Journal of Alloys and Compounds 726 (2017) 1295e1303

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Electroless-deposited Ag nanoparticles for highly stable

energy-efficient electrochemical supercapacitor
Bidhan Pandit, Devika V.S., Babasaheb R. Sankapal*
Nano Materials and Device Laboratory, Department of Physics, Visvesvaraya National Institute of Technology, South Ambazari Road, Nagpur 440010,
Maharashtra, India

a r t i c l e i n f o a b s t r a c t

Article history: Silver (Ag) nanoparticles were synthesized through an electroless deposition providing high surface
Received 30 March 2017 coverage of porous material. The structural and morphological characteristics were investigated along
Received in revised form with electrochemical studies to evaluate the charge storage performance. The nanoparticle morphology
11 July 2017
provides more active sites and diffusion paths for the electrolyte ions resulting in maximum utilization of
Accepted 9 August 2017
Available online 10 August 2017
active electrode material. Ag nanoparticles based electrode not only exhibited a maximum specific
capacitance of 452 F/g (at scan rate of 2 mV/s) and specific energy of 27.8 Wh/kg, but also achieved a
tremendous gain over cyclic stability by retrieving 63% capacitance after 10,000 cycles. Such attractive
Keywords:
Silver nanoparticles
electrochemical behavior of the formed electrode is suitable for the manufacturing of the good quality
Electroless deposition supercapacitors by utilizing a roll-to-roll industrial production technology.
Energy storage © 2017 Elsevier B.V. All rights reserved.
Supercapacitor

1. Introduction demonstrating the usefulness of SNPs in enhancing the properties

Nanoparticle synthesis is an important aspect of modern science
because it reveals novel and subtle properties regarding the dis-
tribution, size, and morphology of the particles [1]. Nanoparticles
and their nanostructured composites provide a facile path for
electrolyte ions to penetrate, thereby resulting in superior elec-
trochemical activities. Many routes are proposed for synthesizing
nanoparticles according to the need for cost-effective, non-toxic,
and environmentally-friendly materials [2]. Simple chemical
routes, such as chemical bath deposition (CBD), successive ionic
layer adsorption and reaction (SILAR), electrodeposition, and elec-
troless deposition are the most easy and effective ways to synthe-
size nanoparticles with the above criteria in mind [3e5].
Over the past few decades, silver nanostructures and nano-
particles have been shown to possess advanced catalytic, electro-
chemical and optical properties that make them attractive for use
in technological applications [6]. Silver nanoparticles (SNPs) have
been synthesized through physical, chemical, and most recently,
biological methods. Many research articles have emerged
* Corresponding author.
E-mail addresses: brsankapal@phy.vnit.ac.in, brsankapal@gmail.com
(B.R. Sankapal).
of active electrode materials for various applications [7, 8]. Yuksel el
al. obtained the specific capacitance of 500.7 F/g by electro-
depositing AgNW/MoO2 with a coaxial structure using 1 M LiClO4
in PC as the electrolyte [9]. Tang et al. reported a specific capaci-
tance of 615 F/g for SSCNTs/PANI/Ag synthesized via the ultrasonic
oxidation-cut method [10]. Shen et al. successfully fabricated a
AgNWs/WO3 electrode that exhibited a specific capacitance of
138.2 F/g [11]. To increase the specific capacitance to as high as
450 F/g, Kalambate et al. synthesized a GNS/AgNPs/PPY composite
using in situ oxidative polymerization [12]. However, the results are
still far away from the desired values despite the encapsulation or
decoration of Ag nanoparticles on different electrode materials. The
majority of works available in the literature concerning the syn-
thesis of silver nanoparticles make use of techniques, such as
electrodeposition, thermal evaporation, sputtering, etc. However,
only a few attempts have been put forth to exploit the benefits of
electroless deposition. Along with low-cost, the time-efficient na-
ture of electroless deposition can be coupled with roll-to-roll
technology for industrial mass production. To our knowledge,
there are no reports available in the literature on the synthesis of a
silver electrode achieved via the electroless deposition method for
supercapacitor applications.
Here, a state-of-art method has been explored to synthesize a
thin film consisting of silver nanoparticles on a stainless-steel (SS)
substrate using electroless deposition at room temperature (300 K)

http://dx.doi.org/10.1016/j.jallcom.2017.08.068
0925-8388/© 2017 Elsevier B.V. All rights reserved.
1296 B. Pandit et al. / Journal of Alloys and Compounds 726 (2017) 1295e1303

Fig. 1. Schematic illustration for the deposition of Ag nanoparticles.

for supercapacitor applications. The as-synthesized electrode pro-

vides excellent results compared to the literature composites
related to Ag nanoparticles. The supercapacitor electrode exhibites
high-energy and high-power densities, which can be used for
practical applications. Hence, the present article focuses on (i) a
simple, low-cost and time-effective chemical route to synthesize Ag
nanoparticles that can be integrated for large area deposition and
roll-to-roll technology, (ii) the surface optimization of the SNPs
which provide relevant electroactive porous cavities for electrolyte
ions with a high capacitance and charge-discharge characteristics,
and (iii) a high-energy, efficient power electrode with a superb
stability of over 10,000 cycles.

2. Experimental

2.1. Synthesis procedure

SNPs were deposited on glass (G) and SS substrates using silver

nitrate (AgNO3) and hydrazine hydrate using an electroless depo-
sition process (Fig. 1). A solution of AgNO3 with a 10-mM concen-
tration was used as the cationic precursor, whereas a 50-mM
solution of hydrazine hydrate (80%) was used as the anionic pre-
cursor in the aqueous medium. The deposition procedure consists
of two steps: 1) well-cleaned substrates were immersed into the
AgNO3 solution for 10 s to initiate the adsorption process; 2) when
the substrates were immersed into the hydrazine solution for 10 s, a
grayish-black-colored film was coated on the substrates. This entire
process was repeated 20 times for optimum film thickness. Finally,
the deposited films were rinsed in double distilled water (DDW)
and used for further characterizations and electrochemical analysis.

2.2. Characterizations

The structure and morphology of the electrodes were analyzed

via Fourier transform infrared spectroscopy (FTIR, Thermo Nicolet,
Avatar 370), X-ray diffraction (XRD, Bruker AXS D8), field emission
scanning electron microscopy (FESEM, JEOL Model JSM-6390LV),
and high-resolution transmission electron microscopy (HRTEM,
Philips EM-CM-12) with a selected area electron diffraction (SAED)
pattern. The absorption spectra were recorded using a UVeVis Fig. 2. (a) FTIR spectra of SS and SS/Ag samples, (b) UVeVis spectra of silver nano-
spectrophotometer (UV-1601, Shimadzu) for the film deposited on particles, (c) X-ray diffraction patterns of bare SS, SS/Ag, and G/Ag.
 B. Pandit et al. / Journal of Alloys and Compounds 726 (2017) 1295e1303
the glass substrate. All of the electrochemical analyses were con-
ducted using a potentiostat (Princeton Applied Research, PARSTAT-
4000, USA). A three-electrode system consisting of Ag/AgCl as the
reference electrode, a platinum wire as the counter electrode, and
an Ag film as the working electrode was engaged to investigate all
of the electrochemical activities by dipping a (1
1)-cm2 dimen-
sion of the active area in 0.5 M of the NaOH electrolyte
(Supplementary information, S1).
The gravimetric weight difference method was used to calculate
the mass loading of the active material on the substrate surface
using formula [13]:
M ¼ m1  m2 (1)
where M signifies the mass of the active electrode material, m2
specifies the mass of the SS substrate without the film, and m1 is
the mass of the SS substrate with the film with an area of (1
1)-
cm2. The average active mass of the electrode material was calcu-
lated to be 0.22 mg/cm2 by performing several measurements for
better accuracy.
3. Results and discussion
3.1. Kinetics of film formation
The film formation mechanism can be well understood as fol-
lows: in the cationic precursor, silver nitrate contributes Agþ ions as
AgNO3 #Agþ þ NO
3 (2)
When the substrate is immersed into the cationic solution, the
Agþ ions become adsorbed onto the substrate surface due to Van
der Waals force. Hydrazine is a powerful reducing agent that
directly reduces pre-adsorbed Agþ ions on the substrate surface to
Ag when the substrate is immersed into the hydrazine solution. The
proposed reaction mechanism for film formation can be predicted
Fig. 3. (aec) FESEM images of Ag thin film at different magnifications, (d) EDS spectra.
1297
as follows:
4Agþ þ N2 H4 /4AgY þ N2 [ þ 4Hþ (3)
3.2. Structural analysis
FTIR spectroscopy was used to evaluate the formation of any
unwanted oxide due to the impact of the environment (Fig. 2a). The
peaks observed at 1648 and 3460 cm1 may be due to the moisture
absorbed during mixing the sample with KBr [14]. Except for these,
no peaks were identified that were related to the contaminations.
Fig. 2b shows the UVeVis absorption spectra for the Ag thin film
on the glass substrate. The Ag nanoparticles exhibited surface
plasmon resonance absorption in the UVeVis region due to the
combined vibration of free electrons with light. As a result, a broad
absorption band was observed at 384 nm, and a similar band has
been reported in the literature [15, 16].
The XRD patterns were collected from 10 to 80 and are shown
in Fig. 2c. The SS/Ag film provides peaks at 2q values of 37.53 and
64.04 corresponding to the (111) and (220) planes with d-spacings
of 0.24 and 0.14 nm, respectively for the face-centered cubic
structure (JCPDS, 04-0783). This is well supported by previously
reported literature on silver nanoparticles [14, 17]. The other peaks
are assigned to the SS. During the deposition process, the proba-
bility to form silver oxide on the SS substrate cannot be entirely
avoided. Hence, for better confirmation, structural analysis was
performed for the silver film deposited on the glass substrate (G/
Ag). The XRD pattern obtained for G/Ag showed additional peaks at
44.36 and 77.40 that only correspond to the (200) and (311) peaks
of silver, respectively.
3.3. Surface architecture
The overall electrochemical reactions are strongly dependent on
1298 B. Pandit et al. / Journal of Alloys and Compounds 726 (2017) 1295e1303
the surface morphology of the electrode material due to their
occurrence at or near to the surface of the electrode. The surface
morphology and composition were studied using FESEM with EDS
analysis (Fig. 3aed). As shown in Fig. 3aec, the surface of the Ag
film showed a compact, dense and well-covered nanoparticle
structure with individual particles having diameters of 20e40 nm.
Agglomerates consisting of primary silver nanoparticles were
observed over some parts on the surface area as well. The size of the
nanoparticles obviously affects the electrochemical behavior
because it is directly associated with the porosity and surface area
of the synthesized electrode materials. A smaller particle size for
the silver nanoparticles produces a more porous surface area than
larger particle sizes, resulting in a maximum capacitance value
through more conductive paths and electroactive cavities [18].
Thus, a porous morphology with a nanoparticle assembly features
more electroactive cavities for electrolyte ions and facilitates elec-
trochemical reactions. Fig. 3d shows the EDS spectra in which a
sharp peak at 3 keV originates from the confined surface plasmon
resonance, confirming the presence of metallic silver [19,20]. Other
elements, such as Cr, Ni, and Fe, emerged due to the use of the SS
substrate.
HRTEM images were analyzed to obtain more information about
the nanostructure and are depicted in Fig. 4aec. The spherical na-
ture of the silver nanoparticles with diameters of 20e40 nm was
confirmed. Moreover, lattice fringes with interplanar spacings of
Fig. 4. (aec) HRTEM images of Ag sample at different magnifications, (d) SAED pattern.
0.24, 0.19, and 0.14 nm could be clearly discerned, which corre-
spond to the (111), (200), and (220) planes, respectively. Similar
adjacent planes were further confirmed via concentric rings in the
SAED pattern and are shown in Fig. 4d.
3.4. Supercapacitive electrochemical studies
The capacitance from cyclic voltammetry (CV) directly depends
upon the operational potential window and nature of the selected
electrolyte [21]. To find the most suitable electrolyte with an op-
timum potential window, CV curves of the Ag film were examined
at a scan rate of 100 mV/s in 0.5 M aqueous solutions of Na2SO4,
Na2SO3, LiCl, LiClO4, KCl, KOH, and NaOH electrolytes (Fig. 5a). Some
of the CV curves display rectangular and symmetric profiles,
revealing the non-faradic charge storage behavior of electric double
layer capacitance (EDLC). In the case of NaOH and KOH electrolytes,
the Ag electrode exhibited faradic behavior as evident from the
well-resolved oxidation and reduction peaks [22]. The Ag electrode
exhibited a maximum specific capacitance in NaOH solution at an
operation potential window from 0.2 to 1.1 V (Fig. 5b). The
concentration of NaOH solution was varied to obtain an optimum
capacitance when keeping the potential window and scan rate
constant (Fig. 5c). We observed that the earlier assumed 0.5 M
concentration is the optimum concentration as shown in Fig. 5d.
The solution with a low concentration (0.25 M) could not provide
 B. Pandit et al. / Journal of Alloys and Compounds 726 (2017) 1295e1303 1299

sufficient amount of electrolyte ions required for the electro-
chemical reactions. A further increase in the concentration (0.75 M)
causes a reduced ionic mobility, resulting in some capacitance drop
[23]. Hence, all of the electrochemical analysis was carried out in
the potential range between 0.2 and 1.1 V in the 0.5 M NaOH
electrolyte.
CV was performed at different scan rates ranging from 100 to
2 mV/s within a voltage range between 0.2 and 1.1 V in the 0.5 M
NaOH electrolyte and is shown in Fig. 6a. The vibrant redox peaks
clearly describe the pseudocapacitive charge storage behavior
which differs from the rectangular-shaped EDLC actions [24]. The
oxidation/reduction equilibrium can be described as follows
Agn0 #Agnþ þ e
The specific capacitance vs. scan rate profile shows an increase
in the specific capacitance with a decrease in scan rate (Fig. 6b). At
lower scan rates, the main capacitive properties arise from inner
active site cavities that endure the redox reaction mechanism.
However, at higher scan rates, electrolyte ions cannot gain full ac-
cess of the inner porous cavities, resulting in a relatively low
capacitance value [25, 26]. The synthesized Ag electrode exhibits a
maximum specific capacitance of 452 F/g at a scan rate of 2 mV/s.
This value is greater than some of the previously reported Ag
nanoparticle encapsulated or decorated composites, such as CNT-
AgNWs (143 F/g) [7], Ag-GNFs/PANI (212 F/g) [8], and AgNWs/
WO3 (138.2 F/g) [11], and GNS/AgNPs/PPY (450 F/g) [12]. Higher
values have been reported by some authors, but they are for
nanocomposites with one or more nanomaterials, such as polymers
or polymer added carbon materials, whereas our report is for a
single silver nanoparticle electrode. Dhibar et al. reported higher
specific capacitance values for Ag-PANI/CNT and Ag-PANI/Gr of 528
and 591 F/g, respectively [27, 28]. In addition, Patil et al. obtained a
specific capacitance of 512 F/g for a Ag/PANI composite [29]. These
values are higher than what we report. However, if our silver
nanoparticles are incorporated into a polymer or high surface area
(4) aligned carbon support, it may boost the specific capacitance values
compared with the reported ones. Moreover, the simple and time-
effective synthesis route is our important advantage as compared
with the reference data.
The Galvanostatic charge-discharge (GCD) characteristics
significantly influence the evaluation of the rate capability of the
electrode material. The GCD profile for various current densities is
shown in Fig. 6c. It shows a non-linear behavior that is different
from the EDLC-derived electrodes where the GCD profile is

Fig. 5. Electrolyte and concentration variation of Ag electrode (a) CV curves at different electrolytes, (b) variation of specific capacitance with different electrolytes, (c) CV curves for
different NaOH concentrations, (d) variation of specific capacitance with different NaOH concentrations.
1300 B. Pandit et al. / Journal of Alloys and Compounds 726 (2017) 1295e1303

Fig. 6. Electrochemical performance of Ag electrode with 0.5 M NaOH electrolyte. (a) CV curves at different scan rates ranging from 2 to 100 mV/s, (b) specific capacitance as a
function of scan rate (c) CD curves at different current densities ranging from 2 to 5 mA/cm2, (d) specific capacitance at a function of current density.

triangular in shape. The non-linear shapes of the Ag electrode of the electrochemical double layer, and (iii) a curved variation for
reveal three altered portions consisting of (i) a rapid IR drop due to the reversible electrochemical processes [30]. The Ag electrode
the internal resistance, (ii) a linear section because of the presence exhibited a maximum specific capacitance of 247 F/g at a current

Fig. 7. (a) Ragone plot of Ag electrode, (b) Cycling stability for 10,000 cycles, inset shows the CV curves for different cycle numbers at 100 mV/s scan rate.
 B. Pandit et al. / Journal of Alloys and Compounds 726 (2017) 1295e1303 1301

Table 1
Summary of the performance characteristics of Ag electrode for several studied Ag composites.

Electrode materials Electrolyte VW (V) SC (F/g) Specific energy (Wh/kg) Specific power (kW/kg) Stability Ref.

R (%) Cycles

CNT-AgNW 1 M H2SO4 1 143 e e 100 3000 [7]

Ag-GNFs/PANI 6 M KOH 1 212 e e e e [8]
AgNWs/WO3 1 M H2SO4 0.7 138.2 e e 95 1000 [11]
GNS/AgNPs/PPY 1 M KCl 1.3 450 81 10.13 92 1000 [12]
Ag-PANI/CNT 1 M KCl 1.6 528 e 4.2 94 1000 [27]
Ag-PANI/CNT 1 M KCl 0.5 591 20.24 0.75 96 1500 [28]
Ag/PANI 1 M H2SO4 1 512 50.01 e 82 2000 [29]
PPY/PAA/Ag 0.1 M H2SO4 0.9 226 17.45 e 63 2000 [31]
Ag/MnO2 1 M Na2SO4 1 293 17.8 0.25 96.8 5000 [32]
AgNPs 0.5 M NaOH 0.9 452 27.8 4.1 63 10,000 Present work

VW ¼ Voltage window; SC ¼ Specific capacitance; R ¼ Retention.

density of 2 mA/cm2. Additionally, the capacitive value of 141 F/g at
the high current density of 5 mA/cm2 indicates an efficient and fast
charge transport through film embedded with Ag nanoparticles
(Fig. 6d). A deviation of the specific capacitance measured from the
CV and CD curves was observed because the capacitance was
measured at a particular potential for CV, but the CD-derived spe-
cific capacitance was calculated for an average potential range
of 0.2 to 1.1 V (vs. Ag/AgCl).
The energy and power densities are the most important assets
for energy storage applications. A specific energy of 17.45 Wh/kg
was obtained by Patil et al. [31] for a polyacrylic acid/polypyrrole/
silver (PPY/PAA/Ag) composite. Xia et al. [32] reported a maximum
specific energy of 17.8 Wh/kg for a Ag/MnO2 hierarchical hetero-
structure. Fig. 7a displays the Ragone plot (specific energy vs.
power plot), from which it can be inferred that the Ag electrode
possessed a maximum specific energy of 27.8 Wh/kg and deliv-
ered a specific power of 4.1 kW/kg which is much greater than in
the earlier reported data (Table 1). Again, a specific power of
10.2 kW/kg was attained with a drop in specific energy to
15.9 Wh/kg. Hence, it is clear that the Ag electrode exhibits a
greater specific energy compared with ordinary capacitors and
delivers a higher power as compared to the conventional
batteries.
An electrochemical stability analysis is vital to evaluate the
practical aspects of electrodes for SC applications. Pseudocapacitive
electrode materials suffer from a lower stability due to the degra-
dation of electrode materials compared with EDLCs [33]. In our
work, CV cycles were repeated 10,000 times at a constant scan rate
of 100 mV/s, and the capacitive retention is depicted as a function
of cycle number in Fig. 7b. The Ag electrode exhibited a long-term
stability with only a 37% deterioration of its initial capacitance
despite being a redox active electrode. Furthermore, the CV curves
maintain their redox-influenced shape even after 10,000 cycles,
exhibiting an excellent sustainability and rate capability for the
active electrode [34].
The internal resistive and capacitive elements and their effects
on the electrochemical studies of the Ag electrode were evaluated
via electrochemical impedance spectroscopy (EIS). The impedance
was measured by varying the frequency range from 100 kHz to
100 mHz and is plotted as Z00 vs. Z0 in the Nyquist plot (Fig. 8a). The
curve shows an almost parallel behavior to the imaginary imped-
ance axis, indicating a perfect capacitive behavior. At relatively
higher frequencies, the intercept of the plot with the X-axis sig-
nifies the total internal resistance (RS) by combining the inherent
substrate resistance, substrate/current controller contact resistance
and interior electrolyte resistance [35]. The Ag film has an RS value
of 3.6 Ohm/cm2 and a low charge transfer resistance (RCT). The
corresponding equivalent circuit adjacent to the Nyquist plot is a
modified Randles circuit that was analyzed using the complex
nonlinear least squares (CNLS) setting method [36]. The ideal ver-
tical alignment of the Nyquist curve is related to the mass capaci-
tance (CL); however, practically it inclined to some angle,
suggesting a presence of an associated resistive element as the
leakage resistance (RL). Finally, the Warburg resistance (W) is
linked to ion diffusion/transport from the electrolyte to the elec-
trode interface [37].
The relaxation time constant ðt0 Þ clearly defines the boundary
between the resistive and capacitive behavior. The low ðt0 Þ value
corresponds to the high-power posture which is in favor of
supercapacitive eccentricity. t0 is usually calculated from t0 ¼ f1
0
using an imaginary frequency component (C00 ) vs. frequency (f) plot
[38] where
00 Z0
C ¼ ; (5)
2pf jZj2
and f0 reveals the characteristic frequency (Supplementary
information, S2).
The estimated value of t0 is 5.7 ms (Fig. 8b), which clearly in-
dicates that the fast charge transport phenomena to the inner pores
during redox reactions take place. The low value of RS and t0 clearly
suggests the excellent electroactive capability of the Ag electrode.
The phase angle as a function of frequency is referred to as the
Bode plot, which is important for explaining the quality of the
active electrode material. An ideal capacitive component indicates
an exact 90 phase angle [39]. From Fig. 8c, it can be observed that
the phase angle is appreciably close to 72 in the low frequency
region, suggesting a good capacitive behavior.
4. Conclusions
A thin film consisting of silver nanoparticles was synthesized
successfully by simple electroless deposition at room temperature
and directly employed as a supercapacitor electrode which
exhibited a maximum capacitance of 452 F/g with a superior long-
term stability (63% after 10,000 cycles). Furthermore, the Ag elec-
trode exhibited a high specific energy of 27.8 Wh/kg by utilizing fast
electron transfer and access of the electrolyte ions using the
freeway provided by the porous nanostructure. The overall superior
performance selects the Ag electrode as a possible nominee for
advanced high-power and effective energy storage technologies.
1302 B. Pandit et al. / Journal of Alloys and Compounds 726 (2017) 1295e1303
Fig. 8. (a) Nyquist plot of impedance from 100 mHz to 100 kHz, inset shows corre-
sponding equivalent circuit, (b) real and imaginary capacitance component vs. fre-
quency plot to compute relaxation time constant, (c) Bode plot.
Acknowledgements
BP gratefully acknowledges VNIT for providing institute fellow-
ship and American Journal Experts for support. BRS acknowledges
the DST/TMD/MES/2k16/09 project from the Govt. of India.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jallcom.2017.08.068.
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