Research Article

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Hydrothermal Synthesis of Phosphate-Functionalized Carbon

Nanotube-Containing Carbon Composites for Supercapacitors
with Highly Stable Performance
Xiaoming Fan, Chang Yu, Zheng Ling, Juan Yang, and Jieshan Qiu*
Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Lab of Fine Chemicals,
School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
*
S Supporting Information

ABSTRACT: Phosphate-functionalized carbon nanotube

(CNT)-containing carbon composites with hierarchical porous
structure have been synthesized by a simple soft-template
hydrothermal method followed by heat treatment. The
resulting carbon composites are characterized by FE-SEM,
TEM, TGA, FTIR microspectroscopy, and nitrogen sorption
techniques. The electrochemical performance of the carbon
composites as electrode materials for supercapacitors is also
investigated. The results show that CNTs can be uniformly
embedded in the carbon matrix, and the phosphate groups
are introduced into the carbon composites successfully. The
addition of CNTs with suitable content significantly improves the rate capability of carbon composites in 6 M KOH aqueous
solution. Cell voltage window can be extended to 1.2 V when increasing the heat treatment temperature of carbon composites to
800 °C, and the resulting composites exhibit highly stable performance in supercapacitors at high current load of 5 A g−1 and
wide cell voltage of 1.2 V.
KEYWORDS: phosphate functionalization, carbon nanotube, fructose, supercapacitor

1. INTRODUCTION “brick-and-mortar” approach and the electrochemical perform-

Carbon materials have received much attention as the electrode ance was further improved.12 Carbon nanotubes (CNTs) have
materials for supercapacitor energy storage device because of been widely used for the electrode materials of supercapacitors
their intriguing properties including low cost, easy availability, owing to the excellent properties such as high electrical
nontoxic nature, environmental friendliness, and stability.1,2 conductivity and relatively large specific surface area with
The energy density, power density, and stable charge−discharge opened mesoporous structure.13,14 Making use of CNTs as
performance for supercapacitors are governed by the carbon nanotexturing agent to make carbon composites with “brick-
electrodes to a great degree. The physical and chemical properties and-mortar” structures where CNTs are embedded in the
of carbon materials are the key factors affecting their electro- carbon matrix can help create networks with opened
chemical performance in supercapacitors. Up to now, various mesoporous structure for ions propagation, which also lead
strategies for tuning the properties of carbon materials with an aim to better electrical conductivity and mechanical stability.
of further enhancing their electrochemical performance have Because of this, various CNT/carbon composites including
been developed by optimizing the pore structure,3,4 introducing activated CNT/carbon15 and biopolymer-based CNT/carbon7
heteroatom functional groups5,6 and coupling with nanocarbons,7,8 have been fabricated, showing highly stable supercapacitive
or pseudocapacitive materials.9,10 Of these strategies available now, performance at high rate.
heteroatom functionalization with phosphate groups is one of the Biomasses and their derivatives are cheap, ubiquitous, and
promising approaches, which can improve the stability of active renewable natural resources, which have been widely used to
oxygen-containing groups on carbon materials during the charging fabricate functional carbon materials by pyrolysis or hydro-
and discharging process and widen the operating voltage window thermal technologies. Compared with the conventional
for higher energy density.11 Highly conductive nanocarbons pyrolysis technology, the hydrothermal approach has been
including carbon nanotube, graphene, and carbon onion as demonstrated to be a powerful technique to convert different
additives have been used to improve the resulting conductivity types of biomasses to hydrothermal carbon materials (HTCs)
of the carbon electrode materials for supercapacitors. This has
been confirmed by the Dai’s group, in which nanocarbons such Received: December 10, 2012
as carbon onion was incorporated in the framework of Accepted: February 28, 2013
mesoporous carbons with high electrical conductivity by Published: February 28, 2013

© 2013 American Chemical Society 2104 dx.doi.org/10.1021/am303052n | ACS Appl. Mater. Interfaces 2013, 5, 2104−2110
ACS Applied Materials & Interfaces Research Article

Scheme 1. Schematic of the Synthesis of the Samples

Figure 2. Thermogravimetric profiles of the carbon composites with

different CNT contents.

Table 1. Electrical Conductivity Values of the Samples

sample C0HC-700 C1HC-700 C2HC-700 C3HC-700
electrical 0.02 0.08 1.52 2.11
conductivity (S m−1)

Figure 3. FTIR spectrum of the C2HC-700 sample.

composites are tested for supercapacitor applications. The

effects of phosphate functionalization and CNT incorporation
are investigated using multiple electrochemical techniques to
obtain electrode materials with high performance.
Figure 1. FE-SEM images of (a) C0HC-700, (b) C1HC-700, (c)
C2HC-700, (d) C3HC-700, and TEM images of (e) C0HC-700, (f) 2. EXPERIMENTAL SECTION
C2HC-700.
2.1. Synthesis of Carbon Composites. The phosphate-function-
alized CNT-containing carbon composites were synthesized by one-
pot soft-template hydrothermal method followed by further heat
with diversified structures by controlling the liquid-phase reaction treatment at different temperatures under nitrogen atmosphere. For a
environment.16 Recently, it has been found that ordered typical run, 4 g of P123 and 2 mL of phosphoric acid were added into
mesoporous HTCs can be made by one-pot self-assembled 68 mL of deionized water under constant stirring until P123 was
process with triblock copolymer as template.17 Hydrothermal dissolved. Then, 50 mg of CNTs (length, 1−2 μm; diameter, 10−
carbon made from fungi also showed good capability as electrode 20 nm) was dispersed in the P123 solution under ultrasound treatment
materials in supercapacitors.18 Nevertheless, these HTCs usually for 2 h, and then 10 mL of saccharide solution containing 3 g of
have relatively small surface area and pore volume, resulting in fructose was added to the CNT dispersion with an additional
poor capacitance.19,20 ultrasonic treatment for 30 min. The mixture was then transferred to a
Teflon autoclave, sealed, and treated at 120 °C for 24 h. The product
In this study, we report on a simple soft-template hy- was separated and dried at 80 °C, followed by further heat treatment at
drothermal method with fructose as a carbon source followed 700 °C under nitrogen atmosphere. A series of samples containing
by heat treatment, which can produce phosphate-functionalized different amounts of CNTs were synthesized by adding 0, 5, 50, and
CNT-containing carbon composites with controlled hierarch- 100 mg of CNTs, which was denoted as CxHC-700 (x = 0, 1, 2, 3
ical porous structure, and the as-prepared functional carbon corresponding to different additive amounts of CNTs). The C2HC

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Figure 4. (a) XPS survey spectrum of the C2HC-700 sample and deconvoluted high-resolution (b) C1s, (c) O1s, and (d) P2p spectra of the C2HC-
700 sample.

Table 2. Deconvolution Results of XPS Spectra of the Nicolet iN10) was used to investigate to surface properties. Thermogravi-
C2HC-700 Sample metric analysis (TGA, Mettler Toledo 851e) was conducted in air from
room temperature to 850 °C at a rate of 10 °C min−1. The X-ray
content position percentage photoelectron spectroscopy (XPS, Thermo ESCALAB 250) measurement
region (at %) (eV) assignment (%)a was performed to analyze the surface properties quantitatively. The
C1s 89.6 283.9 carbide 6.8 electrical conductivities were calculated according the results measured by
284.6 graphite 55.7 the four-probe method using a S-2A four-probe station and Keithley 2400
285.4 R−OH + C−O−C + C− 17.5 Sourcemeter.
O−P 2.3. Electrochemical Measurements. The cyclic voltammetry,
286.5 CO + >CO 10.3 galvanostatic charge−discharge, electrochemical impedance spectros-
288.9 COOH + −C(O)−O−C 7.5 copy (EIS) and galvanostatic cycling test were carried out using CHI
291.2 π−π* 2.2 660D (Shanghai Chenhua, China) electrochemical workstation in a
O1s 8.0 530.3 quinones 12.3 three-electrode cell with 6 M KOH as electrolyte solution. Active
531.6 =O 24.7
materials and binder poly(tetrafluoroethylene) with a mass ratio of
95:5 were pressed onto the nickel foam that were used as the work
532.6 −O− 35.4
electrode. Hg/HgO electrode and Pt foil electrode were used as
533.6 OH 27.6
reference electrode and counter electrode in the three-electrode cell,
P2p 2.5 133.2 phosphates and 100 respectively. Cyclic voltammetry and galvanostatic cycling stability test
pyrophosphates
a
were also carried out in the two-electrode cell assembled by two
Relative percentage of each component deconvoluted from the high- symmetrical work electrode at different cell voltages. The cell was
resolution XPS spectra of C1s, O1s, and P2p. operated at cell voltage of 0.9 V for the first 5000 cycles followed by
another 5000 cycles at a cell voltage of 1.2 V and a current density of
5 A g−1 for cycling test.
sample was also heated at 800 and 900 °C under nitrogen atmosphere
to yield C2HC-800 and C2HC-900 samples.
2.2. Characterizations. Morphologies and microstructures of 3. RESULTS AND DISCUSSION
carbon composites were examined by a field emission scanning Functional carbon composites with hierarchical porous
electron microscopy (FE-SEM, FEI NOVA NanoSEM 450, operated structure were prepared by a simple one-pot soft-template
at 3 kV) and a transmission electron microscopy (TEM, Philips Tecnai
G220, operated at 120 kV). Specific surface area and pore size
hydrothermal reaction of copolymer, CNTs, fructose, and
distribution were calculated based on the nitrogen physical sorption H3PO4 followed by heat treatment. In this approach, as shown
(Micromeritics ASAP 2020). The composites were degassed at 200 °C in Scheme 1, triblock copolymer Pluronic P123 has dual
for 5 h prior to the nitrogen sorption measurement. A Fourier functions, i.e., to help disperse CNTs uniformly and serve as
transform infrared (FTIR) microspectroscopy (Thermo Scientific mesopore template where carbonaceous sol intermediates
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samples is 0, 1.3, 9.3, and 15.3%, respectively. With increasing

the content of CNTs, the electrical conductivity of the carbon
composites also increases because of the high conductivity of
CNTs, and the results are shown in Table 1.
The FTIR microspectroscopy study confirms that the
phosphate groups are present in the composites, as can be
seen in Figure 3. The spectrum shows typical characteristic of
phosphocarbonaceous compounds present in the carbons
materials activated by phosphoric acid. The peak at 1160
cm−1 is due to the stretching vibration of hydrogen-bonded
PO groups and the O−C stretching vibration in the P−O−
Caromatic linkage, and the peak at 1062 cm−1 is assigned to the
symmetrical vibration in polyphosphate chain P−O−P.21 The
XPS spectra of the C2HC-700 sample were also collected to
further analyze the surface chemistry properties of the carbon
composite. The spectrum in Figure 4a indicates the presence of
phosphorus species in the composite and the phosphorus
content is 2.5 at%. High-resolution XPS spectrum of P2p peak
can be deconvoluted into the peak with a binding energy at
133.2 eV, which can be identified as the phosphorus species as
tetra-coordinated phosphorus(V) (Table 2).22,23 The spectra of
C1s peak and O1s peak can be deconvoluted into six
components and four components, respectively, and the results
were summarized in Table 2. The carbon species correspond to
carbide carbon (283.9 eV); graphite carbon (284.6 eV); carbon
in alcohol, ether groups, and/or C−O−P linkage (285.4 eV);
carbon in carbonyl groups (286.5 eV); carboxyl and/or ester
groups (288.9 eV); and π−π* transitions in aromatic rings
(291.2 eV).22 The oxygen species represent quinones (530.3
eV); oxygen double-bonded to carbon (CO) and non-
bridging oxygen in the phosphate groups (PO) (531.6 eV);
Figure 5. (a) Nitrogen adsorption−desorption isotherms and (b) oxygen single-bonded to carbon in C−O and in C−O−P
pore-size distributions of the C0HC-700 and C2HC-700 samples. groups (532.6 eV); and oxygen single bonds in hydroxyl groups
(533.6 eV).22,24
originated from fructose in the hydrothermal process can The porosity of the as-made carbon materials was analyzed
assemble in situ. The phosphate-functionalized CNT-contain- by N2 adsorption technique. Figure 5a is the isotherms of the
ing carbon composites termed as CxHC-T were obtained by C0HC-700 and C2HC-700 samples, showing a combined
heating the precursor CxHC at different temperatures. characteristic of type I/IV isotherms. For the C0HC-700
Figure 1 shows the typical FE-SEM and TEM images of a sample, its BET surface area is 392 m2 g−1. For the C2HC-700
series of carbon composites containing different amounts of sample, its BET surface area is 587 m2 g−1. The pore size
CNTs. In the sample without CNTs, amorphous bulk carbon distribution of the C2HC-700 sample shows a similar
particles can be clearly seen, as shown in Figure 1a. For the hierarchical porous structure in comparison to C0HC-700 in
carbon composites with CNTs, as shown in Figure 1b-d, CNTs the region of 0.5 to 10 nm, of which the difference is that
are well-dispersed in the carbon matrix, and no obvious C2HC-700 contains more larger mesopores (20−50 nm) and
differences are observed though the CNT content varies in the macropores (50−200 nm), as shown in Figure 5b. The average
composites. Further TEM examination (see Figure 1e, f) micropore size of C0HC-700 is 0.54 nm, which is smaller than
reveals that the wormlike disordered mesopores with a 0.59 nm of C2HC-700. The formation of micropores is
diameter of 3−5 nm are present in the C0HC-700 and possibly due to the activation by H3PO4 in the post heat
C2HC-700 samples, where CNTs are uniformly embedded in treatment step. Besides, the mesopores in the C0HC-700 and
the mesoporous carbon matrix (Figure 1f and Figure S3 in the C2HC-700 samples formed by the soft template P123 are 4.4
Supporting Information). It is believed that the wormhole and 5.2 nm, respectively, and this is consistent with the TEM
mesopores are formed because of the self-assembly interaction results (Figure 1e, f). This will demonstrate that the hierarchical
between P123 micelles and carbonaceous sol intermediates pore structures have been formed in the composites.
generated in the hydrothermal step followed by heat treatment. Interestingly, the large mesopores and macropores in the
The uniform dispersion of CNTs in the carbon matrix is due to C2HC-700 sample are due to the presence of CNTs (see
the hydrophobic−hydrophobic interaction between P123 and Figure S2 in the Supporting Information), which can function
CNTs that results in the uniform dispersion of CNTs in water as a fast ion-transport pathway that further improve the rate
under ultrasonic treatment (see Figure S1 in the Supporting capability of the supercapacitors.7
Information). The actual content of CNTs in the carbon To evaluate the effect of CNT on the electrochemical
composites was obtained by thermogravimetric analysis, the performance of the CxHC-700 samples, cyclic voltammetry,
results of which are shown in Figure 2 and Table S1 in the galvanostatic charge−discharge, and electrochemical impedance
Supporting Information. The calculated content of CNTs in spectroscopy (EIS) were recorded in 6 M KOH aqueous
the C0HC-700, C1HC-700, C2HC-700, and C3HC-700 solution in a three-electrode cell. Figure 6a, b show the cyclic
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Figure 6. Cyclic voltammograms recorded at (a) 5 mV s−1 and (b) 100 mV s−1. (c) Galvanostatic charge−discharge curves at 2 A g−1. (d) Specific
capacitances at different current densities. (e) Nyquist plots of the carbon composites heated at 700 °C. (f) Galvanostatic cycling test of C2HC-700
at a current density of 5 A g−1.

voltammetry (CV) curves of the samples at a scan rate of 5 and the C0HC-700 and C1HC-700 samples, the C2HC-700 and
100 mV s−1, respectively. The CV curves for all of the samples C3HC-700 samples show better linear characteristics, indicat-
show good rectangular shapes at 5 mV s−1 (Figure 6a), for ing that the composites containing more CNTs have a better
C2HC-700 and C3HC-700 with a higher CNT content, a faster reversible charge−discharge property. This is in consistent with
electrochemical response is observed, evidencing a better ideal the cyclic voltammetry results. The relationship between the
electrical double layer capacitor (EDLC) behavior. At higher specific capacitance and the current density is also observed in
scan rate of 100 mV s−1 (Figure 6b), the CV curve for the Figure 6d according to the galvanostatic charge and discharge
hydrothermal carbon C0HC-700 without CNTs shows a results collected at different current densities. At a current
completely distorted rectangular shape, in the case of C1HC- density from 0.1 to 10 A g−1, the C2HC-700 and C3HC-700
700 with a CNT content of 1.3 wt %, the shape of CV curve is samples with higher CNT content show higher capacitance
improved to some degree. As the CNT content further retention. Even at a high current density of 10 A g−1, the
increases, the CV curves for the C2HC-700 and C3HC-700 specific capacitances of C2HC-700 and C3HC-700 can remain
with a higher CNT content display relatively good rectangular 78.1% (125 F g−1) and 77.4% (113 F g−1) with the capacity at
shape at the high scan rate, implying that the presence of CNTs 0.1 A g−1 as reference, under the identical conditions, the
dispersed in the carbon matrix can obviously enhance the rate specific capacitances of C0HC-700 and C1HC-700 only remain
capability of carbon composites. 6.3 and 32.7%. The Nyquist plots of C2HC-700 and C3HC-
Figure 6c shows the galvanostatic charge−discharge curves of 700 with higher CNT contents shown in Figure 6e exhibit a
CxHC-700 at a current density of 2 A g−1. In comparison with lower charge transfer resistance and a better capacitive
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ACS Applied Materials & Interfaces Research Article

Figure 7. (a) Cyclic voltammograms of C2HC-700, C2HC-800, and C2HC-900 at 5 mV s−1 and the cell voltage of 0.9, 1.2, and 1.3 V. (b) Regone
plots of C2HC-700 obtained at 0.9 V and C2HC-800 obtained at 0.9 and 1.2 V. (c) Galvanostatic cycling test of C2HC-800 at 5 A g−1 and the cell
voltage of 0.9 and 1.2 V. (d) Nyquist plots of C2HC-700, C2HC-800, and C2HC-900.

behavior. Moreover, the C2HC-700 also shows good cycling and 1.2 V are shown in Figure 7b. The specific energy density of
stability at a high current of 5 A g−1, without any loss in the the two-electrode cell constructed of C2HC-800 at 1.2 V increases
initial capacity even after 2000 cycles, as shown in Figure 6f. to 8.2 W h kg−1, whereas the specific power density is 30 W kg−1.
These improved performance is due to the CNTs dispersed in The C2HC-800 also shows extraordinary electrochemical
the carbon matrix that help create large mesopores and cycling stability while galvanostatic charging and discharging at
macropores for fast ion transport, and improve the mechanical a wide cell voltage of 1.2 V and a high current density of 5 A g−1,
property and electrical conductivity of the carbon composites. as can be seen in Figure 7c. The reason for this is partly due to the
These combined effects bring about the improvements in the fact that the heat treatment at higher temperature significantly
rate capability and cycle stability at high current load.7,15 decreases the equivalent series resistance and the charge transfer
The electrochemical capacitive behaviors of the C2HC-T resistance to a degree (Figure 7d). The prolonged cycling stability
treated at different temperatures were also examined. It has at high current load reported here is also due to the combined
been found that a wider operating cell voltage window can be effect of CNTs that helps enhance the mechanical stability of
achieved by simply increasing the heat treatment temperature CNT/carbon composites during charging and discharging.15
from 700 to 800 °C, as can be seen in Figure 7. The CV curve
of the C2HC-800 sample exhibits an ideal rectangular shape at 4. CONCLUSIONS
a cell voltage of 0.9 V, indicating that C2HC-800 has an ideal In conclusion, phosphate-functionalized CNT-containing car-
EDLC behavior, while the C2HC-700 and C2HC-900 cannot bon composites with hierarchical porous structure have been
withstand at the same cell voltage, which is evidenced by the prepared by an one-pot soft-template hydrothermal reaction of
electrolyte decomposition peaks (Figure 7a). Moreover, copolymer, CNTs, fructose, and H3PO4 followed by heat
C2HC-800 also demonstrates stable EDLC performance even treatment. CNTs networks embedded in the carbon matrix
at higher cell voltage up to 1.2 V, which is very close to the improve the rate capability of carbon composites. Furthermore,
theoretical decomposition potential of water (1.23 V), and the phosphate groups and CNTs jointly contribute to the high
the electrolyte decomposition peak seems to appear at a cell voltage rate performance of carbon composites that have highly stable
of 1.3 V. The wider operating voltage window is believed to be cycling performance at wide cell voltage of 1.2 V and high
due to the highest phosphate groups content in C2HC-800, current load of 5 A g−1.

■
which is similar to the results reported in the literatures.21,22
The phosphate groups can block the nonstable active oxidation
sites.11 Widening the operating voltage up to 1.2 V can ASSOCIATED CONTENT
significantly increase the energy density of the devices since it is *
S Supporting Information
proportional to the square of the cell voltage. Regone plots of The optical photograph of P123-assisted CNTs dispersion.
C2HC-700 obtained at 0.9 V and C2HC-800 obtained at 0.9 Nitrogen adsorption−desorption isotherms and pore size
2109 dx.doi.org/10.1021/am303052n | ACS Appl. Mater. Interfaces 2013, 5, 2104−2110
ACS Applied Materials & Interfaces Research Article

distribution of CNTs. TEM images of the C2HC-700 sample. (22) Puziy, A. M.; Poddubnaya, O. I.; Socha, R. P.; Gurgul, J.;
Volumetric specific capacitances and energy densities of the Wisniewski, M. Carbon 2008, 46, 2113−2123.
samples. Table that summarizes the compositions and proper- (23) Carriazo, D.; Gutierrez, M. C.; Pico, F.; Rojo, J. M.; Fierro, J. L.;
ties of the as-prepared samples. This material is available free of Ferrer, M. L.; Del Monte, F. ChemSusChem 2012, 5, 1405−1409.
(24) Arrigo, R.; vecker, M. H.; Wrabetz, S.; Blume, R.; Lerch, M.;
charge via the Internet at http://pubs.acs.org/.

■
McGregor, J.; Parrott, E. P. J.; Zeitler, J. A.; Gladden, L. F.; Knop-
Gericke, A.; Schlögl, R.; Su, D. S. J. Am. Chem. Soc. 2010, 132, 9616−
AUTHOR INFORMATION 9630.
Corresponding Author
*Address: No. 2 Linggong Road, High Technology Zone,
Dalian City, Liaoning Province, China. E-mail: [email protected].
cn. Tel: +86-411-84986024. Fax: +86-411-84986080.
Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
This work was partly supported by the National Natural
Science Foundation of China (50902016, 20923006, and
U1203292) and Dalian Municipal Science & Technology
Project of China (2011A15GX023).

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