processes

Article
Electrochemical Performance of Aluminum Doped
Ni1−xAlxCo2O4 Hierarchical Nanostructure: Experimental and
Theoretical Study
Deepa Guragain 1 , Romakanta Bhattarai 1 , Jonghyun Choi 2 , Wang Lin 2 , Ram Krishna Gupta 2 , Xiao Shen 1 ,
Felio A. Perez 1 and Sanjay R. Mishra 1, *

1 Department of Physics and Materials Science, The University of Memphis, Memphis, TN 38152, USA;
[email protected] (D.G.); [email protected] (R.B.); [email protected] (X.S.);
[email protected] (F.A.P.)
2 Department of Chemistry, Pittsburg State University, Pittsburg, KS 66762, USA;
[email protected] (J.C.); [email protected] (W.L.); [email protected] (R.K.G.)
* Correspondence: [email protected]

Abstract: For electrochemical supercapacitors, nickel cobaltite (NiCo2 O4 ) has emerged as a new
energy storage material. The electrocapacitive performance of metal oxides is significantly influenced
by their morphology and electrical characteristics. The synthesis route can modulate the morpho-
logical structure, while their energy band gaps and defects can vary the electrical properties. In
addition to modifying the energy band gap, doping can improve crystal stability and refine grain



size, providing much-needed surface area for high specific capacitance. This study evaluates the


electrochemical performance of aluminum-doped Ni1−x Alx Co2 O4 (0 ≤ x ≤ 0.8) compounds. The
Citation: Guragain, D.; Bhattarai, R.; Ni1−x Alx Co2 O4 samples were synthesized through a hydrothermal method by varying the Al to
Choi, J.; Lin, W.; Gupta, R.K.; Shen, X.; Ni molar ratio. The physical, morphological, and electrochemical properties of Ni1−x Alx Co2 O4 are
Perez, F.A.; Mishra, S.R. observed to vary with Al3+ content. A morphological change from urchin-like spheres to nanoplate-
Electrochemical Performance of
like structures with a concomitant increase in the surface area, reaching up to 189 m2 /g for x = 0.8,
Aluminum Doped Ni1−x Alx Co2 O4
was observed with increasing Al3+ content in Ni1−x Alx Co2 O4 . The electrochemical performance of
Hierarchical Nanostructure:
Ni1−x Alx Co2 O4 as an electrode was assessed in a 3M KOH solution. The high specific capacitance
Experimental and Theoretical Study.
of 512 F/g at a 2 mV/s scan rate, 268 F/g at a current density of 0.5 A/g, and energy density of
Processes 2021, 9, 1750. https://
doi.org/10.3390/pr9101750
12.4 Wh/kg was observed for the x = 0.0 sample, which was reduced upon further Al3+ substitution.
The as-synthesized Ni1−x Alx Co2 O4 electrode exhibited a maximum energy density of 12.4 W h kg−1
Academic Editor: Domenico Frattini with an outstanding high-power density of approximately 6316.6 W h kg−1 for x = 0.0 and an energy
density of 8.7 W h kg−1 with an outstanding high-power density of approximately 6670.9 W h kg−1
Received: 3 August 2021 for x = 0.6. The capacitance retention of 97% and 108.52% and the Coulombic efficiency of 100% and
Accepted: 22 September 2021 99.24% were observed for x = 0.0 and x = 0.8, respectively. First-principles density functional theory
Published: 30 September 2021 (DFT) calculations show that the band-gap energy of Ni1−x Alx Co2 O4 remained largely invariant
with the Al3+ substitution for low Al3+ content. Although the capacitance performance is reduced
Publisher’s Note: MDPI stays neutral upon Al3+ doping, overall, the Al3+ doped Ni1−x Alx Co2 O4 displayed good energy, powder density,
with regard to jurisdictional claims in
and retention performance. Thus, Al3+ could be a cost-effective alternative in replacing Ni with the
published maps and institutional affil-
performance trade off.
iations.

Keywords: hydrothermal; Ni1−x Alx Co2 O4 ; electrochemical; cyclic voltammetry; the specific capacitance

Copyright: © 2021 by the authors.

Licensee MDPI, Basel, Switzerland.
1. Introduction
This article is an open access article
distributed under the terms and
Researchers are actively engineering an efficient, clean, and cost-effective electrode for
conditions of the Creative Commons
better electrochemical performance [1]. Conventional capacitors and batteries are broadly
Attribution (CC BY) license (https://
exploited by energy storage devices [2]. Previously, secondary batteries were suitable
creativecommons.org/licenses/by/ electrical energy storage devices, but they were not very satisfactory because of their
4.0/). smaller power density, presence of toxic waste substances, and shorter lifetime [3]. On the

Processes 2021, 9, 1750. https://doi.org/10.3390/pr9101750 https://www.mdpi.com/journal/processes

Processes 2021, 9, 1750 2 of 17

other hand, conventional capacitors display high power density compared to a battery,
but because of their lower energy density, researchers are interested in advanced energy
storing devices that mitigate the demerits of both battery and capacitor. The energy gap
between batteries and capacitors can be bridged by a supercapacitor (SC) [4]. SC electrode
materials must have a large specific surface area, controlled porosity, high electronic con-
ductivity, suitable electroactive sites, high thermal stability, low raw material costs, and
ease of manufacture [5]. Supercapacitors have recently attracted attention due to their
quick charging/discharging, high power density, wide range of working temperatures,
high efficiency, and extended lifespans [6]. SCs are of three types: (i) electrical double layer
capacitance (EDLCs) examples are highly porous carbon materials, (ii) pseudocapacitor
(PCs) examples are transition metal oxides and conducting polymers, and (iii) hybrid
capacitor examples are battery type hybrid devices such as the lithium-ion capacitor [7].
EDLCs store electrical energy in the electric double layer, which occurs at the interface
between the electrode’s active material and the electrolyte by an electrostatic accumula-
tion process. In EDLCs, energy density becomes lower (between 3 and 6 Wh/Kg), and
specific capacitance is restricted because of the specific surface area of the active electrode
material [8]. The ionic double layer’s fast diffusion provides a very rapid discharge profile
and hence high-power densities. PCs, on the other hand, are caused by reversible Faradaic
processes at the electrode surface, which cause charge storage [9]. Moreover, in PCs, the
electrochemical process occurs near the surface of the active electrode material. Thus, it can
give specific capacitance 10–100 times greater than that provided by EDLCs [10]. Moreover,
hybrid capacitors are a combination of both EDLCs and PCs. Usually, hybrid capacitor
electrodes are made from (1) both EDLCs materials and PCs materials; symmetric geometry
(2) with one EDLCs electrode and other PCs or battery type electrode; and asymmetric
geometry (3) with an asymmetric structure with one PC electrode and another rechargeable
battery type electrode [7].
In a pseudocapacitor, a redox reaction takes place between the active electrode material
and the electrolyte. Various kinds of transition metal oxides having higher theoretical
specific capacitance, such as RuO2 [11], MnO2 [12], NiO [13], Ni(OH)2 [14], CuO [15],
Co3 O4 [16], and Co(OH)2 [17], have been investigated as an active electrode material.
However, their poor electronic conductivity [18,19], lower cyclic performance [20,21],
and substantial volume change during the charge/discharge process [22] demand the
development of nanostructured materials to meet the increasing and urgent demands
for energy storing devices. Recently, mixed-transition-metal-oxides (MTMOs), Ax B3−x O4
materials have emerged with promising applications for electrodes. The MTMOs with A
and B metal ions can provide many oxidation states for efficient redox charge reactions [23].
Nickel cobaltite (NiCo2 O4 ) is one of the most valuable electrode materials studied because
of its high theoretical specific capacitance, lower cost, low toxic nature, good redox activity,
higher electrical conductivity, and environmentally benign nature [24]. NiCo2 O4 offers high
specific capacitance due to the presence of Ni and Co ions together, which are responsible
for producing higher electrochemical activity and electrical conductivity [25]. NiCo2 O4 is a
spinel-type, AB2 O4 , binary metal oxide where nickel cations occupy octahedral sites and
cobalt cations are randomly distributed on both tetrahedral and octahedral sites [26].
Doped NiCo2 O4 with various transition metals, e.g., Ni1−x Rux Co2 O4 [27], Ni1−x Mnx
Co2 O4 [28], Ni1−x Crx Co2 O4 [29], Ni1−x Znx Co2 O4 [30], Ni1−x Fex Co2 O4 [31], and Ni1−x Cax
Co2 O4 [32], have been studied to understand the effect on morphology and their electro-
chemical performance. This paper describes a simple hydrothermal method for making
Al3+ doped NiCo2 O4, i.e., Ni1−x Alx Co2 O4 . The study systematically assesses the effect of
Al3+ doping on the crystal structure, morphology, chemical composition, and electrochemi-
cal performance of Ni1−x Alx Co2 O4 . Aluminum ion substitution is favored because of its
inexpensive cost, large abundance, non-toxic nature, and superior corrosion resistance.
First-principles density functional theory (DFT) calculations were employed to assess the
energy band-gap of the doped Ni1−x Alx Co2 O4 .
Processes 2021, 9, 1750 3 of 17

2. Experimental
2.1. Synthesis
The required high purity nitrate salts, viz. Al(NO3 )2 .6H2 O, Co(NO3 )2 .6H2 O, and
Ni(NO3 )2 .6H2 O, were purchased from Sigma Aldrich (St. Louis, MO, USA). Table 1 lists
the required amount of precursor salts needed to prepare Ni1−x Alx Co2 O4 . The nitrate salts
were dissolved in 35 mL of water with a fixed amount of Urea (CO(NH2 )2 ) and stirred for
30 min. The solution was then transferred to a 45 mL Teflon-lined autoclave and maintained
at 190 ◦ C for 12 h, followed by a natural cooling to room temperature. The precipitates
were washed with distilled water and acetone several times by centrifugation and then
dried for 12 h at 80 ◦ C. After this, the as derived metal hydroxide composite particles were
calcined at 350 ◦ C in the air for 3.5 h.

Table 1. Stoichiometry of chemicals used in the synthesis of Ni1−x Alx Co2 O4 .

Ni1−x Alx Co2 O4 , Co(NO3 )2 ·6H2 O Ni(NO3 )2 ·6H2 O Al(NO3 )2 ·6H2 O

Urea (gm)
x (gm) (gm) (gm)
0.0 2.420 1.209 0.000 1.497
0.2 2.485 0.993 0.320 1.497
0.4 2.550 0.765 0.658 1.497
0.6 2.620 0.525 1.016 1.497
0.8 3.850 0.384 1.985 1.497

2.2. Characterization
X-ray diffraction (XRD) was used to examine the crystalline structure of calcined
powder using a Bruker D8 Advance X-ray diffractometer (Bruker, Billerica, MA, USA). The
surface morphology of prepared samples was studied by a scanning electron microscope
(SEM) (at 10 keV using Phenom, Oak Park, CA, USA). Autosorb (Quantachrome, Boynton
Beach, FL 33426, USA, model No. AS1MP) was used to quantify specific surface area
and pore volume at 77K using nitrogen as the adsorbing gas. The Brunauer–Emmett–
Teller (BET) method was used to measure the specific surface area of as-prepared samples.
Also, surface area, average pore volume, and pore radius were obtained from the Barret–
Joyner–Halenda (BJH) model. Between 400 and 1000 cm−1 , FTIR spectra were acquired
using an FTIR spectrometer (Nicolet iS10, Thermo Fisher Scientific, Waltham, MA, USA).
The x-ray photoelectron spectrometer (Thermo Scientific K-alpha, XPS) equipped with a
monochromatic X-ray source at 1486.6 eV, corresponding to the Al Kα line, was employed
to collect XPS data (for the brevity XPS spectra not shown). The atomic weight percent of
elements was determined using XPS.
The working electrode was prepared using nickel foam. Nickel foam was first cleaned
with acetone and 3 M HCl solution for 10 min, which helped remove the oxide layer
from the nickel foam’s surface. After washing and drying the nickel foam, the working
electrode was made by combining 80 wt.% of the synthesized powder, 10 wt. % of acetylene
black, and 10 wt. % of polyvinylidene difluoride (PVDF) with N-methyl pyrrolidinone
(NMP). The slurry paste was obtained after thoroughly mixing the components and pasted
onto the nickel foam. The prepared electrode on nickel foam was placed in a vacuum
oven at a temperature of 60 ◦ C for 10 h. The actual sample loading on nickel foam was
determined by weighing the nickel foam before and after loading the nickel foam sample
using an analytical balance (MS105DU, Mettler Toledo, max. 120 g, 0.01 mg of resolution).
A platinum wire counter electrode, a saturated calomel electrode (SCE) as a reference
electrode, and pasted samples on nickel foam as a working electrode were utilized in the
electrochemical cell. The electrochemical performance of the electrode was assessed in 3 M
KOH as an electrolyte. The electrochemical performance of the as-prepared electrode was
evaluated using cyclic voltammetry (CV), galvanostatic charge-discharge techniques, and
electrochemical impedance spectroscopy (EIS) by using a Versastat4-500 electrochemical
workstation (Princeton Applied Research, Oak Ridge, TN, USA).
Processes 2021, 9, 1750 4 of 17

2.3. DFT Study

First-principles density functional theory (DFT) calculations were performed using
the Perdew–Burke–Ernzerhof (PBE) [33] exchange-correlation functional for self-consistent
calculations and geometry optimization along with the advanced hybrid functional HSE06
method to find the electronic density of states of the Alx Ni1−x Co2 O4 structure. The variable
x ranges from 0 to 1 with a step of 0.25. Calculations were performed using VASP [34]
(Vienna ab initio simulation package) with the projected augmented wave (PAW) [35] type
pseudo-potential and the plane-wave basis set. The exchange and correlation part for the
HSE calculations was described by hybrid functional [36] containing 40% Hartree–Fock
exchange. We used a 4 × 4 × 2 k-points mesh centered at the Gamma point with a plane
wave cutoff of 400 eV, which is enough for the self-consistent calculation. The global break
condition for the electronic and ionic self-consistent (SC) loop was set to be 10−4 eV and
10−3 eV, respectively.

3. Results and Discussion

The room temperature powder XRD patterns of Ni1−x Alx Co2 O4 samples are shown
in Figure 1. The XRD patterns of the as-synthesized doped Ni1−x Alx Co2 O4 are almost
identical and can be assigned to NiCo2 O4 (ICDD card no.02-0770). The diffraction peaks are
located at 18.9◦ , 31.3◦ , 36.8◦ , 38.4◦ , 44.5◦ , 55.4◦ , 59.4◦ , and 65.2◦ can be assigned to the (111),
(220), (311), (222), (400), (422), (511), and (440) agreeing with the standard crystallographic
pattern of spinel NiCo2 O4 phase respectively [37]. The absence of impurities in the XRD
patterns confirms the complete dissolution of Al3+ into the Ni1−x Alx Co2 O4 compound. The
lattice parameter of Ni1−x Alx Co2 O4 is listed in Table 2. As expected, the lattice parameter
of Ni1−x Alx Co2 O4 decreases with the content x due to Al3+ (rion ~0. 535 nm) replacing a
bigger Ni ion (rionic ~0.6 nm). The average crystallite size of the NiCo2 O4 calculated using
Scherrer’s formula [38] is listed in Table 2. The average crystallite size of Ni1−x Alx Co2 O4
falls within the range of 12.28 nm for x = 0.8 to 16.52 nm for x = 0.2. Moreover, sharp
diffraction peaks indicated the crystalline nature of the calcined Ni1−x Alx Co2 O4 nanos-
tructures. The aluminum content in Ni1−x Alx Co2 O4 as determined via XPS (XPS study is
Processes 2021, 9, x FOR PEER REVIEW
not reported here) is listed in Table 2 and is within the accepted range of stoichiometry 5 ofof18
the compound.

Figure1.1.X-ray
Figure X-raydiffraction
diffractionpattern
patternfor
forNi
Ni1−
1-xxAl
AlxxCo
Co2O
2O4.4 .

Table 2. Surface area parameters derived from the adsorption-desorption curve, crystallite size obtained using Scherrer’s
formula, lattice parameter obtained from XRD refinement, and Al3+ content was obtained from the XPS analysis of Ni1-
xAlxCo2O4 compound.

BJH Avg. Lattice

Al Content BET Surface BJH Surface BJH Avg. Pore
Ni1-xAlxCo2O4, x 2 2
Pore Radius Parameter, a Crystallite Size (nm)
Processes 2021, 9, 1750 5 of 17

Table 2. Surface area parameters derived from the adsorption-desorption curve, crystallite size obtained using Scherrer’s
formula, lattice parameter obtained from XRD refinement, and Al3+ content was obtained from the XPS analysis of
Ni1−x Alx Co2 O4 compound.

Al Content Lattice
Ni1−x Alx Co2 O4 , BET Surface BJH Surface BJH Avg. Pore BJH Avg. Pore Crystallite
Determined Parameter,
x Area (m2 /g) Area (m2 /g) Radius (nm) Volume (cc/g) Size (nm)
via XPS a (Å)
0.0 0.00 81.74 89.09 1.419 0.239 8.0983 13.212
0.2 0.37 83.16 126.13 1.423 0.183 8.0804 16.525
0.4 0.57 107.19 120.26 1.522 0.192 8.0666 13.804
0.6 0.79 106.29 128.81 2.144 0.194 8.0585 14.776
0.8 0.89 189.00 354.83 1.593 0.276 8.0449 12.286

Figure 2 shows the SEM images of Ni1−x Alx Co2 O4 as a function of Al3+ content.
Figure 2 shows the gradual evolution of Ni1−x Alx Co2 O4 nanostructures from an urchin-
like architecture for x = 0.0 to nanoplates for x = 0.8. It is evident that the initial urchin
whiskers slowly merge and morph into a plate-like structure with increasing Al content.
The morphology of Ni1−x Alx Co2 O4 is dependent on the Al3+ content in the sample. Usu-
ally, the morphology of hierarchal nanostructures depends on the synthesis techniques and
Processes 2021, 9, x FOR PEER REVIEW
urea concentration [4]. As a dispersing agent, urea helps avoid agglomeration by finely 6 ofsep-
18
arating nanoparticles and plays a vital role in controlling the particles’ morphology [39–41].

Figure2.2.SEM
Figure SEMimages
imagesfor
forNiNi
1− x AlxxCo
1-x Co22OO44samples
samples(a)
(a)xx==0,0,(b)
(b)xx==0.2,
0.2,(c)
(c)x x= =0.4,
0.4,(d)
(d)x x= = 0.6,
0.6, and
and (e)(e)
x =x 0.8 .
= 0.8.

Furthermore, NH NH33reacts
reactswith
withwater
waterto to form NH44+ +and
form NH andOH
OH − , and CO hydrolyzes
Furthermore, −, and 2
CO2 hydrolyzes to
to form Co 2 − ions [42]. Tiny crystalline nuclei are created during the oxide crystal
form Co32− ions 3 [42]. Tiny crystalline nuclei are created during the oxide crystal develop-
development
ment phase, phase,
and and nanoparticles
nanoparticles of this of this oxide
oxide are precipitated
are precipitated by a byrisea in
risepH
in pH caused
caused by
by NH + ions generated from NH owing to urea breakdown at higher temperatures [43,44].
4 3
NH4 ions generated from NH3 owing to urea breakdown at higher temperatures +[43,44].
+
Urea’s hydrolysis leads to a rise in the pH due to the increased release of NH4 in the
Urea’s hydrolysis leads to a rise in the pH due to the increased release of NH4+ in the so-
solution [45]. The urea hydrolysis progresses slowly at milder circumstances and at a
lution [45]. The urea hydrolysis progresses slowly at milder circumstances and at a certain
certain urea level, and the basic solution undergoes supersaturation of the metal-hydroxide
urea level, and the basic solution undergoes supersaturation of the metal-hydroxide spe-
species [46].
cies [46].
Figure 3a shows N adsorption/desorption measurements were performed at 77 K be-
Figure 3a shows N22 adsorption/desorption measurements were performed at 77 K
tween relative pressures of P/Po ~ 0.029 to 0.99. From these curves, BET-specific surface ar-
between relative pressures of P/Po ~ 0.029 to 0.99. From these curves, BET-specific surface
eas and corresponding pore sizes were calculated by the BJH method for all Ni1−x Alx Co2 O4
areas and corresponding pore sizes were calculated by the BJH method for all Ni1-
xAlxCo2O4 (0 ≤ x ≤ 0.8). Figure 2c inset shows the pore distribution. These curves show the

largest number of pores distribution at around 3 nm for all Ni1-xAlxCo2O4. This pore dis-
tribution lies between ~2.0 and 6.0 nm, a range best suited to electrode materials [46]. The
larger pore volume helps boost the diffusion kinetics inside the electrode material
Processes 2021, 9, 1750 6 of 17

(0 ≤ x ≤ 0.8). Figure 2c inset shows the pore distribution. These curves show the largest
number of pores distribution at around 3 nm for all Ni1−x Alx Co2 O4 . This pore distribution
lies between ~2.0 and 6.0 nm, a range best suited to electrode materials [46]. The larger pore
volume helps boost the diffusion kinetics inside the electrode material [40,46,47]. Table 2
lists the measured BJH pore radius, volume, and BET surface area of Ni1−x Alx Co2 O4 sam-
ples. The high surface area of samples, in the range of 81.74–189 m2 /g, indicates that the
Processes 2021, 9, x FOR PEER REVIEW 7 of 18
hydrated electrolyte ions could have an increased contact area at the electrolyte/electrode
surface for the Faradaic redox reaction [48,49].

Figure 3.
Figure 3. (a)(a) Adsorption-desorption
Adsorption-desorptioncurves
curvesand
andinset
insetpore
porevolume
volumedistribution
distributionfor
forNi
Ni1-x1Al Cox2Co
−xxAl O4,2 O
and (b) FTIR
4 , and of Niof1-
(b) FTIR
Al Co O .
Ni1−x Alx Co2 O4 .
x x 2 4

The FTIR spectrum Figure 3b shows two different bands arising from the stretching stretching
vibrations of the metal-oxygen bonds at 534.2 (ν ) and 628.7 (ν ) cm −−11 [1]. For the crystal
the metal-oxygen bonds at 534.2 (ν1 1) and 628.7 (ν2 2) cm crystal
structure ofofNiCo
NiCo2O 2O , the
4,4the ν1 band
ν1 band is attributed
is attributed to M-Oto M-O (M bond
(M = Ni) = Ni)vibrations
bond vibrations in
in octahe-
octahedral
dral coordination,
coordination, whereaswhereas
the ν2the ν2 band
band is attributed
is attributed to M-O
to M-O (M-Co)(M-Co) bondbond vibrations
vibrations in
in tetrahedral
tetrahedral coordination.The
coordination. Thestretching
stretchingvibration
vibration of of Co3+ -O2−2−ininthe
3+-O theoctahedral
octahedral sites is
shown by −1 2+ − at the tetrahedral
shown by the
the FTIR
FTIRspectrum
spectrumatat534.2534.2cmcm−1,, and
and the
thevibration
vibrationofofNi Ni2+-O-O− at the tetrahedral
sites is − 1
sites is indicated
indicated by by the
theFTIR
FTIRspectrum
spectrumatat628.7
628.7cm
cm−1 forfor NiCo
NiCo22O O4,, respectively
respectively [50].
[50]. The
The
presence of these vibration bands indicates that pure phase spinel NiCo
presence of these vibration bands indicates that pure phase spinel NiCo22O44 nanostructures O nanostructures
have formed.
have formed. Table
Table 33 lists
lists the
the band
band positions
positions for
for the
the tetrahedral
tetrahedral and and octahedral
octahedral sites
sites of
of the
the
compound. Aluminum
compound. Aluminum doping doping brings
brings the
the shift
shift of
of the
the stretching
stretching peak peak towards
towards thethe right
right
with an increase
with an increase in Al3+3+content.
in Al content.As Asthe
thevibrational
vibrational frequency
frequency is is inversely
inversely proportional
proportional to
to the mass, the increase in vibrational frequency with Al 3+ is expected due to the lower
the mass, the increase in vibrational frequency with Al is expected due to the lower
3+
atomic weight 3+ replacing the Ni ion.
atomic weight of of Al
Al3+ replacing the Ni ion.

Table 3. Two
Table 3. Two distinct
distinct band
bandpositions
positionsfrom
fromFTIR
FTIRspectrum
spectrumfor
forNi −xAl
Ni11-x AlxCo
x Co
2O2O 4 samples.
4 samples.

Ni1−
Nix Al CoxCo
1-xxAl 2 O42O
, x4, x ν1−(cm
ν1 (cm 1 ) −1
) ν2ν2(cm −1−1
(cm ))
0.0 0.0 534.2534.2 628.7
628.7
0.2 0.2 544.0544.0 645.2
645.2
0.4 551.0 652.7
0.4 551.0 652.7
0.6 553.6 653.9
0.8 0.6 556.1553.6 653.9
665.1
0.8 556.1 665.1

Cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) measurements

give the electrochemical performance of Ni1-xAlxCo2O4 nanostructures. Figure 4a–e shows
the cyclic voltammograms obtained at different scan rates (2–300 mV/s) in a voltage win-
dow of 0–0.6 V (vs. SCE). The Faradaic reaction for NiCo2O4, x = 0 is given by the equation
below [51,52].
Processes 2021, 9, 1750 7 of 17

Cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) measurements

give the electrochemical performance of Ni1−x Alx Co2 O4 nanostructures. Figure 4a–e
shows the cyclic voltammograms obtained at different scan rates (2–300 mV/s) in a voltage
window of 0–0.6 V (vs. SCE). The Faradaic reaction for NiCo2 O4, x = 0 is given by the
equation below [51,52].
MO + OH− ↔ MOOH + e−
Processes 2021, 9, x FOR PEER REVIEW 8 of 18
NiCo2 O4 + OH− + H2 O ↔ NiOOH + 2CoOOH + e−

Figure 4.
Figure 4. (a–e)
(a-e) are
are cyclic
cyclicvoltammetry
voltammetrycurves
curvesofofNiNi xCo
x Alx
1−1-x Co22O
O44, ,electrode
electrode obtained
obtained in the scan
scan range
rangeof
of55mV/s
mV/sto
to300
300mV/s
mV/s
measured in
measured in 3M
3M KOH
KOH electrolytes.
electrolytes. Figure
Figure(f)
(f)specific
specificcapacitance
capacitancevs. vs.scan
scanrate.
rate.

In both the cathodic

cathodic andand anodic
anodic scans,
scans, there
there are
are noticeable
noticeable oxidation
oxidation and
and reduction
reduction
peaks
peaks [53].
[53]. Obtained
Obtained non-rectangular
non-rectangularand andunsymmetric
unsymmetricCV CVcurves
curvesindicate the
indicate thepseudoca-
pseudo-
pacitive nature of electrodes [54]. The CV curves
capacitive nature of electrodes [54]. The CV curves of 1Ni of Ni Al
−x1-xAlCo
x xCo O
22O44 show no extra redox
redox
peaks, implying that Ni Ni1-x
1−Al Al
x xCoCo O redox
x 2O24 redox
4 processes are very similar to NiCo
processes are very similar to NiCo2O4 redox O redox
2 4 pro-
processes.
cesses. The Thepeakspeaks are due
are due to thetoredox
the redox reaction
reaction relatedrelated to M-O/M-O-OH,
to M-O/M-O-OH, where where
M stands M
stands
for Ni orforCo
Niions
or Co ions
[55]. A [55]. A positive
positive shift inshift in oxidation
oxidation peak potential
peak potential and a negative
and a negative shift in
shift in reduction
reduction peak potential
peak potential are found
are found as scan
as scan rate rate increases
increases [56].[56].
ThisThis
PCPC characteristic
characteristic is
is derived from the Faradaic redox reaction related to the reversible reaction of Ni 2+ /Ni 3+
derived from the Faradaic redox reaction related to the reversible reaction of Ni /Ni and 2+ 3+

and 3+ 4+ transitions. Figure 5a–e shows the cyclic stability curves of Ni

Co3+Co
/Co4+/Co
transitions. Figure 5a–e shows the cyclic stability curves of Ni1-xAl1x− x Al
Co 2Ox4Co 2 O4
meas-
measured up to 2000 cycles without any change in the position
ured up to 2000 cycles without any change in the position of redox peaks. of redox peaks.
Processes2021,
Processes 2021,9,9,1750
x FOR PEER REVIEW 98 of 17
18

Figure 5.5. (a–e)

Figure (a–e)are
arecyclic
cyclicstability
stabilitycurves
curvesofofNiNi 1-xAlxCo2O4 measured up to 2000 cycles in 3M KOH electrolyte, (f) peak
1−x Alx Co2 O4 measured up to 2000 cycles in 3M KOH electrolyte, (f) peak
current vs. (scan rate) 1/2, and (g) diffusion and capacitive contribution to the specific capacitance.
1/2
current vs. (scan rate) , and (g) diffusion and capacitive contribution to the specific capacitance.

The Randles–Sevcik
Randles–Sevcikplots plotsofofthe
theNiNi
1-xAlxCo
1−x Alx2O Co4 samples are shown
2 O4 samples in Figure
are shown 5f. When
in Figure 5f.
the scan
When therate is increased
scan from 2 to
rate is increased 300 2mV
from to s300 mV s−1 , the
−1, the anodic peak current
anodic peak(Ipa)current
and the(Ipa
ca-)
thodic
and thepeak current
cathodic (Ipc) current
peak both increase. More
(Ipc ) both precisely,More
increase. the Randles–Sevcik equation shows
precisely, the Randles–Sevcik
that both I and I change linearly with the
equation shows that both Ipa and Ipc change linearly with
pa pc square root of the scan rate (ν
square root of1/2) [57,58].
the scanThese
rate
(ν 1/2
results suggest
) [57,58]. that results
These the electrode–electrolyte interface’s redox events
suggest that the electrode–electrolyte are rapid,
interface’s redox quasi-re-
events
versible,
are rapid,and only limited by
quasi-reversible, andelectrolyte diffusion
only limited [59]. Thediffusion
by electrolyte positive [59].
shift The
of oxidation
positive peak
shift
and
of negativepeak
oxidation shift andof reduction
negativepeakshift potential
of reduction indicate
peakrelatively
potential low electrode
indicate materials
relatively low
resistancematerials
electrode and goodresistance
electrochemical
and good reversibility [1]. reversibility [1].
electrochemical
capacitance was
The calculation of specific capacitance was done
done from
from CVCV curves
curves using
using the the equation
equation
[60]:
below [60]:
R V2
V1 I ∗ V ∗ dV
Csp = (1)
m ∗∫v ∗ (V∗ ∗
2 − V1 ) (1)
Csp =
where I (A) is current, m (g) is the mass of the ∗ active
∗( material, ) v (mV/s) is the scan rate, V1
and
WhereV2 I(V)
(A)are the startm
is current, and(g)end voltage
is the mass of of the
the active
CV scan.material, v (mV/s) is the scan rate, V1
and VFigure 4f shows the C of Ni1−x Alof
2 (V) are the start andspend voltage x Co 2 OCV
the 4 samples
scan. as a function of scan rates. The
obtained
Figurevalues of Csp the
4f shows for Ni
Csp1−ofx Al CoAl
Nix1-x 2O 4 nanostructures
xCo
are 512, 368, 371, 380, and 356 F/g
2O4 samples as a function of scan rates. The ob-
at a scan rate of 2 mV/s for Ni 1 − x Alx Co O
tained values of Csp for Ni1-xAlxCo2O4 nanostructures are 512,
2 4 x = 0.0, 0.2, 0.4, 0.6,371,
368, and380,
0.8,and
respectively.
356 F/g at
Compared to all Ni
a scan rate of 2 mV/s1−for Al x Co
x Ni1-xAl O
2 xCo nanostructures, NiCo
4 2O4 x = 0.0, 0.2, 0.4, 0.6, O 4 0.8, respectively.the
2 and x = 0.0 exhibited highest
Compared
specific capacitance at all scan rates with a maximum value of 512
to all Ni1-xAlxCo2O4 nanostructures, NiCo2O4 x = 0.0 exhibited the highest specific capaci-F/g at 2 mV/s. The
higher electrochemical utilization and high electroactive surface area
tance at all scan rates with a maximum value of 512 F/g at 2 mV/s. The higher electrochem- of the synthesized
nanostructure
ical utilization occur for electroactive
and high O4 , x = area
Ni1−x Alx Co2surface 0. The observed
of the decrease
synthesized nanostructure Al3+
in Csp withoccur
substitution suggests 3+
that in the presence of Al , the Ni and Co in Ni1−x Alx Co2 O4 may
for Ni1-xAlxCo 2O4, x = 0. The observed decrease in Csp with Al3+ substitution suggests that
not behave synergistically as an effective Faradaic charging site as compared with the
in the presence of Al , the Ni and Co in Ni1-xAlxCo2O4 may not behave synergistically as
3+
Ni and Co sites in NiCo2 O4 . Moreover, it can be deduced that, with the increase in Al3+
an effective Faradaic charging site as compared with the Ni and Co sites in NiCo2O4. More-
content, overall effective redox sites have decreased, which leads to a decrease in the
over, it can be deduced that, with the increase in Al3+ content, overall effective redox sites
specific capacitance.
have decreased, which leads to a decrease in the specific capacitance.
The total charge storage process is affected by factors such as the Faradaic contri-
The total charge storage process is affected by factors such as the Faradaic
bution from the insertion process of electrolyte ions, the Faradaic contribution from the
contribution from the insertion process of electrolyte ions, the Faradaic contribution from
charge-transfer process, and due to the high surface area, the contribution from both
the charge-transfer process, and due to the high surface area, the contribution from both
pseudocapacitance and the non-Faradaic contribution from the double layer effects [61].
Processes 2021, 9, 1750 9 of 17

CV data are analyzed at different scan rates and can characterize capacitive effects by
equation [62,63].
I = avb (2)
where the peak current is I (A), the scan rate is v (mV/s), and a and b are adjustable
parameters. The value of b specifies the charge storage mechanism. If b = 1, it indicates
a surface-controlled reaction that the capacitive surface mechanism is dominant, and if
b = 0.5, it indicates a diffusion-controlled Faradaic reaction during the charge storage
mechanism [64]. Figure 5f shows the peak current vs. square root of the scan rate curve.
These curves are fitted with the Equation (2) which gives values of b ~ 0.6239, 0.6398, 0.6218,
0.6134, and 0.5894 for x = 0.0, 0.2, 0.4, 0.6, and 0.8, respectively. That b > 0.5 for all electrodes
indicates both diffusion-controlled and surface-controlled reactions [54]. Moreover, in
Figure 5f, the lower value of the scan rate region has a linear dependence relation with the
square root of the scan rate; this indicates a quasi-reversible electrochemical reaction [65].
Figure 5f also indicates that, at a higher scan rate > 100 mV/s, the ion diffusion is limited to
the surface of the active material of the electrode, i.e., EDLC dominates the pseudocapacitor,
and diffusion of OH− ions can adhere only to the outer layer of the nanostructure, which
contributes less to the electrochemical capacitive behavior [66]. On the other hand, the
Faradaic redox reaction dominates at scan rates < 100 mV/s due to more effective usage of
the working electrode’s active material [67]. Moreover, the diffusion of OH- ions can easily
penetrate deep into the nanostructure’s interlayer, which leads to adsorption of more ions
and hence ends up with higher specific capacitance [68].
The capacitive and diffusion processes are the two mechanisms for current response
at a fixed potential [69,70]. The equation below gives their contributions [71].

Csp = k1 + k2 −1/2 (3)

k1 and k2 are determined from the Csp vs.V− 1/2 linear plot, where k2 is the slope
and k1 is the intercept. k1 indicates diffusion and k2 capacitance contribution to the total
specific capacitance for a given voltage. For the calculation, the specific capacitance is
plotted against the slow scan rate up to a value of 20 mV/s and performed a regression fit
using Equation (3). The obtained value for k1 and k2 was used to determine the fractional
contribution in terms of diffusion and capacitance from total specific capacitance [72], as
given in Figure 5g. Figure 5g shows that the contribution to the current response at a fixed
potential is more diffusive than capacitive and decreases with the Al content.
To further estimate the potential application of as-prepared electrodes for supercapaci-
tors, the galvanostatic charge-discharge (GCD) measurement was performed. GCD was
measured within the voltage window of 0.0 to 0.6 at different current densities between
1 A/g to 30 A/g in 3 M KOH solution are given in Figure 6a–e. These figures indicate
that prepared electrodes of Ni1−x Alx Co2 O4 can charge and discharge rapidly with good
electrochemical reversibility at different constant current densities. As in CV curves, the
non-linear relationship between the potential and time in both the charge-discharge cycle
indicates the capacitance of studied nanomaterials is not constant in between the potential
range and reflects typical PCs behavior [73]. The non-linearity of the GCD curve is a conse-
quence of the Co3+ /Co4+ , and Ni2+ /Ni3+ ions redox reactions with OH− . The discharge
process occurs in three distinct steps. First, there is a rapid potential drop that occurs
owing to the internal resistance. The second is a slow potential decay at an intermediate
time, which is due to the Faradaic redox reaction. The third is a fast potential decay which
is created by electric double layer capacitance [74]. The specific capacitance values for
electrodes of Ni1−x Alx Co2 O4 were calculated by using Equation (4) [75].

I∗t
Csp = (4)
m ∗ ∆V
Processes 2021, 9, x FOR PEER REVIEW 11 of 18
Processes 2021, 9, 1750 10 of 17

Where Csp is the specific capacitance (F/g), I (A) is the charge-discharge current, V (V) is
the potential
where range,
Csp is the m (g)
specific is the mass
capacitance of Ithe
(F/g), (A) electroactive materials and
is the charge-discharge t (s)∆V
current, is (V)
the
discharging
is time.range, m (g) is the mass of the electroactive materials and t (s) is the
the potential
discharging time.

Figure 6.
Figure 6. (a–e) Charge-discharge curves of Ni11-x−Al xCo
x Al 2O4O
x Co 2 , electrode measured
4 , electrode measuredin in
thethe
current density
current window
density window of of
0.75 to 30
0.75 to
A/g under 3 M KOH electrolytes. Figure (f) Comparison of specific capacitance as a function of current density.
30 A/g under 3 M KOH electrolytes. Figure (f) Comparison of specific capacitance as a function of current density.

The pseudocapacitance behavior of electrodes with respect respect to

to their
their discharging
discharging time
time is
is
confirmed by the presence of of voltage
voltage plateau
plateau on
on GCD
GCD curves
curves [76].
[76]. The specific
specific capacitance
capacitance
values of Ni1-x
1−Al xCo
x Al 2O24O
x Co were
4 werecalculated using
calculated Equation
using (4) at
Equation (4)0.5
at A/g are 268,
0.5 A/g 194, 194,
are 268, 192, 192,
176,
and 167
176, andF/g
167for
F/gx =for
0.0,x0.2, 0.4,0.2,
= 0.0, 0.6,0.4,
and0.6,
0.8,and
respectively, and are listed
0.8, respectively, and arein Table
listed4.inFigure
Table 6f
4.
Figure 6f shows
shows the the dependence
dependence of current of current
density density
with with
specific specific capacitance.
capacitance. A decreaseAindecrease
the spe-
in the
cific specific capacitance
capacitance with theofincrease
with the increase of the current
the discharge discharge currentby
is caused is the
caused by the
insufficient
insufficient time
time available foravailable for the
the diffusion of diffusion of theions
the electrolyte electrolyte
into theions into
inner the inner
electrode electrode
surface and
surface and the increase of the potential drop towards higher
the increase of the potential drop towards higher discharge currents [77].discharge currents [77].

Table4.4.Data
Table Dataofofspecific
specificcapacitance obtained
capacitance from
obtained cyclic
from voltammetry,
cyclic voltammetry, specific capacitance
specific obtained
capacitance from charge-discharge
obtained from charge-dis-
charge curves,
curves, energy density,
energy density, anddensity
and power power density
for Ni1−forAl
x xNiCo
1-x Al
O
2 4x Co
. 2 O 4 .

Specific Capacitance at 2 mv/s Specific

Specific Capacitance Specific Capacitance at 0.5
Capacitance Energy
Energy Density
Density PowerDensity
Power Density
x, Content
x, Content
at(F/g)
2 mv/s (F/g) at 0.5 A/g (F/g)
A/g (F/g) (Wh/Kg)
(Wh/Kg) (W/Kg)
(W/Kg)
0.0 0.0 512 512 268 268 12.4 12.4 6316.6
6316.6
0.2 0.2 368 368 194 194 8.9 8.9 6289.1
6289.1
0.4 371 192 9.1 5281.2
0.4 371 192 9.1 5281.2
0.6 380 176 8.7 6670.9
0.6 0.8 380 356 167 176 8.2 8.7 6670.9
4660.4
0.8 356 167 8.2 4660.4

The cyclic stability of Ni1−x Alx Co2 O4 , x = 0.0, and x = 0.8, electrodes were evaluated
by the repeated charge-discharge measurements up to 5000 cycles at a constant current
Processes 2021, 9, x FOR PEER REVIEW 12 of 18
Processes 2021, 9, 1750 11 of 17

The cyclic stability of Ni1-xAlxCo2O4, x = 0.0, and x = 0.8, electrodes were evaluated by
the repeated
density of 10charge-discharge
A/g and 5 A/g in measurements
the potential up to 5000
range cycles0.0
between at and
a constant
0.6 V in current
3 M KOH, den-
sity of 10
shown in A/g and7a,b
Figure 5 A/g in the potential
respectively. range between
The percentage 0.0 and
retention in0.6 V in 3capacitance
specific M KOH, shown was
in Figure 7a,b
calculated respectively.
using The
Equation (5) percentage retention in specific capacitance was calculated
[78].
using equation (5) [78].
% retention in specific capacitance = (C# /C1 ) × 100 (5)
% retention in specific capacitance = (C#/C1)  100 (5)
Where CC## and
where and CC11 are
are specific
specific capacitance at various
capacitance at various cycles
cycles and
and the
the 1st
1st cycle,
cycle, respectively.
respectively.
Hence,
Hence, the % retention in specific capacitance after 5000 cycles for Ni1-xAlxCo22O
the % retention in specific capacitance after 5000 cycles for Ni 1 − x Alx Co O44 xx == 0.0
0.0
and x = 0.8 is 97% and 108.5% respectively. This shows that even after 5000 cycles, the
and x = 0.8 is 97% and 108.5% respectively. This shows that even after 5000 cycles, the
electrode shows outstanding cyclic stability, and hence there is not much high specific
electrode shows outstanding cyclic stability, and hence there is not much high specific
capacitance fade from its initial values in x = 0.0. Similarly, in the case of x = 0.8, the specific
capacitance fade from its initial values in x = 0.0. Similarly, in the case of x = 0.8, the specific
capacitance improves to 108.5% of its initial value, and this suggests an improvement in
capacitance improves to 108.5% of its initial value, and this suggests an improvement in
the surface moistened by electrolyte ions, access of electrolyte ions up to the pore of elec-
the surface moistened by electrolyte ions, access of electrolyte ions up to the pore of elec-
trode materials, and activation of electrodes by electrolyte ions upon cycle repetition [79].
trode materials, and activation of electrodes by electrolyte ions upon cycle repetition [79].
Furthermore, the Coulombic efficiency for x = 0.0 and x = 0.8 is 100% and 99.2%, as shown
Furthermore, the Coulombic efficiency for x = 0.0 and x = 0.8 is 100% and 99.2%, as shown
in Figure 7a,b, respectively.
in Figure 7a,b, respectively.

Figure 7.
Figure 7. (a,b)
(a,b) Cyclic
Cyclic stability
stabilityand
andCoulombic
Coulombicefficiency
efficiencytested
testedatat1010A/g
A/gand
and55A/g
A/g current
current density
densityup
upto
to5000
5000cycles
cyclesinin33M
M
KOH electrolytes
KOH electrolytes for
for Ni
Ni1-xAl
AlxCo
Co2O4, x = 0, and x = 0.8.
O , x = 0, and x = 0.8.
1−x x 2 4

Ragone plots of
of synthesized
synthesizedNiNi1-x
1− Al xCo
x Al 2O42 O
x Co are given
4 are in Figure
given 8a. The
in Figure energy
8a. The (E) and
energy (E)
power
and (P) densities
power are determined
(P) densities using
are determined the equations
using the equationsbelow [32],[32],
below

E =E (1/2)CV
= (1/2)CV
22 (6)
(6)

P =P E/t
= E/t (7)
(7)
Where CC isis the
where the electrodes’
electrodes’ specific
specific capacitance,
capacitance, VV is
is the
the operating
operatingvoltage,
voltage,and
andthe
theletter
lettert
denotes the discharge time in seconds. An excellent-performance supercapacitor
t denotes the discharge time in seconds. An excellent-performance supercapacitor must must ex-
hibit a high value of both energy density and power density together.
exhibit a high value of both energy density and power density together. Figure Figure 8a shows the
the
electrodes with
superior performance of electrodes with an
an energy
energydensity
densityof ofup
uptoto12.4
12.4Wh/kg
Wh/kg for
for xx == 0.0,
up to
with up to aa peak
peakpower
powerdensity
densityofof6670.9
6670.9W/kg
W/kg for
for xx == 0.6. Furthermore, Table 5 compares
compares
the electrodes’ specific capacitances derived from the doping doping ofof transition
transition elements
elements on on
NiCo22O44 using
using thethe hydrothermal
hydrothermal method.
method.
Processes 2021, 9, 1750 12 of 17
Processes 2021, 9, x FOR PEER REVIEW 13 of 18

Figure8.
Figure 8. (a)
(a) Ragone
Ragone plot
plot of
of power
power density
density vs.
vs. energy
energy density, (b) frequency-dependent
density, (b) frequency-dependent real
real impedance
impedance measured,
measured, and
and (c)
(c)
Nyquistplot
Nyquist plotfor
forNi
Ni1-xAl
AlxCo2O4 at open circuit potential obtained in 3M KOH electrolytes.
Co O at open circuit potential obtained in 3M KOH electrolytes.
1−x x 2 4

Table 5. Comparison of specific capacitance of electrodes derived from doping of transition elements on NiCo 2O4 using
Table 5. Comparison of specific capacitance of electrodes derived from doping of transition elements on NiCo2 O4 using the
the hydrothermal method.
hydrothermal method.
Scan Rate Current Density Specific Cap.
Electrode Material
Electrode Material
Scan Rate Specific
Specific Cap.
Cap. (Csp )(Csp)
Current Density Specific Cap. Reference
Reference
(mV/s)
(mV/s) (A/g) (A/g) (Csp ) (Csp)
Ni1−1-xx Ru
Ni Rux xCo
Co 2O4
2 O4 831 F/g, 913 F/g, 1004 F/g,
(x(x= =0.00, 0.02, 0.05,0.05,
0.10, 0.20)
—- —– 1 831 F/g, 913 F/g, 1004
1527 F/g, 1483 F/g
F/g, [27]
0.00, 0.02, 0.10, ---- ----- 1 [27]
1527 F/g, 1483 F/g
0.20)
Ni1−x Mn x Co2 O4
243 F/g (x = 0.3),
—– —- 1 366 F/g (x = 0.5, max), 162 F/g [28]
(x =1.0, 0.7, 0.5, 0.3, 0.0) 243(xF/g (x = 0.3), 366
= 0.7) F/g
Ni1-xMnxCo2O4
Ni1−0.7,
----- ---- 1 (x = 0.5, max), 162 F/g (x = [28]
(x =1.0, x Znx0.5,
Co2 O0.3,
4 0.0) — —- 2 1228 F/g [30]
(x = 0.5) 0.7)
Ni1−1-xx Fe
Ni Znx Co
xCo
2O2O
4 4 2237 F/g at 1 h,2208 F/g at 3 h,
(x = ---
—- —----- 1 2 1976 F/g 1228
at 5 h. F/g [30]
[31]
(x = 1)
0.5)
506 F/g,508 F/g, 2237
Ni1−x Cax Co2 O4 284 F/g, 365 F/g,F/g
317 at 1 h,
F/g,
Ni1-xFexCo2O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8)
2 355 F/g, 934 F/g, 0.5
558 F/g, 253 F/g
[32]
---- ----
571 F/g 1 2208 F/g at 3 h, 1976 F/g [31]
(x = 1)
512 F/g,368 F/g, at 5 h.
Ni
1−x Al Co O
x 2 4 268 F/g, 194 F/g, 192 F/g,
Ni(x
1-xCaxCo2O4 (x = 0.0, 0.2,
= 0.0, 0.2, 0.4, 0.6, 0.8)
2 506 F/g,508
371 F/g, F/g, 355
380 F/g, 0.5 284F/g,
176 F/g,167
365
F/g F/g, 317 F/g, [This study]
2 356 F/g 0.5 [32]
0.4, 0.6, 0.8) F/g, 934 F/g, 571 F/g 558 F/g, 253 F/g
Ni1-xAlxCo2O4 (x = 0.0, 0.2, 512 F/g,368 F/g, 371 268 F/g, 194 F/g, 192 F/g, [This
2The superior electrochemical performance 0.5 of as-synthesized
0.4, 0.6, 0.8) F/g, 380 F/g, 356 F/g 176 F/g, Ni x Alx Co2 Ostudy]
1671−F/g 4 nanos-
tructure electrode materials was further confirmed by the electrochemical impedance
The superior
spectroscopy electrochemical
(EIS) measurement held at performance of as-synthesized
10 mV AC perturbation Ni1-xAlxrange
in the frequency Co2O4
nanostructure electrode materials was further confirmed by
from 10 kHz to 0.05 Hz. Figure 8b shows the tendency of the real part of the impedance the electrochemical imped-
(Z 0 ) tospectroscopy
ance decrease with(EIS) measurement
increasing frequency heldforatall10samples.
mV ACWhen perturbation
x = 0.0, in thethe
it has frequency
lowest
range
real from
part 10 kHz
of the to 0.05 Hz.
impedance. TheFigure
magnitude 8b shows
of thethe tendency
real of the
part of the real part (Z’)
impedance of the imped-
increases
ance
as Al3+ (Z′) to decrease
content increases,withwhich
increasing
affectsfrequency
the rise offor all samples.
grains, When x = and
grain boundaries, 0.0, electrode
it has the
lowest real
interface part of the
resistance. impedance.
Figure 8c showsThe magnitude
the Nyquist plotsof for
theall
real
of part
the Ni of1−theAl
x x impedance
Co 2 4 nanos-
O (Z’)
increases as
tructures. In Al 3+ content increases, which affects the rise of grains, grain boundaries, and
this plot, the NiCo2 O4 nanostructure electrode exhibits a small semicircle that
electrodelow
suggests interface
internalresistance.
resistanceFigure 8c shows
and charge the Nyquist
transfer plotsand
resistance, forhence
all of the
thisNi 1-xAlxCo2O
resistance is4
nanostructures.
smaller 3+
than Al Indoped this plot,
NiCothe NiCo 2O4 nanostructure electrodethe exhibits a small
(Zrealsemicir-
2O 4 . Towards higher frequencies, real part ) of the
cle that suggests
impedance low internal
represents a combinedresistance
resistance andofcharge
contacttransfer resistance,
resistance at activeand hence this re-
material/current
collector
sistance is interface,
smaller ionic
than resistance
Al3+ dopedofNiCo the electrolyte,
2O4. Towards andhigher
intrinsic resistance the
frequencies, of the
realnano-
part
materials
(Zreal) of the used in the electrode
impedance [80]. aThe
represents semicircle
combined at the high-frequency
resistance of contact resistance range isatdue to
active
the Faradaic charge
material/current transfer
collector resistance
interface, (Rctresistance
ionic ) of the redox reaction
of the between
electrolyte, andthe electrode
intrinsic re-
and
sistanceelectrolyte. The decrease used
of the nanomaterials in theindiameter of the[80].
the electrode semicircle indicatesatlower
The semicircle charge
the high-fre-
transfer resistance [81]. These variations of the EIS curve from semicircle
quency range is due to the Faradaic charge transfer resistance (Rct) of the redox reaction towards higher
frequencies
between theand linearity
electrode andtowards
electrolyte.lowerThefrequencies
decrease inrelate to reversible
the diameter of the Faradaic
semicircleredox
indi-
Processes 2021, 9, x FOR PEER REVIEW 14 of 18

Processes 2021, 9, 1750 13 of 17

cates lower charge transfer resistance [81]. These variations of the EIS curve from semicir-
cle towards higher frequencies and linearity towards lower frequencies relate to reversible
Faradaic
reaction redox
and accessreactionof OHand−access
ions into of OHthe ions
−
poreinto of thetheelectrode
pore of the electrode
material. Thismaterial.
behavior Thisof
behavior of the EIS curve describes the PCs properties
the EIS curve describes the PCs properties of the prepared Ni1−x Alx Co2 O4 nanostructure of the prepared Ni 1-xAlxCo2O4

nanostructure
electrode [82].electrode
The slope[82]. of theThe 45slope
◦ portionof the of 45° portion
the curve is of the curve
called Warburg is called Warburg
resistance (Zw )
resistance (Z w) and results from the frequency dependence of ion diffusion/transport in
and results from the frequency dependence of ion diffusion/transport in the electrolyte
the electrolyte
to the electrode tosurface
the electrode
[83,84].surface
The Nyquist [83,84].plot TheisNyquist
a vertical plot
lineis for
a vertical
an idealline for an
electrode
ideal electrode
material, and more material,
is theand moreline
vertical is the vertical line
represents represents
better electrolytebetter electrolyte
diffusion diffusion
and capacitive
and capacitive behavior [85]. Figure 8c shows that R ct is smaller for NiCo2O4 and has a
behavior [85]. Figure 8c shows that Rct is smaller for NiCo2 O4 and has a more vertical line,
more
whichvertical line, which
offers better offers better rate capability.
rate capability.
First-principles
First-principles densityfunctional
density functionaltheory theory(DFT) (DFT) calculations
calculations were were performed
performed using using
VASP 22 [34] (Vienna ab initio simulation package) with the projected augmented wave
VASP [34] (Vienna ab initio simulation package) with the projected augmented wave
(PAW)
(PAW) [35][35] type
type pseudo-potential
pseudo-potential and and thethe plane-wave
plane-wave basis basis set.
set. The
Theexchange
exchangeand andcorre-
corre-
lation
lationpart
partfor forthetheHSEHSEcalculations
calculationswas wasdescribed
describedby byhybrid
hybridfunctional
functional[36] [36] containing
containing a
40% Hartree-Fock exchange. Here, we used a 4 × 4
a 40% Hartree-Fock exchange. Here, we used a 4 × 4 × 2 k-points mesh centered at the × 2 k-points mesh centered at the
Gamma
Gammapoint pointwith withaaplane
planewave wavecutoff
cutoffof of400400eV, eV, which
which is is enough
enough for for the
the self-consistent
self-consistent
calculation.
calculation. The global break condition for the electronic and ionic self-consistent (SC) (SC)
global break condition for the electronic and ionic self-consistent loop
loop wastoset
was set beto10be−4 10 eV and
eV−4and 10−10 3 eV,
−3 eV, respectively. In our calculation, we dealt with a cell
respectively. In our calculation, we dealt with a cell con-
containing
taining 28 atoms 28 atoms as aas a total.
total. The Thevalue value of gaussian
of gaussian smearing
smearing was adjusted
was adjusted to be to be Even
0.20. 0.20.
Even
though though
the ratiothe ofratio
x isof20% x isin20% in the experiment,
the experiment, we chose we25% chose 25%calculations
in the in the calculations
because
because
changing changing
it to 20%itwouldto 20%require
wouldarequire much larger a much larger supercell,
supercell, which eventually
which eventually increases the in-
creases
computing the computing
time and memory time andexcessively.
memory excessively.
Figure 9a shows Figure the 9a shows
side viewthe side
along view
the along
x-axis
of the
the crystal
x-axis of thestructure
crystalof Ni1−x Alof
structure x CoNi2 O
1-x4 , while
Al xCo2OFigure
4, while 9bFigure
shows9b the band-gap
shows variation
the band-gap
from 2.42from
variation eV to 4.82
2.42 eVeV to for
4.82the eVdifferent values of
for the different x. For
values of the
x. Forsystem without
the system Al atom,
without Al
whichwhich
atom, is Ni1 is CoNi 2O 4, the
1Co 2O4,band
the bandgap wasgap wasfound at 2.42
found eV, which
at 2.42 eV, which agrees withwith
agrees the previously
the previ-
reported
ously experimental
reported experimentalvaluesvaluesof 2.06ofeV 2.06[86]eVand [86]2.64
andeV 2.64[87].
eV This
[87]. value is theisminimum
This value the min-
among all the cases of adding Al to the system. Adding
imum among all the cases of adding Al to the system. Adding an Al atom above 0.8, the an Al atom above 0.8, the band-gap
reached its
band-gap maximum
reached value of value
its maximum 4.82 eV of for
4.82the eV case
for thewhere
case Al completely
where Al completelyreplaces Ni, as
replaces
shown in Figure 9a. These results suggest that
Ni, as shown in Figure 9a. These results suggest that the energy band-gap of Nithe energy band-gap of Ni x AlxxCo22 O44
1−1-xAl Co
remainslargely
largely unaltered
unaltered (x (x << 0.8)
0.8) with
with thethe Al 3+
Al substitution,
substitution,which whichtranslates
translatesto to the
the fact
fact
remains 3+

thatthe
that theelectrical
electricalconductivity
conductivityofofNiNi −xxAl
1-x1Al Cox2Co O4 could
O4 2could remain remain unaltered
unaltered withwith the Al the Al3+
3+ sub-

substitution
stitution below below x = In
x = 0.8. 0.8.the
Inabsence
the absence of the of contribution
the contribution of electrical
of electrical conductivity
conductivity to theto
the electrochemical performance of Ni Al Co O at least
electrochemical performance of Ni1-xAlxCo2O4, at least for x < 0.8, it can be concluded that
1 − x x 2 4, for x < 0.8, it can be concluded
thatelectrochemical
the the electrochemical performance
performance of Niof Ni −x Al
1-xAlx1Co
Co2 O4 be
2Ox4 could
could be dictated
dictated by other by factors,
other factors,
such
as morphology, the oxidation potential of participating ions, active metal sites,sites,
such as morphology, the oxidation potential of participating ions, active metal and andthe
the internal
internal resistance
resistance of compound.
of the the compound.

Figure 9.
Figure (a) Side view, along
9. (a) along the
the x-axis
x-axisof
ofthe
thecrystal
crystalstructure
structureand
and(b)
(b)energy
energyband-gap
band-gapofof
NiNi x Al
1−1-x AlxxCo22O44 obtained
obtained from
from
DFT
DFT calculations
calculations as
as aa function
function of
of content,
content, x.
x.
Processes 2021, 9, 1750 14 of 17

4. Conclusions
Finally, a simple and cost-effective technique was developed to report the effect of Al3+
doping on the structural and electrochemical performance of the NiCo2 O4 nanostructure.
The experimental results revealed the dependence of surface area, specific capacitance,
and electrochemical performance of NiCo2 O4 on Al3+ content. The doped compound’s
overall electrochemical performance, viz. energy and power density, was observed to be
significantly superior to other doped NiCo2 O4 compounds. The DFT calculation suggests
that the energy band-gap of Ni1−x Alx Co2 O4 (<0.8) remains largely invariant, and hence
the electrical conductivity. Thus, the observed reduction in the specific capacitance of
doped Ni1−x Alx Co2 O4 could be attributed to the decrease in active redox sites with Al3+
substitution. The study indicates that Al3+ can be an excellent cost-effective substitution for
expensive cobalt in NiCo2 O4 to provide the desired electrochemical performance. Hence,
this work highlights the development of cheaper and more promising electrode doped
materials without sacrificing the performance of NiCo2 O4 .

Author Contributions: Conceptualization and supervision, S.R.M.; methodology, D.G., data col-
lection and validation. J.C., W.L. and F.A.P.; software, R.B. and X.S.; formal analysis, S.R.M. and
R.K.G.; data curation, D.G.; writing—D.G. and X.S.; writing—review and editing, S.R.M. and R.K.G.;
supervision, S.R.M.; project administration, S.R.M.; funding acquisition, S.R.M. All authors have read
and agreed to the published version of the manuscript.
Funding: Dr. Mishra extends thanks to the FRG grant provided by the University of Memphis,
Memphis, TN, USA. Dr. Ram K. Gupta expresses his sincere acknowledgment of the Polymer
Chemistry Initiative at Pittsburg State University, Pittsburg, KS, USA, for providing financial and
research support for this project.
Institutional Review Board Statement: None.
Informed Consent Statement: Not applicable.
Acknowledgments: Authors acknowledge the Integrated Microscopy Center (IMC) at the University
of Memphis for helping with XPS study.
Conflicts of Interest: The authors declare no conflict of interest.

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