J Mater Sci: Mater Electron (2024) 35:708

Tailoring the dielectric and electrochemical

properties of ZnO–CoO with Fe doping for energy
storage devices
Tahir Ejaz1, Haseebul Hassan1, Nimra Muzaffar1, Muhammad Imran1, Asma Zaka1,
Amir Muhammad Afzal1,* , Muhammad Waqas Iqbal1, Samia Safdar2, Munirah D. Albaqami3,
Saikh Mohammad Wabaidur3, Sohail Mumtaz4, and Zubair Ahmad5,*

1
Department of Physics, Riphah International University, Campus Lahore, Lahore, Pakistan
2
Institute of Food Science and Technology, University of Agriculture, Faisalabad, Pakistan
3
Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia
4
Department of Electrical and biological Physics, Kwangwoon University, Seoul, South Korea
5
School of Chemical Engineering, Yeungnam University, 280 Daehak‑Ro, Gyeongsan 38541, Gyeongbuk, Republic of Korea

Received: 16 October 2023 ABSTRACT

Accepted: 20 March 2024 Metal oxides have been extensively researched due to their exceptional electrical
Published online: conductivity and superior specific capacitance, making them pivotal materials in
4 April 2024 the study of supercapattery devices. In this study, zinc oxide mixed with cobalt
oxide with a 50/50 weight, and (ZnO–CoO) nanocomposite was synthesized
© The Author(s), under using a hydrothermal technique. Moreover, the effect of iron (Fe) incorporation
exclusive licence to Springer into the ZnO–CoO heterostructure was investigated. Characterization of the Fe/
Science+Business Media, LLC, ZnO–CoO nanoparticles involved X-ray diffraction (XRD) and scanning elec-
part of Springer Nature, 2024 tron microscopy (SEM) to analyze their crystallinity and phase composition. The
impact of iron doping on the dielectric properties of ZnO–CoO is also evaluated.
The high dielectric constant values were observed at low frequencies in pure
ZnO–CoO. Moreover, tan δ has larger values at lower frequencies and smaller
values at higher frequencies. The Fe/ZnO–CoO composite exhibited superior
electrochemical performance, with a specific capacity of 653 ­Cg−1 compared to
487 C/g for the simple ZnO–CoO composite. In hybrid device, Fe/ZnO–CoO//
AC, the composite electrode showed a specific capacity of 164 ­Cg−1 at 1.0 ­Ag−1.
The device demonstrated an extraordinary energy density of 57 Wh ­kg−1 and an
improved power density of 3600 W/kg. Notably, the device exhibited excellent
capacity retention (CR) of 97% up to 5000 GCD cycles. The device is also show a
high value of Coulombic efficiency of 96% after the stability measurement. These
findings demonstrate the exceptional electrochemical performance and stability
of Fe/ZnO–CoO nanocomposite and provide essential insights into their potential
for use in future energy storage devices.

Address correspondence to E-mail: amir.afzal@riphah.edu.pk; zubair7157@yu.ac.kr

https://doi.org/10.1007/s10854-024-12449-z

Vol.:(0123456789)
708 Page 2 of 15 J Mater Sci: Mater Electron (2024) 35:708

1 Introduction to standard capacitors, opening up new possibilities

for energy storage solutions [10, 11].
The increased need for energy, in conjunction with Pseudo capacitors, electrical double-layer capaci-
the limitations of fossil fuels, has attracted significant tors (EDLCs), and hybrid supercapacitors are the three
interest from researchers in the field of energy stor- main types of supercapacitors [12–14]. Pseudo capaci-
age devices. The main challenge in energy storage tors utilize redox processes for charge storage, result-
systems revolve around both the efficient utilization ing in high specific capacitance but limited charge
of energy and the optimization of storage capacity. transfer and a relatively short cycle life. On the other
Three prominent types of energy storage devices, such hand, EDLCs exhibit a lower specific capacitance as
as, conventional capacitors, batteries, and supercapaci- charges are stored electrostatically on the electrode
tors, are categorized to address these challenges [1]. surface at a constant voltage [15, 16]. Hybrid super-
Among different batteries, lithium-selenium batteries capacitors combine the advantages of both types by
have recently gained attention as a promising candi- leveraging different charge storage mechanisms and
date for energy storage devices due to their appeal- operating potentials, allowing for increased energy
ing characteristics. Se demonstrates a significantly density. In such configurations, hybrid electrode mate-
improved electron transfer capability of 1 × ­10−3 S ­m−1 rials are employed as positive and negative electrodes
and a theoretical volumetric capacity comparable to [17, 18]. Despite their advantages, supercapacitors
3253 mAh ­cm−3 [2]. face limitations in terms of energy storage capacity
Rechargeable aqueous batteries have garnered compared to batteries. This constraint restricts their
significant attention due to their unique advantages, applicability in various scenarios. By combining the
including low cost, a straightforward manufacturing desirable properties of conventional supercapacitor
process, excellent safety profile, remarkable envi- materials with those of pseudocapacitor materials, the
ronmental friendliness, and high ionic conductivity desired hybrid characteristics can be achieved. Super-
[3]. Lithium-ion batteries (LIBs) are considered to be capacitors consist of two essential components: the
highly significant energy storage devices, primarily electrodes and the electrolyte [19, 20]. The electrodes,
due to the favourable attributes of metallic lithium. typically composed of porous carbon materials, play a
These include a remarkable theoretical capacity crucial role in enhancing the surface area and enabling
of 3860 mAh ­cm−2 and a low chemical potential of efficient energy storage. Meanwhile, the electrolyte,
− 3.04 V [4]. Aqueous zinc-ion batteries (AZIBs) have which can be in the form of a fluid or gel, facilitates
attracted considerable interest compared to traditional the movement of ions between the electrodes [21, 22].
lithium-ion, sodium-ion, and potassium-ion batteries Supercapacitors utilize a variety of electrode mate-
due to their fundamental safety, environment-friendly rials, including zinc oxide (ZnO), titanium dioxide
nature, effectiveness, and sustainability attributes [5]. ­(TiO2), and copper oxide/coprous oxide (CoO/Co2O)
Supercapacitors have revolutionized the field of [23]. ZnO is an inexpensive and abundant semiconduc-
energy storage, surpassing the capabilities of batter- tor that plays a crucial role in many areas of organic
ies and conventional electrostatic capacitors [6, 7]. One electronics, including supercapacitors and optoelec-
of the key advantages of supercapacitors lies in their tronics [24, 25]. Zinc oxide (ZnO) is the best choice for
exceptional power density, enabling them to deliver supercapacitor applications due to its exceptional elec-
high power output. As a result, supercapacitors have trical conductivity, high specific surface area, and high
found widespread applications in various industries, stability [26, 27]. Copper oxide has a narrow bandgap
including transportation, renewable energy, electron- of 1.2 eV and often appears steel grey or black in hue.
ics, and medical devices [8, 9]. The rapid advance- Using a wide range of techniques, scientists have suc-
ments in materials, design, and production techniques cessfully manufactured nanoscale CoO in a variety of
have played a pivotal role in making supercapacitors shapes and sizes [28].
a viable option for energy storage in diverse applica- Fe doping in metal oxides enhances electrochem-
tions. This progress builds upon the foundations laid ical performance by increasing specific capaci-
by earlier inventions, particularly the development of tance and energy storage capacity. Fe doping also
capacitors, which eventually paved the way for the improves charge transfer kinetics, enabling faster
emergence of supercapacitors. This groundbreaking electron and ion movement for higher power den-
device exhibited a far greater capacitance compared sities. Additionally, it enhances cycling stability,
J Mater Sci: Mater Electron (2024) 35:708 Page 3 of 15 708

prolonging the lifespan of the supercapacitor [29]. 2 Experimental details

Fe doping allows for the tunability of material prop-
erties, optimizing specific capacitance and energy 2.1 Materials
density. Moreover, when combined with other
dopants or materials, Fe doping can induce syner- The precursors such as, cobalt nitrate hexahydrate
gistic effects, further enhancing overall electrochem- (Co(NO3)2·6H2O), nitric acid ­(HNO3), tartaric acid
ical performance and enabling superior energy stor- ­(C4H6O6), iron nitrate monohydrate (Fe(NO3)3·9H2O),
age capabilities in supercapacitors [30]. zinc nitrate (Zn(NO3)2·6H2O) were purchased from
Ejaz et al. have synthesized iron-doped zinc cop- Sigma Aldrich. The potassium hydroxide (KOH) pel-
per oxide using a hydrothermal synthesis technique. lets, aniline ­(C6H5NH2), carbon black (CB), activated
At 1.5 ­Ag−1, the asymmetric device achieved an out- carbon (AC), ethanol, and methanol were acquired
standing specific capacity of 144 ­Cg−1 [30]. Hassan from Merck. Because all the chemicals utilized in the
et al. have utilized a hydrothermal technique to syn- experiment were of analytical grade, and used with-
thesize ZnSrS//PANI@AC. Their synthesized mate- out any further purifications. All the materials used in
rial demonstrated an exceptional specific capacity, this experiment were 99.9% pure. In this experiment,
reaching up to 148 ­C g −1 . Further the device has deionized (DI) water was utilized for the purpose of
achieved an energy density of 32.88 Wh/kg and washing and preparing the solutions. The reference
power density of 800 W/kg [7]. Zaka et al. have electrode employed in the experiment was made up
successfully synthesized a Fe–Mg/MOF//AC nano- of Hg/HgO, whereas the counter electrode was made
composite using a hydrothermal technique. Their from platinum wire.
electrode achieved an impressive specific capacity
of 220 ­C g −1 when tested at 3 ­m Vs −1. Furthermore,
the device showed outstanding energy and power 2.2 Synthesis of materials
densities of 57 Wh ­k g −1 and 2393 W ­k g −1, respec-
tively, along with excellent cyclic stability, main- The material was synthesized using an easy hydro-
taining 85% of its performance after 1000 charging/ thermal procedure due to its exceptional benefits and
discharging cycles [31]. Yoo et al. have effectively efficiency as compared to other methods. To prepare
employed the electro spun PAN fiber template the solution, 1 M of zinc nitrate (Zn(NO3)2·6H2O) was
method to fabricate (Fe)-doped ­V2O5. The device has mixed in 2 M nitric acid ­(HNO3). The chemical weight
achieved a significant energy density of ­540Whkg−1 was 8.445 g for Zn(NO3)2·6H2O, 7.50435 g for tartaric
and a power density of 600 W/kg [32]. acid, and 30 ml for ­HNO3. The experimental setup was
In this paper, Fe-doped zinc oxide-copper oxide meticulously prepared in a sequential manner. Tar-
(Fe/ZnO–CoO) nanocomposite is synthesized via taric acid was accurately prepared and added drop-
hydrothermal method. The XRD and SEM are used wise into Zn(NO3)2·6H2O solution while continuously
to study the structural and morphological proper- stirring for 50 min. Subsequently, the homogeneous
ties of the electrode material. In addition, the dielec- mixture was transferred into an autoclave and sub-
tric properties were also investigated. Further, we jected to a temperature of 150 °C for 7 h. After cen-
evaluated the electrochemical efficiency of the mate- trifugation at 6000 revolutions per minute, the samples
rial using cyclic voltammetry (CV), electrochemical were thoroughly rinsed with ethanol and deionized
impedance spectroscopy (EIS), and galvanostatic (DI) water. Finally, the samples were dried for 5 h at
charge/discharge (GCD). To evaluate the electro- 75 °C. Similarly, cobalt oxide was prepared using 1 M
chemical properties of battery-grade materials, a of cobalt nitrate hexahydrate (Co(NO3)2·6H2O) along
three-electrode assembly is employed, while an with tartaric acid. A 10.3788 g of cobalt nitrate hexa-
asymmetric device (two-electrode assembly) is uti- hydrate (Co(NO3)2·6H2O) was dissolved into 30 ml
lized for evaluating stability and specific capacity. of ­HNO3. Following the previously mentioned steps,
To assess the stability of the FZCO//AC device, we cobalt oxide (CoO) was effectively obtained as the final
conducted an additional stability test consisting of product. For simplicity, the two materials were mixed
5000 consecutive cycles to determine the capacity in a 50/50 weight ratio in a motor piston and grinded
retention (CR) and Coulombic efficiency (CE). for almost 30–45 min to obtain composite ZnO–CoO,
named ZCO. The second sample was prepared by
708 Page 4 of 15 J Mater Sci: Mater Electron (2024) 35:708

incorporation of Fe doping. The 10% Fe doping was 3 Results and discussion

used in this work. For that purpose, 10 mg of iron
nitrate monohydrate (Fe(NO3)3·9H2O) and 90 mg of X-ray diffraction (XRD) examination was used in order
our first sample ZnO-CoO was mixed. The final prod- to investigate the crystallinity as well as the phase
uct Fe/ZnO–CoO is named FZCO in the below section. of ZCO and FZCO nanoparticles (Fig. 2a). The XRD
Figure 1 highlights all the steps followed for the syn- analysis revealed distinct diffraction peaks at angles
thesis of ZCO and FZCO nanomaterials. of 31.84°, 34.52°, 36.33°, 48.13°, and 56.71°, which were
accurately identified as belonging to the hexagonal
2.3 E
 lectrode preparation and electrochemical phase of zinc oxide (ZnO). These spikes match with
measurement crystallographic planes of (100), (002), (101), (102), and
(110). The lattice constants of the ZnO crystal structure
Ni foam was used as a current collector and substrate were estimated to be a = b = 0.324 nm and c = 0.521 nm,
throughout the electrode fabrication process. To with confirmation provided by the JPCDS card num-
remove any impurities, the substrate was thoroughly ber 36-1451 [33].
cleaned with HCl, ethanol, and water. To make the Prominent peaks were observed at the 2θ values of
slurry, 80% active content (ZCO and FZCO), 10% car- 38.73°, 45.12° and 53.5° corresponding to the crystal
bon black, and 10% PVDF were combined with NMP planes of (111), (200), and (422), respectively, indi-
as the solvent. After 8 h of continuous stirring, this cating the crystallographic structure of the material.
combination effectively coated on a square centimeter These observed crystal planes and their respective 2θ
of washed nickel foam uniformly. The electrode was values closely matched those reported in the JCPDS
then dried at 70 °C for 6 h. The electrochemical proper- card 02-0925, confirming the crystallographic nature
ties of the synthesized material was evaluated through of the synthesized CoO nanoparticles [34]. The XRD
Potentiostat-CS350M (Corrtest Instruments Corp., Ltd. pattern exhibited the polycrystalline nature of the
(Wuhan, China). A 1 M KOH electrolyte solution was synthesized CoO nanoparticles, which exhibited the
used as the working medium for capacitive and elec- monoclinic tenorite phase of the CoO structure. The
trolytic studies. A platinum wire was utilized as the presence of a spike at 20.3° belongs to (113) planes,
counter electrode, while Hg/HgO electrode functioned confirming the presence of ­Fe2O3. In the case of Fe@
as the reference electrode. Co-doped ZnO, the peak that corresponds to the

Fig. 1  A systematic representation of all the steps followed in the hydrothermal method for the synthesis of ZCO, and FZCO and elec-
trode fabrication
J Mater Sci: Mater Electron (2024) 35:708 Page 5 of 15 708

Fig. 2  a Xrd analysis of

ZCO and FZCO, b, c SEM
image of ZCO and FZCO

(111) plane was slightly displaced to a higher angle of Fe dopants. These modifications in surface charac-
of 41.03°. This is in comparison to its location in pure teristics can be associated with factors like increased
ZnO, which was previously at 40°. The Debye-Scherer surface area, secondary phases (such as ­Fe2O3), and
equation was used in order to ascertain the average lattice strain brought on by the inclusion of Fe ions.
crystallite size of both undoped and doped samples. Overall, the SEM analysis helped us to better under-
The full width at half maximum (FWHM) param- stand the microstructural features of ZnO–CoO and
eter was determined using the diffraction peak that Fe-doped ZnO–CoO composites by providing helpful
was seen to be the most intense at a 2 value of 40.01 information regarding the surface properties of these
degrees. Undoped ZCO samples were found to have materials.
an average crystalline size of about 30 nm. In FZCO
sample, the average crystalline size is 55 nm.
SEM analysis was used to evaluate the surface char- 3.1 Dielectric properties
acteristics of composites made of ZnO–CoO and Fe-
doped ZnO–CoO materials, as illustrated in Fig. 2b, The dielectric constant, often referred to as relative
c. The surface characteristics of the materials were permittivity, is a fundamental material property that
visible in the SEM images, which also offered infor- characterizes its ability to store electrical energy within
mation about their microstructural characteristics. In an electric field. Although, precise dielectric constant
the case of purely ZnO–CoO, a smooth surface with values for Fe@Co and Fe@Co@ZnO are not readily
sporadic imperfections was observed, suggesting a accessible. Fe@Co is a hybrid material that brings
uniform distribution of the composite material. The together the properties of iron (Fe) and copper (Co).
surface exhibits different grains that are attributed Copper has a greater dielectric constant, while iron
to the agglomeration of particles of different sizes. In often displays a lower value. Thus, depending upon
contrast, the surface of the Fe-doped ZnO–CoO sam- the proportions of the two elements and the influences
ple appeared rough and more porous, possibly due of the interface, the dielectric constant of Fe@Co can
to the clustering effect induced by the introduction lie between the value of pure iron and pure copper.
708 Page 6 of 15 J Mater Sci: Mater Electron (2024) 35:708

However, Fe@Co@ZnO is a composite material in frequency is a natural phenomenon, as any species

which zinc oxide (ZnO) is added to the Fe@Co matrix. contributing to polarizability tends to exhibit a pro-
The dielectric constant of the semiconductor ZnO gressively greater phase lag relative to the applied
is high. Fe@Co@ZnO is expected to exhibit a higher field as the frequency rises. As the dielectric constant
dielectric constant than Fe@Co due to the addition of drops, insulating grain boundaries are formed around
ZnO to the composite. The interfacial interactions, dis- the grains. The polarization effect regularly reduces
persion, and volume fraction of Fe@Co and ZnO all the electric field, which can cause the dielectric con-
have a role in determining the dielectric behaviour. stant of the material to fall significantly as the fre-
ZnO–CoO is known in the scientific community as a quency rises. The dissipation of energy within a die-
polar molecule due to the presence of a durable dipole lectric system can be quantified by calculating the loss
moment and its ability to react rapidly to an externally tangent (tan), which serves as a commonly employed
applied AC field. The figure illustrates the connection method for measuring dielectric loss. This phenom-
between the frequency of the applied electric field and enon occurs when the polarization of the material lags
the real and imaginary components of the dielectric behind the alternating field applied to it, often due
constant. to impurities and imperfections within the crystal lat-
Figure 3a demonstrates the frequency-dependent tice. This lag is believed to be partially attributed to
behaviour of ε′ at room temperature. The graph illus- domain wall resonance. The imaginary component,
trates that the dielectric constant decreases with the represented as tan δ, can be used to calculate the rela-
increase in the frequency but is essentially constant tionship between the dissipated energy and the real
at the higher frequency values, especially the micro- part of the dielectric constant. This parameter helps
wave frequency range. The high dielectric constant to describe the amount of energy that is dissipated
values observed at low frequencies in pure ZnO–CoO as heat within the material when an electric field is
can be attributed to the prevalence of vacancy-related applied to a dielectric medium.
species such as oxygen vacancies and grain boundary In Fig. 3b, c, the frequency-dependence of ε″ (die-
defects. The drop in dielectric constant with increasing lectric loss) and tan δ (dissipation factor) at room

Fig. 3  a The graphical

representation of the rela-
tion between the dielectric
constant and frequency for
FZCO and ZCO, b Relation
between the dielectric loss
and frequency for FZCO and
ZCO, c Variation of dielectric
loss factor for FZCO and
ZCO
J Mater Sci: Mater Electron (2024) 35:708 Page 7 of 15 708

temperature is illustrated. Notably, it is obvious the spike, which exhibits an exponential change. Con-
dielectric loss significantly drops with increasing fre- versely, raising the positive potential enhances the
quency and eventually stabilizes at a nearly constant electron concentration in the solution relative to the
value. Hence, a high value of εo and, consequently, electrode.
tan δ is observed at low frequencies. Moreover, tan δ CV measurements were conducted in 1 M KOH
has larger values at lower frequencies and smaller val- aqueous solution at a constant potential window of
ues at higher frequencies. It seems sense that signals 0.6 V. Figure 4a, b displays the obtained CV Curves
would become weaker as one goes down in frequency. for various scan speeds ranging from 3 to 50 mV/s.
Space charge, which originates from charge distortion Significant redox peaks were observed in all tested
on a macroscopic scale, may have a role in the polari- samples, confirming that the electrodes possess the
zation of these substances. desired characteristics for battery applications. Elec-
The frequency-dependent conductivity of the mate- trode materials react with hydroxide ions (OH) to
rial increases with rising frequencies, and distinct fre- produce these redox peaks. Notably, when scan rates
quency bands can be identified in a hopping model. rise, these peaks become more evident, indicating the
When an external field is applied, both the hopping increased electrochemical reactions take place at the
rate and the conductivity of the material and perme- electrode–electrolyte interface.
ability enhance, resulting in a decrease in resistance. Figure 4c illustrates a CV comparison of a doped
As a result, samples with higher Fe/Zn compositions and an undoped sample at 3 ­mVs−1. It is clear from
exhibit improved conductivity at higher frequen- the graph that the doped electrode shows superior
cies. In general, the dielectric loss and its frequency- electrochemical performance, primarily attributed
dependence provide information about the electrical to the larger area under the curve. In a three-elec-
properties of the materials. The compound exhibits trode device, the measurement for specific capacity
notable dielectric characteristics, which collectively Qs through CV was carried out with the help of the
contribute to the improvement of energy storage following:
performance. These include moderate dielectric per-
mittivity, exceedingly low dielectric loss, and effec-
mv ∫
vf
(1)
1
Qs = I × VdV
tive dielectric redox behavior. Based on the dielectric vi

here Q stands for the specific capacity, ∫vi I × Vdv

measurements mentioned previously, it can be con- vf
cluded that FZCO exhibits considerable potential as a
explain as the area of the CV curve, and v and m is
material for applications incorporating energy storage.
the scan rate and active mass, respectively. The FZCO
composite performed the best, with a higher specific
3.2 E
 lectrochemical measurement of ZCO capacity of 209 ­Cg−1 at 3 ­mVs−1. The specific capac-
and FZCO composites electrode materials ity of the pure ZCO electrode was 137 C/g, as shown
in Fig. 4d. The ability of an electrode to move charge
The electrochemical properties of ZCO and FZCO
is influenced by several factors, including ion diffu-
composites were investigated using a typical three-
sion within the electrode material, ion adsorption and
electrode setup. Cyclic voltammetry (CV) is an
surface interactions, as well as the charge transport
extremely useful method for assessing the electro-
capacity of the electrode material. The specific capacity
chemical properties of nanoparticles. Characterizing
of the electrodes decreases as the scan rate increases
the properties of a material is facilitated by the dis-
because less time is available for reactions. However,
tinctive morphologies of CV curves. The charge stor-
the rate capacity of the electrodes greatly increases
age capacity is determined through a comprehensive
by raising the proportion of ZCO to 50%, and it stays
analysis of these curves. By connecting the negative
stable even at the maximum sweep rate of 50 ­mVs−1.
terminal to the working electrode, the energy of elec-
To investigate the further electrochemical properties
trons is enhanced, resulting in a more negative charge.
of electrode materials, galvanostatic charge–discharge
An increase in negative polarity induces a reduction
(GCD) measurements are performed. A constant
in the concentration of electrons in the liquid, conse-
potential window of 0.6 V was used for the charge-
quently causing electron transfer from the electrode to
discharge experiments that were conducted in order to
the solution. This transfer manifests as a distinct fara-
explore the electrochemical parameters of ZCO as well
daic current spike, commonly known as the reduction
708 Page 8 of 15 J Mater Sci: Mater Electron (2024) 35:708

Fig. 4  Cyclic Voltammetry a of ZCO at different scan rates, b FZCO, c CV comparison of both samples at 3 ­mVs−1, d Specific capacity
of both samples

as FZCO. Following the execution of charge–discharge less time for ions to interact with the electrode mate-
cycles on the electrodes at different current densities rial at higher current densities, the specific capacity
ranging from 1.0 to 2.2 ­Ag−1. Figure 5a, b indicates the of the battery will be decreased as a consequence. A
GCDs of the ZCO, and FZCO electrodes. The curves comparison of the discharge curves for both materi-
are nonlinear, which indicates that there are redox als is shown in Fig. 5c, which was performed at 1
electrochemical processes taking on at the electrode ­Ag−1. The ZCO sample treated with FZCO exhibited
surface. Charge storage mechanisms may exist at the most extended discharge duration, signifying
either the electrode-electrolyte interface or at the bulk superior electrochemical performance. This compari-
level, and nonlinear charge–discharge curves indicate son highlights the enhanced charge storage capacity
that both types of processes are present. The charge of the material as compared to conventional elec-
storage that was found in this material suited for use trode materials. The specific capacity (Qs) was esti-
in batteries may be attributed to this process. mated from the discharge curves using the formula:
The findings from a comprehensive investiga-
I×t
tion of the impact of FZCO in combination with Qs = , (2)
ZCO revealed that increasing current densities led
m
to shorter discharge durations. Remarkably, even where I represent the current density, t is the dis-
at higher current densities, the discharge curves charge time required for complete discharge, and m is
remained consistent, providing strong evidence for the mass of the active material deposited on the nickel
the stability of electrode material. Because there is foam. The Qs value of FZCO in KOH is 653 ­Cg−1, which
J Mater Sci: Mater Electron (2024) 35:708 Page 9 of 15 708

Fig. 5  GCD measurements of a, b ZCO and FZCO at different current densities, c GCD comparison of both samples at 1 ­Ag−1, d Spe-
cific capacity of both samples

is significantly better than the Qs value of ZCO ­487Cg−1 transfer and promote increased energy density, which
estimated, as shown in Fig. 5d. makes them extremely promising for use in advanced
energy storage devices [38]. Activated carbon is used
3.3 Supercapattery device as the anode, and the active material electrode (Fe/
ZnO–CoO) is used as the cathode in the fabrication
The term Supercapattery emerged by combining the of the hybrid device. Figure 6a illustrates a Whatman
properties of the supercapacitor and battery. Super- filter paper acting as a dielectric medium to separate
capattery has the potential to bridge the gap between these two electrodes.
supercapacitors and batteries [35, 36]. It is a kind of Cyclic voltammetry (CV) of the hybrid device was
energy storage device that combines the positive and performed at various sweep rates ranging from 3 to
negative aspects of batteries and supercapacitors into 100 ­mVs−1. Figure 6b displays the CV plot for the high-
a single package. The charge storage capabilities of performance FZCO//AC asymmetric device. When a
some transition oxide minerals, such as chalcoge- potential is applied to the device, the electrolyte under-
nides and other related compounds, are responsible goes ionization, and the resulting ions move towards
for the formation of this kind of combination [37]. the electrodes, where they participate in oxidation
Increased energy storage capacities can be offered and reduction reactions. The existence of two sepa-
by these transition oxide minerals, along with quick rate mechanisms, faradic and non-faradic (represent-
charge-discharge rates and long cycle life. Supercapa- ing both battery-like and supercapacitor-like behav-
ttery that use these minerals enable effective charge iour), is confirmed by the quasi-rectangular curves.
708 Page 10 of 15 J Mater Sci: Mater Electron (2024) 35:708

Fig. 6  a Diagram representation of a hybrid device with active material (Fe/ZnO–CoO) and activated carbon electrode, b CV graph of
real device, c GCD graphs of Supercapattery device, d specific capacity graph of the real device measured from GCD curves

Notably, the CV of the hybrid device is unchanged specific capacity of (Fe/ZnO–CoO) was determined by
as the scan increases, offering strong evidence of its analyzing the GCD curves of the asymmetric device.
stability and remarkable rate capabilities. When the The remarkable specific capacity value of 164 ­Cg−1 at 1
potential was raised from 0.5 to 1.6 V, the resulting CV ­Ag−1 signifies the superior performance of the device,
curves are appeared in a quasi-rectangular form along as depicted in Fig. 6d.
with forming minor redox peaks, which suggested In Fig. 7a, b, electrochemical impedance spec-
the involvement of faradic processes. Surprisingly, troscopy (EIS) is applied to assess the charge stor-
the trend of the CV curve remained consistent even at age capacity and conductivity of both the undoped
higher sweep speeds, indicating the outstanding rate sample (ZCO) and the doped sample (FZCO). The
capabilities and stability of the fabricated device. Nyquist plot clearly illustrates a reduction in the
In order to examine the electrochemical characteris- overall electrode resistance due to the incorporation
tics of the FZCO//AC device, the galvanostatic charg- of Fe, resulting in the substantial influence of iron
ing/discharging measurements are evaluated at dif- doping on electrode performance. This enhanced
ferent current densities ranging from 1.5 to 2.5 ­Ag−1, material conductivity is a direct result of the doping
as represented in Fig. 6c. The symmetry and consist- process, which creates an additional pathway for the
ency observed in the GCD cycles affirm the durability movement of charge carriers. Electrical impedance is
and impressive high-rate capacity of the device. The the total resistance for ZCO its value was 1.135U, and
J Mater Sci: Mater Electron (2024) 35:708 Page 11 of 15 708

Fig. 7  a, b EIS representation of ZCO and FZCO, c, d BET graphs of ZCO and FZCO

for FZCO, 1.047U was encountered by the passage of exhibits superior electrochemical characteristics such
current in an electrical circuit. as improved specific capacitance and cycle stability.
The Brunauer-Emmett-Teller (BET) method was Energy density (Ed) and power density (Pd) are fun-
utilized to calculate the charge absorption of the damental parameters that must be considered in order
material. The BET analysis technique was used to to assess the operational capability of electrochemi-
estimate the surface area and determine the adsorp- cal devices. Therefore, both parameters are estimated
tion isotherm. Although this technique is widely uti- using the following relations;
lized for a wide range of materials, it is effective for
Cs (ΔV )
those that have type II or type IV isotherm curves Ed = , (3)
[39]. The BET isotherm related to both ZCO and 2 × 3.6
FZCO materials is shown in Fig. 7c, d. The composite
material experienced a remarkable 100 ­m2g−1 surface Pd =
Ed × 3600
, (4)
area and a 0.542 ­cm3g−1 pore volume. Surprisingly, Δt
the average pore size of 28 nm suggests improved where ΔV indicates the voltage range, and Δt is the
ion mobility. Due to its large surface area and ideal discharge period of the device. The FZCO//AC elec-
pore size, the results strongly suggest the significant trode exhibited a power density of 3600 W/kg and an
charge storage ability of FZCO. When compared to energy density of 57 Wh/kg, as illustrated in Fig. 8a.
previous hybrid materials, FZCO larger surface area
708 Page 12 of 15 J Mater Sci: Mater Electron (2024) 35:708

Cyclic stability is a crucial parameter for assess- Table 3  Energy and power density of different materials with
ing the endurance and reliability of the device. The this work
FZCO//AC hybrid device was evaluated for up to 5000 Literature E (Wh/kg) P (W/kg)
cycles. The Columbic efficiency (CE) of the electrode
Fe@ZnCuO//AC [30] 44.12 850
was calculated using the formula (η = tD/tC × 100%),
ZnSrS//PANI@AC [7] 32.88 800
as depicted in Fig. 8b. Remarkably, after completing
Fe-Mg/MOF [31] 57 2393
the 5000 cycles, the device exhibited an impressive
(Fe)-doped ­V2O5 [32] 540 600
Coulombic efficiency (CE) of 96% and maintained a
Fe3C/Fe@NC [41] 72 830
capacity retention of 97%. The charging and discharg-
Fe-doped NiCo2O4@rGO [42] 93.5 455
ing times over the 5000 cycles for the hybrid device are
MnS@CNTs [43] 53.3 7995
presented in Fig. 8c (Tables 1, 2 and 3).
NiCoS@CNTs [44] 40.5 2000
It is important to estimate the nature and charge
CoS [45] 1 37
storage system of the device these the b-values are
This work 57 3600
employed. According to Fig. 8d, these b-values are
obtained by fitting a linear relationship between the
logarithm of the peak current and the logarithm of
4 Conclusion
the scanning rate. The b-value of a material is a key
factor in determining whether it serves as a battery,
In this research, we synthesized iron-zinc cobalt
supercapacitor, or hybrid supercapacitor. Specifically,
oxide (Fe/ZnO–CoO) using a hydrothermal synthe-
when examining the fabricated electrode material, it is
sis method. We employed X-ray diffraction (XRD)
classified as a battery type if the b-values lie between
and scanning electron microscopy (SEM) to investi-
zero and 0.5. Conversely, it is classified as a superca-
gate the structural properties. For a comprehensive
pacitor type if the b-values range from 0.8 to 1.0. Mate-
electrochemical analysis of both doped and undoped
rials with b-values ranging from 0.5 to 0.8 are typically
materials, a three-electrode assembly was employed,
classified as asymmetric supercapacitors [40]. The
utilizing CV and GCD techniques. Remarkably, the
b-values obtained for the FZCO//AC device indicate
Fe/ZnO–CoO nanocomposite electrode exhibited an
that the charge storage in this system is a result of a
impressive specific capacity (Cs) of 653 ­Cg−1. Moreo-
synergistic interaction between faradaic and capacitive
ver, a symmetric supercapacitor device delivered an
mechanisms.
unexpectedly high charge capacity (Cs) of 164 ­Cg−1
at 1.0 ­Ag−1. Boasting an energy density of 57 Wh/kg
and an impressive power density of 3600 W/kg, iron-
Table 1  Surface morphology characteristics of both samples doped zinc cobalt oxide is considered as an exception-
Matrials Surface area Pore size (nm) Pore ally effective electrode material for hybrid devices.
­(m2/g) volume The effect of iron doping on the dielectric properties
­(cm3/g) of ZnO–CoO is also observed. The exceptional elec-
trochemical results demonstrate that Fe/ZnO–CoO
ZCO 45 20 0.17
is a highly desirable material for energy harvesting
F@ZCO 100 28 0.542
devices.

Table 2  Comparison of
Materials Specific capacity No of cycle Capacity reten- Coulombic
different properties of
­(Cg−1) tion (%) efficiency
materials with this work
(%)

Fe3C/Fe@NC [41] – 4000 91.4 –

Fe@ZnCuO//AC [31] 144 15000 – 98
ZnSrS//PANI@AC [7] 148 5000 90 90
Fe-Mg/MOF//AC [31] 220 1000 85 81
(Fe)-doped ­V2O5 [32] – 160 85 –
This work 164 5000 97 96
J Mater Sci: Mater Electron (2024) 35:708 Page 13 of 15 708

Fig. 8  a Energy and power density graph of the device, b Coulombic efficiency and capacity retention of the FZCO//AC electrode,
c Charging/discharging time estimated against 1200 cycles of FZCO//AC electrode, d b-value graph of FZCO//AC

Author contributions Declarations

T.E, H. H, N. M, M. I, A. Z, A. M. A, M. W. I and S. S Conflict of interest The authors declare that they

worked on experiment, data collection, analysis, and have no conflict of interest.
interpretation of results. T.E, H. H, N. M, M. I, A. Z,
A. M. A, M. W. I, S. S, M.D.A, S.M.W, S.M and M.Z.A Ethical approval The submitted work should be
helped during the calculation process and reviewed original and should not have been published else-
the manuscript. where in any form or language.

Funding
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