Journal of Asian Ceramic Societies

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Facile preparation and characterization of

novel manganese doped nickel oxide based
nanostructured electrode materials for application
in electrochemical supercapacitors

Gopalakrishnan Srikesh & Arputharaj Samson Nesaraj

To cite this article: Gopalakrishnan Srikesh & Arputharaj Samson Nesaraj (2020) Facile
preparation and characterization of novel manganese doped nickel oxide based nanostructured
electrode materials for application in electrochemical supercapacitors, Journal of Asian Ceramic
Societies, 8:3, 835-847, DOI: 10.1080/21870764.2020.1793477

To link to this article: https://doi.org/10.1080/21870764.2020.1793477

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JOURNAL OF ASIAN CERAMIC SOCIETIES
2020, VOL. 8, NO. 3, 835–847
https://doi.org/10.1080/21870764.2020.1793477

FULL LENGTH ARTICLE

Facile preparation and characterization of novel manganese-doped nickel

oxide-based nanostructured electrode materials for application in
electrochemical supercapacitors
Gopalakrishnan Srikesh and Arputharaj Samson Nesaraj
Department of Applied Chemistry, Karunya Institute of Technology and Sciences (Deemed to be University), Coimbatore, India

ABSTRACT ARTICLE HISTORY

Mn doped NiO nanostructured materials with composition Ni1-xMnxO1-δ (where x = 0.01, 0.03, Received 29 April 2020
0.05, 0.07, 0.09) (MNO) were prepared by simple facile chemical synthesis route. The structural, Accepted 25 June 2020
particulate and microstructural characteristics of the Mn-doped NiO nanostructures were KEYWORDS
studied by studied by XRD, FTIR, particle size analysis, EDAX, SEM and HRTEM techniques. Mn-doped NiO;
The XRD peaks of all the materials were indexed to the face-centred cubic (FCC) crystalline nanostructured electrode;
structure. FTIR spectra revealed the presence of NiO bending vibration mode between 432.07 supercapacitors
to 492.83 cm-1. Particle size patterns and SEM photographs confirmed the presence of nano­
sized grains apart from few bigger sized grains. The diameter of grains was mostly found to be
in the range of 30.04 to 591.16 nm. Presence of appropriate composition of elements was
confirmed by EDAX data. Polycrystalline behaviour of Ni0.95Mn0.05O1-δ was exhibited by HRTEM
data. The electrochemical phenomena of Ni1-xMnxO1-δ were studied by cyclic voltammetry
(CV), galvanostatic charge – discharge and electrochemical impedance measurements in 6 M
KOH aqueous solution. Among the samples studied, Ni0.95Mn0.05O1-δ electrode exhibited
maximum specific capacitance of 369.6 Fg-1 at a current density of 0.5 Ag-1. From the
characterization data, Mn-doped NiO nanostructures appear to be the good electrode materi­
als for electrochemical supercapacitor applications.

1. Introduction nanocomposite [14,15] based materials were used in

supercapacitors. NiO-based electrode materials were
The electrochemical supercapacitors are received
considered as one of the best materials for supercapa­
much attention now-a-days especially in research and
citor applications for the past one or two decades.
development because of their high level of delivering
Sathishkumar et. al [16]. synthesized Cu2+-doped NiO
electrical power for prolonged duration. Super capaci­
electrode materials by simple chemical precipitation
tors are used in many industrial fields such as, aviation,
method. NiO: Cu2+ (0.025 M) has exhibited the specific
defense, medical, transportation, etc. Mainly these
capacitance of 372 Fg−1. Han et. al [17]. studied the
devices are being developed since they don’t cause
inductive effect in Mn-doped NiO nanosheet arrays.
any environmental pollution like other hydrocarbon-
They found that these materials exhibited an
based electrical devices [1]. The electrochemical capa­
enhanced specific capacitance than pure NiO
citors, i.e. supercapacitors are generally utilized in
nanosheet arrays. Ag/NiO honeycomb structured
applications which are in need of more power such
nanoarrays were prepared by hydrothermal method
as satellites, electric vehicles, robot devices, etc.
and these nanoarrays delivered a specific capacitance
because of their high specific power (~ 10 kW kg−1)
of 824 Fg−1 at a specific current of 2.5 Ag−1 [18]. In our
[2]. The supercapacitor has following components: two
earlier work, we synthesized Co and Mn codoped NiO
electrode materials which are divided by a separator
nanocrystalline materials as electrode materials by
(usually an ionic permeable membrane) and both the
chemical synthesis route. Ni0.95Co0.025Mn0.025O1−δ
electrodes are united by an electrolyte medium [3].
showed a specific capacitance of 673.33 F g−1 at a cur­
Among the different components, electrode material
rent density of 0.5 A g−1 [19]. Ce-doped NiO nanoflakes
is a very significant and critical component because
were synthesized by sol-gel method and they exhib­
which determines the capacity of a supercapacitor [4].
ited a specific capacitance of 2444 F g−1 which is three
For getting superior performance in supercapacitors,
times that of the pure NiO materials [20]. La3+-doped
the type and composition of an electrode is very
NiO microspheres with porous structure was prepared
important. The electrode materials, such, as, metal
simple hydrothermal method. 1.5 mol% La3+-doped
oxides [5,6], doped metal oxides [7–9], carbon-based
NiO showed a good specific capacitance of 253 F g−1
materials [10,11], conducting polymers [12,13], and

CONTACT Arputharaj Samson Nesaraj drsamson@karunya.edu Department of Applied Chemistry, Karunya Institute of Technology and Sciences
(Deemed to be University), Coimbatore 641 114, India
© 2020 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group on behalf of The Korean Ceramic Society and The Ceramic Society of Japan.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
836 G. SRIKESH AND A. S. NESARAJ
and better cycling stability (34% capacity increase after
500 cycles) [21]. CoxNi1-xO (where x = 0, 0.0, 0.1, 0.2,
0.3, 0.4) nanoparticles were synthesized by the sol-gel
technique. Co0.4Ni0.6O gave better charge storage
capacity and showed a specific capacitance of 379
Fg−1 [22]. Gd-doped NiO-based materials were synthe­
sized by a facile hydrothermal route using urea as the
hydrolysis controlling agent. Ni0.98Gd0.02O showed
a specific capacitance of 1190 Fg−1 at a current density
of 2 Ag−1 [23]. ZnO/NiO core–shell composites
embedded with Au nanoparticles showed excellent
electrochemical characteristics with long-term cycling
stability and specific area capacitance of 4.1 Fcm−2 at
a current density of 5 mAcm−2 [24].
Zhao et. al [25] have synthesized Sn-doped Mn3O4
/C nanocomposite using Pluronics P123 (EO20PO70
EO20) as both structure-directing agent and carbon
source. The electrochemical performance of the sam­
ple was tested in 6 M KOH which resulted in a high
specific capacitance of 216 F g−1 at current density of 5
A g−1, and 93% capacitance retention remained after
10,000 charge/discharge cycles. Zhao et. al [26] have
prepared MnO2/GO (graphene oxide) composites with
novel multilayer nanoflake structure, and a carbon
material derived from Artemia cyst shell with genetic
3D hierarchical porous structure (HPC). An asymmetric
supercapacitor was fabricated using MnO2/GO as posi­
tive electrode and HPC as negative electrode material.
The optimized asymmetric supercapacitor could be
cycled reversibly in the high voltage range of 0–2 V
in aqueous electrolyte, which exhibits maximum
energy density of 46.7 Wh kg−1 at a power density of
100 W kg−1 and remains 18.9 Wh kg−1 at 2000 W kg−1.
Additionally, such device also shows superior long
cycle life along with ∼100% capacitance retention
after 1000 cycles and ∼93% after 4000 cycles. Wang
et. al [27] have constructed a novel interface-rich core-
shell structure with (NH4)(Ni,Co)PO4 · 0.67 H2
O nanosheets @ single crystal microplatelets
(NH4)(Ni,Co)PO4 · 0.67 H2O (NCoNiP@NCoNiP) via
a facile two-step hydrothermal method, taking advan­
tage of etching induced Kirkendall effect and Ostwald
ripening. Specifically, a maximum specific capacity of
190.3 mAh g−1 and ultrahigh rate performance with
capacity retention of 96.1% from 1 to 10 Ag−1 in
a three-electrode test. Simultaneously, the hybrid bat­
tery-supercapacitor devices based on NCoNiP@NCoNiP
exhibits a high energy density of 44.5 Wh kg−1 at
a power density of 150 Wkg−1, which maintains
30 Wh kg−1 at high power density of 7.4 kWkg−1 with
capacitance retention 77.5% after 7000 cycles. Wang
et. al [28] have synthesized a multihierarchical struc­
ture with (NH4)(Ni, Co)PO4·0.67H2O microplatelets and
(Ni, Co)3(PO4)2·8H2O ultrathin nanopieces anchored on
reduced graphene oxide (NCNP/RGO) via a mild hydro­
thermal approach. Specifically, a specific capacity
of 993 F g–1 is obtained in the three-electrode
measurement, with ultrahigh capacity retention of
81.2% (807 F g–1) from 0.5 to 32 A g–1. The hybrid
device constructed with the as-prepared NCNP/RGO
as anode and a hierarchical porous carbon (HPC) as
cathode offers a very superior energy density of 42.1
Wh kg–1 at a power density of 73 W kg–1, which
remains 32 Wh kg–1 at 14 kW kg–1. Meanwhile, the as-
prepared hybrid capacitor exhibits a remarkable
cycling stability (96.5% capacitance retention after
10000 cycles). The capacity contribution of capacitive
behavior for the hybrid device is analyzed as 91.1% at
25 mV s–1. Tie et. al [29] have summarized the advan­
tages and disadvantages of different type electrode
materials such as the carbon-based material of double-
layer capacitance materials, metal oxides, conductive
polymers of pseudocapacitance materials, the different
type battery-type materials, and the materials can be
built for acid battery-supercapacitors and alkaline bat­
tery-supercapacitors in their review article recently.
In this research work, we report the synthesis and
physico-chemical characterization of Mn-doped NiO
(Ni1-xMnxO1-δ; where x = 0.01, 0.03, 0.05, 0.07, 0.09)
(MNO) nanostructured materials by facile chemical
preparation route. The electrochemical performance
of Mn-doped NiO nanostructured electrodes in 6 M
KOH aqueous solution was studied by cyclic
voltammetry(CV), galvanostatic charge-discharge and
impedance techniques. The obtained results were
reported and discussed in order to choose them as
electrode material in electrochemical supercapacitor
applications.
2. Materials and methods
2.1. Materials
The chemicals such as nickel nitrate hexa hydrate (98%,
Loba Chemie,India), manganese nitrate tetra hydrate
(97%, Loba Chemie, India), sodium hydroxide (≥ 97%,
Merck, India), ethanol (99.9%, Changshu Yangyuan,
China), N,N di-methyl-acetamide (99%, Loba Chemie,
India) and polyvinylidene fluoride (PVDF) were as used
in the experiment. All the chemicals were used as such
without any further purification.
2.2. Preparation of Ni1-xMnxO1-δ (where x = 0.01,
0.03, 0.05, 0.07, 0.09) (MNO) nanostructured
materials
Mn-doped NiO nanostructured materials were pre­
pared by a simple facile chemical route.
Stoichiometric amounts of nickel nitrate hexa hydrate
(Ni(NO3)2.6H2O), manganese nitrate tetra hydrate
(Mn(NO3)2·4H2O) and sodium hydroxide were dis­
solved in double distilled water (100 ml) as per the
details indicated in Table 1. In a typical preparation,
aqueous solutions of nickel nitrate hexa hydrate and

Table 1. The amount and concentration of metal nitrates and
alkali used to prepare different compositions of Mn-doped NiO
nanostructured materials [Aqueous solutions were prepared in
100 ml double distilled water].
Concentration Concentration
of Ni(NO3)2.6H2 of Mn(NO3)2.4H2 Concentration
Sample O/Wt(g) O/Wt(g) of NaOH/Wt(g)
Ni0.99Mn0.01O1-δ 0.099 M/2.878 0.001 M/0.0251 0.2 M/0.8
Ni0.97Mn0.03O1-δ 0.097 M/2.820 0.003 M/0.0753 0.2 M/0.8
Ni0.95Mn0.05O1-δ 0.095 M/2.762 0.005 M/0.1255 0.2 M/0.8
Ni0.93Mn0.07O1-δ 0.093 M/2.704 0.007 M/0.1757 0.2 M/0.8
Ni0.91Mn0.09O1-δ 0.091 M/2.646 0.009 M/0.2259 0.2 M/0.8
manganese nitrate tetra nitrate were added very
slowly to the aqueous solution of sodium hydroxide
kept in a magnetic stirrer. They were mixed thoroughly
@ 1500 rpm at room temperature for about 3 hours.
The pH of the solution was maintained as > 9 by
adding extra sodium hydroxide pellets, if necessary.
The resultant precipitate (Ni(OH)2 + Mn(OH)2) was fil­
tered and washed with 9:1 v/v of water: ethanol mix­
ture many times until all the soluble impurities were
removed completely. Then, the filtered precipitate was
dried at 60°C for 6 hours in a hot air oven. Finally, the
dried product was heat treated at 150, 300, 450, and
600°C for 2 hours each in an atmosphere of air to get
phase pure Ni1-xMnxO1-δ nanostructured materials.
The proposed reaction during the synthesis of Mn-
doped NiO nanostructures is shown in equation – 1.
2.3. For preparing Ni1-xMnxO1-δ (where x = 0.01,
0.03, 0.05, 0.07, 0.09)
ð1 xÞNiðNO3 Þ2 :6H2 O þ xMnðNO3 Þ2 :4H2 O þ 2NaOH
! Ni1 x Mnx O1 δ þ 2NaNO3 þ xH2 O
(1)
2.4. Physico-chemical characterization of
materials
The XRD of the synthesized samples were measured by
Shimadzu XRD6000 X-ray diffractometer using CuKα
radiation model. The lattice parameter were found by
by DOS computer programming. The crystallite size of
the samples was calculated by Debye–Scherrer’s for­
mula (equation – 2) from the concerned XRD patterns.
D ¼ kλ=β cos θ (2)
Where, D = crystallite size, K = numerical constant
(~0.9), λ = the wavelength of X-rays (for Cu Kα radia­
tion, λ = 1.5418 Å), β = full width at half maximum
(FWHM) (in radians), and θ = diffraction angle for the
peak. The theoretical density (DX) of the samples was
calculated as per the equation – 3.
3 were very sharp which indicate that the samples are
Dx ¼ Z:M=N:V g:cm (3)
JOURNAL OF ASIAN CERAMIC SOCIETIES 837
Where, Z = number of chemical species in the unit cell,
M = molecular weight of the sample (g.mol−1),
N = Avogadro’s number (6.022 x 1023 mol−1), and
V = the volume of the crystalline unit cell. Fourier
transform infrared (FT-IR) spectra of the Ni1-xMnxO1-δ
(MNO) were recorded using Bruker IFS 66 V FTIR spec­
trometer using KBr pellet technique in the wave num­
ber range of 400–4000 cm−1. The particle diameter of
the samples was measured by Zetasizer nano ZS90,
Malvern Instruments Ltd, UK. The surface morphology
and the elemental composition of the samples were
studied by means of scanning electron microscope
(SEM), JEOL model JSM-6360 instrument. The HR TEM
of the best performed material was measured by HR
TEM – JEOL JEM 2100 model.
2.5. Electrode preparation and electrochemical
characterization of materials
The active material (Ni0.99Mn0.01O1-δ/Ni0.97Mn0.03O1-δ
/Ni0.95Mn0.05O1-δ/Ni0.93Mn0.07O1-δ/Ni0.91Mn0.09O1-δ),
and poly vinylidene Fluoride (PVDF) binder were mixed
in the weight ratio of 9:1 with the addition of N, N di-
methyl-acetamide solvent (approximately 5–10 ml).
They were stirred thoroughly in a magnetic stirrer set-
up for about 12–16 hours at room temperature until
homogeneous slurry is formed. The slurry was coated
on to a graphite sheet having a specific are of
1 × 1 cm2. A 0.5 mg portion of active material was
used as the loading material.
The electrochemical performance was checked by
using CH1660 C electrochemical work station. The elec­
trochemical measurements such as cyclic voltammetry,
charge-discharge characterization, and impedance
measurements were performed using three electrode
system with Ni1-xMnxO1-δ as the working electrode,
platinum as the counter electrode and saturated calo­
mel electrode (SCE) as the reference electrode with 6.M
potassium hydroxide (KOH) as the electrolyte.
3. Results and discussion
3.1. XRD analysis of Mn-doped NiO
nanostructured materials
Figure 1 presents the XRD patterns obtained on Ni0.99
Mn0.01O1-δ, Ni0.97Mn0.03O1-δ, Ni0.95Mn0.05O1-δ, Ni0.93
Mn0.07O1-δ, and Ni0.91Mn0.09O1-δ nanostructured materi­
als. As seen in Figure 1, all the observed peaks were well
indexed to face-centered cubic (FCC) crystalline struc­
ture of NiO (JCPDS card No. 71–1179). The obtained 2θ
diffraction peaks found in the samples were indexed as
(111), (200), (220), (311), and (222) crystal planes of NiO.
A small peak appeared at 2θ = 18° may be due to the
presence of NiMn2O4 as reported [30]. All other peaks
highly crystalline in nature. The crystallographic
838 G. SRIKESH AND A. S. NESARAJ

Figure 1. XRD patterns obtained on (a) Ni0.99Mn0.01O1-δ, (b) Ni0.97Mn0.03O1-δ, (c) Ni0.95Mn0.05O1-δ, (d) Ni0.93Mn0.07O1-δ, and (e) Ni0.91
Mn0.09O1-δ nanostructured materials.

parameters, such as lattice parameter, unit cell volume, materials. From Figure 2, it was found that a broad
crystallite size and theoretical density of the Mn-doped absorption band present in the region 432.07–492.83 ­
NiO nanostructured materials were calculated and pre­ cm−1 because of NiO bending vibration mode as
sented in Table 2. The lattice constant (=a) values were reported [33]. A peak found in all the samples near at
found to be in range of 4.165–4.173 Å which is in 2500 cm−1 is due to the presence of CO2 as reported
agreement with the reported data for NiO prepared by [34,35].
RF sputtering method (a = 4.17 Å) [31]. The obtained
crystallite size and theoretical density values of Mn-
3.3. Particle size analysis of Mn-doped NiO
doped NiO were also in accordance with our previously
nanostructured materials
reported data for undoped NiO synthesized by combus­
tion route [32]. Light scattering method was used to measure the
particle size of the Mn-doped NiO nanostructured
materials. About 10 mg of sample was sonicated in
3.2. FTIR analysis of Mn-doped NiO 100 ml of double distilled water for 20–30 minutes
nanostructured materials before the analysis. The particle size curves obtained
on Mn-doped NiO nanostructured materials are
Figure 2 presents the FTIR spectra obtained on Ni0.99
shown in Figure 3. From the Figure, it was found
Mn0.01O1-δ, Ni0.97Mn0.03O1-δ, Ni0.95Mn0.05O1-δ, Ni0.93
that the particle diameter of the samples is present
Mn0.07O1-δ, and Ni0.91Mn0.09O1-δ nanostructured
in the range of 181.8–687.4 nm. Maximum intensity of
particles was found in nm range. It was noticed that
Table 2. XRD data obtained on Mn-doped NiO nanostructured the high temperature calcination process enhanced
materials. the particle size in few particles. Further, the particle
Unit size of the samples was enhanced with respect to the
Unit cell cell Crystallite Theoretical formation of impurity phase of NiMn2O4 as found in
Crystal parameter volume size density
Sample structure “a” (Å) (Å3) (nm) (g/cc) XRD data. The particle characteristics of Mn-doped
Standard NiO Cubic 4.178 72.92 – 6.80 NiO nanostructured materials are presented in
(JCPDS No. (F.C.) Table 3.
71–1179)
Ni0.99Mn0.01O1-δ Cubic 4.173 72.66 16.4 6.82
(F.C.)
Ni0.97Mn0.03O1-δ Cubic 4.171 72.56 14.7 6.82 3.4. EDAX analysis of Mn-doped NiO
(F.C.) nanostructured materials
Ni0.95Mn0.05O1-δ Cubic 4.165 72.25 14.67 6.84
(F.C.)
Ni0.93Mn0.07O1-δ Cubic 4.171 72.56 14.7 6.81
The EDAX spectra obtained on Mn-doped NiO-based
(F.C.) nanostructured materials are reported in the
Ni0.91Mn0.09O1-δ Cubic 4.165 72.25 16.4 6.83 Figure 4. The elemental composition data obtained
(F.C.)
on Mn-doped NiO nanostructured materials are
 JOURNAL OF ASIAN CERAMIC SOCIETIES 839

Figure 2. FTIR spectra obtained on (a) Ni0.99Mn0.01O1-δ, (b) Ni0.97Mn0.03O1-δ, (c) Ni0.95Mn0.05O1-δ, (d) Ni0.93Mn0.07O1-δ, and (e) Ni0.91
Mn0.09O1-δ nanostructured materials.

Figure 3. Particle size analysis patterns obtained on (a) Ni0.99Mn0.01O1-δ, (b) Ni0.97Mn0.03O1-δ, (c) Ni0.95Mn0.05O1-δ, (d) Ni0.93Mn0.07
O1-δ, and (e) Ni0.91Mn0.09O1-δ nanostructured materials.

Table 3. Particle characteristics data obtained on Mn-doped 3.5. SEM studies obtained on Mn-doped NiO
NiO nanostructured materials.
nanostructured materials
% Diameter Average particle size
Sample Intensity (nm) (nm)
The morphology of the Mn-doped NiO samples are
Ni0.99Mn0.01O1-δ 100 122.6 687.4
Ni0.97Mn0.03O1-δ 100 163.9 198.1 characterized using SEM. The SEM images obtained on
Ni0.95Mn0.05O1-δ 100 155.5 181.8 Ni0.99Mn0.01O1-δ, Ni0.97Mn0.03O1-δ, Ni0.95Mn0.05O1-δ, Ni0.93
Ni0.93Mn0.07O1-δ 100 146.2 261.8
Ni0.91Mn0.09O1-δ 100 419.2 656.2 Mn0.07O1-δ, and Ni0.91Mn0.09O1-δ are presented in Figure
5. SEM images clearly reveal a well defined joint-cube
shaped grains in the samples. These cube shaped grains
presented in Table 4. From the data, it was clearly may be composed of nanoparticles. It is noteworthy to
understood that the elements are present in appro­ mentioning that the SEM image of all the samples
priate level as per the stoichiometric composition in shows a similar kind of morphology. This confirms that
the samples. the different level of Mn doping on NiO does not affect
840 G. SRIKESH AND A. S. NESARAJ

Figure 4. EDAX spectra obtained on (a) Ni0.99Mn0.01O1-δ, (b) Ni0.97Mn0.03O1-δ, (c) Ni0.95Mn0.05O1-δ, (d) Ni0.93Mn0.07O1-δ, and (e) Ni0.91
Mn0.09O1-δ nanostructured materials.

Table 4. Elemental composition (EDAX) data obtained on Mn- nanoparticle was analyzed with HR-TEM. HR-TEM
doped NiO nanostructured materials. photographs obtained on Ni0.95Mn0.05O1-δ are
Atomic weight % of the elements indicted in Figure 6. From the Figure 6, it was
Samples Ni Mn O found that the diameter of the particles is present
Ni0.99Mn0.01O1-δ 53.35 0.71 45.95
Ni0.97Mn0.03O1-δ 51.52 1.25 47.23
in the range of 2–20 nm. The unidirectional fringe
Ni0.95Mn0.05O1-δ 48.90 2.23 48.88 patterns of Ni0.95Mn0.05O1-δ clearly revealed poly­
Ni0.93Mn0.07O1-δ 50.35 3.56 46.08 crystalline behavior of the sample. The SAED pat­
Ni0.91Mn0.09O1-δ 44.77 4.28 50.96
tern of Ni0.95Mn0.05O1-δ also showed the presence of
clear diffraction rings in the material which also
confirmed the polycrystalline behavior of the sam­
the morphology in a greater extent. Aggregation found
ple. The d spacing values are in agreement with the
in the samples may due to high temperature calcination
XRD patterns and reported data on NiO [36].
process as discussed in particle size analysis. The SEM
image clearly indicated the presence of nanosized
grains in the range of 30.04–59.16 nm in the samples. 3.7. Electrochemical studies obtained on Mn-
doped NiO nanostructured materials
The electrochemical characteristics of the Mn-doped
3.6. HR-TEM studies obtained on Ni0.95Mn0.05O1-δ
NiO nanostructured electrode materials for electroche­
nanostructured materials
mical capacitors were studied by cyclic voltammetry
To know more about the nanostrucural characteris­ (CV), galvanostatic charge – discharge and electroche­
tics in a more detailed manner, Mn-doped NiO mical impedance measurements in 6 M KOH

Figure 5. SEM images obtained on (a) Ni0.99Mn0.01O1-δ, (b) Ni0.97Mn0.03O1-δ, (c) Ni0.95Mn0.05O1-δ, (d) Ni0.93Mn0.07O1-δ, and (e) Ni0.91
Mn0.09O1-δ nanostructured materials.
electrolyte solution. It was reported that NiO-based
electrodes in alkaline electrolyte store charges at the
electrode/electrolyte interface (electric double layer)
and electrode surface (through redox reactions) [37].
3.8. Cyclic voltammetry (CV) studies
Figure 7 displays the CV curves of Ni0.99Mn0.01O1-δ,
Ni0.97Mn0.03O1-δ, Ni0.95Mn0.05O1-δ, Ni0.93Mn0.07O1-δ, and
Ni0.91Mn0.09O1-δ nanostructured electrode materials for
different scan rates. The capacitive behavior of materi­
als can be studied by CV technique since it is consid­
ered as a powerful electrochemical tool. The CV curves
shown in Figure 7 revealed the presence of rectangular
shape in both anodic and cathodic directions which
shows the occurrence of ideal capacitive behavior in all
the samples. Also, all CV curves are similar to each
other with small variations which may be due to dif­
ferent dopant levels of Mn on NiO as reported [38]. The
specific capacitance values were increased for the
JOURNAL OF ASIAN CERAMIC SOCIETIES 841
samples upto the dopant level of 5 mol % after which
the values were decreased especially for 7 mol% and
9 mol % because of the formation of sharp insulating
NiMn2O4 phase as reported in XRD data.
3.9. Capacitive retention studies
Figure 8 shows the capacitance retention graph
obtained on Ni0.95Mn0.05O1-δ since this composition
conducts high current when compared with other
compositions. Because of this, this Ni0.95Mn0.05O1-δ
was subjected to run for 1000 cycles in CV at a scan
rate 100 mVS−1. The studies obtained with Ni0.95
Mn0.05O1-δ electrode revealed that the capacity
retention % increases upto 200 cycles after that
the capacitance retention % reduces upto 500 cycles
and then the capacity rention % again raises. This
shows that Ni0.95Mn0.05O1-δ electrode material has
stable capacitance behavior up to 1000 cycles with
slight deviations during the cycling process.
842 G. SRIKESH AND A. S. NESARAJ
Figure 6. HRTEM images (a,b, and c) and the selected area electron diffraction (SAED) pattern (d) obtained on Ni0.95Mn0.05O1-δ
nanostructured material.
Therefore, this composition (Ni0.95Mn0.05O1-δ) may
be suitable as an electrode for multiple cycles in
electrochemical supercapacitors in alkaline medium.
3.10. Galvanostatic charge – discharge studies
The galvanostatic charge-discharge curves obtained
on Ni0.99Mn0.01O1-δ, Ni0.97Mn0.03O1-δ, Ni0.95Mn0.05O1-δ,
Ni0.93Mn0.07O1-δ, and Ni0.91Mn0.09O1-δ nanostructured
electrode materials are shown in the Figure 9 in the
potential window of 0.3 V at various current densities
(0.5, 1, 1.5, 2, and 2.5 Ag−1) in 6 M KOH electrolyte
medium. From these curves, it was clear that all the
obtained graphs are in triangular shapes which is indi­
cative of the capacitive behavior of the electrode mate­
rials and these results are in agreement with the CV
data. The specific capacitance can be calculated from
according to the following equation-4:
1 [39]. The appearance of semi-circle in the high fre­
Cs ¼ I:Δt=m:ΔVFg
Where I is the discharge current (A), Δt is the dis­
charge time (s), m is the mass of the electro active
material (g), and ΔV is the potential difference (V).
The obtained specific capacitance of the prepared
electrode materials Ni0.99Mn0.01O1-δ, Ni0.97Mn0.03O1-δ,
Ni0.95Mn0.05O1-δ, Ni0.93Mn0.07O1-δ, and Ni0.91Mn0.09O1-δ
were found to be 180.5 Fg−1, 278.6 Fg−1, 369.6 Fg−1,
286.5 Fg−1, and 157.9 Fg−1 respectively. As reported in
CV, the specific capacitance values of first three sam­
ples i.e. upto 5 mol % Mn dopant levels were increased
and for the remaining samples, the specific capaci­
tance values were decreased i.e. beyond 5 mol %
dopant levels because of the formation of sharp insu­
lating phase NiMn2O4.
3.11. Electrochemical impedance spectroscopy
(EIS) studies
The electrochemical impedance curves obtained on on
Ni0.99Mn0.01O1-δ, Ni0.97Mn0.03O1-δ, Ni0.95Mn0.05O1-δ, Ni0.93
Mn0.07O1-δ, and Ni0.91Mn0.09O1-δ nanostructured elec­
trode materials are shown in the Figure 10. From the
Figure 10, it was understood that all the samples exhib­
ited distorted semi circle in the high frequency region
and a straight line and a smaller Warburg portion in
between the semicircle and slope of the line as reported
(4)
quency portion on the real axis reveals the charge-
transfer resistance, which shows that the electrolyte
ions are reacted completely with electroactive materials
and indication of the conductivity of the electrodes. The
straight line appears at low frequency region at an
angle of almost 45º exhibits “Warburg resistance” that
indicates the ion diffusion resistance of the charged
ions in the presence of Mn-doped NiO. The presence
of straight line in the low frequency region reveals the
 JOURNAL OF ASIAN CERAMIC SOCIETIES 843

Figure 7. CV curves obtained on (a) Ni0.99Mn0.01O1-δ, (b) Ni0.97Mn0.03O1-δ, (c)Ni0.95Mn0.05O1-δ, (d) Ni0.93Mn0.07O1-δ, and (e) Ni0.91
Mn0.09O1-δ nanostructured electrode materials at various scan rates ranging from 10–100 mVs−1 in 6 M KOH electrolyte and (f) CV
of the electrode materials at the scan rate of 100 mVs−1.

Figure 8. Capacitance retention graph of Ni0.95Mn0.05O1-δ electrode material obtained by CV upto 1000 cycles at the scan rate of
100mVs−1 in the potential window of 0.3 to −0.5 V.
844 G. SRIKESH AND A. S. NESARAJ

Figure 9. Galvanostatic charge-discharge curves obtained on (a) Ni0.99Mn0.01O1-δ, (b) Ni0.97Mn0.03O1-δ, (c) Ni0.95Mn0.05O1-δ, (d) Ni0.93
Mn0.07O1-δ, (e) Ni0.91Mn0.09O1-δ at various current densities ranging from 0.5 to 2.5 Ag−1 in 6 M KOH electrolyte, and (f) overall
comparison of the electrode materials (S-1 to S-5 is sample a–e) at 0.5 Ag−1 current density.

ideal capacitance behavior of the Mn-doped NiO elec­
trode materials as reported in the literature [40,41].
4. Conclusions
Facile chemical precipitation can be used effectively to
prepare Ni0.99Mn0.01O1-δ, Ni0.97Mn0.03O1-δ, Ni0.95Mn0.05O1-
δ, Ni0.93Mn0.07O1-δ, and Ni0.91Mn0.09O1-δ nanostructured
electrode materials. The XRD data of Mn-doped NiO
was well matched with the reported JCPDS data for NiO
(JCPDS No. 71–1179) and the all the samples were
indexed into FCC crystalline structure. The crystallite size
of the samples was found in the range of 14.6–16.4 nm.
The presence of metal-oxygen bond was confirmed by
FTIR data from the broad band found at 432.07–
492.83 cm−1. Particle size analysis showed that the
particles are in the range of 181.8–687.4 nm. SEM data
revealed that the presence of joint cubic-like grains in the
range of 30.04–59.16 nm. EDAX showed that the pre­
sence of appropriate elements in the samples with
expected atomic wt.% as per stoichiometric composition.
HRTEM data of Ni0.95Mn0.05O1-δ presents a clear structure
in the range of 2–20 nm with polycrystalline behavior.
SAED pattern confirmed the presence of diffraction rings
in accordance with the XRD data. Excellent capacitive
behavior of the materials was confirmed by their rectan­
gular CV curves. From the galvanostatic charage–dis­
charge (CD) studies, it was noticed that the sample
Ni0.95Mn0.05O1-δ resulted with maximum specific capaci­
tance value (396.6 Fg−1) among all other samples. The EIS
of the all the samples resulted with a distorted semicircle
in high frequency region and an inclined line in low
 JOURNAL OF ASIAN CERAMIC SOCIETIES 845

Figure 10. Electrochemical impedance spectra (EIS) obtained on (a) Ni0.99Mn0.01O1-δ, (b) Ni0.97Mn0.03O1-δ, (c) Ni0.95Mn0.05O1-δ, (d)
Ni0.93Mn0.07O1-δ, (e) Ni0.91Mn0.09O1-δ nanostructured electrode materials, and (f) Comparative EIS spectra obtained on Mn-doped
NiO nanostructured electrode materials.

frequency region. The presence of straight line in the low Disclosure statement
frequency region revealed the ideal capacitance behavior
No potential conflict of interest was reported by the
of the Mn-doped NiO electrode materials. From the authors.
results, it is proposed that Mn-doped NiO-based nanos­
tructured materials can be considered as alternate elec­
trode materials for applications in electrochemical Funding
supercapacitors.
This work was supported by the University Grants
Commission [No. F./2013-14/RGNF-2013-14D-O BC-TAM
Acknowledgments -56465].

ASN thanks Karunya Institute of Technology and Sciences for

promoting nanomaterials electrochemistry research activity in
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