Ionics

https://doi.org/10.1007/s11581-018-2527-1

ORIGINAL PAPER

Zinc oxide nanoparticles and activated charcoal-based nanocomposite

electrode for supercapacitor application
Mahendra Singh Yadav 1 & Narendra Singh 1 & Santosh M. Bobade 2

Received: 12 October 2017 / Revised: 12 February 2018 / Accepted: 10 March 2018

# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
In the present work, zinc oxide (ZnO) nanoparticles (NPs) have been synthesized at room temperature using co-precipitation
method for the use as an electrode material by forming a composite with activated charcoal (AC) powder for its application in
electrochemical supercapacitor. For synthesizing of ZnO nanoparticles, dry zinc chloride (ZnCl2) and sodium hydroxide (NaOH)
have been used as the initial precursors. The obtained ZnO nanopowder has been calcined at 400, 500 and 600 °C for 2 h. The
nanoparticles have been characterized by powder X-ray diffraction analysis (XRD), scanning electron microscopy (SEM),
transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). The nanocomposite has also been
investigated by synchrotron radiation-based X-ray photoelectron spectroscopy (XPES). Supercapacitor cells (symmetrical) have
been fabricated by making use of different composition of zinc oxide (ZnO) nanoparticle-activated carbon (AC). Electrochemical
properties of the prepared nanocomposite electrodes and fabricated supercapacitor cells have been characterized using a.c.
impedance, cyclic voltammetry (CV) and charge–discharge (CD) techniques by using 6 M KOH and 1 M NaOH as the
electrolytes. The optimized composition is 1:1 (mass ratio) of ZnO and activated charcoal, and 600 °C for 2 h is an optimized
temperature for synthesis of nanoparticles. The specific capacitance of the supercapacitor cells is stable up to 2000 cycles at
100 mV cm−2, which show that the device has good electrochemical reversibility and cycle life with 6 M KOH and 1 M NaOH
electrolyte.

Keywords Nanoparticles . Nanocomposite . XRD . SEM . TEM . XPES . Supercapacitor

Introduction cell [2], fuel cell [3], battery [4] and supercapacitor [5] are
essential elements in the energy conversion–storage–delivery
In the present scenario of rapid development in the global sequence system and have gained great attention in the
economy, the conventional non-renewable energy resources twenty-first century. Batteries and supercapacitors both are
such as fossil fuels are depleting, and it is also leading to mainly considered as the possible energy storage systems with
drastic changes in environmental conditions. Thus, it is highly a number of distinctive advantages and large potential appli-
essential to establish a clean, an efficient, sustainable energy cations [1, 6]. However, both the energy system has its own
sources, and also advanced technologies related to energy advantages and drawbacks. To make these applications com-
conversion, and storage systems [1]. The efficient, environ- mercially viable for daily use, they still require further
mental friendly and economical energy devices such as solar improvements.
Electrochemical capacitor is known as an ultracapacitor,
and it is also called as supercapacitors which is an energy
* Mahendra Singh Yadav storage system. In recent time, it has attracted major
mahsinyad18@gmail.com attention and also considered as the most favourable
candidate for next-generation energy storage systems because
1
Department of Electronics and Communication Engineering, Jaypee
it has higher power density, better cycling lifespan, fast charg-
University of Engineering and Technology, Guna, Madhya ing–discharging, highly efficient, safe, wide range of operat-
Pradesh 473226, India ing temperature and environment friendly in comparison to
2
Department of Physics, Jaypee University of Engineering and batteries [7–9]. Supercapacitor fills the gap between the con-
Technology, Guna, Madhya Pradesh 473226, India ventional capacitor and the batteries. Therefore, such
 Ionics

characteristics make them the most promising candidate in application and optoelectronic as well. ZnO is a semiconduct-
different applications, such as hybrid vehicles, portable elec- ing material having band gap of 3.37 eV, which offers distinct
tronics, space or military devices, and backup energy systems optical and bio compatible property. In recent time, ZnO nano-
[10]. particles have also been projected as a promising candidate for
The performance of ultracapacitor is determined by its el- bio-application compared to other metal oxide nanoparticles
ements, specifically, the electrodes, electrolytes and the cur- [30]. ZnO is one of those metal oxides that can be easily syn-
rent collectors. The properties and the nature of the electrode thesized. Further, it is environmentally friendly, and useful in
materials are deciding factors for the energy storage mecha- several applications such as medical, industrial and technical
nism in ultracapacitor. According to the types of electrode applications. Its morphology determines the physical properties
materials and charge storage mechanisms, the ultracapacitor that can be exploited for various applications leading to the
is classified into two classes, namely electric double layer momentum to the development of a large variety of methods
capacitors (EDLCs), which uses electrodes from different de- for synthesizing the nanoparticles [31]. ZnO nanoparticles
rivatives of carbon that includes activated carbon, carbon (NPs) exhibit great features, such as high ultraviolet (UV) ab-
aerogel, carbon nanotubes and graphene [11, 12], and sorption, long lifespan and large surface to volume ratio [32].
pseudocapacitors or redox capacitors, which utilizes transition The large surface to volume ration leads to the application as a
metal oxides, including zinc oxide (ZnO), ruthenium oxide catalyst [33], gas sensor [34], active filler used for rubber and
(RuO2), manganese oxide (MnO), nickel oxide (NiO), cobalt plastic, anti-virus agent inside coating and UV absorber inside
oxide (CoO) [13–16] or conducting polymer electrodes in- cosmetics [35, 36], solar cell [37], and varistors [38], and elec-
cluding polypyrrole, PANI [17–20]. trical and optical devices [39, 40]. ZnO nanoparticles can be
In EDLCs, the charge storing process occurs by electrostat- synthesized by different synthesis methods including sol–gel
ic adsorption and desorption at the electrode–electrolyte inter- technique [41], mechanical milling [42], organometallic synthe-
face, whereas in the case of pseudocapacitor, it is assisted by sis [43], spray pyrolysis [44], thermal evaporation [45], mech-
the fast and reversible redox reactions [21, 22]. It is also called anochemical synthesis [46], microemulsion synthesis [47], RF
faradic process. It is well-known that every approach has its plasma synthesis [48], supercritical water processing [49], self-
individual limitations, such as lower capacitance and energy assembling [50], hydrothermal processing [51], vapour trans-
density in the case of EDLCs, and limitations, such as poor life port process [52], sonochemical or microwave-assisted synthe-
cycle problem in the case of pseudocapacitors. Hybrid or sis [53], direct precipitation [54] and homogeneous precipita-
asymmetrical configuration of a supercapacitor can be fabri- tion [55]. Out of all these methods, co-precipitation and sol–gel
cated by using both the classes, namely EDLC and method provide better control over the nucleation, aging and
pseudocapacitor. In a hybrid supercapacitor, one of the elec- growth of nanoparticles in solution. The co-precipitation meth-
trodes is made of carbonaceous materials, while the other elec- od is simple and economical for the bulk production of nano-
trode is made of metal oxides or conducting polymers [15]. particles [56].
The performance of ultracapacitor can be enhanced by im- In this paper, we report a cost-effective and simple co-
proving the nature, and properties of the electrode, electrolytes precipitation method to synthesize the uncapped ZnO nano-
and the current collectors. In the case porous carbonaceous particles for energy storage device applications, for example,
electrodes, on addition of metal oxide (ruthenium oxide, zinc an electrode material for supercapacitors. The synthesized
oxide, manganese oxide, nickel oxide, cobalt oxide), its per- ZnO NPs have been characterized using powder X-ray diffrac-
formance is amplified [23–26]. At this point, the oxide addi- tion (XRD), Fourier transform infrared spectroscopy (FTIR),
tives generate faradic capacitance to improve the supercapac- scanning electron microscopy (SEM), transmission electron
itor performance parameters. In the case of ruthenium oxide- microscopy (TEM) and selected area electron diffraction
based supercapacitors, its toxicity and expensiveness are the (SAED). The synthesized uncapped ZnO nanoparticles were
major barriers to its use in commercial application. At the used with activated charcoal (AC) powder for making the
same time, considering the cost-effective solution and en- nanocomposite. The synthesized ZnO–AC nanocomposite
hanced performance of the supercapacitor, the electrical con- has been characterized to investigate the surface morphologi-
ductivity of economically viable transition metal oxides needs cal properties using SEM and electronic properties by syn-
to be improved. For example, zinc oxide (ZnO) is known as chrotron radiation-based X-ray photoelectron spectroscopy
inexpensive and environmentally friendly materials for (XPES). In the present work, to evaluate the performance of
supercapacitor electrode application relative to the ruthenium the developed ZnO–AC nanocomposite electrode material,
oxide. symmetrical supercapacitors have been fabricated with 6 M
Currently, semiconductor nanoparticles have globally KOH electrolyte and the supercapacitors with 1 M NaOH as
attracted attention due to its huge potential in the field of bio- an electrolyte counterpart. The electrochemical performance
applications and opto-electronics [27–29]. Specifically, the II– of fabricated ZnO–AC nanocomposite electrode-based
VI group semiconductors have been widely employed for bio- supercapacitors cells (EDLCs) has been characterized using
Ionics

a.c. impedance spectroscopy, cyclic voltammetry and galva- The X-ray diffraction (XRD) pattern of ZnO nanoparticles
nostatic charge–discharge techniques. has been recorded using D8 Brucker, USA, diffractometer.
The diffractogram has been recorded using high-intensity
CuKα radiation (λ = 1.5406 Å) and the angle (2θ) in the range
Experimental between 10° and 80°. The ZnO nanoparticles and the compos-
ite formed by ZnO nanoparticle-activated charcoal (AC) sur-
Materials face morphology have been examined by SEM, EVO-18 Carl
Zesis scanning electron microscopy (SEM). Further, ZnO
In this work, zinc oxide (ZnO) nanoparticles are synthesized nanoparticles have been also analysed with the help of TEM
using co-precipitation method. This synthesis method gives and selected area electron diffraction (SAED) pattern using a
numerous advantages in comparison with other synthesis Technai G2T30, U-Twin (FEI, The Netherlands) transmission
methods, for example, low synthesis temperature, small size electron microscopy (TEM). The prepared zinc oxide (ZnO)
particle and straight forwardness of processing. The initial nanoparticles have also been characterized using FTIR
precursors used in this work are zinc chloride dry (ZnCl2) (Shimadzu IRAfinity-1) in the range of 4000–400 cm−1 with
procured from Merck (Mw = 136.30 g mol−1), sodium hydrox- KBr pellet as a standard. Prepared ZnO–AC nanocomposite
ide flakes (NaOH) with molecular weight Mw = 40 g mol−1 was also characterized using synchrotron radiation-based X-
and activated charcoal powder are procured from Loba ray photoelectron spectroscopy (XPES) beamline (BL-14), on
Chemie. All the precursors are used without any additional Indian synchrotron indus-2.
purification. For preparation, precursor solutions are used in
double distilled water (DDW). The detail of the ZnO NPs Preparation of electrodes
synthesis process is explained in the following section.
The mixture of the prepared ZnO NPs procured activated char-
Methods coal (AC) powder and 10 wt% PVdF-HFP (Sigma-Aldrich) in
a mass ratio of 45:45:10, respectively, was added in acetone
Synthesis of zinc oxide (ZnO) nanoparticles leading to formation of a gel. The prepared gel was coated on
the graphite sheet procured from Alfa Aesar, USA. Keeping
Zinc oxide nanoparticles have been synthesized using a co- polyvinylidene fluoride co-hexa fluoro propylene (PVdF-
precipitation method starting with dry zinc chloride, and sodi- HFP) concentration constant, the concentration of AC (Loba
um hydroxide as an initial precursor. In the synthesis process, Chemie) and ZnO was varied. Composition with 1:1, 1:2 and
1 M dry zinc chloride (ZnCl2) has been dissolved in 100 ml of 1:3 ratio was formulated by adding AC and ZnO, respectively.
double distilled water, with constant stirring for 30 min for its These prepared electrodes were dried at 80 °C for a period of
absolute dissolution. Likewise, 2 M NaOH (sodium hydroxide) 12 h. Further, the electrode weight with an accuracy of 0.1 mg
has also been prepared in 100 ml of double distilled water by has been measured with the help of a Sartorius BT 224 S ana-
constant magnetic stirring for 20 min [57]. NaOH (sodium lytical balance. For the electrode materials, the graphite sheet
hydroxide) solution acts as a precipitating agent, and it has been has been used as a current collector. Filter paper soaked with
poured drop by drop into continuously stirred zinc chloride electrolyte 6 M KOH was used as a separator. Similarly,
solution. The process has been carried out at room temperature supercapacitor with 1 M NaOH was also fabricated [57].
which lasts for 5 h resulting into whitish cloudy solution. The
white precipitate has been washed several times by double dis- Electrochemical measurements
tilled water to remove the residue and unwanted impurities.
Later on, the nanoparticles have been separated by filtration The supercapacitor cells were fabricated with optimized com-
Whatman filter paper 42 that has been used for filtering out position of 6 M potassium hydroxide (KOH) and 1 M sodium
the particles followed by drying process at 100 °C for 2 h in hydroxide (NaOH) and ZnO–AC nanocomposite-based elec-
the oven. The final powder has been calcined at 400, 500 and trodes, respectively. The electrolyte was sandwiched between
600 °C temperatures for 2 h in a muffle furnace and air ambient. two symmetrical electrodes to form a supercapacitor.
The calcined powder has been ground to obtain the fine powder Electrochemical measurement of fabricated supercapacitor
of ZnO that has been used for further analysis. In the entire cells was carried out on the two-electrode system having fol-
process, the chemical reactions taking place are as follows: lowing configuration:
Cell A : ZnO−AC j KOH ð6MÞ j ZnO−AC
ZnCl2 þ 2NaOH→ZnðOHÞ2 þ 2 NaCl ð1Þ Cell B : ZnO−AC j NaOH ð1MÞ j ZnO−AC
where ZnO–AC is the zinc oxide-activated charcoal nano-
composite, and KOH (6 M) and NaOH (1 M) are the opti-
ZnðOHÞ2 →Δ ZnO þ H2 O ð2Þ mized electrolytes used in this work.
 Ionics

Electrochemical measurement of the fabricated superca- Similarly, charge energy is calculated by integrating, i.e.
pacitor cells was carried out by a.c. impedance spectroscopy, finding the area under the GC curve [58].
cyclic voltammetry and galvanostatic charge–discharge tech-
t ðumax Þ
niques using computer-controlled CHI 608C, CH E int=C ¼ I∫tðumin Þ U ðt Þdt ð8Þ
Instruments, USA.
The a.c impedance measurements were carried out in the The energy efficiency is evaluated by taking a ratio as
frequency range from 10 mHz to 100 kHz. The overall capac-
itance C of the supercapacitor cells from a.c. impedance spec- E int=D
troscopy was calculated by using the following mathematical ηE ¼ ð9Þ
E int=C
formula:
1 The energy density and power density of the capacitor cells
C¼− }
ð3Þ have also been calculated with the help of the following math-
Z ω
ematical expressions:
where Z″ is the imaginary part of the complex impedance and 1
ω is the angular frequency. Energy density ¼ CV 2 ð10Þ
2
The single electrode-specific capacitance of the capacitor
1 CV 2
cells was calculated by multiplying the overall capacitance by Power density ¼ ð11Þ
a factor of two and dividing by the mass of the single electrode 2 Δt
material. where Δt is the time interval, V is the cell working voltage and
The capacitance values from cyclic voltammetry were cal- C is the calculated capacitance values.
culated by using the following mathematical relation:
i
C¼ ð4Þ
s
Results and discussion
where s is the scan rate and i is the measure of constant
current. XRD analysis
The charge–discharge measurement of the supercapacitor
cells has been carried out on the constant current density, and The crystalline structure and purity of synthesized ZnO nano-
its Cd (discharge capacitance) has been evaluated from the particles (NPs) have been confirmed from the powder XRD
linear part of the discharge curves using the following relation (X-ray diffraction) pattern. The significant intensity peaks po-
[58]: sition is in agreement with that of JCPDS file no. 00-036-
1451. The XRD spectrum of the synthesized uncapped zinc
Δt oxide (ZnO) nanoparticles (NPs) is shown in Fig. 1. All the
Cd ¼ i ð5Þ
ΔV peaks have been indexed using wurtzite hexagonal phase of
zinc oxide (ZnO) NPs. It clearly shows the formation of
where Δt is the time interval for the voltage change ΔV and i is wurtzite ZnO nanoparticles. The X-ray diffraction data is also
the constant current. in agreement with that of the electron diffraction pattern. The
The Columbic efficiency η has been evaluated with the broadening of peaks in XRD spectrum clearly indicates the
help of the following formula, and in this process, the same formations of nanoparticles. Further, from the XRD pattern
current is used for charging and discharging, at the same time reveals no impurity peak. It means that the synthesis of ZnO
[58]: nanoparticles with no detectable impurity has been achieved
by this process. From the peak position, the lattice constants
tD
ηt ¼ *100% ð6Þ a = 3.2447 Å, c = 5.2069 Å and c/a = 1.6047 Å have been
tC
calculated, which is also in agreement with that of JCPDS file
no. 00-036-1451. The lattice constants a and c are calculated
where tC and tD are the galvanostatic charging and discharging using the following relation [59]:
times, respectively.


In the case of nonlinear GC/GD characteristic, the dis- 1 4 h2 þ hk þ k 2 l2
charge energy is calculated by integrating, i.e. finding the area ¼ þ ð12Þ
d 2hkl 3 a2 c2
under the GD curve [58].

t ðumin Þ where a and c are the lattice constants, while the interplanar
E int=D ¼ I∫tðumax Þ U ðt Þdt ð7Þ distance is d and miller indices are (h k l).
Ionics

The bond length, L, of Zn–O has been calculated using the

following relation [59]:
 2 !
a2 1
L¼√ þ −u *c2 ð15Þ
3 2

where the positional parameter in the wurtzite structure is

represented by u. It measures the distance via which every
atom is displaced with respect to the next atom along the c
axis. The value of u has been quantified by following mathe-
matical relations [59]:

a2
u¼ þ 0:25 ð16Þ
3c2
u increases with decrease in c/a ratios. The four tetrahedral
Fig. 1 XRD pattern of the synthesized ZnO nanoparticles at 600 °C distances remain constant by varying tetrahedral angle with
the variation in c/a ratios. The bond length of Zn–O is deter-
From the XRD pattern of synthesized uncapped ZnO NPs, mined to 1.9813 Å, while the reported bond length (L) of Zn–
the maximum intensity is observed for the peak (100) planes O within the unit cell of the zinc oxide and neighbouring
and it is utilized to evaluate the average particle size of syn- atoms is 1.9767 Å [59]. The value of bond length determined
thesized uncapped ZnO nanoparticles using Debye–Scherrer matches with the bond length of Zn–O in the unit cell.
formula [59], as given below:
kλ
d¼ ð13Þ SEM and TEM analysis
βcosθ

where grain size is represented by d, FWHM (full width at half The morphology and micro-structural properties of synthe-
maximum) of peak (in radian) represented by β, Scherrer con- sized uncapped zinc oxide (ZnO) NPs have been investigated
stant represented by k, which is linked to the index (h k l) and using SEM (scanning electron microscopy). The scanning
shape of the particles, the value of k for spherical particles electron microscopy images of the synthesized uncapped
taken as 0.9, the Bragg diffraction angle represented by θ ZnO NPs at different magnification are shown in Fig. 2a–d.
and the wavelength of X-ray (Cu Kα, λ = 1.5406 Å) represent- The SEM images show the formation of high-density
ed by λ. The value of the full width at half maximum nanocluster containing closely packed ZnO nanorods having
(FWHM) is determined from the 2θ value of maximum inten- different diameters. A few of the tiny particle aggregates make
sity peak, and it is utilized for determining crystalline size of secondary particles due to its high surface energy and very
the zinc oxide (ZnO) NPs. The higher values of the full width small size. Since most of the particles are found in groups,
at half maximum (FWHM) and broadening of peak also con- so it is difficult to calculate the accurate grain size of the
firm the formation of nano-crystalline nature of ZnO NPs. The synthesized uncapped ZnO NPs using SEM image. Thus,
average particle size of uncapped zinc oxide (ZnO) the exact grain size of uncapped zinc oxide NPs has been
nanocrystals calculated from Eq. (13) is approximately evaluated with the help of XRD data.
32.30 nm. The XRD data JCPDS file no. 00-036-1451 were Figure 3a–c shows a TEM image obtained for the
compared with the experimentally recorded X-ray diffraction synthesized uncapped zinc oxide (ZnO) NPs at different
data and listed in Table 1. magnifications, and the size parameters of TEM images
The amount of defects in the prepared sample is described indicate that the ZnO nanoparticle morphology is iden-
by dislocation density (δ). The length of the dislocation lines tical with that of morphology observed by SEM. The
per unit volume of the crystal is known as dislocation density transmission electron microscope image also revealed
(δ), and it is determined with the help of the following equa- the formation of nanostructured ZnO. A selected area
tion [59]: electron diffraction (SAED) pattern of synthesized ZnO
NPs is shown in Fig. 3c. The SAED pattern shows
1 distinct bright lines that confirm the preferential orien-
δ¼ ð14Þ
d2 tation of nanocrystals instead of irregular. The SAED
pattern indicates that the phase of ZnO nanoparticles
where d is the crystallite size. The calculated value of d (dis- has been polycrystalline in nature and the distance be-
location density) is 8.4998 × 10−4 (nm)−2. tween crystalline planes has been consistent with the
 Ionics

Table 1 Standard XRD data of hexagonal ZnO from JCPDS and recorded data of synthesized ZnO nanoparticles

Hexagonal wurtzite ZnO (JCPDS No. 00-036-1451) Recorded data of ZnO Nanoparticles

d (Å) 2θ (h k l) Intensity (%) d (Å) 2θ (h k l) Intensity (%)

2.81430 31.770 100 57 2.81001 31.82 100 62.02

2.60332 34.422 002 44 2.60346 34.42 002 46.24
2.47592 36.253 101 100 2.48407 36.13 101 100.00
1.91114 47.539 102 23 1.91223 47.51 102 22.59
1.62472 56.603 110 32 1.62823 56.47 110 30.77
1.47712 62.864 103 29 1.47784 62.83 103 24.92
1.40715 66.380 200 4 1.40903 66.28 200 05.36
1.37818 67.963 112 23 1.37734 68.01 112 20.53
1.35825 69.100 201 11 1.35946 69.03 201 11.48
1.30174 72.562 004 2 1.30022 72.66 004 03.90
1.23801 76.955 202 4 1.23794 76.96 202 04.18

standard pattern of a wurtzite ZnO crystal structure. The Figure 4a, b shows the scanning electron micrographs of
diffraction lines of the SAED pattern clearly indicate the ZnO-activated charcoal (1:1) nanocomposite coated on the
nanoscale crystallinity of the ZnO particles with prefer- graphite sheet substrate. From the SEM image, it is clearly seen
entially oriented polycrystalline nature. that the zinc oxide (ZnO) NPs and powder of activated charcoal

Fig. 2 SEM image of synthesized ZnO nanoparticles at 600 °C at different magnifications of a 30.6, b 98.33, c 31.33 and d 71.98 K
Ionics

Fig. 3 TEM image of synthesized ZnO nanoparticles at 600 °C at different resolutions of a 0.5 μm, b 200 nm and c SAED Pattern

are mixed together uniformly to make its nanocomposites. The Zn–O (metal oxide) bond. The peaks in the range of 1400–
agglomerated particles contain neck with their neighbours, and 1500 cm−1 related to the C=O bonds may be due to the presence
they form extended spindle-like shapes intermitted by voids. of CO2 molecules from the environment. The peak obtained at
The existences of voids have been developed in the nanocom- 2362.79 cm−1 was also correlated to the C=O bonds. The
posite because of migration of vacancy from the nanoparticles adsorbed band at 1622.13 and 3614.60 cm−1 are obtained be-
grain boundary or activated charcoal pores. This type surface cause of the O–H bending vibrations due to the presence of
morphology is ideal for the making of energy storage devices water molecules on the surface of ZnO nanoparticles or proba-
such as a supercapacitor electrode material. It will give high bly due to atmospheric moisture. The peaks related to C=O and
surface area, which is capable to yield better value of O–H bending vibrations respectively reduce slowly for sample
capacitance. calcined at higher temperature.

FTIR analysis XPES analysis

The recognition of the atomic arrangement and the chemical To find out the complete information about elemental compo-
bonds present in the samples were carried out using Fourier sition and oxidation states of the metal cations present in
transform infrared spectroscopy (FTIR), in which percentage ZnO–AC nanocomposite, synchrotron radiation-based X-ray
transmission and wave number are the output. The FTIR spec- photoelectron spectroscopy (XPES) is performed. Figure 6a
trum of the ZnO nanoparticles was measured in the range of shows full survey scan in the range of 0 to 1200 eV. XPS
4000–400 cm−1 using KBr pellet. Figure 5 shows the FTIR spectrum clearly indicates the presence of Zn, O and carbon
spectrum of the synthesized ZnO nanoparticles using co- elements in the ZnO–AC nanocomposite coated on graphite
precipitation method. The various bands were observed in the sheet. The presence of Zn and O in XPS survey scan spectrum
FTIR spectra. In FTIR spectrum, the peaks obtained at 443.63 due to ZnO nanoparticles are confirmed. Figure 6b–e shows
and 1020.34 cm−1 are correlated with the stretching vibration of the high-resolution XPS spectrum of Zn 2s, Zn 2P1/2, Zn 2P3/2,

Fig. 4 SEM image of ZnO-activated carbon nanocomposite electrode at different resolutions of a 10 and b 2 μm
 Ionics

line for ideal capacitor. While in the case of real capacitors, the
impedance plot appears similar to that of resistance and ca-
pacitance in parallel configuration. At low frequency, an in-
clined line along with a semicircle at high frequency appears.
From the semicircular region of impedance plot, the bulk re-
sistance (Rb) and charge transfer resistance (Rct) of electrolyte
systems, as represented in the inset of Fig. 7a, can be deter-
mined. In general, Rct may be considered as a contribution
coming from two components, namely electronic resistance
of ZnO–AC nanocomposite and contact resistance between
the active layer and current collector, while the second com-
ponent arises due to the electrolyte resistance. Ionic resistance
contribution may come from the ionic resistance of electrolyte
and electrolyte present in pores at interface. Typical imped-
ance spectra of capacitor cell A and cell B are shown in
Fig. 5 FTIR spectrum of synthesized ZnO nanoparticles at 600 °C
Fig. 7a, c, in which it is clearly seen that almost vertical line
up to lower frequency region that confirms formation of a
O1s and C1s. The strong peaks at 1044.1 eV for 2P1/2 and double layer at electrode–electrolyte interface and also proves
1021.1 eV for Zn 2P3/2 indicate the presence of Zn2+. The O 1s the ideal double layer capacitive nature of interfacial region.
peak can be fitted with two peaks having binding energy of With the help of the intercepts on real axis, we determined
529.29 and 531.81 eV, and these two peaks are assigned to the the various parameters that include Rb (bulk resistance) and
oxygen bound C–O species and O in Zn environment, respec- Rct (charge transfer resistance) and they are tabulated along
tively (Fig. 6d). Similarly, The C 1s peak can be fitted with with the overall capacitance values in Table 3.
two peaks having binding energy of 284.14 and 287.61 eV, The impedance spectrum for cell A and cell B with different
and these two peaks are assigned to sp2 hybridized carbon and three compositions of nanocomposite electrode is shown in
the oxygen bound C–O species, respectively (Fig. 6e). In the Fig. 7b, d. Out of the different three compositions, the compo-
XPS spectrum, one strong peak of fluoride at 686.70 eV also sition in a 1:1 ratio of ZnO–AC-based supercapacitor cell A and
exists. The existence of a peak for fluorine can be attributed to cell B shows highest capacitance and least resistance. In the
the impurities in a graphite sheet which is used as substrate case of cell A, considerably higher value of capacitance was
material for depositing ZnO–AC nanocomposite. Three peaks obtained in comparison with cell B, and it is possibly due to the
of less intensity are also observed in XPS spectrum of ZnO– appropriate tuning of existing nanocomposite pores of the elec-
AC nanocomposite; it appears due to Cu-based sample holder trodes with ions in the electrolyte. Therefore, it is proposed that
on which XPS samples were mounted. XPS results clearly nanocomposite electrode of ZnO–AC (1:1) is the optimized
show that the presence of the synthesized ZnO–AC in the composition for electrode materials.
nanocomposite contains Zn, O and carbon elements. The The impedance spectra in Fig. 7a, c have been additionally
strong carbon peak appears in the XPS spectrum due to the analysed using a simulation technique with the help of the
presence of activated charcoal powder in the nanocomposite. modified Randal’s equivalent circuit that includes R1 (contact
The corresponding energies for Zn, O and carbon and corre- or bulk resistance), C1 (double layer capacitance), R2 (charge
sponding binding energy are tabulated in Table 2. transfer resistance) and W1 (Warburg component), as shown in
Fig. 7e, f for both the cells. The R1 indicates the resistance of
the electrolyte–electrode–current collector. The double layer
Electrochemical characterization capacitance (C1) is in parallel connection with R2 and repre-
sents the double layer capacitance (normally lying in the range
Impedance spectroscopy analysis of μF) between the ionic charge of the electrolytes and the
electronic charges of the electrodes. The data fitting for cell A
Impedance spectroscopy is a versatile technique for electro- and cell B has been carried out with the help of Z-view soft-
chemical characterization. This technique provides informa- ware (SAI ZPLOT impedance analyser) provided in Fig. 7e, f.
tion about various parameters correlated to the electrolyte bulk The data fitting using modified Randle circuit has been carried
properties and various parameters related to the electrode– out for both the cells. The chi-squared minimized to the 0.004
electrolytes interface. For example, the capacitance at low and 0.003 for both circuits. The obtained values of fitting
frequency, equivalent series resistance and faradic resistance parameters R1, C1, R2 and W1 are given in Table 4. The results
can be determined using impedance spectroscopy. It is well- obtained from the impedance plot and from the data fitting of
known that the impedance spectrum gives a vertical straight experimentally recorded impedance data are in good
Ionics

Fig. 6 XPES spectrum of ZnO–AC nanocomposite. a Full survey scans. b Zn 2s. c Zn 2P1/2, Zn 2P3/2. d O1s. e C1s

agreement. The W1 connected in the series of R2 is represented fitting of both cells (that are near to 0.5, as given in Table 3)
by the position of Warburg region, which is located between point out the slope of the Warburg transition line almost 45°,
the semicircle and the spike impedance plot. As shown in and this is related to the porous nature of the electrodes.
Fig. 7a, c (inset) for cell A and cell B, the Warburg impedance Figure 7e, f provides the simulated a.c. impedance plot using
line/region has been observed for both the cells. The length of equivalent circuit and experimental plot for EDLC cell A and
this line represents the three different components that are cell B. From Table 4, it is clearly observed that the low value
diffusion resistance (WR), diffusion coefficient (WT) and of bulk resistance (R1) of the electrolyte material is attributed
Warburg exponent (WP). The WP values obtained from the to the presence of liquid electrolyte which shows liquid-like
 Ionics

Table 2 The corresponding energies for Zn, O and carbon in various electrode at low scan or charge/discharge rate. C″(ω) is the
energy levels
imaginary part of the complex capacitance and stands for the
S. no. Elements Peaks position (eV) Remarks energy dissipation by an irreversible processes that leads to a
hysteresis. C′(ω) and C″(ω) are expressed as follows:
1. Zn 2s 1195.68 Nanocomposite
Z ′′ ðωÞ
2. Cu 2s 1096.20 Sample holder C ′ ð ωÞ ¼ − ð18Þ
3. Zn 2p1/2 1044.27 Nanocomposite ωjZ ðωÞj2
4. Zn 2p3/2 1021.14 Nanocomposite
Z ′ ð ωÞ
5. Cu 2p1/2 951.20 Sample holder
C ′′ ðωÞ ¼ ð19Þ
6. Cu 2p3/2 931.20 Sample holder ωjZ ðωÞj2
7. F 1s 686.70 Impurity in graphite
8. O 1s (i) 529.29 Oxygen bound C–O species where Z′(ω) and Z″(ω) are the real and imaginary parts of the
(ii) 531.81 Zn–O–Zn bonds complex impedance Z(ω). ω is the angular frequency and it is
9. C 1s (i) 284.14 sp2 hybridized carbon given by ω = 2πf.
(ii) 287.61 Oxygen bound C–O species Figure 8a, b represents the variation of C′(ω) and C″(ω)
10. Zn 3s 139.70 Nanocomposite with frequency of cell A and cell B. It can be seen from the
11. Zn 3p 89.20 Nanocomposite plots that ZnO–AC nanocomposite as an electrode material
enhanced the real and imaginary parts of the complex capac-
itance. From Fig. 8a, it can be seen that at lower frequency of
conductivity mechanism of the KOH and NaOH electrolytes 10 mHz, the values of capacitance are found to be 57.5 and
and in turn improve the overall device performance. 36.0 mF cm−2 for cell A and cell B, respectively. With the
Furthermore, lower value of charge transfer resistance (R2) increase in frequency, the capacitance exhibits a frequency-
indicates the fast transfer of charges at the electrode–electro- dependent behaviour, and C′(ω) drops sharply in the region of
lyte interfaces, suggesting the better pore accessibility of 0.01–10 Hz. At higher frequency, the capacitance is insignif-
ZnO–AC electrodes to the ions of electrolyte; thus higher icant and the EDLCs behave like a pure resistor. This change
values of capacitance are achieved. Further, porous morphol- in value of C′(ω) depends on many parameters such as the
ogy of ZnO–AC electrodes provides electrolyte penetration in porous structure of the electrode, the electrode thickness and
the inner area of the electrode, thus enhancing the electrode– nature of the electrolyte used. The imaginary part of capaci-
electrolyte contact and hence reducing the internal resistance tance C″(ω) with frequency is given in Fig. 8b. It can be seen
making it more suitable for energy storage device applications from the plots that the values of C′(ω) increase towards lower
such as supercapacitors. Combining all the tabulated results, it frequency, whereas it gets shifted towards higher frequency in
can be inferred that lower values of bulk resistance, charge the case of C″(ω), which is an indicative of good capacitive
transfer resistance and Warburg element are a typical merit of behaviour for ZnO–AC nanocomposite-based EDLCs. The
ZnO–AC-based electrode materials for EDLCs having a high relaxation time constant (τ0) also known as a dielectric relax-
specific capacitance and excellent power ability. ation time of the supercapacitor related to the figure of merit of
the supercapacitor. The insight of relaxation time constant, τ0,
is basically a quantitative measure of how fast the device can
Complex capacitance and power analysis be charged and discharged reversibly. It is representing one of
its discharge characteristics. The relaxation time constant,
To explore the electrochemical properties of fabricated capac- τ0 = 1/f0 can be calculated from the plots of C′(ω) and C″(ω)
itor cells, further, real part C′(ω) and imaginary part C″(ω) of as a function of frequency. The real part of the complex ca-
complex capacitance C(ω) as a function of frequency were pacitance C′(ω) is decreasing asymptotically with frequency.
analysed. At lower frequencies, real part of C(ω) represents It is the property of the electrode structure and electrode/
the capacitance of electrode materials, whereas imaginary part electrolyte interface. Relaxation time constant (τ0) can be de-
corresponds to the hysteresis of materials and is a representa- termined from the frequency corresponding to the half of the
tion of energy dissipation by some irreversible processes. maximum value of C′(ω). The value of τ0 can be determined
The impedance–frequency behaviour has been studied with by the change of imaginary part of the complex capacitance
the help of a complex model of the capacitance. The complex C″(ω) with frequency goes through a maximum at a frequency
capacitance is given by the following mathematical expression: fo. Figure 8b shows the variation of C″(ω) with frequency for
C ðωÞ ¼ C ′ ðωÞ jC ′′ ðωÞ ð17Þ supercapacitor cell A and cell B assembly study in this work.
The plots show a characteristic hysteresis for all the
where C′(ω) is the real part of the complex capacitance. The low supercapacitor cell assembly investigated in this work. It can
frequency value of C′(ω) corresponds to the capacitance of the be noted that the symmetric cell assembly based on zinc oxide
Ionics

Fig. 7 a Typical impedance plot of the cell A in inset shows Rb and Rct. b plot (black) and simulated plot (red) at room temperature and in inset
Typical impedance plot for cell A at compositions of 1:1, 1:2 and 1:3. c shows equivalent circuit model). f Electrochemical impedance spectra
Typical impedance plot of the cell B in inset shows Rb and Rct. d at 10 mHz for cell B (experimental plot (black) and simulated plot (red)
Impedance plot for cell A at compositions of 1:1, 1:2 and 1:3. e at room temperature and in inset shows equivalent circuit model)
Electrochemical impedance spectra at 10 mHz for cell A (experimental

nanoparticle-activated charcoal supercapacitors with 6 M

KOH and 1 M NaOH shows a clear peak formation. S ðωÞ ¼ PðωÞ þ jQðωÞ ð20Þ
The plots of normalized active power |P|/|S| and reactive pow-
er |Q|/|S| of the complex power vs. frequency (expressed in log- where P(ω) is the real part of complex power which is
arithmic scale) for cell A and cell B are shown in Fig. 8c, d. also known as active power and Q(ω) is the imaginary
Complex power of the fabricated cell was calculated by part of complex power and is also known as reactive
using the following relation: power.
 Ionics

Table 3 Electrical parameters of an EDLC cells from impedance analysis

Cell Rb (Ω cm2) Rct (Ω cm2) 10 mHz Rb (Ω cm2) Rct (Ω cm2) 100 mHz

R (Ω cm2) C R (Ω cm2) C

(mF cm−2)a (F g−1)b (mF cm−2)a (F g−1)b

A 0.26 0.96 36.8 58.9 42.1 0.26 1.15 5.9 53.5 38.2
B 0.99 1.46 84.1 38.1 27.2 0.99 2.18 18.1 27.2 19.4
a
Overall capacitance of the cell
b
Single electrode-specific capacitance of the cell

P(ω) and Q(ω) are evaluated by using the following rela- electrochemical capacitor from a purely resistive to a purely
tion: capacitive behaviour. For a frequency, f > l/τ0, it behaves as a
pure resistor and for f < l/τ0, and it acts as a pure capacitor. In
PðωÞ ¼ ω C ′′ ðωÞ jΔV rms j2 ð21Þ this investigation, we used the complex power analysis meth-
od. It is the most significant approach for estimating the figure
QðωÞ ¼ −ω C ′ ðωÞjΔV rms j2 ð22Þ of merit of the supercapacitor cell assembly. Figure 8c, d
shows the plots of |P|/|S| and |Q|/|S| of the complex power
where jΔV rms j2 ¼ ΔV√2max with ΔVmax being the maximum am- against frequency for the respective supercapacitors based
plitude of the a.c. signal. on the high surface area porous zinc oxide electrodes. These
The power dissipated into the system can be calculated parameters show the expected tendency as discussed above.
from the normalized active power which is denoted by |P|/ The value of τ0 has been calculated from the intersection of
|S|. The plots of normalized power with the frequency showed two plots at a frequency fo. The calculated relaxation time
in Fig. 8c, d represent the relaxation time constants for the constant τ0 for the fabricated cell A and cell B is found to be
respective supercapacitor cell assembly. The power dissipated of the order of 417.7 and 549.7 m s, respectively. From the
into the system can be analysed from the normalized active observed values, it is clearly seen that the cell A based on the
power represented by |P|/|S|. At high frequency, when the 6 M KOH system is able to deliver its stored energy almost 1.3
supercapacitor acts as a pure resistor, all the power is dissipat- times faster at a high power in comparison of cell B based on
ed into the system (P = 100%). On the other hand, no power is the 1 M NaOH system.
dissipated into a pure capacitance at low frequency. Actually,
Fig. 8c, d shows that the values of |P|/|S| and |Q|/|S| show Cyclic voltammetry studies
reverse trends with frequency. The relaxation time constant
τ0 (= 1/fo) can be determined with the help of the crossing of Cyclic voltammetry (CV) is a useful technique to determine
two curves that occur at a frequency fo; it is also known as the capacitive performance and electrochemical property of
resonance frequency. The relaxation time constant τ0 related the supercapacitor electrodes. The CV responses have been
to a phase angle of 45°, and it is representing the transition of analysed to extract a different type of information, as well as

Table 4 Parameter values from fitted impedance equivalent circuit for cell A and cell B

Element Value Error (±) Value Error (±)

Cell A Cell B

R1 (contact or bulk resistance) (Ω cm2) 0.27 0.01 1.13 0.03

C1 (double layer capacitance) (μF cm−2) 53.92 2.11 16.48 1.01
R2 (charge transfer resistance) (Ω cm2) 0.73 0.02 1.11 0.04
W1 (Warburg component)
1. WR (diffusion resistance) (Ω cm2) 2.01 0.02 6.46 0.44
2. WT (diffusion coefficient) 0.08 0.01 0.12 0.01
3. WP (Warburg exponent) 0.46 0.01 0.43 0.05
R3 (grain boundary resistance) (Ω cm2) 1.22 0.34 3.17 0.73
C2 (limit capacitance) (F cm−2) 0.14 0.02 0.06 0.01
α (chi-squared value) 0.004 0.003
Ionics

Fig. 8 a Bode plots for real part of cell A and cell B. b Bode plots for of normalized active power |P|/|S| and reactive power |Q|/|S| as a function
imaginary part of cell A and cell B. c Plots of normalized active power |P|/ of frequency for cell B
|S| and reactive power |Q|/|S| as a function of frequency for cell A. d Plots

the charge storage nature at individual interfaces within the specific capacitance of supercapacitor cell based on ZnO–
cathodic and anodic regions along with the complete behav- AC (1:1) nanocomposite electrode shows the higher values
iour of the supercapacitor cells. Cyclic voltammetry (CV) among all other compositions of nanocomposite.
analysis can be performed in a two electrode system configu- Approximately, all the supercapacitor cells show a feature-
rations. From the cyclic voltammetry response, the complete less peak within anodic and cathodic area in the potential
behaviour of the supercapacitor cell A and cell B can be de- range of − 0.8 to 0.8 V, and it has been confirmed that all the
duced. The cyclic voltammetry (CV) behaviour of synthesized electrode materials are used in this work of non-redox nature.
uncapped ZnO nanopowder at different three calcined temper- Furthermore, in figure, all the CV curve of ZnO–AC nano-
ature is shown in Fig. 9a. All the CV curves have been mea- composite electrode shows ideal behaviour, and it clearly
sured at constant scan rate of 50 mV s−1 and provided in shows that ZnO–AC nanocomposite electrode material has
Fig. 9a for a cell containing 6 M KOH as an electrolyte. The good electrochemical properties. In this study, the cyclic volt-
cyclic voltammetry curve related to ZnO nanoparticles syn- ammetry results also agree with a.c. impedance spectroscopy
thesized at a 600 °C calcination temperature indicates a supe- results. ZnO–AC nanocomposite capacitance values are en-
rior response in the comparison with other calcination temper- hanced because of the combined effect of the excellent elec-
ature. Therefore, it has been considered as an optimized cal- trical conductivity and higher surface area with homogenous
cination temperature in this work. At a higher calcination tem- pore size distribution of the nanocomposite materials. The CV
perature, the synthesis of nanoparticles having less surface response of cell A and cell B at various scan rates changing
area is favourable and may be one of the reasons to this poor from 1 to 100 mV s−1 was carried out, which are shown in
cyclic voltammetric behaviour. Fig. 9b, d, respectively.
Cyclic voltammetry curves of ZnO–AC nanocomposite From the CV curve, it is clearly observed that cyclic
electrodes deposited on a graphite sheet substrate in three voltammetry (CV) behaviour is approximately near to per-
mass ratios (1:1, 1:2 and 1:3) are shown in Fig. 9c, e. The fect rectangular shape still at the higher value of scan
 Ionics

Fig. 9 a CV of pure ZnO nanoparticles prepared at different calcination Cyclic voltammogram of cell B at different scan rates. e Cyclic
temperatures of 400 (a), 500 (b), and 600 °C (c) at a scan rate of voltammogram of cell B at compositions of 1:1, 1:2 and 1:3. f Variation
50 mV s−1. b Cyclic voltammogram of cell A at different scan rates. c of the specific capacitance of cell A and cell B as a function of scan rates
Cyclic voltammogram of cell A at compositions of 1:1, 1:2 and 1:3. d

rates. It exhibits capacitive behaviour and it also shows 341.6 F g−1 EDLC cell A. Similarly, the values of capac-
the quick switching of the ions at the electrode–electrolyte itance of 469.4 mF cm−2 are determined from the CV
interfaces. At higher scan rates, CV response of ZnO–AC curve, which is equivalent to single electrode-specific ca-
nanocomposite electrode material that becomes a small pacitance of 335.3 F g−1 for cell B. It approximately
deviation in the rectangular shapes has been observed. It matches with the observed values from a.c. impedance
has been caused by practically present ESR (equivalent analysis and charge–discharge measurement. The specific
series resistance) within real capacitors. The values of capacitance of ZnO–AC nanocomposite-based superca-
capacitance determined from the CV curve were deter- pacitor cells at various scan rates is tabulated in Table 5.
mined, and it is of the order of 478.2 mF cm−2, which is The comparison with reported capacitance values from the
equal to the specific capacitance of single electrode of literature is made in Table 6.
Ionics

Table 5 Specific capacitance values of AC–ZnO nanocomposite-based supercapacitor cells at different scan rates

Cell A Cell B

Materials Scan rate (mV s−1) Specific capacitance Specific capacitance

(mF cm−2) (F g−1) (mF cm−2) (F g−1)

AC–ZnO (1:1) 50 76.0 54.3 42.3 30.2

AC–ZnO (1:2) 50 18.2 13.0 12.8 9.2
AC–ZnO (1:3) 50 9.9 7.1 9.8 7.0
AC–ZnO (1:1) 100 72.5 51.8 37.7 26.9
75 73.9 52.8 39.6 28.3
50 76.0 54.3 42.3 30.2
40 76.9 54.9 44.0 31.5
30 77.9 55.7 46.2 32.9
20 79.6 56.8 49.8 35.6
10 82.2 58.7 53.4 38.1
5 96.7 69.1 95.9 68.5
3 160.1 114.4 158.5 113.2
2 239.6 171.2 237.4 169.6
1 478.2 341.6 469.4 335.3

Figure 9f shows the change in the specific capacitance with necessary, in order to test the charging–discharging capability
scan rate for fabricated supercapacitor cells A and cell B. In of the nanocomposite materials used for making supercapac-
the beginning, a minute decrement in the capacitance values itor cells. The charge–discharge behaviour of supercapacitor
was obtained at the lower scan rates, and it has been caused by cell A and cell B for initial 1 cycle at a different current density
the consumption of charge of the loosely bound surface (constant) is shown in Fig. 10a, b, respectively. The cells have
groups at the electrode–electrolyte interfaces; afterwards, ap- been charged from 0 to 0.8 V to maintain the cells under safety
proximately constant and stable capacitance values were ob- limit. The charge–discharge behaviour of the optimize com-
tained at the higher scan rate, and it points out the quick position of ZnO–AC nanocomposite-based cell A and cell B
switching behaviour of the ions of the fabricated ZnO–AC shows a triangular-shape and exhibiting a linear discharge
nanocomposite-based EDLCs on the interfaces. It confirms profile, which represents its EDLCs capacitive nature. The
the appropriateness of ZnO–AC nanocomposite for its use in specific capacitance 50.9 F g−1 of the fabricated cell A has been
the fabrication of supercapacitor cells as an electrode material. obtained at 2 mA cm−2 current density. Similarly, the specific
capacitance 25.1 F g−1 of the fabricated cell B has been obtain-
Charge–discharge studies ed at 2 mA cm−2 current density. In the voltage, an initial abrupt
change during charging and discharging of both the cells has
The galvanostatic charge–discharge is a most consistent tech- been observed. It has been attributed to the IR drop across the Ri
nique to determine the electrochemical specific capacitance of (internal resistance). It is also well-known that the ESR (equiv-
supercapacitor cells under controlled situation. The fabricated alent series resistance) of the fabricated cells leads to such ob-
supercapacitor cell A and cell B in this study has also been servation. The internal resistance, Ri, has been evaluated from
tested with charge–discharge method, It is extremely the voltage drops. It may be observed that in this work, the

Table 6 Published research data of ZnO–AC-based supercapacitors with different electrolytes

Composite electrode Configuration Electrolyte Specific Reference

capacitance (F g−1)

ZnO/AC Metal oxide/carbon 6 M KOH 178.2 [60]

ZnO/AC Metal oxide/carbon 0.1 M Na2SO4 160 [61]
ZnO/AC Metal oxide/carbon 1 M Na2SO3 116 [62]
ZnO/AC Metal oxide/carbon 1 M H2SO4 127 [63]
ZnO/AC Metal oxide/carbon 6 M KOH 341.6 This work
 Ionics

Fig. 10 a Charge–discharge curve of cell A at different current densities. 2.0 mA cm−2. d Variation of the specific capacitance of cell A and cell
b Charge–discharge curve of cell B at different current densities. c B as a function of current density. e Variation in the IR drop of cell A and
Charge–discharge curve of cell A and cell B at a current density of cell B as a function of current density. f Ragone plot of cell A and cell B

values of internal resistance of the fabricated EDLC cell A been measured at different current densities such as 0.4, 0.8,
decrease in comparison with the fabricated EDLC cell B. 1.2, 2.0, 2.8, 3.6, 4.0 and 8.0 mA cm−2 as represented in
Lower value of internal resistance (Ri) is important in every Fig. 10a, b, respectively.
energy storage system leading to low energy dissipation during Figure 10c shows the charge–discharge behaviour of
charge–discharge processes. supercapacitor cell A and cell B for initial 1 cycle at
The charge–discharge pattern of cell A and cell B has been 2.0 mA cm−2 (constant) current density, which clearly indi-
measured at different current densities keeping applied poten- cates that the cell A performance is better relative to the cell B.
tial constant. For example, the galvanostatic charge–discharge Discharging time for cell A is almost double to that of cell B
behaviour of fabricated supercapacitor cell A and cell B has which is suggestive of better energy storage.
Ionics

Table 7 Typical charge–discharge characteristics of an EDLC cells at current density of 2.0 mA cm−2

Cell Ri (Ω cm2) Discharge capacitance, Cd Working Energy density Power density Columbic Energy
voltage (V) (Wh kg−1) (kW kg−1) efficiency (ηt) efficiency (ηE)
(mF cm−2)a (F g−1)b % %

A 5.7 71.3 50.9 0.8 4.5 1.6 89.86 72.65

B 14.9 35.1 25.1 0.8 2.2 1.1 72.52 47.29
a
Overall capacitance of the cell
b
Single electrode-specific capacitance of the cell

Figure 10d shows the corresponding specific capacitance (η) of fabricated supercapacitor cell A and cell B are given
as a function of current density, which reveals that an increase in Table 7. The energy density and power density of fabricated
in current densities and the specific capacitance decreases for EDLC cells have been evaluated by mathematical expression
both cells, while the rate of decay in cell A is relatively lower Eqs. 10 and 11, respectively. It has been observed from the
compared to that of cell B. reported energy density values in the table that are relatively
From charge–discharge pattern, ohmic resistance (Ri) is also lower in comparison with the rechargeable batteries, while
analysed. It also depends on the current density of charge–dis- power density is relatively higher and hence it is most desir-
charge. Figure 10e shows the ohmic resistance (Ri) curves of able candidate as a power source for application point of view.
capacitor cell A and cell B as a function of current density, Figure 10f shows the ragone plot for cell A and cell B. It is
which reveals that the ohmic resistance increases with increase used for performance comparison purpose of various energy
in current densities for both the cells. Ohmic resistance with storage devices. The power densities of fully charged
respect to applied current densities is almost linear. A very small supercapacitor has been plotted as the function of energy den-
ohmic resistance is observed for cell A compared to that of cell sity at different current densities. From a ragone plot of cell A
B, which indicates that the cell A performance is better in com- and cell B, it can be clearly observed that the power density
parison to cell B, mainly at high current densities, which defi- gradually decrease with increase in energy density. It can be
nitely promotes the improvement of power density without concluded that the cell A performance is better than the Cell B.
compromising energy density. This is a direct measurement of The experimentally observed energy and power density are to
resistance offered by the electrode material during the discharge be 4.52 Wh kg−1 and 1.62 kW kg−1 for cell A, respectively.
process of cell A and cell B. Similarly, the energy and power density values have been
The discharge capacitance (Cd) has been evaluated from obtained,0 and they are of 2.22 Wh kg−1 and 1.08 kW kg−1
the discharge characteristics. The linear part of it has been for cell B, respectively.
analysed to calculate the capacitance value using Eq. (5).
The values of discharge capacitance Cd, internal resistance
Ri, specific energy, power density and columbic efficiency Cyclic stability

The cycling efficiency of a supercapacitor cell is the most

significant parameter as far as application is considered. The
electrochemical cycling stability of the fabricated supercapac-
itor with optimized ZnO–AC nanocomposite electrodes was
carried out. The CV measurement was repeated 2000 times at
constant 100 mV s−1 scan rate. Figure 11 shows the specific
capacitance of fabricated EDLC cells with the numbers of
cycle. The value of specific capacitance has been determined
at various cycles, and it is almost constant for supercapacitor
cell A and cell B. it represents an almost negligible drop in the
specific capacitance value under a complete cycling process.
Moreover, it has been observed that in this work, the specific
capacitance is approximately constant and for both the cell A
and cell B. However, it can be observed that the specific ca-
pacitance of a supercapacitor initially for few cycle increases
and later it remains almost constant. The possible reason for
Fig. 11 Variation of the specific capacitance of cell A and cell B as a such behaviour is redox reaction which may be taking place in
function of voltammetric cycles at a scan rate of 100 mV s−1 the case of supercapacitor containing KOH as an electrolyte.
 Ionics

The current density for cell with ZnO–AC as electrode mate- in ISUD, RRCAT, Indore, for providing XPES data. Mr. M S Yadav is
also thankful to Dr. Salil Modak and Dr. Rajneesh Atre Dept. of Physics,
rials and KOH as an electrolyte is more compared to the com-
Jaypee University of Engineering and Technology, Guna, Madhya
bination of ZnO–AC and NaOH. [64] Pradesh, India, for valuable suggestions and help.

Compliance with ethical standards

Conclusions Conflict of interest The authors declare that they have no conflict of
interest.
In this study, hexagonal wurtzite ZnO nanoparticles with nar-
row size distribution and rod shape were synthesized success-
fully using a co-precipitation method, and it is characterized References
using various structural characterization tools, for example
SEM, TEM, XRD and FTIR. Further, the composite forma- 1. Conway BE (1999) Electrochemical supercapacitors: scientific fun-
tion has also been confirmed from the results. XPS investiga- damentals and technological applications. Springer, New York
tion has confirmed that the reduction in particle size of ZnO 2. Green MA, Emery K, Hishikawa Y, Warta W, Dunlop ED (2015)
Solar cell efficiency tables (version 45). Prog. Photovoltaics: Res
has not changed the chemical environment of Zn. The synthe- Appl 23:1–9
sized uncapped ZnO NPs were employed in three different 3. Galeano C, Baldizzone C, Bongard H, Spliethoff B, Weidenthaler
mass ratios with powder of activated charcoal to make nano- C, Meier JC, Mayrhofer KJJ, Schüth F (2014) Carbon-based yolk–
composite electrodes for supercapacitor device application. shell materials for fuel cell applications. Adv Funct Mater 24:220–
232
The EDLC (symmetrical) cells were made by sandwiching
4. Zhang T, Imanishi N, Shimonishi Y, Hirano A, Takeda Y,
1 M NaOH and 6 M KOH as electrolytes between two iden- Yamamoto O, Sammes N (2010) A novel high energy density
tical electrodes (of ZnO–AC nanocomposite). The electro- rechargeable lithium/air battery. Chem Commun 46:1661–1663
chemical performance of the fabricated EDLC cells was mea- 5. Jokar E, Shahrokhian S (2015) Synthesis and characterization of
sured with the help of cyclic voltammetry, a.c. impedance NiCo2O4 nanorods for preparation of supercapacitor electrodes. J
Solid State Electrochem 19:269–274
spectroscopy and charge–discharge methods. The obtained 6. Schalkwijk WAV, Scrosati B (2002) Advances in lithium-ion batte-
results show that ZnO–AC (1:1) nanocomposite electrodes ries. Springer, New York
give the good capacitive behaviour; it may be because of the 7. Simon P, Gogotsi Y (2008) Materials for electrochemical capaci-
good compatibility of nanoparticles and activated charcoal tors. Nat Mater 7:845–854
powder in 1:1 ratio. The specific capacitance has been obtain- 8. Liu C, Li F, Ma L, Cheng H (2010) Advanced materials for energy
storage. Adv Mater 22:E28–E62
ed in the case of supercapacitor cell A that is of the order of 9. Xu K, Zou R, Li W, Liu Q, Liu X, An L, Hu J (2014) Design and
478.2 mF cm−2, which is equivalent to the specific capaci- synthesis of 3D interconnected mesoporous NiCo2O4@CoxNi1-
tance of single electrode that is 341.6 F g−1. In the same x(OH)2 core–shell nanosheet arrays with large areal capacitance

way, the improvement in the specific capacitance of and high rate performance for supercapacitors. J Mater Chem A
2:10090–10097
supercapacitor cell B has been obtained that is of the order
10. Ren Y, Wei H, Huang X, Yang B, Wang J, Ding J (2014)
of 469.4 mF cm−2, which is equivalent to the specific capac- Fabrication of NiO nanowires/G composite as electrode material
itance of single electrode that is 335.3 F g−1. The power den- for high performance supercapacitor. Int J Electrochem Sci 9:7206–
sity is 1.62 kW kg−1 and energy density is 4.52 Wh kg−1 for 7216
supercapacitor cell A, while for cell B, the power and energy 11. Xu G, Zheng C, Zhang Q, Huang J, Zhao M, Nie J, Wang X, Wei F
(2011) Binder-free activated carbon/carbon nanotube paper elec-
density values were found to be 1.08 kW kg −1 and trodes for use in supercapacitors. Nano Res 4:870–881
2.22 Wh kg−1, respectively. The value of columbic efficiency 12. Zheng C, Zhou X, Cao H, Wang G, Liu Z (2014) Synthesis of
(ηt) has been achieved to be 89.86 and 72.52% of the fabri- porous graphene/activated carbon composite with high packing
cated cell A and cell B, respectively. On combining all the density and large specific surface area for supercapacitor electrode
material. J Power Sources 258:290–296
results, it possibly is concluded that the nanocomposite based
13. Sieben JM, Morallón E, Cazorla-Amorós D (2013) Flexible ruthe-
on ZnO–AC (1:1) is a suitable material for the electrode in an nium oxide-activated carbon cloth composites prepared by simple
energy storage device such as a supercapacitor. electrodeposition methods. Energy 58:519–526
14. Huang T, Qiu Z, Wu D, Hu Z (2015) Bamboo-based activated
Acknowledgements Financial support to Mr. Mahendra Singh Yadav carbon @ MnO2 nanocomposites for flexible high-performance
from the Jaypee University of Engineering and Technology, Guna, supercapacitor electrode materials. Int J Electrochem Sci 10:
Madhya Pradesh, India, is gratefully acknowledged. We are thankful to 6312–6323
Prof. Ashok K. Nagawat, Dr. K. V. R. Rao, Dr. B.L. Choudhary, Mr. 15. Hwang SG, Ryu SH, Yun SR, Ko JM, Kim KM, Ryu KS (2011)
Sachin Surve and Mr. Deepak from the University Science Behavior of NiO–MnO 2 /MWCNT composites for use in a
Instrumentation Centre (USIC), University of Rajasthan, Jaipur, for pro- supercapacitor. Mater Chem Phys 130:507–512
viding SEM and FTIR data. Mr. M S Yadav is thankful to Dr. U. K. 16. Lota K, Sierczynska A, Lota G (2011) Supercapacitors based on
Goutam, Dr. R. K. Sharma and Mr. Jaspreet Singh from Beamline-14, nickel oxide/carbon materials composites. Int J Electrochem 2011:
Technical Physics Division of Bhabha Atomic Research Centre, Mumbai, 1–6
Ionics

17. Rakhi RB, Chen W, Alshareef HN (2012) Conducting polymer/ 37. Wang ZS, Huang CH, Huang YY, Hou YJ, Xie PH, Zhang BW,
carbon nanocoil composite electrodes for efficient supercapacitors. Cheng HM (2001) A highly efficient solar cell made from a dye-
J Mater Chem 22:5177–5183 modified ZnO-covered TiO2 nanoporous electrode. Chem Mater
18. Li N, Xiao Y, Xu C, Li H, Yang X (2013) Facile preparation of 13:678–682
polyaniline nanoparticles via electrodeposition for supercapacitors. 38. Wu J, Xie CS, Bai ZK, Zhu BL, Huang KJ, Wu R (2002)
Int J Electrochem Sci 8:1181–1188 Preparation of ZnO–glass varistor from tetrapod ZnO
19. Hu C, He S, Jiang S, Chen S, Hou H (2015) Natural source derived nanopowders. Mater Sci Eng B 95:157–161
carbon paper supported conducting polymer nanowire arrays for 39. Feldmann C (2003) Polyol-mediated synthesis of nanoscale func-
high performance supercapacitors. RSC Adv 5:14441–14447 tional materials. Adv. Fundam Mater 13:101–107
20. Shi Y, Pan L, Liu B, Wang Y, Cui Y, Bao Z, Yu G (2014) 40. Wu R, Xie CS (2004) Formation of tetrapod ZnO nanowhiskers and
Nanostructured conductive polypyrrole hydrogelsas high-perfor- its optical properties. Mater Res Bull 39:637–645
mance, Fexible supercapacitorelectrodes. J Mater Chem A 2: 41. Chu SY, Yan TM, Chen SL (2000) Characteristics of sol–gel syn-
6086–6091 thesis of ZnO-based powders. J Mater Sci Lett 19:349–352
21. Wu JB, Guo RQ, Huang XH, Lin Y (2013) Construction of self- 42. Damonte LC, Mendoza-Zélis LA, Soucase BM, Hernández-
supported porous TiO2/NiO core/shell nanorod arrays for electro- Fenollosa MA (2004) Nanoparticles of ZnO obtained by mechan-
chemical capacitor application. J Power Sources 243:317–322 ical milling. Powder Technol 148:15–19
22. Li X, Sun W, Wang L, Qi Y, Guo T, Zhao X, Yan X (2015) Three- 43. Kahn ML, Monge M (2005) Size and shape-control of crystalline
dimensional hierarchical self-supported NiCo2O4/carbon nanotube zinc oxide nanoparticles: a new organometallic synthetic method.
core–shell networks as high performance supercapacitor electrodes. Adv Funct Mater 3:458–468
RSC Adv 5:7976–7985 44. Zhao XY, Zheng BC, Li CZ, Gu HC (1998) Acetate-derived ZnO
23. Taer E, Deraman M, Talib IA, Hashmi SA, Umar AA (2011) ultrafine particles synthesized by spray pyrolysis. Powder Technol
Growth of platinum nanoparticles on stainless steel 316L current 100:20–23
collectors to improve carbon-based supercapacitor performance. 45. Dai ZR, Pan ZW, Wang ZL (2003) Novel nanostructures of functional
Electrochim Acta 56:10217–10222 oxides synthesized by thermal evaporation. Adv Funct Mater 13:9–24
24. Bichat MP, Raymundo-Piñero E, Béguin F (2010) High voltage 46. Ao WQ, Li JQ, Yang HM, Zeng XR, Ma XC (2006)
supercapacitor built with seaweed carbons in neutral aqueous elec- Mechanochemical synthesis of zinc oxide nanocrystalline.
trolyte. Carbon 48:4351–4361 Powder Technol 168:148–151
25. Stepniak I, Ciszewski A (2010) Grafting effect on the wetting and 47. Singhal M, Chhabra V, Kang P, Shah DO (1997) Synthesis of ZnO
electrochemical performance of carbon cloth electrode and polypro- nanoparticles for varistors application using Zn-substituted aerosol
pylene separator in electric double layer capacitor. J Power Sources of microemulsion. Mater Res Bull 32:239–247
195:5130–5137 48. Sato T, Tanigaki T, Suzuki H, Saito Y, Kido O, Kimura Y, Kaito C,
Takeda A, Kaneko S (2003) Structure and optical spectrum of ZnO
26. Wen B, Zhang S, Fang H, Liu W, Du Z (2011) Electrochemically
nanoparticles produced in RF plasma. J Cryst Growth 255:313–316
dispersed nickel oxide nanoparticles on multi-walled carbon nano-
49. Viswanathan R, Lilly GD, Gale WF, Gupta RB (2003) Formation of
tubes. Mater Chem Phys 131:8–11
zinc oxide-titanium dioxide composite nanoparticles in supercritical
27. Singh N, Mehra RM, Kapoor A, Sog AT (2012) ZnO based quan-
water. Ind Eng Chem Res 42:5535–5540
tum dot sensitized solar cell using CdS quantum dots. J Renewable
50. Koh YW, Lin M, Tan CK, Foo YL, Loh KP (2004) Self-assembly
Sustainable Energy 4(1):013110
and selected area growth of zinc oxide nanorods on any surface pro-
28. Rosenthal SJ, Chang JC, Kovtun O, McBride JR, Tomlinson ID
moted by an aluminum precoat. J Phys Chem B 108:11419–11425
(2011) Biocompatible quantum dots for biological applications.
51. Zhang H, Yang D, Ji Y, Ma XY, Xu J, Que DL (2004) Low tem-
Chem Biol 18:10–24
perature synthesis of flowerlike ZnO nanostructures by
29. Jin T, Sun D, Su JY, Zhang H, Sue HJ (2009) Antimicrobial efficacy cetyltrimethylammonium bromide-assisted hydro thermal process.
of zinc oxide quantum dots against listeria monocytogenes, J Phys Chem B 108(13):3955–3958
Salmonella enteritidis and Escherichia coli O157:H7. J Food Sci 52. Yu WD, Li XM, Gao XD (2005) Catalytic synthesis and structural
74(1):M46–M52 characteristics of high-quality tetrapod-like ZnO nanocrystals by a
30. Li M, Lv X, Ma X, Sun F, Tang L, Wang Z (2007) Direct synthesis modified vapor transport process. Cryst Growth Des 5(1):151–155
of monodispersed ZnO nanoparticles in an aqueous solution. Mater 53. Hu XL, Zhu YJ, Wang SW (2004) Sonochemical and microwave-
Lett 61(3):690–693 assisted synthesis of linked single-crystalline ZnO rods. Mater
31. Ratkovich A, Penn RL (2009) Zinc oxide nanoparticle growth from Chem Phys 88:421–426
homogenous solution: influence of Zn:OH, water concentration and 54. Wang JM, Gao L (2003) Synthesis and characterization of ZnO
surfactant additives. Mater Res Bull 44(5):993–998 nanoparticles assembled in one-dimensional order. Inorg Chem
32. Akhoon SA, Rubab S, Shah MA (2015) A benign hydrothermal Commun 6:877–881
synthesis of nanopencils-like zinc oxide nanoflowers. Int Nano Lett 55. Kim JH, Choi WC, Kim HY, Kang Y, Park YK (2005) Preparation
5:9–13 of mono-dispersed mixed metal oxide micro hollow spheres by
33. Yu DH, Cai RX, Liu ZH (2004) Studies on the photodegradation of homogeneous precipitation in amicro precipitator. Powder
rhodamine dyes on nanometer-sized zinc oxide. Spectrochim Acta Technol 153:166–175
A 60:1617–1624 56. Oliveira APA, Hochepied JF, Grillon F, Berger MH (2003)
34. Curridal ML, Comparelli R, Cozzli PD, Mascolo G, Agostiano A Controlled precipitation of zinc oxide particles at room tempera-
(2003) Colloidal oxide nanoparticles for the photocatalytic degra- ture. Chem Mater 15(16):3202–3207
dation of organic dye. Mater Sci Eng C Biomim Mater Sens Syst 57. Yadav MS, Singh N, Kumar A (2018) Synthesis and characteriza-
23:285–289 tion of zinc oxide nanoparticles and activated charcoal based nano-
35. Li AK, Wu WT (2003) Synthesis of monodispersed ZnO nanoparti- composite for supercapacitor electrode application. J Mater Sci:
cles and their luminescent properties. Key Eng Mater 247:405–410 Mater Electron. https://doi.org/10.1007/s10854-018-8672-5
36. Lin HM, Tzeng SJ, Hsiau PJ, Tsai WL (1998) Electrode effects on 58. Laheaar A, Przygocki P, Abbas Q, Beguin F (2015) Appropriate
gas sensing properties of nanocrystalline zinc oxide. Nanostruct methods for evaluating the efficiency and capacitive behavior of
Mater 10:465–477 different types of supercapacitors. Electrochem Commun 60:21–25
 Ionics

59. Bindu P, Thomas S (2014) Estimation of lattice strain in ZnO nano- 63. Madhu R, Veeramani V, Chen SM, Veerakumarc P, Liu SB,
particles: X-ray peak profile analysis. J Theor Appl Phys 8:123–134 Miyamoto N (2016) Functional porous carbon-ZnO nanocompos-
60. Kim CH, Kim BH (2015) Zinc oxide/activated carbon nanofiber ites for the high- performance biosensors and energy storage appli-
composites for high-performance supercapacitor electrodes. J cations. Phys Chem Chem Phys 18:16466–16475
Power Sources 274:512–520 64. Younghwan Im SK, Byeong SK, Kyoung SP, Tae WC, Jin SL,
61. Selvakumar M, Bhat DK, Aggarwal AM, Iyer SP, Sravani G (2010) Misook K (2016) Electrochemical performance of three shaped
Nano ZnO-activated carbon composite electrodes for ZnO nanoparticles prepared in LiOH, NaOH and KOH alkaline
supercapacitors. Physica B Condens Matter 405:2286–2289 solutions as anodic materials for Ni/Zn redox batteries. Korean J
62. Ho MY, Khiew PS, Isa D (2014) Electrochemical studies on Chem Eng 33(4):1447–1455
nanometal oxide-activated carbon composite electrodes for aque-
ous supercapacitors. Funct Mater Lett 7:1440012 (1-4)