Journal of Energy Storage 86 (2024) 111146

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Journal of Energy Storage

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Research Papers

Morphology modulation of MnFe2O4 thin film electrode for enhanced

performance of hybrid supercapacitor
Rushiraj P. Bhosale a, Sambhaji S. Kumbhar b, Shraddha B. Bhosale b, Rahul R. Salunkhe c,
Vinita A. Kadam d, Sagar P. Pardhi e, Sandeep S. Gholap f, Chandrakant D. Lokhande b, *, Vinayak
S. Jamadade a, *
a
Department of Physics, D.P. Bhosale College, Koregaon, Satara 415516, India
b
Centre for Interdisciplinary Research, D. Y. Patil Education Society, Kolhapur 416 006, India
c
Department of Physics, Indian Institute of Technology Jammu Jagti, Jammu, J & K 181221, India
d
Department of Physics, Yashwantrao Chavan Institute of Science Satara (Autonomous), Karmaveer Bhaurao Patil University, Satara 415001, India
e
Department of Physics, Karmaveer Bhaurao Patil College, Urun Islampur 415409, India
f
Agency for Science, Technology and Research (A-STAR), Singapore 138634, Singapore

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

Keywords: The preparation of binder-free manganese ferrite electrodes has garnered significant interest in hybrid energy
Electrodeposition storage devices. This interest stems from their notable electrochemical activity, which is primarily attributed to
Hybrid supercapacitor morphological modulation. Therefore, this study outlines an uncomplicated and scalable synthetic method uti­
Manganese ferrite
lizing electrodeposition (ED) to synthesize manganese ferrite electrodes. These electrodes were synthesized with
Morphology modulation
Thin film
varying deposition time. By structural analysis, the MnFe2O4 phase of synthesized thin films is confirmed. With
an increase in the deposition time, the modulation in the morphology of manganese ferrite thin films is evident,
progressing from nanoflakes to nanorods. The most favorable deposition time for the manganese ferrite elec­
trode, featuring a worm-like morphology, achieved the highest specific capacitance of 227 F g− 1 at a current
density of 2 A g− 1. Additionally, the hybrid solid-state supercapacitor device (HSSD) demonstrated a maximum
specific capacitance of 70.1 F g− 1 with specific energy (SE) of 35.1 Wh kg− 1 at a specific power (SP) of 3.1 kW
kg− 1, while retaining 81.1 % of its capacitive performance over 5000 cycles. This research introduces a scalable
method for preparing manganese ferrite electrodes without binders, which can serve as cathode in hybrid energy
storage devices suitable for real-world applications.

1. Introduction cars, has prompted the development of transportable forms of energy. In

the report, Bosch’s (2007–2022 current state of affairs and expenditure
Global energy consumption is increasing exponentially as a result of prospects of supercapacitor market in China), the worldwide market of
the rising population and fast industrialization. As a result, energy has supercapacitors has extended US dollars up to $16 × 109 in 2015, and
been given top priority in addressing the needs of our modern civiliza­ evaluators look for the market of the supercapacitor to outrun in 2020
tion [1]. Fossil fuels currently serve as the primary source of energy and up to $92.3 × 109, with a 39 % multiple yearly growth rates. From this
provide the diverse spectrum of energy needs in various industries. view, the progress of the supercapacitor market in the whole world is
Unfortunately, the availability of fossil fuels is steadily decreasing, and rising [3]. The development of extremely effective energy conversion as
our planet is constantly in danger as a result of the massive environ­ well as storage technologies has been a continuous endeavor in this
mental degradation these sources produce. According to some studies, context. Due to their high energy/power densities, prolonged lives, and
by the middle of the century, the world’s energy needs would have quick charging-discharging capabilities, energy storage technologies
doubled, and by 2100, they would have tripled [2]. In addition, the including supercapacitors, fuel cells, and rechargeable batteries are
widespread use of electronic gadgets, such as wearable technology, regarded as viable options for meeting a variety of energy demands [4].
digital cameras, laptops, and mobile phones, as well as hybrid electric Supercapacitors, also known as ultra-capacitors, are among the most

* Corresponding authors.
E-mail addresses: l_chandrakant@yahoo.com (C.D. Lokhande), vinayakjamadade@gmail.com (V.S. Jamadade).

https://doi.org/10.1016/j.est.2024.111146
Received 18 November 2023; Received in revised form 14 February 2024; Accepted 28 February 2024
Available online 7 March 2024
2352-152X/© 2024 Elsevier Ltd. All rights reserved.
R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

Fig. 1. Schematic illustration of electrodeposition setup.

Fig. 2. (a) The XRD patterns, (b) FT-IR spectra of MnFe2O4 thin films (MF1 to MF3).

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R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

Fig. 3. The SEM images of MF1 (a, b). MF2 (c, d). MF3 (e, f). Samples at ×10,000 and at ×60,000 magnifications.

attractive devices for storing energy because of their high power density and hybrid electric vehicles, Supercapacitor research is exploding, and
(PD) (>10 kW kg− 1), fast rate capability, and extended cycle span scientists have achieved significant advancements in this area. Their
(>10,00,000 cycles). Supercapacitors have a distinct advantage over main objective is to increase the high PDs of supercapacitors while
batteries in that their PDs are higher. Even while they have energy reducing their EDs, enabling them to serve as a main source of energy
densities (EDs) that are many times greater than those of conventional similar to batteries.
capacitors, compared to fuel cells and batteries, they are nonetheless According to the charge storage mechanism, supercapacitors are
significantly lower. Supercapacitors thus fill a need by bridging the categorized into three types; electric double-layer capacitors (EDLC),
energy and power gap between fuels/batteries and conventional pseudocapacitors, and hybrid capacitors. Which pseudocapacitor, the
dielectric capacitors. Since 1957, when Becker first requested a patent quick faradaic reactions occurring at the surface of the electrode, has a
on an electrochemical capacitor, a lot of work has been spent on larger specific capacitance (Cs) than EDLC. Pseudocapacitor also has the
studying effective supercapacitors [5,6]. High PD has been particularly benefit of being inexpensive. However, as conductivity is crucial for
needed in recent years to fulfill the growing demands of advanced ap­ achieving high ED and PD, pseudocapacitor materials are only used in a
plications including energy incremental backups, electronic gadgets, selected number of applications.

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R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

Fig. 4. N2 adsorption/desorption isotherm of (a) MF1, (b) MF2, and (c) MF3 samples.

In the recent couple of decades, spinel ferrites have had great analyst separation of charge. It is also referred to as electrochemical capacitors
expeditions because of their creativity flexibility of small losses of eddy or ultracapacitors. The key factors affected by morphology include
current, larger electrical resistivity, the giant value of dielectric con­ surface area, porosity, and the accessibility of active sites [12]. Higher
stants, excessive initial permeability, and adequate saturation magne­ surface area materials have more electrochemical reaction sites, which
tization [7–9]. Due to their superior electrical and magnetic properties, increases their capacity to store charge. Because of their high surface
they are widely used in various gadgets such as cell phones stage areas, nanomaterials including flakes, nanowires, and nanorods are
shifters, large frequency transformer cores, switches, resonators, and good candidates for supercapacitor applications. Improved ion diffusion
more [10]. and electrolyte accessibility via porous materials lead to improved
In comparison to traditional electrochemical capacitors, metal ferrite charge storage and quicker charge/discharge rates. Mesopore materials
electrodes exhibit dramatically improved capacitance performance and are often favored for supercapacitor electrodes. The morphology can
offer high specific energy and specific power. However, these kinds of influence the electrical conductivity of the material. Well-connected
capacitors still face a lot of difficulties because of the low cycle stability structures, such as networks of nanorods or nanoflakes, facilitate effi­
of faradaic electrodes [11]. In the ongoing search for innovative elec­ cient electron transport, reducing internal resistance and enhancing
trode materials, material costs, and ecological sustainability remain overall device performance [13]. Through functionalization, materials’
major obstacles. Compared to monometallic oxides, metal iron oxide surface chemistry can be changed to optimise their interaction with
(MFe2O4) materials such as MnFe2O4, CuFe2O4, NiFe2O4, etc. exhibit electrolytes, which improves capacitance and stability [14].
rich redox properties and improved electrochemical conductivity. The Manganese ferrite has drawn a lot of interest because of its dielectric
spinel ferrites acquire a cubic spinel structure with two unique adjacent qualities, low dielectric losses, affordability, wide availability, eco-
lattice sites: tetrahedral and octahedral sublattices, particularly those friendliness, and noteworthy electrochemical reactivity. This has
that contain the metallic divalent cation M2+. Among these materials, prompted in-depth investigation and study. J. Kwon et al. studied
MFe2O4 (where M might be Mn, Co, Ni, Zn, or Mg) has drawn a lot of MnFe2O4 hybrid supercapacitors via hydrothermal synthesis. For
attention as a thoroughly studied pseudocapacitive electrode material. instance, these supercapacitors displayed a remarkable specific capaci­
MnFe2O4 provides different morphologies as well as better electro­ tance of 282 F g− 1 and showed extraordinary cyclic stability, main­
chemical performance. The supercapacitive performance of materials is taining 85.8 % of their retention over 2000 cycles [15]. Using a
largely determined by their morphology. Supercapacitors are energy solvothermal synthesis method, Z. Li et al. synthesized MnFe2O4
storage devices that store electrical energy by the electrostatic colloidal nanocrystals. The findings of their study achieved a specific

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R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

Fig. 5. (a) Full survey spectrum, (b) Mn 2p spectrum, (c) Fe 2p spectrum, (d) O 1s XPS spectrum of the MF2 sample.

capacitance of 88.4 F g− 1 at 1 A g− 1 with 69.2 % retention over 2000 performance of manganese ferrite thin film electrodes. Additionally, the
cycles [16]. A viable electrospinning process was used in the study by Y. ideal manganese ferrite electrode was used as the cathode and a man­
Liu et al. to encapsulate MnFe2O4 nanodots inside porous N-doped ganese oxide (MnO2) electrode served as the anode in the construction of
carbon nanofibers. This method demonstrated outstanding high-rate the hybrid solid-state supercapacitor device (HSSD) configurations. The
performance obtained 305 mAh g− 1 even at 10000 mA g− 1 and a pro­ discussion included measurements and a display of the supercapacitive
longed cycling lifespan maintained over 90 % capacity retention over properties of the hybrid energy storage device.
4200 cycles [17]. P. Junlabhut et al. [18] synthesized MnFe2O4 nano­
particles via the chemical co-precipitation method and studied the 2. Experimental section
structural properties of MnFe2O4 nanoparticles. A composite material
made of PANI and MnFe2O4 nanocubes decorated on flexible graphene 2.1. Chemicals and substrate cleaning process
with a specific capacitance of 338 F g− 1. This composite was created
utilizing a chemical oxidative polymerization process that was reason­ Without any additional processing, each material was used as
ably straightforward, affordable, and environmentally benign by K. received. The following chemicals were bought from Sigma Aldrich:
Sankar et al. for the utilization of a supercapacitor [19]. ferrous chloride (FeCl2), manganese chloride (MnCl2), sodium sulphate
In this context, the development of materials using electrodeposition (Na2SO4), and nitric acid (HNO3). To prepare solutions for, double
stands as an intriguing and creative approach, providing the dual pur­ distilled water (DDW) was used. Zero-grade polishing paper was used to
poses of morphology alterations and the deposition of active materials polish stainless steel (SS) substrate (304 grade)and further cleaned with
for supercapacitor applications. To prepare manganese ferrite thin film standard process, In addition, the SS substrate was rinsed with acetone
electrodes, while varying the deposition time, a binder-free one-step and ultrasonicated for 15 min in DDW. These cleaned substrate were
electrodeposition method was used in this study. As the deposition time used for the deposition of manganese ferrite thin films.
variation of manganese ferrite was systematically changed, the changes
in the structure and morphology of thin films formed from manganese
2.2. Synthesis of manganese ferrite thin films
ferrite were investigated using structural and morphological character­
ization studies. Additionally, research was done to determine how
Electrodeposition (ED) method was used to prepare manganese
changes in structural and morphological impact the pseudocapacitive
ferrite thin films from precursors of manganese chloride and ferrous

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R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

Fig. 6. (a) Comparative CV curves of MF series at a 50 mV s− 1 scan rate, (b) CV curves of the MF2 electrode, (c) plot of the log of current density vs log of scan rate
(d) plot of the total charge against the reciprocal of the square root of potential scan rate for MF series electrodes, (e) comparative charge contribution of MF series
electrodes, and (f) charge contribution of MF2.

chloride in an aqueous solution. Fig. 1 depicts the electrodeposition transform-infrared spectroscopy (FT-IR) was recorded using an Alpha
configuration schematically. This assembly consists of a graphite plate (II) Bruker unit and used for the identification of functional groups
of area 1 × 5 cm2 that serves as the counter electrode, a sizable SS of 1 × present in MnFe2O4 thin film. The surface area and pore size distribution
5 cm2 as the working electrode, and an Ag/AgCl as the reference elec­ of MnFe2O4 were evaluated using Brunarer–Emmett-Teller (BET) and
trode. In this paper, for first time we report a facile, low-cost, and Barrette-Joyner-Halenda (BJH) techniques on BEL-SORP-II mini
electrodeposition approach for the synthesis of a MnFe2O4 porous (Japan), respectively. All electrochemical measurement were carried
nanoflakes-like structure on an SS substrate for supercapacitor appli­ out using ZIVE MP1 multichannel electrochemical workstation.
cation. In a typical process, precursor electrolytes for the deposition of
MnFe2O4 film comprised of aqueous 0.1 M FeCl2 and 0.05 MnCl2 solu­ 3. Results and discussion
tions, with the pH being maintained at 3.2 by adding HNO3 drop-by-
drop. During electrodeposition, deposition time was optimized to get 3.1. The formation manganese ferrite thin film mechanism
good quality adherent and uniform MnFe2O4 film. The SS substrate was
dipped into the solution and a potential of 1.6 V/Ag/AgCl was applied Binder-free manganese ferrite thin film electrodes was produced on
for 3, 4, and 5 min. to achieve different thicknesses of MnFe2O4 films SS substrate using a electrodeposition method. The synthesis process is
which are denoted as MF1, MF2, and MF3 respectively. After electro­ described in detail in the experimental section, and a custom-designed
deposition, a green-colored thin film was formed on the SS substrate. electrochemical cell is illustrated schematically in Fig. 1. During the
The MnFe2O4 coated thin film was then dried at room temperature electrodeposition process, a metal layer is deposited onto another metal
followed by annealing in air at 400 ◦ C for 3 h in a tube furnace. After 3 h through the exchange of electrons with ions in the precursor solution,
of annealing, the green-colored thin film samples was converted to a which involves an oxidation-reduction reaction. In this work, manga­
black-colored film. nese ferrite thin films (MF series samples) were prepared at different
deposition time to obtain different thickness and morphology. In syn­
thesis process, nitric acid was used as an oxidizing agent and reaction
2.3. Characterizations
bath was kept at room temperature for 3, 4, and 5 min. The dissociation
of manganese chloride, ferrous chloride, and nitric acid in aqueous
X-ray diffraction pattern (XRD) was used to determine the crystal
medium is given in Eq. (1),
structure of the prepared material. (Rigaku miniflex-600) using the Cu
Kα radiation (λ = 1.5406 Å) operated at 30 kV and 15 mA within the 2θ MnCl2 + 2FeCl2 + 12HNO3 →MnFe2 O4 + 2NO2 + 2Cl2 + (6 − x)H2 O (1)
range 10◦ to 80◦ . The morphological and elemental analysis of MnFe2O4
Further,
thin film was examined on JEOL JSM-IT200 scanning electron micro­
scopy (SEM) and Energy dispersive spectroscopy (EDS). Fourier

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R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

1
Fig. 7. (a) Comparative GCD curves of MF series at a 2 A g− current density, (b) GCD curves MF2, (c) graph of specific capacitance vs current density of MF series
electrodes, (d) EIS plot of MF series, and (e) stability plot.

MnFe2 O4 + 2Cl2 + (6 − x)H2 O→MnFe2 O4 + 2HCl (2) angle. The average crystal size of the MF1, MF2, and MF3 samples for
the (311) plane are 17.57 nm, 32.51 nm, and 25.67 nm, respectively.
Thus MnFe2O4 was successfully produced on SS substrate. Opti­
Improving crystalline characteristics in manganese ferrite can poten­
mizing the reaction time to 3 min and maintaining a potential of 1.6 V/
tially contribute to prolonging the durability of electrodes. The obtained
Ag/AgCl are the ideal conditions for obtaining a uniform and firmly
crystal structure contributes to cycle life extension by resisting degra­
adherent material deposit on a stainless steel (SS) substrate. It was noted
dation during electrochemical processes. [21].
that the uniformity of the deposited film was compromised when the
The FT-IR spectra that correspond to the study of chemical bond
deposition time was below 3 min. The obtained mass loading of MF
vibrations within the time variation MF series are shown in Fig. 2(b).
series thin films are 0.32, 0.65, and 0.97 mg cm− 2 (MF1, MF2, and MF3,
Within the region of 400–4000 cm− 1, the FT-IR peak properties of the
respectively) Conversely, when the deposition time exceeded 5 min., the
synthesized MF series thin films were examined. Within the spectral
result was the formation of thin films with a powdery texture, attrib­
region extending from 400 to 700 cm− 1, the metal oxide (M-O) bonds in
utable to excessive material overgrowth.
manganese ferrite stretch vibrationally. In the case of ferrites, the po­
sition of oxygen atoms nearest to the metallic ions causes the positioning
3.2. Structural and morphological study of these ions within tetrahedral and octahedral sub-lattices. The lower-
frequency peaks (δ0) at 468.9 cm− 1 are vibrations at octahedral places is
To investigate the crystalline arrangements within the synthesized related to the Fe–O bonds in MnFe2O4 and is responsible for the ab­
thin film electrodes (MF series), X-ray diffraction (XRD) technique were sorption peaks at (δ0) [22]. The elevated-frequency peak (δ1) at 572.5
used. Fig. 2(a) provides the XRD patterns of sample MF1 to MF3. Fig. 2 cm− 1 corresponds to the intrinsic vibrations occurring at tetrahedral
(a) shows strong peaks corresponding to the crystal lattice planes (220), locations, according to the analysis of the vibrational spectra of ferrites
(311), (422), and (440) of the MnFe2O4 spinel structure. These findings the characteristic peak (δ1) in the FT-IR spectra is associated with a
support the existence of a cubic crystal structure and are consistent with vibration caused by the bending of the Mn–O band [23]. The stretching
the crystallographic arrangement stated in JCPDS card no. 74-2403. The vibrational band characteristic of FeO-OH molecule is represented by
peaks denoted by a ‘#’ is of SS substrate. The intensity of the diffraction the (δ2) at 1107.9 cm− 1 [24]. The peak at (δ3) is attributed to C–C bond
peak (311) seen in the MF2 sample is higher than in the other samples at 1381.1 cm− 1. Wavenumber of 16 74 cm− 1 is the absorption band
(MF1 and MF3) due to uniformly and firmly adherent deposition of connected to the stretching vibration of water molecules is obtained at
material. Scherrer equation was used to calculate the effect of deposition (δ4). The peak (δ5) located at 2922.5 cm− 1 indicates that C–H bonds
time on the size of crystalline structures in MnFe2O4 [20], are vibrating in a stretching manner. Furthermore, the broad spectral
range between 2996.9 and 3656.4 cm− 1 suggests that the water adsor­
D=
Kλ
(3) bed inside the created material is the source of the stretching vibrations
βcosθ of O–H bands (δ5). The synthesized MF series samples show almost
identical peak spectrum, which supports the existence of similar
where D is the size of the crystallites, K is a constant, λ is the X-ray chemical linkages in the manganese ferrite material and supports the
wavelength, β is the full-width half-maxima, and θ is the diffraction

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R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

Fig. 8. (a) Schematic representation of solid device, (b) CV curves of HSSD, (c) GCD, and (d) plot of specific capacitance vs current density.

presence of structural water in the thin film samples that were formed. and oxygen remains relatively consistent across the samples in the MF
The FT-IR analysis shows that hydrous manganese ferrite thin films were series. The EDS analysis results validate a variation in the deposition
synthesized. time in the manganese ferrite thin films, which is accountable for the
The SEM images for sample MF1, MF2, and MF3 are provided in changes in both structure and morphology. Hence, the outcomes of both
Fig. 3(a-f). It is observed that MnFe2O4 thin film synthesized by ED EDS and SEM analyses corroborate the morphology modulation across
method by varying deposition time influences the morphological the samples MF1, MF2, and MF3. This variation ultimately exerts an
transformation from interconnected nanoflakes to nanorods impact on the supercapacitive performance of the thin-film electrodes.
morphology during the formation of films at constant potential of 1.6 V/ The BET study was used to analyse the surface area of the electro­
Ag/AgCl. MnFe2O4 thin films with a sample of MF1 has formed inter­ deposited MF series samples, and the BJH was used to investigate the
connected nanoflakes-like morphology as shown in the Fig. 3(a, b) at distribution of pore size. In a variety of relative pressures (P/P0), Fig. 4
different magnifications. After increasing the deposition time (4 min), (a-c) shows the nitrogen sorption isotherm of MF series samples. The
the modulation in the morphology of MF2 thin film is observed, from obtained specific surface area (pore size) of 28 m2 g− 1 (10.2 nm), 42 m2
nanoflakes to worm-like structure as displayed in Fig. 3(c, d). Further, g− 1 (5 nm), and 33.2 m2 g− 1 (9.6 nm) for MF1, MF2, and MF3,
increasing deposition time up to (5 min) MF3 thin film sample, the respectively. The type-IV isotherms for MF series samples, indicate the
worm-like morphology converted into nanorods as shown in the Fig. 3(e, mesoporous nature. The mesoporous structure of prepared material may
f). The rate of the chemical reaction is influenced by the deposition time, enable easy electrolyte ion penetration, suitable for ion transfer within
which, in turn, leads to a change in the material morphology, tran­ the electrode, resulting in improved electrochemical properties [25].
sitioning from a nanoflakes to nanorods. The result illustrate that the From the SEM image, the surface morphology of an MnFe2O4 electrode
deposition time of manganese ferrite thin films play a crucial role in is highly relevant in the charge-storing process. The electrode large
determining morphology of the material, resulting in variations between surface area and porous shape enhance the electrode ability to engage
nanoflakes to nanorods forms. with the electrolyte and give it a large number of active redox sites. The
The chemical composition and the presence of elements in the increase in the surface area leads to an increase in charge storage
samples was analyzed through EDS examination, and the results are capacitive.
depicted in Fig. S1 (see ESI). In the MF series samples, the presence of The XPS of MF2 thin film sample was used to investigate deeper
manganese, iron, and oxygen elements is evident, confirming the for­ information regarding the composition and oxidation state of the sam­
mation of manganese ferrite shown in EDS spectrum (Fig. S2) (see ESI). ple. The spectrum is calibrated with the reference energy value of C 1s of
EDS images demonstrated a peak corresponding to Mn, Fe, and O ele­ 284.8 eV. The full XPS spectrum of manganese ferrite in Fig. 5(a) il­
ments with atomic percentages of 16.07 %, 36.47 %, and 47.46 %, lustrates that the sample is composed of Mn, Fe, O, and C elements.
respectively for MF2 sample. The atomic percentage of manganese, iron, Fig. 5(b) shows Mn 2p spectrum deconvoluted into the Mn 2p3/2 and Mn

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R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

Fig. 9. (a) Ragone plot of the HSSD, (b) EIS plot, and (c) plot of capacitive retention vs cycle number.

2p1/2 correspond to the binding energies of 641.2 eV and 652.9 eV, 3.3. Electrochemical characterization of manganese ferrite thin film
respectively. These peaks show the existence of a pair of Mn ionic spe­
cies, with three peaks confirmed at 642.2, 640.7, and 645.8 eV associ­ The electrochemical behaviour of electrodes derived from the time-
ated with Mn2+, Mn3+, and satellite, respectively [26]. Fig. 5(c) displays varied MF series in a 1 M Na2SO4 solution was evaluated by using cy­
the XPS spectrum of Fe 2p and it deconvoluted into the Fe 2p3/2 and Fe clic voltammetry (CV), galvanostatic charge-discharge (GCD), electro­
2p1/2 at binding energies of 710.5 eV and 724.5 eV, respectively. After chemical impedance spectroscopy (EIS), and cycling stability tests.
the deconvolution, Fe 2p3/2 and Fe 2p1/2 peaks are splitted into the two Fig. 6(a) shows example comparative CV curves of the MF series elec­
distinct peaks of Fe3+ and Fe2+. Specifically, in the MF2 sample, the Fe trodes, measured at a scanning rate of 50 mV s− 1, in a potential window
2p3/2 region displayed binding energies of 710.3 and 712.78 eV for Fe3+ of 0 to − 1.2 V/Ag/AgCl. The trend seen in Fig. 6(a) shows that the
and Fe2+, respectively, alongside the observation of a satellite peak at current response within the CV curves of electrodes rises as the increase
719.25 eV. Furthermore, Fe 2p1/2 peak splitted binding energies of in deposition time, peaking at the MF2 electrode. Additionally, when the
724.3 eV and 726.6 eV for Fe3+ and Fe2+ respectively, with a satellite deposition time increases then 4 min, the current response within the CV
peak being observed at 732.5 eV. The presence of both Fe3+ and Fe2+ curve decreases. Therefore, the increased current response in the CV
indicates that the material is ferrimagnetic, which means that it has both curve of MF2 electrode has a greater capacity for charge storage than the
ferromagnetic and antiferromagnetic properties [27]. Fig. 5(d) shows other thin film electrodes (MF1 and MF3). The MF2 electrode CV curves
the XPS spectrum of the O 1s. In the case of the MF2 sample, the fitting in Fig. 6(b) at various scan rates ranging from 5 to 100 mV s− 1, shows an
lines exhibited a satisfactory agreement with the observed spectrum. increase in the current response, the scan rate is increased. The
Three distinct peaks are observed with binding energies centred at remaining electrodes (MF1 and MF3) CV plots, which were obtained at
530.12 eV (O1), 531.82 eV (O2), and 532.90 eV (O3). These peaks were scan rates ranging from 5 to 100 mV s− 1, are shown in Fig. S3(a, b) (see
attributed to oxygen atoms bonded to the metal, oxygen defect sites with ESI). In MF2 electrode CV curves, more intense redox peaks are observed
low oxygen coordination, and hydroxide species originating from than in the other electrode CV curves.
surface-adsorbed water molecules, respectively. Notably, the peak in­ Additionally, a concentrated effort is being made to thoroughly un­
tensity at 531.82 eV was significantly enhanced for MnFe2O4, suggesting derstand the mechanism for storing charges of the MF series electrodes
that varying the deposition time can effectively generate a substantial by looking into their outstanding electrochemical kinetics. The Power
number of stable oxygen vacancies [28]. Therefore, the XPS findings law, which governs the relationship between scan rate (υ) and peak
confirm the existence of manganese, iron, and oxygen within the man­ current (i) in the CV loop area, as,
ganese ferrite thin film. In summary, the XPS analysis verifies the
i = aʋb (4)
effective synthesis of manganese ferrite material through the ED
method. The variables ‘a’ and ‘b’ are adjustable parameters in Eq. (4), with

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R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

Fig. 10. (a-c) The photographs of HSSD demonstration by glowing LED lamp and (d) Ragone plot of comparative literature devices.

the value of ‘b’ generated from the gradients created by graphing the the data shown in Fig. 6(e) the charge contribution of the MF series, the
logarithms of (i) and (ʋ). When ‘b’ is close to 0.5, the diffusion- diffusive contribution is higher in the MF2 electrode than the other
controlled process of electrochemical charge storage predominates, samples concerning a scan rate. Fig. 6(e) shows that at a 5 mV s− 1 scan
and when ‘b’ is close to 1, the surface capacitive process predominates rate, the MF2 electrode exhibits a much higher capacitive charge
[29]. According to Fig. 6(c), the ‘b’ values for MF1, MF2, and MF3 are contribution of about 91 % compared to the other samples. The MF2
calculated as 0.58, 0.69, and 0.89, respectively. The results, between the electrode charge contribution displayed in Fig. 6(f). Fig. S3(c, d) (see
range of 0.5 to 1, demonstrate that a variety of charge storage processes, ESI) shows the distribution of capacitive and diffusive charges for the
including pseudocapacitive and diffusion-controlled ones account for remaining samples (MF1 and MF3).
the majority of the total current. The increase in pseudocapacitive Additionally, the GCD behaviour of the electrodes in MF series was
contribution in manganese ferrite thin films is correlated with the investigated using the refined potential range spanning from 0 to − 1.2
modulation in morphology as indicated by the rise of b values from MF1 V/Ag/AgCl. The results of the analysis, which was carried out with a
to MF3. The graph depicting Qtotal against ν− 1/2 is presented in Fig. 6(d), constant current density of 2 A g− 1, are shown in Fig. 7(a). In a com­
where the Y-axis intercept signifies the capacitive contribution of the MF parison study, it was discovered that the MF2 electrode, in contrast to
series electrodes. the other electrodes (MF1 and MF3), displayed prolonged charging and
Additionally, by using the Trasatti approach [30], it is possible to discharging durations. This finding points to significant capacity of the
evaluate the surface capacitive component of charge storage, which electrode material for energy storage. In Fig. 7(b), the GCD analysis of
furthered our understanding of the kinetics of electrode charge storage. the MF2 electrode at various current densities is shown. The GCD pro­
This analysis explains the existence of pseudocapacitive behaviour files of the other MF series electrodes at various current densities
brought on by external charge storage at the surface as well as battery- ranging from 2 to 6 A g− 1 are also shown in Fig. S4(a, b) (see ESI). MF2
like behaviour (diffusion-controlled). The full examination of the cur­ electrode exhibits a higher charge-discharge reactivity, as shown by the
rent response derived from CV is used to quantify the battery-type analysis of GCD, which is due to the electrode large surface area
charge (Qd) and pseudocapacitive surface charge (Qs). According to resulting from a unique nanorod structure and the intercalation of

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R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

charge storage mechanism. Specific capacitance is calculated using the The enhanced charge transfer capabilities of the HSSD are further
GCD curves of MF series electrodes with a different current density. explored in the EIS investigation, as shown in Fig. 9(b). The initial low
Fig. 7(c) displays the corresponding values. As a result, MF2 electrode values of Rs (0.41 Ω) and Rct (165.8 Ω) for the HSSD before stability
outperforms other MF1 and MF3 electrodes in the MF series, exhibiting a testing are caused by lower electrical resistance in the electrodes and
significant specific capacitance of 227 F g− 1 when subjected to a current improved contact between the electrolyte and electrodes with minimal
density of 2 A g− 1. MF2 electrode improved electrochemical perfor­ ohmic losses. After 5000 cycles, Rs (0.23 Ω) and Rct (244.6 Ω) were still
mance is due to the appropriate deposition time (4 min.), as well as the present, demonstrating the HSSD’s excellent stability. As seen in Fig. 9
large surface area that is offered by the nanorod-like structure. (c), 5000 successive GCD cycles at a constant current density of 5 A g− 1
The Fig. 7(d) contains the outcomes of the EIS investigation and the are used to evaluate the HSSD’s continuous stability. The HSSD dem­
accompanying Nyquist plots. A linear segment at low frequencies and a onstrates capacitive retention of ~81.1 % after 5000 GCD cycles.
semicircular shape at higher frequencies are consistently observed in the Moreover, the finding of current work with regarding the perfor­
MF series electrodes. The starting point of the Nyquist plot and the mance of SE and SP are compared to results obtained with MF electrode-
circumference of the projected semicircle are, respectively, the equiva­ based energy storage devices, and further details are presented in
lent series resistance (Rs) and charge transfer resistance (Rct) values. Table S1 (see ESI). The SE and SP values for the HSSD device outperform
Curve simulation and fitting analysis make it clear that MF2 significantly previously stated for the MF. The Ragone plot depicts electrode-based
has lower values of Rs and Rct than MF1 and MF3 electrodes. Thus, the energy storage systems. (Fig. 11(a). Evidently, HSSD devices showed
higher surface area promotes rapid exchange of electrons during elec­ higher SE and SP than the previously reported work. K. Sankar and R.
trochemical reactions between electrolyte and electrode contribute to Selvan [19] prepared manganese ferrite graphene wrapped PANI
stability and longevity of electrochemical device. According to the ob­ (MGP//AC) hybrid supercapacitor device, which delivered maximum Cs
tained Rs and Rct measurements, the MF series electrodes were values of of 37.5 F g− 1 at 10 mA cm− 2. The obtained SE of 10.25 Wh kg− 1 at SP of
1.2 Ω and 198 Ω for MF1, 1.1 Ω and 170 Ω for MF2, 1.4 Ω and 195 Ω for 3076 W kg− 1 with 100 % retention after 2000 cycles. P. Makkar and N.
MF3. Additionally, each MF series electrode exhibits significant inclines Ghosh [31] fabricated asymmetric device of 80MnFe2O4-20rGO//rGO,
at certain frequencies, indicating a reduced Warburg impedance (the which contains 80MnFe2O4-20rGO as a positive electrode and rGO as a
resistance to electrolyte ion diffusion). As a result, the significant negative electrode. The achieved Cs of 90 F g− 1 at 1 A g− 1 with SE of
improvement in MF2 nanorods electrode performance is attributed to 28.12 Wh kg− 1 at 750 W kg− 1 SP. The obtained retention of 95 % over
the faster diffusion of ions. The most effective electrode (MF2) was 4000 cycles. The MnFe2O4-NiS-Prous Carbon//Porous Carbon asym­
tested for cyclic stability endurance after 5000 cycles of GCD at a current metric device fabricated by Makkar et al. [32]. The achieved SE of 89
density of 5 A g− 1. Cyclic stability endurance was measured by the Wh kg− 1 at 1500 W kg− 1 SP. Also, fabricated flexible solid asymmetric
maintenance of capacitive retention up to ~89.3 % as shown in Fig. 7(e). device of same electrodes and PVA used as a separator, which delivered
The present electrochemical behaviour shown by the MF2 electrode Cs of 364 F g− 1 at 2 A g− 1 with 98 % capacitive retention over 10,000
amplifies the success of electrodeposited manganese ferrite thin films as cycles. Li et al. [33] prepared MnFe2O4/graphene// MnO2/carbon
a redox electrode in energy storage devices. asymmetric supercapacitor device. The obtained Cs of 60 F g− 1 at 10 mV
s− 1 scan rate with SE of 25.9 Wh kg− 1 at 225 W kg− 1. Geng et al. [34]
3.4. Hybrid solid-state supercapacitor device (HSSD) fabricated MnFe2O4@C//AC supercapacitor device, which delivered SE
of 27 Wh kg− 1 at 290 W kg− 1 SP. The achieved capacitive retention of
As a result of solid device potential use in portable and flexible 93.1 % after 5000 cycles. These are some reports on manganese ferrite
electronic devices, the hybrid solid supercapacitor device concept has supercapacitor devices, in which 80MnFe2O4-20rGO//rGO [31] and
attracted a lot of attention in scientific study. Due to its leak-resistant, MnFe2O4-NiS-Prous Carbon//Porous Carbon [32] asymmetric devices
lightweight, and remarkable stability, it also has other advantageous are obtained maximum Cs than present work. Due the manganese ferrite
features including easy mobility and handling. The HSSD can also be is composite with carbon-based materials and current collector is used as
produced in a variety of shapes and sizes to meet the demands of diverse a nickel foam (NF). The carbon-based materials are porous materials,
application scenarios. The HSSD is fabricated by combining the MF2 which having high surface area and it beneficial for improve the
with MnO2 electrodes in a PVA-Na2SO4 gel electrolyte, as shown in a supercapacitive performance. The NF add its self-capacitance [35],
schematic illustration in Fig. 8(a). while this study used SS as a current collector and it does not contribute
The electrochemical study of MnO2 thin film electrode is displayed in in the electrochemical reaction. Although this study utilized simply SS
Fig. S5 (see ESI). As shown in Fig. S6 (see ESI), the optimal potential substrate for conductivity, the redox process occurring in alkaline
window of the HSSD was measured by analyzing CV curves at 50 mV s− 1 electrolyte is avoided; thus, the resultant SE and SP are derived from the
between various higher cutoff voltages in the 0 to 1.5 V and extending MF2 and MnO2 materials.
up to 2.0 V range. The oxygen evolution mechanism creates a sharp Additionally, two devices are connected in series and used to light a
surge in current after the maximum cell voltage is increased above 1.9 V. lamp with 12 white LEDs to do a practical evaluation of the HSSD.
In conclusion, the appropriate voltage range for CV and GCD in the Fig. 10(a-c) shows this evaluation. The connected devices were used to
device investigation ranges from 0 to 1.9 V based on the analysis of discharge power to the bulb after 30 s of charging. A significant amount
potential window variation. The CV plots for the HSSD device were of specific power is produced by the HSSD, as evidenced by the lamp
obtained in a 0–1.9 V voltage window at various scan rates ranging from intense initial glow following discharge. Furthermore, the LED lamp’s
5 to 100 mV s− 1, as shown in Fig. 8(b). The comparable structure of CV continuous brightness indicates that the HSSD has good SE.
curves at increased scan rates shows that the device can endure greater In conclusion, the performance of hybrid supercapacitor devices has
scan rates. Furthermore, the current response under CV increases, as the been greatly improved by using binder-free, mesoporous, hydrous, and
scanning rate increases. GCD curves for different current densities, crystalline warm-like particles produced through the electrodeposition
ranging from 3.3 to 5 A g− 1, are shown in Fig. 8(c). The combined ability method. a) Initially by using the electrodeposition method with varying
of both electrodes to store charge using pseudocapacitive and EDLC deposition time, we produced thin film electrodes with a mesoporous
mechanisms is confirmed by the non-linear GCD Figure. The HSSD structure with a greater surface area (42.1 m2 g− 1). This led to a smaller
performs admirably, as shown in Fig. 8(d), with a capacitance of 70.1 F average particle size (5.14 nm) and more electrically active sites for the
g− 1 Cs at a current density of 3.3 A g− 1. Along with these metrics, the storage of electrical charge. b) The decreased EIS values for Rs (solution
HSSD showed specific energy (SE) and specific power (SP) metrics with resistance) as well Rct (charge transfer resistance) are likely attributed
values of 35.1 Wh kg− 1 and 3.1 kW kg− 1, respectively, as shown in Fig. 9 for the binder-free fabricating procedure and the superior compatibility
(a). with the hydrous MF material and the electrolytic solution. c)

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R.P. Bhosale et al. Journal of Energy Storage 86 (2024) 111146

Furthermore, the disordered crystalline MF particles provide greater org/10.1016/j.est.2024.111146.

activity sites and structural flexibility, resulting in more effectively
electrode storage ability and consistency with respect of electrochemical References
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