Current Applied Physics 20 (2020) 628–637

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Current Applied Physics

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Investigation of electrochemical performance of MgNiO2 prepared by sol-gel T

synthesis route for aqueous-based supercapacitor application
S. Maitraa, R. Mitraa,b, T.K. Natha,c,∗
a
School of Nano-Science and Technology, Indian Institute of Technology Kharagpur, W.B, India
b
Department of Metallurgy and Materials Engineering, Indian Institute of Technology Kharagpur, W.B, India
c
Department of Physics, Indian Institute of Technology Kharagpur, W.B, India

A R T I C LE I N FO A B S T R A C T

Keywords: In this work, we have successfully synthesized MgNiO2 using a sol-gel wet chemical synthesis technique named
Sol-gel MNO - 3. Electrochemical measurements in the presence of aqueous 1 M Li2SO4 electrolyte indicate that MNO - 3
Aqueous electrolyte samples exhibit a capacitance value of about 30 F/g and an energy density of about 20 Wh/kg. Subsequently, in
Supercapacitor the experiment involving aqueous 0.5 M Na2SO4 electrolyte system, it has been found that the capacitance for
Charge-discharge
MNO - 3 sample is about 34 F/g and the energy density is about 23 Wh/kg for MNO - 3 sample. Finally, in the
Energy density
presence of aqueous-based 1 M Mg(ClO4)2 electrolyte, MNO - 3 sample is found to exhibit a capacitance of about
26 F/g and an energy density of about 17 Wh/kg, respectively. In all three electrolyte systems, the MNO -3
sample exhibit a long cycle capacitance retention of greater than 85% for 1000 charge-discharge cycles.

1. Introduction
The modern-day world is driven by new-age technology. The
driving force behind this new technology revolution of the twenty-first
century is our ability to generate, store, and utilize energy resources.
Renewable sources like solar, hydrothermal, wind, etc. are being in-
creasingly looked upon as a suitable alternative to fossil fuels like coal,
petroleum, and other forms of hydrocarbon. This new focus on re-
newable energy sources is being pursued as a means of sustainable
development, protecting the interest of future generations as well as a
pollution-free green energy harvesting option to preserve the environ-
ment [1–3].
Since the introduction of commercial Lithium-ion batteries in the
early 90s, scientists and engineers from academia and industries have
invested a considerable amount of money and manpower in improving
the efficiency of lithium-ion batteries using different combinations of
cathode, anode and electrolyte combination. One of the techniques of
achieving high-performance battery characteristics that have gained
widespread attention is the use of nanostructured materials having
large surface areas compared to their bulk counterparts. It is used as
cathode materials for lithium-ion batteries. While the research towards
the improvement of the performance of lithium-ion battery (LIB) by
using different materials gained momentum in the last two decades, it
also became clear that the lithium-based energy storage system suffered
from certain drawbacks, which were difficult to overcome. These
drawbacks include less earth abundance, high material cost, less volu-
metric capacity, formation of dendritic morphology which results in
shorting of anode and cathode, formation of solid electrolyte interphase
(SEI) layer near the anode surface, use of organic-based electrolytes
(requiring expensive glove box set-up), the inability to use pure lithium
metal as an anode due to safety concerns, etc. among other factors
[4–6]. While there was a concerted effort to address some of these
difficulties associated with LIBs using different electrode, electrolyte
combinations [7–9], beginning of work on similar rechargeable battery
systems such as Sodium-ion batteries (SIB) [10,11], Magnesium ion
batteries (MIB) [12–14], Aluminum ion batteries (AIB) [15–19], etc., it
has been possible to address some of these difficulties. However, since
they work on similar ionic intercalation based charge storage me-
chanisms like LIBs, they also suffer from similar drawbacks like slow
charge-discharge processes, low cycle lifetime, etc. among others. In
this context, research on supercapacitor devices gained momentum,
which is based on a radically different charge storage mechanism to
overcome the drawbacks of LIBs.
Supercapacitors are a major class of energy storage devices where
energy is stored as a mechanism of charge storage between two elec-
trodes of a capacitor device, separated by an electrolyte medium. In
other words, it works as an electrochemical capacitor device and holds
some advantages over a traditional lithium-ion battery in terms of
performance. These advantages include fast charging-discharging,
longer cycle lifetime (sometimes up to 105), high power density, use of

∗
Corresponding author. School of Nano-Science and Technology, Indian Institute of Technology Kharagpur, W.B, India.
E-mail address: tnath@phy.iitkgp.ac.in (T.K. Nath).

https://doi.org/10.1016/j.cap.2020.02.013
Received 16 November 2019; Received in revised form 31 January 2020; Accepted 19 February 2020
Available online 21 February 2020
1567-1739/ © 2020 Korean Physical Society. Published by Elsevier B.V. All rights reserved.
S. Maitra, et al.
aqueous-based electrolytes, use of cheaper materials like metal oxides
and carbon-based materials and finally, it possesses an electro-
chemically fully reversible charging process. There are two broad ca-
tegories of supercapacitor based devices. First is an electric double-
layer capacitor (EDLC) materials, where charges are stored as an elec-
tric double-layer or Helmholtz layer near the electrode's surfaces. It is
mainly found in materials derived from carbon like activated carbon,
carbon nanotube, graphene, hard carbon, charcoal, biochar, etc. These
materials exhibit a smooth cyclic voltammetry profile, which is rec-
tangular in shape. The charge-discharge plot tends to be triangular with
equal charging and discharging times. The second major type of su-
percapacitor material consists of pseudocapacitor type materials where
charge storage is in the form of a redox reaction at the surface of the
electrode. The presence of redox centers in electrode materials like
metal oxides initiates a faradaic reaction at the surface of the electrode,
which acts as a charge storage mechanism. The examples include metal
oxides like Ruthenium oxides (RuO2), Manganese oxide (MnO2), among
others. The CV profile, in this case, is non-rectangular fish-shaped,
which may include some redox peaks. The charge-discharge profile is
non-linear and has different charging and discharging times. Then we
find a third category of devices which exhibit battery like character-
istics featuring an intercalation type charge storage mechanism and are
sometimes classified under pseudocapacitor type materials in the sci-
entific literature. These materials also show a fish-shaped CV profile
and a non-linear charge-discharge graph [20–23].
There are various techniques adopted to improve the performance
of a supercapacitor device. Firstly, one can increase the surface area of
the electrode material by using nanomaterials instead of bulk materials,
and this can facilitate access of mobile ions from the electrolyte solution
to a large number of surface atoms [24]. Secondly, one can tune the
morphology of the nanomaterial so as to maximize the surface area
[25]. The surface area in contact with the electrolyte has to be en-
gineered to attain the maximum electrochemical performance. Here we
also find several reports that porous nanomaterials exhibit better
electrochemical performance over rigid nanostructures owing to their
porous structure which allows mobile electrolyte ions to penetrate the
surface and reach deeper into the core of the electrode material parti-
cles [26]. Thirdly, there is also an effort to put into the use of organic-
based electrolyte instead of aqueous electrolytes, so as to increase the
voltage window of operation [27]. Fourthly, people are also trying to
merge the chemistry of operation of a battery and a supercapacitor
device. This hybrid device is called supercapattery functions by com-
bining a battery-type electrode and a supercapacitor type electrode to
obtain a powerful device that exhibits a high energy density in addition
to a high power density [28]. Finally, there is also a proposal to mix
redox additive into the electrolyte to improve the electrochemical
performance [29]. These are some of the research directions which are
being pursued, in addition to searching novel materials and electrolyte
combinations.
While there is a huge effort being focused on the improvement of
supercapacitor performance in general, especially with the use of var-
ious metal oxides and metal chalcogenides for electrode materials, we
find that less attention is paid into the application of magnesium-based
oxides and sulfides for energy storage devices. They have been used on
a few occasions for magnesium-ion battery (MIB) applications. For in-
stance, Zheng et al. [30] made a magnesium ion battery using Mag-
nesium Cobalt Silicate (MgCoSiO4) as cathode material and magnesium
ribbon as an anode. Huang et al. [31] used Magnesium Iron Fluor-
ophosphates MgFePO4F as a suitable cathode in Magnesium ion battery.
NuLi et al. [32] used Magnesium manganese silicate Mg1·03Mn0·97SiO4
as a cathode and magnesium ribbon anode for magnesium battery ap-
plication. Orikasa et al. [33] used magnesium ribbon as an anode and
MgFeSiO4 as cathode in a magnesium battery. However, there are very
few instances where these types of magnesium-based oxides, sulfides,
phosphates, etc., are being used for aqueous-based supercapacitor ap-
plications. Here in this work, we have tried to address this issue.
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Current Applied Physics 20 (2020) 628–637
In this work, our primary objective is to develop Magnesium Nickel
Oxide (MgNiO2) compound using a sol-gel synthesis route. Three
electrode-based electrochemical measurements performed in 1 M
Li2SO4, 0.5 M Na2SO4 and 1 M Mg(ClO4)2 based aqueous electrolyte
systems, revealed a maximum capacitance value of 34 F/g, an energy
density of about 23 Wh/kg, a power density of about 550W/kg, a wide
electrochemical voltage window of 2.2 V, and finally a capacitance
retention of 87.38% after 1000 charge-discharge cycles. The novelty of
our work lies in the low-cost synthesis of Magnesium Nickel Oxide
nanoparticles for use aqueous lithium, sodium, and magnesium ion-
based supercapacitor applications, demonstrating a wide voltage
window and respectable energy and power density in comparison with
other reported supercapacitor materials which are based on acidic, al-
kaline and neutral based aqueous electrolyte systems.MgNiO2 can be
considered as potential electrode materials for futuristic environment-
friendly energy storage applications.
2. Experimental details
2.1. Chemicals reagents
Magnesium Oxide (MgO) was procured from Merck, India. Nickel
Nitrate Hexahydrate (Ni(NO3)2·6H2O), Nitric acid (HNO3),
Triethanolamine (C6H15NO3) were procured from Merck India.
Electrolytes used in these experiments: Lithium Sulphate Monohydrate
(Li2SO4·H2O), Sodium Perchlorate Monohydrate (NaClO4·H2O) were
purchased from Merck, India and Magnesium Perchlorate (Mg(ClO4)2
was purchased from Sigma Aldrich, USA. All the chemicals used in the
synthesis process has a purity greater than 99.9%. De-ionized water
used was obtained from a DI water plant of Merck Millipore in the lab.
2.2. Characterization tools
High-Resolution X-Ray Diffraction (HRXRD) patterns were recorded
by a diffractometer manufactured by Philips Pan-Analytical X'pert PRO
using Cu Kα radiation (λ = 1.542 Å). Field Emission Scanning Electron
Microscopy (FESEM) microstructure imaging was carried out by a
Merlin FESEM instrument manufactured by Carl Zeiss (Germany) for
imaging the morphology of the sample. High-Resolution Transmission
Electron Microscopy (HRTEM) with Selected Area Electron Diffraction
(SAED) attachment (JEM-2100F Field Emission Electron Microscope)
manufactured by Jeol (Japan) was used for microstructural analysis.
Fourier Transform Infrared (FTIR) Spectroscopy was carried out using a
Nicolet 6700 FTIR machine manufactured by Thermo Fischer Scientific
(USA). X-Ray Photoelectron Spectroscopy (XPS) was performed using a
Ulvac Phi 5000 Versaprobe 2 instrument (Japan). Raman Spectroscopy
was carried out using the T6400 instrument by Jovin Y von Horiba
(USA), employing an Argon laser (λ = 514 nm). Electrochemical
measurements were carried out using an Electrochemical workstation
and different electrodes, manufactured by CHI Instruments (USA).
2.3. Synthesis of MgNiO2 by chemical sol-gel technique
Here, 0.2015 g of MgO was dissolved in 10 ml HNO3 solution. After
some time, 1.454 g of Ni(NO3)2·6H2O was dissolved in the above
mixture along with the addition of 40 ml of DI water. 1.33 ml of
Triethanolamine (C6H15NO3) was then added as a chelating agent drop
by drop to the above mixture to initiate a sol-gel mechanism. The
mixture was stirred overnight for 180 °C and allowed to dry for another
24 h. The dried gel was collected and ground to a fine powder in a
mortar pestle and calcined at 900 °C for 4 h in a muffle furnace. After
that, the sample was allowed to cool to room temperature, and the final
product was collected. The resultant sample was named as MgNiO2 – 3
or MNO- 3.
The growth mechanism is proposed as the following: Magnesium
oxide in the presence of nitric acid (HNO3) dissociates into Mg2+ions
S. Maitra, et al.
Fig. 1. Sol-gel growth mechanism of MNO – 3 sample.
and nitrate ions (NO32−). Nickel nitrate, on the other hand, dissociates
into Nickel ions (Ni2+) and nitrate ions (NO32−). Triethanolamine
(C6H15NO3) hydrolyzes into C6H12NO33− free radicals and H+ ions.
Magnesium ions, Nickel ions, and Triethanolamine ions present in the
solution, under the application of 180 °C heat, forms a metal-organic
based oligomeric precursor complex, thus forming the gel which is
dried. After calcining the sample at 900 °C, this complex breaks down
into MgNiO2 seeds. These seed particles grow into larger particles, and
the final product obtained is named MNO – 3. This process is depicted
in Fig. 1.
3. Results and discussions
3.1. Structural characterization
High-Resolution X-ray Diffraction (HRXRD) studies were conducted
on our sample MNO – 3, and the recorded diffraction pattern is shown
in Fig. 2(a). The recorded pattern shows well-defined peaks and a high
level of crystallinity. The peaks in the XRD spectra are believed to
originate from (111), (200), (220), (311), and (222) crystallographic
planes. The MgNiO2 samples have a cubic structure with space group
Fm-3m (225), and the spectra matches well with the standard XRD
powder diffraction data of JCPDS card no.: 00-024-0712 [34]. MgNiO2
Fig. 2. (a) HRXRD pattern and (b) FTIR spectra of MNO -3 sample.
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Current Applied Physics 20 (2020) 628–637
has a structural resemblance to the Rock Salt structure of NaCl.
The FTIR Spectroscopy measurement was performed on our sample
MNO - 3 as shown in Fig. 2(b) in order to identify the chemical bonds
present in them. For MNO - 3 sample, the peak found at 3433 cm−1 is
attributed to –OH vibrational frequency, the peak at 519 cm−1 is be-
lieved to originate from Mg–O vibrational bond frequency, and the peak
at 443 cm−1 is attributed to that of Ni–O vibrational bond frequency.
The peak, which is attributed to –OH bond, is believed to originate from
the surface water molecules, which are present due to absorbed
moisture on the sample surface. The peaks observed from sample are in
good agreement with the standard values reported in the literature
[35,36].
Morphological analysis of our samples was carried out using FESEM
based characterization. The FESEM image of MNO- 3 are shown in
Fig. 3(a). The MNO - 3 sample exhibited spherical shaped particle
morphology with an average diameter of 40–50 nm. We also find a
certain degree of agglomeration, which may be the result of calcination
at a high temperature. This type of morphology exhibits an enhanced
surface area that is suitable for electrochemical applications. The cor-
responding EDX map of the MNO - 3 sample is shown in Fig. 3(b), and it
indicates the presence of Mg, Ni, and O in an approximate atomic
percentage ratio of close to 1:1:2.
We have also recorded HRTEM images of MNO – 3, as shown in
S. Maitra, et al.
Fig. 3. (a) FESEM image; (b) EDX Spectra; (inset) Elemental map; (c) HRTEM image; (d) Lattice resolution image; (inset) SAED pattern; (e) Fitted Raman
Spectroscopy measurement results of MNO- 3 sample.
Fig. 3(c). MNO - 3 sample exhibited particles of diameter 30–50 nm. But
it showed some degree of agglomeration (forming bigger particles of
size greater than 100 nm), which is common among samples synthe-
sized at high temperature. We found a clear SAED pattern, which is
attributed to the presence of a high degree of crystallinity, as shown in
the inset of 3(d). MNO- 3 sample showed a ring pattern. Lattice re-
solution image of MNO - 3 sample, as shown in Fig. 3(d) has an inter-
planar spacing 2.04 Å, and it matches closely with the d spacing of the
characteristics peak of (220) plane, as given in (JCPDS card no.: 00-
024-0712) where d = 2.09 Å.
Raman Spectroscopy measurements were carried on MNO – 3, as
shown in Fig. 3(e). We have also resolved the obtained spectroscopic
data and fitted it into four peaks. The peak obtained at 435 cm−1 is
attributed to one phonon(1P) TO mode, and the peak obtained at
532 cm−1 is attributed to LO mode. The peak found at 924 cm−1 is
believed to originate from (2P)TO + LO modes, whereas the peak
found at 1073 cm−1originates due to 2 LO modes. The Raman modes
found in our samples originate mostly due to the presence of NiO since
MgO does not exhibit any Raman modes [37]. The data obtained from
our sample broadly match the data found elsewhere in the literature
[37]. The Raman data positively confirms the phase purity of our
samples.
X-Ray Photoelectron Spectroscopic (XPS) measurements were per-
formed on MNO - 3 sample, as shown in Fig. 4. From the XPS data, the
Mg 2p peak is identified at 48.913 eV (shown in Fig. 4(b)) [38]. The O
1s spectra (shown in (d)) is fitted and resolved into two peaks: one peak
identified at 529.349 eV belongs to metal-oxygen bond, and the other
peak found at 531.08 eV originates due to organic C–O bond. This may
be attributed to the remnants of hydrolyzed Triethanolamine
C6H12NO33− free radicals. The Ni 2p spectra (shown in Fig. 4 (c)) is
fitted and resolved into four separate peaks: Ni 2p3/2 peaks is identified
at 854.71 eV; Ni 2p3/2 satellite peak is found at 860.858 eV; Ni 2p1/2 is
identified at 872.801 eV, and Ni 2p1/2peak is found at 879.613 eV. Here
also, the Ni 2p peak position matches well with the standard Binding
energy values of Nickel in NiO form [39]. The different XPS peaks and
their corresponding binding energies of MNO - 3 sample are listed in
Table 1.
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Current Applied Physics 20 (2020) 628–637
3.2. Electrochemical measurements
3.2.1. MgNiO2 based electrode for lithium-ion supercapacitor application
Cyclic Voltammetry (CV) is an important electrochemical mea-
surement apparatus, which is used to measure the amount of charge
stored in a material during electrochemical cycling. In CV measure-
ments recorded in a three-electrode set-up, a voltage is applied between
the working electrode (W.E) and the reference electrode (R.E) having a
triangular type waveform with respect to time varied between an initial
and final voltage, and the corresponding current is recorded between
the working electrode (W.E) and counter electrode (C.E). It is a pow-
erful tool that can easily record minute electrochemical phenomenon
like charge storage on the electrode surface, a faradaic reaction in the
electrode, the reaction of electrolyte, etc. The CV profile is used to
distinguish between Electrically Double Layered Capacitor (EDLC) type
materials, which tends to possess a rectangular-shaped CV profile and
pseudocapacitor materials. This has a non-rectangular CV profile re-
sembling a fish-shaped loop, and sometimes it has some well-defined
redox peaks. The capacitance of the material can be calculated from the
CV profile using the formula:
Vf
1
C=
2mvΔV
∬ I dV
Vi
where m is the active mass of the electrode material; v is the scan speed
(mV/sec), I is the current, and ΔV is the voltage window. The nu-
merator integral gives us the area under the CV curve. Vi is the initial
voltage, and Vf is the final voltage [40].
In this experiment, we have used MNO - 3 sample as the active
electrode material coated on a glassy carbon-based working electrode
and saturated calomel electrode (S·C.E) as reference electrode and
platinum wire as the counter electrode. The electrolyte used was 1 M
Lithium Sulphate (Li2SO4) dissolved in water. The applied voltages
were scanned at (25, 50, 75,100,125 and 150) mV/sec. MNO - 3 sample
exhibited a fish-shaped CV profile (shown in Fig. 5(a)), which indicates
a pseudocapacitor type underlying electrochemical mechanism of these
types of electrodes. Mobile lithium ions (Li+) from the aqueous elec-
trolyte solution get access to the electrode surface area and initiates
redox reactions at the surface, as well as some amount of intercalation,
occurs in between the interatomic layers of MgNiO2 crystal structure
during electrochemical cycling operation [41]. The lithium ions initiate
S. Maitra, et al. Current Applied Physics 20 (2020) 628–637

Fig. 4. XPS Spectra MNO- 3 sample: (a) Full Spectrum; (b) Fitted Mg 2p spectra; (c) Fitted Ni 2p spectra and (d) Fitted O 1s spectra.

a faradaic redox chemical reaction, which is displacive in nature. The
chemical reaction involving oxidation and reduction of Mg (+2)/Mg
(0) and Ni (+2)/Ni (0) redox couple at the surface of the electrode is
given as follows:
MgNiO2 + 4 Li+ + 4e− ↔ Mg + Ni + 2Li2O
2 Li2O + Mg + Ni ↔ MgO + NiO + 4 Li
The reduction peaks of Mg and Ni associated with the first equation
is a broad overlapped peak, which is obtained at −0.08V for MNO - 3.
Similarly, the oxidation peak overlaps at 0.2V for MNO – 3. The peaks
indicate that a faradaic redox reaction indeed takes place, and confirms
the pseudocapacitive nature of our samples. Some lithium ions might
also get trapped in the interstitial and voids of the samples during cy-
cling. The capacitance recorded for MNO - 3 is about 20 F/g (at 25 mV/
s). From the Capacitance vs. Scan speed plot (shown in Fig. 5(b)), we
clearly observe that with an increase in scan speed, the corresponding
capacitance decreases. This phenomenon is attributed to the fact that
ions present in the electrolyte, which constitutes the electrochemical
current, are heavier than electrons and cannot follow the rapidly
varying voltages applied at the external circuit between the working
electrode and the reference electrode [42].
Galvanostatic charge-discharge or Chronopotentiometry is an im-
portant technique for electrochemical analysis of an energy storage
device like supercapacitors, batteries, and fuel cells. Here the change in
potential or voltage of a device is recorded corresponding to change in
time in response to an applied constant current. After the charging
cycle, the polarity of the constant current is reversed to allow the dis-
charge to take place. The voltage waveform is generally triangular in
nature with respect to time and can be used to differentiate between an
Electrical Double Layer Capacitor (EDLC) material, which possesses a
near-linear triangular-shaped charge-discharge profile and a pseudo-
capacitor material which exhibits a non-linear triangular-shaped po-
tential profile. The capacitance of the electrode material can be calcu-
lated from the discharge curve as:
C=
Idt
mdV
where C is the capacitance in (F/g), I is the constant applied current in
(A/g), dt is the discharge time, m is the active mass of electrode ma-
terial in (g) and dV is the change in voltage during the discharge pro-
cess or the voltage window [43].
In this experiment, we have used MNO - 3 sample as the electrode
material on which we performed three electrode-based electrochemical
charge-discharge measurements. The charge-discharge profiles of MNO
- 3 sample and the Capacitance (F/g) vs. Current (A/g) are shown in
Fig. 5(c). MNO - 3 sample was subjected to a constant current of
(0.5,0.75,0.85, 1, 1.25,1.5 and 1.75) A/g. MNO - 3 sample exhibited a
capacitance of about 30 F/g (at 0.5 A/g). We also observe that the
capacitance decreases with increasing current since an increasing con-
stant current tends to make the discharge process faster [41]. This is
evident from the Capacitance (F/g) vs. Current (A/g) plot, as shown in
Fig. 5(d). Non-linear nature of the charge-discharge curve indicates
pseudocapacitor type charge storage with an underlying mechanism

Table 1
XPS analysis results MNO – 3 sample showing all the resolved peaks obtained by fitting.
Name of Sample Mg 2p peak O 1s peak (eV) Ni 2p3/2 peak Ni 2p3/2 satellite peak Ni 2p1/2 peak Ni 2p1/2 satellite peak
(eV) (eV) (eV) (eV) (eV)

MgNiO2 -3 (MNO -3) 48.913 529.349 (metal-oxide 531.08 (organic C–O 854.71 860.858 872.801 879.613
bond) bond)

632
S. Maitra, et al.
Fig. 5. Electrochemical measurements in 1 M Li2SO4 aqueous electrolyte: (a) Cyclic Voltammetry profile; (b) Capacitance (F/g) vs Scan speed (mV/sec); (c) Charge-
discharge profile; (d) Capacitance (F/g) vs Current (A/g); (e) Nyquist Plot; (inset) Fitting equivalent circuit; (f) Fitting parameter table.
consisting of a redox reaction involving Mg (+2)/Mg (0) and Ni (+2)/
Ni (0) as evident from the peaks obtained in the CV profile.
Electrochemical Impedance Spectroscopy (EIS) based AC impedance
measurements were performed on the MNO - 3 sample in a three
electrode-based set-up as described previously. A small ac voltage of
5 mV amplitude was applied for a frequency range between 1 Hz and
1 MHz, and the corresponding real and imaginary impedances were
recorded. The obtained Nyquist plot of MNO - 3 sample, in this case, is
shown in Fig. 5(e). The recorded impedance data from the Nyquist plot
are fitted using an electrochemical equivalent circuit: Rs(CdlRct)W, as
shown in the inset of Fig. 5(e), where Rs is the series resistance in (Ω),
Cdl is the double layer capacitance in (F), Rct is the charge transfer re-
sistance in (Ω), and W is the Warburg impedance term in (Ω). Warburg
impedance involves the ion diffusion resistance factor, which plays a
major role in the ionic diffusion. The high-frequency semicircle portion
of the impedance data is related to the formation of solid electrolyte
interphase (SEI) film formed at the surface of the electrode, which in-
hibits further ionic movement. The extracted parameters are shown in
Fig. 5(f). From the fit, the obtained series resistance, Rs, value is
28.49 Ω, and the Warburg impedance is 3.143 × 10−4 Ω.
3.2.2. MgNiO2 based electrode for sodium-ion supercapacitor application
In this experiment, we have performed Cyclic Voltammetry MNO - 3
sample in the presence of an aqueous solution of 0.5 M Sodium
Sulphate (Na2SO4) using the same three-electrode set-up, as described
previously. The Voltage scans applied in this case was (25, 50, 75, 100,
125, and 150) mV/sec. The observed CV profile of MNO - 3 sample in
this experiment (shown in Fig. 6(a)) indicates pseudocapacitor type
behavior. Using the capacitance formula described previously, we have
calculated that the capacitance of MNO - 3 sample is about 15 F/g (at
25 mV/s). It seems that the charge storage mechanism is a redox-based
oxidation/reduction reaction at the electrode surface, initiated by mo-
bile Na+ ions present in the solution, given as:
MgNiO2 + 4Na+ +4e− ↔ Mg + Ni + 2Na2O
2Na2O + Mg + Ni ↔ MgO + NiO + 4Na
Here a broad reduction overlapped peak was obtained at −0.53V,
and a broad overlapped oxidation peak was obtained at 0.24V. Also,
there is some intercalation of mobile Sodium ions (Na+) from the
electrolyte into the crystal lattice structure of MgNiO2 [43], in addition
to some Na+ ions from the electrolyte accumulates on the electrode
surface and gets trapped into the interstitials and voids present in the
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Current Applied Physics 20 (2020) 628–637
microstructure. The capacitance in this experiment also decreases with
increasing voltage scan rates, as is evident from Fig. 6(b).
Charge-discharge measurements were performed on the MNO - 3
sample in the presence of 0.5 M Na2SO4 aqueous solution, and the
potential vs. time profiles are shown in Fig. 6(c). Using the capacitance
formula described previously, we have calculated the capacitance of
about 34 F/g (at 0.5 A/g). The capacitance here, too, decreases with an
increase in current, as observed previously, and is shown in Fig. 6(d).
AC impedance studies were performed using the same three elec-
trodes set up. The electrolyte used in this study was an aqueous solution
of 0.5 M Sodium sulphate (Na2SO4). The real and imaginary part of the
impedance data obtained is plotted as a Nyquist plot and shown in
Fig. 6(e). The data is subsequently fitted to an electrochemical
equivalent circuit: Rs(Q(RctW)), and it is shown in the inset of Fig. 6(e),
where Rs is the series resistance in Ω, Rct is the charge transfer re-
sistance in Ω. W is the Warburg Impedance associated with ion diffu-
sion resistance and Q is the constant phase element that is associated
with admittance Yo and power n. The high-frequency semicircle is
closely associated with the solid electrolyte interphase (SEI) film, si-
milar to the previous case. From the extracted parameters, the series
resistance Rs is found to be 35.2 Ω, and the n factor of constant phase
element is 0.8013. These parameters are shown in Fig. 6(f).
3.2.3. MgNiO2 based electrode for magnesium ion supercapacitor
application
In this experiment, the MNO – 3 sample was subjected to the Cyclic
Voltammetry test in presence of a water-based 1 M Mg(ClO4)2 elec-
trolyte solution using the three-electrode set-up. The voltages were
scanned at the rate of (25, 50, 75,100,125 and 150) mV/sec. The CV
profile obtained in this experiment is shown in Fig. 7(a). The capaci-
tance is calculated using the previously described formula. The capa-
citance value is about 13 F/g (at 25 mV/s). Charge storage in this ex-
periment is also a pseudocapacitive one which proceeds via initiation of
redox reaction by mobile Magnesium (Mg+2) ions at the surface of the
electrode material. We have obtained a broad reduction peak at
−0.58V and a broad oxidation peak at 0.02V. The redox chemical re-
action involving Mg (+2)/Mg (0) and Ni (+2)/Ni (0) redox pairs is
given as the following:
MgNiO2 + Mg+2 +2e− ↔ Mg + Ni + MgO
MgO + Mg + Ni ↔ MgO + NiO + Mg
Also, some amount of intercalation into the crystal structure of
S. Maitra, et al. Current Applied Physics 20 (2020) 628–637

Fig. 6. Electrochemical measurements in 0.5 M Na2SO4 aqueous electrolyte: (a) Cyclic Voltammetry profile; (b) Capacitance (F/g) vs Scan speed (mV/sec); (c)
Charge-discharge profile; (d) Capacitance (F/g) vs Current (A/g); (e) AC Impedance Nyquist Plot; (inset) Fitting equivalent circuit; (f) Fitting parameter table.

MgNiO2 by mobile Mg+2 ions happens apart from ions getting trapped
into interstitials and voids present at electrode surface similar to the
previous cases [44,45]. The Capacitance vs. Scan speed plot is shown in
Fig. 7(b), which indicates that the capacitance decreases with in-
creasing scan speed, as observed previously.
Charge-discharge measurements were conducted in the presence of
aqueous solution of 1 M Magnesium Perchlorate (Mg(ClO4)2) electro-
lyte. The charge-discharge profile is shown in Fig. 7(c). The calculated
capacitance is about 26 F/g (at 0.5 A/g). The capacitance value de-
creases with increasing current applied (shown in Fig. 7(d)) owing to
faster discharge rates at high current similar to previous cases.
AC impedance studies were conducted in the presence of 1 M Mg
(ClO4)2 aqueous electrolyte solution. The Nyquist plot obtained on the
basis of the real and imaginary part of impedance values, in this case, is
shown in Fig. 7(e). The inset picture shows the electrochemical
equivalent circuit: Rs(Q(RctW)), to which the Nyquist data for both of
our sample are fitted. These notations are already defined in the pre-
vious experiment. The series resistance is found 20.83 Ω, as shown in
Fig. 7(f).
3.2.4. Long term cyclic stability test
Long cycle stability test is an important electrochemical test to
measure the performance of an energy storage device, in a real-world
like operating conditions. It includes multiple cycles of charging and
discharging, which mimics the operation of the energy storage devices
throughout its service life and also measures its performance change
over this time period. Here in this experiment, we have performed long
cycle stability MNO - 3 samples for the different electrolyte systems, as
shown in Fig. 8. In the case of 1 M Li2SO4 aqueous electrolyte system,
we have found that the MNO - 3 sample, under the application of 1.5 A/
g current, showed a capacitance retention of 88.12% after 1000 cycles,
as evident from Fig. 8(a). In the case of 0.5 M Na2SO4 aqueous elec-
trolyte systems, MNO - 3 sample retained 87.38% capacitance after
1000 cycles, for 2A/g applied current, as shown in Fig. 8(b). In the third
experiment performed in the presence of 1 M Mg(ClO4)2 aqueous
electrolyte, the MNO - 3 sample retained 87.43% capacitance under 2
A/g applied current for 1000 charge-discharge cycles, as depicted in
Fig. 8(c). The inset picture of each of these three plot shows some of the
recorded charge-discharge cycles. The loss in capacitance is attributed
to several factors like changes occurring in the microstructure at

Fig. 7. Electrochemical measurements in 1 M Mg(ClO4)2 aqueous electrolyte: (a) Cyclic Voltammetry profile; (b) Capacitance (F/g) vs Scan speed (mV/sec); (c)
Charge-discharge profile; (d) Capacitance (F/g) vs Current (A/g); (e) EIS based Nyquist Plot; (inset) Fitting equivalent circuit; (f) Fitting parameter table.

634
S. Maitra, et al. Current Applied Physics 20 (2020) 628–637

Fig. 8. Long term stability test showing (a)

Capacitance retention (%) vs cycle number (a) In
presence of 1 M Li2SO4 (at 1.5A/g); (b) In presence of
0.5 M Na2SO4 (at 2A/g); (c) In presence of 1 M Mg
(ClO4)2 (at 2A/g); the inset pictures in each figure
shows some of the corresponding charge-discharge
cycles; (d) Ragone plot of MNO - 3 sample for dif-
ferent aqueous electrolyte systems.

electrode-electrolyte interphase, residual immobile changes at the
electrode surface, leaching of electrode material into the electrolyte, the
formation of surface passivation layers, etc. However, the capacitance
retention in each case was greater than 85%, after 1000 charge-dis-
charge cycles.
3.2.5. Energy density and power density
Energy density and power density are important figures of merit
which quantify the performance of an energy storage system. The en-
ergy density (E) is normally expressed in Wh/kg and can be calculated
from the charge-discharge plot using the formula:
1 cling. The microstructure found in our samples has sufficient porosity,
2
C(ΔV)2
E= Wh/kg
3.6
where C is the capacitance in (F/g) and ΔV is the voltage window in
volts [46].
On the other hand, power density (P) can be calculated from the
charge-discharge plot using the following formula:
3600
P= E× W/kg
Δt
where E is the energy density in Wh/kg, and Δt is the discharge time in
secs [47].
In Table 2, we have shown the selected energy density and power
density, which is calculated from the charge-discharge plot for three
different electrolyte systems at a particular applied constant current.
We have compared these values with the results found in the literature
for other supercapacitor devices based on acidic, alkaline, and neutral
based aqueous electrolyte systems. The energy density tends to decrease
with a decrease in capacitance at higher current, whereas the power
density increases. The corresponding Ragone plot showing the energy
density and power density relation is shown in Fig. 8(d).
3.3. Discussion
From the experimental results, we can conclude that MgNiO2 ex-
hibits good structural stability towards repeated electrochemical cy-
which allows for easy diffusion of ions, and networked structure offers
efficient conduction of electrons. Thus, it allows low charge transfer
resistance and a large number of electrochemically active sites.
However, we observe capacitance loss upon long cycle charge-dis-
charge experiments due to change in the microstructure at the elec-
trode-electrolyte interface and other factors discussed previously. Also,
electrochemically inactive species are produced during the surface
redox reactions like Li2O and Na2O, which degrades the overall elec-
trochemical performance. Again, the larger surface area of the electrode
material sometimes also attracts a bigger surface electrolyte interface
(SEI) passivating films, which may impede the smooth intercalation
kinetics of mobile Li+, Na+, and Mg+2 from the electrolyte towards
electrode surface [47,48]. Nonetheless, MNO - 3 sample exhibited good
electrochemical performance in terms of capacitance, energy and power

Table 2
Energy density and power density comparison of MNO– 3 sample for different aqueous electrolyte systems in comparison with some known results, available in
scientific literature.
Name of the electrode material Aqueous electrolyte system Energy density (Wh/kg) Power density (W/kg) Reference

Phosphorous enriched carbon 1M H2SO4 16.3 33 [49]

Nitrogen and oxygen containing hierarchical porous carbon frameworks 1M H2SO4 37.4 197 [50]
Porous NiCo2O4 nanotubes 2M KOH 38.5 205 [51]
Mesoporous MnO2 1M Li2SO4 28.8 70 [52]
MNO - 3 1 M Li2SO4 19.938 549.988 This work
MNO - 3 1 M NaClO4 22.913 549.996 This work
MNO - 3 1 M Mg(ClO4)2 17.280 549.978 This work

635
S. Maitra, et al.
density and a wide voltage window of operation in three different
aqueous-based electrolyte systems. This confirms the suitability of our
samples in lithium, sodium, and magnesium-based aqueous super-
capacitor application.
4. Summary and conclusion
In summary, in this work, we have reported the successful synthesis
of the MgNiO2 compound using the sol-gel synthesis technique. HRXRD
results confirmed that MNO – 3 sample exhibit a cubic structure with
space group Fm-3m (225), and matches well with standard XRD powder
diffraction data of JCPDS card no.: 00-024-0712. The FTIR spectra
confirmed the presence of Mg–O and Ni–O chemical bonds in addition
to some –OH bond, and it is believed to originate from surface water
molecules. The Raman and XPS data confirmed the phase purity and the
proper oxidation states of the elements present. The FESEM and HRTEM
images revealed a 40–50 nm particle size for MNO - 3 compound and it
exhibited a high level of crystallinity. In the presence of 1 M Li2SO4
aqueous electrolyte showed a capacitance of about 30 F/g, an energy
density of about 20 Wh/kg, and a power density of about 550 Wh/kg, at
a constant current of 0.5 A/g current. For 0.5 M Na2SO4 aqueous
electrolyte system, at a current of 0.5 A/g, MNO - 3 exhibited a capa-
citance of about 34 F/g, an energy density of about 23 Wh/kg, and a
power density of about 550 W/kg. In the case of aqueous 1 M Mg
(ClO4)2 electrolyte system, capacitance is about 26 F/g (at 0.5 A/g). The
energy density is found as about and 17 Wh/kg, whereas power density
is found as about 550 W/kg. Furthermore, the MNO - 3 sample showed
a capacity retention of greater than 85%, after 1000 charge-discharge
cycles, in all three electrolyte systems, indicating the long term stability
of our samples. In addition, they exhibited a wide voltage window and
compatibility with aqueous-based lithium, sodium, and magnesium
electrolyte systems. This points to their suitability for green energy
storage applications. However, further work is needed for under-
standing of their behavior in the actual two electrode-based coin cell
and screw cell type devices. Also, in the future, some research should be
initiated regarding the electrochemical compatibility of these types of
materials in organic electrolyte systems as well as on flexible substrates.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgment
The authors would like to acknowledge Dr. S.D. Das (Department of
Physics, IIT Kharagpur) for going through the entire manuscript care-
fully. The authors would also like to acknowledge the Central Research
Facility (CRF) of IIT Kharagpur, for the structural and spectroscopic
measurements. The authors further acknowledge Dr. P. K. Chakraborty
(Department of Chemistry, IIT Kharagpur) for the electrochemical
measurements. One of the authors, SM would like to acknowledge the
financial support of the Institute Ph.D. fellowship of IIT Kharagpur
(MHRD), India.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cap.2020.02.013.
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