NWs were dispersed in water: ethanol solution (1:1 ratio v/v) and Py
monomer was added to the same solution under mild mixing. AgNO3 solution (with

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equivalent molarity to Py monomer) was then added to the mixing solution. The mixing was
continued for 3 hours and then the solution was rested for overnight. The precipitate was

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filtered and washed with excess deionized water and then stored in water for 24 hours.

Supercapacitor electrodes were prepared using Ag NW/PPy nanocomposites,

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conductive additive carbon black and binder polytetrafluoroethylene (PTFE) with a weight
ratio of 80/10/10, respectively. Fabricated electrodes were cut into small discs (8 mm

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diameter) and dried at 80 °C for 3 hours.
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Characterization
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Scanning electron microscopy (SEM, FEI Nova Nano FEG-SEM 430, operated at 10 kV) was
used to investigate the morphology of the fabricated nanocomposites. High contrast
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transmission electron microscopy (CTEM) was performed on a FEI Tecnai G2 Spirit BioTwin
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CTEM microscope, operated at 120 kV. Specimens for CTEM analysis, were diluted in
ethanolic solution and transferred onto holey carbon-coated copper grids. Fourier transform
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infrared spectroscopy (FT-IR) measurements were performed using an Agilent 600 Series FT-
IR spectrometer and KBr pellets. X-Ray photoelectron spectroscopy (XPS) measurement was
carried out for chemical identification of the constituent elements and XPS spectra were
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collected using PHI 5000 VersaProbe spectrometer. High-resolution scans of the Ag (3d), C
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(1s), O (1s) and N (1s) spectral regions were performed for the qualitative analysis. C (1s) line
at 285 eV 1as used for reference and charge correction of the binding energies (BE). Raman
spectroscopy was carried out on a Renishaw inVia Raman microscope (532 nm). X-Ray
photoelectron spectroscopy (XPS) measurements were carried out for the evaluation of the
chemical state and identification of the constituent elements. X-Ray powder diffraction
(XRD) measurements were performed on a Rigaku D/Max-2000 diffractometer at Bragg-
Brentanno geometry with Cu Kα radiation operating at 40 kV. Thermogravimetric analysis
(TGA) was performed using an airflow and a heating rate of 50 cm3 min-1 and 10 °C min-1,

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respectively, with a Perkin Elmer TGA7 Thermogravimetric Analyzer. For electrochemical
measurements, Gamry Reference 3000 potentiostat/galvanostat system was used in two-
electrode configuration. Home-mode Swagelok cells were used for the electrochemical
measurements. A Sartorius Research R200D microbalance was used to measure the weight of
electrode active materials and it was measured as 1.94 mg/electrode (3.88 mg/device) for Ag
NW/PPy4.

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Results and Discussion

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In-situ chemical oxidation polymerization of Py monomer on the surfaces of the Ag

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NWs is achieved by the Ag+ ions in the presence of AgNO3 according to the balanced
equation (I). The standard reduction potential of the Ag+ ions to Ag0 is 0.8 V and is well
matched and suitable for the oxidation potential of the Py monomer (0.8 V) [44, 45].

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Conformal and continuous deposition of polymer layer on Ag NWs is a concentration and
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time-dependent process. In this study, reaction and the aging time are kept constant and the
concentration-dependent polymer thickness change is monitored. 4 different sets of Ag
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NW/PPy nanocomposites with Ag NWs abbreviated as Ag NW/PPy1-4 are fabricated under

the same reaction conditions. The Ag NW core and PPy shell nanostructures are formed due
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to the strong metal-π bond interactions [40]. Polyol synthesis of Ag NWs and in-situ chemical
oxidation polymerization of Py monomer resulted in the network-like core-shell morphology
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as illustrated schematically in Figure 1 (a).

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(I)
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SEM is used to analyze the surface morphologies of the fabricated nanocomposites.

SEM images of bare Ag NW and Ag NW/PPy nanocomposites are provided in Figure 1 (b)-
(f). In-situ polymerization of Py monomer took place on the surface of Ag NWs and a
uniform core-shell structure of the Ag NW/PPy nanocomposites was clearly observed due to
emission differences of the electrons between Ag NWs and PPy. The thickness (diameter)
values of the core-shell Ag NW/PPy nanostructures measured from SEM images are tabulated
and provided in Table 1. High magnification SEM images of Ag NW/PPy nanocomposites
revealed that the polymer layer thickness increases gradually with the Py monomer

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concentration in the reaction media. It is observed that the NW morphology is maintained for
all core-shell nanocomposites. It is evident from the SEM images that the individual NWs are
homogeneously coated with the PPy layer. PPy layer is also observed at the randomly formed
junction points, which resulted in the fabrication of porous, 3D architectures. Porous 3D
structure of the Ag NW/PPy nanocomposites may allow high mobility and easy electrolyte
ion access to all surfaces of the nanocomposite electrodes.

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In-situ welded junctions of the nanocomposites mainly contain PPy, while only a few
of them contain Ag NWs. Both materials in the nanocomposite have high intrinsic

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conductivity and the overall electrical conductivity of the fabricated nanocomposites is
limited with the junctions in the 3D network. In addition to conductivity, rich and tunable

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openings of the nanocomposites are highly favored for the obtainment of superior
electrochemical properties.

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XRD patterns of the bare Ag NW and Ag NW/PPy nanocomposites are shown in
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Figure 2 (a). All diffraction peaks around 38.1°, 44.4°, 64.5 °, and 77.4 ° can be indexed to
(111), (200), (220) and (311) planes of Ag (JCPDS card 04-0783), respectively [17, 18]. The
intensity of the observed Ag diffraction peaks is changed with respect to the PPy shell
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thicknesses. Peaks associated with PPy are not observed in the XRD patterns of the
nanocomposites, which is attributed to the low crystallinity of the PPy polymer [40].
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Diffraction peaks for (200), (220) and (311) become more pronounced upon PPy coating, due
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to the formation of elemental Ag during the synthesis of PPy as dictated in equation I.

Raman spectroscopy is used to analyze the chemical structure of the fabricated

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nanocomposites. The Raman spectra of the bare Ag NW and fabricated Ag NW/PPy

nanocomposites within the spectral range of 200-2000 cm-1 are provided in Figure 2 (b). The
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Raman spectrum of bare Ag NWs is shown for comparison and the observed peaks are due to
the residual polyvinylpyrrolidone (PVP) layer on the Ag NWs. PVP is used for the polyol
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synthesis of Ag NWs and act as a stabilizing agent. For the Ag NW/PPy nanocomposites,
observed bands located at 912, 1005, 1072, 1365, 1408 and 1556 cm−1 are marked for PPy
shell and they are characteristic bands of the PPy polymer. The bands at 912 and 1072 cm−1
belong to C-H out-of-plane and in-plane deformation, respectively. The band at 1005 cm−1
corresponds to ring deformation. The Py ring stretching shows bands at 1365 and 1408 cm−1.
The peak at 1603 cm−1 is assigned to stretching of the C=C bonds [40, 46]. The bands at 912,
1005, 1072 cm−1 are very weak and thus further chemical structure analysis of the samples are
conducted through FT-IR analysis. FT-IR spectra of the bare Ag NW, PPy and Ag NW/PPy
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nanocomposites are provided in Figure 2 (c). For Ag NWs, the bands at 3450 and 1655 cm-1
are due to the O-H and C=O stretching, respectively, showing the residual PVP layer on the
Ag NWs [45]. The characteristic PPy peaks are observed both for bare PPy and Ag NW/PPy
nanocomposites. The bands are located at 1550 and 1477 cm-1 are assigned to the pyrrole ring
and C-N stretching, respectively. The bands at 1383 and 924 cm-1 are related to C-H
stretching mode, 1303 and 1188 cm-1 are related to C-N stretching modes, and 1041 cm-1 is

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related to in-plane N-H vibration mode. The peak at 783 cm-1 is attributed to the out-of plane
ring vibration mode of C-C and C-H bonds [47-50].

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Thermal gravimetric analysis (TGA) is conducted to determine PPy content in the
fabricated nanocomposites. TGA analysis is performed in air to avoid the carbonization of

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PPy in nitrogen atmosphere [44]. Apparent weight gain around 200 °C in bare Ag NW sample
is due to the oxidation of Ag, as shown in Figure 2 (d). At higher temperatures, the residue is

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only elemental Ag. For Ag NW/PPy nanocomposites, the PPy shell thickness affected the
thermal stability of the nanocomposites and different decomposition temperatures are
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observed. As shown in the Figure 2 (d), residual Ag content is quite high (75 - 85 wt.% at 800
°C) and it is originated both from Ag NWs and Ag from equation I.
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To further characterize the morphology of the Ag NW/PPy nanocomposites, high

contrast TEM analysis was conducted. TEM image of Ag NW/PPy4 is provided in Figure
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3(a). PPy layer homogeneously covers the entire surface of Ag NW networks as evidenced in
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low- and high-resolution TEM images.

XPS measurements were carried out to further characterize the bare Ag NWs and Ag
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NW/PPy nanocomposites. XPS results of the bare Ag NWs and Ag NW/PPy nanocomposite
were provided in Figure 3 (b)-(f). XPS survey spectrum (Figure 3 (b)) of the bare Ag NWs
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and Ag NW/PPy nanocomposite have signals from C, O, N and Ag species, which come from
the components of Ag NWs and PPy. High resolution XPS spectra of C 1s and O 1s are
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provided in Figure 3 (c) and (d), respectively. It is well-known that XPS collect data from the
surface of material within a depth of 5 to 10 nm and bare Ag NWs and nanocomposite
electrodes have almost the same C 1s intensity. The thin PVP layer on the Ag NWs resulted in
high intensity C 1s signal (Figure 3(c)). In Figure 3(d), Ag NWs have a high intensity signal
from O 1s, which is due to oxygen moieties in the PVP layer, while the O 1s signal is quite
low in intensity for Ag NW/PPy4. In Figure 3 (e), core level N 1s spectrum of Ag NW/PPy
nanocomposite is highly intense than that of the Ag NWs. The high resolution Ag 3d core

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level XPS spectrum (Figure 3 (f)) presents two major peaks at binding energies of 373.4 and
367.4 eVs due to Ag 3d3/2 and Ag 3d5/2 species, respectively. The spin-energy separation of
6.0 eV agrees well with the reported values for the elemental Ag0 [14, 21, 51].

In order to investigate the electrochemical properties of the fabricated Ag NW/PPy

nanocomposites, symmetrical supercapacitor devices are fabricated and subjected to cyclic
voltammetry (CV) measurements in a voltage window of 0-0.5 V using various electrolytic

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solutions (lithium sulfate (Li2SO4), potassium chloride (KCl), potassium iodide (KI) and
potassium hydroxide (KOH)). This voltage window is particularly chosen because it provides

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a safe operating window for Ag NWs, preventing their irreversible oxidation [18, 52]. CV
results of the Ag NW/PPy nanocomposite supercapacitor devices with various electrolytes at

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a scan rate of 1 mV s-1 are provided in Figure 4. Although it has been demonstrated that acidic
electrolytes perform reasonably well with the PPy electrodes, presence of Ag NWs limited the
use of acidic electrolytes within the coaxial electrodes [39]. In the case of sulfuric acid, Ag+

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ions are known to dissolve in sulfate containing electrolyte solutions [52, 53]. On the other
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hand, aqueous electrolytes such as KI, KCl and KOH showed promising electrochemical
performance (Figure 4). KOH outperformed other potassium-based electrolytes due to the
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hydrogen bond formation on the PPy surface. In addition to aqueous electrolytes, an organic
electrolyte (1 M LiClO4 in PC) is demonstrated with limited performance due to low mobility
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of electrolyte ions (results not shown here).

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The main benefit of the core-shell structure of Ag NW/PPy nanocomposites is the

improvement of the charge transfer between Ag NW core and PPy shell layer. Fabricated
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nanocomposite structure shows advanced charge storage properties due to the conducting
inner Ag NW core. This improvement is only limited at the junction points, which are mostly
PPy. Electrolyte ions are transported among the large openings of the 3D structure of the
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nanocomposites and these nanocomposites show good performance. CV results of the

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fabricated nanocomposite devices with different PPy shell thicknesses are provided in the
Figure 5. As shown, fabricated devices have almost rectangular CV shapes. It is clear from
the Figure 5 that the increased PPy layer thickness results in higher capacitance values.

Fabricated nanocomposite Ag NW/PPy4 is also tested under different scan rates and
the obtained CV results are provided in Figure 6 (a). Ag NW/PPy4 nanocomposite
supercapacitor showed encouraging electrochemical properties at high scan rates and it almost
preserved its rectangular shape. During the CV measurements, the deviations from the
rectangular shape of the CV curves may be due to difficulties in existing charge transfers on
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the inner active surfaces. These results showed that the fabricated nanocomposites have good
charge storage and transfer properties.

Charge storage characteristics of the Ag NW/PPy4 supercapacitor device are also

investigated by galvanostatic charge-discharge (GCD) measurements at different current
densities, results of which are provided in Figure 6 (b). Galvanostatic measurements are
conducted in a voltage window of 0 to 0.5 V in 1 M KOH electrolyte. For electrochemical

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measurements, only PPy contents are taken into consideration and current densities are
calculated with respect to PPy contents in the nanocomposites. Ag NW/PPy4 device had

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almost linear GCD profiles and showed similar charge-discharge profiles at different current
densities with a limited IRdrop confirming the pseudocapacitive property of the PPy. This is

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attributed to the highly conductive nature of the core-shell architecture, which also facilitated
the charge transfer. GCD results are in good correlation with the CV results. As shown in the

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Figure 6 (b), fabricated supercapacitor device has a limited internal resistance drop (IRdrop)
(3.7 Ω) in the GCD curves. The equivalent series resistance due to electrolyte resistance,
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electrode resistance and contact resistance might be responsible for this IRdrop.

Discharge energy (E), cell capacitance (Ccell) and specific capacitance (Csp) of the
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fabricated devices are calculated using GCD curves provided in Figure 6 (b) using the
following equations [54]:
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2
4
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=     =  = 


 

 
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,where I (A) is the applied discharge current, V (V) is the discharge voltage range after IRdrop,
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t (s) is the discharge time and m (g) is the total mass of active materials in both electrodes.
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Ccell has two serially connected identical electrodes and contains the total mass of both
electrodes. Therefore, calculated Csp is 4 times higher than the Ccell value [55]. The specific
capacitance of the fabricated Ag NW/PPy nanocomposite supercapacitors with respect to the
applied current densities is provided in Figure 7 (a). Fabricated nanocomposites with a thick
PPy shell layer had higher specific capacitance values compared to the nanocomposites with
thinner PPy layers. A specific capacitance of 509.0 F g-1 at a current density of 0.31 A g-1 is
obtained for Ag NW/PPy4 nanocomposite supercapacitor device. To our best knowledge, this
is one of the highest specific capacitance for a PPy containing device reported so far [6]. Csp

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decreased to 237.3 F g-1 at a current density of 15.5 A g-1. This change is reasonable, because
the current density increases 50 times while the specific capacitance approximately decreases
to half of its initial value. Slow electrochemical processes as a result of difficulties in the
charge transfer at the inner parts of the porous electrode structures can cause a dynamic
resistance, which might be responsible for this behavior.

Capacity retention is an important parameter in evaluating the life span of the

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fabricated supercapacitor devices. Fabricated Ag NW/PPy nanocomposite supercapacitor
devices are cycled for 10000 times and the obtained results are provided in the Figure 7 (b). It

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is clearly seen from the figure that the capacity retention gets improved as the PPy shell
thickness increases. Ag NW/PPy1 nanocomposite supercapacitor device had the thinnest shell

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layer and showed the worst capacity retention value. On the other hand, Ag NW/PPy4
nanocomposite with the thickest shell layer showed the highest capacity retention value of

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almost 90 % after 10000 GCD cycles. AN
To clarify the electrochemical characteristics of the fabricated supercapacitor devices,
electrochemical impedance spectroscopy (EIS) is also performed. EIS behaviors of the
fabricated devices are measured within a range of 100 kHz to 0.01 Hz using 5 mV AC
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perturbation. Nyquist plots of the supercapacitor devices are provided in Figure 8. Nyquist
profile of the nanocomposite supercapacitors is dedicated to the electrochemical interactions
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on the surfaces of electrodes. Typically, supercapacitor devices act as a resistance within high
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frequency region, while they behave like a capacitance within low frequency region. The
sharp slope of the curves in the low frequency region is assigned to the pseudocapacitive
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properties of the fabricated devices. As shown in the Figure 6 inset, different semicircle
formations are observed and Ag NW/PPy4 had the smallest semicircle among the measured
devices. The high conductivity of the coaxial nanocomposite architecture resulted in
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improved charge transfer within the high frequency region.

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Energy (Ed) and power densities (Pd) of the fabricated supercapacitors are calculated
using the following equations:

E 3600 ∗ E
E = P = III
m ∗ 3.6 t

,where E (Ws) is the discharge energy, m (g) is the total mass of active materials in both
electrodes and the t is the galvanostatic discharge time. The energy density is calculated to be

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4.27 Wh kg-1 at a power density of 60.7 W kg-1. More significantly, the energy density of the
Ag NW/PPy4 nanocomposite was still as high as 0.42 Wh kg-1 even at a high power density
of 2,145.1 W kg-1. In order to compare the fabricated energy storage devices, Ragone plot is
provided in Figure 9. According to the Ragone plot, power density of the fabricated
supercapacitors is found to be within the medium power range. These results are quite
encouraging in view of the Ag NW/PPy nanocomposite fabrication, which will be a very

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promising electrode material for high-rate supercapacitor applications.

In order to compare our obtained results with those in literature regarding PPy, Table 2

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is prepared. Results from this work and literature are tabulated in terms of specific
capacitance, type of electrolyte, potential/voltage window. It is clear that the obtained specific

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capacitance result in this work is one of the highest results in the literature. Reported highest
capacitance known to date is associated with MoS2 nanosheets - PPy based electrodes [24]. As

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known the highly pseudocapacitive properties of MoS2 nanosheets [56], PPy would have a
limited contribution to the total specific capacitance of MoS2-PPy based electrodes. In this
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study, PPy is utilized as the only pseudocapacitive material.
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Conclusions
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In summary, we have demonstrated a one-step solution based route for the fabrication of co-
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axial Ag NW/PPy nanocomposites with tunable polymer shell thickness. These

nanocomposites were then utilized for the fabrication of supercapacitors. High conductivity of
the core Ag NWs and the polypyrrole shell layer enhanced the charge transfer. We have
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examined the effect of PPy shell thickness in nanocomposite form on the electrochemical
performance of the supercapacitors. The measured specific capacitance, maximum power and
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energy density were 509.0 F g-1, 60.7 W kg -1

, 4.27 Wh kg-1 for the Ag NW/PPy4
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nanocomposite supercapacitor device, respectively. The fabricated supercapacitors showed

promising stability, while the variation in Csp was found to be less than 10 % over 10000
charge/discharge cycles. In addition, Ag NW/PPy4 supercapacitor device showed large
specific capacitance, high rate performance and remarkable charge/discharge stability. The
enhanced electrochemical properties were mainly attributed to the sound nanocomposite
construction that allowed efficient fabrication of pseudocapacitive PPy shell, accelerated
charge transport and improved the stability of the polymer at the optimum PPy shell
thickness.

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Acknowledgements

Authors declare no competing financial interests.

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Figure Captions

Figure 1. (a) Schematic illustration of core-shell Ag NW/PPy nanocomposite formation.

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High-resolution SEM images of (b) Ag NW and (c)-(f) Ag NW/PPy nanocomposite

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electrodes with different PPy thicknesses.

Figure 2. (a) XRD patterns, (b) Raman spectra, (c) FT-IR spectra and (d) TGA analysis

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results of bare Ag NW and Ag NW/PPy nanocomposite electrodes.
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Figure 3. (a) TEM image of Ag NW/PPy nanocomposite electrodes. Inset shows a higher
resolution TEM image. (b) XPS survey spectra of bare Ag NWs and Ag NW/PPy
nanocomposite electrodes. (c) C 1s, (d) O 1s, (e) N 1s and (f) Ag 3d core level XPS of bare
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Ag NW and Ag NW/PPy nanocomposite electrodes.

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Figure 4. Cyclic voltammetry results of the fabricated Ag NW/PPy4 nanocomposite

supercapacitors using different electrolytes at a scan rate of 1 mVs-1.
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Figure 5. CV results of the fabricated Ag NW/PPy nanocomposite supercapacitors in 1 M

KOH electrolyte at a scan rate of 1 mV s-1
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Figure 6. (a) CV results of the fabricated Ag NW/PPy4 nanocomposite supercapacitors at

different scan rates. (b) GCD results of fabricated Ag NW/PPy4 nanocomposite
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supercapacitors with 1 M KOH aqueous electrolyte at different current densities ranging from
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0.31 to 15.5 A g-1.

Figure 7. (a) Csp of Ag NW/PPy nanocomposite supercapacitor devices as a function of

current density. Lines are for visual aid. (b) Capacity retention of Ag NW/PPy nanocomposite
supercapacitor devices measured through a constant GCD over a voltage range of 0 to 0.5 V.

Figure 8. EIS spectra of Ag NW/PPy nanocomposite supercapacitor devices measured within

the range of 100 kHz to 0.01 Hz at a 5 mV AC amplitude. Inset shows high frequency region
of the EIS spectra.

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Figure 9. Ragone plot of the fabricated supercapacitor devices.

Table Captions

Table 1. Change in the Ag NW/PPy thickness with respect to Py monomer concentration.

Table 2. A comparison of various PPy containing supercapacitor electrode materials (SWNT:

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single-walled carbon nanotubes, OCNTF: oxidized carbon nanotubes grown on carbon fiber,
Ex-GF: exfoliated graphene on graphite foil, PPy@C: carbon coated PPy, EG-RGO: ethylene

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glycol reduced graphene oxide, MWNT: multi-walled carbon nanotubes, ACNF: activated
carbon nanofibers, AC: activated carbon, NS: nanosheets).

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Table 1. Yuksel et al.

Ag NW Conc.

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Name Py Conc. (mg/ml) Thickness (nm)
(mg/ml)
Ag NW/PPy1 2.5 0.34 112 ± 9

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Ag NW/PPy2 5 0.34 220 ± 10
Ag NW/PPy3 10 0.34 473 ± 35

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Ag NW/PPy4 20 0.34 962 ± 45
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Ag NW* - - 70 ± 2
*Given for comparison.
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Table 2. Yuksel et al.

Potential or Current Specific

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Electrode Materials Electrolyte Voltage density or Capacitance Refs.
window (V) Scan rate ( F g-1 )
0.1-0.8 V vs

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SWNT-PPy 7.5 M KOH 10 mA g-1 265 [30]
Ag/AgCl
3.0 M 0.0-1.0 V vs
PPy-graphene 1.5 A g-1 350 [38]
NaClO4 Ag/AgCl

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-0.8-0.5 V vs
Ex-GF/PPy 3.0 M KCl 1.0 A g-1 351 [57]
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1.0 M -0.2-0.7 V vs
PPy@C 100 mV s-1 114 [58]
H2SO4 Ag/AgCl
1.0 M
OCNTF/PPy 0.0-1.0 V 2.5 mA cm-2 305 [9]
LiClO4
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PVA - 0.0-1.0 V vs
PPy Hydrogel 0.2 A g-1 380 [5]
H2SO4 Ag/AgCl
-1.0-0.0 V vs
1 mV s-1
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PPy/carbon aerogel 6.0 M KOH 433 [59]

Hg/HgO
0.0-0.9 V vs
0.5 A g-1
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MoS2 NS - PPy 1.0 M KCl 695 [24]

Ag/AgCl
1.0 M -0.3-0.7 V vs
EG-RGO/PPy 0.5 A g-1 420 [37]
H2SO4 Ag/AgCl
0.5 M -0.8-1.0 V vs
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PPy-Ag NP 1 mV s-1 282 [60]

K2SO4 SCE
-0.8-0.8 V vs
PPy on Ti foil 1.0 M KCl 10 mV s-1 480 [61]
SCE
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1.0 M
SWNTS@MnO2/PPy 0.0-0.8 V 0.1 A g-1 353 [62]
Na2SO4
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0.0-0.9 V vs
CNT@PPy@MnO2 2.0 M KCl 2 mV s-1 325 [42]
SCE
1.0 M
MWNT/PPy 0.6 1 mV s-1 163 [31]
H2SO4
MWNT/ACNF/
6.0 M KOH 0.0-0.9 V 1 mA cm-2 333 [63]
PPy
0.5 M β- -1.2-0.9 V vs
AC/PPy 1 mV s-1 354 [36]
NSA SCE
Graphite fiber/ 0.0-0.8 V vs
1.0 M KCl 1 mA cm-2 400 [64]
PPy Ag/AgCl
w-PEDOT-PSS/ 1.0 M
0.0-0.8 V 100 mV s-1 70 [65]
PPy Na2SO4
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Ag NW/ PPy 1.0 M KOH 0.50 0.31 A g-1 509
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Highlights
• 3D core-shell Ag NW/PPy nanocomposites were utilized as supercapacitor electrode.
• Nanocomposite electrodes showed high capacity retention.
• A Csp of 509 F g-1 was obtained at a current density of 0.31 A g-1.

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