Electrochimica Acta 199 (2016) 290–296

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Preparation of nickel-cobalt nanowire arrays anode electro-catalyst

and its application in direct urea/hydrogen peroxide fuel cell
Fen Guo, Kui Cheng* , Ke Ye, Guiling Wang, Dianxue Cao*
Key Laboratory of Superlight Materials and Surface Technology of Ministry of Education, College of Materials Science and Chemical Engineering, Harbin
Engineering University, Harbin 150001, PR China

A R T I C L E I N F O A B S T R A C T

Article history: Nickel-cobalt nanowire arrays (Ni-Co NWAs) electrode is prepared by one-step galvanostatic
Received 18 October 2015 electrodeposition with a polycarbonate membrane as the template. By adjusting the Co proportion in
Received in revised form 26 January 2016 the Ni and Co bath solution into 10%, the optimal Ni-Co NWAs electrode in terms of relatively lower onset
Accepted 29 January 2016
potential and highest current density towards urea electro-oxidation is obtained. Its catalytic
Available online 1 February 2016
performance is investigated by constructing single direct urea/hydrogen peroxide (H2O2) fuel cell.
Results show that a peak power density of 7.4 mW cm
2 and an open circuit voltage of 0.92 V are achieved
Keywords:
at room temperature when 9.0 mol L
1 KOH and 0.33 mol L
1 urea are used as the anolyte, H2SO4 and
fuel cell
urea
H2O2 as the catholyte. Additionally, the urea/H2O2 fuel cell also demonstrates excellent stability during
nickel-cobalt nanowire arrays short term duration test.
polycarbonate template ã 2016 Elsevier Ltd. All rights reserved.
hydrogen peroxide

1. Introduction
Urea, usually used as agricultural fertilizer, recently, has been
considered as a preferable candidate for hydrogen production in
alkaline medium due to its abundance (such as urea in the
laboratory, AdBlue, human urine or industrial sewage), stability
and non-toxicity. Compared with producing hydrogen through
urea electrolysis and then retrieving energy from hydrogen [1], the
form of fuel cell adopting urea directly as the fuel is more
straightforward, which can meet both the aims of generating
electricity and purifying pollutant.
In 2010, Tao et al [2] developed a working direct urea fuel cell
for the first time with a home-made anion exchange resin (AER)-
polyvinyl alcohol (PVA) blends membrane used as the alkaline
electrolyte and humidified oxygen worked as oxidant. The open
circuit voltage (OCV) and peak power density reached 0.5 V and
0.54 mW cm
2, respectively. It was indicated that the direct urea
fuel cell was a feasible and promising novel type fuel cell to make
waste profitable. Nevertheless, the cell performance was still
considerably lower than that of other fuel cells. In order to further
improve the cell performance, the electro-catalysts with high
performance for urea electro-oxidation are urgently needed. In
general, nickel has been known to be an effective material for urea
* Corresponding authors. Tel.: +86 451 82589036; fax: +86 451 82589036.
E-mail addresses: chengkui@hrbeu.edu.cn (K. Cheng),
caodianxue@hrbeu.edu.cn (D. Cao).
electro-oxidation [3,4]. Botte and co-workers [5] pointed out that
the effective catalyst components of Ni electrode for urea electro-
oxidization was NiOOH. However, the formation potential of
NiOOH from Ni(OH)2 was as high as ca. 0.25 V (vs. Ag/AgCl) in
5.0 mol L
1 KOH, therefore the operation voltage of direct urea fuel
cell would be impaired by the large overpotential. Asgari et al. [6]
found that the cobalt doping would increase the charge-accep-
tance of nickel electrode, further result in lowering the NiOOH
formation potential. A similar phenomenon has also been reported
by Xu and the co-workers [7]. Inspired by these, the performance
of urea electro-oxidation would be facilitated if binary or multiple
catalyst materials with synergistic effect are introduced.
The cathode oxidant of direct urea fuel cell, oxygen, is a versatile
oxidizer for many types of fuel cells [8–11]. Whereas, from an
operational point of view, liquid hydrogen peroxide (H2O2)
oxidizer provides more advantages, such as easy storage, reduced
pumping requirements, simplified heat removal, etc [12]. It has
also been proved that H2O2 electro-reduction has faster kinetics
than oxygen reduction. Li’s group [13]. developed a direct
hydrazine/H2O2 fuel cell. This type of fuel cell gave an OCV of
1.6 V and a high power density of 470 mW cm
2, much larger
than that with oxygen oxidant (0.9 V and 73.9 mW cm
2,
respectively) [14]. Using H2O2 as the oxidant of direct urea fuel
cell will increase the theoretical OCV to 2.51 V, higher than that
with oxygen (in acidic medium: 1.98 V; in alkaline medium: 1.15 V).
Moreover, the direct urea/H2O2 fuel cell would be more compact
because both urea and H2O2 are in aqueous form. The electrode and
overall reactions are described as below:

http://dx.doi.org/10.1016/j.electacta.2016.01.215
0013-4686/ ã 2016 Elsevier Ltd. All rights reserved.
 F. Guo et al. / Electrochimica Acta 199 (2016) 290–296
Anode: CO(NH2)2 + 8KOH @ N2 + 6H2O + K2CO3 + 6 K+ + 6e
,
EO =
0.75 V vs. SHE
Cathode: 3H2O2 + 3H2SO4 + 6e
@ 6H2O + 3SO42
, EO = 1.76 V
vs. SHE
Overall reaction: CO(NH2)2 + 3H2O2 + 3H2SO4 + 8KOH ! K2CO3+
3 K2SO4 + N2 + 12H2O, EO = 2.51V (3)
Based on the above discussion, in this paper, we attempt to
assemble a direct urea/H2O2 fuel cell by using Ni-Co binary anode
catalyst. The molar ratio of nickel and cobalt source was varied to
achieve optimal Ni-Co NWAs electrode for urea electro-oxidation
in terms of relatively lower onset potential and highest oxidation
current density. Finally, a direct urea/H2O2 fuel cell is assembled by
using the optimized Ni-Co NWAs electrode as an anode catalyst,
and Pd/carbon fiber cloth electrode as a cathode catalyst. The
effects of KOH and urea concentrations on the performance of
direct urea/H2O2 fuel cell were investigated. The stability of fuel
cell was examined at a constant discharge current density. Results
shows that direct urea/H2O2 fuel cell is a practical and promising
new type of fuel cell.
2. Experimental
2.1. Preparation of the Ni and Ni-Co NWAs catalysts
The polycarbonate template (PCT) was first covered with the
cooled low melting point alloy (65  C) to form a working electrode.
Then, the metallic Ni-Co was directly electroformed into the pores
and on the surface of PCT from a Ni and Co bath solution, which
consists of 1.0 mol L
1 of nickel sulfate and cobalt sulfate (varying
cobalt source proportion into 0%, 10%, 30% and 50%), 0.2 mol L
1 of
nickel chloride, 0.6 mol L
1 of boric acid, 5 mmol L
1 of saccharin
and 0.15 mmol L
1 of sodiumlauryl sulfate [15] by a galvanostatic
electrodeposition method. A negative current density of

40 mA cm
2 was constantly applied to the working electrode for
about 4 hours. After electrodeposition, PCT membrane was
dissolved in methylene chloride, and free-standing Ni-Co NWAs
electrode is obtained.
2.2. Physical characterization
The features of as-made electrode were characterized using
scanning electron microscopy (SEM, JEOL JSM-6480), transmission
electron microscopy (TEM, JEM-2010FEF, 200 kV) equipped with
Fig 1. (A) Schematic representation of direct urea/H2O2 fuel cell configuration; (B) E-t curve during galvanostatic electrodeposition process when cobalt proportion in the
bath solution is 10%.
291
an energy dispersive X-ray spectrometer (EDS) and X-ray diffrac-
(1) tion (Rigaku TTR III) with Cu Ka radiation (l = 0.1514178 nm). The
cobalt proportion in the Ni-Co nanowires was measured by
inductively coupled plasma emission spectrometry (ICP, Xseries II,
Thermo Scientific). Briefly, the nanowires in the polycarbonate
(2) template were first dissolved in aqua regia solution and then
diluted to a 1 L solution for the ICP measurement.
2.3. Three-electrode system and overall fuel cell tests
Cyclic voltammetry(CV) measurements were conducted in
5.0 mol L
1 KOH with or without 0.33 mol L
1 urea using the Ni-Co
NWAs electrodes connected to an electrochemical work station
(AutolabPGSTAT302, Eco Chemie). The platinum foil and a
saturated Ag/AgCl electrode (0.1981 V vs. SHE) were used as
counter electrode and reference electrode, respectively. All
potentials in this work were referred to the reference electrode.
A schematic representation of direct urea/H2O2 fuel cell configu-
ration is shown in Fig. 1A. The cathode catalyst, Pd/carbon fiber
cloth (denoted as Pd/CFC), was prepared according to our previous
work [16]. Cation exchange membrane (nafion1 115, Dupont) was
used as polymer electrolyte to separate anode and cathode
catalysts [17]. Before use, the cation exchange membrane was
pretreated by boiling in 5% H2O2 for 1 hour and de-ionized water
for 1 hour successively. Graphite material and serpentine style
were employed for bipolar plates. The anolyte (urea and KOH) and
catholyte (H2O2 and H2SO4) were pumped into the anode and
cathode sides by a peristaltic pump at a flow rate of 10 mL min
1.
The direct urea/H2O2 fuel cell tests were carried out by a computer-
controlled E-load system (Arbin, USA) under ambient conditions.
3. Results and discussions
3.1. Characterization and optimization of Ni-Co NWAs electrode
The Ni-Co NWAs electrodes are fabricated by one-step
galvanostatic electrodeposition from the Ni and Co bath solution.
Fig. 1B shows the potential behavior versus time (E-t) when the
cobalt proportion in the bath solution is 10%. Clear seen, once the
current is applied, the potential shows a huge drop from
0.71 V to

1.26 V, which corresponds to the ohmic potential drop. After that,
the charging of electric double layer closely proceeds, resulting in a
potential rise. Next, the nickel and cobalt ions initially in the pores
of PCT are preferentially electro-deposited. The ions diffuse from
bulk into pores until the pores are filled with metallic Ni-Co, which
are reflected in the lower potential region before 70 s of E-t curve
(stage 1). There is a gradual increase of potential after 70 s and then
292 F. Guo et al. / Electrochimica Acta 199 (2016) 290–296
a flat potential is maintained, indicating that the metal is over-
plated on the surface of PCT to form a Ni-Co support (stage 2). Since
mass transport in the pores is hindered, larger driving force is
needed. Therefore the potential of stage 1 is lower than that of
stage 2. The electrodeposition process is illustrated in the inset of
Fig. 1B. The multi-stage electrodeposition process in PCT or anodic
aluminum oxide (AAO) template by observing i-t curve, instead of
E-t curve has also been reported by other researchers [18–20].
Fig. 2A is the digital photograph of Ni-Co NWAs electrode before
dissolving PCT. The PCT appears a shiny and black side after
electrodeposition. Fig. 2B and the inset show the top and side
views of Ni-Co NWAs, respectively. After dissolving the PCT, the
nanowires are released. The nanowires contact tightly with the
rough Ni-Co support. Conglomeration inevitably occurs between
the top of the nanowires, which further forms a series of mountain
ranges-like. Based on previous reports [21]. the channels of PCT
were induced by random ion beams, hence, unlike the ordered
anodic aluminum oxide channels, the grown nanowires here
intersect with each other in random directions. The spaces
between NWAs ranges and every single nanowire can offer
reactants or products easy access to transfer into or away from
the electrode. TEM and high-resolution TEM (HR-TEM) were also
used to characterize the morphology of as-prepared Ni-Co
nanowires. The individual nanowire surface is smooth and its
diameter is ranged from 65.37 nm to 96.20 nm, as shown in Fig. 2C.
The wire diameter is a little larger than the pore diameter of PCT,
which can be attributed to the fact that the deposits stretched the
pores. As illustrated by HR-TEM image (Fig. 2D), distinct lattice
fringes are detected, with the interplanar spacing distance of ca.
0.175 nm, well indexed to the (200) planes of Ni (0.176 nm) or Co
(0.177 nm) face-centered cubic (fcc) crystal.
Fig. 3A provides the STEM image of the as-prepared sample. The
associated EDS mapping images (Fig. 3B and C) and elemental line
scanning profiles (Fig. 3D) strongly evidence the homogeneous
existence of Ni and Co elements. Additionally, the Co proportion is
34.01% based on the EDS analysis, which is consistent with the ICP
Fig. 2. (A) Digital photograph of Ni-Co NWAs electrode; SEM images of Ni-Co NWAs electrode in top (B) and side (inset) views; TEM (C) and HR-TEM (D) images of Ni-Co
nanowires (cobalt proportion in the bath solution is 10%).
result (33.37%). To further understand the structures of Ni-Co
support and Ni-Co NWAs, they are separately examined by XRD.
The XRD profiles of PCT, Ni-Co NWAs embedded in PCT and Ni-Co
support are shown in Fig. 3E. Except for the broad diffraction peak
of polycarbonate between 10 and 40 , the Ni-Co support and Ni-
Co NWAs show three diffraction peaks at 2u = 44.47, 51.71 and
76.21, which can be indexed to diffractions from the (111), (200)
and (220) planes of fcc structure of metallic Ni and Co. No other
impurity peaks are observed by XRD. In addition, the (220)
diffraction peak of the bimetallic nanowire (inset of Fig. 3E) shows
a visible shift from their standard positions of Ni (JCPDS No. 04-
0850) and Co (JCPDS No. 15-0806), which suggests the alloyed
crystalline structure of NiCo. Still, the existence of physical mixture
of metallic Ni and Co cannot be ruled out because the diffraction
peaks of Ni have little difference with that of Co.
Fig. 4A shows the CV curves of four kinds of Ni-Co NWAs
electrodes prepared with varied molar ratios of cobalt sulfate (0%,
10%, 30% and 50%) in 5.0 mol L
1 KOH at a scan rate of 10 mV s
1,
respectively. It is revealed that Ni 10 electrode (the cobalt
proportion is 0%) typically demonstrates a pair of Ni(OH)2/NiOOH
redox peaks. Three oxidation peaks are observed when Ni
9 electrode (the cobalt proportion is 10%) is measured, which
are ascribed to the transformation reactions of Co(OH)2/CoOOH,
CoOOH/CoO2 and Ni(OH)2/NiOOH along the positive potential
direction successively[22]. When the cobalt content increases to
30% (Ni 7), an overlap of redox peaks occurs. As the Co content
increases to 50% (Ni 5), the oxidation current density of Ni(OH)2/
NiOOH reaction drastically declines. Fig. 4B-E show the cyclic
voltammograms of Ni 10, Ni 9, Ni 7 and Ni 5 electrodes in
5.0 mol L
1 KOH with and without 0.33 mol L
1 urea respectively.
In Fig. 4B, after adding urea, the current density of Ni 10 electrode
rises just after the NiOOH is formed from Ni(OH)2, proving that
urea electro-oxidation reaction occurs on NiOOH[23]. The onset
potential and peak current density of Ni 10 electrode are 0.25 V and
170 mA cm
2, respectively. In Fig. 4C, the reaction activity of urea
electro-oxidation on Ni 9 electrode is greatly facilitated with an
 F. Guo et al. / Electrochimica Acta 199 (2016) 290–296
Fig. 3. STEM image (A) of Ni-Co nanowire, and the associated element mappings of Ni (B), Co(C); (D) The cross-sectional compositional line profiles. Inset shows the
corresponding STEM images. (D) XRD patterns of PCT, Ni-Co NWAs embedded in PCT and Ni-Co support. Inset is the enlarged (220) diffraction peak region. (Cobalt proportion
in the bath solution is 10%).
onset potential of 0.19 V as well as a high oxidation current density
of 380 mA cm
2 at 0.6 V. However, as shown in Fig. 4D, Ni
7 electrode reveals the catalytic activity degradation compared
with Ni 9 electrode. Ni 5 electrode in Fig. 4E even achieves an
oxidation peak current density of only 79 mA cm
2. It is indicated
that more cobalt content would bring about disadvantageous
effect on urea electro-oxidation reaction rate. Botte et al. [23] and
Wu et al. [24] pointed out that cobalt was non-active for urea
electro-oxidation. As a consequence, the excessive cobalt would
lessen the active nickel amount and undoubtedly, the catalytic
activity of Ni-Co NWAs electrode declines. Fig. 4F summarizes the
correlations between cobalt proportion by ICP, onset potential,
oxidation current density and cobalt proportion in the bath
solution. By adjusting the cobalt molar content into 0%, 10%, 30%
and 50%, the corresponding cobalt proportions in Ni-Co NWAs are
0%, 33.37%, 64.39% and 76.87%, respectively. The onset oxidation
potential gradually decreases as more cobalt source is added. Ni
9 electrode has lower onset potential and much higher oxidation
current density than Ni 10 electrode. Ni 7 has an onset potential of
12 mV smaller than Ni 9 electrode, but the oxidation current
density of Ni 7 electrode is almost reduced down to half of that of
Ni 9 electrode. It is illustrated in previous studies that the addition
of cobalt would promote a displacement of Ni(OH)2/NiOOH redox
processes to less positive potential [6,25]. As a result, the onset
potential of urea electro-oxidation would be lowered. Moreover,
Wu et al. [24] evidenced that the inclusion of cobalt raised the
293
electrical conductivity of nickel powder by experimental deter-
minations. The improvement of electrical conductivity from Ni
10 to Ni 9 electrode benefits the electron transfer of urea electro-
oxidation reaction on the premise that cobalt has no significant
negative influence. Based on the above experimental results, Ni
9 electrode is found to have the best catalytic activity towards urea
electro-oxidation in terms of relatively lower onset potential and
highest oxidation current density.
3.2. Direct urea/hydrogen peroxide fuel cell tests
Fig. 5A shows the plots of both cell potential (E) and power
density (P) versus current density (j) for single direct urea/H2O2 fuel
cell operating with 0.33 mol L
1 urea and 5.0 mol L
1 KOH in the
anolyte, 2.0 mol L
1 H2O2 and 2.0 mol L
1 H2SO4 in the catholyte at
room temperature( 25  C). The four as-prepared Ni-Co NWAs
electrodes (Ni 10, Ni 9, Ni 7 and Ni 5) and Pd/CFC electrode
separately work as anode and cathode catalysts. Clear seen, the
open circuit voltages of Ni 10, Ni 9, Ni 7 and Ni 5 are very close to
one another. The power densities of Ni 10 and Ni 5 are much lower
than that of Ni 9 and Ni 7. Ni 7 has higher power density than that of
Ni 9 from 8 mA cm
2 to 23 mA cm
2, while its discharge current
density is only 33 mA cm
2. Ni 9 gives the largest discharge current
density of 45 mA cm
2 and an OCV of 0.83 V, leading to a peak
power density of 5.03 mW cm
2, which indicates not only the best
cell performance among four anode catalysts but also greatly
294 F. Guo et al. / Electrochimica Acta 199 (2016) 290–296

Fig. 4. (A) Magnified section of cyclic voltammograms of Ni 10, Ni 9, Ni 7 and Ni 5 electrodes in 5.0 mol L
1 KOH at a scan rate of 10 mV s
1; cyclic voltammograms of Ni 10 (B),
Ni 9 (C), Ni 7 (D) and Ni 5 (E) electrodes in 5.0 mol L
1 KOH with and without 0.33 mol L
1 urea at a scan rate of 10 mV s
1; (F) correlation between cobalt proportion by ICP,
onset potential, oxidation current density and cobalt proportion in the bath solution.

enhanced cell performance compared with that of previously
reported direct urea fuel cells(6 mA cm
2, 0.65 V and 1.5 mW
cm
2) [26]. In conclusion, Ni 9 also shows superior performance
than other three anode catalysts in the overall fuel cell system.
In the present configuration, many possible side reactions may
occur in the cell potential range, for example, the electrochemical
oxidation of Ni/Co, the reaction of OH
and H+ in the anolyte and
catholyte. In order to prove the superiority of catalysts and to
confirm the fuel cell performance is really contributed by the
electrochemical oxidation of urea, two blank tests are performed
with only graphite flow field as catalysts and without urea in the
anolyte, respectively. As shown in Fig. 5B, when without urea in the
anolyte, the open circuit voltage is 0.79 V, lower than that with
urea (0.83 V). The peak power density without urea is 0.89 mW
cm
2, which is much lower than that with urea, 5.03 mW cm
2,
implying the existence of other side reactions is almost negligible.
Inset of Fig. 5B shows the E(j) and P(j) curves obtained only with
the graphite flow field acted as catalysts. Under same compositions
of fuel feeding, the peak power density is lower than 0.1 mW cm
2,
indicating that the high performance was attributed to the as-
made Ni-Co NWAs and Pd/CFC catalysts.
Fig. 6 compares the current-cell potential and current-power
density characteristics of direct urea/H2O2 fuel cell employing
different KOH concentrations. The urea concentration in the
anolyte is kept at 0.33 mol L
1. The catholyte is 2.0 mol L
1 H2O2
and 2.0 mol L
1 H2SO4. As can be seen, the OCV increases as more
KOH is added in the anolyte. The addition of 9.0 mol L
1 KOH and
0.33 mol L
1 urea greatly enhances the performance of direct urea/
H2O2 fuel cell by increasing the OCV up to 0.92 V and current
density up to 50 mA cm
2 giving a peak power density close to
7.4 mW cm
2. The power density and discharge current density are
suppressed with further increase of KOH concentration to 10 mol
L
1, which may be caused by the less availability of urea in the
anode [27]. Moreover, the high viscosity of KOH would also give
rise to retarding the movability of the charge carrier in the anolyte
[14].
Fig. 7 shows the dependence of cell performance on urea
concentration. The KOH concentration is fixed at 9.0 mol L
1.
Compared with the OCV variation caused by the KOH

Fig. 5. (A) Plots of cell potential and power density versus current density with four Ni-Co NWAs anodes. Anolyte: 0.33 mol L
1 urea + 5.0 mol L
1 KOH. Flow rate: 10 mL min
1.
Operation temperature: 25  C; (B) Two blank tests with graphite as the catalysts (inset) and without urea in the anolyte, which is in comparison with that adding urea in the
anolyte, respectively. Anode: Ni 9. Flow rate: 10 mL min
1. Operation temperature: 25  C.
 F. Guo et al. / Electrochimica Acta 199 (2016) 290–296
Fig. 6. Dependence of cell performance on KOH concentration. Anode: Ni 9.
Anolyte: 0.33 mol L
1 urea + x mol L
1 KOH (x = 5.0, 7.0, 9.0 and 10). Flow rate:
10 mL min
1. Operation temperature: 25  C.
concentration, the urea content has less effect on the OCV of direct
urea/H2O2 fuel cell. As shown in Fig. 7A, the cell potential in the
low-current density region (such as 0 mA cm
2 7.0 mA cm
2)
increases with urea concentration up from 0.11 mol L
1 to 1.1 mol
L
1 and then falls at 1.43 mol L
1. The power density of 1.1 mol L
1
urea at 7.0 mA cm
2 shows the highest value among all the urea
concentrations (Fig. 7B). However, in the high-current density
region, the peak power density increases from 0.11 mol L
1 urea to
0.33 mol L
1 while 0.77 mol L
1 or more urea content leads to the
deteriorated cell performance. According to Eq. (1), KOH reacts
with urea in a stoichiometric ratio of 8. It should be also noted that
KOH not only functions as reactants but also the supporting
electrolyte. Herein, in order to pursue better cell performance, the
suitable [KOH]/[urea] ratio is needed. Results show that the anolyte
containing 9.0 mol L
1 KOH and 0.33 mol L
1 urea is preferable,
meaning that the inadequate (0.11 mol L
1, 82:1 stoichiometry)
and excess (0.77, 1.1 and 1.43 mol L
1, 12:1, 8:1 and 6:1 stoichiome-
try) urea at fixed KOH concentration would both suppress the urea
electro-oxidation reaction and the cell performance. The urea
concentration in human urine is 0.33 mol L
1, suggesting that urine
can be also used as a promising fuel for the direct urea/H2O2 fuel
cell instead of a waste.
Fig. 8 presents the cell potential behavior with time during a
short term duration test on direct urea/H2O2 fuel cell at a constant
Fig. 7. Plots of cell potential versus current density (A) and power density versus current density (B). Anode: Ni 9. Anolyte: 9.0 mol L
1 KOH + x mol L
1 urea (x = 0.11, 0.33, 0.77,
1.1 and 1.43).
295
Fig. 8. Duration test on the direct urea/H2O2 fuel cell. Anode: Ni 9. Anolyte:
9.0 mol L
1 KOH + 0.33 mol L
1 urea. Flow rate: 10 mL min
1. Operation tempera-
ture: 25  C.
current load of 15 mA cm
2 and at 25  C. 9.0 mol L
1 KOH + 0.33
mol L
1 urea and 2.0 mol L
1 H2SO4 + 2.0 mol L
1 H2O2 are con-
stantly applied to the anode and cathode compartments,
respectively. Both of the flow rates for anolyte and catholyte are
10 mL min
1. The cell is first rested till a relatively stable OCV is
observed. A concern should be mentioned that there is a probable
cross-over when the pH value of anode and cathode compartments
is different, which as consequence would affect the cell potential
and stability. The current results show the cell potential remains at
about 0.35 V during 1 hour duration test, leading to an almost
constant power density of 5.3 mW cm
2. The direct urea/H2O2 fuel
cell appears to be very stable in the case of a cell mounted with Ni-
Co NWAs anode and Pd/CFC cathode catalysts.
4. Conclusions
In this paper, a direct urea/H2O2 fuel cell was successfully
developed by using Ni-Co NWAs as the anode. The Ni-Co NWAs
anode catalyst was optimized in terms of relatively lower onset
potential and highest current density for urea electro-oxidation
through adjusting the cobalt molar content into 10% in the nickel
and cobalt bath solution. When 9.0 mol L
1 KOH + 0.33 mol L
1
urea and 2.0 mol L
1 H2SO4+ 2.0 mol L
1 H2O2 were respectively
used as anolyte and catholyte, an open circuit voltage of 0.92 V and
296 F. Guo et al. / Electrochimica Acta 199 (2016) 290–296
maximum power density of 7.4 mW cm
2 were achieved at room
temperature. The cell showed excellent stability during short term
test at a constant discharge current density of 15 mA cm
2. The
results demonstrate that direct urea/H2O2 fuel cell is a practical
and promising new type of fuel cell.
Acknowledgements
We gratefully acknowledge the financial support of this
research by National Nature Science Foundation of China
(21503055), the China Postdoctoral Science Foundation
(2015M571390), the Natural Science Foundation of Heilongjiang
Province of China (QC2015015), the Heilongjiang Postdoctoral
Fund (LBHZ14054, LBH-TZ0609), the Major Project of Science and
Technology of Heilongjiang Province (GA14A101), and Fundamen-
tal Research Funds for the Central Universities (HEUCF20151004).
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