Journal of Alloys and Compounds 851 (2021) 156046

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Ultrafine chromium oxide (Cr2O3) nanoparticles as a pseudocapacitive

electrode material for supercapacitors
Imran Shafi a, Erjun Liang a, *, Baojun Li b
a
MOE Key Laboratory of Materials Physics, School of Physics, Zhengzhou University, 100 Science Road, Zhengzhou, 450001, China
b
College of Chemistry, Zhengzhou University, 100 Science Road, Zhengzhou, 450001, China

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

Article history: In contemporary electrochemical supercapacitors, the capacitive nature of the energy storage mecha-
Received 30 October 2019 nism seems to become an approaching alternative to lithium ion batteries in near future. In this context,
Received in revised form herein, we have investigated Cr2O3 ultrafine particles with excellent structural and electrochemical
22 May 2020
features as a promising capacitive energy candidate for supercapacitors. We have reported both, the EDL
Accepted 11 June 2020
Available online 12 July 2020
and pseudocapacitive features of ultrafine Cr2O3 nanoparticles during charging-discharging process in
aqueous solution (6 M KOH) and also separated these features by using the mathematical equation for
total current “i(V) ¼ k1v1/2þ k2v” in the Voltammogram. Along with the unique electrochemical char-
Keywords:
Cr2O3nanoparticles
acteristics, the aforementioned analysis for Cr2O3 nanoparticles is done for the first time. Furthermore, a
Pseudocapacitance superior specific capacitance of 340 F g1 at a specific current density of 0.5 Ag-1 along with an excellent
Capacitive and diffusion controlled current cycling retention of 85% after 3000 cycles is obtained. On coupling with an activated carbon electrode,
Cyclic voltammetry (CV) the asymmetric supercapacitor demonstrated the remarkable specific energy and the power density of
Galvanostatic charging/discharging (GCD) 12.5 Wh kg1 and 312.5 W kg1 respectively.
Electrochemical impedance spectroscopy © 2020 Elsevier B.V. All rights reserved.
(EIS)

1. Introduction of storage, the charge is stored near to the surface of the material by
the faradaic reactions [3]. A higher specific energy is featured by
Because of the wide range of applications, the electrochemical such type of reactions without compromising the cyclic stability of
energy devices and related energy storage mechanisms have the EDLCs electrodes. Pseudocapacitance followed by higher spe-
become an active area of research [1]. Supercapacitors and batte- cific energy density is exhibited by a few transition metal oxides
ries, both involve different electrochemical reactions, and their (TMOs) along with their excellent cyclic life. While, some other
energy capability is determined by the nature of corresponding TMOs have at least shown the signatures to be the pseudocapaci-
energy storing phenomenon. For instance, lower specific energy, tive candidates [4e8].
higher specific power, short charging span and better cyclic The present article elucidates the electrochemical properties of
retention than the lithium ion batteries is provided by the electric the orthorhombic Cr2O3nanoparticles for which the fast charging/
double layer supercapacitors (EDLCs) [2]. However, this technology discharging mechanisms based on the insertion and deinsertion of
is limited by the activated carbon based electrodes because they are the lithium ions leads towards a high specific energy throughout
attributed to have a shorter potential window (<1V). One of the the material. Though the electrical conductivity of Cr2O3 is not as
possible reasons for this is that the activated carbon becomes superior as for some other TMOs however, its theoretical capacity is
weaker and relatively poor conductors due to their high surface very high (1058 mAh g1). Therefore, a significant attention is
area and porosity and secondly all the internal specific area which is received by Cr2O3 nanoparticles and Cr2O3 based nanocomposites
linked with the walls of micropores cannot be accessed by the ions. in last a demi-decade. It is revealed by a recent research work that
Therefore, in order to get the enhanced level of specific energy and the Cr2O3 engineered at nanoscale have the signatures of the
power, another energy storage mechanism known as “Pseudoca- capacitive nature of charge storage and both; the faradaic and the
pacitance” is under the focus of nowadays researchers. In this type surface controlled charge storage mechanisms are reported [9].
However, the general CV behavior and the charge storage in this
study are due to the sharp peaks associated with the faradaic re-
* Corresponding author. actions only. The CV area is very low while the GCD based
E-mail address: [email protected] (E. Liang).

https://doi.org/10.1016/j.jallcom.2020.156046
0925-8388/© 2020 Elsevier B.V. All rights reserved.
2 I. Shafi et al. / Journal of Alloys and Compounds 851 (2021) 156046

capacitance is 55 F g1 only. A few more reports on the use of Cr2O3 (1000 W, 400  C) microwave irradiation environment for 2-min. A
nanoparticles and Cr2O3nanocomposites for the electrode of pale green solid product was obtained after the centrifugation at
supercapacitors are available but, along with the lower GCD based 10,000 RPM for 10-min. The final product was calcined at 700  C for
capacitance of 203 F g1, 257 F g1 and 300 F g1 respectively, they 1-h under “Ar” protection. The schematic illustration of the syn-
all have ignored to use the CV behavior for identification of the thesis process is given in Scheme 1.
nature of the charge storage in the Cr2O3 electrodes. Secondly, none
of these studies include the pseudocapacitive features of faradaic 2.3. Characterizations
reactions with a broad CV surface area [10e12]. To the best of our
knowledge, no one has analyzed and separated the excellent The structural and compositional analysis was carried out by
capacitive or pseudocapacitive type of charge storage for Cr2O3 using Raman spectroscopy in a continuous scanning from 200 to
nanoparticles by using the mathematical equation for total current 1700 cm1 while, X-ray diffraction (XRD) was performed between
“i(V) ¼ k1v1/2þ k2v” in the Voltammograms yet. This is very 10 - 80 at a voltage (V) ¼ 40 kV and current (I) ¼ 30 mA with a Ni-
important to use the alternative mathematical/theoretical means to filtered Cu-Ka radiation. The energy band gap was analyzed by
identify and then isolate the capacitive current response from the using the theoretical and experimental means. The size and the
non-capacitive parts, which is a prerequisite for the use of a ma- shape of the materials were observed by a Tunneling electron mi-
terial in supercapacitor applications. Till now, it has been assessed croscopy (TEM)JEOL JEM (2100F) under an accelerating potential of
from the general CV and GCD behaviors whether it is capacitive or 200 KV while, the surface morphology of the samples was observed
non-capacitive outcome without any solid grounds. The electro- by using the Scanning electron microscopy (SEM). The electro-
chemical performance of Cr2O3 nanoparticles is reported to be chemical performance was analyzed under the Zahner-Ennium-E4
linked with some of its characteristics including the controlled (German) electrochemical work station for Cyclic voltammetery
mesoporous structure, large surface area, lower grain size and ex- (CV) measurements for varying current response at a fixed scan
istence of various types of defects [13e16]. The possible redox re- rate(mV s1),Galvanostatic charging/discharging (GCD) measure-
actions (Cr4þ/Cr3þ) are as following; ments at constant specific current (Ag1), Electrochemical imped-
ance spectroscopy (EIS) and the frequency dependant Bode and the
CrO(OH) þ OH # CrO(OH)2 þ e e
(charging) electrical admittance plots. All these measurements were recorded
for Cr2O3 nanoparticles in 6 M KOH (an aqueous electrolyte).
e e
CrO(OH)2 þ OH # CrO(OH)3 þ e (discharging)
3. Results and discussion
Moreover, the Cr2O3 is also reported to have a variety of appli-
cations in magnetism, gas sensors, photo catalysis and super- 3.1. Material structures
carcapacitors [17e20].
Keeping in view the aforementioned gaps in the electrochemical The structural and compositional (vibrational) properties of the
properties of the Cr2O3 nanomaterials and other TMOs, along with Cr2O3 nanoparticles synthesized by a Sol-gel method and analyzed
the lower electrochemical performance of the Cr2O3 nanomaterials by Raman spectroscopy are shown in Fig. 1(a). In Fig. 1 (a), the peaks
synthesized by conventional methods, we have synthesized the located around 550 cm1 are due to the vibrations of CreO lattice
Cr2O3 ultrafine nanoparticles by a Sol-gel route and conducted their [21] while the peaks around 296 cm1, 350 cm1, 528 cm1and
structural and the electrochemical screening. For a deep insight 615 cm1 can be attributed to E1g and the fifth peak around
regarding the identification of the nature of the charge storage 550 cm1 is allocated as A1g. Altogether these peaks are termed as
(diffusion controlled or surface controlled) from the voltammo- Raman active modes for Cr2O3 [22]. The XRD spectrum of the Cr2O3
grams (CV), we have used the “b” value in the power law; “I ¼ anb”. nanoparticles performed in a continuous scanning range from 10 -
A mathematical equation for the total current; “i(V) ¼ k1v1/2þ k2v” 80 at a voltage (V) ¼ 40 kV and current (I) ¼ 30 mA with a Ni -
is used to separate the capacitive and non-capacitive components filtered Cu - Ka radiation is shown in Fig. 1(b). The characteristics
of the total current. Furthermore, a superior specific capacitance peaks in XRD spectra for the Cr2O3 nanoparticles correspond to a
based specific energy and power values are also reported in this well crystallizes rhombohedral Cr2O3 (space group R-3c,
study. a ¼ 0.4957 nm, b ¼ 0.4957 nm and c ¼ 1.3592 nm). Furthermore, in
a wide range of the Cr2O3 planes, any other type of peak is not
2. Experimental detected in XRD spectrum which means that our product is highly
pure.
2.1. Materials Being an important aspect of the electronic conductivity, the
energy band gap of the Cr2O3 nanoparticles was investigated by
All the reagents used in this work were purchased from theoretical and experimental means. Fig. 1(c and d) shows the
Shanghai Macklin Biochemical Co., Ltd. China and used directly theoretical and experimental band gap of the Cr2O3 nanoparticles
without further purification. respectively. The theoretically estimated energy band gap for the
Cr2O3 nanoparticles in Fig. 1(c) is 2.65 eV while it is 2.6 eV from the
2.2. Synthesis of Cr2O3 nanoparticles absorbance data obtained in the UV-spectroscopy in Fig. 1(d). Both
the results are in agreement with the results of [23]. A suitable
In this study, a Sol-gel method was used for the preparation of energy band gap facilitates the transfer of the electrons between
Cr2O3ultrafine nanoparticles. We have used Cr(NO3)3$9H2O and conduction and valence bands during the faradaic reactions and
triethanolamine (TEA) as precursor and the template materials results in an improved charge storage and hence the capacitance
respectively while, water is used as a green solvent. The entire re- too. The SEM and TEM images of the Cr2O3 nanoparticles are shown
action is completed under a high power microwave irradiation in Fig. 1(eej).Fig. 1(e) witnesses the successful synthesis of ultrafine
environment. In the typical reaction, the appropriate amount of Cr2O3 nanoparticles while, the uniform distribution of ultrafine
30 mmol triethanolamine (TEA, C6H15NO3) was mixed with 50 ml Cr2O3 nanoparticles is also manifested by the TEM image Fig. 1(f) at
of 0.2 M aqueous solution of Cr(NO3)3$9H2O. The solution was 20 nm, which is in good agreement with the surface morphology of
stirred vigorously for 2-h and then subjected to high power the samples. The general observation of the surface morphology of
 I. Shafi et al. / Journal of Alloys and Compounds 851 (2021) 156046 3

Scheme 1. The schematic illustration for the synthesis process of ultrafine Cr2O3 nanoparticles.

samples at 100 nm, shown in Fig. 1(g) indicates that the individual During the capacitance analysis from the voltammograms or CV,
particle size is extremely small and the surface morphology is well for a constant capacitance (C), the above relation (C ¼ vI ) gives a
controlled, which is directly related with the Brunauer-Emmett- rectangular plot. Similarly, the galvanostatic charging/discharging
Teller (BET) area and hence with electrochemical outcomes. Simi- (GCD) curves are also used to calculate the capacitance at a constant
larly the inset of Fig. 1(h) shows the lattice fringes in HRTEM at current. Therefore, in accordance with the above relation (C ¼ vI )
2 nm in which the fringe spacing matches with (110) plane ultrafine the rate of increase in the potential during the charging is constant
Cr2O3 nanoparticles. Fig. 1(i) shows the SAED image of ultrafine and as a result, triangular GCDs should be obtained for a
Cr2O3 nanoparticles while; the diameter of the nanoparticles is supercapacitor.
found uniform (shown in Fig. 1(j) and falls within the range of The composite CV curves in a scan range from 5 to 25 mV s1 for
22e27 nm. the Cr2O3 nanoparticles are illustrated in Fig. 3(a). An enhanced
The (BET) surface area and the pore size of the Cr2O3 nano-
area enclosed by the CV curves along with broad oxidation and
particles evaluated by N2-adsorption/desorption isotherms are reduction peaks is observed. The CV curves have displayed an
shown in Fig. 2(a and b) respectively. Fig. 2(a) shows a type - IV of
extended potential window of 1V from -ve to þ ve potential as
the isotherm which suggests the existence of a range of pore sizes. reported for Co(OH)2 on graphene nanosheets in the carbon elec-
The adsorption/desorption hysteresis from the relative pressure of
trodes for EDLCs [26]. The broad oxidation and reduction peaks
0.4e0.9 indicates the existence of the mesopores on the surface of during charging and discharging are due to the conversion of Cr3þ
the samples while, the presence of the micropores is witnessed by a
into Cr4þ and vice versa. The process is also followed by the
vertical tail near the relative pressure “1” [24]. A very high BET area insertion and deinsertion of Liþ ions [27e29].Notably, fast and well
of 219.9 m2 g1 was obtained for the Cr2O3 nanoparticles. The most
sustained faradaic reactions in which electrochemical intercon-
probable pore width in the samples is 4.2 nm and a DFT area of version between the electrode and the electrolyte takes place
132 m2 g1 is linked with the pore width > ¼ 0.465 nm.
originates the Pseudocapacitance [29].For an increase in scan rate,
the peak current is also increasing while there is no change in shape
3.2. Electrochemical screening of ultrafine Cr2O3 nanoparticles
and the position of the oxidation/reduction peaks. This behavior
witnesses an excellent rate capability of the Cr2O3 nanoparticles
The electrochemical screening tests such as Cyclic voltamme-
[31]. Furthermore, the specific current obtained from the CV in
tery (CV) measurements for varying current response at a fixed Fig. 3(a) at a scan rate of 10 mV s1 is 11 A g1 which is equal to the
scan rate(mV s1),Galvanostatic charging/discharging (GCD) mea-
current response of the spinal transition metal oxides which are
surements at a constant specific current (A g1), Electrochemical considered most suitable candidates for the Pseudocapacitance and
impedance spectroscopy (EIS) at an increasing frequency and the
are being investigated by the majority of the researchers [4e8,30].
frequency dependant Bode and the electrical admittance plots were The logarithmic peak current (Ipeak) verses logarithmic scan rate is
executed for the Cr2O3 nanoparticles. In the electrochemical studies
shown in Fig. 3(b). The logarithmic peak current is linearly pro-
of any material, the voltammogram (CV) based results are really portional to the logarithmic scan rate, which shows that the current
very important for the evaluation of the total capacitance and the
response is due to the surface limited reactions [33].
nature of storage mechanism. A well known proportionality rela- For a deep insight of the nature of the current from the CV
tionship among the charge stored (Q), capacitance (C) and the curves, an isolated Cr2O3 nanoboat recorded at a scan rate of
potential (V) for a capacitor including supercapacitors is given by; 25 mV s1 is shown in Fig. 3(c). But, before going into further dis-
“Q ¼ CV”. Where, “C” is a constant and is directly proportional to cussion about the nature of the charge storage mechanism
the area ratio of the dielectric/electrode at interface and the dis- (whether it is a capacitive or a diffusion control response) we need
tance between two plates of the capacitors. For a linear variation of to know briefly about their background. If the intercalation of the
the applied potential (V) with time (t) it becomes; V ¼ V0 þ vt, Liþ is allowed by the electrode material and clear and well sus-
where “V0” is the starting potential and “v” is the linearly varying tained peaks (due to the transfer of electrons in a faradaic reaction)
potential rate. The above relation can also be deduced as [25], along with a pure or an average rectangular CV shape are obtained,
then it is typically a pseudocapacitive behavior. While, if no faradaic
dQ dU dC dU
¼ C: þ U: ¼ C: reaction takes place, it means charge is stored electrostatically and
dt dt dt dt
known as electric double layer (EDL, also capacitive in nature) type
Or of storage [34,35]. Now, referred to Fig. 3(c), the Cr2O3 nanoboat is
divided into three well maintained regions, ReI, ReII and ReIII. The

dQ dU I region ReI is ideally rectangular and regarded as EDL (capacitive)
C¼ ¼
dt dt v charge storage. Except this, there are two more aspects for this
4 I. Shafi et al. / Journal of Alloys and Compounds 851 (2021) 156046

Fig. 1. (a) The Raman spectra of the Cr2O3 nanoparticles, (b) The XRD spectra of the Cr2O3 nanoparticles, (c) Theoretical band gap of the Cr2O3 nanoparticles by first principles, (d)
The UV-absorbance spectra and energy band gap of the Cr2O3 nanoparticles, (e) The SEM image of the Cr2O3 nanoparticles at 200 nm, (f) The TEM image of the Cr2O3 nanoparticles
at 20 nm, (g) The TEM images of the Cr2O3 nanoparticles at 100 nm, (h) The TEM image of Cr2O3 nanoparticles at 100 nm (inset of Fig. 1 (h) shows the HRTEM image of the Cr2O3
nanoparticles), (i) The SAED Cr2O3 nanoparticles and (j) The particle size distribution of the Cr2O3 nanoparticles.

region being capacitive in nature. First is that the average capaci- have the same magnitude of capacitance at each point [37].
tance remains almost same throughout the potential window as for Therefore, it can be attributed as a capacitive type of charge storage
the case of RuO2 [36] and secondly, the practical capacitance is not and the presence of OH in the storage process suggests that it may
constant point to point for the whole potential window, because in be likely an intercalation type of Pseudocapacitance [38]. The re-
the presence of electrochemical reactions, this is not possible to gions ReII and ReIII have both, the capacitive and diffusion (as
 I. Shafi et al. / Journal of Alloys and Compounds 851 (2021) 156046 5

Fig. 2. (a) The adsorption/desorption curves for Cr2O3 nanoparticles and (b) The pore size distribution for the Cr2O3 nanoparticles.

separated by Dunn’s relation in later part) type of current response. Therefore, the power law for total current must be obeyed by the
It is noteworthy here that most of the charge storage occurs at the peak current on the voltammogram [42]. Fig. 4(a) shows that the
middle part of the voltammogram and this region falls magnitude of power factor “b” which is used to determine the
between 0.2 e 0.4 V in the case of Cr2O3 nanoparticles and is nature of charge storage is “0.9” for the scan rate “>15 mV s1”
shown in a pseudorectangle in Fig. 3(d). which means that the capacitive storage is dominating in this re-
This is a pseudocapacitive CV behavior and indicates that most gion. Similarly, “b” value is decreased to “0.66”(an intermediate
of the charge storage occurs at a short potential widow (0.2 e value) for the scan rate “<15 mV s1” indicates that there is a small
0.4 V) for the Cr2O3 nanoparticles so, it will reduce the overall percentage of O2 diffusion control current response at lower slew
charge storage of the Cr2O3 based supercapacitor at full potential rate. The same behavior is also manifested by the Dunn’s separation
window (1V) and hence the capacitance too. Therefore, in order to for the total current response shown in Fig. 4(b). According to the
expand the energy storage window, we need to use some external Dunn’s equation, i(V) ¼ k1v1/2þ k2v, the total current response can
treatments such as using a faradaic aqueous electrolyte (as in our be divided into two parts; diffusion and the capacitive controlled
case where the potential window is extended from 0.6 to 1V with a currents. Where, “v” is the fixed scan rate, “k1v1/200 is the diffusion
negligible variation in the charge storage at full potential window controlled currents while “k2v” is the surface controlled capacitive
from 0.4 e 0.6 V) or the acidic treatment of carbon nanotubes in currents. By finding the values of “k1” and“k200 from the y-intercept
the literature [39,40]. and the slope of the “v½” verse “i/v½“plot respectively, we can do
Keeping in view the aforementioned aspect of the maximum the needful [43].
energy storage at short potential window, herein, we have also It can be seen in Fig. 4(b) that at a scan rate of 25 mV s1, the
presented a comparison of the CVs for short and full potential capacitive nature of the charge storage (81%) is overwhelming the
window at 25 mV s1 in Fig. 3(e). It has been found from this diffusion controlled storage (19% only). This behavior for the whole
comparison that though the maximum charge is stored at short scan range (5e25 mV s1) is shown in CV curves in supplementary
potential window but the enclosed area for the short potential information (S1), while, the percentage of the capacitive and
window is only 61% of the total area for full potential window. diffusion control parts in the same scan range is given in the bar
Which means that a significant CV portion (39%) of the full po- graph in Fig. 4(c). The Dunn’s separation for short potential window
tential window (- 0.4e0.6 V) is not contributed by the CV for a short is also compared with the full window in Fig. 4(d). Although the
potential window. Therefore, for Cr2O3 nonmaterials, it is not rec- major part (94%) of CV obtained at a short window is capacitive in
ommended to consider a short potential window only for the sack nature but it is only 65% of the total capacitance response at full
of getting a purely pseudocapacitive behavior as explained by Park window. The percentage capacitive contribution for some other
et al. too for C-cloth electrode [41].Secondly, 6 M KOH can suc- materials for a comparison with our work is given in Table 1.
cessfully maintain the charge storage throughout the potential The use of alternative means along with the experimental re-
window for the Cr2O3 nonmaterials electrodes and devices. sults for the separation of capacitive current response from the
Another important aspect of this comparison is that there is an noncapacitive effects at variable scan rate has provided us the
increase in the specific capacitance for the short potential window reasonable grounds to claim that this work is really useful in
but the specific energy calculated is found much lower at short supercapacitor applications and also enables to find the suitable
potential window than the full potential window. This is because of working potential range according to the stability of the working
the low potential (0.6 V) at short potential window as compared electrode for supercapacitor. For example, by increasing the scan
with full potential window (1V). A well maintained CV pattern for rate beyond certain limit, the “b” value decreases, which means
short potential window from 5 to 25 mV s1 is also shown in Fig. 3 that at a particular higher scan potential, the non-capacitive cur-
(f). rents will dominate the capacitive one and the electrode may not
Moreover, after identifying the nature of the total current be further suitable for supercapacitors.
response by using the power law “I ¼ avb” at a fixed potential, total The composite galvanostatic charge-discharge (GCD) curves for
current in the voltammograms (CVs) can be split into its capacitive constant specific current density from 0.50 to 0.90 A g1 are shown
and diffusive components by using the Dunn’s equation. As, in in Fig. 5(a). The curves are roughly triangular with a prolonged
anionic type of intercalation, the adsorption of OH over the surface discharging time as elaborated in Fig. 5(b). This is an isolated GCD
of electrode and diffusion of O2 within the bulk is involved. curve at a specific current density of 0.50 A g1. The discharge time
6 I. Shafi et al. / Journal of Alloys and Compounds 851 (2021) 156046

Fig. 3. (a) The CV curves for full potential window at a scan range from 5 to 25 mV s1, (b) Cathodic and anodic current fit from 5 to 25 mV s1, (c) Isolated nanoboat for full potential
window at a scan rate of 25 mV s1, (d) Isolated pseudorectange for a short potential window, (e) Comparison of the composite behavior at short and full potential window and (f)
The CV curves for short potential window at a scan range from 5 to 25 mV s1.

is 7.96 min against a charging of 5.36 min only, which is 1.48 times probably lag behind the specific energy of a lithium ion batteries
of the charging time. Except the prolonged discharging time, there [46,47]. A remarkable specific capacitance of 340 F g1 at a specific
are clear signatures of faradaic reactions at the middle of GCD curve current density of 0.5 A g1 is obtained from the GCD results.
giving rise to an increase in discharge energy and also verifying the The EIS results of the Cr2O3 nanoparticles before and after 3000
faradaic type of the CV behavior of the Cr2O3 nanoparticles. The cycles are shown in Fig. 5(c). The equivalent series resistance (ESR)
charging time between 10-s to 10-min is a suitable time range for obtained from the intercept of the semi circle is 0.5 U, which is
the pseudocapacitive supercapacitors to dominate the energy and increased to 0.7 U after 3000 cycles. A bode plot which is used to
power of lithium ion batteries because the specific energy stored in show the frequency dependence of the impedance is shown in
the supercapacitors for a charging time more than 10 min will Fig. 5(d). In an electrical circuit, for any component to be a perfect
 I. Shafi et al. / Journal of Alloys and Compounds 851 (2021) 156046 7

Fig. 4. (a)The anodicfit for the “b” value for the separation of diffusion and capacitive controlled current response, (b) The Dunn’s separation for diffusion and capacitive parts of the
current response,(c) Percentage contribution of the diffusion and capacitive control current response at varying scan rate (full potential window) and (d) Comparison of the Dunn’s
separation forthe current response at short and fullpotential window.

Table 1
The comparison of the present work with the other Cr2O3 and Cr2O3 composites used as electrode materials for supercapacitors.

Materials Capacitive response (%) Scan rate (mVs1) Ref.

Tin Sulphide 84 1 [44]

TiO2/Graphene 90.2 10 [45]
ReMoO3-x 75 1 [32]
Cr2O3 nanoparticles 81 25 Present Work

resistive, the potential drop and corresponding current response are available in the literature however, it is hard to find the specific
are always parallel to each other. Here, the electrical impedance is energy and specific power values for isolated Cr2O3 nanoparticles
decreasing with increasing frequency and the electrical component based electrodes and supercapacitor devices. A comparison of the
is becoming resistive. It means that the admittance (Ohm1) is capacitance values reported in our work with those in the literature
increasing. Fig. 5(d) inset shows that the frequency dependant is given in Table 2.
admittance increases sharply for lower frequencies however, it It is clear from the above mentioned results that the Cr2O3
becomes constant for higher frequencies. The well sustained cyclic nanoparticles synthesized by a facile Sol-gel method have dis-
retention of 85% for the Cr2O3 nanoparticles after 3000 cycles is played a superior capacitance than the reported materials in the
shown in Fig. 5(e), while Fig. 5(f) shows the Ragone placement of literature which are synthesized by the conventional methods.
the present work. The superior specific energy and the power Moreover, our synthesis methods along with the superior electro-
density of 12.5 Wh kg1 and 312.5 W kg1 for the Cr2O3 nano- chemical outcomes including the specific capacitance value, CV and
particles lies not only well inside the region for the electrochemical GCD results have provided an entirely new roadmap for the
supercapacitors, but its specific energy value falls well inside the investigation of the Cr2O3 nanoparticles for the electrode of the
battery region which underscore the excellent electrochemical supercapacitors in future. The results are fully supported by the
ability of the Cr2O3 nanoparticles synthesized by the Sol-gel frequency dependant Bode plot. However, still there is an urgent
method. Despite of the fact that a few reports on the use of the need for the more detailed investigations of the Cr2O3 nano-
Cr2O3 nanoparticles and Cr2O3 nanocomposites for supercapacitors materials as electrode materials for supercapacitor applications.
8 I. Shafi et al. / Journal of Alloys and Compounds 851 (2021) 156046

Fig. 5. (a) The GCD curves for the Cr2O3 nanoparticles from 0.50 to 0.90 A g1, (b) The comparison of charging and discharging features of the Cr2O3 nanoparticles, (c) The Nyquist
plot of the Cr2O3 nanoparticles before and after cycling, (d) The frequency dependant Bode plot for the Cr2O3 nanoparticles (Fig. 5(d) inset is the frequency dependance admittance
plot for the Cr2O3 nanoparticles), (e) The cycling retention of the Cr2O3 nanoparticles after 3000 cycles and (f) The Ragone placement of the present work.

Table 2
The comparison of the present work with the other Cr2O3 and Cr2O3-composites used as electrode materials for supercapacitors.

Materials Synthesis methods Capacitance (F g1) Specific current density (A g1) Electrolyte (KOH) Ref.

Cr2O3 Hydrothermal 130 1 1 [48]

Cr2O3/C Carbonization 291 0.25 6 [11]
Cr2O3/MWCNTs Hydrothermal 257 0.25 1 [49]
Cr2O3 nanoparticles Sol-gel 201/340 0.90/0.50 6 Present work
 I. Shafi et al. / Journal of Alloys and Compounds 851 (2021) 156046 9

4. Summary diffusion-limited redox reactions for aqueous supercapacitors, J mat sci 53

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Imran Shafi: Conceptualization, Methodology, Investigation,
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Writing - original draft. Erjun Liang: Supervision, Writing - review [21] S. Khamlich, E. Manikandan, B.D. Ngom, J. Sithole, O. Nemraoui, I. Zorkani,
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through Liþ intercalation pseudocapacitance, Nat. Mater. 12 (6) (2013) 518.
[23] A.B.C. Ekwealor, Variations OF optical and structural properties with tem-
There is no conflict of interest between the authors. perature for CrxOy thin films synthesized IN A polymer matrix BY chemical
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Acknowledgement
Cr2O3-carbon composite as a high performance pseudocapacitorelectrode
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