Asymmetric and Three Electrode Study of Hydrothermally
Fabricated CTAB-CuFeO2 Delafossite for Supercapacitor
Abrar Qamar
Registration No. 2021-GCBT-118
Session: 2021-2025
Department of Physics,
Govt. Graduate College Taunsa Sharif,
Ghazi University (Affiliated)
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Asymmetric and Three Electrode Study of Hydrothermally
Fabricated CTAB-CuFeO2 Delafossite for Supercapacitor
CERTIFICATE
This report serves as a verified record of the research conducted by Abrar Qamar, S/O of
Qamar-Ud-Din, with Roll No. 2021-GCBT-118 and Session 2021–2025 at Govt. Graduate
College Taunsa Sharif affiliated Gazi University, Pakistan, and entitled " Asymmetric and
Three Electrode Study of Hydrothermally Fabricated CTAB-CuFeO2 Delafossite for
Supercapacitor," which was partially submitted in fulfilment of the requirements for the
award of the Bachelor of Science degree.
Supervisor Head of Department
Hafiz Muhammad Tahir Farid Atta Muhammad Khosa
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ABSTRACT
The energy is the basic need of this modern world and renewable energy storage devices are
in demands. Among these devices, supercapacitors (SCs) are the well-known storage devices
to fulfill these demands. Recently, delafossites materials have acknowledged a lot of interest
as prospective electrochemical energy storing devices. In this paper the basic hydrothermal
technique was used to fabricate CTAB-CuFeO2 electrode for supercapacitors. X-ray
diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, energy dispersive
X-ray spectroscopy, thermogravimetric analysis, scanning electron microscopy, and Bernauer
Emmett Teller were used to determine the structural, functional, bonding, elemental, thermal,
morphological, and surface area of the fabricated materials. The electrochemical potential of
CTAB CuFeO2 electro was evaluated via three-electrode system in basic (KOH) media. Here,
several electrochemical tests were used to examine the electrode's electrochemical efficiency.
The CuFeO2-coated Ni-foam electrode showed outstanding cycle stability and a high Cs up to
1074 F/g and 264 F/g at 1 A/g in three electrode setup and asymmetric test. From these results,
CTAB CuFeO2 proved as suitable material for SC’s applications.
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ACKNOWLEDGEMENT
First, I want to express my gratitude to Allah Almighty. Who is wonderful, kind and
compassionate. Allah can write and read for me. Allah is the one who created the universe as
a whole.
I am special thankful to Allah that He created me in the ummah of Hazrat Muhammad
(PBUH). Hazrat Muhammad (PBUH) is the syed-ul-Ambiya. Hazrat Muhammad (PBUH)
is the last prophet of Allah and introduced Islam. The Holy Quran is revealed on the Holy
prophet Hazrat Muhammad (PBUH). That is good gift for us. So, I am very thankful to my
Holy prophet Hazrat Muhammad (PBUH).
With great pleasure, I would like to express my gratitude to my supervisor, Dr. Hafiz Tahir
Farid, as well as to Prof. Dr. Sulman Waheed and the Head of the Physics Department, Atta
Muhammad Khosa, for their invaluable guidance, smart suggestions, and supportive
supervision that helped me complete this dissertation. I sincerely appreciate their oversight. I
must express my sincere gratitude to them for all of their advice from the start of the thesis to
its completion. I truly appreciate Prof. Dr. Hafiz Muhammad Tahir Farid, for providing me
with all the resources I need for the synthesis and characterization.
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Tabel of content
Chapter # 01 ..................................................... Error! Bookmark not defined.
1. Introduction ............................................................................................. 6
Chapter # 02 ................................................................................................ 8
2. Literature Review .................................................................................... 8
2.1. Introduction .......................................................................................... 8
2.2. Literature Review ................................................................................. 8
Chapter # 03: ..............................................................................................10
3. Experimental and methodology..............................................................10
3.1. Introduction ........................................................................................ 10
3.2. Used chemicals .................................................................................... 10
3.3. Fabrication of CuFeO2........................................................................ 10
3.4. Hydrothermal Method ........................................................................ 11
3.5. Apparatus ........................................................................................... 12
3.5.1. Autoclave ......................................................................................... 12
3.5.2. Oven ................................................................................................. 12
3.5.3 Centrifuge ......................................................................................... 13
3.5.4. Hot plate........................................................................................... 13
3.5.5. Physical characterization of material .............................................. 14
3.5.6. Electrode preparation ..................................................................... 14
3.5.7. Electrochemical testing .................................................................... 15
Chapter # 4 .................................................................................................17
4. Results and analysis ................................................................................17
4.1. Physical assessment ............................................................................ 17
4.2. Electrochemical results ......................................................................221
4.3. Asymmetric (ASC) ...............................................................................29
Chapter # 5 .................................................................................................29
Conclusion ..................................................................................................30
References…………………………………………………………………………………………………30
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Chapter # 01
1. Introduction
In 21th century, the pollution level and energy cries increase due to addition of multiple
industries and factories which used fossil fuels. Due to a concerning increase in pollutants and
the continuing dependency on non-renewable sources of energy, the evolution of renewable
sources energy has become a top priority [1]. The scientific community has acknowledged
that renewable energy systems can effectively and easily supply uninterruptible energy
demands in the residential and commercial sectors [2]. A different types of renewable energy
conversion sources has been invented like solar, wind, hydropower etc. But researchers are
currently facing various obstacles in developing a stable and long-lasting sustainable energy
storing devices [3]. Currently, various kinds of energy storage devices like capacitors,
batteries, and supercapacitors (SCs) are available. Among them, Electrochemical
supercapacitors (ECs) have gotten a significant amount of interest as a potential energy storage
device [4]. ECs also known as ultracapacitors, are highly classy integrated energy storage
devices with a high power density (Pd), long-term cyclic stability, and a cost-effective design
[5].
ECs have two types on their energy storage capability [6]. The first one is electric double-layer
capacitors (EDLCs), that are fabricated via carbon material and use ion adsorption to store the
energy. The other type is called "pseudo-capacitors" which store and release ions via faradic
electrochemical processes on electrode surfaces [7, 8]. The electrodes of pseudo-capacitors
(PC) have been fabricated by TMOs like NiO, Co2O3, RuO2, and conducting polymers like
PANI etc. Because of their higher energy density and the quick charge and discharge
characteristics of faradaic processes, pseudo-capacitors can store more energy than EDLCs.
The SCs contained electrods, separator and electrolyte but electrode is the main part of SCs
also known as the heart of the capacitor [9]. The knownelectrode material for SCs including
activated carbon, graphene, carbon nanotubes, polymers like polyaniline, polypyrrole, and
transition metal oxides (TMO’s) such as cobalt oxide (Co₃O₄), manganese dioxide (MnO₂),
and nickel oxide (NiO) [10]. Recent study shows that the materials used to construct
SC electrodes have a significant impact. For example, a material with a greater surface area,
stability, and strong conductivity will perform better. All of the regularly used electrode
materials have particular drawbacks, including low energy density, low electrical
conductivity, and a limited capacity for charge storage [11].
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Several solutions have been developed to increase the material's electrochemical performance
while maintaining structural stability. Nanoparticles (NPs), nanosheets, nanowires (NWs), and
nanotubes are some of the strategies that have been prepared and tested to improve the SCs
performance [12]. NWs are one of the best alternatives to ECs due to their capacity to offer a
wide surface area, minimize ionic distance, and help in charge transfer and separation. Due to
their high-power density, variety of transition metal oxide composites, including ZrO2, NiO2,
MnO2, ZnO2, and Co3O4, have been extensively employed as electrode candidates with rapid
redox kinetics [13]. ZnO2 has several benefits, including low cost, stability, and catalytic
activity [14].
The metal oxide having compositions such as ABO4, ABO2, AB2O4 (A and B denote the
metals' lowest and highest oxidation states, respectively) are used as electrode for ECs [15].
ABO2 nanostructures are Bi-metal oxides with A = Ag+, Cu+, while B = Fe3+, Cr3+, and Zn3+
like CoFeO2 or CuCrO2 nanostructures also well known as delafossite. ABO2 delafossite-
based on copper (Cu) have intriguing properties due to its exceptional layered structure,
increased optical and electrical capabilities, and higher specific capacitance (Cs) values [20,
21]. Moreover, copper is the second highest conductive material in the word. Thus, the
fabrication of delafossite based on copper could be a good choice. Moreover, iron hase
variable valency and good conductivity. Thus, the synergetic effect of these two materials can
help to attained a good Cs with long stability for SCs.
Thus, the above discussion motivates to fabricate a delafossite CuFeO2 using a simple
hydrothermal method. Hydrothermal technique helps to fabricate the nanoparticles with good
crystallinity and morphology. The successful fabrication of CuFeO2 nanoparticles were
confirmed by different physical techniques. The electrochemical performance of this
delafossite were tested in (KOH) basic media via asymmetric and three electrode study. The
generated delafossite CuFeO2 electrode-based electrochemical supercapacitor demonstrates
an excellent Cs of 1074 F/g and 264 F/g at 1 A/g through GCD analysis and has excellent
stability after 3500 cycles.
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Chapter # 02
2. Literature Review
2.1. Introduction
This chapter covers the literature on metal based Oxide (delafossite) nanoparticles produced
by several techniques. Each chapter of the literature review covers into considerable detail on
several types of strategies.
2.2. Literature Review
According to Singh et al. [17], a pseudocapacitive ABO₂-type asymmetric supercapacitor cell,
AgFeO₂@C‖K₀.₄MnO₂·xH₂O, was successfully fabricated via a chemical flux method for
large-scale energy storage applications. The AgFeO₂@C composite served as the negative
electrode, while K₀.₄MnO₂·xH₂O was employed as the positive electrode material. The
asymmetric device demonstrated excellent electrochemical performance in an alkaline
electrolyte. The optimized cell exhibited a high specific capacitance of 136.68 F g⁻¹ at a
current density of 0.5 A g⁻¹, along with remarkable cyclic stability and energy density. The
superior electrochemical behavior was attributed to the synergistic interaction between
AgFeO₂ and the conductive carbon matrix, which enhanced the charge transport and redox
activity. These findings indicate that the AgFeO₂@C‖K₀.₄MnO₂·xH₂O system is a promising
candidate for next-generation battery type supercapacitors designed for efficient and scalable
energy storage applications.
Lee et al. [18], investigated delafossite CuCrO₂ nanoparticles as potential electrode
materials for electrochemical supercapacitors. The CuCrO₂ nanoparticles were synthesized
using a simple sol gel method, followed by calcination to obtain a phase-pure delafossite
structure. Structural analysis confirmed the formation of a rhombohedral CuCrO₂ phase with
well-defined crystallinity and nanosized morphology, which provided a large active surface
area favorable for charge storage. Electrochemical characterization demonstrated excellent
pseudocapacitive behavior, high reversibility, and good cyclic stability in both acidic and
alkaline electrolytes. The material exhibited a specific capacitance of 140 F g⁻¹ at 1 A g⁻¹,
attributed to fast surface redox reactions and efficient electron/ion transport through the
delafossite framework. These findings highlight CuCrO₂ as a promising transition metal oxide
based electrode material for high-performance and stable supercapacitor applications.
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Singh et al. [19], explored the electrochemical performance of delafossite AgFeO₂ as a
pseudocapacitive electrode material in a neutral aqueous Na₂SO₄ electrolyte. The AgFeO₂ was
synthesized using a chemical route and exhibited a well-defined rhombohedral delafossite
phase with uniform nanosized morphology. Electrochemical studies revealed that the material
demonstrated excellent redox activity and stable pseudocapacitive behavior, primarily due to
the synergistic interaction between Ag⁺ and Fe³⁺ cations facilitating fast charge transfer
processes. The electrode achieved a specific capacitance of 108.64 F g⁻¹ at a current density
of 0.5 A g⁻¹, along with good rate capability and cyclic stability. These results indicate that
AgFeO₂ is a promising delafossite type material for use in neutral electrolyte-based energy
storage systems, combining high reversibility, environmental compatibility, and structural
stability.
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Chapter # 03:
3. Experimental and methodology
3.1. Introduction
This chapter contains the methods I used to fabricate Delafossite. I used a hydrothermal
technique. The samples were characterized using X-ray diffraction, antioxidant activity, photo
degradation, and antibacterial scavenging activity.
3.2. Used chemicals
To the preparation of CuFeO2, iron nitrate nona-hydrate (Fe(NO3)3·9H2O, 98%), cetyl-
trimethyl ammonium bromide (CTAB, C19H42BrN, 98%), sodium hydroxide (NaOH, 99.9%),
copper nitrate hexahydrate (Cu (NO3)2.6H2O, 98.0–103%), and ethanol (CH3CH2OH, 96%)
were obtained from Sigma Aldrich. Because they were all utilized precisely as intended, no
further purification needed and used.
3.3. Fabrication of CuFeO2
For the preparation of CuFeO2, 0.15 g of CTAB were add in 25 mL of deionised water and
ethanol, then 5 mL of a 4.0 M NaOH solvent was added in it. After mixing the previously
indicated solution for three hours at room temperature, 0.5 M of Cu (NO3)2.6H2O and
Fe(NO3)3·9H2O (0.5 M) were mixed simultaneously. Then required drops of hydrazine were
add in it. Then this mixture was filled in 100 mL autoclave and heated at 160 ℃ for overnight.
The solution was centrifuge by centrifugation and repeatedly washing with deionised water
and ethanol, after centrifugation, the fabricated material was dried out at 70 ℃ for 4 hours in
oven and the reddish-brown precipitate was grinded and stored for testing [22].
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Scheme 1: Preparation of ctab-CuFeO2 nanoparticles via hydrothermal process.
3.4. Hydrothermal Method
In 1839, R. W. Bunsen won credit for manufacturing barium and strontium carbonates at
pressures and temperatures above 200°C and 100 bars. Crystal development was found in 1845
by E. Schafhautl, who utilized pressure pots to convert dissolved insoluble acids. When Roy
and Osborn began researching the system AL2O3, H2O in 1948, it became obvious that only
the hydrothermal state could form certain crystalline phases, such as tetra and pentavalent ions
as well as hydrolysed ions. Roy and Tuttle published the first extensive research of mineral
synthesis in hydrothermal settings in 1956. Roy and co-workers used the hydrothermal
technique to synthesize the whole spectrum of 7, 10, and 14 clay minerals, as well as chosen
zeolite families with a wide diversity of compositions, for the first time in 1950-70. This
method was used to explain how water under high pressure and temperature affected the earth's
crust, resulting in the formation of minerals, rocks, and ore deposits. One of the most
wellknown experimental methods for producing nanoparticles and nano composites is the
hydrothermal approach. These nanoparticles and Nano composites have uses in
electromechanical, electronic, optical, permanent magnet storage systems, porcelain, and other
fields. The hydrothermal technique can produce materials and molecules that are difficult to
obtain using earlier approaches because they demand a precise temperature and pressure for
synthesis and development. It is crucial to bear in mind that in order to duplicate the factor in
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the crystal formation during the hydrothermal process, substances and components that are to
be formed must resist heat and pressure.
3.5. Apparatus
3.5.1. Autoclave
It's a hydraulic warm technique advanced development responsive container. Inorganic
compounds were created using a different concentration controlling methodology, although
proven to be exceedingly harmful. The autoclave's ability must be intense order to sustain an
unusually disruptive behavior for an extended period of time at high weight and temperature.
To choose an autoclave, the heating and high-pressure test conditions were applied. To reduce
autoclave consumption, autoclaves were generally manufactured of tempering iron,
aluminium, cobalt, titanium, and Ni composites and coated in Teflon material.
Figure 1: Autoclave
3.5.2. Oven
A typical piece of equipment in forensic, electronics, materials processing, and research labs
is the laboratory oven. These ovens often give pinpoint temperature control and homogenous
temperatures throughout the heating process.
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Figure 2: Oven
3.5.3 Centrifuge
In scientific and manufacturing environments low-speed centrifuges are commonly used in
the disciplines of biology, pharmacology, and biochemistry. Radioimmunoassay and cell or
nanoparticle isolation typically performed using a relatively low-rotation machine with a
maximum speed of 4,000 r/min and a power supply of 220 V 50 Hz. In a relative sense 4000
rpm was performed at maximum centrifugal force as shown in Figure. 3.
Figure 3: Centrifuge Machine
3.5.4. Hot plate
In a laboratory, hot plates are used as a heat source to heat objects and fluids consistently. They
are rated much safer than traditional Bunsen burners because there is no open flame involved,
just a heated plate. Hot plates come in a wide range of variations to satisfy varied needs. There
are multiple designs for temperature control and the plate can be composed of various
materials.
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Figure 1: Magnetic stirrer hot plate
3.5.5. Physical characterization of material
The crystal phase of fabricated CuFeO2 was examined via using an Advance-D8 Bruker
powder XRD equipment (λ=1.541A) across a 2θ = 10◦ to 70◦ range. The elemental and
morphological composition of synthesized material were evaluated using energy dispersive
X-ray spectroscopy (Nova Nano-SEM 450 equipped) with an EDX detector. The bonding and
material structure were analysed by Raman spectroscopy. The Fourier transform infrared
spectroscopy (FTIR) was used to analysis the functional group of fabricated material through
Bruker Alpha FTIR spectrometer. Thermal stability was tested by thermogravimetric analysis
(TGA).
3.5.6. Electrode preparation
To make the electrode, NF was cut into little pieces (1.5 × 1.5 cm2). Before activation, these
small particles were sonicated for 30 minutes in HCl, DI water, and ethanol. Following that,
these pieces (NF) were heated up at 40 ℃ overnight to dry them out. To conduct
electrochemical examination, the electrode coated material are prepared by [Link]. To get the
best storage performance for the CuFeO2 electrode, the solution was dropped cast over the
previously cleaned NF. Following that, the activated NF was left in the oven to dry for 5 hours.
The NF bits were loaded and dried before being utilized in electrochemistry experiments.
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3.5.7. Electrochemical testing
Galvanostatic charge and discharge (GCD), cyclic voltammetry (CV), Electrochemical
impedance spectroscopy (EIS), and chronoamperometry were performed on the potentiostat
(CorrTest-CS350M). For the electrochemical studies using the usual three-electrode
technique, the fabricated CuFeO2 was deposited on NF which work as working, pt wire as
counter and Ag/AgCl used as reference electrode in a 3M KOH electrolyte. The
electrochemical cell was washed before use with a 1:3 solution of HCl and HNO3. After that,
it was dried at 60 °C and cleaned on a regular basis with acetone and DI water.
CV is a technique for investigating the redox properties of materials, and electrochemical
system. CV was conducted between potential window (ΔV) -0.05 to +0.6 V at several scan
rates of 5-50 mV s-1. To find the Cs from the CV curve, using formula shown Equation. (1)
[23]:
𝑉
∫𝑉 𝑢 𝑑𝑣×𝐼
Cs = 𝑚 × 𝑆 × 𝛥𝑉
𝑠
(1)
I indicate current, and the CV redox peaks were used to calculate dv (potential change). In a
CV polarised research, m, ∆V, and S represent the loaded mass, applied potential window,
and scan rate, respectively.
GCD is a method used to study the charging and discharging capacity of SCs. Additionally,
Cs was determined at various j using the GCD from Equation. (2)
𝐼 × 𝑑𝑡
Cs = 𝑚 × 𝛥𝑉 (2)
And the Equ. (4) and (5) can be used to calculate specific power and particular energy.
1
Ed = 2 Cs (ΔV)2 (3)
𝐸𝑑
Pd = (4)
𝑡
In GCD the potential window is denoted by ∆V, while t represents the discharge period at a
certain j.
ESCA is an essential parameter for measuring electrochemical activity. The non-faradic
region of CV curve was used to examine at 10 to 50 mV s-1 scan rates. Then slope and double-
layer capacitance (Cdl) was determined. For ECSA, the Cdl was divided by the Cs of the surface
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electrode, which typically varies from 0.01 up to 0.05 mF cm−2. The value of Cs (0.04 mF
cm−2) was taken from the literature. ECSA was determined using the formula: [24].
𝑠𝑙𝑜𝑝𝑒𝑎𝑛𝑜𝑑𝑖𝑐 −𝑠𝑙𝑜𝑝𝑒𝑐𝑎𝑡ℎ𝑜𝑑𝑖𝑐
𝐶𝑑𝑙 = (5)
2
𝐶𝑑𝑙
ECSA = ⁄𝐶 (6)
𝑠
In EIS, the charge transfer resistance (Rct) and solution resistance (Rs) are measure for
evaluating resistivity or conductivity. All EIS tests used the same parameters of AC and DC
amplitude of ±0.5 at frequency 105– 0.1Hz [25].
The stability of generated CuFeO2 is validated by chronoamperometry. The
chronoamperometry was carried out for 30 hours at a potential 0.75V.
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Chapter # 4
4. Results and analysis
4.1. Physical assessment
XRD analysis is necessary to define the structural properties of CTAB CuFeO₂, which
significantly impacts its performance in supercapacitors. In figure.1 (a) the XRD curves for
CTAB CuFeO2 are displayed. The CTAB CuFeO2 delafossite shown peaks at 2θ° angles 31.3°,
34.5°, 35.7°, 55.3°, 61°, and 64.8° which have hkl values (006), (101), (012), (018), (110), and
(1010) from JCPDS card number 01-075-2146. According to the XRD analysis, the crystal
structure of the delafossite CuFeO2, belongs to the 3R polytype class. The 3R polytype relates
to the R-3m space group and defines a rhombohedral structure [26, 27]. The (012) crystal
plane diffraction peak has a significantly higher strength then the other peaks, which indicate
that it has a supported growth direction [18]. This result confirms that the CTAB CuFeO2
structure was effectively created. The 3R polytype (012) strongest peak can be found at ~
35.7°. Despite the Scherer method's superior accuracy and capacity to compute essential
material properties such as phase composition, strain (ε), and structural parameters and the
Williamson-Hall (W-H) methodology for crystallite size remains underutilised.
In 1953 the derivation of the W-H equation improves upon the P. Scherrer equation, which
was developed before 1918 [28]. G.K. Williamson and his assistance gives the W-H technique.
The total XRD peak broadening is [29]:
βtotal = βcrystal + βmicro-strain (7)
and the Scherrer equation is:
𝐾𝜆
𝐷 = 𝛽𝑐𝑜𝑠𝜃 (8)
From this 𝛽 value is:
𝐾𝜆
𝛽(𝑐𝑟𝑦𝑠𝑡𝑎𝑙) = 𝐷𝑐𝑜𝑠𝜃 (9)
And micro strain (ℇ) is:
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𝛽
ℇ= (10)
4𝑡𝑎𝑛𝜃
From this equation 𝛽 is:
𝛽(𝑚𝑖𝑐𝑟𝑜𝑠𝑡𝑟𝑎𝑖𝑛) = 4ℇ tan 𝜃 (11)
Then total value of β from equation (9) and (11) is:
𝐾𝜆
β (total) = + 4ℇ tan 𝜃 (12)
𝐷𝑐𝑜𝑠𝜃
The average value of crystalline size is 14.2 nm which is calculated through above equations
of W.H plot. The graph of W.H plot betw een β cosθ and 4 sinθ which is shown in figure.1
(c).
In addition to XRD, FTIR analysis is a useful tool for evaluating functional groups
and material structure. figure.1 (b) displays the FTIR spectra of synthetic materials in the 400–
4000 cm-1 region. Two extremely strong bands were clearly seen in the lower frequency range
at around ~450 and ~560 cm-1 and on the other hand two O-H bond seen in high frequency
range as shown in below graph at ~1640 cm-1 and ~3390 cm-1, respectively. Fe-O stretching
vibration visible at ~560 cm-1 band, while the Cu-O stretching vibration is responsible for band
at ~450 cm-1 [30, 31].
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Figure 1: (a) XRD (b) FTIR and (c) W.H plot of CTAB CuFeO2
In the Raman spectroscopy of CTAB CuFeO2 delafossite, the oxygen vibration, metal oxygen
interaction, and crystal symmetry were studied. In figure.2 (a) the Raman spectra show
significant peaks at 355 and 640 cm−1, indicating Eg and A1g vibrations in CTAB CuFeO2
delafossite. The Eg mode corresponds to a triangular frame vibration which was perpendicular
to the x-axis, whereas the A1g mode is commonly thought to represent the Cu single bond with
O bond along the x-axis. These outcomes are compatible with previous research about the
delafossite structures [32].
TGA gives significant details on a thermal stability. In figure.2 (b) the TGA graph of CTAB
CuFeO2 was shown that the initial weight loss in the sample resulted from a decrease in
hydroxyl and humidity. The weight remained constant between 400 and 1300 ℃, but
decrease significantly at 1350 ℃ since it is so close to the melting point [33].
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Figure 2: (a) Raman graph of CTAB CuFeO2, (b) TGA graph of CTAB CuFeO2
SEM analysis is used to confirm the morphologies and microstructures of fabricated material,
the CTAB CuFeO2 enhanced morphological image at 200 nm is shown in figure.3 (a). The
fabricated material exhibits a flaky morphology and layered on one another, as shown in the
SEM image. The SEM picture of CTAB CuFeO2 shows the sample growth pattern that is
uneven distribution, resulting in the appearance of large-surface-area nanoparticles of flaky
shape which are loaded on each other [34]. The diameter of CTAB CuFeO2 is measured by
using Jiamge and then the value of average particle size are measured (21.73 nm) as show in
figure.3 (b).
EDX spectrum was used to analysis the present of elements in fabricated CuFeO2 material. In
the figure.3 (c), the EDX spectrum of CTAB CuFeO2 was clearly display the present of Cu,
Fe, and O peaks which show the successful fabrication of CTAB CuFeO2. The lack of
unnecessary elemental peaks indicates the material's purity, and the result of XRD and FTIR
are good considered.
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Figure 3: (a) SEM of CTAB CuFeO2, (b) average particle size CTAB CuFeO2, (c) EDX of
CTAB CuFeO2 (d) BET graph of CTAB CuFeO2
BET analysis was used to study the most significant components for determining specific
surface area and dispersion. In the figure.3 (d), it was clearly seen that CTAB CuFeO2
delafossiate show type IV isotherm [35].The calculated specific surface area of synthesized
delafossiate CTAB CuFeO2 is 65.4 m2g-1, which affects the capacitance.
4.2. Electrochemical results
The CV, GCD, EIS, and chronoamperometry techniques are used to measure the
electrochemical performance of fabricated delafossiate (CTAB CuFeO2) electrode in a 3.0 M
KOH electrolyte. The CV plots of CTAB CuFeO2 NPs electrode are shown in below figure.4
(a) with scan rates of 5 to 50 mV s-1, with a potential range (-0.05 to +0.6 V). When an
individual pair of oxidation-reduction peaks appears between the oxidative and conductive
peaks in the CV band (figure.4 (a)) of the CTAB CuFeO2 electrode, particularly at lower sweep
rates, it indicates the faradaic process. The value of Cs is measured by using equation (1)
which is already mention above is 875 F/g at 5 mV s-1 as shown in below figure.4 (b). The
quasi-symmetrical redox peaks of the CTAB CuFeO2 electrode coating material shows
the pseudo-capacitance behaviour [36]. In the increasing sweeping speed, the cathodic
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and anodic bands expand towards the negative and positive potentials shown in below figure.4
(c), the graph shows the linear connection between In (scan rates) and (Epa - Epc), to find the
value of R2. The black line (anodic peak) has a value of 0.993, whereas the red line (cathodic
peak) has a value of 0.991.
Figure 4: (a) CV graph (b) Specific capacitance (c) Anodic and cathodic peaks, of CuFeO2
The outstanding capacitance behaviour of the CuFeO2/NF electrode was confirmed using
GCD testing at ΔV from 0 to 0.5 V. GCD curves of CuFeO2 at current density (1 to 5 A/g) are
given in (figure.5 (a)). The calculated Cs of CTAB CuFeO2 varies from 485 to 1074 F/g when
j decreases from 5 to 1 A/g are measured using equation (2) as shown in below figure.5 (b).
The value Ed and Pd of CTAB CuFeO2 are measured by using equation (3) and (4) are 23.85
Wh kg-1 and 199.5 W kg-1 as shown in figure.5 (c). The electrode of CTAB CuFeO2 have
higher capacitance over longer discharge times due to conductivity. The GCD results
confirmed the electrode materials capacitance behaviour while the ability of pseudocapacitive
22 | P a g e
behaviour was verified through nonlinear discharge curves with little potential loss. When j
increased from 1 to 5 A/g, the CTAB CuFeO2 electrode showed greater rate stability. The
comparison table of fabricated material with different already reported materials are shown in
Table1.
Table 1: Comparison table of different oxides
Serial no. Material Cs (F/g) j (A/g) Electrolyte Electrode Referenc
e
1 NRGO–NiCoO2 58 0.5 3 M KOH Ni foam [37]
2 AgFeO2@C||K0.4MnO2 50.32 0.5 1M Carbon [17]
. xH2O Na2SO4 paper
3 CuCr(1x)Mgx/2Tix/2O2 247 0.5 1.0 M KOH Ni foil [38]
4 CuCo0.5Ti0.5O2 284 0.5 0.1 M KOH glassy [27]
carbon
5 AgFeO2 110.5 1 1M Nickel [19]
Na2SO4 foam
6 CuFeO2 129 1 1.0 M KOH Ni foam [39]
7 CuFeO2 610 1 1.0 M glassy [40]
Na2SO4 carbon
8 CTAB CuFeO2 1074 1 3 M KOH Ni Foam Present
work
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Figure 5: (a) GCD graph (b) Specific capacitance (c) Ed and Pd of CuFeO2
The ECSA is a significant parameter in the electrochemical evaluation of material electrode
which were used in energy storage applications. Non-faradic component of CV was scan at
(0.80 to 0.90 V) against RHE with scan rates of 10-50 mV s−1, as shown in below figure. 6
(a). To find Cdl, a line is drawn in the centre of graph and find the Δj then plot a graph between
scan rates and Δj, and fitted to get slope. From the slope, the Cdl value are founded through
above equation (5) and give the value of Cdl 10.15 mF and then from the determined Cdl value,
the value of ECSA is founded through the above equation (6) and get 253.5 m2 g-1 value shown
in (figure.6 (b)).
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Figure 6: (a) ECSA graph (b) Cdl value of CuFeO2
The EIS (Nyquist plot) of CuFeO2 at varies frequency range from 1Hz to 100 kHz were shown
in figure.7 (a). The fitted plots display the tiny semicircle consisting frequency using
imaginary portion (-Z") on the y-axis and the actual impedance portion (Z') on the x-axis. In
contrast to previous study, the semicircular shape of generated electrode indicated that it was
pseudocapacitive. The tiny semicircle on the CuFeO2 electrode indicates a lower Rct for the
electrolyte interaction. Electrodes can sustain low Rs value up to 0.94 Ω due to ionic diffusion
at electrode interfaces.
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Figure 7: (a) EIS graph of CuFeO2, (b) Chronoamperometry of CuFeO2, (c) CV stability of
CuFeO2
The electrode material stability of CuFeO2 at a given potential of 0.75 V was investigated using
chronoamperometry as shown in figure.7 (b). As shown in above chronoamperometry graph,
the electrode material lightly down round about shows constant stability up to 20 hours at 530
mA cm-1. From CV stability test, the cycle shows low current loss and remains same after
3500th cycle as shown in figure.7 (c).
4.3. Asymmetric (ASC)
Furthermore, the ASC test of fabricated material was done through two electrode system (3 M
KOH) in which fabricated material CTAB CuFeO2 electrode work as +Ve electrode while the
activated carbon (AC) electrode work as -Ve and the both electrodes are separated through a
filter paper in a 3 M KOH solution. The CV curve of carbon-activated and fabricated material
CuFeO2 is analysed at scan rate (5 mV s-1) as shown in figure.8 (a) to confirm the Cs of both
materials. ASC CV curves of CuFeO2 were recorded at several scan rates of (10-50 mV s-1) in
a ΔV = 0-1.65 V as shown in below figure.8 (b). The CV curves of fabricated material was
26 | P a g e
also tested at different ΔV from 0.8 to 1.8 V at constant scan rate (20 mV s-1) as shown in
below figure.8 (c). However, because the electrolyte reduces due to the formation of hydrogen
or oxygen, the leakage current increases significantly when the window rises over 1.65 V,
which can be clearly observed in window 0-1.8, the leakage current is shown via circular
dotted shape. As a result, the ΔV of 1.65 V was taken to complete the ASC's electrochemical
tests. These CV curves of (figure.8 (b)) were used to find the Cs of fabricated ASC. The ASC
show excellent performance via maintain a Cs of 174 F/g at (10 mV s-1) as shown in below
figure.8 (d). Moreover, the figure.8 (d) shows that when scan rate increases the value of Cs
got to be decreased due large ion diffusion. The feature ΔV of 0 to 1.65 V and are obtained at
several scan rates show good capacitive behaviour and a fast charge/discharge feature shown
in below figure.8 (e).
Figure 8: (a) Carbon activated and CuFeO2, (b) CV graph, (c) CV graph at constant scan rate
(20 mV s-1) different ΔV, (d) Cs graph, (e) Capacitive and diffusion graph of ASC CuFeO2
To properly evaluate ASC's performance, the fabricated material was examined at different
current densities via GCD test (figure.9 (a)). The confirmation of ΔV was also done at same
current via different ΔV as shown in below figure.9 (b) and when ΔV is increases from 1.6 to
1.8 then GCD graph shows a linear charged line. The Cs of electrode was driven through above
equation (9). The obtained GCD curves of ASC were used to find the Cs and results indicate
that ASC possess a Cs of 264 F/g at 1 A/g and the Cs value at an others Cd are given in figure.9
(c) in column graph. The Ed and Pd value are determined by above equation (3) and (4) and
these values were 82.5 Wh kg-1 and 750 W kg-1 respectively, Ed also increases with the
decrease of Pd as shown in figure.9 (d).
27 | P a g e
Figure 9: (a) ASC GCD graph, (b) ASC GCD graph at constant scan rate (20 mV s-1) different
ΔV, (c) Cs graph, (d) Ed and Pd graph, (e) EIS graph of ASC CuFeO2
EIS graph was conducted at open circuit potential, through a frequency range of 10 mHz-100
kHz and potential 5 mV. The Nyquist plot of ASC electrode is given in figure.9 (e). The graph
was used to find the Rs value of ASC and the calculate Rs was 0.27 Ω as shown in figure.9 (e).
28 | P a g e
Chapter # 5
Conclusion
In this work, simple hydrothermal process was employed to successfully synthesise CTAB
CuFeO2 nanostructure for Asymmetric and 3 electrode study. A number of Physical
characterizations were performed like XRD and SEM confirmed that the fabricated material
has the crystallite size 14.3 nm and flaky morphology. BET and TGA confirmed good surface
area and thermal stability. For electrochemical study, CTAB CuFeO2 was coated on NF, it
served as working electrode during 3-electrode study in electrolyte (3.0 M KOH). The newly
developed CTAB CuFeO2 delafossiate achieved a high Cs 1074 F/g and Ed of 23.85 Wh kg-1
also a Pd of 199.5 W kg-1 and also works effectively on 3500 cycles. Furthermore, the
fabricated material CTAB CuFeO2 also tested by two electrode system as ASC where CTAB
CuFeO2 act (+Ve) and AC (-Ve) electrode. Both were separated by filter paper and GCD test
confirmed that ASC device has Cs of 264 F/g and Ed of 82.5 Wh kg-1 and Pd of 750 W kg-1.
These findings show that the fabricated material CTAB CuFeO2 is a useful electrode for ASC
supercapacitors. Moreover, this material CTAB CuFeO2 electrode could be a better choice for
other energy storage and conversion applications.
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