Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Surfactant induced increase in supercapacitor activity for nickel

manganese oxide
Aparna Rai, Maurya Gyanprakash ⇑, Chandresh Kumar Rastogi ⇑, Biswajit Mandal
Centre for Advanced Studies, Lucknow 226031, India

a r t i c l e i n f o a b s t r a c t

Article history: In this work, we are reporting the impact of ligand on the synthesis and electrochemical properties of
Available online xxxx nickel manganese oxide nanoparticles. We have prepared bare and cetyltrimethylammonium bromide
(CTAB) coated nickel manganese oxide nanoparticles using the hydrothermal method at 120 °C. The
Keywords: comparative analysis of these two samples showed that the CTAB coated nickel manganese oxide
Nickel Manganese Oxide (NMO) (NMO) displays superior electrochemical characteristics due to the presence of a higher number of active
Electrochemical Ni2+ sites. Further, the galvanostatic charge and discharge (GCD) analysis for both bare and CTAB coated
Galvanic charge discharge (GCD)
samples showed an increase in the discharging time with the number of GCD cycles. But the increased
discharging time is higher for the CTAB coated nanoparticles which are attributed to an increase in the
number of active Ni2+ sites in this case. In addition, the physicochemical processes before and after
cycling showed a decrease in the adsorption resistance, which is further attributed to an increase in
activity with the cycling. Therefore, it is anticipated that the surfactant presents at the surface of the
nano-catalyst and the cycling alters the morphology and number of active sites.
Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Confer-
ence on Advances in Materials Science, Communication and Microelectronics.

1. Introduction
According to the reports, the global population is expanding
quickly and the augmentation of the populace impacts the envi-
ronment and the world’s temperature by consuming fossils ener-
gizing, chopping down timberlands, and cultivating live stocks.
Therefore, it is indispensable to take action to preserve our natural
resources and regulate global energy consumption. Since almost
everything around us requires energy and people’s inordinate uti-
lization of petroleum derivatives has quickly drained it while the
deteriorating climatic contamination is making long haul and
potentially irreversible harm to our atmosphere. All the while, it
is critical to guarantee admittance to energy for the financial turn
of events and to improve the superiority of life in rising countries
[1]. To fulfil this surplus energy demand in an environmentally
manner, the other alternative approaches based on renewable
energy resources (e.g., solar energy harvesting, photo-catalysis,
electro-catalysis, etc.) should be developed. At present, various
⇑ Corresponding authors.
E-mail addresses: gyan@cas.res.in (M. Gyanprakash), chandresh@cas.res.in
(C. Kumar Rastogi), biswajit@cas.res.in (B. Mandal).
efficient energy storage devices are available in the market such
as batteries, fuel cells, regular capacitors, hydrogen storage sys-
tems, electrochemical capacitors, and so on. Each device have dif-
ferent storage mechanisms with diverse applications [2].
A standard capacitor comprises two parallel plates isolated by a
dielectric medium stores charge between the plates as electric
potential energy in the microfarad range. Conversely, a dielectric
is supplanted by a conductive medium (i.e., electronic/ionic) to
deliver high-power abilities (>10 kW/kg) in the mill farad range.
Another class of energy storing device gadgets are batteries due
to their higher energy density. But it is also having some limita-
tions like low power density, phase transformation, and when
worked at high rates it creates heat that is extremely unsafe [3].
Electrochemical capacitors, or supercapacitors or ultracapaci-
tors, overcome any issues between high-power capacitors and
high-energy batteries. The phenomenon of storing charge in an
electrochemical capacitor is the same as of traditional capacitors
however thousands of farads can be stored by them. There are
three main types of supercapacitors which are as follows; 1) elec-
trochemical double layer capacitor (EDLC), 2) hybrid supercapaci-
tors and 3) pseudo-capacitors. The basic difference between all
three is the principle behind the charge storage mechanism. EDLC

https://doi.org/10.1016/j.matpr.2022.08.150
2214-7853/Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Advances in Materials Science, Communication and
Microelectronics.

Please cite this article as: A. Rai, M. Gyanprakash, C. Kumar Rastogi et al., Surfactant induced increase in supercapacitor activity for nickel manganese oxide,
Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2022.08.150
A. Rai, M. Gyanprakash, C. Kumar Rastogi et al. Materials Today: Proceedings xxx (xxxx) xxx

consists of high-power densities and is highly reversible and also
stores charges with the help of non-faradic processes. While
pseudo-capacitors have higher energy densities but are lower than
the batteries and are less reversible in nature as well as store
charges by the faradic process. Lastly, a hybrid capacitor which is
the arrangement of both pseudo-capacitor and EDLC increases both
power and energy densities [4].
The best electrode materials such as RuO2 and IrO2 demon-
strated high cycle capacity, high value of specific capacitance for
SCs. The value of the capacitance can arrive up to 720F/g that has
been ascribed on the way in the direction of the close designs of
hydrous ruthenium oxide with jumbled structure holding simple
vehicle pathways [5]. In recent times, many researchers build up
various substitution for IrO2 and RuO2, such as MnOx, CoOx, NiOx,
and so forth, to bring down the cost of electrode material utilizing
environmentally well-disposed materials [6]. However, lower
specific capacitance has been recorded with these transition metal
oxides. For pseudo-capacitors nickel oxide expresses an impression
of having a capable electrode material because of their amazing
electrochemical exhibition, naturally sincere and insignificant cost
[7].
Throughout the years’ many researchers have worked on nickel
manganese-based electrode material for supercapacitor applica-
tions. Sumanta Sahoo et al. fabricated NiMn2O4 a better-quality
electrode material using a hydrothermal method. They reported a
757F/g specific capacitance value at 1 A/g current density and
depicted 93 % of maintenance of specific capacitance after 2000
cycles [8]. While Hongmei Wei et al. fabricated nanostructured spi-
nel NiMn2O4 arrays for superior execution of supercapacitors and
additionally explored binder-free electrodes. They observed
662.5F/g and 370.5F/g specific capacitances at 1 A/g current den-
sity after comparison with Mn2O3 in different electrolytes in differ-
ent electrolytes in the three-electrode framework. On nickel foam
substrate NiMn2O4 has shown superior presentation which recom-
mended that for supercapacitors it would become potential elec-
trode material [9].
Surfactants are natural mixtures made out of two chemical
parts leaves behind various polarities, a head bunch with a partial-
ity for polar stages, and a tail bunch that is drawn to non-polar
stages. Because of their primary uniqueness, surfactants can be
broadly used to decrease the surface and interfacial strain between
at least two stages. Their propensity to produce self-collected
structures in the arrangement can likewise prompt the develop-
ment of micelles with breadths going from nanometres to
micrometres. The amphiphilic idea of surfactants makes them rea-
sonable for use in various modern items, including medications,
consumption inhibitors for safeguarding steel and other destruc-
tive metals [10].
In this work, we modulated the size of the nickel manganese
oxide nanoparticles with the help of CTAB surfactant. The reduced
size of nanoparticles showed the high supercapacitor activity due
the presence of Ni2+ state nickel. Impedance analysis further sup-
ports the above analysis with the help of adsorption resistance
and adsorption capacitance.
at 1:1 in the solution. Next, a 0.5 mM of NaOH in 10 ml de-ionized
water were dissolved and then the solution was added drop wise
and suspension suddenly appeared with a light green colour pre-
cipitate. Further, continuous stirring was done at room tempera-
ture for 4 h and the solution turned light brown. Thereafter the
solution was kept in a Teflon-coated stainless-steel autoclave for
120 °C for 20 h, after which it was centrifuged and washed with
DI water and absolute ethanol 3–4 times, then dried at 80 °C for
3 h. The obtained resultant product was calcinated in a muffle fur-
nace at 300 °C for 3 h. Similarly, CTAB coated nickel manganese
oxide sample has been prepared by following the same procedure
but only with the addition of 1 mM CTAB with 2.5 mM nickel
nitrate hexahydrate (Ni (NO3)2
6H2O) and 2.5 mM manganese
nitrate tetrahydrate (MnN2O6
4H2O) into 50 ml DI water.
2.1. Electrode Preparation:
Carbon paper was used as a substrate to deposit the material.
We washed the substrate several times using DI water, ethanol,
and acetone each for 10 min and thereafter kept it for drying.
5 mg nanoparticles were dispersed in 1 ml ethanol using sonica-
tion for 15 min. 5 lL nafion was added and mixed well-using son-
ication before transferring 100 lL to the pre-cleaned carbon paper.
Nanoparticles loaded carbon substrates were then dried in an oven
for 2 h.
3. Results and discussion
3.1. Physical Characterisation
Fig. 1 shows the X-ray diffraction (XRD) patterns of bare and
CTAB coated nickel manganese oxide powder samples. The pat-
terns depict the presence of three peaks at  37.5, 43.2, and 63.5
which are attributed to 311, 400, and 440 planes of cubic nickel
manganese oxide [12]. The crystallite size has been calculated for
both the sample using the Debye-Scherrer formula given below:
0:9k
D¼
bCosh
Where k, h, and b correspond to the wavelength of X-ray radia-
tion, half of Bragg diffraction angle of the diffraction peak, and full
width at half maximum (FWHM), respectively. The estimated crys-
tallite sizes for bare and CTAB coated samples are found to be 5.6
and 7.6 nm, respectively.

2. Experimental methods:

We have prepared two samples by hydrothermal method viz.,

[11]; (i) bare nickel manganese oxide, (ii) CTAB coated nickel man-
ganese oxide. For the preparation of undoped bare nickel man-
ganese oxide, firstly a 2.5 mM aqueous solution of nickel nitrate
hexahydrate (Ni (NO3)2
6H2O), and 2.5 mM manganese nitrate
tetrahydrate (MnN2O6
4H2O) were dissolved into 50 ml de-
ionized (DI) water under continuous stirring. The ratio of nickel Fig. 1. XRD patterns of bare and CTAB coated nickel manganese oxide nanoparticles
nitrate hexahydrate and manganese nitrate tetrahydrate was kept (NMO).

2
A. Rai, M. Gyanprakash, C. Kumar Rastogi et al.
Fig. 2. Scanning electron microscopy (SEM) images of (a) bare and (b) CTAB coated NMO nanoparticles.
Fig. 2 shows the SEM image of bare and CTAB coated
nanoparticles.SEM image of bare particles shown in Fig. 2(a)
depicts the formation of disc shape particles of nickel manganese
oxide, while the SEM image of CTAB coated particles shown in
Fig. 2(b) exhibited the presence of relatively smaller size particles.
3.2. Electrochemical characterisation
Fig. 3 shows the CV curves of nickel manganese oxide with and
without CTAB surfactant recorded at the scan rate of 5 mV/s. CTAB
coated nickel manganese oxide shows a peak around 0.4 V, while
in bare nickel manganese oxide the intensity of peak around
0.4 V is low. The peak around 0.4 V corresponds to Ni2+/Ni3+ con-
version, and in the reverse scan, the peak around 0.15 V corre-
sponds to Ni3+/Ni2+ conversion [13]. The intensity of the peak is
directly proportional to the concentration of Ni2+ in the sample.
On comparing the CV curve of both samples, the Ni2+ concentration
is higher in CTAB coated nickel manganese oxide compared to the
bare nickel manganese oxide sample. It is due to the effect of the
surfactant in the system, the presence of surfactant reduces the
particle size of nickel manganese oxide as shown previously in
the SEM image. The reduction in particle size increases the number
of active sites, which increases the current density as shown by the
peak current in CTAB coated nickel manganese oxide. On the other
hand, in the bare sample, the low current density is due to the high
particle size of nickel manganese oxide. Thus, the reduction in par-
ticle size increases the Ni2+ present at the surface. The increased
Fig. 3. Cyclic voltammetry (CV) curves of bare and CTAB coated nickel manganese
oxide. The CV curves show the presence of Ni2+/Ni3+ oxidation peak around 0.4 V v/s
Ag/AgCl.
3
Materials Today: Proceedings xxx (xxxx) xxx
Ni2+ at the surface can be utilized for the supercapacitor
application. For this, we did the galvanostatic charge–discharge
(GCD) analysis for both samples.
Fig. 4 shows the GCD analysis of bare and CTAB coated nickel
manganese oxide. All GCD analysis is done at 1A/g charging and
discharging rate. From Fig. 4, the CTAB coated particles show an
increase in the charging and discharging time with the number
of cycles. It is due to the opening of the new active sites. On the
other hand, the bare nickel manganese oxide showed a slight
increase in charging and discharging time, which showed the low
number of active sites opening. The comparison of the charging
and discharging times of both samples showed the higher charging
and discharging time of the CTAB coated nickel manganese oxide
sample. It is due to the presence of a high number of active sites
caused by surfactant via the reduction in the particle size as dis-
cussed in the CV and SEM section. The continuous increase in
charging and discharging sample shows the sample is still active
and can be cycled further till their charging and discharging time
reduces. Thus, the CTAB coated nickel manganese oxide sample
showed good activity towards the supercapacitor charging/dis-
charging application. The activity of the sample depends on the
physicochemical processes occurring at the sample/electrolyte
interface; to explore this we did the impedance analysis.
Fig. 5 shows the Nyquist plot of all samples before and after
GCD analysis. It shows the presence of one semicircle followed
by the tail at the lower frequency part. The semicircle part shows
the effect of double-layer capacitance (Cdl) with the adsorption
resistance (Ra), while the low-frequency part shows the effect of
Fig. 4. Galvanostatic charge discharge analysis of nickel manganese oxide and CTAB
coated nickel manganese oxide with number of cycles. The curves show the
increase in cycling time for CTAB coated nickel manganese oxide.
A. Rai, M. Gyanprakash, C. Kumar Rastogi et al.
Fig. 5. Nyquist plot for fresh nickel manganese oxide and CTAB coated nickel
manganese oxide, 500 cycled nickel manganese oxide, and CTAB coated nickel
manganese oxide shows the decrease in the adsorption resistance for both samples.
Table 1
Tabulated values of the adsorption resistance, adsorption capacitance and double
layer capacitance obtained by the equivalent circuit fitting to Nyquist plot shown in
Fig. 5.
Sample Ra (X- Ca
cm2) (mF)
Fresh nickel manganese oxide (NMO) 52.8 46
500 cycled nickel manganese oxide(NMO) 41.7 2449
Fresh CTAB coated nickel manganeseoxide 37.8 512
(NMO)
500 cycled CTAB coated nickel manganese 22.6 3291
oxide (NMO)
the adsorption capacitance (Ca) (pseudo-capacitance) [14]. Thus,
we fitted the Nyquist plot with the (Rs(RaCdl)Ca) circuit, where Rs
is the solution resistance between the sample and the reference
electrode [15]. Table 1 shows the typical values of the circuit ele-
ments. From Table 1, the CTAB coated nickel manganese oxide
shows a higher pseudo-capacitance before and after cycling than
the bare nickel manganese oxide. It is due to the high Ni2+ present
at the surface which is caused by the surfactant synthesized low
nickel manganese oxide particles. Also, the double-layer capaci-
tance for CTAB coated nickel manganese oxide possesses a higher
value before and after the cycling. The higher double-layer capac-
itance for CTAB coated nickel manganese oxide is attributed to the
low particle size of nickel manganese oxide in the presence of CTAB
surfactant. In a similar mode, the adsorption resistance is higher in
the bare sample than CTAB coated nickel manganese oxide sample.
The adsorption resistance is attributed to the adsorption reaction
rate occurring at the active site. The lower Ra attributes to the
higher reaction rate and vice versa. Thus, from impedance analysis,
the effect of lower particle size in the CTAB modulated nickel man-
ganese oxide produces a high number of Ni2+ sites which enhances
the charge storing capacity.
4. Conclusions
The activity of the supercapacitor catalyst can be enhanced by
increasing the number of active sites. The number of active sites
can be enhanced via the nano-structuring of the sample. The CTAB
surfactant reduces the particle size of nickel manganese oxide
chemically. The obtained sample of CTAB coated nickel manganese
Materials Today: Proceedings xxx (xxxx) xxx
oxide showed increased supercapacitor activity, which is
attributed to the reduced particle size, enhancing the Ni2+ present
at the surface. The GCD analysis confirmed that the CTAB coated
nickel manganese oxide possesses a higher charge storage capacity
due to the presence of a higher number of the active site (Ni2+) giv-
ing rise to enhanced charging and discharging time. Finally, the
impedance analysis showed the cycled sample possess a higher
pseudo-capacitance due to the presence of Ni2+ at the surface.
Thus, low particle size and high Ni2+ in CTAB coated nickel man-
ganese oxide showed higher activity.
Data availability
Data will be made available on request.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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