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Rational Design of Metal-Organic Framework Derived

Full paper
Hollow NiCo2O4 Arrays for Flexible Supercapacitor
and Electrocatalysis
Cao Guan,* Ximeng Liu, Weina Ren, Xin Li, Chuanwei Cheng,* and John Wang*

both supercapacitors and electrocatalysis

Metal-organic frameworks (MOFs) are promising porous precursors for the due to the fact that they can provide rich
construction of various functional materials for high-performance electrochem- reaction sites and short ion diffusion
ical energy storage and conversion. Herein, a facile two-step solution method length as well as release the strain during
the electrochemical reactions, thus main-
to rational design of a novel electrode of hollow NiCo2O4 nanowall arrays on taining the integrity of the electrodes.[11–19]
flexible carbon cloth substrate is reported. Uniform 2D cobalt-based wall- For example, a novel hollowed cubic NiS
like MOFs are first synthesized via a solution reaction, and then the 2D solid nanoframe electrode was achieved by
nanowall arrays are converted into hollow and porous NiCo2O4 nanostructures anion exchange of a Ni–Co MOF with
through an ion-exchange and etching process with an additional annealing S2− ions, which demonstrated enhanced
capacitive performance for electrochem-
treatment. The as-obtained NiCo2O4 nanostructure arrays can provide rich
ical capacitors.[20] Aijaz et al. report a Co@
reaction sites and short ion diffusion path. When evaluated as a flexible elec- Co3O4 encapsulated in N-doped carbon
trode material for supercapacitor, the as-fabricated NiCo2O4 nanowall electrode nanotube-grafted carbon polyhedral elec-
shows remarkable electrochemical performance with excellent rate capability trode derived from a cobalt MOF as a
and long cycle life. In addition, the hollow NiCo2O4 nanowall electrode exhibits bifunctional electrocatalyst with excellent
promising electrocatalytic activity for oxygen evolution reaction. This work catalytic performance under alkaline con-
ditions.[21] Despite the progress achieved
provides an example of rational design of hollow nanostructured metal oxide to date, most of the reported MOF-based/
arrays with high electrochemical performance and mechanical flexibility, derived materials are limited to micro-/
holding great potential for future flexible multifunctional electronic devices. nanoparticles. In addition, most of the pre-
mentioned MOF-derived hollow structures
are in powder forms, which include the
1. Introduction unwanted polymer binder and carbon addictive in electrochem-
ical reaction.[22] These “dead mass” can block the active sites
Metal-organic frameworks (MOFs) have been regarded as a and the resulted inflexibility of the electrodes can set a big bar-
promising class of advanced materials for gas adsorption, rier for the potential usage in flexible electronics.[23–27] As such,
sensing, supercapacitors, and catalysis, owing to their crystal- it would be of great interest to develop 2D MOFs and MOFs
line structures with high porosities and tunable functionali- derived arrayed structures on flexible current collector, which
ties.[1–6] In particular, due to their porous structures with high may offer unique physical and chemical properties with larger
surface areas, MOFs are ideal sacrificial templates to derive surface area and more accessible active sites.[28–33]
into various porous active materials, such as carbonaceous Herein, we report a novel approach to fabricate hollow and
materials, metal oxides, and metal phosphides.[7–10] Hollow porous NiCo2O4 nanowall arrays on flexible carbon cloth cur-
and porous electrode materials have shown great potential for rent collector. This strategy involves in the construction of 2D
cobalt-based MOF solid nanowall arrays on carbon cloth and
an ion-exchange and etching reaction process with Ni(NO3)2 in
ethanol followed by a thermal treatment. This unique electrode
Dr. C. Guan, X. M. Liu, X. Li, Prof. J. Wang
Department of Materials Science and Engineering design processes several advantages as follows. First, the highly
National University of Singapore hollow and porous structures allow the intimate electrolyte pen-
117574, Singapore etration and fast ion/mass transport. Second, the flexible and
E-mail: msegc@nus.edu.sg; msewangj@nus.edu.sg conductive carbon cloth with tight connection to the NiCo2O4
W. N. Ren, Prof. C. W. Cheng arrays can be directly used as electrode without any binder
Shanghai Key Laboratory of Special
Artificial Microstructure Materials and Technology
additives, which can ensure high mechanical stability and elec-
School of Physics Science and Engineering tric conductivity. Third, the unique 2D nanostructures exhibit
Tongji University high surface area and shortened ion diffusion length, which
Shanghai 200092, P. R. China is beneficial to improve the electrochemical performance. As
E-mail: cwcheng@tongji.edu.cn a demonstration, a flexible supercapacitor is assembled with
DOI: 10.1002/aenm.201602391 the hollow NiCo2O4 nanoarrays as cathode, which achieves

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Figure 1.  Schematic illustration of the formation of hollow NiCo2O4 nanostructure from 2D structure can be described as a hydrolysis-
Co-MOF solid nanowalls.
a high gravimetric density of 31.9 W h kg−1 at 2.9 kW kg−1, a
maximum power density of 27.3 W h kg−1 at 22.9 kW kg−1, and
excellent cycling ability. Moreover, the electrocatalytic property
of the hollow NiCo2O4 nanowall arrays for oxygen evolution
reaction is evaluated, which also exhibits superior performance
in terms of low onset potential (1.49 V vs reversible hydrogen
electrode (RHE)) and excellent stability.
2. Results and Discussion
2.1. Material Fabrication and Characterizations
The synthetic strategy for the hollow NiCo2O4 nanowall arrays
is schematically depicted in Figure 1 (see the Experimental
Figure 2.  SEM images of a–c) 2D Co-MOF nanowall, d–f) Ni–Co LDH hollow nanostructure, and g–i) NiCo2O4 hollow nanostructure. The arrows in
(f) and (i) indicate the hollow feature of the materials.
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Section for details). First, a facile solution
method was carried out to grow cobalt-based
2D MOF solid nanowall arrays (noted as
Co-MOF) on a flexible carbon cloth substrate.
Then, through a subsequent ion exchange/
etching process using Ni(NO3)2 in ethanol,
the Co-MOF will be etched and simultane-
ously Ni–Co layered double-hydroxide (noted
as Ni–Co LDH) will deposit on the surface,
resulting into a hollow wall structure. In this
step, the hollowing strategy for the nano-
controlled ion exchange and etching process
(Ni2+ + 2H2O = Ni(OH)2 + 2H+, where the
H+ will etch the MOF and promote the deposition of Ni–Co
LDH), which is efficient to create a central void space.[34,35]
After a thermal treatment in air, the layered double-hydroxide
will be decomposed and become porous, thus highly hollow
and porous as well as crystallized NiCo2O4 nanostructures can
be obtained on carbon cloth substrate (noted as CC@NiCo2O4),
which can be directly used as a flexible electrode for both super-
capacitor and electrocatalysis.
The 2D Co-MOF with nanowall morphology are prepared
on flexible carbon cloth via a modified solution method.[36]
The scanning electron microscopy (SEM) observations in
Figure 2a,b indicate the uniform coverage of the 2D Co-MOF
on carbon cloth surface. From an enlarged view in Figure 2c,
one can see the solid nature of these Co-based nanowalls with
smooth surfaces. The X-ray diffraction (XRD) patterns of the
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Co-MOF in Figure S1a (Supporting Information) confirm that
the crystalline Co-MOF precursors have a layered phase
without any impurities,[36,37] and the corresponding energy-
dispersive X-ray spectroscopy (EDX) spectrum (Figure S1b,
Supporting Information) verifies the existence of N and C ele-
ments from the organic ligand. Figure 2d–e shows the typical
morphology of Co-MOF after the transformation in the pres-
ence of Ni(NO3)2. It can be observed that the overall 2D struc-
tures and the uniform coverage of the materials on the carbon
cloth are maintained after the reactions, and small nanoflakes
appear on the surfaces of the 2D walls. From an enlarged SEM
image in Figure 2f, we can even see the 2D structures become
“semitransparent” (marked with an arrow), indicating that the
hollow structures have been formed. The full transformation
of the Co-MOF is also revealed by the disappeared Co-MOF
peaks in XRD patterns and the lack of N signal in EDX spectra
(Figure S1c, Supporting Information). It is worth mentioning
that short-time etching process will result in insufficient etching
and semihollow structures, and excess dosage of Ni(NO3)2 will
lead to the overgrowth of nanoflakes and severe etching with
the destruction of the 2D arrays (Figure S2, Supporting Infor-
mation). After annealing the Ni–Co LDH nanostructure in air,
the nanoarrays have been completely maintained (Figure 2g,h).
As shown in Figure 2i, it can be seen that the hollow feature
is clearly revealed by the top open area, and the surface of the
hollow structure has been covered with interlinked ultrathin
nanoflakes, indicating that hollow and porous nanowall arrays
have been formed on the carbon cloth. All the XRD peaks of the
hollow nanoarrays (Figure S1a, Supporting Information) can
be assigned to the NiCo2O4 phase (JCPDS card: 20-0781)[38,39]
Figure 3.  TEM images of a) 2D Co-MOF, b,c) Ni–Co LDH hollow nanostructure, and d,e) NiCo2O4 hollow nanostructure. f) HRTEM image of hollow
NiCo2O4 nanostructure with the SAED pattern inserted.
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without noticeable signals of residues, and its corresponding
Full paper
EDX result (Figure S1d, Supporting Information) reveals a Co/
Ni atomic ratio of about 1.8, further confirming the formation
of NiCo2O4 nanoarrays.
The structure evolution from solid Co-MOF nanowalls to
hollow NiCo2O4 nanowalls is further revealed by transmis-
sion electron microscopy (TEM) characterizations. As shown
in Figure 3a, the 2D Co-MOF precursor has a solid feature
with typical height of ≈1 µm. After the reactions with Ni(NO3)2
(Figure 3b,c), a hollow structure can be clearly observed with
sharp contrast between the grained shell and the central void
space, indicating the formation of Ni–Co LDH nanostructures.
From a magnified observation in Figure 3c, we can see that the
surface of the hollow nanowall has been uniformly entangled
with small nanoflakes (≈50 nm in length). After annealing the
Ni–Co LDH nanostructures (Figure 3d), the hollow structure
can be well preserved. As displayed in Figure 3e, the surface of
the nanostructures is composed of many interconnected nano-
particles with small diameters of ≈10 nm. High-resolution TEM
image of the hollow nanostructure is shown in Figure 3f, from
which the lattice fringes of 0.286 and 0.244 nm match well with
the (220) and (311) planes of NiCo2O4 (JCPDS card: 20-0781).[40]
The selected area electron diffraction (SAED) patterns (inset in
Figure 3f) further demonstrate the cubic crystalline structure
of the NiCo2O4 nanostructures (JCPDS card: 20-0781), noticing
that no apparent signals of NiO or Co3O4 can be detected from
the high-resolution TEM (HRTEM) and SAED.
The X-ray photoelectron spectroscopy (XPS) measurement
is further carried out to study the chemical composition of the
hollow NiCo2O4 nanoarrays, as shown in Figure 4. Broad scan
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(b) annealing the Co-MOF precursor in air is

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(a) CC@NiCo2O4 O 1s

Ni 2p
also tested, and detailed characterization

Co 2p
of the solid Co3O4 nanowalls can be found
Intensity (a.u.)

Intensity (a.u.)
in Figure S3 (Supporting information).

O 1s
The representative cyclic voltammetry (CV)
curves of the CC@NiCo2O4 at scan rates of
5–100 mV s−1 are provided in Figure S4a

C 1s
(Supporting information). Apparent redox
peaks can be observed from the CV curves,
1200 1000 800 600 400 200 0 536 532 528 which can be assigned for the Faradic reac-
Binding Energy (eV) Binding Energy (eV) tion between Ni2+/Ni3+, Co3+/Co4+ with
OH −.[44–46] From the CV curves of CC@
(c) Ni 2p Ni 2p3/2 (d) Co 2p Co 2p3/2 NiCo2O4, the peak positions only shift a
Ni 2p1/2 little when the scan rate increased from 5 to
s s Co 2p1/2
Intensity (a.u.)

Intensity (a.u.)
s very good reversibility. The galvanostatic
890 880 870 860 850 810 800
Binding Energy (eV) Binding
Figure 4.  XPS spectra of CC@NiCo2O4. a) Broad scan, b) O 1s, c) Ni 2p, and d) Co 2p of the and CC@Co3O4 at a same current den-
sample.
of the CC@NiCo2O4 shows the element of C, Co, Ni, O without
any other impurities (Figure 4a). The O1 s spectra in Figure 4b
can be well fitted with three subpeaks: the peak at 529.6 eV is
the typical metal–oxygen bonds, and the peaks at 531.3 and
531.8 eV correspond well to the defects with low oxygen and
adsorbed water at or near the surface, respectively.[41,42] The Co
2p spectrum in Figure 4c can be fitted into both Co2+ and Co3+
each accompanied with a shakeup satellite, and the Ni 2p spec-
trum in Figure 4d can be also best fitted into Ni2+ and Ni3+ each
accompanied with a shakeup satellite. These results indicate
that the surface of the NiCo2O4 nanostructures contains Co ,
Co3+, Ni2+, and Ni3+, which is in good agreement with previous
results on NiCo2O4.[41,43]
2.2. Supercapacitive Property
Based on the above discussions, a novel hollow NiCo2O4
nanoarray directly grown on carbon cloth substrate can be
realized from a 2D Co-MOF precursor. The resulted hollow
and porous NiCo2O4 nanostructures can not only provide suf-
ficient reaction sites, short ion diffusion length, buffer the
volume change, but also ensure direct mechanical and electrical
connection with the flexible carbon support, making it a very
promising electrode material for flexible energy storage and
electrocatalysis applications.
To evaluate the electrochemical performance, the CC@
NiCo2O4 is first investigated as a supercapacitor electrode using
a three-electrode system. A Pt plate is used as the counter
electrode, and an Hg/HgO is used as the reference electrode.
A 2 m KOH (potassium hydroxide) aqueous solution is used
as the electrolyte. For comparison, the solid Co3O4 nanowalls
on carbon cloth (noted as CC@Co3O4) obtained by directly
100 mV s−1, indicating that the electrode has
s charge–discharge (GCD) curves of the CC@
CoNi2O4 in the same voltage range are illus-
trated in Figure S4b (Supporting informa-
tion). All the charge–discharge curves have
790 780 770 almost the same voltage plateaus, matching
Energy (eV) well with the CV results. Figure 5a com-
pares the GCD curves of the CC@CoNi2O4
sity of 10 mA cm−2. The discharge time of
CC@NiCo2O4 is longer than that of CC@
Co3O4, indicating that the capacitance is improved (the CV and
GCD curves of the CC@Co3O4 can be found in Figure S4c,d
in the Supporting Information). Noting that the carbon cloth
contributes very little (less than 0.5%) to the total capacitance
(Figure S4e,f, Supporting Information). Figure 5b shows the
specific capacitance as a function of the current density for the
two electrodes. At a small current of 2.5 mA cm−2, the CC@
CoNi2O4 exhibits a high capacitance of 1055.3 F g−1 and a high
capacitance of 483.3 F g−1 can be maintained even when the
current density increased to 60 mA cm−2, suggesting that 45.8%
2+ of the capacitance can be remained when the current increased
24 times. On the other hand, the CC@Co3O4 delivers a capaci-
tance of 823.4 F g−1 at 5 mA cm−2, and it drops to 44.3% when
the current density increased 16 times. The enhanced capaci-
tance and rate capability of the CC@NiCo2O4 can be attributed
to the unique hollow and porous structures that can provide suf-
ficient reaction cites and short ion diffusion length. To confirm
this, the Brunauer–Emmett–Teller (BET) surface areas of the
two electrodes have been tested, and the CC@NiCo2O4 shows
a surface area of 11.6 m2 g−1, which is larger than that of CC@
Co3O4 (8.4 m2 g−1). In addition, the direct contact between the
active materials with the carbon support can also ensure elec-
tron transport highway for fast reaction at high rates. To further
demonstrate the potential application of the CC@NiCo2O4 for
flexible energy storage devices, a flexible asymmetric superca-
pacitor was assembled using the CC@NiCo2O4 as the cathode
and a nitrogen-doped carbon flakes on carbon cloth (CC@NC)
as the anode with a poly(vinyl alcohol) (PVA)–KOH solid-state
electrolyte[47] (detailed characterizations of CC@NC are shown
in Figure S5 in the Supporting Information). The CV curves of
the CC@NiCo2O4//CC@NC full cell are shown in Figure S6a
(Supporting Information), in which quasirectangular curves
without sharp redox peaks can be observed, showing that the

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2.3. Oxygen Evolution Reaction

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As the NiCo2O4 material is a good oxygen
evolution catalyst for water splitting,[51–53]
the self-supported NiCo2O4 hollow arrays
can provide large electroactive surface area
without the usage of binders, and the elec-
tron transfer can be also enhanced by direct
electronic contact. The flexible electrode also
provides potential opportunity to be inte-
grated with other functional flexible elec-
tronic devices. The electrocatalytic activity
of as-fabricated hollow NiCo2O4 nanoarrays
was also evaluated. The tests were conducted
in a typical three-electrode cell system with
1 m KOH (pH = 14) electrolyte. A Pt plate is
used as the counter electrode, and a saturated
calomel electrode (SCE) is used as the refer-
ence electrode. The electrochemical imped-
ance spectroscopy (EIS) of the samples are
first recorded and the Nyquist plots of CC@
NiCo2O4 and CC@Co3O4 are presented in
Figure 5. a) Comparison of GCD curves of CC@NiCo2O4 and CC@Co3O4 at 10 mA cm−2. Figure 6a. In the high-frequency region,
b) The plots of specific capacitances versus current densities for CC@NiCo2O4 and CC@Co3O4.
the intercept of X axis for CC@NiCo2O4 is
c) Ragone plots of the CC@NiCo2O4//CC@NC full cell. The values reported from other MOF-
based supercapacitors are inserted for comparison. d) Cycling test result of the full cell. Digital smaller than that for CC@Co3O4, showing
images of the full cell under flat, bending, and twisting states during the test are inserted. that the bulk resistance of the hollow elec-
trode is smaller. The radius of the semicircle
of CC@NiCo2O4 is also smaller than that
full cell has good capacitive properties. The GCD curves of of CC@Co3O4, showing that the charge transfer resistance of
the full cell are shown in Figure S6b (Supporting Informa- the hollow structure is smaller. In the low-frequency region, a
tion), where all the curves have almost linear charge–discharge more vertical line for the CC@NiCo2O4 is observed, indicating
characteristics. At a current density of 5 mA cm−2, the asym- that the NiCo2O4 nanoarrays have lower ionic diffusion resist-
metric supercapacitor delivers a capacitance of ≈89.7 F g−1, and ance than the solid Co3O4 electrode. Figure 6b shows the linear
≈76.8 F g−1 can be maintained when the cur-
rent density is increased eight times, showing
excellent kinetic behavior (Figure S6c, Sup-
porting Information). Figure 5c shows the
Ragone plot (power density (P) vs energy den-
sity (E)) of the CC@NiCo2O4//CC@NC, and
data obtained from other reported MOF-based
solid-state supercapacitors are also inserted
for comparison. From the Ragone plot, the
CC@NiCo2O4//CC@NC full cell express a
maximum energy density of 31.9 W h kg−1 at
a power density of 2.9 kW kg−1, and it main-
tains 27.3 W h kg−1 at a peak power density
of 22.9 kW kg−1, which is comparable to the
previously reported MOF-based supercapaci-
tors.[9,44,48–50] Figure 5d further shows the
excellent cycling stability and mechanical flex-
ibility of the full cell, that 86.7% of the initial
capacitance can well preserved after 20 000
cycles of charge–discharge at 5 mA cm−2,
even when the full cell was bended/twisted
during the test (inset in Figure 5d). The SEM
image (Figure S6d, Supporting Information)
of the CC@NiCo2O4 after cycling tests shows Figure 6.  a) Nyquist plots, b) polarization curves, and (c) Tafel plots of CC@NiCo O and CC@
2 4
that the structure has been well maintained, Co3O4. d) Stability and flexibility test of CC@NiCo2O4 at 1.57 V versus RHE with typical flat and
further confirming the stable cycling ability. bending status as inserted.

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sweeps of CC@NiCo2O4 and CC@Co3O4 at 5 mV s−1, from
Full paper
which the onset potential of CC@NiCo2O4 is only ≈1.49 V
(vs RHE) and it is ≈30 mV lower than that of CC@Co3O4. In addi-
tion, the NiCo2O4 nanoarrays exhibit higher current densities
across the entire potential window than those for CC@Co3O4,
indicating a clear higher catalytic activity of the hollow nano-
structure. Furthermore, to reach anodic current densities of
10 mA cm−2, the potential required for CC@NiCo2O4 is only
1.57 V, which is among the most active NiCo2O4 electrocata-
lysts[54–67] (a detailed comparison can be found in Table S1 in
the Supporting Information). The Tafel slope of CC@NiCo2O4
is 72 mV per decade as shown in Figure 6c, which is a little
lower than that of CC@Co3O4 (75 mV per decade). The capaci-
tances of the two electrodes are further tested to illustrate the
electrochemical active surface areas (Figure S7, Supporting
Information). The calculated electrochemical double-layer
capacitance of CC@NiCo2O4 (0.088 F cm−2) is ≈4.8 times larger
than that for CC@Co3O4 (0.015 F cm−2), further confirming
the better electrocatalytic performance for the hollow NiCo2O4
nanoarrays. As such, the enhanced electrocatalytic property
of the CC@NiCo2O4 electrode can be due to the hollow and
porous structures, which can provide rich reaction cites and
short ion diffusion length. To further evaluate the stability and
flexibility of the CC@NiCo2O4 as an oxygen evolution reaction
catalyst, the electrode was tested under a constant potential
(1.57 V vs RHE) for 20 h, with the first 10 h under flat status
and the last 10 h under bended status. As shown in Figure 6d,
the current density of CC@NiCo2O4 remained flat during the
20 h test, and the bending of the electrode did not influence
much of the current density, indicating high electrochemical
stability. To further confirm the stability, the postmortem study
has been carried out (Figure S8, Supporting Information), from
which the structure of CC@NiCo2O4 is well maintained after
the long-time test.
3. Conclusions
In summary, we have designed and fabricated novel hollow
NiCo2O4 nanoarrays on flexible carbon cloth through a facile
two-step strategy with 2D Co-MOF solid nanowall arrays as pre-
cursors and templates. Excellent electrochemical performances
both for flexible supercapacitor and electrocatalytic oxygen evo-
lution reaction properties of the CC@NiCo2O4 electrode were
demonstrated, which can be attributed to unique hollow and
porous structures that provide rich reaction cites and short
ion diffusion length. This work opens new opportunities for
rational design of various complex hollow structure arrays for
high-performance flexible electrochemical storage and conver-
sion devices.
4. Experimental Section
Material Synthesis—Preparation of CC@Co-MOF: An aqueous solution
containing 2-methylimidazole (C4H6N2, 40 mL, 0.4 m) was quickly added
into the aqueous solution of Co(NO3)2·6H2O (40 mL, 50 × 10−3 m),
after which a piece of clean CC substrate (2 × 5 × 0.036 cm3, the upper
side and back side protected with by polytetrafluoroethylene tape) was
immersed into the mixture solution. After reaction for 4 h, the sample
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was then taken out, cleaned with deionized water, and vacuum dried
overnight.
Material Synthesis—Preparation of CC@Ni–Co LDH: A piece of CC@
Co-MOF was immersed into an ethanol solution (100 mL) containing
Ni(NO3)2·6H2O (0.3 g). After stirring the solution for 15 min, the sample
was taken out, washed with ethanol, and dried at 60 °C. Decreasing the
reaction time to 5 min will result in insufficient etching, while prolonging
the reaction time to 30 min will result in the overgrowth of nanoflakes.
Material Synthesis—Preparation of CC@NiCo2O4: A piece of CC@Ni–
Co LDH was annealed in air at 350 °C for 2 h with a ramp rate of
2 °C min−1. The mass loading of NiCo2O4 was ≈0.60 mg cm−2.
Material Synthesis—Preparation of CC@Co3O4: A piece of
CC@Co-MOF was annealed in air at 350 °C for 2 h with a ramp rate of
2 °C min−1. The mass loading of Co3O4 was ≈0.69 mg cm−2.
Material Synthesis—Preparation of CC@NC: A piece of CC@Co-MOF
was annealed in Ar at 800 °C for 2 h with a ramp rate of 1 °C min−1, after
which the sample was immersed in 3 m FeCl3 aqueous solution for 6 h,
washed with clean water, and dried at 60 °C. The mass loading of Co3O4
was ≈0.8 mg cm−2.
Material Characterization: Samples were characterized using SEM
(Zeiss, 5.0–20.0 kV), TEM (JEOL-2100F), XPS (AXIS Ultra), and XRD
(Bruker D8 diffractometer). The mass of electrode materials was also
recorded by an AX/MX/UMX Balance (METTLER TOLEDO, maximum
= 5.1 g; delta = 0.001 mg). To measure the surface area of the electrode
materials, nitrogen adsorption–desorption isotherms were measured
on a Micromeritics ASAP 2020 at 77 K. Before measurements, samples
were outgassed at 120 °C for 6 h, and the specific surface areas were
calculated using the BET method.
Electrochemical Characterization: Electrochemical measurements
were conducted using Solartron 1470E at room temperature. (a)
Supercapacitor test: For three-electrode system test, CC@NiCo2O4 (or
CC@Co3O4 and CC@NC) was directly used as the working electrode
without any metal support or other current collector. A Pt plate and
an Hg/HgO were used as the counter electrode and the reference
electrode, respectively. KOH (2 m) was used as the electrolyte.
The specific capacitance (C) of the electrodes was calculated by:
C = It/mV, where I is the discharge current, V is the discharge
voltage, t is the discharge time, and m is the active mass of the
electrode. For the full cell assembly, to optimize the charge between
the two electrodes, the mass of the two electrodes were balanced
by C− × m− × V− = C+ × m+ × V+, where C− and C+ are the specific
capacitances of the negative and positive electrodes, m− and m+ are
the active mass loadings of the negative and positive electrodes, and V−
and V+ are the voltage window of the negative and positive electrodes,
respectively. To assemble the full cell, first a solid-state electrolyte
was fabricated by dissolving 6 g PVA into 30 mL H2O and then mixed
with 30 mL 4 m KOH solution at 85 °C, then the two electrodes were
immersed into the electrolyte and left under ambient conditions for
2 min before they were assembled face-to-face, noticing that the polymer
electrolyte acted as both the electrolyte and the ion-porous separator.
After the electrolyte was solidified, a mechanically robust full cell could
be packed and tested. The energy density (E) and power density (P) of
the full cell were calculated by: E = 21 CV 2, P = E/t, where C is the specific
capacitance of the full cell, V is the discharge voltage, t is the discharge
time, and m is the active mass of the electrodes. (b) Electrocatalytic
test: The catalytic activity was tested in a standard three-electrode
system in 1 m KOH solution (pH = 14) after purging with oxygen
for 30 min, using a Pt plate and a SCE as the counter and reference
electrode, respectively. CC@NiCo2O4 (or CC@Co3O4) was directly
used as the working electrode. EIS measurements were carried out by
applying an AC voltage with 5 mV amplitude in a frequency range from
0.1 Hz to 100 kHz at open circuit potential. The polarization curves were
measured at 5 mV s−1 and iR corrected, and all the measured potentials
were referred to RHE using the following equation: E(RHE) = E(SCE)
+ 0.0592 × pH + 0.241. The electrochemical double-layer capacitance
(Cdl) was determined from the CV curves measured in a potential range
without redox process by: Cdl = I/ν, where I is the charging current
(mA cm−2), and ν is the scan rate (mV s−1).
Adv. Energy Mater. 2017, 7, 1602391
www.advancedsciencenews.com
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This research was supported by the 973 Program (Grant No.
2013CB632701), the National Natural Science Foundation of China
(Grant No. 51202163). This project was also supported by Academic
Research Fund (AcRF) Tier 1 R-284-000-146-112, conducted at the
National University of Singapore.
Received: October 28, 2016
Revised: December 1, 2016
Published online: January 25, 2017
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