Inorganic Chemistry Communications 154 (2023) 110998

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Inorganic Chemistry Communications

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Short communication

Nanoarchitectonics of Bi2CuO4 electrodes for asymmetric Bi2CuO4//AC

solid-state device in supercapacitor application
R.G. Bobade a, U.T. Nakate b, P. Roasiah c, M. Ouladsmane d, B.J. Lokhande e, R.C. Ambare a, *
a
Department of Physics, KMC, College, Khopoli, Khopoli-410203 (University of Mumbai), M.S. India
b
Department of Polymer-Nano Science and Technology, Jeonbuk National University, 567 Baekje-daero, Deokjin-gu, Jeonju-si, Jeollabuk-do 54896, Republic of Korea
c
Department of Physics, Saveetha School of Engineering, Saveetha Institute of Medical and Technical Sciences (SIMATS), Thandalam, Chennai 602 105, India
d
Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia
e
Lab of Electrochemical Studies, School of Physical Sciences, PSAH Solapur University, Solapur, Maharashtra, India

A R T I C L E I N F O A B S T R A C T

Keywords: The fashionable investigates the bismuth oxide nano-materials were synthesized using bismuth nitrate as an
Electrodeposition ingredient. The samples were deposited using the electrodeposition technique via an aqueous route with varying
Bi2CuO4-Thin Film deposition time variations. Prepared samples were annealed at 573 K in a muffle furnace. All deposited thin film
Electrode
electrodes were physical and electrochemical characterized via X-ray diffraction (XRD), Field emission scanning
Electrochemical characterization:
Supercapacitor
electron microscopy (FE-SEM), Elemental mapping, Energy dispersive X-ray spectroscopy (EDX), Contact Angle,
Bi2CuO4//AC (ASSD) X-ray photoelectron spectroscopy (XPS) and supercapacitive measurements. XRD of all deposited samples reveals
polycrystalline nature with a tetragonal crystal structure. FE-SEM shows revolutionary morphological images of
spruce leaf-like architecture. EDX analysis shows the elemental mapping of the deposited materials. TEM revels
the formation of nano granules structures indicating the formation of the crystalline bismuth oxide. XPS confirms
the formation of Bi2CuO4. All samples show the hydrophilic nature of deposited materials from contact angle.
Cyclic voltammetry (CV), Galvanostatic charge–discharge (GCD), and impedance measurements are used to
examine the supercapacitive characteristics in an aqueous 1 M KOH electrolyte. All CV curves show mixed
capacitive nature. The results of the investigations are highest specific capacitance (SC) of 706.47F/g at a scan
rate of 2 mV/s was calculated. The specific energy (SE) of 49.89 Wh/kg, and specific power (SP) of 17.51 kW/kg
were calculated at 40 mA/cm2 current density. The capacitive nature and internal resistance were observed using
the Nyquist plot for the optimized electrode which is about 2.11 Ohm. CV, GCD, and impedance measurements
are used to characterize the electrochemical parameters of the asymmetric supercapacitors device (Bi2CuO4//
AC) asymmetric solid-state device (ASSD). All CV curves show mixed capacitive nature. The results of the in­
vestigations are the highest specific capacitance of 98.71F/g at a scan rate of 5 mV/s was investigated. The SE of
30.14 Wh/kg, and SP of 2.08 kW/kg were calculated at 10 mA/cm2 current density. The capacitive nature and
internal resistance were observed using the Nyquist plot for the optimized electrode which is about 1.25 Ω.

1. Introduction issues are with some renewable energy sources, like wind, solar and tidal
power [3–5]. These renewable technologies provide a considerable
Today’s biggest challenge in front of the world is to develop envi­ amount of electrical energy, which needs to be stored and delivered
ronmentally friendly powerful energy and power storage devices for through an efficient mechanism [6–7]. One of the most popular energy
hybrid electrical vehicles. In the recently developed energy storage de­ storage methods among some of the different devices is that of super­
vices sector for advanced technologies, battery-supercapacitor hybrid capacitors. Fast charging, a large amount of power, and improved cycle
(BSH) devices have garnered considerable study focus. A viable energy stability makes them the best choice, specific capacitance (SCs) has
storage system being found is now a major global concern due to the attracted an increasing amount of interest [8–9]. The prevalent use of
worsening energy crisis and its effects on the environment, such as SCs is still constrained by their lower energy density when compared to
greenhouse emissions [1–2]. The most effective ways to address these widely accessible fuel cells and batteries. Therefore, focused research is

* Corresponding author.
E-mail addresses: revanambare@gmail.com, bjlokhande@gmail.com (R.C. Ambare).

https://doi.org/10.1016/j.inoche.2023.110998
Received 8 May 2023; Received in revised form 26 June 2023; Accepted 27 June 2023
Available online 29 June 2023
1387-7003/© 2023 Elsevier B.V. All rights reserved.
 R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

Fig. 1. Schematic of Bismuth oxide deposited on copper substrate by electrodeposition (ED).

being done to increase SCs energy density while maintaining their en­ [47], Bi2O3//Graphite (7 Wh/Kg at 2040 W/Kg in iron permeable sheet
ergy density and power density [10–13]. Creating ASCs, which are now /1M KOH) [48], Bi2O3//Graphite (11 Wh/Kg at 720 W/Kg in paper/6M
known as devices that retain one electrode charge using a capacitive KOH) [49], NiO@Co3O4@GQDs//AC (38 Wh/Kg at 750 W/Kg in PVA/
system while a second electrode does so use a Faradaic process, is one KOH) [50], Bi2O3//Graphite (13 Wh/Kg at 793 W/Kg in paper/6M
way to handle this problem. Because of their great charge/discharge KOH) [51], Ni/Co-TC//AC (37 Wh/Kg at 802 W/Kg in PVA/KOH) [52],
rate, high specific power (SP), and dimensional stability, SCs are thought Ni-Cu-Co-O//AC (53 Wh/Kg at 700 W/Kg in PVA/KOH) [53], NixCoy
to be essential storage devices for energy. [14,15]. MoxO//AC (22 Wh/Kg at 3.5 W/Kg in filter paper/1M KOH) [54],
Bismuth oxide-based nanoparticles (NPs) compounds have attracted Bi2CuO4//AC (30.14 Wh/Kg at 10.42 KW/Kg in PVA/1M KOH) [In this
a lot of attention for a variety of uses, including applications in optics work], this ASSD shows higher SP. According to these findings, the
and catalysis, biosensors, rechargeable batteries, sensing applications, Bi2CuO4 composite electrode (sample E9) is a very likely candidate to be
and energy application [16]. These applications include stability in the used as the positive electrode in performance-oriented energy storage
electrolytic method [17], Superior chemical insolubility and bioactivity devices.
[21], a high surface area [18], intriguing thermally and electrically The simple costless electrodeposition method is investigated in this
transport capabilities [19], and low toxicity [20]. According to recent study to produce binder-free bismuth oxide nanostructures on copper
investigations, bismuth and Bi2O3 nanocomposites have shown high SC substrates at different deposition times. X-ray diffraction (XRD), scan­
and extended charge–discharge cycle activities as an anode material for ning electron microscope (FE-SEM), and EDAX were used to thoroughly
electromechanical supercapacitors. [22]. and also, bismuth oxide investigate the structural characterizations of as-fabricated electrodes.
(Bi2O3) and its aspects might be advantageous materials for use in Cyclic voltammetry, galvanostatic charge–discharge, and electro­
supercapacitors due to their low toxicity and cost-effectiveness. Bi2O3 is chemical impedance spectroscopy were used to assess the electro­
well known for its condition of many oxidations, minimal conductivity, chemical performance (EIS).
diverse morphologies, and outstanding electro catalytic activity [23,24].
It consists of four major two independent phases and two crystalline 2. Experimental Investigation:
structures. They are monoclinic α-Bi2O3, tetragonal β-Bi2O3, cubic (BCC)
υ-Bi2O3, and (FCC) δ-Bi2O3 and nonstoichiometric phases are Bi2O2.33, 2.1. Materials
Bi2O2.75. α-Bi2O3 and δ-Bi2O3 are more stable under normal atmospheric
conditions, but β-Bi2O3 and υ-Bi2O3 is meta-stable at temperatures below Nitric acid (69% Extra pure) and bismuth nitrate (98% Extra pure)
750 K [25–27]. Ahmed AL-Osta et al. [28] used a straightforward and were the only solvents and chemicals utilized in this work; they were
affordable electrochemical deposition chemical technique to describe a both acquired from Loba Chemi Pvt. Ltd. in Mumbai and were put to use
unique spruce leaf-like copper bismuth oxide (CuBi2O4) nanostructures without additional purification. To create the electrodes made of bis­
film on stainless steel (SS) substrate, resulting in a high capacitance muth oxide, all solutions were made from scratch using distilled water
(540F/g) and excellent cyclic stability. Ali A. Ensafi et al. [29] the (DW).
copper-bismuth oxide (CuBi2O4) nanoparticles delivered a peak capac­
itance of (647F/g) and maintained 80% capacitance after 500 GCD cy­ 2.2. Substrate cleaning
cles when they were electrochemically placed on stainless steel.
Compared to previously described equivalent systems, such as A fine-grade polish paper was used to mirror polish the copper
ECNF@Bi2O3//CF@NiCo2O4 (25 Wh/Kg at 786 W/Kg in 1 M KOH) substrates before they were washed with liquid detergent. These

2
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R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

polished substrates were washed for a minute in diluted 10% H2SO4. 40 ◦ C to activate the ions in the solution. The moisture was subsequently
These freshly cleaned and dried copper substrates were utilized to create removed from the electrodes by placing them for 30 min inside a fume
functional electrodes by depositing thin layers of Bi2CuO4. hood. A sandwich-like arrangement of two of these Bi2CuO4//AC com­
posite electrodes with ion-gel electrolytes was used. The mass loading of
2.3. Electrodeposition and growth mechanism the electrode is Bi2CuO4//AC (ASSD device) 0.0045 gm. To get rid of
any remaining solvent and humidity, the fully produced device was kept
Using precursor Bi+ cations and NO–3 anions, which essentially move at room temperature for an hour.
randomly in the electrolyte solution, ED was used to create bismuth All deposited electrodes were characterized physically and electro­
oxide film electrodes on a copper substrate. Due to the presence of a chemically. The electrochemical investigation SC associated with the
large number of ions, the Cu substrate becomes negatively charged when working electrode was calculated using the relations reported in Elsevier
between the anode and cathode is placed an additional electric power by R.C. Ambare, et al. [31].
source. Under the influence of columbic electrostatic forces, the posi­ ∫ Vc
1
tively charged cations (Bi+) were drawn toward the negatively charged SC = I(V)dV (1)
mv(Vc − Va ) Va
Cu cathode surface. On the Cu substrate, the cations are reduced to
initiate the growth process. According to active sites and applied current Where SC is the specific capacitance, V is the scan rate in (mV/s), (Vc
density, a specific pattern of deposition growth can be seen. In electro­ − Va) is the potential window, I (V) denotes the current in (mA), and m is
deposition, the hydrogen evolution reaction (HER), which is caused by the deposited mass of active material dipped in an electrolyte of unit
the reduction of H+ ions at cathodic over-potential, is accompanied by area (1 cm2). The SE and SP were calculated using the relations.
hydrogen bubbles in the electrodeposition techniques [38-40]. SE =V×IWd ×td (2)
SP =V×IW (3)
d

2.4. Synthesis of bismuth oxide electrodes

Here, (V) is the applied voltage, (Id) is the discharging current and
(td) is the discharging time in hours, (W) is the weight of the active part
When bismuth nitrate was dissolved in water at a concentration of
of the electrode in grams.
0.05 M, a heterogeneous reaction took place in the container, producing
a turbid white solution. A few drops of nitric acid were added to the
solution and stirred continuously for up to three hours to eliminate the 2.7. Characterization details
turbidity. The prepared homogenous clear solution was used for the
further preparation of the bismuth oxide on a copper substrate [30]. The To determine crystal structure, plane orientations, and phase purity,
binder-free bismuth oxide electrodes were deposited using the electro­ X-ray diffraction (XRD) spectrum was conducted using a (Rigaku D/max
deposition technique with a constant concentration (0.0125 M) and 2550 Vb+/PC 18 kW with Cu Kα, λ = 1.5406) diffractometer within the
potential (5 V). Electrodes were deposited by variations in the deposi­ range of diffraction angle (2θ) 100 to 1000. Microstructure analysis is
tion time, such as 5, 7, and 10 min. All deposited samples were dried at done using a Hitachi S-4800, 15 kV field emission scanning electron
room temperate for 30 min and after annealing in a muffle furnace for microscope (FE-SEM). Utilizing the Holmark HO-IAD-CAN-01 instru­
one hour at 573 K for further analysis. The annealed samples were ment, the prepared electrode’s contact angle was measured. The weight
nomenclature as E6, E9, and E10 for 5, 7, and 10 min, respectively. The of the deposition material was calculated using the weight difference
mass loadings of the electrodes E6, E9, and E10 are 0.0032 gm, 0.0034 method using a 1x10-6 high-accuracy analytical microbalance (Tap­
gm, and 0.0033 gm etc. Fig. 1 shows the schematic of bismuth oxide son’s-100 TS). TEM: Manufactured Hitachi (H-7650) Electron source-
deposited on copper substrate by electrodeposition. Initially obtained LaB6, Accelerating voltage- 80 ~ 120 kV, Point resolution (nm)-0.36,
hydroxide film in black color after annealing its converts into yellow. Line resolution (nm): 0.24, Magnification - HC mode - x200 ~ x200,000,
HR mode – x 4,000 ~ x600,000, Field rotation: ±90 ˚(15 ˚step) for a
2.5. Synthesis of AC electrodes magnification range of x1,000 to x40,000. XPS analysis was recorded on
a Thermo ESCAlab 250Xi spectrometer with Al ka (1486.7 eV) mono­
Polyvinyl alcohol PVA (1 g) was mixed with double-distilled water chromatic source of radiation. Horiba Fluorog-2 Jobnyvon spectrometer
(10 mL) to make a PVA solution that was vigorously stirred at 80 ◦ C for was used to measure photoluminescence (PL) spectra at 365 nm exci­
2 h. The PVA solution was then mixed with activated carbon for 2 h at tation wavelength. The electrochemical properties of three electrode
800C. Finally, the prepared PVA/AC solution was placed in a desiccator cells of the Bi2O3 film electrode were investigated using a computer-
to protect it from moisture. Onto the washed copper substrate, the controlled potentiostat (HCH 600D SPL. electrochemical analyzer/
produced homogenous slurry was cast. Following the coating’s flat­ workstation). The CV of the prepared electrodes (size 1.5 cm2) was
tening of the slush with a doctor blade of 10 cm by 15 cm in size and performed in 1 M KOH using platinum wire as a counter electrode and
150–300 m in thickness, the wet-coated thin film was produced. After saturated Ag/AgCl as a reference electrode in the supercapacitive study.
being dried at ambient temperature for three hours, the samples were Using relation (1), the obtained CV curves were used to calculate the SC.
then tempered for six hours at 373 K in an electric furnace. The mass Charge discharge was investigated using a Chronopotentiometry tech­
loading of electrode is 0.0011 gm. nique at various current densities. To determine the internal resistance
of a supercapacitor cell, a multi-frequency impedance measurement was
2.6. Fabrication of the ASSD device (Bi2CuO4//AC) performed in the frequency range of 1 mHz − 1 MHz using an AC signal.
Using ZsimpWin software the standard and observed data is matched.
PVA solution was made by vigorously stirring double-distilled water
(10 mL) and polyvinyl alcohol (1 g) at 80 ◦ C for two hours. The PVA 3. Results and discussion
solution was then given 1 M KOH, and the mixture was stirred for 2 h at
80 ◦ C. Finally, a desiccator was used to protect the prepared PVA/KOH 3.1. Reaction kinetics
(ion-gel) solution from moisture. The Bi2CuO4//AC hybrid electrodes
and ion-gel as a solid-state electrolyte were put together in a sandwich The prepared aqueous solution of bismuth nitrate was deposited on a
configuration to create the Bi2CuO4//AC weldment supercapacitor. The copper substrate via electrodeposition. The formation of Bi2CuO4 ex­
constructed Bi2CuO4//AC hybrid electrodes were submerged in the plains as follows:
electrolytic solution for 10 min to allow the electrolytic to diffuse into 2Bi(NO3 )2 .6H2 O + H2 O + HNO3 →2Bi(OH)3 + 2N2 + 7O2 + 4H2 + HNO3
the Bi2CuO4//AC combination after the ion-gel electrolyte was heated to

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R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

Fig 2. a) X-ray diffraction patterns of Bi2CuO4 prepared by varies deposition time, b) Standard and observed XRD.

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R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

Fig. 3. (a-c) FE-SEM images of E6, E9 and E10 sample respectively at 1 µm scale bar. (d-f) FE-SEM images of E6, E9 and E10 sample respectively at 200 nm scale bar
and Wettability images of E6, E9 and E10 sample respectively.

Obtained Bi(OH)3 annelid at 573 K. direction. The crystallite size associated with all samples was calculated
using Scheer’s Formula [30].
CuSubtate(573K)
2Bi(OH)3 ̅̅̅̅̅̅̅̅̅̅̅
̅→ Bi2 CuO4 + H2 ↑ + 2H2 O↑
0.9λ
d= (4)
Final obtained Bi2 CuO4 used for further characterizations like XRD, βcos[03B8]
FE-SEM, Elemental mapping, EDAX, XPS, TEM, CV, CP, and Impedance
The average crystalline size of samples E6, E9, and E10 are 35.08 nm,
spectroscopy.
41.59 nm, and 47.98 nm respectively. Fig. 2 (b) shows the standard and
observed XRD plot. The calculated lattice constants a = 8.8531 Å, b =
3.2. X-ray diffraction analysis 8.8531 Å, c = 5.7059 Å, are in good agreement with standard lattice
constants [a = 8.5100 Å, b = a = 8.5100 Å, c = 5.8140 Å, XRD-Match
Fig. 2 (a) XRD patterns of E6, E9, and E10 samples. All samples show card no. 96–100-6029]. The micro strain was further calculated using
polycrystalline nature. The measured “d” values match with the stan­ the following equation (5) [55]. The calculated values for micro strain
dard “d” values from the XRD-Match card no. with good accuracy were 0.018.
(96–100-6029), indicating the formation of Bi2CuO4 with the tetragonal β
crystal structure. All samples show orientation peaks along (2 2 0), ε= (5)
4tan[03B8]
(0 1 2), (1 3 0), (2 2 2), (4 1 1), (4 2 1), (3 3 2), and (3 1 4) directions.
Sample E6 exhibits maximum orientation peaks along the (3 1 4)

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R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

Fig. 4. (a) The EDAX mapping image of E9 (Bi2CuO4), and (b-d) Elemental mapping images showing the individual distribution of Bi, Cu, and O. (e) EDAX spectrum
with percentage of chemical elements present in E9 electrode (Bi2CuO4), (f-g) TEM images of sample E9 electrode (Bi2CuO4).

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R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

Fig. 5. (a) XPS survey scan of E9 (Bi2CuO4), (b) of Bi 4f, (c) C 1 s, (d) O 1 s, (e) Cu 2p.

3.3. FE-SEM and TEM analysis hydrophilic nature of contact angle. The contact angle is determined by
the material’s surface morphology and chemical composition. The
As-prepared materials’ surface morphology was examined using FE- Elemental mapping analysis of the E9 sample is shown in Fig. 4 (a-d).
SEM analysis. Fig. 3 (a-f) shows FE-SEM micrograph images of Bi2CuO4 The image shows that all of the elements Bi, Cu, and O are present. The
electrodes. The figure was seen at a lower magnification and scaled to 1 presence of chemical elements and their compositional ratio were
µm in Fig. 3 (a-c), while the image was observed at a higher magnifi­ analyzed using EDAX mapping. Fig. 4 (e) shows the existence of
cation with a scale bar of 200 nm in Fig. 3 (d-f). The spruce leaf-like chemical elements such as Bi, Cu, and O that were confirmed for
architecture of the Bi2CuO4 electrode is confirmed by the low- Bi2CuO4. It was confirmed that Bi2CuO4 Nanomaterials had formed by
magnified image in Fig. 3 (a-c). Similar results were reported by the substantial compositions analysis findings obtained by EDAX shown
Ahmed AL-Osta et al. [28] the leaf-like structure is further composed of in Fig. 4 (e). In the spectrum, the quantity in weight % of Bi, Cu, and O
different size nanoparticles, as seen in the higher magnified image Fig. 3 were 67.09%, 24.28%, and 8.63% respectively. The details of the EDAX
(d-f). These NPs are well-connected to form twigs or branch-like struc­ spectra of (Bi2CuO4) NPs values measured in weight % are listed in Fig. 4
tures with a high surface area. The contact angle variation of bismuth (e). Fig. 4 (f-g) shows the TEM images of the optimized E9 electrode
oxide (Bi2CuO4) thin films deposited on the copper substrate at different (Bi2CuO4). TEM image shows the formation of nano granules of struc­
deposition times are shown in Fig. 3 (d-f). All of the samples have a tures indicating the formation of the crystalline bismuth oxide deposited

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R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

Fig. 6. (a) cyclic voltammetry of Bi2CuO4 for as-prepared E6, E9, E10 and Cu substrate annealed at 573 K electrodes scanned in 1 M KOH at 2 mV/s scan rate. (b)
Copper oxide (substrate) scanned for CV in 1 M KOH electrolyte solution for various scan rates in mV/sec. (c) Bismuth oxide deposited on Copper (Cu) prepared
electrode E9 scanned for CV in 1 M KOH for various scan rates in mV/sec. (d) The charge–discharge of Bi2CuO4 as-prepared on Cu substrate E6, E9, E10 and Cu
substrate in 1 M KOH electrolyte at 40 mA/cm2. (e) Charge-discharge curves of Copper oxide (substrate) scanned for various current densities in mA/cm2. (f) Charge-
discharge curves of bismuth oxide deposited on copper substrate electrode E9 scanned for various current densities in mA/cm2. (g) Variation of energy and power
with specific current for annealed E9 (Bi2CuO4) electrode.

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R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

Table 1
A comparison study presents an electrochemical performance of present work over bismuth oxide-based electrode materials.
Working Electrode Deposition Method Substrate Electrolyte Specific Capacitance (SC) in F/g References

Bi2O3 Electrochemical Deposition Copper Electrode 1M NaOH 98 [16]

CuBi2O4 Electrodeposition Stainless Steel 1M NaOH 540 [28]
CuBi2O4 Electrochemical Deposition Stainless Steel 6M KOH 647 [29]
Bi2O3 Spray Pyrolysis Technique Nickel Foam 1M Na2SO4 322.5 [31]
Bi2O3 Sol-gel Method Nickel Foam 6M KOH 528 [45]
Bi2O3/AC Precipitation Method Nickel Foam 6M KOH 466 [46]
Bi2CuO4 Electrodeposition Copper Substrate 1M KOH 706.47 In this work

on a copper substrate (Bi2CuO4). It shows a plaquette-like (flake) increase the deposition time your specific capacitance goes down, SCs
structure, similar results presented by S. Anandana et al. [44]. In simple obtained from the E10 electrode were 234.06 at 2 mV/s scan rate in 1 M
terms, copper ions in (Bi2CuO4) are coordinated by square oxygen ion KOH. All CV curve shows mixed capacitive behaviour. CV analysis of the
planes, which are then stacked on top of one another in a bewildered prepared electrode was made by using an electrochemical analyzer at
manner to form one-dimensional copper ion chains. This assembled different scan rates. Fig. 6 (b) displays the CV curves of copper oxide
structure may be the result of joining units made up of edge-sharing electrodes in the potential window of − 1 to 0.7 V vs. Ag/AgCl, recorded
CuOn units prescribed in planar arrays [44]. at various scan rates from 2 to 100 mV/s in 1 M KOH. Broad and tiny
peaks may be seen on all CV curves, showing heterogeneous capacitive
3.4. XPS analysis behaviour. Significant oxidation peaks with a modest reduction peak
were seen in all CVs. A substantial area under the curve with a wide
The materials formulation and the chemical oxidation of the com­ oxidation peak was seen for the electrode Cu. The redox peaks them­
ponents contained in the developed materials depicted in Fig. 5 were selves demonstrated that the implanted substance was pseudo capaci­
investigated using XPS analysis. Bi, C, O, and Cu elements are present in tive. Fig. 6 (c) represents the effect of scan rate variation of sample E9
Sample-E9 (Bi2CuO4) a composite, depicted in Fig. 5 (a), according to scanned for various scan rates observed from the CV curve with an in­
the XPS complete survey scan spectrum. equivalent outcomes reported crease in scan rates such as 2, 10, 50, and 100 mV/s. The SC is 706.47,
by P.J. Mafa et al. [31,43] were seen in Fig. 5 (b), which showed two 504.09, 282.98, and 147.24F/g, respectively. According to Table 1, the
adoring peaks of Bi 4f at 158.78 eV and 164.08 eV (for Bi2CuO4). These highest specific capacity attained in this study is greater than that noted
peaks corresponded to doublet spin-orbital photoelectron emission from in the literature. The scan rate variation shows that SC associated with
the Bi 4f7/2 and Bi 4f5/2 states. Fig. 5 (c) shows the carbon–carbon single materials decreases, which could be due to the scan rate effect [33]. The
bond C–C peak at 284.4 eV, the C-O-C peak at 286.3 eV, and the O-C = O specific capacitance obtained was higher than that of a few other re­
peak at 288.2 eV [41,42] can all be seen in the high-resolution C 1 s ported Bi2CuO4-based supercapacitor electrodes [28,29]. The peaks for
spectra of the combination. Two photoelectron peaks are seen in the O 1 the Bi2CuO4 electrode were produced by the reduction of Bi (III) to
s detailed spectra, as illustrated in Fig. 5(d). The oxygen in the spinel metal Bi (at − 0.45 V) and the oxidation of Bi metal to Bi (III) (at 0.83 V)
structural lattice that is present in the metal–oxygen-metal (M− O− M) respectively [34]. The Bi2CuO4 electrode has a larger cumulative area of
bond is responsible for the peak at 530.2 eV. The existence of (-C-O–H-) the CV loop, which is mostly due to its improved electrical properties
is shown by the peaks at 531.3 eV. The aforementioned carbon bonds and easier ion transport. The observed redox behavior of the Bi2CuO4
may offer a quick electron transfer platform to give the material a high electrode was similar to that of the Bi2O3 electrode. The redox behavior
conductivity. Additionally, the oxygen-containing functional groups on of Bi2O3 and Bi2CuO4 in the inclusion of OH– ions [35]. High crystal­
the copper substrate may interact with the NPs via covalent chemical linity may enhance electrochemical performance and reliability during
bonding, static attraction, or van de Waal’s forces to increase the charge–discharge cycling [32]. Low porosity and surface area are
durability of the hybrid material [41,42]. Fig. 5 (e) displays the high- responsible for low specific capacitance values, while high porosity,
precision XPS spectra of Cu 2p in Bi2CuO4. With a horizontal separa­ which makes it easier for electrolyte ions to diffuse through Bi2CuO4
tion of 20.1 eV, it displayed two prominent peaks that were respectively electrode material, may be responsible for high specific capacitance
centered at 933.2 eV and 953.3 eV and corresponded to the photoelec­ values. The E9 electrode’s high capacitance, which was attributed to the
tron emission from Cu 2p3/2 and Cu 2p1/2 microstates. Due to the Bi2CuO4 nanoparticles’ larger crystal sizes and their improved connec­
different chemical environments and interactions with other compo­ tivity, increased charge transportation. There are numerous nooks and
nents in the sample-E9 combination, these primary peaks have been spaces between those leaf structures that make it easy to insert the KOH
dropped back to the binding energy. This occurrence illustrates how electrolyte ions.
Bi2CuO4 may behave as an electron recipient, allowing electrons insert
the material and change the electron density nearby Cu+. P.J. Mafa et al. 3.5.2. Charge discharge studies
[43] have reported similar outcomes. Additionally, the Cu 2p spectrum The Chronopotentiometry (CP) method was used to evaluate the
of Bi2CuO4 has satellite peaks at 941.3 eV, 943.5 eV, and 962.4 eV. electrochemical performance of the Bi2CuO4 electrode. Fig. 6 (d) depicts
These satellite peaks provided evidence that the materials included the charge–discharge behavior of Bi2CuO4 prepared on a copper sub­
divalent copper [43]. strate with various deposition times E6, E9, E10, and Cu substrate when
scanned in 1 M KOH electrolyte at 40 mA/cm2. The highest SE and SP
3.5. Electrochemical characterization associated with materials were calculated to be approximately 49.89
Wh/kg and 35.01 kW/kg. Fig. 6 (e) Charge-discharge curves of Cu
3.5.1. Cyclic voltammetry analysis electrode scanned for various current densities in mA/cm2. All char­
All electrochemical characterizations were performed in the 0–0.9 V ge–discharge curve shows mixed capacitive behavior with an increase in
potential range. Fig. 6 (a) represents the CV curves of all deposited current density materials showing a decrease in time. Fig. 6 (f) Charge-
samples deposited on the copper substrate (Bi2CuO4) at various depo­ discharge curves of the E9 electrode at various current densities mA/cm2
sition times like 5,7, 10 min and Cu substrate. Electrode E6, E9, E10, and like 40, 50, 60, and 80 of SE and SP are 49.89, 35.01, 16.02, 21.01 Wh/
Cu substrate were scanned in a potential window from (-1 to 0.7) in 1 M kg and 17.51, 21.88, 26.26, 35.01 kW/kg respectively. All char­
KOH at 2 mV/s scan rate. At 2 mV/s scan rate, the maximum specific ge–discharge curves exhibit mixed capacitive behavior as current den­
capacitance obtained from the E9 electrode was 706.47F/g. If you sity increases, while time decreases. This behavior results from a

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R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

(e) E9
(f)
Cu

Fig.7. Bismuth oxide deposited on Copper (Cu) prepared electrode (E9) and Copper oxide (substrate) scanned in 1 M KOH impedance a, c) Nyquist plot and b, d)
Bode plot respectively, Match nyquist plot and inset shows the equivalent circuit of (e) Electrode E9, (f) Cu substrate.

reduction in the active sites in nanostructures that are utilized at higher brought on by the Faradaic reactions results in a depressed semicircle in
current densities. In other words, the nanostructure electrolyte inter­ the higher frequency zone, and the capacitive nature is seen at the lower
action would be limited at greater current densities because the elec­ frequency region. Internal resistance (Ri) was measured to be 1.96 Ω.
trolyte ions wouldn’t have enough time to react and reach the electrode The Bode curve for a Cu electrode carried in 1 M KOH is shown in Fig. 7
surface. As a result of the electrolyte ions’ limited ability to diffuse to the (d). According to the figure, the capacitive nature predominated at low
electrode surface, the electrode’s capacitance will decrease [36]. All frequencies, and the phase angle gradually grew as frequency climbed.
charge–discharge curves exhibit the IR drop at discharge time. The In other words, as the frequency is increased, the material exhibits
materials’ irreversible nature makes it possible. The decrease in specific resistive nature at high frequency and confirms its capacitive nature at
energy (SE) and increase in specific power (SP) with an increase in low frequency, indicating that resistive nature may be dominating. Fig. 7
specific current demonstrated that the current Bi2CuO4 electrode was (e) shows the matched Nyquist plot of sample E9 (Bi2CuO4) electrode.
active and competitive for ECs application shown in Fig. 6 (g). The Nyquist plot for sample E9 (Bi2CuO4) electrode attained via
experiment and ordinary curves fit analyzed by ZsimpWin simulation
3.5.3. Impedance spectroscopy analysis software. The inset of Fig. 7 (e) displays matched equivalent circuit for
EIS was used to scan the internal resistance and capacitive nature of sample E9 (Bi2CuO4) electrode having circuitry parameters viz charge
the E9 electrode. The Nyquist impedance plot of hypothetical and actual transfer resistance Rct = R1 = 2.083 Ω, R2 = 1.395 Ω, R3 = 10.65 Ω, R4
values is displayed in Fig. 7 (a). In the three-region plot, the charge- = 95.33 Ω, R5 = 0.06623 Ω, Q1 = 1.5 × 10-4F, Q2 = 4.7 × 10-4F, Q3 =
transfer resistance is brought on by the results of the Faradaic reaction 385F, and C1 = 4.952 × 10-6F. Fig. 7 (f) shows the matched Nyquist plot
in a depressed semicircle at the higher frequency region, and the of Cu substrate and inset displays a matched equivalent circuitry pa­
capacitive nature is seen at the lower frequency region. 2.11 Ω was the rameters are R1 = 0.01 Ω, R2 = 2.77 Ω, R3 = 4.13 Ω, R4 = 0.36 Ω, Q1 =
measured internal resistance (Ri). The Bode plot for the E9 electrode 7.97 × 10-7F, Q2 = 1.13 × 10-2F, C1 = 8.74 × 10-3F.
transport at OCP − 0.43731 V at 5 mA amplitude in 1 M KOH is shown in
Fig. 7 (b). According to the plot, capacitive nature predominated at knee
frequency and phase angle increased slowly as frequency increased. As 3.6. Asymmetric supercapacitors device (Bi2CuO4//AC):
the frequency is increased, the phase angle decreases, indicating that the
resistive nature of the material may eventually predominate; in other In 1 M KOH ion-gel, an asymmetric solid-state device (ASSD) was
words, the material demonstrated its resistive nature at high frequencies created by designing and fabricating the E9 electrode as the positive
and its capacitive nature at low frequencies. The internal resistance and electrode and the AC electrode as the negative electrode. To explore the
capacitive nature of Cu electrode were scanned by using EIS. The electrolytic capabilities of the ASSD device, Bi2CuO4/AC was built. In a
Nyquist impedance plot of virtual and real values is displayed in Fig. 7 two-electrode system, the positive and negative electrodes of the ASSD
(c). In the three-region graph, the charge-transfer resistance (Rct) device must have equal mass loading. The connection between the
positive and negative electrode charges, Q + and Q-, is known as the

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R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

charge balance relationship.

Fig. 8 (a) Shows the cyclic voltammetry of Bi2CuO4 electrode and AC
deposited on a copper substrate, electrodes scanned in 1 M KOH (ion-
gel) at 2 mV/s scan rate. The working potentials of the AC cathode and
E9 anode for the three-electrode system are shown in Fig. 8(a) as − 1.30
to 0.73 V and − 0.94 to 0.70 V, respectively. This suggests that the
Bi2CuO4/AC ASSD device’s operating potential can be expected to be up
to 1 V [37]. The CV curves of the Bi2CuO4//AC ASSD collected at
varying scanning rates are shown in Fig. 9 (a). CV curves were obtained
at various scan rates from 5 mV/s to 100 mV/s, with potentials ranging
from − 1.50 to 0.51 V vs (Ag/AgCl). The CV plots reveal obvious visual
peaks that correlate to normal faradaic activity during both forward and
reverse scans and a minimal change with an increase in scan rate,
indicating high Columbia efficiency and a low internal impedance of the
Bi2CuO4/AC ASSD device. The specific capacitance of 5, 10, 20, 50, and
100 mV/Sec are 98.71, 67.52, 43.94, 26.41, and 18.37F/g respectively.
Obtained the maximum specific capacitance at 5 mV/Sec is 98.71F/g.
Fig. 8. a) CV curves of E9 and AC electrodes at a scan rate of 2 mV/s Fig. 9 (b) shows the GCD curves of the Bi2CuO4//AC ASSD device, which
respectively. was tested at various current densities within a voltage potential

Fig. 9. (a) Bi2CuO4//AC (ASSD) scanned for CV in 1

M KOH polymer solution for various scan rates in mV/
sec. (b) Charge-discharge curves of Bi2CuO4//AC
(ASSD) scanned for various current densities in mA/
cm2. (c) Variation of energy and power with specific
current for ASSD device (Bi2CuO4//AC). (d) Stability
curve of ASSD device (Bi2CuO4//AC) prepared device
scanned for CV in 1 M KOH at 5 scan rates in mV/sec.
(e, f) Bi2CuO4//AC (ASSD) scanned in 1 M KOH
polymer solution impedance e) Nyquist plot, f) Bode
plot respectively, (g) Match Nyquist plot of ASSD
device (Bi2CuO4//AC) and inset shows equivalent
circuit.

(g)
ASSD

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R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

Fig. 10. Demonstration of ASSD device (Bi2CuO4//AC) of E9 electrode.

window of − 1.50 to 0.51 V. As the current density rises, their SCs Fig. 9 (e). In the three-region plot, the charge-transfer resistance (Rct) is
gradually decrease. This is because the positive electrode’s high current brought on by the results of the Faradaic reaction in a depressed semi­
density does not allow for enough time for the redox reaction to occur. circle at the higher frequency region, and the capacitive nature is seen at
Calculate maximum specific energy and specific powers were 30.14 Wh/ the lower frequency region. 1.25 Ω was the measured internal resistance
kg and 10.42 kW/kg respectively. Fig. 9 (c) sown the current of the ASSD (Ri). The Bode plot for the Bi2CuO4//AC ASSD device carried at OCP −
device (Bi2CuO4//AC) was shown to be active and competitive for ECs 0.43731 V at 5 mA amplitude in 1 M KOH polymer solution is shown in
application by the decrease in specific energy (SE) and increase in spe­ Fig. 9 (f). Fig. 9 (g) exhibits the experimental and standard Nyquist
cific power (SP) with an increase in specific current. Fig. 9 (d) depicts graph of the ASSD device (Bi2CuO4//AC) obtained by simulation using
the method of changing the potential window of the SC from − 1.50 to ZsimpWin software and the inset of it shows an equivalent circuit. The
0.51 V vs. Ag/AgCl for 5000 cycles at a scan rate of 5 mV/s. The ASSD circuitry considerations of ASSD device (Bi2CuO4//AC) are R1 = 1.163
(Bi2CuO4/AC) device was charged at 2.01 V. along with a cycle number- Ω, R2 = 137.1 Ω, R3 = 2078 Ω, C1 = 7.383 × 10-5F, Q1 = 0.00417F, W1
dependent graphic of its capacitance retention ratio. According to the = 4.04 × 10-9 Ω. Fig. 10 (a) shows how one red LED might be lit up using
graph, SC can decrease by as many as 2000 cycles while maintaining a wrist-worn devices. A single red LED was flashed for over a minute when
96.87F/g. additionally, when the cycle count grows, the ASSD device two single units were linked in sequence. Its applicability as a flexible
(Bi2CuO4/AC) exhibits a constant 96.87F/g SC up to 5000 cycles. The energy storage device for real-world applications is shown in Fig. 10 (a).
Bi2CuO4 electrode’s excellent crystallinity and chemical stability,
which permit rapid ion transport with shorter diffusion lengths, are 4. Conclusions
responsible for the stable SC. SC decreased till 2000 cycles. After 5000
cycles, the ASSD device (Bi2CuO4/AC) displays impressive cycling sta­ In conclusion, simple one-step electrodeposition techniques were
bility and outstanding reversibility with a high capacitance retention of used to create Bi2CuO4 nanostructures, which were then directly applied
98.15% and an exceptional Columbic efficiency of 98.15%. After 2000 as supercapacitor electrodes. The bismuth oxide NPs are uniformly
cycles, just 1.85% of the specific capacitance degraded. Fig. 9 (e) dis­ grown over the copper substrate while the electrodeposition scan rate is
plays the Nyquist plots of the Bi2CuO4//AC ASSD device in the fre­ optimized. As a consequence, the conductive support is effective, the ion
quency range of 1.0 Hz to 10 kHz. The morphology, physical diffusion channels are condensed, and the energy transfer channels are
characteristics, and chemical composition of the electrode for a given rapid, all of which help to provide an exceptional rate capability.
electrolyte polymer solution determine the different resistances, such as Bi2CuO4 electrode accordingly offered a high specific capacitance. An
internal and charge transport. EIS was used to scan the internal resis­ ASSD that was put together with Bi2CuO4 as the anode electrode dis­
tance and capacitive nature of the Bi2CuO4//AC ASSD device. The plays outstanding redox capability, especially due to the negative elec­
Nyquist impedance plot of hypothetical and actual values is displayed in trode’s AC and high energy density (49.89 Wh/kg at a power density of

12
R.G. Bobade et al. Inorganic Chemistry Communications 154 (2023) 110998

17.51 kW/kg). For electrodes, the Nyquist plot provides an internal [8] R.C. Ambare, S.R. Bharadwaj, B.J. Lokhande, Spray pyrolysed Mn: Co3O4 thin film
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Sec, and the maximum specific energies and powers were 30.14 Wh/kg composite with Co3O4 by potentiodynamic electrodeposition for better
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by novel cathodic dispersion of bulk bismuth electrodes, Electrochim. Acta 54
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