Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-020-03170-8

Facile solvent deficient synthesis of mesoporous ­Co3O4 nanoparticles

for electrochemical energy storage
R. M. Kore1 · B. J. Lokhande1

Received: 26 October 2019 / Accepted: 24 February 2020

© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
High surface area, mesoporous metal oxide nanoparticles play a significant role in the electrochemical charge storage applica-
tions. A facile solvent-deficient approach has been reported for synthesis of high surface area, mesoporous ­Co3O4 nanoparti-
cles for the electrochemical energy storage. A precursor is obtained by grinding hydrated cobalt nitrate salt with ammonium
bicarbonate for 25 min without addition of any true solvent. Further, the precursor is annealed at 300 ℃ to obtain ­Co3O4 from
as prepared untreated precursor and after rinsing using deionized water. The XRD, Raman and FTIR spectra revealed the
single-phase formation of ­Co3O4. SEM shows granular-type morphologies with two distinct size for two different samples.
The BET analysis confirms mesoporous nature with specific surface area of 135 and 193 ­m2g−1 for samples obtained from
untreated and rinsed precursors. The maximum specific capacitance of ­Co3O4 obtained from untreated and rinsed samples
are 184 and 349 ­Fg−1. A very fewer equivalent series resistance of 2.24 Ω and 1.91 Ω has been observed, respectively.

1 Introduction phones, etc. However, the energy density of the ECs limits
their ample use [5, 6].
The intense growth in world population, industrialization Relying on the active materials used and the charge
and advancement in modern technology have made the storage mechanism, ECs are distinguished in two different
energy-based appliances as the everlasting quest of human- types; electrochemical double-layer capacitor (EDLCs) and
ity. The energy-based appliances plays an important role in pseudocapacitor. In EDLCs, carbon-based active materials
the development of human civilization. The energy stor- with high surface area such as MWCNT, graphene etc. were
age, a key intermediate step towards versatile and effective used, which store charges at electrode/electrolyte interface.
energy applications, has grained great attention. As a conse- While in pseudocapacitors or redox supercapacitors, fast
quence, significant research has been made in the processing and reversible surface or near-surface reactions occurs for
and development of energy storage materials and methods charge storage in electrode materials such as transition metal
[1–4]. Even though in the field of consumer electronics, oxides as well as electrically conducting polymers [7]. Cur-
lithium-ion batteries have made considerable advances, rent research mainly focused on the various transition metal
electrochemical supercapacitors (ECs) have some significant oxides, such as R
­ uO2, ­MnO2, NiO, Cd(OH)2, ­Co3O4, ­Fe2O3,
striking properties, such as higher power density than bat- ­TiO2and ­V2O5 as an electrode material for energy storage
teries, fast charging and large cycling stability over repeated application [8–18]. Among these, cobalt hydroxide or oxide
charge–discharge. Such kind of different properties makes are promising candidates for application in electrochemical
ECs a promising candidate for various applications such as capacitors due to their low cost, great reversibility, and high
hybrid electric vehicles, frequency regulation in smart grids theoretical specific capacitance i.e. 3560 ­Fg−1 [19]. How-
as well as portable electronic devices, such as, camera, smart ever, when ­Co3O4 is explored as an electrode material it
is not able to achieve that much high-specific capacitance
values. To address these issues of low specific capacities,
significant efforts have been devoted during the synthesis
* B. J. Lokhande
bjlokhande@yahoo.com of ­Co3O4 to alter and control morphologies and nanostruc-
tures including nanorods [20], nanosheets [21], nanowires
1
Lab of Electrochemical Studies, School of Physical Sciences, [22] porous nanostructures, [23] and nanoparticles, [24]
Punyashlok Ahilyadevi Holkar Solapur University, Solapur, etc. Ordinarily, hierarchically nano-sized porous materials
M. S. 413255, India

13
Vol.:(0123456789)
 Journal of Materials Science: Materials in Electronics

exhibits high porosity, large surface area, more accessible the moles of anion (i.e. ­NO3−) of the metal salt [26]. The
sites with low density and well organized porosity at differ- obtained mixture called precursor, was then annealed in two
ent length scales, which are very important in energy storage different stages, (i) untreated and (ii) after rinsing at 300 ℃
and conversion, catalysis, photocatalysis, adsorption, separa- for 2 h to get ­Co3O4 nanoparticles. The samples hereafter,
tion, gas sensing, electron and ion transport, and mass load- labeled as U-CO and R-CO for the samples annealed without
ing and diffusion, etc. The hierarchy of porosity, structural, rinsing (i.e. untreated) and with rinsing.
morphological and component levels in the materials is also
key for their high performance in all kinds of applications 2.2 Characterizations
[22–24]. In the context, various methods have been explored
for synthesis of different nanostructures of ­Co3O4, such as To get the information about the phase transformation
hydrothermal, solvothermal, wet chemical synthesis, elec- and thermal decomposition temperature of the precursors
trochemical precipitation etc. [20–24]. obtained during the solvent-deficient synthesis thermo-
In the present study, the synthesis of mesoporous C ­ o 3O 4 gravimetric analysis was carried using SDT-2960 using TA
nanoparticles is carried in solvent-deficient environment. Instruments, USA. X-ray diffraction (XRD) pattern analysis
The method has been successfully employed for the syn- was performed using Rigaku D/max 2550 Vb + 18 kW X-ray
thesis of a vast range of metal hydroxide/oxide nanomateri- diffractometer with Cu Kα radiation (λ = 0.15405 nm), to
als/nanoparticles suggesting the versatility of the method investigate the phase, crystal structure and crystallite size of
for preparation of metal oxide nano materials [24–27]. The obtained U-CO and R-CO samples. The crystallite size (D)
obtained products are usually phase-pure and crystallize in was determined using the Scherer’s relation D = 0.9λ/βcosθ.
thermodynamically favorable nanoscale phase. The prod- Further, Raman and Fourier transform infra-red (FTIR)
ucts do not exhibit low-crystallinity problem like many other spectroscopy of both the samples was carried for the phase
aqueous solution methods, as well as, excellent chemical confirmation of both the samples using the Invia I- Renishaw
purity can be achieved due to the absence of capping agents. Raman spectrometer and Nicolet 560 FTIR spectrophotom-
The products formed in the solvent-deficient environment eter, respectively. The scanning electron microscopy (SEM
are mesoporous with very high surface area and so are prom- – S-4300 Hitachi, Japan) was used to analyze the surface
ising candidates for different applications. morphological and EDX analysis. Surface area and pore
Here, nanoparticles of two distinct size have been syn- size/volume was evaluated by the BET and BJH analysis,
thesized. In addition, the surface area as well as distinct by Quantachrome NOVA 1000e apparatus.
pore volume in the solvent-deficient environment has been
observed in the solvent-deficient environment. Further, 2.3 Electrochemical measurements
through various analysis/measurements like XRD, FTIR,
RAMAN, BET, SEM, TEM, SAED and electrochemical The electrochemical characterizations were taken by elec-
characterizations, it has been corroborated that structural, trochemical analyzer CHI660D (CH Instruments, USA) in
morphological, microstructural and surface area properties the 1.0 M KOH aqueous solution. The working electrodes
have significant effect on the electrochemical performance of ­Co3O4 nanoparticles were prepared using the mixture of
of the ­Co3O4 nanoparticles. electrochemically active material 80 wt%, acetylene black
10 wt% and polyvinylidene fluoride (PVdF) 10 wt%. The
prepared mixture was converted to a slurry by adding few
2 Experimental drops of NMP (n-methyl 2-pyrrolidone) solvent. The slurry
was uniformly coated on the stainless-steel strips (1 × 5
2.1 Synthesis of ­Co3O4 nanoparticles ­cm2) and dried at 80 ℃ for 8 h. Microbalance, TAPSON-
Model 100-TS has been used to determine the weight of
The solvent-deficient approach reported by Smith et  al. the active material. The active mass is around 1.12 mg and
has been utilized for the mesoporous C ­ o3O4 nanoparticles 1.24 mg for the U-CO and R-CO electrodes, respectively.
synthesis [25]. The synthesis is carried by using the cobalt The electrochemical characterization was carried by cyclic
nitrate-hexahydrate salt (Co(NO3)2·6H2O) and ammonium voltammetry (CV), galvanostatic charge discharge (CD) and
bicarbonate ­(NH4HCO3) without using any solvent. The ana- electrochemical impedance spectroscopy (EIS). The specific
lytic grade chemicals purchased from SD Fine chemicals pvt. capacitance (Cs) is determined using the formula [13].
Ltd. were used without further purification. Double distilled V

mv Vc − Va ∫Va
water was used for the rinsing of the reacted species. For
c
1
CS = I(V)dV (1)
grinding of the hydrated cobalt nitrate salt (Co(NO3)2·6H2O)
( )

and ammonium bicarbonate together agate mortar and pes-

tle have been used. The moles of bicarbonate should equal

13
Journal of Materials Science: Materials in Electronics

where, Cs is the specific capacitance, ν is scan rate ­(mVs−1), 3.2 Thermo‑gravimetric, structural

(Vc − Va) is the CV window, I (V) shows the current (mA), and spectroscopic measurements:
and m is the deposited mass of the active material for unit
area (here 1 ­cm2) dipped in electrolyte. Thermo-gravimetric analysis (TGA) of the untreated and
Specific capacitance (Cs) also calculated from galvano- rinsed precursors was carried in air in between the range
static charge–discharge curves, 25–800 ℃ (Fig. 1a) to obtain the information about the ther-
mal decomposition temperature during the annealing. For
IΔt
CS = (2) the untreated precursor, the total weight loss is 76.91% has
mΔv
been observed, whereas for the rinsed precursor the weight
where I is the constant current density, Δt is the discharge loss is 33.98%. Here, for untreated precursors the weight
time. loss is more as compared to the rinsed precursors, as the
untreated precursor comprises the mixture of N ­ H4NO3,
Co(OH)2, ­Co2(OH)3(NO3)3 and C ­ o2(OH)(NO3)·H2O, as
3 Results and discussion shown in Eq. 3. Conversely, the rinsed precursors contains
only Co(OH)2, since, the ­NH4NO3 is getting dissolved
3.1 Plausible mechanism for the formation of ­Co3O4 through the reaction given in Eq. 4. In addition, rinsing
nanoparticles prior to annealing prevents these nitrate compounds such
as ­Co2(OH)3(NO3)3 and ­Co2(OH)(NO3)·H2O from forming,
The plausible reaction mechanism involved in the solvent- i.e. the nitrate ligand substitutes for one of the hydroxide
deficient synthesis for the formation of the mesoporous ligands as the ­H2O solvent evaporates. In the untreated pre-
­Co3O4 nanoparticles is similar to our earlier report [26, cursors, the weight loss of 76.91 wt% occurred between 140
27]. In short it consists two different steps. The cobalt and 275 ℃, is attributed to the removal of water as well
nitrate hexahydrate and ammonium bicarbonate are ini- as decomposition of N ­ H4NO3 which occurs above 160 ℃
tially grinded together, forming the mixture of Co(OH)2, [26, 27]. The 13.17 wt% weight loss observed between 25
­C o 2(OH) 3(NO 3) 3, ­C o 2(OH)(NO 3)·H 2O and ­N H 4NO 3 as and 200 ℃, is attributed to the removal of water present in
given in Eq. 3 [25]. During the aggregation of the precur- the as-synthesized Co(OH)2 precursors. The sudden weight
sor the agglomerates were formed around the intercalated loss (16.14%) between 200 and 250 ℃ is attributed to the
spectator ions/molecules such as NH−4 , NO−3  , ­H2O etc. which decomposition of Co(OH)2 precursors. After 300 ℃, weight
plays the role as template in the solvent-deficient synthe- of the Co(OH)2 precursors no longer changes, indicating
sis. The removal of these spectator ions during annealing the complete decomposition of Co(OH)2 precursor and the
provides the mesoporous nature to C ­ o3O4 nanoparticles stable residue can reasonably be attributed to the pure C
­ o3O4
after the ions were removed. The ­Co3O4 nanoparticles phase. Hence, the synthesized precursor was calcined at 300
formed after the annealing the precursors without rins- ℃ for 2 h to form pure ­Co3O4 phase.
ing stage results into the larger grains, which occurs, as XRD spectra of U-CO and R-CO samples has been shown
the byproducts C ­ o2(OH)3(NO3)3 and C ­ o2(OH)(NO3)·H2O in Fig. 1b. Broad diffraction peaks of various intensity sup-
and ­NH4NO3, formed during the grinding reaction limits port for the better crystallinity of the obtained products.
the crystallite size of cobalt oxide to be > 100 nm. In con- The diffraction peaks observed at 31.31°, 36.90°, 38.61°,
trast, during the rinsing of the precursors before annealing 44.88°, 55.74°, 59.44°, 65.34°, and 77.47° are correspond-
results into the replacement of the ­NO3− ligand and ­H2O by ing to (220), (311), (222), (400), (422), (511), (440) and
the ­OH− (hydroxide ions) and forms amorphous Co(OH)2. (533) planes matched with JCPDS: 76-1802, confirms the
Hence, by rinsing and thus preventing these compounds spinal cubic phase of C­ o3O4 indicating the formation of sin-
from forming, the crystallite size of these materials tends gle-phase cobalt oxide. The intensities of the characteristic
to lie below 20 nm [25]. This drastic decrease in the grain peaks of the XRD spectra are strong, indicates the highly
size as well as crystallite size, is further supported through crystalline nature of the samples. However, the samples
various characterizations. R-CO has broadened peaks as compared to that of U-CO,
Grind
� Co(OH)2 + Co2 (OH)3 NO3 3
( ) ( )
Co NO3 2 ⋅ 6H2 O + 2NH4 HCO3 (S) ���������→ (3)
Heat
+ Co2 (OH)(NO)3 ⋅ H2 O + NH4 NO3 �������→
� nano Co3 O4

Rinsing
(4) indicates that the size decreasing effect which was occurred
NH4 NO3 (l) ������������→
� N2 O(g) + 2H2 O
due to the inclusion of the rinsing step before annealing. The
average crystallite size for the sample U-CO and R-CO is

13
 Journal of Materials Science: Materials in Electronics

Fig. 1  a thermo-gravimetric analysis curves of the untreated and rinsed precursors, b X-ray diffraction pattern, c RAMAN spectra and d FTIR
spectra of the samples U-CO and R-CO

around 132 nm and 70 nm, respectively. The size decrements and 2886 cm−1 for the samples U-CO and R-CO, respec-
add to the increase of the active surface area of the rinsed tively, can be related to N–H bond [31]. Here, the Raman
samples, which is more favorable for the electrochemical and FT-IR spectrum, clearly endorses for the formation of
charge storage system. cobalt oxide nanoparticles.
Figure 1c shows the Raman spectrum obtained for both
the samples U-CO and R-CO. Five obvious Raman peaks 3.3 Morphological, microstructural and elemental
located at 186, 465, 507, 596, and 661 cm−1, corresponds analysis
to three F2g, one Eg and one A1g Raman active modes of the
­Co3O4 nanoparticles, respectively [28]. The Raman peaks To observe the surface morphology of the samples and
with the phonon symmetries are due to lattice vibrations of microstructural analysis SEM and TEM imaging was carried
the spinal arrangement, in which C ­ o2+ and C
­ o3+ cations are as shown in Fig. 2a–f. Figure 2a, b corresponds to the cobalt
respectively situated at tetrahedral and octahedral site in the oxide nanoparticles obtained from the annealing of the pre-
cubic lattice. cursors without rinsing i.e. U-CO. It shows spherical granu-
Figure  1d shows the FT-IR spectrum of cobalt oxide lar type morphology. As, the precursors were not rinsed, the
in the range 4000–400 cm−1. The broad bands for sample byproducts available in the mixture restricts the growth of
U-CO centered at 3414 cm−1 are assigned to O–H bending the ­Co3O4 particles towards nanoscale. 130–150 nm is the
modes of water [29]. The absorption peaks at 662, 566 cm−1 grain size of the C
­ o3O4 nanoparticles obtained for U-CO
for U-CO and 665, 579 cm−1 for R-CO are assigned to the sample. However, the grain size was drastically decreased
Co–O modes [30]. The other absorption peak at 2902 cm−1 for the sample R-CO prepared from the rinsed precursors,

13
Journal of Materials Science: Materials in Electronics

Fig. 2  Scanning electron micro-

graph images of a, b ­Co3O4
nanoparticles obtained from
untreated precursors (U-CO), c,
d ­Co3O4 nanoparticles obtained
from rinsed precursors (R-CO),
e, f TEM and SAED pattern of
R-CO sample

which is around 40–60 nm. This may have been occurred distribution of 40–60 nm. The SAED pattern endorses for
because, during the rinsing step these byproducts were get the crystalline behavior of the cobalt oxide nanoparticles.
dissolved and enable the particle size to reduce towards Figure 3a, b shows the EDAX pattern of both the samples
nanoscale. The obtained results clearly endorse for the pro- U-CO and R-CO, respectively. The elemental analysis con-
posed plausible formation mechanism, where the byproducts firms the existence of only cobalt and oxygen content. These
formed during the grinding reaction restrict the growth of results endorses for the formation of phase-pure samples of
the cobalt oxide particles towards nanoscale. However, dur- cobalt oxide in both the cases, without any impurity.
ing the rinsing step these byproducts were get dissolved and
enable the particle size to reduce towards nanoscale. 3.4 BET surface area analysis
Figure 2e, f corresponds to the TEM and SAED pat-
tern analysis of R-CO sample which endorses for the SEM Electrode materials surface area and the porosity is an
and XRD results, respectively. The TEM analysis confirms essential parameter in the electrochemical characteristics.
the formation of the R-CO samples with the average size Hence, to obtain the information about surface area, pore

13
 Journal of Materials Science: Materials in Electronics

Fig. 3  EDAX analysis for the samples a U-CO and b R-CO

volume and distribution of pore size, N

­ 2 adsorption–desorp- c­ cg−1 is observed for U-CO and R-CO samples, respectively.
tion analysis was carried. The Fig. 4a, b shows the isotherm Formerly, it has been confirmed that the larger surface area
of ­N2 adsorption–desorption and respective distribution of assists to advance the capacitive performance by allowing
pore size for both the samples U-CO and R-CO, respec- the electrolyte ion diffusion into the active sites for the redox
tively. A type IV irreversible isotherm endorsing for the reaction [33, 34]. Usually, high surface area, mesoporous
mesoporous nature of C ­ o3O4 nanoparticles is obtained for nature and larger pore volume of the materials supports for
the samples U-CO and R-CO [32]. The BET surface area better electrochemical performance because they provide
calculated for the samples U-CO and R-CO are 135 m ­ 2g−1 shorter ion diffusion distance and low-resistant pathways
2 −1
and 193 m­ g , respectively. Furthermore, the mesoporous during the electrochemical reactions.
nature has been observed for both the samples endorsed by
BJH pore size analysis data. The distribution of pore size
centered at around 5–6 nm indicates unimodal pore size hav-
ing the average pore volume about 0.383 ­ccg−1 and 0.470

Fig. 4  a ­N2 adsorption–desorption isotherm and b BJH pore size distribution curve for the samples U-CO and R-CO

13
Journal of Materials Science: Materials in Electronics

3.5 Electrochemical characterizations Table 1  Electrochemical parameters from CVs for U-CO and R-CO
samples
Electrochemical performance has been investigated in a Samples EO (mV) ER (mV) ∆EO,R = EO
three-electrode cell configuration in 1 M KOH electrolyte. – ER (mV)
The typical cyclic voltammetry (CV) curves at 5­ mVs−1 scan U-CO 341 404 63
rate within a potential window of 0–0.5 V (vs. S.C.E.) of R-CO 348 390 42
both the samples is shown in Fig. 5a. Table 1 represents
the electrochemical parameters derived from the CV curves − EO and ER are defined as the oxidation (anodic peak) potential and
are. The redox peaks observed instead of typical rectan- reduction (cathodic peak) potential, respectively
gular shapes, in CV curve sweeps clearly indicating that,
the faradic redox reaction are responsible for the capacitive CoOOH + OH− → CoO2 + H2 O + e− (6)
behavior of both the samples. These redox peaks endorses
the reversible conversion between different oxidation states
of cobalt. The related redox reactions are described as fol- In both CV curves, the symmetry of cathodic sweeps
lows in Eqs. 5, 6; [21, 35] to the respective anodic sweeps is absent, which clearly
indicates some irreversibility is present in redox process of
Co3 O4 + OH− + H2 O → 3CoOOH + e− (5) U-CO and R-CO samples. Usually, redox-active materials in
pseudocapacitors involve faradic reactions, where the kinetic
realization of ideal reversibility of positive and negative

Fig. 5  a Cyclic voltammetry curves for the samples U-CO and R-CO at 5 m ­ Vs−1, b, c CV curves with respect to different scan rates for samples
U-CO and R-CO, respectively. d Variation of specific capacitance with respect to scan rate obtained from CV curves

13
 Journal of Materials Science: Materials in Electronics

sweeps is difficult. In addition, ohmic resistance contrib- specific capacitance analyzed from CV curves is 184 F ­ g−1
−1
utes to the kinetic irreversibility of redox reaction. Here, and 349 F­ g for the samples U-CO and R-CO, respectively.
the ohmic resistance is caused by electrolyte ion diffusion In contrast, to endorse the Cs values calculated from the
during ­OH− charge intercalation–de-intercalation process at CV curves galvanostatic charge–discharge measurement
the electrodes [12]. The reversibility in the redox reaction was carried for both the samples U-CO and R-CO over the
can also been predicted from the over-potential (∆EO,R), potential window 0–0.4 V at current densities from 2 to
where smaller value of over-potential resembles to better 10 mA cm−2. Figure 6a shows the charge–discharge curve
reversibility and vice versa. Among both the samples, R-CO of both the samples U-CO and R-CO. The nonlinear nature
showed highest reversibility (∆EO,R = 42 mV), while U-CO of the CD curves endorses for the redox nature of charge
confirmed the least reversibility (∆EO,R = 63 mV). The sam- storage process. Figure 6b, c shows the CD curves at cur-
ple which shows high reversibility in redox reactions are rent densities from 2 to 10 mA ­cm−2 for both the samples.
suitable to produce high capacitances. Compared with the Figure 6d represents the variation of the specific capacitance
U-CO sample, the R-CO sample shows high reversibility value with respect to different current densities. The maxi-
with maximum area under curve, endorses for the better mum obtained specific capacitance from the charge–dis-
electrochemical properties of R-CO. Figure 5b, c shows CV charge curves are 166 F ­ g−1 and 330 ­Fg−1 for the samples
curves of the samples U-CO and R-CO at scan rates 5–100 U-CO and R-CO, respectively.
­mVs−1, respectively. Figure 5d indicates the variation of the From the electrochemical characterizations, it was
Cs with respect to scan rate. The maximum value of the observed that the sample U-CO has less area under the CV
curve as compared to the R-CO sample, clearly endorses

Fig. 6  a Galvanostatic charge discharge curves for the samples U-CO d Variation of specific capacitance with respect to current density
(at 1.6 A­ g−1) and R-CO (at 1.8 A ­ g−1), b, c curves with respect to obtained from Galvanostatic charge discharge curves
different current density for samples U-CO and R-CO, respectively.

13
Journal of Materials Science: Materials in Electronics

relatively high electrochemical performance. The similar The electrochemical performance and suitability of
trend of the specific capacitance was also obtained from ­Co3O4 nanoparticles as a supercapacitor electrode material
the CD curves, where the sample R-CO has the lager dis- has been analyzed using the electrochemical impedance
charge time than that of U-CO sample. The better perfor- spectroscopy (EIS) within the frequency range of 0.01 Hz to
mance of R-CO can be endorsed to the fact that the particle 1 MHz with a potential amplitude of 5 mV/SCE at the open
size of the R-CO is drastically decreased during the rinsing, circuit potentials 0.202 V, 0.281 V for U-CO and R–CO
which facilitate for the increased specific surface area and samples, respectively. Figure 7a shows the Nyquist plot of
volume to the cobalt oxide nanoparticles, endorsed by the both samples and inset shows the matched equivalent circuit.
BET measurement. In addition, the variations in the Cs val- The expanded view of high frequency region is highlighted
ues calculated from CV and CD measurement curves were in Fig. 7b. The corresponding circuitry parameters are pro-
observed for both the samples. This divergence in the results vided into the Table 2.
could be attributed as the specific capacitance values ana- For a supercapacitor, electronic and the ionic contri-
lyzed from CV curves were at the definite potential, while butions comprise equivalent series resistance (ESR). The
that of calculated from CD curve measurements is the aver- electronic resistance involves the electronic intrinsic resist-
age capacitance over the potential range 0–0.4 V. Hence, ance of ­Co3O4 nanoparticles. The interfacial resistance has
some discrepancy has been observed in the CS values due been contributed by the particles-to-current collector and
to the averaging [36, 37]. The Cs values were decreasing particles-to-particles interfaces. The electrolyte resistance
with increase in the scan rate as well as with the current in mesopores and the ionic (diffusion) resistance (i.e. charge
density. This has been observed since at higher current den- transfer resistance, Rct) of ions intercalating in small pores
sities as well as scan rate the ion transport into mesoporous [26, 38–41]. The intercept of real impedance at high frequen-
network was restricted due to the slow diffusion of ions that cies gives the value of ESR which is 2.24 Ω for the samples
are entering within the electrode materials. This trend of U-CO and 1.91 Ω for R-CO sample, respectively. However,
electrochemical performance is in good agreement with that Rct for the samples U-CO and R-CO is 17.34 Ω and 16.56
of the nitrogen adsorption–desorption results. In contrast to Ω, respectively. These results emphasize that higher surface
U-CO, sample R-CO possess large surface area which corre- area and superior pore volume of R-CO than U-CO sample
sponds to the improvement in the electrochemical properties. provides very low impedance and consequently easy access

Fig. 7  a Electrochemical impedance spectra for the samples U-CO and R-CO (inset shows matched equivalent circuit) b extended view of the
Nyquist plot in the high frequency region with frequency magnitudes

Table 2  Circuitry parameters of Electrode RS (Ω) Rct (Ω) C1 (µF) C2 (F) Q (C) R1 (Ω) R2 (Ω)
matched equivalent circuit for
samples U-CO and R-CO U-CO 2.24 17.34 238 0.0495 0.01646 1.45 × 1014 9.81 × 1010
R-CO 1.91 16.56 358 0.0726 0.02851 9 × 1013 7.35 × 1010

13
 Journal of Materials Science: Materials in Electronics

precursors is 77.8% and 82.1%, respectively, after 1000

cycles.

Acknowledgements  Authors are thankful to IITBNF, IIT Bombay, for

providing characterization facility under Indian Nanoelectronics Users
Program (INUP) sponsored by Deity, Government of India. Authors
are also thankful to the Research for Resurgence Foundation for the
scientific discussion regarding the works.

References
1. L. Dai, Functionalization of graphene for efficient energy conver-
sion and storage. Acc. Chem. Res. 46, 31–42 (2013)
2. P. Simon, Y. Gogotsi, Capacitive energy storage in nanostruc-
tured carbon-electrolyte systems. Acc. Chem. Res. 46, 1094–1103
(2013)
3. X. Xia, Y. Zhang, D. Chao, C. Guan, Y. Zhang, L. Li, X. Ge, I.M.
Bacho, J. Tu, H.J. Fan, Solution synthesis of metal oxides for elec-
Fig. 8  Cycling stability study of the samples U-CO and R-CO trochemical energy storage applications. Nanoscale 6, 5008–5048
(2014)
4. M. Li, P.W. Yuan, S.H. Guo, F. Liu, J.P. Cheng, Design and syn-
to ­OH– ions intercalation/de-intercalation into the electrode thesis of Ni-Co and Ni-Mn layered double hydroxides hollow
microspheres for supercapacitor. Int. J. Hydrogen Energy 42,
material.
28797–28806 (2017)
In addition, stability study of the electrode is one of the 5. R.R. Salunkhe, Y.H. Lee, K.H. Chang, J.M. Li, P. Simon, J. Tang,
essential parameter used to verify the characteristics of N.L. Torad, C.C. Hu, Y. Yamauchi, Nanoarchitectured graphene-
supercapacitor. The electrochemical stability is estimated based supercapacitors for next-generation energy-storage applica-
tions. Chem. Eur. J. 20, 13838–13852 (2014)
from CV curves at the 100 m ­ Vs−1 scan rate for 1000 cycles. 6. L.L. Zhang, X.S. Zhao, Carbon-based materials as supercapacitor
Figure 8 demonstrates capacity retention of different sam- electrodes. Chem. Soc. Rev. 38, 2520–2531 (2009)
ples with respect to cycle numbers. The % capacity reten- 7. P. Simon, Y. Gogotsi, Materials for electrochemical capacitors.
tion is 77.8% and 82.1%, for the samples U-CO and R-CO, Nat. Mater. 7, 845–854 (2008)
8. R.R. Bi, X.L. Wu, F.F. Gao, L.Y. Jiang, Y.G. Guo, L.J. Wan,
respectively. This physical characteristics and electrochemi- Highly dispersed ­RuO2 nanoparticles on carbon nanotubes: facile
cal performance of the ­Co3O4 nanoparticles supports for the synthesis and enhanced supercapacitance performance. J. Phys.
suitability of the solvent-deficient approach for the synthesis. Chem. C114, 2448–2451 (2010)
9. Y.R. Ahn, M.Y. Song, S.M. Jo, C.R. Park, Electrochemical capaci-
tors based on electrodeposited ruthenium oxide on nanofibre sub-
strates. Nanotechnology 17, 2865–2869 (2006)
4 Conclusion 10. Q.Y. Liao, S.Y. Li, H. Cui, C. Wang, Vertically-aligned gra-
phene@Mn 3O 4nanosheets for a high-performance flexible
In summary, using a robust, scalable solvent-deficient route all-solid-state symmetric supercapacitor. J. Mater. Chem. A 4,
8830–8836 (2016)
synthesis, the C­ o3O4 nanoparticles were successfully syn-
11. R.M. Kore, A.V. Thakur, B.Y. Fugare, B.J. Lokhande, Reagent
thesized. The obtained ­Co3O4 nanoparticles got two distinct ratio dependent physical properties and electrochemical perfor-
features by just altering the procedure of annealing the pre- mance of NiO nanoparticles synthesized using solvent deficient
cursors before and after rinsing. The XRD, RAMAN and approach. AIP Conf. Proceed. 1942–1, 140069 (2018)
12. R.M. Kore, R.S. Mane, M. Naushad, M.R. Khan, B.J. Lokhande,
FTIR spectroscopy confirms formation of the single-phase
Nanomorphology-dependent pseudocapacitive properties of NiO
­Co3O4 nanoparticles. The rinsing step included provides electrodes engineered through a controlled potentiodynamic elec-
special effect resulting into the crystallite size and grain size trodeposition process. RSC Adv. 6, 24478–24483 (2016)
decrement as endorsed by the XRD and scanning electron 13. S. Patil, S. Raut, R. Gore, B. Sankapal, One-dimensional cadmium
hydroxide nanowires towards electrochemical supercapacitor.
micrographic images. The purity of the samples was deter-
New J. Chem. 39, 9124–9131 (2015)
mined by EDAX analysis. Further, the significant change 14. Q. Liao, N. Li, S. Jin, G. Yang, C. Wang, All-solid-state sym-
in the surface area and electrochemical performance of the metric supercapacitor based on ­Co3O4 nanoparticles on vertically
­Co3O4 nanoparticles has also been observed and confirmed aligned graphene. ACS Nano 9, 5310–5317 (2015)
15. G.C. Li, X.N. Hua, P.F. Liu, Y.X. Xie, L. Han, Porous C ­ o 3O 4
from the BET and electrochemical measurement. The bet-
microflowers prepared by thermolysis of metal-organic framework
ter electrochemical performance of cobalt oxide nanopar- for supercapacitor. Mater. Chem. Phys. 168, 127–131 (2015)
ticles endorses for the potential candidate as an electrode 16. B.Y. Fugare, A.V. Thakur, R.M. Kore, B.J. Lokhande, Spray pyro-
material in energy storage appliances. The capacity reten- lysed Ru:TiO2 thin film electrodes prepared for electrochemical
supercapacitor. AIP Conf. Proceed. 1942, 140010 (2018)
tion for ­Co3O4 samples obtained from untreated and rinsed

13
Journal of Materials Science: Materials in Electronics

17. A.V. Thakur, B.J. Lokhande, Electrolytic anion affected charge 29. K. Nakamoto, Infrared Spectra of Inorganic and Coordination
storage mechanisms of ­Fe3O4 flexible thin film electrode in KCl Compound, 4th edn. (Chemical Industry Press, Beijing, 1991)
and KOH: a comparative study by cyclic voltammetry and gal- 30. J.A. Gaddsden, Infrared Spectra of Minerals and Related Inor-
vanostatic charge–discharge. J. Mater. Sci.: Mater. Electron. 28, ganic Compound, 1st edn. (Butterworth, London, 1975)
11755–11761 (2017) 31. R.A. Nyquist, R.O. Kagel, Infrared Spectra of Inorganic Com-
18. C.C. Hu, C.M. Huang, K.H. Chang, Anodic deposition of porous pounds (Academic Press, New York, 1971)
vanadium oxide network with high power characteristics for pseu- 32. C. Sangwichien, G.L. Aranovich, M.D. Donohue, Density func-
docapacitors. J. Power Sources 185, 1594–1597 (2008) tional theory predictions of adsorption isotherms with hysteresis
19. L. Wang, Z.H. Dong, Z.G. Wang, F.X. Zhang, J. Jin, Layered loops. Colloids Surf. A 206, 313–320 (2002)
α-Co(OH)2 nanoconesas electrode materials for pseudocapacitors: 33. X. He, M. Yang, P. Ni, Y. Li, Z.-H. Liu, Rapid synthesis of hollow
understanding the effect of interlayer space on electrochemical structured ­MnO2 microspheres and their capacitance. Colloids
activity. Adv. Funct. Mater. 23, 2758–2764 (2013) Surf. A 363, 64–70 (2010)
20. X. Xu, J. Shen, N. Li, M. Ye, Microwave-assisted in situ synthesis 34. G. Sundara, B. Raj, A.M. Asiri, A.H. Qusti, J.J. Wu, S. Anandan,
of cobalt nanoparticles decorated on reduced graphene oxide as Sonochemically synthesized ­MnO2 nanoparticles as electrode
promising electrodes for supercapacitors. Int. J. Hydrogen Energy material for supercapacitors. Ultrason. Sonochem. 21, 1933–1938
40, 13003–13013 (2015) (2014)
21. Y.Y. Gao, S.L. Chen, D.X. Cao, G.L. Wang, J.L. Yin, Electro- 35. X. Qing, S. Liu, K. Huang, K. Lv, Y. Yang, Z. Lu, D. Fang, X.
chemical capacitance of ­Co3O4 nanowire arrays supported on Liang, Facile synthesis of ­Co3O4 nanoflowers grown on Ni foam
nickel foam. J. Power Sources 195, 1757–1760 (2010) with superior electrochemical performance. Electrochim. Acta 56,
22. S.K. Jesudoss, J. Judith Vijaya, P. Iyyappa Rajan, K. Kaviyarasu, 4985–4991 (2011)
M. Sivachidambaram, L. John Kennedy, H.A. Al-Lohedan, R. 36. V.V. Jadhav, R.M. Kore, N.D. Thorat, J.M. Yun, K.H. Kim, R.S.
Jothiramalingame, M.A. Munusamy, High performance multi- Mane, C. O’Dwyer, Annealing environment effects on the elec-
functional green C ­ o3O4 spinel nanoparticles: photodegradation trochemical behavior of supercapacitors using Ni foam current
of textile dye effluents, catalytic hydrogenation of nitro-aromatics collectors. Mater. Res. Express 5, 125004 (2018)
and antibacterial potential. Photochem. Photobiol. Sci. 16, 766– 37. B. Saravanakumar, K.K. Purushothaman, G. Muralidharan, Inter-
778 (2017) connected ­V2O5 nanoporous network for high-performance super-
23. K. Kaviyarasu, A. Raja, P.A. Devarahan, Structural Elucidation capacitors. ACS Appl. Mater. Interfaces 4, 4484–4490 (2012)
and spectral characterization of C ­ o3O4 nanoflakes. Spectrochim. 38. Z.B. Wen, Q.T. Qu, Q. Gao, X.W. Zheng, Z.H. Hu, Y.P. Wu, Y.F.
Acta A 114, 586–591 (2013) Liu, X.J. Wang, An activated carbon with high capacitance from
24. M.H. Sun, S.Z. Huang, L.H. Chen, Y. Li, X.Y. Yang, Z.Y. Yuan, carbonization of a resorcinol–formaldehyde resin. Electrochem.
B.L. Su, Applications of hierarchically structured porous materi- Commun. 11, 715–718 (2009)
als from energy storage and conversion, catalysis, photocatalysis, 39. G.T. Anand, D. Renuka, R. Ramesh, L. Anandaraj, S. John Sunda-
adsorption, separation, and sensing to biomedicine. Chem. Soc. ram, G. Ramalingam, C. MariaMagdalane, A.K.H. Bashird, M.
Rev. 45, 3479–3563 (2016) Maazad, K. Kaviyarasu, Green synthesis of ZnO nanoparticle
25. S.J. Smith, B. Huang, S. Liu, Q. Liu, R.E. Olsen, J. Boerio-Goates, using Prunus dulcis (Almond Gum) for antimicrobial and super-
B.F. Woodfield, Synthesis of metal oxide nanoparticles via a capacitor applications. Surf. Interfaces 17, 100376 (2019)
robust “solvent-deficient” method. Nanoscale 7, 144–156 (2015) 40. C. Xiong, T. Li, Y. Zhu, T. Zhao, A. Dang, H. Li, X. Ji, Y. Shang,
26. R.M. Kore, B.J. Lokhande, Hierarchical mesoporous network M. Khan, Two-step approach of fabrication of interconnected
of amorphous α—Ni(OH)2 for high performance supercapaci- nanoporous 3D reduced graphene oxide-carbon nanotube-poly-
tor electrode material synthesized from a novel solvent deficient aniline hybrid as a binder-free supercapacitor electrode. J. Alloys
approach. Electrochim. Acta 245, 780–790 (2017) Compd. 695, 1248–1259 (2017)
27. R.M. Kore, B.J. Lokhande, A robust solvent deficient route syn- 41. S.K. Meher, P. Justin, G. Ranga Rao, Nanoscale morphology
thesis of mesoporous F ­ e2O3 nanoparticles as supercapacitor elec- dependent pseudocapacitance of NiO: influence of intercalating
trode material with improved capacitive performance. J. Alloys anions during synthesis. Nanoscale 3, 683–692 (2011)
Compd. 725, 129–138 (2017)
28. G.X. Wang, X.P. Shen, J. Horvat, B. Wang, H. Liu, D. Wexler, J. Publisher’s Note Springer Nature remains neutral with regard to
Yao, Hydrothermal synthesis and optical, magnetic, and superca- jurisdictional claims in published maps and institutional affiliations.
pacitance properties of nanoporous cobalt oxide nanorods. J. Phys.
Chem. C 113, 4357–4361 (2009)

13