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Highly Ordered Mesoporous CuCo2O4 Nanowires, a Promising


Solution for High-Performance Supercapacitors
Afshin Pendashteh,, Seyyed Ebrahim Moosavifard, Mohammad S. Rahmanifar, Yue Wang,
Maher F. El-Kady,, Richard B. Kaner,*, and Mir F. Mousavi*,,

Department of Chemistry, Tarbiat Modares University, Tehran 14115-175, Iran


IMDEA Energy Institute, ECPU, Avenida Ramon de la Sagra 3, 28935 Mostoles, Madrid, Spain

Faculty of Basic Science, Shahed University, Tehran 18151-159, Iran

Department of Chemistry, Faculty of Science, Cairo University, Giza 12613, Egypt

Department of Chemistry and Biochemistry, California NanoSystems Institute, University of California, Los Angeles (UCLA),
Los Angeles, California 90095, United States

S Supporting Information
*

ABSTRACT: The search for faster, safer, and more ecient energy storage
systems continues to inspire researchers to develop new energy storage
materials with ultrahigh performance. Mesoporous nanostructures are
interesting for supercapacitors because of their high surface area, controlled
porosity, and large number of active sites, which promise the utilization of
the full capacitance of active materials. Herein, highly ordered mesoporous
CuCo2O4 nanowires have been synthesized by nanocasting from a silica SBA-15
template. These nanowires exhibit superior pseudocapacitance of 1210 F g1 in
the initial cycles. Electroactivation of the electrode in the subsequent 250 cycles
causes a signicant increase in capacitance to 3080 F g1. An asymmetric
supercapacitor composed of mesoporous CuCo2O4 nanowires for the positive
electrode and activated carbon for the negative electrode demonstrates an
ultrahigh energy density of 42.8 Wh kg1 with a power density of 15 kW kg1
plus excellent cycle life. We also show that two asymmetric devices in series can eciently power 5 mm diameter blue, green, and
red LED indicators for 60 min. This work could lead to a new generation of hybrid supercapacitors to bridge the energy gap
between chemical batteries and double layer supercapacitors.

INTRODUCTION
The rapidly growing demand for electric vehicles and portable
electronics has stimulated a great deal of research to develop
high-performance electric energy storage devices.13 Supercapacitors, also known as ultracapacitors or electrochemical
capacitors, are considered one of the most reliable energy storage
devices mainly due to their capability of providing quick bursts of
energy and long lifespan. Current supercapacitors use carbonbased materials and store charge through non-Faradaic electric
double layers (EDL). Capitalizing on Faradaic redox reactions,4,5
metal oxide- or conducting polymer-based pseudocapacitors6,7
show considerably higher specic capacitances than carbonbased supercapacitors.8 Transition metal oxides are considered
especially promising as electrode materials for the next generation of supercapacitors due to their multiple oxidation states.9
However, their poor electrical conductivity and cycling stability
have so far hindered practical applications.10 Therefore, it is a great
challenge to boost the electrochemical performance of pseudocapacitive materials by carefully controlling their structure at the
nanoscale and by designing the cell structure.1115
Since only the surface of metal oxides can eectively contribute
to the total capacitance, the preparation of porous metal oxide
2015 American Chemical Society

nanostructures represents a promising solution toward harvesting their full capacitance.16 In addition, pore sizes and their
distribution directly aect the ability of a material to function
eectively as a supercapacitor. Therefore, development of nanoporous materials, especially metal oxides (consisting of micropores, <2 nm; mesopores, 250 nm; and macropores, >50 nm)
with an extended range of pore sizes, can provide a promising
method to enhance the capacitive performance due to enhanced
surface area and short electron-/ion-transport pathways.11
From a wide range of pseudocapacitive materials, spinel
structures containing binary or ternary mixtures of metal oxides
are of great interest for energy storage applications.1719 Among
the various types of these structures, spinel cobaltites (MCo2O4)
are promising because of the presence of mixed valence metal
cations that provide higher electronic conductivity and electrochemical activity in comparison with single-component
oxides.1820 This makes MCo2O4 a promising electrode material
not only for supercapacitors but also for Li-ion batteries.2023
Received: February 23, 2015
Revised: April 16, 2015
Published: April 20, 2015
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DOI: 10.1021/acs.chemmater.5b00706
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Chemistry of Materials

facilitated ion transport. This is advantageous to nanostructures


with poorly accessible pores in which only a fraction of the
material can contribute to charge storage (Figure 1).

CuCo2O4 is an interesting cobaltite spinel because of its low cost


and nontoxicity. Here, in order to improve the kinetics of the
electrode toward fast ion insertion/deinsertion, CuCo2O4
nanostructures, such as nanoparticles and nanowires, have
been studied. Previously, Wang et al. synthesized CuCo2O4
nanowire arrays on a carbon-fabric substrate and obtained a
relatively low specic capacitance of 57.8 F g1 at a current
density of 1.25 A g1.20 They then boosted the capacitive performance by fabricating coreshell CuCo2O4@MnO2 heterostructured nanowire arrays to achieve a maximum specic
capacitance of 327 F g1. Recently, we fabricated cauliower-like
CuCo2O4 nanostructures via a simple urea combustion method,
which provided a maximum specic capacitance of 338 F g1
(at 1 A g1) with good rate capability and cycling stability.24
Although these studies have demonstrated the promise of
CuCo2O4 electrodes, the reported specic capacitances are still
far from values obtained for other oxides, resulting in supercapacitors with low energy density. While the performance of
these nanostructured CuCo2O4 is better than the bulk material,
the preparation of CuCo2O4 nanostructures with aligned porosity
and improved electronic and ionic conductivities has yet to be
realized. Such materials would greatly improve the charge storage
capacity of CuCo2O4 electrodes and their rate capability.
By combining the unique properties of nanowires with a
controlled porous structure, improved performance can be
achieved, as illustrated in Figure 1. The nanowires oer large

EXPERIMENTAL SECTION

All chemicals were directly used as purchased without further


purication.
Synthesis of Mesoporous SBA-15 Silica Template. A mesoporous
silica template with hexagonal P6mm symmetry (SBA-15) was prepared
according to previous reports.25,26 Tetraethyl orthosilicate (TEOS) was
used as the silica source, and a hydrothermal reaction was performed in
an autoclave at 100 C for 24 h. The nal solid product was calcined at
550 C (2 min1) for 3 h to obtain the SBA-15 silica template.
Synthesis of Highly Ordered Mesoporous CuCo2O4. A 0.01 mol
amount of Cu(NO3)23H2O and 0.02 mol of Co(NO3)26H2O were
dissolved in 10 mL of doubly distilled water. A 2 mL aliquot of the
solution was added to 2 g of SBA-15 and then dispersed in 80 mL of
n-hexane under stirring for 8 h. The mixture was then ltered and dried
at 60 C. The obtained powder was calcined at 400 C (1 min1) for 5 h
and the resulting material treated two times with a hot aqueous KOH
solution (2.0 M) to remove the silica template, washed with water, and
then dried at 60 C. This sample is denoted as HOCuCo2O4.
Synthesis of Disordered Mesoporous CuCo2O4. A 0.0025 mol
amount of Cu(NO3)23H2O, 0.005 mol of Co(NO3)26H2O, and
0.025 mol of urea were dissolved in 50 mL of distilled water. The
solution was transferred to an autoclave and heated to 180 C for 6 h.
The obtained precipitate was ltered, washed several times with water
and ethanol, and then dried at 60 C. Next, the powder was calcined at
400 C for 5 h and is denoted as DOCuCo2O4.
Materials Characterization. The crystal phase of each sample was
examined using powder X-ray diraction (XRD, Philips Xpert
diractometer with Co K radiation ( = 0.178 nm) generated at
40 kV and 40 mA with a step size of 0.02 s1). The sample morphology
was characterized by scanning electron microscopy (SEM, Philips and
JEOL-JSM-6700) and transmission electron microscopy (TEM, Philips
EM 208 and FEI Technai G2 TF20 operated at 200 kV). The nitrogen
(N2) sorption measurements were performed using a Belsorp instrument at 77 K. The specic surface area was calculated using the Brunauer
EmmettTeller (BET) method, and the porosity distribution was obtained
from the desorption branch of the isotherm using BarrettJoynerHalenda
(BJH) analysis.
Electrochemical Measurements. The electrochemical measurements of the prepared samples were performed in a three-electrode
conguration in 6 M KOH electrolyte. The working electrodes were
prepared by mixing active material, carbon black, and polyvinylidene
uoride (PVDF) (10% solution in N-methyl-2-pyrolidone) with a mass
ratio of 75:20:5. A 5% solution of the mixture in isopropanol was sprayed
onto Ni foam as the current collector. The prepared electrodes were
dried at 60 C overnight. A Pt plate was used as the auxiliary electrode
and Hg/HgO as the reference electrode. An Autolab PGSTAT30 was
employed to measure the electrochemical properties of the samples
through cyclic voltammetry (CV) and electrochemical impedance
spectroscopy (EIS). The EIS measurements were conducted at open
circuit potentials. A Solartron battery test unit equipped with Cell Test
software (v. 3.5.0) was used for galvanostatic chargedischarge (GCD)
measurements.
Asymmetric Cells. Asymmetric supercapacitors were assembled by
integrating a HOCuCo2O4 positive electrode with an activated carbon
(AC) negative electrode in 6 M KOH electrolyte solution. A cellulosic
paper was used as the separator. It should be mentioned that in order to
utilize its full pseudocapacitance, the positive electrode was electroactivated before integration into the asymmetric cell by running
continuous charge/discharge for 250 cycles in a three-electrode setup.
The as-fabricated HOCuCo2O4//AC asymmetric supercapacitors
were then subjected to CV, GCD, and EIS measurements. Finally, the
cycle life of this asymmetric supercapacitor was tested over 5000 charge/
discharge cycles at a current density of 6 A g1.

Figure 1. Schematic comparison of the pore accessibility in the highly


ordered (HO) HOCuCo2O4 and disordered (DO) DOCuCo2O4
mesoporous samples.

accessible specic surface area and eective sites for redox


reactions, making it possible to fully utilize the charge storage
ability of CuCo2O4. In addition, the aligned and interconnected
pores provide eective contacts between the nanowires and the
electrolyte ions resulting in shortened ion diusion pathways and
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DOI: 10.1021/acs.chemmater.5b00706
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Chemistry of Materials

Figure 2. Schematic preparation steps of highly ordered mesoporous CuCo2O4 nanowires via nanocasting from a silica template.

Figure 3. Powder XRD patterns of the as-prepared CuCo2O4 samples (a) and small-angle XRD pattern of the HOCuCo2O4 sample (b). TEM images
of the sample from dierent orientations: (c) view from the top showing the tips of the nanowires and (d) a side view of the nanowire bundle. (e)
HRTEM image of the sample and (f) corresponding SAED pattern.

RESULTS AND DISCUSSION


Highly ordered mesoporous CuCo2O4 nanowires (HOCuCo2O4)
were synthesized by nanocasting from a silica SBA-15 hard template
(Figure 2). Moreover, a nontemplate hydrothermal route was
employed to synthesize a disordered porous sample (DOCuCo2O4).

The composition of the samples has been characterized via XRD


(Figure 3a). All diraction peaks can be indexed to the pure cubic
spinel phase of copper cobaltite (JCPDS File No. 001-1155).17
The sharp peak at 1.07 in a low-angle XRD pattern for
HOCuCo2O4 (Figure 3b) can be indexed as the (100) reection
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Figure 4. Electrochemical characterizations of the highly ordered mesoporous (HOCuCo2O4) and disordered mesoporous (DOCuCo2O4) samples as
supercapacitor electrode material: (a) CV curves of the samples at a scan rate of 5 mV s1; (b) chargedischarge proles of the samples at a current density
of 2 A g1; (c) chargedischarge proles of the HOCuCo2O4 at various current densities ranging from 2 to 20 A g1; (d) calculated capacitance as a
function of current density; (e) cycling performance of the HOCuCo2O4 sample at various current densities of 2, 5, 10, and 20 A g1 during 4250 cycles;
and (f) Nyquist plots of the HO and DO samples. The inset shows the proposed equivalent circuit: ESR, Rct, W, CPE1, and CPE2 refer to equivalent series
resistance, Faradaic charge transfer resistance, Warburg impedance, double layer capacitance, and Faradaic pseudocapacitance, respectively.

of the P6mm space group anticipated for the replica supramolecular structure of SBA-15,17 showing the complete replication of the SBA-15 mesoporous system by CuCo2O4.
Scanning electron microscopy was employed to investigate the
samples morphologically, showing uniform elongated-shaped
particles for the HOCuCo2O4 sample (Supporting Information
(SI) Figure S1a,b). Magnied SEM images zooming into the
HOCuCo2O4 particles from dierent viewing directions reveal
each particle is further comprised of three-dimensional porous
structures (SI Figure S1c,d). In contrast, the DOCuCo2O4
sample is comprised of nonuniform particles with a broad particle
size distribution (i.e., 50 to >600 nm), with no internal porous
structures (SI Figure S1e,f).
The highly ordered mesopores of the HOCuCo2O4 sample
is evident through TEM (Figure 3c,d). A porous particle comprised of oriented CuCo2O4 nanowires (as viewed from the top)
shows the tips of the nanowires (Figure 3c) clearly corroborating
the hexagonal arrangement of the replica in the orientation of
(100) planes created by the template. In Figure 3d, a side-view
image (i.e., from the elongated direction) of such a particle
illustrates that the HOCuCo2O4 sample is comprised of individual nanowires organized into parallel bundles with sizes in the
range of a few hundred nanometers in length. The mesostructure
regularity can be seen through all of the particle domains
(SI Figure S2a,b), demonstrating that no obvious nonporous
particles were formed. As can be observed in Figure 3d, the
diameter and the interwire spacing (i.e., pores) of the oriented
nanowires are estimated to be around 7.2 and 2.9 nm, respectively, in good agreement with the previous reported values for
the SBA-15 silica template.27 A high-resolution TEM (HRTEM)

image of the HOCuCo2O4 sample (Figure 3e) reveals that


the nanowires are comprised of nanocrystalline domains of the
spinel cobaltite. Lattice fringes with a d-spacing of 0.47 nm are
observed, corresponding to the (111) crystallographic plane of
the cubic spinel CuCo2O4. On the other hand, TEM images of
the DOCuCo2O4 (SI Figure S2c,d) reveal a disordered porous
structure, with pore sizes ranging from 3 to 15 nm. The disordered characteristic of the pores hinders their access to the
electrolyte and feasibility of fast ion movements which signicantly suppresses electrochemical reactions. This is especially
important in supercapacitor applications.
In order to further investigate the crystallographic characteristics of the mesoporous sample, selected area electron diraction
(SAED) was performed (Figure 3f). The ring diraction pattern
illustrates the polycrystalline nature of the mesoporous nanowires. The diraction rings show d-spacings in agreement with
reference values (SI Table S1) that can be indexed to the (111),
(220), (311), (400), (422), (440), and (511) planes of the spinel
CuCo2O4, which is consistent with the XRD results in Figure 3a.
Nitrogen (N2) adsorptiondesorption measurements were
conducted to evaluate the pore sizes, their distribution, and the
BrunauerEmmettTeller (BET) surface area of the samples. SI
Figure S3a,b clearly shows the mesostructural features of the
sampletypical type IV isotherms including type H1 hysteresis
loops.28 Accordingly, BET surface areas of 59.34 and 37.08 m2 g1
(SI Table S2) were obtained for the HOCuCo2O4 and
DOCuCo2O4 samples, respectively.
The electrochemical performances of the samples as supercapacitor electrodes were evaluated in a three-electrode conguration using 6 M KOH solution as the electrolyte. Figure 4a
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OH anions remarkably enhances the utilization of the internal


and external surfaces of the HOCuCo2O4 electrode, a phenomenon that is signicantly restricted to the external surfaces in
the DOCuCo2O4 sample (Figure 1).31,32
In order to test the rate capability of the electrodes, charge
discharge measurements were performed at various current
densities ranging from 2 to 20 A g1. The corresponding proles
for the HOCuCo2O4 electrode are shown in Figure 4c, demonstrating the maintenance of voltage plateaus even when operated
at a high current density of 20 A g1. The calculated specic
capacitances for the HOCuCo2O4 and DOCuCo2O4 electrodes versus the applied current density are presented in Figure 4d.
As can be seen, with a 10-fold increase in current density from
2 to 20 A g1, 64% of the initial capacitance was retained in the
HOCuCo2O4 electrode, indicating its high rate capability. This
contrasts with the DOCuCo2O4 electrode, which shows only
about 35% capacitance retention after the increased current
density. This suggests that the interconnected channels in the
HOCuCo2O4 provide ecient ion transport within the
electrode even when tested at high current densities (Figure 1).
To further demonstrate the advantages of the HOCuCo2O4
electrode architecture on its electrochemical behavior, the
cycling performance was tested using sequential charge/
discharge curves and the results are presented in Figure 4e.
The specic capacitance increases upon cycling reaching
an ultrahigh capacitance of 3080 F g1 in the course of the rst
250 cycles at a current density of 2 A g1. This remarkable
increase in capacitance may be attributed to structural activation
and full pore opening during insertion/deinsertion of ions
through the mesopore channels and possibly micropore channels
of the sample.33 Such an increase in capacitance during initial
cycling has been previously observed.24,34 After 1000 cycles at
2 A g1, the electrode was tested at progressively increased
current densities. Despite the sudden change of the applied
current density, the electrode exhibits relatively stable capacitance. We observe some uctuations at higher current densities,
which could be attributed to partial degradation of fragile walls
of smaller pores due to consecutive insertion/deinsertion of ions
at high rates. After 4000 continuous cycles at varying current
densities, the current was turned back to 2 A g1. Remarkably,
93.5% of the capacitance after activation can still be delivered
and maintained for another 250 cycles without any noticeable
changes. This interesting cycling performance demonstrates the
suitability of HOCuCo2O4 electrodes for practical energy storage.
Based on the preceding overall electrochemical performance,
the unique highly ordered mesoporous CuCo2O4 on Ni foam
electrode has been found to be at least comparable or superior
to other copper cobaltite electrodes, single-component metal
oxides including CuO and Co3O4, and binary metal oxides as a
supercapacitor electrode material (Supporting Information
Table S3).
Electrochemical impedance spectroscopy (EIS) was performed to provide further insight into the electrochemical
behavior of the electrodes, respectively. Figure 4f shows Nyquist
plots for HOCuCo2O4 and DOCuCo2O4 electrodes. In
accordance with a CNLS tting using the proposed equivalent
circuit (Figure 4f, inset), the diameter of the semicircle, which
corresponds to the charge transfer resistance, is signicantly
smaller in the HOCuCo2O4 electrode (3.77 ) when compared to that of the DOCuCo2O4 electrode (10.6 ). The
x-intercept of the Nyquist plot suggests a very small equivalent
series resistance (ESR) for the HOCuCo2O4 electrode (0.54 )
as opposed to 0.96 for the DOCuCo2O4 electrode. These

shows cyclic voltammetry (CV) of the HOCuCo2O4 and


DOCuCo2O4 samples at a scan rate of 5 mV s1. For both
samples, the shape of the CV curves indicates pseudocapacitive
behavior arising from Faradaic reactions of the Co4+/Co3+ and
Cu2+/Cu+ redox pairs. The exact electrochemical behavior of
copper and cobalt oxides in strong alkaline solutions needs
further investigation due to several possible phases for these
cations and the complex nature of the system. A possible
mechanism is that by initiating the scan from cathodic potentials,
CoOOH29 and CuOH may form at the outer surface of the
CuCo2O4 electrode, according to the following equation:
CuCo2O4 + H 2O + e 2CoOOH + CuOH

(1)

Then, by sweeping the potential toward positive values, redox


reactions occur as follows:
CoOOH + OH CoO2 + H 2O + e

(2)

CuOH + OH Cu(OH)2 + e

(3)

The area under the CV curve is proportional to the charge


stored during the anodic and cathodic scans, while the specic
capacitance (i.e., the capacitance per unit mass of electrode active
material) can be calculated using the equation

Cs =

i dv/mv

(4)

where i dv is the integration of the current during discharge


(i.e., cathodic scan), m is the loading mass of the active material,
and is the scan rate. Accordingly, a high specic capacitance of
about 1150 F g1 is obtained for the HOCuCo2O4 sample,
much larger than the value obtained for the DOCuCo2O4
sample (260 F g1). Moreover, CV measurements for the
samples at various scan rates ranging from 5 to 80 mV s1
(SI Figure S4a,b) showed a slight increase in peak separations
that is likely due to a small ohmic resistance and polarization. The
linear dependence of peak current density against the square root
of the scan rate in both samples (SI Figure S5) illuminates the
diusion control characteristic of the redox reaction that can
be understood by dependency of the reactions (eqs 2 and 3) on
the diusion of the OH ions.
In order to evaluate applicability of CuCo2O4 as supercapacitor electrode materials, chargedischarge measurements
were conducted at dierent current densities. Figure 4b shows
the real time curves for HOCuCo2O4 and DOCuCo2O4
samples at a current density of 2 A g1, in a potential range of
00.5 V. The voltage plateau is characteristic of pseudocapacitance due to charge storage based upon Faradaic redox reactions
at the electrodeelectrolyte interface (in good agreement with
the CV curves).
The specic capacitance is calculated by the formula

Cs = (I t )/(mV )

(5)

where I is the discharge current, t is the discharge time, m is the


mass of the active material, and V is the potential window.30
Here, a specic capacitance as high as 1210 F g1 (areal
capacitance of 0.6 F cm2) is obtained for the HOCuCo2O4
sample at a current density of 2 A g1, which is more than 4 times
greater than that achieved by DOCuCo2O4 (270 F g1). Taking
advantage of its highly ordered mesoporous structure, the
HOCuCo2O4 sample provides thorough access of the electrode surface to the electrolytic ions, resulting in superior capacitance
performance in comparison with the DOCuCo2O4 sample. In
other words, the presence of abundant diusion channels for
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of the electrode. All of these observations demonstrate the importance


of mesoporous pseudocapacitive nanowires for supercapacitor
electrodes. The high surface area of the nanowires provides more
active sites for charge transfer, thus increasing the overall capacity of
the electrodes. In addition, the aligned mesopores facilitate ion
transport kinetics during charge/discharge processes.
Up to this point, we have only discussed the electrochemical
performance of HOCuCo2O4 in a three-electrode conguration. To further evaluate the HOCuCo2O4 electrode for real
applications, asymmetric supercapacitors were made by integrating the HOCuCo2O4 electrode as the positive electrode (after
activation by 250 cycles), activated carbon (AC) as the negative
one, and a cellulosic paper as the separator in 6 M KOH solution.
This conguration combines a high-energy electrode with a highpower electrode to produce a hybrid energy storage system with
the best attributes of both. In order to achieve the maximum
capacitance and best cycle life, the masses of positive and negative
electrodes were adjusted according to the following equation:

results demonstrate that the HOCuCo2O4 aligned nanowires


have lower interparticle resistance and better contact with the
current collector than the DOCuCo2O4 electrode. Further
investigations indicate that the slope of the linear section at
low frequencies is steeper (Table 1), a characteristic of pure
Table 1. Electrical Parameters for CuCo2O4 from EIS
Measurements at OCP
circuit elements

HOCuCo2O4

DOCuCo2O4

ESR ()
Rct ()
n1a
n2a

0.544
3.77
0.860
0.982

0.960
10.6
0.821
0.890

The slope of the linear section at low frequencies is steeper for the
HOCuCo2O4 sample (phase elements, n, is 0.86 and 0.98 for CPE1 and
CPE2, respectively), while these values obtained for the DOCuCo2O4
electrode are 0.82 and 0.89, characteristic of pure capacitive behavior.

capacitive behavior. This structural activation behavior becomes even


better after 300 cycles of charge and discharge (SI Figure S6),
indicating facilitated ion diusion and electrolyte access to the surface

for Q + = Q

m+
C V
=
m
C+ V+

(6)

Figure 5. (a) CVs and (b) chargedischarge curves for the HOCuCo2O4//AC asymmetric supercapacitor; (c) specic capacitances and (d) Ragone
plot of the asymmetric supercapacitor at various current densities; (ee) Photographs showing two supercapacitors in series which can light up blue,
green, and red LED indicators, respectively, during 60 min.
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DOI: 10.1021/acs.chemmater.5b00706
Chem. Mater. 2015, 27, 39193926