Content uploaded by Rahul B. Patil
Author content
All content in this area was uploaded by Rahul B. Patil on Apr 30, 2024
Content may be subject to copyright.
Iranian Journal of Materials Science and Engineering, Vol. 21, Number 1, March 2024
RESEARCH PAPER
1
Structural, Optical, and Supercapacitive Properties of Pure, Nickel, and
Molybdenum Ion Doped Trimanganese Tetraoxide (Mn3O4) Thin Films
Tanaji. S. Patil1,*, S. M. Nikam1, R. S. Kamble2, R. B. Patil3, M. V. Takale4, S. A. Gangawane5,*
* tanajipatil11 @gmail.com, gangawane.satish98@gmail.com
1 Department of Physics, Bhogawati Mahavidyalaya, Kurukali, Shivaji University Kolhapur, Maharashtra, India
2 Department of Chemistry, Bhogawati Mahavidyalaya, Kurukali, Shivaji University Kolhapur, Maharashtra, India
3 Department of Physics, Shri. Yashwantrao Patil Science College Solankur, Shivaji University Kolhapur,
Maharashtra, India
4 Department of Physics, Shivaji University Kolhapur, Maharashtra, India
5 Department of Physics, Doodhsakhar Mahavidyalaya Bidri, Shivaji University Kolhapur, Maharashtra, India
Received: December 2023 Revised: March 2024 Accepted: March 2024
DOI: 10.22068/ijmse.3527
Abstract: The trimanganese tetraoxide (Mn3O4) nanostructured thin films doped with 2 mol% of nickel (Ni) and
molybdenum (Mo) ions were deposited by a simple electrophoretic deposition technique. The structural, optical,
and morphological studies of these doped thin films were compared with pure Mn3O4 thin films. X-ray diffraction
(XRD) confirmed the tetragonal Hausmannite spinel structure. The Fourier transform infrared spectroscopy (FTIR)
provided information about the molecular composition of the thin films and the presence of specific chemical bonds.
The optical study and band gap energy values of all thin films were evaluated by the UV-visible spectroscopy
technique. The scanning electron microscopy (SEM) illustrated the morphological modifications of the Mn3O4 thin
films due to doping of the nickel and molybdenum ions. The Brunauer Emmett Teller (BET) method has confirmed
the mesoporous nanostructure and nanopores of the thin films. The supercapacitive performance of the thin films
was studied by cyclic voltammetry (CV), and galvanostatic charge discharge (GCD) techniques using the three-
electrode arrangement. An aqueous 1M Na2SO4 electrolyte was used for the electrochemical study. The 2 mol%
Ni-doped Mn3O4 thin film has shown maximum specific capacitance than pure and Mo-doped Mn3O4 thin films.
Hence, this study proved the validity of the strategy - metal ion doping of Mn3O4 thin films to develop it as a potential
candidate for electrode material in futuristic energy storage and transportation devices.
Keywords: Electrophoretic deposition, Doping by metal ions, Mesoporous, Pseudocapacitors.
1. INTRODUCTION
Greater energy density, highly reversible,
exceptional cyclic life, and potential to transport
high power are the key aspects that attracted the
researchers towards the supercapacitors [1, 2].
Metal oxides were widely used as electrodes in
various energy storage devices which were
reported earlier. RuO2 and IrO2 are the popular
oxide nanomaterials employed as electrode
materials, but their applicability was limited due
to their high cost and complicated synthesis.
Other oxides such as vanadium, iron, manganese,
and copper were also studied [3, 4], but lower
cost, higher availability, great stability, and
environment-friendly nature are the key
parameters of manganese oxide as a fascinating
and emerging nanomaterial. Among other oxides
of manganese, the Hausmannite Mn3O4 is the
most stable and frequently used nanomaterial.
Due to a variety of morphologies and different
oxidation states, the spinel Mn3O4 nanomaterial
has wide applications like sensors, catalysts,
batteries, ion exchange, and supercapacitors.
Many reports on its physical and chemical
synthesis are available [5, 6, 7, 8].
Here, the most versatile electrophoretic
deposition technique is used to deposit the thin
films, in which the stoichiometry of the
depositing layer can be controlled easily and
deposited on a larger area with a low-cost
apparatus. In it, the ionic particles are dispersed in
the suspension, moved by the electric force, and
deposited on an oppositely charged electrode by
applying a DC voltage [9]. The uniformity and
thickness of thin films were affected by
parameters like temperature, pH, concentration,
and applied potential [10]. Many reports were
available on morphology, size, and crystallinity-
dependent optical, supercapacitive, and catalytic
properties of Mn3O4 nanomaterials [11]. Thus, the
doping of metal ions is a fruitful strategy to
modify these properties of nanomaterials.
Especially, the metallic atoms having comparable
[ DOI: 10.22068/ijmse.3527 ] [ Downloaded from ijmse.iust.ac.ir on 2024-03-17 ]
1 / 10
Tanaji. S. Patil et al.
2
radius with depositing materials atoms can alter
the properties and morphology by occupying
different positions in the nanostructure. Various
doping metal ions such as Fe, Li, Co, Cr, and Ni
are reported [12, 13, 14], however, very few
reports are available on the doping of Ni and Mo
ions in the Mn3O4 nanostructure [15, 16].
In this work, nickel and molybdenum are the
dopants, due to their larger availability, low cost,
and radius comparable with manganese.
Therefore, they can easily substitute the Mn ions
in the Mn3O4 spinel nanostructure. Here, the
XRD, FTIR, UV visible, SEM, and BET studies
of pure, 2 mol% Ni, and 2 mol% Mo doped
Mn3O4 thin films are executed. Also, how the Ni
and Mo ion doping enhances the supercapacitive
performance of the Mn3O4 thin films is examined.
2. EXPERIMENYAL PROCEDURES
2.1. Materials
Manganese sulfate hexahydrate (MnSO4·7H2O),
hexamine (HMTA) ((CH2)6N4), sodium sulphate
(Na2SO4), nickel nitrate (Ni (NO3)2·6H2O),
ammonium molybdate (NH4)6Mo7O24 and
ammonia (NH3) were of analytical grade
purchased from Thomas Baker India Pvt. Ltd and
used without any further purification.
2.2. Electrophoretic Deposition of Thin Films
For electrophoretic deposition of the pure Mn3O4
thin films on a stainless-steel (SS) electrode, 50
ml of 0.05 M MnSO4 and 50 ml 0.05 M HMTA
solutions were prepared using double distilled
water and both stirred for 30 minutes. Then, both
solutions were mixed and an appropriate amount
of ammonia was added for the whitish-yellow
precipitation and stirred vigorously for 120
minutes. Later, the well-cleaned SS and graphite
electrodes were vertically immersed in the above
solution.
The constant potential of value 1.1 Volts was
applied across the electrodes for 30 minutes to
deposit a well-adherent thin film of Mn3O4 which
was denoted by M. These thin films were dried at
room temperature in air. By the same procedure,
the Ni and Mo-doped Mn3O4 thin films were
deposited at a temperature of 343K by adding 2
mol% of nickel nitrate and ammonium molybdate
in the MnSO4 solution. These doped dark black
colored Mn3O4 thin films were indicated as MM
and MN [17, 18].
2.3. Characterizations
For the crystal system information, the thin films
were analyzed by x-ray diffractometer (XRD,
AXS DS Advance, Bruker) having Cu-Kα
radiation of x-ray with a scanning rate of value
2/min. The Debye-Scherrer formula was used to
find crystallite size (D).
D =
(1)
Where k - 0.9 is known as the shape factor, =
0.1541 nm - the wavelength of Cu-k x-rays,
- FWHM (in radian) of peak, and – the angle of
diffraction. With the help of FTIR spectroscopy
(ALPHA, Bruker, Germany), the study of the
FTIR spectrum of thin films in the range of 400–
4000 cm-1 was executed. A UV visible NIR DRS
Spectrophotometer (V770, Jasco, Japan) was
used for optical study and band gap determination
of the thin films. The morphology of the surface
of the thin films was captured with the SEM
equipment (JEOL, JSM-IT200). The BET-
Surface area analyzer is employed for the
measurement of surface area and pore size of
nanostructured thin films. The CHI660E
workstation was employed for the evaluation of
the electrochemical performances. For it, a three-
electrode cell arrangement was used in which the
deposited thin film was the working electrode, Pt
wire was the counter electrode, and saturated
calomel electrode (SCE) was the reference
electrode.
3. RESULTS AND DISCUSSION
3.1. X-ray Diffraction Studies
The X-ray diffraction patterns for pure, Ni, and
Mo-doped Mn3O4 thin films are shown in Fig. 1.
All the peaks in the diffraction pattern were
indexed according to JCPDS card no. 01-1127,
space group I41/amd confirms the spinel
tetragonal Haumannite structure of Mn3O4 [17-
19]. As the peaks of any impurity are not observed
it approves the suitability of the electrophoretic
deposition technique for the deposition of
nanostructured thin films. The crystallinity of the
Mn3O4 thin films reduces due to metal ion doping.
The Mo-doped thin films have lower crystallinity
than the Ni-doped and pure Mn3O4 thin films
which is indicated by low intense peaks in their
diffraction patterns. As the ionic radius of Mo is
smaller than Mn and Ni, the intensity of peaks in
its diffraction pattern reduces due to the formation
[ DOI: 10.22068/ijmse.3527 ] [ Downloaded from ijmse.iust.ac.ir on 2024-03-17 ]
2 / 10
Iranian Journal of Materials Science and Engineering, Vol. 21, Number 1, March 2024
3
of disarrangements in the Mn3O4 structure due to
the presence of Mo ions [20]. The Debye-Scherrer
relation is used to evaluate average crystallite size
(D), and hence the dislocation energy (δ) and
microstrain (ε) are also evaluated [21]. The
structural study reveals that the average crystallite
size increases while dislocation density and
microstrain decrease for Mo-doped thin film than
pure Mn3O4 thin film and average crystallite size,
dislocation density, and microstrain are decreased
for Ni-doped thin film, which is displayed in
Table 1.
Fig. 1. XRD patterns of MN, MM, M thin film [17,
18].
Table 1. Structural Parameters of M, MM, and MN
thin films.
Thin
films
Average
crystallite
size (nm)
Dislocation
density (δ) x
1015 m -2
Micro
strain
(ε)
M
152
0.432
0.1248
MM
182
0.301
0.1052
MN
76
1.732
0.1027
3.2. FTIR Studies
FTIR spectra, studied in the wavenumber range
400 to 4000 cm-1 for MN, MM, and M thin films
are illustrated in Fig. 2. The intense absorption
peaks at 410, 520, and 620 cm-1 signify the
stretched vibrations of Mn-O at octahedral and
tetrahedral sites of the Mn3O4 nanostructure. The
bending vibrations of O-H in locked moisture in
the MM thin film are represented by the peak at
1620 cm-1. The presence of Mo and Ni is
identified by FTIR spectra containing reduced
intense peaks. The slight shifting of all Mn-O
peaks in the case of MM and MN thin films
indicates the replacement of dopant ions in the
tetrahedral place of Mn ions [22]. The decrease in
intensity of these peaks is due to variations in the
amplitude of the vibratory motion of Mn ions that
are vibrating at their natural frequency due to
incident radiation in the presence of the dopant
ions [23].
Fig. 2. FTIR spectra of MM, M, MN thin films.
3.3. UV Visible Spectroscopy
The UV-visible absorption spectra (Absorbance
vs. Wavelength) of MM, M, and MN thin films
are shown in Fig. 3 a). It contains two absorption
peaks at 258 nm, and 294 nm for M, MM, and MN
thin films due to highly energetic Mn2+/Mn3+
interactions. The low intense peak at wavelengths
425, 410, and 470 nm of M, MM, and MN thin
films indicate the d-d transitions of Mn3+ ions
which is explained by the Jahn–Teller effect [24].
At higher wavelengths, the absorption decreases
for all thin films with the least absorption for MM
and higher absorption for MN thin film. The
graph of (αhυ)2 versus the energy of the photon
(hυ) for the MM, M, and MN thin films is shown
in Fig. 3b) and is useful to calculate band gap
energy with the help of the Tauc equation [25].
(αhυ)= A (Eg– hυ)n (2)
With absorption coefficient (α), band gap energy
(Eg), and a constant (A) with n values 1/2 and 2
representing direct and indirect transitions. The
linear curve signifies the direct band gap of the
values 3.26 eV for M, and 3.30 eV for MM and
MN thin films due to the quantum confinement
effect [26]. This slightly increased band gap
energy due to doping of Mo and Ni ions causes an
improvement in their conductivity and hence their
supercapacitive behavior. These observed band
gap values also signify the suitability of these thin
films in optoelectronic types of equipment such as
LEDs.
20 30 40 50 60 70 80
(413)
(314)
(105)
JCPDS No: 00-001-1127
(220)
(211)
MM
MN
M
Intensity (a.u.)
2 (degree)
4000 3500 3000 2500 2000 1500 1000 500
O-H
Mn-O
Transmittance (%)
Wavenumber (cm)-1
MM
M
MN
[ DOI: 10.22068/ijmse.3527 ] [ Downloaded from ijmse.iust.ac.ir on 2024-03-17 ]
3 / 10
Tanaji. S. Patil et al.
4
Fig. 3. a) Optical absorption spectra, b) Band gap energy diagram of MM, M, and MN thin films.
3.4. Scanning Electron Microscopy (SEM)
Morphology of the nanostructure is a crucial
aspect that affects the electrochemical
performance of thin films. SEM images
illustrated in Fig. 4 a), b), and c) represent the
morphology of the surface of nanostructured M,
MM, and MN thin films. The SEM image of the
M thin film illustrates the grass-like nanostructure
of random orientation with grain size or average
crystallite size of 150 nms.
The MM thin film has porous and spongy
nanostructure having a grain size or average
crystallite size in the range of 150-200 nms and
the MN thin film has interrelated nanoflake
morphology with greater porosity but decreased
grain size or average crystallite size of value of
100 nms. Thus, the morphology and porosity
alteration in the Mn3O4 thin film due to the
doping of Mo and Ni ions causes enhanced
supercapacitive performance [24].
3.5. Brunauer-Emmett-Teller (BET)
Fig. 5 a) shows the nitrogen adsorption/ desorption
isotherms of the M, MM, and MN thin films and
Fig. 5 b) displays their pore size distribution
curves obtained from the desorption isotherms.
These nitrogen isotherms are of type IV, confirm
the of all thin films and are observed in the range
of 0.3 to 1 P/P0 [27]. Table 2 illustrates the BET
specific surface area, pore volume, and pore size
of the pure M, MM, and MN thin films. It
elucidates the effect of dopant on the porosity of
Mn3O4 nanostructured thin films. The surface
area is almost doubled in both doped (MM and
MN) thin films than in pure (M) thin films. The
pore volume decreases to nearly a partial amount
for MN thin film and increases doubly for MM
thin film than the pure M thin film. The value of
pore size slightly increases for MM thin film and
decreases almost to one third value for MN thin
film than that of the pure M thin film.
Fig. 4. SEM images of (a) M, (b) MM, and (c) MN thin film.
[ DOI: 10.22068/ijmse.3527 ] [ Downloaded from ijmse.iust.ac.ir on 2024-03-17 ]
4 / 10
Iranian Journal of Materials Science and Engineering, Vol. 21, Number 1, March 2024
5
Fig. 5. a) Nitrogen adsorption/desorption isotherms, b) pore size distribution of the MM, MN, and M thin films.
Table 2. BET Parameters M, MM, and MN thin
films.
Thin
films
Surface area
(m2 g-1)
Pore
volume
(cm3 g-1)
Pore size
(nm)
M
12.77
0.12
32.39
MM
27.26
0.2855
41.49
MN
27.47
0.068
10.08
Thus, all BET parameters reveal that the doped
Mn3O4 thin films have higher porosity and surface
area than the pure Mn3O4 thin film [28], which
becomes beneficial for charge transportation and
enhanced supercapacitive performance.
3.6. Supercapacitive Studies
3.6.1. Cyclic voltammetry studies
It is an important electrochemical feature to
estimate the electrochemical performance of thin
film electrodes. Fig. 6 a) to d) illustrates the cyclic
voltammetry (CV) curves of MN, MM, and M
thin films at different scan rates of 10, 20, 50, and
100 mV s-1. The quasi-rectangular nature of the
CV curve shows both electrochemical double-
layer capacitive and pseudocapacitive behavior
for pure M thin films. Almost rectangular shapes
of CV curves with some smaller redox peaks for
MM and MN thin films represent their
exceptional pseudocapacitive nature due to the
rapid, repetitive, and consecutive redox reactions
at the surface by the adsorption of electrolyte
cations. Also, some extent of charge storage
occurs at the interface of the electrode–electrolyte
by the formation of an electric double layer that
confirms the synergistic effect between the
dopant and Mn3O4 nanostructure [29]. The CV
curves of the MN thin film electrode enclose a
larger area and hence have a higher surface-to-
volume ratio due to increased electrochemically
active centers on the surface which is responsible
for the subsequent improvement in the specific
capacitance. Also, its narrow pores provide a
more stable structure for ion intercalation/
removal into/out forming a double layer. The MM
thin film electrode also shows an excellent
supercapacitive performance, since it has a
smaller surface area and porosity than the MN
thin film but larger than the M thin film electrode.
The shape of CV curves for all thin films changes
with increasing scan rate due to lowered
electrochemical activities by creating active sites
in the presence of electrolytic ions [27].
3.6.2. Galvanostatic charge/discharge studies
The electrochemical study of the electrophoretically
deposited M, MM, and MN thin film electrode is
carried out by the galvanostatic charge/discharge
method in the potential range 0 to 0.7 V vs. SCE at
different current density values. Fig. 7 illustrates the
charge/discharge curves recorded at current
densities of 0.3 and 1 A g-1. It elucidates the nearly
symmetrical charge-discharge curves and confirms
an excellent pseudocapacitive behavior due to
surface.
[ DOI: 10.22068/ijmse.3527 ] [ Downloaded from ijmse.iust.ac.ir on 2024-03-17 ]
5 / 10
Tanaji. S. Patil et al.
6
Fig. 6. The cyclic voltammetry curves of MN, MM, and M thin films at scan rates a) 10, b) 20, c) 50, and d) 100
mV s-1.
Redox reactions in mesoporous nanostructured
thin films [20]. Due to narrow pores and high
surface area, the MN and MM thin films exhibit
an excellent supercapacitive performance than the
M thin film electrode.
Table 3. The specific capacitance values of
nanostructured M, MM, and MN thin film electrodes.
Thin
films
Current density
(A g-1)
Specific capacitance
(F g-1)
M
0.3
172
1
142
MM
0.3
414
1
338
MN
0.3
720
1
630
By analyzing discharge curves and using
equation 3, the specific capacitance values of
nanostructured MM, MN, and M thin film
electrodes are determined and shown in Table 3.
Cs= /Δt
(3)
Where i - the discharge current (A), ΔV - the
potential window (V), Δt - the discharging time
(s), and m - the mass of the deposited materials in
the electrodes (g cm−2).
Thus, the MN and MM thin film electrodes have
higher specific capacitance values than the M thin
film electrode due to the larger accessible surface
area, enhanced electrical conductivity, and
surface redox reactions [30, 31].
4. CONCLUSIONS
In summary, the pure, 2 % Mo and Ni doped
Mn3O4 thin films were deposited on a stainless-
steel substrate via an easy and cheap
electrophoretic deposition technique and an
enhanced supercapacitive was observed for the Ni
and Mo doped Mn3O4 thin films. The XRD
analysis showed that all thin films have a
[ DOI: 10.22068/ijmse.3527 ] [ Downloaded from ijmse.iust.ac.ir on 2024-03-17 ]
6 / 10
Iranian Journal of Materials Science and Engineering, Vol. 21, Number 1, March 2024
7
tetragonal Hausmannite spinel structure.
Fig. 7. The galvanostatic charge-discharge curves of M, MN, and MM thin films at current densities of 0.3 and 1 A g-1.
The average crystallite size and microstrain
increase for Mo-doped and decrease for Ni-doped
thin films while the dislocation density decreases
for Mo-doped and increases for Ni-doped thin
films than pure Mn3O4 thin film. FTIR studies
showed the impurity-free deposition of pure, Ni,
and Mo-doped Mn3O4 films. The UV visible
spectroscopy measurements of all thin films have
shown identical optical properties but greater
band gap energy values due to the presence of
dopant. The surface morphological change was
also observed due to doping which was confirmed
by the SEM studies. The pure thin films have
nanowire-like structures, Ni-doped thin films
have nanoflake structures while the Mo-doped
thin films have nanostructured structures. BET
analysis elucidated that Ni-doped thin film has
narrow pores, higher porosity, and surface area
than
Mo-doped and pure Mn3O4 thin films.
Supercapacitive studies elucidated a larger
specific capacitance of value 720 F g-1 for Ni-
doped Mn3O4 thin film and 374 F g-1 for Mo-
doped Mn3O4 thin film than the pure Mn3O4 thin
film. Due to features such as affordability, easy
synthesis with morphological tuning, and
excellent supercapacitive performance, the doped
Mn3O4 thin films could be a promising candidate
to use as electrodes in energy storage and
transportation devices.
ACKNOWLEDGMENT
The authors are thankful to the Coordinator,
Sophisticated Analytical Instrument Facilities
(SAIF) center, Shivaji University Kolhapur, CFC-
Devchand College Arjunnagar, Nipani, CFC-
Y.C. Institute of Science, Satara, CFC- Jaysingpur
college, Jaysingpur, and Department of Physics,
Shivaji University, Kolhapur for providing the
characterization facilities to carry out this
research work in a successful manner.
CREDIT AUTHORSHIP CONTRIBUTION
STATEMENT
Tanaji S. Patil: Synthesis, characterizations, and
writing; S. M. Nikam: Synthesis; R. S. Kamble:
Writing - review and editing; R. B. Patil, M. V.
Takale, S.A. Gangawane: Supervision. All
authors read and approved the final manuscript.
DECLARATION OF COMPETING
INTEREST.
There are no conflicts to declare.
REFERENCES
[1]. Gautham Prasad, G., Shetty, N., Thakur, S.,
Rakshitha, & Bommegowda, K. B.
Supercapacitor technology and its
applications: A review. IOP Conference
Series: Materials Science and Engineering,
2019, 561(1). https://doi.org/10.1088/1757-
899X/561/1/012105.
[2]. Şahin, M., Blaabjerg, F., &
Sangwongwanich, A. A Comprehensive
Review on Supercapacitor Applications
[ DOI: 10.22068/ijmse.3527 ] [ Downloaded from ijmse.iust.ac.ir on 2024-03-17 ]
7 / 10
Tanaji. S. Patil et al.
8
and Developments. Energies, 2022, 15(3),
674. https://doi.org/10.3390/en15030674.
[3]. Liang, R., Du, Y., Xiao, P., Cheng, J.,
Yuan, S., Chen, Y., Yuan, J. and Chen, J.
Transition metal oxide electrode materials
for supercapacitors: a review of recent
developments. Nanomaterials, 2021, 11(5),
1248.
https://doi.org/10.3390/nano11051248.
[4]. An, C., Zhang, Y., Guo, H., & Wang, Y.
Metal oxide-based supercapacitors: progress
and prospectives. In Nanoscale Advances
2019, 1(12), 4644–4658). Royal Society of
Chemistry.
https://doi.org/10.1039/c9na00543a.
[5]. Chen, C., Ding, G., Zhang, D., Jiao, Z.,
Wu, M., Shek, C. H., Wu, C. M. L., Lai, J.
K. L., & Chen, Z. Microstructure evolution
and advanced performance of Mn3O4
nanomorphologies. Nanoscale, 2012, 4(8),
2590–2596.
https://doi.org/10.1039/c2nr12079h.
[6]. Gnana, B., Raj, S., Asiri, A. M., Wu, J. J., &
Anandan, S. Synthesis of Mn3O4 Nanoparticles
via Chemical Precipitation Approach for
Supercapacitor Application. Jj.Alloys and
Compounds,. 2015,
https://doi.org/10.1016/j.jallcom.2015.02.16
4.
[7]. Cao, S., Han, T., Peng, L., & Liu, B.
Hydrothermal preparation, formation
mechanism and gas-sensing properties
of novel Mn3O4 nano-octahedrons.
Materials Letters, 2019, 246, 210–213.
https://doi.org/10.1016/j.matlet.2019.02.1
27.
[8]. Yang, Y., Huang, X., Xiang, Y., Chen,
S., Guo, L., Leng, S., & Shi, W.
Mn3O4 with different morphologies
tuned through one-step electrochemical
method for high-performance lithium-ion
batteries anode. Journal of Alloys
and Compounds, 2019, 771, 335–342.
https://doi.org/10.1016/j.jallcom.2018.08.
328.
[9]. Park, Y., Kang, H., Jeong, W., Son, H.,
& Ha, D.-H. Electrophoretic Deposition
of Aged and Charge Controlled
Colloidal Copper Sulfide Nanoparticles.
Nanomaterials, 2021, 11(1), 133.
https://doi.org/10.3390/nano11010133.
[10]. Sarkar, P., & Nicholson, P. S.
Electrophoretic deposition (EPD):
Mechanisms, kinetics, and application to
ceramics. In Journal of the American
Ceramic Society 1996, 79(8), 1987–2002.
https://doi.org/10.1111/j.1151-
2916.1996.tb08929.x.
[11]. Sukhdev, A., Challa, M., Narayani, L.,
Manjunatha, A. S., Deepthi, P. R., Angadi,
J. V., Mohan Kumar, P., & Pasha, M.
Synthesis, phase transformation, and
morphology of hausmannite Mn3O4
nanoparticles: photocatalytic and antibacterial
investigations. Heliyon, 2020, 6(1), e03245.
https://doi.org/10.1016/j.heliyon.2020.e03
245.
[12]. Almontasser, A., & Parveen, A. Probing
the effect of Ni, Co and Fe doping
concentrations on the antibacterial
behaviors of MgO nanoparticles. In
Scientific Reports. Nature Publishing
Group UK. 2022, 12(1), 7922.
https://doi.org/10.1038/s41598-022-
12081-z.
[13]. Zhang, X., Xu, Y., Li, D., & Zhang, Y. The
effect of metal ions doping on the
electrochemical performance of molybdenum
trioxide. Electrochimica Acta, 2018, 283, 149–
154.
https://doi.org/10.1016/j.electacta.2018.06
.166.
[14]. Iqbal, M., Ali, A., Ahmad, K. S., Rana, F.
M., Khan, J., Khan, K., & Thebo, K. H.
Synthesis and characterization of transition
metals doped CuO nanostructure and their
application in hybrid bulk heterojunction
solar cells. SN Applied Sciences, 2019,
1(6), 1–8. https://doi.org/10.1007/s42452-
019-0663-5.
[15]. Patra, T., Panda, J., & Sahoo, T. R.
Modification of structural, optical, and
dielectric properties of Mn3O4 NPs by
doping of Nickel ions. Journal of Materials
Science: Materials in Electronics, 2023,
34(15), 1224. https://doi.org/10.1007/s10854-
023-10624-2.
[16]. Naiknaware, A. G., Chavan, J. U., Kaldate,
S. H., & Yadav, A. A. Studies on spray
deposited Ni doped Mn3O4 electrodes for
supercapacitor applications. Journal of
Alloys and Compounds, 2019, 774, 787–
794.
https://doi.org/10.1016/j.jallcom.2018.10.
[ DOI: 10.22068/ijmse.3527 ] [ Downloaded from ijmse.iust.ac.ir on 2024-03-17 ]
8 / 10
Iranian Journal of Materials Science and Engineering, Vol. 21, Number 1, March 2024
9
001.
[17]. Patil, T. S., Kothavale, V. P., Malekar, V.
P., Kamble, R. S., Patil, R. B., Gurav, K.
V., Takale, M. V., & Gangawane, S. A.
Effect of Nickel (Ni) Ion Doping on the
Morphology and Supercapacitive
Performance of Mn3O4 Thin Films. Journal
of Electronic Materials, 2024, 53(1), 394–
407. https://doi.org/10.1007/s11664-023-
10765-4.
[18]. Patil, T. S., Kamble, R. S., Patil, R. B., Takale,
M. V., & Gangawane, S. A. Enhanced
supercapacitive performance of
electrophoretically deposited nanostructured
molybdenum-doped Mn3O4 thin films.
International Journal of Materials Research.
2023. https://doi.org/10.1515/ijmr-2022-
0414.
[19]. Liu, Z., Zhang, L., Xu, G., Zhang, L., Jia,
D., & Zhang, C. Mn3O4 hollow microcubes
and solid nanospheres derived from a metal
formate framework for electrochemical
capacitor applications. RSC Advances,
2017, 7(18), 11129–11134.
https://doi.org/10.1039/c7ra00435d.
[20]. Immanuel, P., Senguttuvan, G., Chang, J.
H., Mohanraj, K., & Kumar, N. S. Effect of
Cr doping on Mn3O4 thin films for high-
performance Supercapacitors. Journal of
Materials Science: Materials in
Electronics, 2021, 32(3), 3732–3742.
https://doi.org/10.1007/s10854-020-
05118-4.
[21]. K. Mohanraj, D. Balasubramanian, J. C.
Synthesis and characterization of
ruthenium-doped CdO nanoparticle and its
n-RuCdO/p-Si junction diode application.
Journal of Alloys and Compounds, 2019, 779,
762-775.
https://doi.org/10.1016/j.jallcom.2018.11.264.
[22]. Said, L. Ben, Inoubli, A., Bouricha, B., &
Amlouk, M. High Zr doping effects on the
microstructural and optical properties of
Mn3O4 thin films along with ethanol
sensing. Spectrochimica Acta Part A:
Molecular and Biomolecular
Spectroscopy. 2017, 171, 487-498.
https://doi.org/10.1016/j.saa.2016.08.014.
[23]. Shelke, A. R., Ghodake, G. S., Kim, D.,
Ghule, A. V, Kaushik, S. D., Lokhande, C.
D., & Deshpande, N. G. Correlation of
structural, transport and magnetic
properties in La1ÀxZrx MnO3 manganite
samples. Ceramics International, 2016, 42
(10), 12038-12045.
https://doi.org/10.1016/j.ceramint.2016.04
.131.
[24]. Sayyed, S. G., Shaikh, A. V., Dubal, D. P.,
& Pathan, H. M. Paving the Way towards
Mn3O4 Based Energy Storage Systems. ES
Energy & Environment, 2021, 14, 3–21.
https://doi.org/10.30919/esee8c522.
[25]. Boukhachem, A., Boughalmi, R.,
Karyaoui, M., Mhamdi, A., Chtourou, R.,
Boubaker, K., & Amlouk, M. Study of
substrate temperature effects on structural,
optical, mechanical and opto-thermal
properties of NiO sprayed semiconductor
thin films. Materials Science and
Engineering B: Solid-State Materials for
Advanced Technology, 2014, 188, 72–77.
https://doi.org/10.1016/j.mseb.2014.06.00
1.
[26]. Hosny, N. M., & Dahshan, A. Facile
synthesis and optical band gap calculation
of Mn3O4 nanoparticles. Materials
Chemistry and Physics, 2012, 137(2), 637–
643.
https://doi.org/10.1016/j.matchemphys.20
12.09.068.
[27]. Hanifehpour, Y., Mirtamizdoust, B.,
Cheney, M. A., & Joo, S. W. Facile
synthesis, characterization and BET study
of neodymium-doped spinel Mn3O4
nanomaterial with enhanced photocatalytic
activity. Journal of Materials Science:
Materials in Electronics, 2017, 28(16),
11654–11664.
https://doi.org/10.1007/s10854-017-6968-
5.
[28]. Maruthapandian, V., Pandiarajan, T.,
Saraswathy, V., & Muralidharan, S.
Oxygen evolution catalytic behaviour of Ni
doped Mn3O4 in alkaline medium. RSC
Advances, 2016, 6(54), 48995–49002.
https://doi.org/10.1039/C6RA01877G
[29]. Wang, T., Wang, L. X., Wu, D. L., Xia, W.,
& Jia, D. Z. Interaction between nitrogen
and sulfur in co-doped graphene and
synergetic effect in supercapacitor.
Scientific Reports, 2015, 5, 1–9.
https://doi.org/10.1038/srep09591.
[30]. Peng, D., Duan, L., Wang, X., & Ren, Y.
Co3O4 composite nano-fibers doped with
[ DOI: 10.22068/ijmse.3527 ] [ Downloaded from ijmse.iust.ac.ir on 2024-03-17 ]
9 / 10
Tanaji. S. Patil et al.
10
Mn4+ prepared by the electro-spinning
method and their electrochemical
properties. RSC Advances, 2021, 11(39),
24125–24131.
https://doi.org/10.1039/d0ra10336e
[31]. Fleischmann, S., Mitchell, J. B., Wang, R.,
Zhan, C., Jiang, D. E., Presser, V., &
Augustyn, V. Pseudocapacitance: From
Fundamental Understanding to High
Power Energy Storage Materials. Chemical
Reviews, 2020, 120(14), 6738–6782.
https://doi.org/10.1021/acs.chemrev.0c001
70.
[ DOI: 10.22068/ijmse.3527 ] [ Downloaded from ijmse.iust.ac.ir on 2024-03-17 ]
Powered by TCPDF (www.tcpdf.org) 10 / 10
