Letter

pubs.acs.org/NanoLett

New Graphene Form of Nanoporous Monolith for Excellent Energy

Storage
Hui Bi, Tianquan Lin, Feng Xu, Yufeng Tang, Zhanqiang Liu, and Fuqiang Huang*,,

CAS Key Laboratory of Materials for Energy Conversion and State Key Laboratory of High Performance Ceramics and Superne
Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China

State Key Laboratory of Rare Earth Materials Chemistry and Applications and Beijing National Laboratory for Molecular Sciences,
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
S Supporting Information
*

ABSTRACT: Extraordinary tubular graphene cellular material of a tetrahedrally

connected covalent structure was very recently discovered as a new supermaterial
with ultralight, ultrasti, superelastic, and excellent conductive characteristics, but no
high specic surface area will keep it from any next-generation energy storage
applications. Herein, we prepare another new graphene monolith of mesoporous
graphene-lled tubes instead of hollow tubes in the reported cellular structure. This
graphene nanoporous monolith is also composed of covalently bonded carbon
network possessing high specic surface area of 1590 m2 g1 and electrical
conductivity of 32 S cm1, superior to graphene aerogels and porous graphene
forms self-assembled by graphene oxide. This 3D graphene monolith can support
over 10 000 times its own weight, signicantly superior to CNT and graphene cellular
materials with a similar density. Furthermore, pseudocapacitance-active functional
groups are introduced into the new nanoporous graphene monolith as an electrode
material in electrochemical capacitors. Surprisingly, the electrode of 3D mesoporous
graphene has a specic capacitance of 303 F g1 and maintains over 98% retention after 10 000 cycles, belonging to the list for
the best carbon-based active materials. The macroscopic mesoporous graphene monolith suggests the great potential as an
electrode for supercapacitors in energy storage areas.
KEYWORDS: Graphene, nanoporous monolith, pseudocapacitance, energy storage

and thermal/electromagnetic shielding/cloaking are possible to

be achieved with the further developments.
Here, we attempt to prepare another new graphene monolith
of mesoporous graphene-lled tubes instead of hollow tubes in
the reported cellular structure. As expected, this graphene
nanoporous monolith is composed of covalently bonded
carbon network possessing high electrical conductivity and
large surface area, superior to graphene aerogels, and porous
graphene forms self-assembled by graphene oxide,7,8,11,12 which
generally have a poor conductivity (0.1210 S cm1) and
moderate surface area (100300 m2 g1). These porous
graphene materials are usually of electrochemical double layer
capacitance, whose values are typically below 200 F g1.12
Furthermore, proper surface functional groups introduced into
this monolith, similar to N-contained groups in conducting
polymers (polyaniline: theoretical capacitance up to 2000 F
g1),13,14 causes additional electrochemical pseudocapacitance
(also known as Faradaic capacitance), which is the direction for
ultrahigh capacitance in carbon-based materials.

ltralight cellular materials with large specice surface area,

high mechanical stability, and outstanding conductive
properties are considered to be very unique materials for
electrochemical energy storage, catalysis and sensing, and
biomedical applications.1,2 Such highly conductive nanoporous
carbon species are rare, although new tubular or nanoporous
carbon-based structures have attracted much attention. So far,
due to weak, inhomogeneous connections of building blocks via
van der Waals, frictional, or bondings, all of the reported
carbon micro/nanotube (CMT/CNT),35 reduced graphene
oxide (RGO),6,7 and RGO/CNT8,9 aerogels, foams, and
sponges have inadequate electrical conductivity. Very recently,
a new tubular graphene cellular material was reported, whose
3D architecture is constructed from a tubular graphene network
with a tetrahedrally connected covalent bonding fabricated by
template-directed chemical vapor deposition (CVD) technique.10 This extraordinary 3D graphene architecture has a large
surface area of 970 m2 g1, hydrophobic, 99.9% porous
macroscopic structure with the ultralow density of 1.6 mg
cm3, superelasticity (>95% reversible strain), excellent
mechanical strength, and electrical conductivity, which are 1
2 orders of magnitude higher than reported carbon-based
cellular materials.39 Based on the multifunctional material and
new unique preparation, many applications in energy, catalysis,
2015 American Chemical Society

Received: September 28, 2015

Revised: November 29, 2015
Published: December 7, 2015
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graphene monolith suers from slight framework shrinkage in

shape (Figure 1b) and well maintains its 3D structural integrity
(Figure 1c).
The SiO2 template has a free-standing macro-/mesoporous
structure and is easily scaled up by a very simple solgel
method. Carbon species formed by the decomposition of CH4
freely go inside macroporous structure of SiO2 template, and
diuse into mesoporous structure, and segregate on the surface
of the SiO2 surface to uniformly form graphene. Therefore,
there is essentially no limit to the large-scale production of 3D
graphene for the CVD technique using such open-structure
template. For example, approximately 10 g of 3D nanoporous
graphene was produced per batch using a CVD furnace
equipped with a quartz tube 50 mm in inner diameter. More
importantly, the preparation strategy can be further developed
to use other 3D templates with controllable pore size for the
fabrication of bulk 3D nanoporous graphene with a large
specic surface area, excellent structural integrity, and high
electrical conductivity for energy-related areas.
The 3D graphene monolith is the rst sample of bulk
hierarchical macro-/mesoporous structure constructed with
single- to double-layer graphene from hard-template CVD
preparation. As shown in Figure 2ac, the 3D graphene

In this work, a highly electrical conductive graphene

nanoporous monolith is proposed with pseudocapacitanceactive functional groups, which is a 3D bulk material on
macroscopic scale, but 2D material made up of double-layer
graphene on microscopic scale. No such macroscopic macro-/
meso-porous graphene form has been reported to date. The 3D
graphene monolith can support over 10 000 times its own
weight and shows an electrical conductivity of 32.5 S cm1, the
large surface area of 1591 m2 g1, and the pore volume of 2.62
cm3 g1, signicantly superior to the reported CNT and
graphene cellular materials.7,8,11,12 The unique nanoporous
graphene exhibits a high specic capacitance of 303 F g1 and
excellent long-term stability (over 98% retention after 10 000
cycles) for supercapacitor (SC) devices. The signicant
pseudocapacitance is demonstrated to improve the SC
performance, which is attributed to the successful introduction
of O-contained groups onto this 3D graphene.
Nanoporous graphene monolith was fabricated by SiO2
template-directed CVD method, as illustrated in Figure 1a.

Figure 1. (a) Schematic synthesis of graphene nanoporous monolith

(3D GR) using mesoporous silica template. (b) Photographs of
graphene monoliths. (c) 17.0 mg graphene nanoporous monolith ( 8
mm, the inset of part c) supporting a 200 g counterweight without
structural collapse.

Figure 2. (a) Low magnication FESEM image of 3D graphene

nanoporous monolith. (b, c) Surface and cross-sectional FESEM
images of an individual microrod. (d) High magnication FESEM
image of an individual microrod.

The as-obtained SiO2 template has a cylindrical shape with a

diameter of 0.9 cm and a height of 3.5 cm and weighs about
0.54 g, and the template dimension can be easily scaled up for
future applications by using a large volume of reaction
container (see Figure S1a,b in the Supporting Information).
The SiO2 template has a hierarchical architecture, which is built
up from SiO2 microrods with the diameters and lengths of 15
m and 1020 m, respectively (see Figure S1c,d in the
Supporting Information). Additionally, the SiO2 template also
shows a rich mesoporous structure with the specic surface area
of 557 m2 g1 and the mean porous size of 6.7 nm (see Figure
S1e,f in the Supporting Information). After the graphene
growth on the 3D SiO2 template by CVD method at 1100 C,
the elemental mapping of EDS further conrms the continuous
growth of graphene on the 3D SiO2 template (see Figure S2 in
the Supporting Information). After the etching of the SiO2
skeleton by a dilute HF solution, the 3D graphene monolith
was subsequently dried by freezing drying, showing that the 3D

monolith not only copies the interconnected 3D scaold

structure of the SiO2 template on the micrometer scale, the
graphene but also almost completely inherits the mesoporous
structure of SiO2 template on the nanometer scale. A large
amount of hollow nanorods integrate into a building up unit for
the formation of graphene microrods (Figure 2d), which are
internally connected to each other to nally construct a
covalently bonded hierarchical porous graphene monolith. The
3D graphene monolith has lower densities () of 4060 mg
cm3 than the SiO2 template ( = 242.6 mg cm3). The 3D
graphene monolith not only has macrostructural integrity but
also exhibits good mechanical property. Its yield stress and
modulus can exceed 0.15 and 9.5 MPa, respectively (see Figure
S3 in the Supporting Information). For example, a 17.0 mg 3D
graphene monolith can support a counterweight of 200 g
without structural collapse (Figure 1c). That is, the 3D
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graphene monolith can support over 10 000 times its own
weight, signicantly superior to CMT, CNT, and graphene
cellular materials.5,15,16 The 3D graphene monolith has an
electrical conductivity of 25.2 S cm1, and the 3D graphene
can be annealed at 2200 C for 1 h to further enhance
conductivity up to 32.5 S cm1, which is much higher than
those of commercial activated carbon (Kuraray YP-50, 5.5 S
cm1 of electrical conductivity) and order mesoporous
carbon,17 porous graphene,18,19 etc.
High-resolution transmission electron microscopy
(HRTEM) analyses were employed to investigate the 3D
graphene microstructure, as shown in Figure 3a. The 3D

Figure 4. (a) Raman spectra of 3D graphene and annealed 3D

graphene. (b) N2 adsorptiondesorption isotherms and (c) pore size
distributions of 3D graphene. (d) C 1s XPS spectra of 3D graphene
and annealed 3D graphene.

nanorods.21 The corresponding EELS spectrum shows two

peaks at 285 and 291 eV (see Figure S4c in the Supporting
Information), which correspond to electron transitions from
the 1s electronic states (or K-shell) to * and * states,
respectively,9,10 similar to the spectrum exhibited by graphite,
conrming that the sp2 bonds of the 3D graphene. The dspacing of the graphene nanorods in the microrods,
corresponding to the (002) plane of carbon, is between 0.34
and 0.37 nm (see Figure S4df in the Supporting Information).
Nitrogen adsorption (Figure 4b) indicates that the specic
surface area, average pore diameter, and pore volume of the 3D
graphene monolith are 1591 m2 g1, 5.5 nm, and 2.62 cm3 g1,
respectively (Figure 4c), which are comparable to bamboo-like
graphitic carbon nanober22 and holey graphene.23 According
to the theoretical surface area of graphene (2630 m2 g1), the
3D graphene is typical single- and double-layer structure,
consistent with HRTEM results.
X-ray photoelectron spectroscopy (XPS) spectra (Figure 4d
and 5a) show the 3D graphene sample mainly consists of
carbon atoms and some amount of oxygen (4.62 wt %), much
higher than that (0.6 wt %) of the annealed 3D graphene. For
the C1s spectrum comparison of the 3D graphene, the highly
intensive peak of 3D graphene associated with the binding
energy (284.7 eV) of sp2 hybridized carbon atoms, and three
weak peaks at 285.3 eV, 286.7 eV, and 289.3 eV associated
with OH, CO, and CO, respectively.24 The O-contained
functional groups formed on the graphene edge can be further
conrmed by Fourier transform infrared spectra (FTIR) spectra
(Figure 5b), clearly indicating that the functional groups can
change the reactivity of graphene edges, and enhance the
wetting characteristics.25 The crystalline quality of the annealed
3D graphene has been improved greatly, as the X-ray diraction
(XRD) results are shown in Figure 5c. That is, some unstable
carbon atoms (such as graphene edge defects, O-contained
functional groups, etc.) or small crystallite carbon are removed,
but the removal of unstable carbon species are unfavorable to
the increase of the electrochemical activity for the 3D graphene.
Moreover, TGA analysis (Figure 5d) further suggests that the
burning temperature of carbon in 3D graphene is 706 C and

Figure 3. (a,b) Low- and high-magnication HRTEM images of 3D

graphene.

graphene monolith has high porosity and exhibits the

semitransparent structure under the electrical beam of
HRTEM. Figure S4a (Supporting Information) reveals that
the microrods in 3D graphene monolith are made up of hollow
graphene nanorods, which have the diameters of 3.07.0 nm
and the lengths of 1020 nm. HRTEM images (Figure 3b and
S4b in the Supporting Information) show that the nanorods of
graphene monolith consist of double-layer graphene dominantly. Additionally, a ring-like pattern of selected area electron
diraction (SAED) conrms the graphitic and polycrystalline
structure of the synthesized graphene monolith (inset of Figure
S4a in the Supporting Information), which is due to the
presence of small size graphene and a large amounts of
defective edges. In short, the 3D graphene monolith is a highly
resilient open-cell system and can be distilled into three levels
of hierarchy at three distinct length scales: mesoporous
microrod (length: 1020 m, and diameter: 15 m), hollow
nanorod (length: 1020 nm, and diameter: 57 nm), and
hollow nanorod wall thickness (0.31.0 nm).
Raman spectrum of the 3D graphene sample (Figure 4a)
includes D (1339 cm1), G (1588 cm1), and 2D (2670
cm1) bands, respectively. The intensity ratio of D band to G
band (ID/IG) is 2.51, and the large ID/IG may be due to a
nite size of sp2-hybridized crystallites and some amount of
structural defects in 3D graphene, which in turn reduce the
intensity ratio of 2D band to G band (I2D/IG = 0.51) and
broaden the 2D band (the full width at half-maximum (fwhm)
is 78 cm1). In order to verify this, the 3D graphene was
further annealed at 2200 C for 1 h. The corresponding I2D/IG
ratio greatly increases up to 0.76, and the fwhm signicantly
decreases down to 55 cm1. These features well validate that
the great majority of 3D graphene is double-layer structure.20
However, for the annealed 3D graphene, the large ID/IG ratio
(1.21) and the presence of shoulder peak at 1620 cm1
indicate the existence of the defective edges of graphene
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graphene. Equivalent series resistance of the 3D graphene and

annealed 3D graphene (Figure 6b) was similar to smaller than
1.7 , smaller than that (2.0 ) of YP-50. The straight line in
the low frequency region in Nyquist plot suggests that process
inside electrode is not ion diusion limited, and the SC behaves
more like an ideal capacitor. Note that there was nearly no
semicircle in the high-frequency region, indicating the ultrasmall transfer resistance of the 3D graphene. The specic
capacitance is 303 F g1 at a current rate of 0.5 A g1 (Figure
6c), and the electrode is also able to deliver a rather high
specic capacitance of 153 F g1 at 40 A g1 (Figure 6c and
S5a,b in the Supporting Information). These values are much
higher those of the annealed 3D graphene, YP-50, and porous
graphene,18,19,26,27 and comparable to previously reported
exible bamboo-like graphitic carbon nanober22 and holey
graphene paper.23 All of the nearly rectangular CV curves at the
scan rates of 5200 mV s1 (see Figure S5c in the Supporting
Information) indicate the features of the low contact resistance
and excellent high rate for the 3D graphene electrode.
Volumetric capacitance is an important parameter for the
portable applications. The 3D graphene active material was
pasted onto large surface area, high electrical conductive, and
porous 3D graphene network. Although the highly compressive
3D graphene network has very small capacity contribution (see
Figure S6a in the Supporting Information), the volumetric
capacitance of the composite electrode with high mass loading
of 5.0 mg cm2 still can reach up to 126.0 F cm3 at a scan rate
of 5 mV s1 (see Figure S6b in the Supporting Information).
Further measurements were performed in 1 M H2SO4 in a
two-electrode system to investigate the electrochemical
capacitance of the actual device, as shown in Figure 6d. The
3D graphene device still maintains the rectangular-shaped cyclic
voltammogram even at a high potential scan rate of 200 mV
s1. Despite the presence of structure defects and functional
groups in 3D graphene, no apparent redox peaks are observed
in the two-electrode system, compared with the three-electrode
system, which is similar to previously reported results.16 The

Figure 5. (a) XPS, (b) FTIR, (c) XRD spectra, and (d) thermal
analysis of 3D graphene and annealed 3D graphene.

increases to 742 C for the annealed 3D graphene sample,

indicating good thermal stability of the 3D graphene monolith.
The 3D graphene monolith possesses large surface area, rich
nanoporous structure, and high electrical conductivity, which
has been demonstrated as an excellent electrode of great
application potential in SC applications. Capacitance performance comparison of the 3D graphene, annealed 3D graphene,
and YP-50 electrodes in 1 M H2SO4 in a three-electrode cell
were studied by scanning cyclic voltammetry (CV) at a scan
rate of 50 mV s1 in a range of 0.1 to 0.8 V vs Ag/AgCl
(Figure 6a). The CV curve of 3D graphene is nearly
rectangular, indicating the excellent capacitance behavior.
Notably, compared with the annealed 3D graphene, the 3D
graphene electrode shows additional redox peaks which
contribute to additional peusdocapacitance, which results
from the presence of O-contained functional groups on the

Figure 6. Electrochemical performances measured in a three-electrode system. (a) CV curves at a scan rate of 50 mV s1 of YP-50, 3D graphene, and
annealed 3D graphene. (b) Nyquist impedance plot of YP-50, 3D graphene, and annealed 3D graphene. (c) Capacitance change at various current
densities of YP-50, 3D graphene, and annealed 3D graphene. Electrochemical performances of the 3D graphene device measured in a two-electrode
system. (d) Cyclic voltammograms at dierent scan rates. (e) Capacitance retention plot with cycle number. Inset shows the CV curves comparison
at a scan rate of 50 mV s1 before and after 10 000 cycles. (f) Energy density at dierent power density of 3D graphene, activated carbon,28 carbon
nanoonion,29 carbon nanotube,30 graphene,31 N-doped carbon nanober,32 and graphene/mesoporous carbon33 active materials in aqueous
electrolytes.
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capacitance for a single electrode Csingle (F g1) can be
calculated to be 243 F g1 at a current density of 1.0 A g1 (see
Figure S7a in the Supporting Information), which is slightly
lower than that measured in three-electrode system (272 F
g1). Notably, the voltage drop at the beginning of the
discharge is extremely small (0.02 V) at a current density of
1.0 A g1, suggesting a very low equivalent series resistance in
the symmetric SC. The 3D graphene electrode retains 98.1%
and 98.6% capacitance even after 10 000 cycles at the scan rates
of 5 mV s1 and 50 mV s1, respectively (Figure 6e and S7b,c in
the Supporting Information). The CV and galvanostatic
chargedischarge curves at dierent scan rates and current
densities indicate good capacitance reversibility and durability
of the 3D graphene as supercapacitor (Figure 6ce, S5, S7 in
the Supporting Information). The specic energy density of the
device is 13.7 W h kg1 at a current density of 0.5 A g1 (Figure
6f). It is noteworthy to mention that specic energy still is 7.1
W h kg1 with a high specic power of 6.2 kW kg1 at a current
density of 10 A g1, which is higher than previous reported
activated carbon,28 carbon nanoonion,29 carbon nanotube,30
graphene,31 N-doped carbon nanober,32 and graphene/
mesoporous carbon33 active materials for symmetric supercapacitors in aqueous electrolytes.
The 3D graphene monolith of covalently bonded mesoporous graphene-lled tubes enhances the kinetics of ion and
electron transport in electrodes and at the electrode/electrolyte
interface. The introduction of O-contained functional groups
on 3D graphene can improve the wettability (contact angle:
52, see Figure S8a in the Supporting Information) and the
electroactive surface area (1591 m2 g1) in the electrolyte to
further supply more active sites and additional redox
capacitance, resulting in high capacity, superior rate capability,
and long-term stability. For comparison, the annealed 3D
graphene has higher purity of carbon sp2 hybrid structure and
higher electrical conductivity (32.5 S cm1) than 3D
graphene. However, after the removal of the unstable graphene
species (such as edges, small domains, O-contained functional
groups, etc.), the annealed 3D graphene has hydrophobic
characteristic, and its contact angle reaches up to 119 (see
Figure S8b,c in the Supporting Information). Although the
annealed 3D graphene can maintain similar pore size to 3D
graphene, its specic surface area greatly decreases down to 557
m2 g1 (see Figure S9 in the Supporting Information).
Eventually, the poor wettability and reduced surface area result
in the capacitance degradation. In addition, compared with
commercial activated carbon of a larger specic surface (1700
m2 g1), its low electrical conductivity of only 5.5 S cm1 and
the absence of eective functional groups only lead to the
moderate electrochemical performance. Therefore, the key of
obtaining high SC capacitance is how to balance the structural
defects, functional groups, specic surface area, and electrical
conductivity of carbon-based active materials.
In conclusion, we have rst fabricated another new graphene
monolith of mesoporous graphene-lled tubes constructed
from single- to double-layer graphene via template-direct CVD
technique. The graphene monolith has a structural hierarchy
from nanometer to micrometer, and to centimeter scale, and
exhibits a substantially large surface area of 1590 m2 g1 and an
electrical conductivity of 32 S cm1, greatly superior to
traditional carbon-based porous materials. The 3D graphene
monolith can support over 10 000 times its own weight,
signicantly superior to CNT and graphene cellular materials
with a similar density. The 3D graphene electrode delivers a

high specic capacitance of 303 F g1 and over 98% retention

after 10 000 cycles, and energy density, based on 3D graphene
electrode, reaches up to 13 W h kg1. This easy and inexpensive
synthesis strategy provides an applicable route to develop 3D
macro-/meso-porous graphene with strong potential for use in
energy-related applications.

ASSOCIATED CONTENT

S Supporting Information
*

The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acs.nanolett.5b03923.
Experimental details, additional characterization data, and
supporting gures (S1S9) (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected].
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
Financial support from the NSF of China (Grants 51202274,
61376056, 91122034, 51125006), Science and Technology
Commission of Shanghai (Grants 13JC1405700 and
14520722000), and Key Research Program of Chinese
Academy of Sciences (Grant KGZD-EW-T06), is acknowledged.

REFERENCES

(1) Gibson, L. J.; Ashby, M. F. Cellular solids: structure and properties;

Cambridge University Press: Cambridge, 1997.
(2) Nardecchia, S.; Carriazo, D.; Ferrer, M. L.; Gutierrez, M. C.; del
Monte, F. D. Chem. Soc. Rev. 2013, 42, 794830.
(3) Cao, A.; Dickrell, P. L.; Sawyer, W. G.; Ghasemi-Nejhad, M. N.;
Ajayan, P. M. Science 2005, 310, 13071310.
(4) Hashim, D. P.; Narayanan, N. T.; Romo-Herrera, J. M.; Cullen,
D. A.; Hahm, M. G.; Lezzi, P.; Suttle, J. R.; Kelkhoff, D.; MunozSandoval, E.; Ganguli, S.; Roy, A. K.; Smith, D. J.; Vajtai, R.; Sumpter,
B. G.; Meunier, V.; Terrones, H.; Terrones, M.; Ajayan, P. M. Sci. Rep.
2012, 2, 363.
(5) Mecklenburg, M.; Schuchardt, A.; Mishra, Y. K.; Kaps, S.;
Adelung, R.; Lotnyk, A.; Kienle, L.; Schulte, K. Adv. Mater. 2012, 24,
34863490.
(6) Qiu, L.; Liu, J. Z.; Chang, S. L. Y.; Wu, Y.; Li, D. Nat. Commun.
2012, 3, 1241.
(7) Hu, H.; Zhao, Z.; Wan, W.; Gogotsi, Y.; Qiu, J. Adv. Mater. 2013,
25, 22192223.
(8) Sun, H.; Xu, Z.; Gao, C. Adv. Mater. 2013, 25, 25542560.
(9) Kim, K. H.; Oh, Y.; Islam, M. F. Nat. Nanotechnol. 2012, 7, 562
566.
(10) Bi, H.; Chen, I. W.; Lin, T. Q.; Huang, F. Q. Adv. Mater. 2015,
27, 59435949.
(11) Qiu, L.; Liu, J. Z.; Chang, S. L. Y.; Wu, Y.; Li, D. Nat. Commun.
2012, 3, 1241.
(12) Choi, B. G.; Yang, M.; Hong, W. H.; Choi, J. W.; Huh, Y. S. ACS
Nano 2012, 6, 40204028.
(13) Li, H.; Wang, J.; Chu, Q.; Wang, Z.; Zhang, F.; Wang, S. J. Power
Sources 2009, 190, 578586.
(14) Wu, Q.; Xu, Y. X.; Yao, Z. Y.; Liu, A. R.; Shi, G. Q. ACS Nano
2010, 4, 19631970.
(15) Bi, H.; Huang, F.; Liang, J.; Tang, Y.; Lu, X.; Xie, X.; Jiang, M. J.
Mater. Chem. 2011, 21, 1736617370.
(16) Bryning, M. B.; Milkie, D. E.; Islam, M. F.; Hough, L. A.;
Kikkawa, J. M.; Yodh, A. G. Adv. Mater. 2007, 19, 661664.
353

DOI: 10.1021/acs.nanolett.5b03923
Nano Lett. 2016, 16, 349354

Letter

Nano Letters
(17) Qie, L.; Chen, W.; Xu, H.; Xiong, X.; Jiang, Y.; Zou, F.; Hu, X.;
Xin, Y.; Zhang, Z.; Huang, Y. Energy Environ. Sci. 2013, 6, 24972504.
(18) Lee, J. S.; Kim, S. I.; Yoon, J. C.; Jang, J. H. ACS Nano 2013, 7,
60476055.
(19) Yoon, J. C.; Lee, J. S.; Kim, S. I.; Kim, K. H.; Jang, J. H. Sci. Rep.
2013, 3, 1788.
(20) Bi, H.; Sun, S.; Huang, F.; Xie, X.; Jiang, M. J. Mater. Chem.
2012, 22, 411416.
(21) Seo, D. H.; Kumar, S.; Ostrikov, K. Carbon 2011, 49, 4331
4339.
(22) Sun, Y. M.; Sills, Y. B.; Hu, X. L.; Seh, Z. L.; Xiao, X.; Xu, H. H.;
Luo, W.; Jin, H. Y.; Xin, Y.; Li, T. Q.; Zhang, Z. L.; Zhou, J.; Cai, W.;
Huang, Y. H.; Cui, Y. Nano Lett. 2015, 15, 38993906.
(23) Xu, Y. X.; Chen, C. Y.; Zhao, Z. P.; Lin, Z. Y.; Lee, C.; Xu, X.;
Wang, C.; Huang, Y.; Shakir, M. I.; Duan, X. F. Nano Lett. 2015, 15,
46054610.
(24) Bi, H.; Zhao, W.; Sun, S.; Cui, H.; Lin, T.; Huang, F.; Xie, X.;
Jiang, M. Carbon 2013, 61, 116123.
(25) Luo, H.; Shi, Z.; Li, N.; Gu, Z.; Zhuang, Q. Anal. Chem. 2001,
73, 915920.
(26) Cui, C.; Qian, W.; Yu, Y.; Kong, C.; Yu, B.; Xiang, L.; Wei, F. J.
Am. Chem. Soc. 2014, 136, 22562259.
(27) He, Y.; Chen, W.; Li, X.; Zhang, Z.; Fu, J.; Zhao, C.; Xie, E. ACS
Nano 2013, 7, 174182.
(28) Burke, A. Electrochim. Acta 2007, 53, 10831091.
(29) Gao, Y.; Zhou, Y. S.; Qian, M.; He, X. N.; Redepenning, J.;
Goodman, P.; Li, H. M.; Jiang, L.; Lu, Y. F. Carbon 2013, 51, 5258.
(30) Yu, C. J.; Masarapu, C.; Rong, J. P.; Wei, B. Q.; Jiang, H. Q. Adv.
Mater. 2009, 21, 47934797.
(31) Lei, Z. B.; Christov, N.; Zhao, X. S. Energy Environ. Sci. 2011, 4,
18661873.
(32) Chen, L. F.; Zhang, X. D.; Liang, H. W.; Kong, M. G.; Guan, Q.
F.; Chen, P.; Wu, Z. Y.; Yu, S. H. ACS Nano 2012, 6, 70927102.
(33) Lei, Z. B.; Liu, Z. H.; Wang, H. J.; Sun, X. X.; Lu, L.; Zhao, X. S.
J. Mater. Chem. A 2013, 1, 23132321.

354

DOI: 10.1021/acs.nanolett.5b03923
Nano Lett. 2016, 16, 349354