Journal of Alloys and Compounds 652 (2015) 39e47

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Journal of Alloys and Compounds

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

Electrochemical preparation of CuBi2O4 nanoparticles on nanoporous

stainless steel as a binder-free supercapacitor electrode
Ali A. Ensafi*, N. Ahmadi, B. Rezaei
Department of Chemistry, Isfahan University of Technology, Isfahan, 84156e83111, Iran

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

Article history: In this work, copper-bismuth oxide (CuBi2O4) nanoparticles were supported on nanoporous stainless
Received 10 June 2015 steel by a simple electrochemical deposition method and then was employed as a binder-free electrode
Received in revised form for supercapacitor application. The structure and surface morphologies of the nanoparticles-supported
9 August 2015
on nanoporous stainless steel were investigated using X-ray diffraction spectroscopy, energy disper-
Accepted 27 August 2015
sive X-ray spectroscopy and scanning electron microscopy. The electrochemical properties of the pro-
Available online 1 September 2015
posed electrode were examined using cyclic voltammetry and galvanostatic chargeedischarge
techniques in different electrolytes. The results showed that the proposed electrode exhibited a
Keywords:
Copper bismuth oxide
maximum specific capacitance of 144 mA h g
1 or 647 F g
1 at a current density of 1.0 A g
1 in
Nanoparticles 6.0 mol L
1 KOH with excellent long-term cycling stability (80% capacitance remained after 500 charge
Nanoporous stainless steel edischarge cycles). The proposed nanostructure is a suitable candidate for electrode material in energy
Supercapacitor storage devices.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction surface area. Moreover, study the recent review by Dubal et al. on
metal oxides nanoparticles such as MnO2 [8], NiO [9], SnO2 [10]
Electrochemical capacitors, also known as ultracapacitors or Co3O4 [11] and Fe3O4 [12] are a group of very promising anode
supercapacitors, are emerging as a class of high-power energy- materials for improving energy density of supercapacitors.
storage devices that fit the gap between conventional batteries and Good electrochemical stability [13], large surface area [14],
conventional capacitors [1]. Energy in supercapacitors can be interesting thermal and electrical transport properties [15],
stored by two different mechanisms: 1): non-faradic charge sepa- nontoxic nature [16], excellent chemical inertness and biocom-
rations at the interface between a solid electrode and an electrolyte patibility [17] has generated significant interest in bismuth oxide
(termed double-layer capacitance) and 2): reversible redox re- based compounds for several applications such as optical applica-
actions at/near the surface of an electrode (termed pseudo- tions, catalysis, biosensor, gas sensors and fuel cells [18]. Based on
capacitance) or a combination of both [2]. Supercapacitors have recent studies, bismuth and bismuth oxide based nanocomposites
long life cycle, high power density, high charge discharge rate and have shown high specific capacitance and long chargeedischarge
no short circuit concern that are of concern with existing energy cycle operations as an electrode material in the field of electro-
storage devices like fuel cells and batteries [3]. However, low en- chemical supercapacitors [19].
ergy density storage has hindered their use in on a larger scale. To In this work, CuBi2O4 nanoparticles with the spinel structure
solve this problem, one of the most intensive approaches is the were electrochemically deposited on nanoporous stainless steel
development of new electrode materials for supercapacitors. current collector. Nanoporous stainless steel was chosen due to its
Recently, different classes of carbon based nanomaterials including high surface area, acceptable corrosion resistance, good conduc-
carbon nanotubes [4], carbon nanofibers [5], carbon aerogels [6] tivity, plus low cost. Pseudo-capacitance properties of the con-
and activated carbons [7] have been taken into consideration as a structed nanocomposite were studied using cyclic voltammetry
cathode material due to their good electrical conductivity and high and galvanostatic chargeedischarge techniques. It has been found
that the capacitance properties and cycling stability of the pro-
posed anode material are comparable to, and even better than
other reported bismuth oxide based electrodes.
* Corresponding author.
E-mail addresses: aaensafi@gmail.com, Ensafi@cc.iut.ac.ir (A.A. Ensafi).

http://dx.doi.org/10.1016/j.jallcom.2015.08.226
0925-8388/© 2015 Elsevier B.V. All rights reserved.
40 A.A. Ensafi et al. / Journal of Alloys and Compounds 652 (2015) 39e47

2. Material and methods 3. Results and discussion

2.1. Chemical and apparatus 3.1. Characterization of the electrode materials

Perchloric acid (70% HClO4), nitric acid, ethylene glycol, potas- The morphology of the prepared nanostructures were investi-
sium hydroxide, sodium hydroxide, sodium sulfate, copper nitrate gated by FE-SEM. Fig. 1A shows the highly ordered patterns of
and bismuth nitrate were purchased from Merck. Stainless steel nanopores are formed on the surface of SS substrate after its
type 304 was purchased from local market. All other chemicals anodization at 35 V. As shown in Fig. 1D, the morphology of the
used in this study were of analytical grade and purchased from CuBi2O4 particles on common SS was aggregated and disordered,
Merck or Aldrich. Doubly distilled water was used for the prepa- while as can be seen in the top and cross sectional of the SEM
ration of all solutions. images (Fig. 1B and C), the CuBi2O4 nanoparticles are well deposited
The morphology of samples was observed by field emission on the nanoporous SS surface with an average particles diameter of
scanning electron microscopy (FEeSEM, Hitachi S4160) at an about 50e100 nm. These results revealed that the morphology of
accelerating voltage of 20 kV. The EDX spectra of samples were electrodeposited CuBi2O4 film strongly depends upon morphology
recorded using a Philips XLS instrument in ambient condition. and nature of the substrate. Fig. 1E shows the XRD pattern of the
Powder X-ray diffraction (XRD) of the samples was performed on a CuBi2O4 nanostructure. The strong diffraction peaks at the Bragg
Bruker D8/Advance Xeray diffractometer with CoeKa radiation angles of 24.3 , 32.6 , 38.8 , 43.9 ,54.8 , 62.4 , and 71.9 indicated
(l ¼ 1.7890 Å). that the CuBi2O4 with kusachiite structure was successfully syn-
Electrochemical impedance spectroscopy experiments were thesized (PDF # 00-042-0334). The average particle size of CuBi2O4
carried out using a computer controlled Autolab (PGSTAT302N, nanoparticles was calculated as 78 nm based on the XRD peaks
EcoeChemie, The Netherlands) with NOVA 1.10 software. Electro- width, using the Scherrer equation. The results of bulk composition
chemical capacitive behavior of prepared materials as determined analysis obtained by EDX (Fig. 1F) revealed that the molar ratio of
by cyclic voltammetry and galvanostatic chargeedischarge in a Bi:Cu in the nanostructure was about 2:1, which confirms the for-
three-electrode cell system incorporating a working electrode, a mation of CuBi2O4 nanostructures.
Hg/HgO reference electrode and a Pt wire counter-electrode in
different electrolytes using an Ivium potentiostat/galvanostat
(pocket STAT Model). Anodizing was performed using a homemade 3.2. Electrochemical behavior of CuBi2O4
DC power supply.
Cyclic voltammograms of CuO, Bi2O3 and CuBi2O4 electrodes
2.2. Electrode preparation were recorded in 6 mol L
1 KOH solution in a potential range
of
0.90 to 0.10 V) vs. Hg/HgO) at a scan rate of 20 mV s
1. As shown
A 304 type stainless steel (SS) rod (with a diameter of 6 mm) was in Fig. 2A, for CuO, during the anodic sweep the peaks at potentials
embedded into Teflon to obtain an electrode with a geometric sur- around
0.45 V and
0.20 V are due to the transitions of Cu0/Cu(I)
face area of 0.28 cm2. Before growing the nanoporous structure on and Cu(I)/Cu(II), respectively. During the cathodic sweep, the peaks
the surface of the SS current collector, the electrodes were polished at potentials around
0.40 V and
0.75 V can be ascribed to Cu(II)/
with emery paper and cleaned by ultrasonication in deionized wa- Cu(I) and Cu(I)/Cu0 transitions, respectively [22]. The observed
ter. Nanoporous structured film was formed on the SS surface via the peaks for Bi2O3 electrode are due to the reduction of Bi(III) to metal
anodization process described in our previous work [20]. Briefly SS Bi (at
0.84 V) during the negative sweep and oxidation of Bi metal
anode was placed 1 cm away from a copper plate (cathode) in the to Bi(III) (at
0.50 V) during the positive sweep [23]. The observed
ethylene glycol electrolyte containing 5.0% (vol.%) HClO4, and then redox behavior of CuBi2O4 electrode (Fig. 2A) was similar to that of
anodized at a constant voltage of 35 V for about 15 min. During the Bi2O3 electrode whereas the integral area of the CV loop was higher
anodization process, the electrolyte was stirred vigorously and the in case of CuBi2O4 electrode, which is mainly ascribed to the
temperature was maintained between 0 and 5  C. The prepared improved electrical conductivity and facilitated ion diffusion. The
electrode was washed using deionized water and ethanol for 10 min Bi2O3 and CuBi2O4 redox behaviors, in the presence of OH
ions,
using an ultrasonic bath and dried in a nitrogen stream. can be described by the following reactions [24]:
The method of Hahn et al. [21] was used to prepare CuBi2O4
nanostructure, with the exception that nanoporous SS was used During the cathodic sweep:
instead of fluorine-doped tin oxide. The electrodeposition was
performed from a solution containing 10% of nitric acid and
Bi(NO3)3.5H2O/Cu(NO3)2.3H2O with molar ratio of 2:1. The elec- Bi2 O3 or CuBi2 O4 /BiO

2 (1)
trodeposition was carried out by three-electrode system in a glass
cell using potentiostatic mode of Autolab Potentiostat/Galvanostat BiO


2 /BiO2 ðadsÞ (2)
instrument at an applied of
0.50 V) vs Ag/AgCl). The working
electrode for the deposition was a nanoporous SS rod and the
reference electrode was an Ag/AgCl electrode (3 M KCl). The BiO

2

2 ðadsÞ þ e /BiO2 ðadsÞ (3)
counter electrode was a platinum wire. After deposition, the
working electrodes were annealed in a muffle furnace (in air at


500  C for 2 h) to form CuBi2O4 nanostructure. The weights of the 2H2 O þ 3BiO2
0
2 ðadsÞ /2BiO2 ðadsÞ þ 4OH þ BiðadsÞ (4)
active materials were calculated by subtraction of the weight of the
nanoporous SS electrode, before and after deposition of the active During the anodic sweep:
materials on the electrode surface, by six digit analytical electronic
balance (SartoriuseCPA2P, Germany). The loading process of the
Bi2O3 or CuO on the nanoporous SS was similar to that of CuBi2O4 Bi0ðadsÞ /Biþ þ e
(5)
but Bi(NO3)3$5H2O plus Cu(NO3)2$3H2O mixed solution was
replaced with Bi(NO3)3$5H2O or Cu(NO3)2$3H2O, respectively.
 A.A. Ensafi et al. / Journal of Alloys and Compounds 652 (2015) 39e47 41

Fig. 1. SEM image of: A): Nanoporous SS; B): Top view of CuBi2O4 nanoparticles supported on nanoporous SS; and C): Cross sectional view of CuBi2O4 nanoparticles supported on
nanoporous SS; D): CuBi2O4 particles on common SS. E): XRD pattern of CuBi2O4 nanoparticles. F): EDX Spectra of CuBi2O4 nanoparticles.

Bi2O3:
0.63 and CuBi2O4:
0.64 V vs. Hg/HgO). All the three
þ 3þ
3Bi /Bi þ 2Bi0ðadsÞ (6) electrodes show semicircle behaviors in the high frequency
domain. The high-frequency semicircle in pseudo-capacitors is
caused by a resistive term (Rct) attributed to the charge transfer
3OH
þ Bi3þ /BiðOHÞ3 (7) limiting process at the interface of the electrode material and
electrolyte [25]. As shown in Fig. 2B, the diameter of the semicircle
for CuBi2O4 is smaller than the semicircle diameters for CuO and
BiðOHÞ3 /BiOOH þ H2 O (8)
Bi2O3 and this means that charge transfer resistance is lower in
Electrochemical impedance spectroscopy (EIS) is an electro- CuBi2O4e electrolyte interface in comparison with two other
chemical method for evaluation of capacitance properties of elec- electrodes. In the low frequency range, CuO impedance plot shows
trode materials. The most popular way to run EIS measurements is a straight line with about 45 to real axis. Such behavior indicated
collecting the electrochemical supercapacitor impedance data at that the process is diffusion controlled, but impedance plots of
the open-circuit potential [3], so the frequency response of the Bi2O3 and CuBi2O4 show nearly vertical lines in the low frequency
electrodes (CuO, Bi2O3 and CuBi2O4) in 6 mol L
1 KOH as an elec- domain which reveals the presence of pseudo-capacitive behavior
trolyte was examined in the frequency range of 100 kHz to 10 mHz [26]. Bi2O3 also showed a small Warburg domain with a 45 slope
at open circuit potential (open circuit potentials: CuO:
0.60, (Inset of Fig. 2B), this behavior shows the involving of the
42 A.A. Ensafi et al. / Journal of Alloys and Compounds 652 (2015) 39e47

Fig. 2. A: Cyclic voltammograms, and B: Nyquist plots of a: CuBi2O4, b: Bi2O3, and c: CuO in 6.0 mol L
1 KOH. Inset B: equivalent electrical circuit comparable with Nyquist diagram
of CuBi2O4.

electrolytes diffusion to the electrode surface in electrochemical intermediates have been produced during the charge (Bi/Bi(III))
processes. Analysis of the EIS data was performed using ZView 2.3 and discharge (Bi(III)/Bi) process, so the charge and discharge
(Scribner Associates, Inc.) on the basis of Macdonald's algorithm curves are different in shapes from each other, which leads to an
using a complex nonlinear least square approximation method overall asymmetric chargeedischarge curve. Such behaviors have
[27]. Inset of Fig. 2B shows the equivalent electrical circuit model been reported for other bismuth based capacitors in alkaline elec-
used for fitting of the EIS data of CuBi2O4 electrode. The equivalent trolytes [28,29]. The specific capacitances of the electrode materials
circuit consisting of the bulk solution resistance (R1), the charge were calculated via the following equation:
transfer resistance (R2), the resistance related to the ion diffusion
(W1), the double-layer capacitance (CPE1) and the limit capacitance Specific capacitances ¼ It=ðDV$DmÞ (9)
(C1). The presence C1 in equivalent electrical circuit, confirms the
pseudo-capacitance properties of CuBi2O4 electrode [8]. Where I(A) is the discharge current, t(s) is the discharge time, DV(V)
To further confirm the superior capacitance performance of the is the potential window and Dm(g) is the mass of the active ma-
proposed electrode material, the galvanostatic chargeedischarge terial. The results show that the specific capacitance of CuBi2O4
tests of CuBi2O4, Bi2O3 and CuO were conducted in a potential (647 F g
1) is higher than for Bi2O3 (421.5 F g
1) and for CuO
window of 0.00 to
0.80 V) vs. Hg/HgO) in 6 mol L
1 KOH at (40 F g
1), which are in agreement with the cyclic voltammetry and
1.0 A g
1 (Fig. 3). As can be seen in this figure, the discharge curves the EIS results.
of the CuBi2O4 and Bi2O3 show asymmetric shapes due to the two
steps voltage change of the active materials, which consist of an 3.3. Electrolyte effect
initial voltage loss (due to the internal resistance of the electrode/
active material), and a prolonged plateau (based on [Bi(III)4Bi] Cyclic voltammetric measurements and galvanostatic char-
transition) [28]. As shown in equations (1)e(8), different geedischarge tests in different electrolytes were performed to
 A.A. Ensafi et al. / Journal of Alloys and Compounds 652 (2015) 39e47 43

Fig. 3. Galvanostatic chargeedischarge tests of a: CuBi2O4, b: Bi2O3, and c: CuO in 6.0 mol L
1 KOH at a current density of 1.0 A g
1.

investigate the electrochemical properties and the specific capaci- seen, the shapes of the CV curves are different from an ideal rect-
tance of the electrode material (CuBi2O4). Fig. 4 shows the cyclic angular shape, which indicates that capacitance mainly resulted
voltammograms of CuBi2O4 in 1.0 mol L
1 Na2SO4 solution, in from pseudocapacitance due to the faradaic redox reactions of the
1.0 mol L
1 NaOH solution, in 1.0 mol L
1 KOH solution and in electroactive materials [30]. As stated in Section 3.2, the redox
6.0 mol L
1 KOH as electrolytes in different scan rates. As can be behavior of CuBi2O4 in alkaline media (Fig. 4B, C and 4D) can be

Fig. 4. Cyclic voltammograms of CuBi2O4 in A: 1.0 mol L
1 Na2SO4; B: 1.0 mol L
1 NaOH; C: 1.0 mol L
1 KOH; and D: 6.0 mol L
1 KOH electrolytes in different scan rates, E: specific
capacitance vs. scan rates for different electrolytes.
44 A.A. Ensafi et al. / Journal of Alloys and Compounds 652 (2015) 39e47

Fig. 5. Galvanostatic chargeedischarge tests of CuBi2O4 in different electrolytes at a current density of 1.0 A g
1.

Fig. 6. Galvanostatic chargeedischarge tests of CuBi2O4 in 6.0 mol L
1 KOH at different current densities A: 1.0, 2.0, 3.0 and 5.0 A g
1. B: 10.0, 15.0, 20.0, and 25.0 A g
1; Inset of A:
plot of specific capacitance vs. current density.
 A.A. Ensafi et al. / Journal of Alloys and Compounds 652 (2015) 39e47 45

explained using equation (1)e(8), which is indicates the role of ions vs. Naþ [32]. Higher ionic mobility of Kþ ions facilitates the
hydroxyl ions in charge storage properties of this compound. On diffusion of hydroxide ions (counter anion of Kþ in KOH electrolyte)
the other hand, the redox behavior of CuBi2O4 in neutral solution, to the electrode surface, thereby this caused higher electro-
Na2SO4 (Fig. 4A), is much differ from the behavior in alkaline so- deeelectrolyte interaction and higher charge storage [30].
lutions and is based on the intercalation of sodium ions into the The specific capacitances of the CuBi2O4 electrode was calcu-
crystalline structure of CuBi2O4. The following equation can be lated from their CVs in different scan rates according to the
explained the charge storage mechanism of CuBi2O4 in 1.0 mol L
1 following equation [29]:
of Na2SO4 solution [19,31]:
Z
ðCuBi2 O4 Þsurface þ xNaþ þ xe
/Nax ðCuBi2 O4 Þsurface (10) Specific capacitance ¼ Idv=ð2  DE  Dm  yÞ (11)
As shown in Fig. 4AeD, CuBi2O4 in 6.0 mol L
1 KOH has a highest
redox peak currents and integrated current area in comparison Where !Idv represents the area under voltammetric curve, DE(V) is
with the other electrolytes. As stated in Section 3.2, the redox the potential window, Dm(g) is the mass of the active material and
behavior of CuBi2O4 is depends on hydroxide ions. Therefore, ʋ (V s
1) is the potential scan rate. The specific capacitances were
higher capacitance of the proposed material in 1.0 mol L
1 NaOH in calculated, using the above equation, for the different electrolytes
comparison with 1.0 mol L
1 Na2SO4 solution and also in as shown in Fig. 4E. The data shows that there is a gradual decrease
6.0 mol L
1 KOH vs. 1.0 mol L
1 KOH can be ascribed to the higher in the specific capacitance values of the electrode materials with
concentration of hydroxide ions in those solutions. Higher con- increasing the potential scan rate. This behavior can be attributed to
centration of hydroxide ions facilitate the redox reaction of CuBi2O4 the higher diffusion of the electrolytic ions into the active sites of
and lead to more stored charge in the electrode. The higher the electrode materials at low scan rates. At higher scan rates, the
capacitance of the electrode materials in 1.0 mol L
1 KOH vs. diffusion effect limits the migration of the electrolytic ions, thereby
1.0 mol L
1 NaOH solution can be attributed to the smaller hydrated this caused some of the active surface of the nanostructures to
radius (3.31 Å) and higher conductivity (73 cm2/Umol) of Kþ ions in become inaccessible for charge storage [33].
comparison with the hydrated radius of Naþ ions (3.58 Å) and its The effects of different electrolytes were also investigated using
conductivity (50 cm2/Umol), which enhanced the mobility of Kþ galvanostatic chargeedischarge at 1.0 A g
1 (Fig. 5). The results

Fig. 7. Longeterm cycle stability of CuBi2O4 A: supported on nanoporous SS; and B: supported on common SS at a current density of 10 A g
1 in 6.0 mol L
1 KOH.
46 A.A. Ensafi et al. / Journal of Alloys and Compounds 652 (2015) 39e47

Table 1
Capacitance comparison of different bismuth oxides based electrodes for supercapacitor application reported in other works.

Working electrode Current density Specific capacitance (mA h g
1) Specific capacitance (F g
1) Reference

SWCNT/BiVO4 2.5 A g
1 110 395 [28]

BiPO4 2 mA cm
2 100 302 [29]
Bi2WO6 0.5 mA cm
2 169 608 [30]
Bi2O3 1 mA cm
2 19 98 [35]
BiFeO3 1 mA cm
2 16 81 [36]
Graphene/Bi2O3 10 A g
1 189 757 [37]
Nanoporous SS/CuBi2O4 1 A g
1 144 647 This work

shows that the capacitance decreases in the order of 6.0 mol L
1 material for supercapacitor applications. In this way, CuBi2O4
KOH (647 F g
1) > 1.0. mol L
1 KOH (365 F g
1) > 1.0. mol L
1 NaOH nanoparticles were electrochemically deposited on nanoporous SS
(312 F g
1) > 1.0 mol L
1 Na2SO4 (55 F g
1), which is in agreement and characterized with SEM, XRD, EDX and CV. The capacitance
with the obtained capacitance values by the CVs. Therefore, behavior of the proposed material in different aqueous electrolytes
6.0 mol L
1 KOH was selected as an electrolyte for subsequent (1.0 mol L
1 Na2SO4, 1.0 mol L
1 NaOH, 1.0 mol L
1 KOH and
experiments. 6.0 mol L
1 KOH) was studied. CuBi2O4 shows highest capacitance
To further evaluate the application potential of CuBi2O4 as an for both CV (534 F g
1 in scan rate of 5 mV s
1) and galvanostatic
electrode material for supercapacitors in 6.0 mol L
1 KOH, galva- chargeedischarge (144 mAh g
1 or 647 F g
1 in the discharge
nostatic chargeedischarge measurements were carried out in this current of 1.0 A g
1) techniques in 6 mol L
1 KOH. Also, it was found
electrolyte at various current densities (ranging from 1.0 to that the presence of nanopores on SS improves the capacitance and
25.0 A g
1), as shown in Fig. 6A and B. It was found that the long-term stability of the electrode material. Facile preparation,
capacitance decreased with increasing the chargeedischarge cur- low cost, eco-friendly and long-term stability demonstrate that
rent density (inset of Fig. 6A). This behavior is due to the decrease in CuBi2O4 on nanoporous stainless steel have potential applications
the degree of utilization of the nanostructure active sites at higher as an electrode material for supercapacitors.
current densities. In another word, at higher current densities, as a
result of an inadequate response time for the electrolyte ions to Acknowledgments
reach the surface of the electrode, the nanostructureeelectrolyte
interaction would be limited. Thus, the capacitance of the electrode The authors wish to thank Iran National Science Foundation
will decrease due to the limitation of the diffusion of the electrolyte (INSF, project No. BN073) and Isfahan University of Technology
ions to the electrode surface [34]. Research Councils for financial support of this work.

3.4. Stability (the role of nanoporous SS current collector)

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