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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
3919
DOI: 10.1021/acs.chemmater.5b00706
Chem. Mater. 2015, 27, 39193926
Article
Chemistry of Materials
EXPERIMENTAL SECTION
DOI: 10.1021/acs.chemmater.5b00706
Chem. Mater. 2015, 27, 39193926
Article
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.
DOI: 10.1021/acs.chemmater.5b00706
Chem. Mater. 2015, 27, 39193926
Article
Chemistry of Materials
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)
DOI: 10.1021/acs.chemmater.5b00706
Chem. Mater. 2015, 27, 39193926
Article
Chemistry of Materials
(1)
(2)
CuOH + OH Cu(OH)2 + e
(3)
Cs =
i dv/mv
(4)
Cs = (I t )/(mV )
(5)
DOI: 10.1021/acs.chemmater.5b00706
Chem. Mater. 2015, 27, 39193926
Article
Chemistry of Materials
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.
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