Materials Chemistry and Physics 292 (2022) 126732

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Materials Chemistry and Physics

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Morphological, magnetic and electrochemical studies of Mn1-xSrxFe2O4 by

co-precipitation approach
A. Anitha a, A. Loganathan b, *
a
Department of Physics, Annamalai University, Annamalai Nagar, 608002, Chidambaram, Tamilnadu, India
b
Engineering Physics Section (FEAT), Annamalai University, Annamalai Nagar, 608002, Chidambaram, Tamil Nadu, India

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Pure and Sr2+ doped MnFe2O4 electrode

delivered high specific capacitance of Relation between Energy and Power density of MF, and MSF9 electrodes.
381F/g at 1A/g.
• It shows long-term cycling stability for
2000 cycles at 5A/g.
• VSM study confirmed, the Mn1-
xSrxFe2O4 was potential candidate for
memory storage materials.

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

Keywords: The influence of Sr2+ on the structure, topography, magnetic, and electrochemical behavior of MnFe2O4 pre­
Mn1-xSrxFe2O4 pared by co-precipitation approach. The unique products were characterized by Thermogravimetric and Dif­
Co-precipitation route ferential Thermal Analysis (TG-DTA), X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR)
Energy storage device
and Scanning Electron Microscope with Energy Dispersive X-Ray Analysis (EDX), X-ray Photoelectron Micro­
scopy (XPS), Brunauer-Emmett-Teller (BET) and Vibrating Sample Magnetometer (VSM). XRD pattern declares
the cubic structure with a mean crystallite size decrease from 49.54 nm to 34.6 nm. Metal oxide bands were
identified for all samples using Fourier Transform Infrared Spectroscopy. The BET analysis exhibit a specific
surface area of 22.89 m2/g. Magnetic investigations revealed a steady drop in saturation magnetization, rema­
nence, and an increase in the coercive field with increasing Sr2+ content. The electrochemical behavior of pure
(MF) and doped manganese ferrite (MSF9) electrodes was investigated using KOH electrolytes by Voltammetry,
Charge–Discharge Spectroscopy, and Electrochemical Impedance Spectroscopy. A three-electrode setup with a
high specific capacity of 381F/g at 1A/g was attained. Sr2+ (9%) doped MnFe2O4 electrode have excellent
surface mobility and high conductivity than pure MnFe2O4 electrode. The synthesized electrodes deliver (MSF9)
a higher energy density of 68Whkg− 1 at a power density of 5400 Wkg− 1 at 5A/g. Such excellent capacitive
performances were due to fast charge transport and self-assembled robust microstructural stability.

* Corresponding author.
E-mail address: aloganathan64@gmail.com (A. Loganathan).

https://doi.org/10.1016/j.matchemphys.2022.126732
Received 28 November 2021; Received in revised form 19 July 2022; Accepted 5 September 2022
Available online 8 September 2022
0254-0584/© 2022 Elsevier B.V. All rights reserved.
A. Anitha and A. Loganathan
1. Introduction
Magnetic ferrite nanoparticles, at the forefront of Nanoscience and
Nanotechnology, have extensive and intriguing applications in a wide
range of technical and scientific fields. It has excellent features such as
high saturation magnetization, low coercivity, low retentivity, super­
paramagnetic behavior, desirable dielectric properties, and a large sur­
face area to volume ratio within the nanoscale regime. Such ideal
properties of ferrite nanoparticles have conquered infinite and
numerous research fields such as biomedicine, environmental remedi­
ation, catalysis, high-density magnetic storage, photo catalysis, high-
frequency range devices, and in the medical field as magnetic fluid hy­
perthermia for cancer therapy [1]. Manganese ferrite (MnFe2O4)
nanoparticles, spinel ferrite nanomaterials, is one of the important
magnetic metal oxide nanoparticles with distinctive physical and
chemical properties. The high pseudo capacitance, multi-oxidation
states, power delivery, and cycling stability of MnFe2O4 nanoparticles
in supercapacitors have attracted the attention of researchers [2]. Using
MnFe2O4 nanoparticles in electrode material increases accessible active
surface area while decreasing OH− ion diffusion channel length [3].
MnFe2O4 colloidal nanocrystal assemblies (CNAs) were used as elec­
trode material by Guo et al. [4]. It exhibits the capacitance of 56.2 at
2A/g and the capacitive retention is 59.4% after 2000 cycles. Compo­
sition and preparation method are influential parameters on physico­
chemical properties of MnFe2O4 nanoparticles. Plenty of synthesis
routes are available to synthesize manganese ferrite (MnFe2O4) nano­
particles such as combustion reaction, emulsion evaporation, chemical
reduction, co-precipitation, hydrothermal method, micro emulsions,
sonochemical route, sol-gel, ball milling and electrospinning etc.,
Among them, the co-precipitation route is a conventional method to
prepare all kinds of metal oxide nanoparticles, due to their simplicity,
economic, efficiency, less toxic and less time consuming and large-scale
synthesis of manganese ferrite nanoparticles with controlled particle
size, morphology, high saturation magnetization, and providing good
spinel ferrite nanoparticles [5].
In this regard, the emergence of novel materials and the enlargement
of a new energy storage approach is a crucial aspect in providing the
energy demands supply yet avoiding the use of fossil fuels to a great
extent [6]. Alternative technologies and materials for reducing CO2
emissions throughout the energy conversion process must be developed
and expanded to reach human society. As a result, in recent years, a
large number of research activities have been directed towards alternate
energy generating and storage applications, such as batteries, solar cells,
supercapacitors, and hybrid batteries [7,8]. In recent decades, research
on supercapacitors has been conducted to fill the gap for immediate
power sources. Based on the charge storage technique, supercapacitors
are widely categorized into two types: Double layer capacitors and
Psedocapacitors [9]. The psedocapacitors have electrochemical charge
storage ability, which are most highly reliant on metal oxides and binary
metal oxides-based electrodes, and the faradaic redox reaction between
electrode and electrolyte must be thoroughly explored. According to
recent publications, an increase in capacitance can be obtained not only
by using redox electrode materials but also by selectively choosing an
electrolytic solution that strengthens the capacity to store and discharge
reactions in a short amount of time [10–12]. In general, Mn-based
nanoparticles have high capacitance due to the intrinsic features of
reversible redox reaction on the surfaces of the electrode layer, and
several papers on Mn-based nanomaterials for electrode material are
available. For example, Zang et al. studied carbon nanotubes (CNTs)
derived from metal-primitive structure (MOFs) of electrodes in
Mn-based proportional supercapacitors for improved retention of en­
ergy [13]. Similarly, photocatalytic surface modification of MnFe2O4
nanoparticles was investigated, and its impact on inherent multiple
fluorescence and unique photocatalytic capabilities is explored [14].
MnFe2O4 nanofiber has been proven by Liu et al. as a high-performance
sodium-ion battery anode, with a high rate capability of 305 mAh/g at
2
Materials Chemistry and Physics 292 (2022) 126732
10,000 mA/g and 90% holding capacitance after 4200 cycles [15]. The
PANI/MnFe2O4 nanocomposite has been developed as a novel
ultra-capacitor electrode material, with an overhead specific capaci­
tance of 371F/g (at 1A/g in 1 M H2SO4) and outstanding steady cycle life
with 86% capacity retention even succeeding 2000 cycles [16]. To the
best of our knowledge, there is no report on the substitution of strontium
ion with manganese ferrite spinel structure in an energy storage devices
[17–20]. As a result, we used co-precipitation method to investigate the
effect of strontium substitution on the structural, magnetic, and super­
capacitor properties of manganese ferrite nanoparticles [Mn1-x Srx Fe2O4
(x=0(MF), 0.03(MSF3), 0.06(MSF6), 0.09(MSF9), 0.12(MSF12)]. This
work results in a new design guide for three electrode nanoparticles
using the co-precipitation process.
2. Material and methods
2.1. Materials
To make Mn–Sr mixed ferrite nanoparticles, stoichiometric amounts
of manganese (II) nitrate tetra- hydrate (purity 99.99%), iron (III) ni­
trate anhydrous (purity 99.99%), strontium nitrate (purity 99.99%), and
sodium hydroxide (NaOH) all from sigma Aldrich, and used without any
further purification.
2.2. Synthesis of Mn1-xSrxFe2O4
Chemical co-precipitation was used to produce the expected nano-
sized ferrites. AR grade manganese (II) nitrate [Mn(NO3)2.4H2O], iron
(III) nitrate [Fe(NO3)2.9H2O], and strontium (II) nitrate [Sr
(NO3)2.4H2O] were used as the starting materials for the Mn0.8 Sr0.2
Fe2O4 samples. The MnSr: Fe ratio was maintained at 1:2. All of the
starting pure components were dissolved in double distilled water one
by one and combined to make an aqueous solution. For 1 h, the 6 M
NaOH was gently added to the combined solution while constantly
stirring at 80 ◦ C. At the same time, the pH was kept at 11–12 to ensure
that only metal cations precipitated. It was cleaned many times with
distilled water and ethanol to remove contaminants before being dried
at 80 ◦ C for 6 h. Finally, black powder was obtained and annealed at
900 ◦ C for 5 h. For all doping concentrations, the same procedure was
used.
2.3. Electrochemical measurements
The prepared electrode was created by physically mixing the work­
ing electrodes (MF & MSF9 samples), conducting carbon (carbon black),
and a binder (PVDF) in a 75:20:5 weight ratio. NMP (N-methyl-2-pyr­
rolidone) was used as a solvent for a slurry. The homogeneous slurry was
applied to the 1×1 cm2 nickel foam and dried for 12 h in an 80 ◦ C hot air
oven. The active ingredient’s weight was determined using weight
disparity before and after coating. Cyclic voltammetry (CV), Galvano
static charge/discharge (GCD), and electrochemical impedance spec­
troscopy were used to assess electrode material’s energy storage capa­
bilities. The three-electrode arrangement was adopted, to determine the
electrochemical characteristics of MnFe2O4 materials that were both
pure and doped with Sr2+ electrodes. The working and counter elec­
trodes were made of MF & MSF9 materials coated on nickel foam and
platinum respectively. In the neutral electrode, an Ag/Agcl reference
electrode. Based on the electrodes, the active potential range was altered
and fixed at 0–0.6V with different scan rates (10–50 mV/s), and the
subsequent current densities were measured.
2.4. Characterizations
The thermogravimetric (TG) and differential thermal (DTA) studies
were performed using TG-DTA (NETZSCH-STA 449 F3 JUPITER). X-ray
powder diffraction (BRUKER-binary V4 analytical diffractometer) was
A. Anitha and A. Loganathan Materials Chemistry and Physics 292 (2022) 126732

used to examine the crystalline phase and structure of produced nano­ 3.2. Structural analysis (XRD)
particles, with Cu Kα as the radiation source (1.541 A0). A scanning
electron microscope (SEM) equipped with energy dispersive ray spec­ The XRD technique was used to examine the structural parameters of
troscopy was used to evaluate the morphology of the produced samples prepared samples, as shown in Fig. 2. All the samples show seven
(EDS). Infrared (IR) spectra analyzed with a Fourier transform infrared diffraction peaks at 2 thetas of 18⁰, 29.66⁰, 32.84, 34.93⁰, 42.55⁰, 56.17⁰,
spectrophotometer using Thermal Nicolet - 380 in the range of and 61.69⁰. When compared to JCPDS card numbers 74–2403, the
4000–400 cm− 1 confirmed the metal-oxygen vibration and functional product samples show high purity of spinel structure [24,25]. There are
groups present in the samples. N2 adsorption–desorption isotherms were no more peaks seen in samples MF, and MSF3. However, in samples
measured at 77 K using Quanta chrome autosorb IQ2, N2 adsorption/ MSF6, MSF9, and MSF12, we identified a secondary phase of γ-FeO3
desorption unit. The electron binding energies of the elements were matching with card numbers 89–5892, resulting in a high Sr2+ content
investigated using (XPS, Kratos XSAM800) Analytical Spectrometer X- value [26]. The small secondary peaks were appear in MSF6 sample but
ray photoelectron Spectroscopy. VSM model Cryogenic-3639 was used in MSF9 sample’s pattern clearly confirmed that the presence of sec­
to examine the magnetic characteristics, with a measured maximum ondary phase. And the presence of additional peaks in MSF12 is due to
field of 20 KOe. A Biologic (SP-300) workstation was used to charac­ the solubility limit of Sr ions in the Spinel structure. The crystallite size
terize the electrochemical performance rate of 50 ◦ C/min (DTA). (D) for the samples MF, MSF3, MSF6, MSF9, and MSF12 was calculated
using the Debye-Scherer formula from the intense peaks corresponding
3. Results and discussion to the indices (1 1 1), (2 2 0), (222), (3 1 1), (2 1 1), (3 3 3), and (4 4 0).
The dislocation density is defined as the extension of dislocated lines per
3.1. The thermal analysis unit volume of the crystal, and the micro strain is defined as the strain
that causes nanoparticle deformation at one part per million (ppm) [27].
TG-DTA was used to investigate the MF (MnFe2O4), and MSF3 (3% Sr Other structural characteristics such as crystalline size, micro strain,
doped MnFe2O4) nanoparticle’s thermal behavior. The progression of dislocation density, lattice constant, and were estimated using XRD data
weight loss (TG) and heat flow (DTA) versus temperature is depicted in
Fig. 1(a and b). In the current study, five stages of decompositions were
found in the TG-DTA curve. The first stage was observed from 38 ◦ C to
127 ◦ C and from 29 ◦ C to 98⁰c for pure and 0.03 M Sr-doped manganese
ferrite samples, corresponding to adsorbed water molecules, resulting in
mass losses of 4% and 4%, respectively [21]. In the second step, the
organic decomposition temperatures of pure and Sr doped materials
were recorded from 127 ◦ C to 271 ◦ C and from 98 ◦ C to 277 ◦ C and
respectively, which were responsible for mass losses of 5% and 4.95%,
respectively. This indicated the degradation of organic components such
as nitrate, chlorides, and so on [22]. In the third phase, the mass losses
on the TG curve were 3% and 1.51%, with DTA temperatures from
271 ◦ C to 485 ◦ C and 277 ◦ C to 497 ◦ C for samples that were both pure
and Sr-doped manganese ferrite, corresponding weight loss implies that
the development of oxides and the disintegration of hydroxide groups
from the raw materials [23]. The experimental DTA curve reveals
endothermic peaks from 485 ◦ C to 738 ◦ C and 497 ◦ C to 815 ◦ C, which
correspond to the weight losses 2% and 1.17% on the TG curve. The
creation of ferrite was established at a temperature from 738 ◦ C to
900 ◦ C and 815 ◦ C to 900 ◦ C as a result of these findings. Both samples
showed weight losses were 2% and 1.44% respectively. Then above
900 ◦ C implies the formation of high crystallization nature. From the
overall observation, Sr doped samples showed less weight loss (13.07%)
compared to pure samples (16%). This may be due to the restriction of
crystal growth by relatively large size Sr2+ ions.
Fig. 2. XRD Analysis of Mn1-xSrxFe2O4 (MF, MSF3, MSF6, MSF9, and MSF12)
nanoparticles.

Fig. 1. TGDTA Analysis for pure(a) and Sr doped MnFe2O4(b).

3
A. Anitha and A. Loganathan Materials Chemistry and Physics 292 (2022) 126732

by the following equation, 3.3. FTIR-analysis

D = 0.9λ ∕ βcosθ
ε = β cos θ ∕ 4
δ = 1 ∕ D2
a = d (h2+k2+l2)1/2
X-ray density of present samples was calculated by using
ρ = 8 M/NAa3
Where, a-is the lattice constant, d-the interplanar spacing, and hkl-the
index of the XRD reflection peak. Where D, λ, θ and, β denotes the
average crystallite size, the wavelength of X-ray (1.5406 A⁰), the Bragg’s
angle, and the full width at half maximum (in radian) respectively. M is
molecular weight and NA is the Avogadro number (NA = 6.025 × 1023
particles per mole) [28]. The measured density (ρm) for cylindrical
pellets of samples
ρm = m/r2h
where m represents mass, r is a radius, and h represents pellets height.
Specific Surface Area:
(1) FTIR spectra of pure and strontium doped manganese ferrite recor­
(2) ded at room temperature in the wavenumber range of 4000 to 400 cm− 1
are shown in Fig. 3. The bands of the Mn1-xSrxFe2O4 nanoparticles in the
(3) range of 591.63-455.21 cm− 1 showed the presence of M − O stretching
vibration. The higher (591.63–619.46 cm− 1) and lower frequency
(4)
(455.21–452.54 cm− 1) peaks indicate the metal occupied in tetrahedral
and octahedral sites. The tetrahedral site has a higher frequency range as
compared to the octahedral sites respectively. The absorption peaks are
(5) shifted to a larger frequency range of the sample from MSF3 to MSF12,
which is due to the dopant Sr2+ ions with a larger ionic radius [31]. Also,
a slight change in the sample MSF9 peaks of spectra is due to the adding
of greater ionic radius of Sr2+ ions relative to Fe3+ .
3.4. BET analysis
The nitrogen adsorption/desorption isotherm and accompanying
BJH (Barrett-Joyner-Halenda) results were presented in Table 2. The
(6)
surface area (SA) is a critical parameter in delivering long battery life in
supercapacitors (MF & MSF9). The particle size was calculated by using
the following formula [32],

S = 6000/DxDp m2/g (7) DBET = 6000/ρBET (10)

Where Dx, -x-ray density, Dp is crystallite size in nm. DBET is the particle size (nm), ρ is the density of MnFe2O4 (3.38 cm3/
Table 1 shows the calculated structural properties of lattice constant, g), MnSrFe2O4 (5.06 cm3/g). The samples MF and MSF9 advertised a
crystallite size, micro strain, dislocation density, volume of unit cell, X- type IV isotherm with a patent loop as shown in Fig. 4, this is the evi­
ray density (ρx), specific surface area and measured density (ρm) of dence of the formation of the mesoporous structures. The MF (21.45 m2/
prepared nanoparticles. The increase in the values of x-ray density with g) and MSF9 (22.89 m2/g) samples have the nearest surface area, pore
doping of Sr2+ concentration can be seen in the calculated values. The x- volume, and having mesoporous nature may be advantageous for
ray density value for smaller particles is found to be greater. With the boosting electrochemical behavior.
addition of Sr2+ ions, the lattice constant began to rise. Because Sr2+ has
a greater ionic radius (1.32A⁰) than Mn2+ (0.83A⁰), it should replace
Mn2+ and fill octahedral positions rather than the tetrahedral sites
inhabited by ferric ions. As a result, Mn2+ atoms moved from tetrahedral
to octahedral positions due to Sr2+ increased. As a result, the concen­
tration of Sr2+ at the surface layer, this shift may have slowed grain
development. As a effect, the increased radius causes strain, which in­
fluences the crystal structure. From MF to MSF9, the average crystallite
size reduced from 49.54 to 34.6 nm, then climbed to 42.8 nm for the
MSF12 sample. This increase was caused by agglomeration, which is a
frequent occurrence in ferrites [29]. The distance between magnetic ions
in tetrahedral site LA and octahedral site LB is estimated via hopping
lengths.

LA = a√3/4 (8)

LB = a√2/4 (9)
2+
With increased Sr content, both the LA and LB hopping lengths
decrease. This is due to the substitution process and cation redistribu­
tion. The value of X-ray density and measured density increases with
decreasing crystallite size [30].

Fig. 3. FTIR Analysis of Mn1-xSrxFe2O4 nanoparticles.

Table 1
Structural parameters of pure and Sr substituted Mn Ferrite Lattice constant, crystallite size, micro strain, volume of unit cell, X-ray density, radii of tetrahedral and
octahedral sites, specific surface Area, Measured density, dislocation density of Mn1-xSrxFe2O4 NPs.
Sample a(A0) D311 ξ×10− 4
Volume of Unit cell(a3) ρx (gm/cm3) L0A A L0B A Specific surface Area Measured density(106) (ρm) δ × 1014

MF 8.51 49.54 3 616.29 4.97 3.68 2.97 24.36 3.38 4.09

MSF3 8.511 47.8 4 615.87 4.98 3.68 2.97 25.17 3.48 4.37
MSF6 8.513 46.2 4 615.01 4.99 3.65 2.95 25.94 4.89 4.68
MSF9 8.54 34.6 7 614.83 4.98 3.63 2.93 26.82 5.06 8.3
MSF12 8.45 42.8 3 614.35 5.16 3.65 2.95 27.15 6.71 5.46

4
A. Anitha and A. Loganathan
Table 2
Surface analysis (BET).
Sample SBET(m2/g) DBET (nm) Pore Volume(cm/g) pore size(nm)
MF 21.45 7.79 0.045 1.7040
MSF9 22.89 5.1 0.048 1.7041
3.5. SEM study
The grain size, surface area is the crucial parameter that affects the
ferrite’s Magnetic and Electrochemical properties of MF, MSF3, MSF6,
MSF9 and MSF12 nanoparticles. Fig. 5(a-e), shows the uniform distri­
bution from MF to MSF9 and at a higher Sr2+ concentration (MSF12),
irregularly shaped particles were observed. The grains exhibit cubic
shapes in the nanometer range. The average grain size distributions were
55.80 nm, 52.71 nm, 50.78 nm, 44.25 nm, and 40 nm using the Image J
software. The inclusion of Sr2+ content inhibits grain growth in
MnFe2O4. Less agglomeration has present in ferrite particles offers the
most active surface area, making them ideal for electro catalytic activity
in energy storage devices. As seen in Fig. 5(f-j), the strong signals from
EDX data, Mn2+, Fe3+, Sr2+, and O2 elements are present in the nano­
structured MF, MSF3, MSF6, MSF9, and MSF12 nanoparticles and it is
evidence of synthesized molecule is entirely based on MnFe2O4 and
MnSrFe2O4 nanoparticles without any impurity.
3.6. XPS analysis
XPS is a strong technique for determining the chemical components,
electron configuration, and chemical bond of a compound’s constituent.
The binding energies ranged from 100 to 800 eV in the wide scan XPS
spectra for the pure and Sr2+ doped (x = 0.09) MnFe2O4 materials, as
shown in Fig. 6(A) (a-d) & 6B (a-e). This analysis examines the binding
energy and the presence of elements in the samples MF & MSF9. Fig. 6
(A) (a) & 6B (a) shows a wide scan spectrum of MF and MSF9 which
confirms the presence of Mn, Fe, Sr, and O. The Fe 2p1/2 and Fe 2p3/2 for
the Fe3+ state are represented by two signals at 724.25eV and 710.35eV
(MF) and 723.40eV and 710.28eV (MSF9) in verifying the valence of
iron in the samples, which confirms the existence of oxidation state of
Fe3+, then the spectra show the Mn2p, which has two main bond energy
peaks appearing at 662.71eV and 641.05eV and 652.64eV and 641.29eV
respectively [33]. This indicates that the electronic state of Mn in the
MF, MSF9 samples is +2. The spectrum has two strong peaks at
528.51eV and 530.17eV representing the O1S [34]. The weak peak at
528.51eV denotes that the O element is present in the lattice structure of
Mn–Sr–Fe–O–H and another peak at 530.17eV promote the H–O–H
structure. Sr 3d5/2 and Sr 3d3/2 photoelectron peaks were seen at
133.41ev and 135.13ev, respectively, in Fig. 6(B) (e). Sr 3d5/2 was
Fig. 4. N2 adsorption-desorption and pore size distribution of MF and MSF9 sample.
5
Materials Chemistry and Physics 292 (2022) 126732
ascribed to Sr–O bonds, while Sr 3d3/2 was used to confirm Sr2+ exis­
tence [35]. These results have resembled EDX Analysis.
3.7. VSM analysis
Fig. 7 shows the magnetic hysteresis loops for pure and Sr2+ doped
manganese ferrite nanoparticles and calculated magnetic parameters
such as saturation magnetization (Ms), remanent magnetization (Mr),
coercivity (Hc), squareness ratio (Mr/Ms), magnetic anisotropy constant
(k) and magnetic moment (μs) are listed in Table 3. By using the
following formulae. [36].
​ K = Hc × Ms /0.98 (11)
μs = MW × Ms ∕5585 (12)
where MW is the molecular weight of the prepared sample in g/mol, Ms
is saturation magnetization in emu/g. Fig. 7 predicts the magnetization
behavior curves that explain soft ferromagnetic behavior. The analysis
depicts that the saturation magnetization (Ms) decreases with increasing
dopant concentration Sr2+ from 58.75 emu/g to 31.00 emu/g. The
surface anisotropic potential of nano-scale ferrites causes the magneti­
zation of nanoparticles to decrease with decreasing crystallite size.
These results seem to indicate that for Sr concentration above 9% which
promotes weak ferromagnetic phases. As a result, as the strontium
concentrations increase, the Ms and Mr drop while the Hc rises. These
observations from the samples reveal the potential use of these ferrite
nanoparticles for memory applications. As a result, according to the
Stoner-Wohlfarth model, Coercivity is inversely proportional to satura­
tion magnetization [37]. Crystallite size, cation alignments, surface
morphology, and super exchange interactions via the mediating oxygen
O2− anions all influence the magnetic characteristics of MnSrFe2O4.
Cation settling between tetrahedral (A) and octahedral (B) has a sig­
nificant influence on magnetization (B). However, for composition x =
0, the greater B–B interaction too decreases the magnetization of the
B-site due to high Mn2+ ion concentration in A-site and Fe3+ ions at the
B-site [41]. Three forms of super exchange, interactivity are elaborate in
Néel’s collinear model: A-B, A-A, and B–B. In this case, the A-B inter­
action is more powerful than the A-A and B–B interactions [38]. Sr2+
ions migrate to the B-site and transfer Fe3+ ions from the B-site to the
A-site when the Sr2+ ion concentration rises [39]. The canting of spins of
B-site iron ions decrease as the iron amount of the A-site increases. As a
result, the magnetization was reduced due to the lower iron content at
B-site. The magnetization of A and B sublattices is calculated, to get the
net magnetic moment (M). M = MB-MA is the mathematical expression
for this. As a result, the net magnetic field shrinks. The initial rise in
magnetization was seen, which was attributed to the dominance of spin
canting effects over the combined effects of increased and decreased
A. Anitha and A. Loganathan
Fig. 5. SEM micro images and EDX Spectrum of Mn1-xSrxFe2O4 nanoparticles(x = 0 (a, f), 0.03 (b, g), 0.06 (c, h), 0.09(d,i), and 0.12 (e, j)). And histograms (MF,
MSF3, MSF6, MSF9, and MSF12).
iron ions at A and B sites, respectively [40].
3.8. Electrochemical analysis
The CV analysis showed that the battery component’s charge transfer
is based on Mn current curves, while the battery-like component’s
conduction mechanism is dependent on Fe current curves, which are
both known to be completely reversible [41]. Fig. 8(a and b), shows the
6
Materials Chemistry and Physics 292 (2022) 126732
cyclic voltammetry curves, GCD curves (c),(d), EIS analysis (e), current
density Vs specific capacitance(f) of MF and MSF9 electrodes and Energy
density Vs Power density (g) of MSF9 electrode. The following equation
[42] was used to calculate the specific capacitance values: (Table 4)
Csp = Q/mΔv. (13)
Where Csp (F/g) is the specific capacitance of the electrode materials, Q
(C) is the average charging and discharging process, m(g) is the mass of
A. Anitha and A. Loganathan Materials Chemistry and Physics 292 (2022) 126732

Fig. 6. XPS wide spectrum of pure(MF) and Sr doped MnFe2O4(MSF9), (A, B(a)-wide spectra),(A,B(b)- Fe 2p), (A,B(c)-Mn 2p), (A,B(d)-O 1S, (B(e)-Sr 3d).

Table 3
VSM analysis.
X Ms Mr Hc nB K× Remanance ratio
(emu/g) (emu/g) (Oe) 104 (Mr/Ms)

MF 58.75 1.98 29.58 2.42 0.17 0.033

MSF3 72.92 7.08 115.06 3.02 0.85 0.097
MSF6 43.53 7.43 250.19 1.81 1.1 0.170
MSF9 41.89 10.06 484.97 1.75 2.07 0.240
MSF12 31.00 10.12 828.64 1.30 2.6 0.326

the active electrodes, and ΔV(V) is the potential window. Furthermore,

Fig. 7. VSM Analysis of Mn1-xSrxFe2O4 nanoparticles.
the observed CV profile corresponds exactly to convey description of
pseudo capacitance. In the CV curve, the scan rate increases, the
improved electrochemical response causes a greater current production.
Because the area under the CV curves for all scan rates is higher for Case
MSF9 but smaller for Case MF. As a result, the lower scan rate situation
correlates to smaller electro-kinetic events. However, with a greater
scan rate, the electrode responds to a higher current value because the
charge is more concentrated. Accumulation rises at the electrode surface
[43]. The storage process in energy storage devices is mostly caused by
the surface electrochemical reaction process, which means that the bulk

7
A. Anitha and A. Loganathan Materials Chemistry and Physics 292 (2022) 126732

Fig. 8. CV curves (a, b) for MF, MSF9, GCD curves (c, d) for MF, MSF9, EIS(e), Current density Vs Specific capacitance (f), Energy density Vs Power density (g), MSF9
stability curve for 2000 cycles (h).

Table 4
Specific capacitance of MF and MSF9 electrodes at different scan rates
Ct = I Δ t/m ΔV (14)
employing CV studies. E = 1/2 [C 2
(ΔV) ] (15)
sp
Scan rates (mV) Potential(V) Specific capacitance (F/g)
P = E/Δt (16)
MF MSF9

10 0.6 376 648 Where Ct (F/g), I (A), t (sec), m(g), V (V), E (Wh/kg), P (W/kg) - are the
20 0.6 256 352 specific capacitance, applied current, discharge time, the total mass of
30 0.6 187 205 the active electrodes, potential window, energy density and power
40 0.6 147 134
density of the active electrodes respectively. The calculated specific
50 0.6 122 95
capacitances for MF and MSF9 are 126, 60, 55, 53 and 44 F/g observed
at 1, 2, 3, 4, and 5 A/g current density, and 381, 366, 279, 204, and 192
process cannot occur [44–46]. Furthermore, the supercapacitor’s qual­ Fg-1 at 1, 2, 3, 4 and 5 A g− 1 respectively (Table 5). As a result, the
ities of electrode materials are influenced by aqueous ionic radius, highest charges can be retained in small current levels. Based on the
conductivity, and electrolyte ion mobility. The size of the electrolyte research findings, it is determined that the composition of the electrolyte
ions radii plays a vital role in the ion transfer process [47]. According to has a huge impact on the electrochemical performance of super­
the research, increasing the scan rate has a major impact on the peak capacitors. Fig. 8(g).Shows the energy density vs power density graph.
currents of the electrodes. In the illustration, the anodic curve for sample Case MSF9 and MF have energy densities of 68 Whkg− 1 and 22.68
MSF9 has a prominent peak. In terms of electrochemical performance, Whkg− 1 for power densities of 5400Wkg − 1 and 5315 Wkg − 1. The
sample MSF9 exceeds the other sample MF. The specific capacitances, greater power density in electrode MSF9 is due to the electrolytic
energy density, and power density were calculated based on the interaction of the electrolyte and electrode being enhanced. According
Equation. to Chaudhary et al., Our energy and power densities and specific

8
A. Anitha and A. Loganathan Materials Chemistry and Physics 292 (2022) 126732

Table 5 electrode can be used in supercapacitor applications as an efficient

Specific capacitance of MF, MSF9 electrode at different current density electrode.
employing GCD studies.
Potential Current Specific Energy Density Power density CRediT authorship contribution statement
(V) density (A/g) capacitance (Wh/kg) (W/kg)
(F/g)
A. Anitha: Software, Validation, Formal analysis, Resources, Data
MF MSF9 MF MSF9 MF MSF9 curation, Writing – original draft, Writing – review & editing, Visuali­
0.6 1 126 381 22.68 68 1080 1371 zation. A. Loganathan: Conceptualization, Methodology, Supervision.
0.6 2 60 366 10.8 65.88 2160 2156
0.6 3 55 279 9.9 50.22 3300 3240
0.6 4 53 204 9.54 36.72 4336 4590 Declaration of competing interest
0.6 5 44 192 7.92 34.56 5315 5400
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
capacitance of MSF9 electrode is higher in comparison with previously
the work reported in this paper.
reported [48–52].The subsistence of homogeneous surface structure,
mesostructured, and greater oxygen hole in the MSF9 electrode is pri­
Data availability
marily responsible for this enhanced performance. The MF electrode, on
the other hand, demonstrated an insufficient redox reaction, reduced
Data will be made available on request.
charge-storage characteristics, along with a mostly larger IR drop.
Furthermore, the supercapacitors values for MF and MSF9 electrodes
drop with increasing current densities, which is owing to an inadequate References
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