ARTICLE

Direct Synthesis of Highly Porous

Interconnected Carbon Nanosheets
and Their Application as High-
Performance Supercapacitors
Marta Sevilla* and Antonio B. Fuertes

Instituto Nacional del Carbón (CSIC), P.O. Box 73, Oviedo 33080, Spain

ABSTRACT An easy, one-step procedure is proposed for the synthesis of highly

porous carbon nanosheets with an excellent performance as supercapacitor
electrodes. The procedure is based on the carbonization of an organic salt, i.e.,
potassium citrate, at a temperature in the 750
900 °C range. In this way, carbon
particles made up of interconnected carbon nanosheets with a thickness of
<80 nm are obtained. The porosity of the carbon nanosheets consists essentially of
micropores distributed in two pore systems of 0.7
0.85 nm and 0.95
1.6 nm.
Importantly, the micropore sizes of both systems can be enlarged by simply increasing the carbonization temperature. Furthermore, the carbon nanosheets
possess BET surface areas in the ∼1400
2200 m2 g
1 range and electronic conductivities in the range of 1.7
7.4 S cm
1 (measured at 7.1 MPa). These
materials behave as high-performance supercapacitor electrodes in organic electrolyte and exhibit an excellent power handling ability and a superb
robustness over long-term cycling. Excellent results were obtained with the supercapacitor fabricated from the material synthesized at 850 °C in terms of
both gravimetric and volumetric energy and power densities. This device was able to deliver ∼13 Wh kg
1 (5.2 Wh L
1) at an extremely high power
density of 78 kW kg
1 (31 kW L
1) and ∼30 Wh kg
1 (12 Wh L
1) at a power density of 13 kW kg
1 (5.2 kW L
1) (voltage range of 2.7 V).

KEYWORDS: porosity . carbon . diffusion . supercapacitor . energy storage

P
orous carbons have recently attracted which results in relatively large diffusion
widespread attention in relation to paths (>5 μm). This is a serious drawback
their application in energy storage as it severely limits the ion-transport kinetics
systems such as double-layer electrochemi- within the pores, resulting in a dramatic
cal capacitors (EC) and Li-ion batteries,1
5 reduction in EC performance at high current
owing to the following important proper- densities (high power).7 In order to over-
ties: (a) their good electronic conductivity, come this problem, it is crucial to reduce the
(b) high chemical stability, (c) low cost and effective diffusion paths. Two strategies
wide availability, and (d) large surface area have been adopted for this purpose. Wang
ascribed to pores whose size can be tuned et al. described the fabrication of carbon
and adapted for specific applications. These powders with a hierarchical porous struc-
properties have made these materials the ture that combines macropores, meso-
preferred choice of manufacturers for fabri- pores, and micropores.8 The macropores
cating electrodes for EC systems. More spe- act as ion-buffering reservoirs, the meso-
cifically, porous carbons with high surface pores serve as channels for the rapid trans-
areas and a porosity made up of narrow port of ions, while the micropores are the * Address correspondence to
[email protected].
micropores in the ∼0.7
1 nm range con- locations for the charge accommodation in
stitute the best option for supercapacitors the double electrical layer. Thus, relatively Received for review February 26, 2014
because they exhibit the largest specific large carbon particles are able to offer short and accepted April 9, 2014.
capacitance values (up to ∼14 μF cm
2 in effective diffusion paths, thereby improving
Published online April 14, 2014
organic electrolyte).6 Usually these micro- EC performance. An alternative synthesis 10.1021/nn501124h
porous carbons are fabricated in the form of strategy is based on the fabrication of 3D,
granular powders made up of particles >10 μm, 2D or 1D nanometer-sized porous carbon C 2014 American Chemical Society

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 ARTICLE
particles (<200 nm) that provide short diffusion paths
(<100 nm). Several multistep procedures have been
reported for the fabrication of 3D porous carbon
nanoparticles, but they all require expensive reagents,
and production on a large scale is therefore com-
plicated.9
11 Similarly, procedures for the production
of highly porous carbon nanofibers (1D) have also
turned out to be complicated, and only a small number
of reports about them have recently appeared.12
14
2D porous carbon nanostructures constitute a better
alternative because they are easier to prepare, and
their thinness entails short diffusion distances.
Graphene is a good example of a 2D carbon nano- Scheme 1. Synthesis scheme for the preparation of porous
carbon nanosheets from potassium citrate. (1) Pyrolysis of
structure. However, it has been observed that gra- the organic moiety and formation of K2CO3; (2) decomposi-
phene nanosheets tend to aggregate (self-restacking) tion of K2CO3 with formation of K2O (gasification and
during the preparation of the electrode, which results chemical activation reactions); (3) reduction of K2O with
formation of metallic K (chemical activation and K intercala-
in a substantial loss of active surface area and a tion processes); (4) removal of potassium inorganic com-
reduction in electrochemical performance.15 To over- pounds (washing).
come this problem, the intercalation of several types of
carbon particles (i.e., porous microspheres, nanotubes, high-surface area porous carbon nanosheets (PCNS).
carbon black, etc.) in between the graphene sheets has The PCNS are interconnected forming a desert rose-like
been investigated.16
19 However, this additional step structure that impedes these flat carbon nanoparticles
introduces a certain amount of complexity into the from aggregating and therefore improves the ion
synthesis process. An alternative strategy to avoid diffusion rates. We envisage that a carbon material
restacking face-to-face when packed into an electrode with these properties will exhibit a good performance
is based on the synthesis of curved/crumpled graphene as EC electrodes. The procedure for fabricating the
sheets20
22 or folding graphene.23,24 Such morphology PCNS involves the carbonization of potassium citrate
increases the effective surface area providing signifi- by means of a synthesis strategy recently developed in
cantly improved supercapacitor performance, although our laboratory.29 The synthesis method is illustrated
the values of specific surface area achieved are still lower in Scheme 1. It is worth noting that these carbon
than 1000 m2 g
1. materials can be easily produced in only one-step by
In relation to these problems, the preparation of using as precursor a widely available cheap substance.
nonaggregated highly porous amorphous carbon nano-
sheets has generated increasing interest.25,26 Fan RESULTS AND DISCUSSION
et al. reported the fabrication of mesoporous carbon Formation and Structural Characteristics of Porous Carbon
nanosheets with a unique pillared architecture that Nanosheets. The heat-treatment of potassium citrate
avoids the restacking of the carbon sheets and thereby under an inert atmosphere directly leads to the forma-
improves EC performance.27 The synthesis procedure tion of desert rose-like particles composed of inter-
requires several steps and the use of previously synthe- connected carbon nanosheets with a certain amount
sized MgO planar nanoparticles as template. In addi- of inorganic impurities (i.e., potassium compounds).
tion, such prepared carbon particles have a relatively These impurities can be easily removed by washing
low surface area (<900 m2/g) and a porosity made up of with diluted hydrochloric acid. The potassium com-
mesopores (∼7 nm) instead of micropores, the latter pounds generated during heat-treatment have a cru-
being more appropriate for application in electroche- cial role in the development of the microporous
mical capacitors. More recently, Wang et al. showed network. First, potassium carbonate is formed
that highly porous interconnected carbon nanosheets (<650 °C) and then decomposed at higher tempera-
obtained in a two-step procedure that involves the tures (K2CO3 f CO2 þ K2O). The CO2 thus produced
hydrothermal carbonization of vegetal fibers (i.e., reacts with carbon (CO2 þ C f 2CO) to generate
hemp bast) followed by chemical activation with microporosity. At the same time, metallic potassium
KOH exhibit a very good performance as EC is produced via the reduction of K2O by carbon (K2O þ
electrodes.28 However, all these processes are some- C f 2K þ CO). This potassium plays a crucial role in the
what complex and require several steps. For these generation of additional porosity because its vapors
reasons, the development of facile synthesis proce- are intercalated between the graphene layers, causing
dures for producing nonaggregated highly porous the swelling and disruption of the carbon
carbon nanosheets is still a challenge to be overcome. microstructure.30 The pyrolysis and gasification
In this paper, we present a template-free one- processes that occur during the heat treatment of
step procedure for the fabrication of nonaggregated potassium citrate can be monitored by means of

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Figure 1. (a,b) SEM images of interconnected carbon nanosheets of sample CK-850. Inset in (a) shows a photograph of a desert
rose, and inset in (b) displays a high-magnification detail revealing the thinness of the carbon nanosheets. (c) TEM image of a
CK-900 nanosheet highlighting its porous structure. (d) HRTEM image of the edge of a carbon nanosheet of CK-850. Inset in (d)
shows the FFT pattern revealing the amorphous structure of the carbon nanosheets of CK-850.

thermogravimetric analysis. The TGA curve in Figure S1 The thickness of the carbon nanosheets was deter-
(Supporting Information (SI)) clearly shows two weight mined by means of electron energy loss spectroscopy
loss steps in the temperature ranges of 200
500 °C (EELS) applied to numerous particles (Figure S4 (SI)).
and 700
900 °C, which can be ascribed to the decom- The calculated values are in the 30
80 nm range for
position of the organic moiety and the gasification the CK-850 sample. Furthermore, the transmission
process, respectively. The washing step removes com- electron microscopy (TEM) image in Figure 1c confirms
pletely the inorganic impurities as confirmed by the that the carbon samples derived from the carboniza-
XPS general spectra depicted in Figure S2 (SI) for the tion of potassium citrate are made up of highly porous
samples CK-850 and CK-900, which show that the particles with a 2D morphology. The HRTEM micro-
carbon particles do not contain any inorganic impurity photograph shown in Figure 2d, which was taken on
and they are mainly composed of carbon (>93 at %), the edge of a CK-850 nanosheet, clearly reveals that the
with less than 6.5 at % oxygen. The above results porosity is made up of randomly oriented narrow
demonstrate that the use of potassium citrate as micropores, thereby anticipating the results obtained
carbon precursor allows the integration of the carbo- from the nitrogen physisorption measurements (vide
nization and activation processes in only one step, infra). Additional HRTEM images of the samples CK-800
simplifying the production of porous carbons and CK-900 are provided in Figure S5 (SI). The FFT
considerably. patterns included in Figure 1d and Figure S5 (SI)
The microstructure and morphology of the carbon evidence the amorphous structure of the carbon nano-
samples were examined by scanning electron micro- sheets. This is corroborated by the XRD patterns and
scopy (SEM). Figure 1a shows that the architecture of Raman spectra displayed in Figure 2, which are typical
the carbon samples resembles that of a desert rose (see of carbonaceous materials with an amorphous-like
inset in Figure 1a). Indeed, these particles are an structure. Thus, broad and low-intensity (002) and
assembly of fully interconnected carbon nanosheets (100) bands can be identified in the XRD patterns in
(see Figure S3 (SI)) of extreme thinness as suggested by Figure 2a, and broad and overlapping D (1351 cm
1)
the high-magnification SEM image in Figure 1b (inset). and G (1587 cm
1) bands are registered in the first

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Figure 2. (a) XRD patterns and (b) Raman spectra of the carbon nanosheets.

order Raman spectra in Figure 2b. The deconvolution nanosheets exhibit high Brunauer
Emmett
Teller
of these two overlapping bands gives rise to two (BET) surface areas and large pore volumes. The pore
additional peaks commonly identified in poorly orga- volume increases steadily with temperature from
nized carbons: (i) 1135 cm
1, assigned to disordered 0.59 cm3 g
1 (750 °C) to 1.30 cm3 g
1 (900 °C), whereas
graphitic lattice (A1g symmetry)31 or sp3-rich phase,32 the BET surface area increases from 1360 m2 g
1 at
and (ii) 1486 cm
1, ascribed to amorphous sp2-bonded 750 °C to 2220 m2 g
1 at 850 °C and then slightly
forms of carbon.33,34 It is worth noting that a slight decreases to 2130 m2 g
1 at 900 °C. Moreover, analysis
increase of ordering is registered with the increase of of the porosity by means of the Dubinin
Radushkevich
the carbonization temperature. Thus, the ID/IG ratio (D
R) method confirms that these samples are essen-
decreases from 0.905 for CK-750 to 0.834 for CK-900. tially microporous, the micropore volume constituting
Nitrogen physisorption measurements were carried more than 80% of the total pore volume (see Table 1),
out at
196 °C to analyze the textural characteristics of except for the sample synthesized at 900 °C, whose
the carbon nanosheets obtained by the carbonization micropore volume accounts for ∼60% of the total pore
of potassium citrate at several temperatures: 750, 800, volume.
850, and 900 °C. The N2 sorption isotherms and the The electronic conductivity of the powder samples
pore size distributions (PSDs) deduced by means of the was measured using a four-probed method. The home-
QSDFT method are shown in Figure 3a,b, respectively. made apparatus employed for such measurements
The isotherm profiles displayed in Figure 3a can be allowed the simultaneous determination of con-
categorized as being of type I, indicating that the ductivity and packing density. These PCNS exhibit
porosity is mainly made up of micropores. More inter- electronic conductivities in the range of 1.7
7.4 S cm
1
estingly, as the temperature of carbonization increases (load pressure: 7.1 MPa), the conductivity being en-
from 750 to 900 °C, a widening of the knee of the hanced with the increase of the synthesis temperature.
isotherms takes place, which suggests an enlargement Especially remarkable is the conductivity of CK-900 (i.e.,
of the micropore size as the temperature increases. 7.4 S cm
1), which is close or superior to that of materials
This is confirmed by the pore size distributions in normally used as conductive additives for the preparation
Figure 3b, which clearly show a shift in the PSD toward of supercapacitor electrodes, such as Super P (8.6 S cm
1)
larger pore sizes as the carbonization temperature or Super C65 (5.2 S cm
1). It is, as well, higher than that of
increases. Interestingly, the PSDs reveal the presence commercial activated carbons used in supercapacitors,
of two pore systems in the micropore range. The main such as Supra 50, which possesses a conductivity of
maximum shifts from 0.7 to 0.85 nm as the carbon- 4.3 S cm
1. With regards to the packing density, as is
ization temperature increases from 750 to 900 °C, usual for many nanomaterials,35 they possess relatively
whereas the second pore system is enlarged from low packing densities, decreasing from 0.50 g cm
3 at
0.95 nm (750 °C) to 1.6 nm (900 °C). Moreover, it can 750 °C to 0.27 g cm
3 at 900 °C (load pressure: 7.1 MPa).
be seen that, whereas the sample prepared at 750 °C is Electrochemical Performance. The carbon nanosheets
exclusively microporous, the samples prepared at T g presented here have a unique structure that combines
800 °C exhibit pores of up to 4
5 nm. The textural an extreme thinness (diffusion paths <40 nm) and a
parameters of the synthesized carbons are presented very large surface area (up to ∼2200 m2 g
1), which
in Table 1. These results show that the carbon can be ascribed to micropores and small mesopores.

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Figure 3. (a) Nitrogen sorption isotherms and (b) pore size distributions deduced by means of the QSDFT method for the
PCNS prepared at different carbonization temperatures in the 750
900 °C range.

This result suggests a good match between the pore

TABLE 1. Textural Properties of Porous Carbon size and electrolyte ions size. On the other hand,
Nanosheets
it can be observed that even at a scan rate as high
SBET Vp Vmicro Vmeso as 200 mV s
1, capacitance fading is as low as 14
32%
sample code T (°C)a (m2 g
1) (cm3 g
1)b (cm g
1)c (cm3 g
1)d (see Figure S6d (SI)). Especially remarkable is the
CK-750 750 1360 0.59 0.54 (0.8 nm) 0.05 behavior of the CK-850 and CK-900 samples, which
CK-800 800 1940 0.96 0.77 (1.4 nm) 0.19 retain 55
61% of their specific capacitance at the very
CK-850 850 2220 1.11 0.84 (1.6 nm) 0.27 large scan rate of 1 V/s (Figure 4c and Figure S6 (SI)).
CK-900 900 2160 1.30 0.82 (1.9 nm) 0.48 Indeed, capacitance retention is better in the case of
a
Carbonization temperature. b Pore volume at P/P0 ∼ 0.95. c Micropore volume the samples synthesized at higher temperatures owing
was determined by applying the Dubinin
Radushkevich (D
R) method to N2 to the higher electronic conductivity and also probably
adsorption branch; the mean micropore size, deduced by the D
R method, is
to the existence of two micropore systems (see PSD in
indicated in brackets. d Mesopore volume obtained by the difference between pore
Figure 3b) in which the larger micropores facilitate the
volume (Vp) and micropore volume (Vmicro).
transport of ions to the narrower micropores. Electro-
Besides, they exhibit good electronic conductivity. chemical impedance spectroscopy measurements
They present therefore the appropriate characteristics further confirm the favorable performance of the
for advanced electrochemical capacitors. To confirm carbon nanosheets prepared at higher temperatures.
this, the electrochemical properties of PCNS were This can be deduced from an analysis of the frequency
measured in organic electrolyte, i.e., 1 M TEABF4/AN, response of the normalized capacitance (CEIS/CEIS,1mHz)
using a two-electrode cell system. The cyclic voltam- for the SCNS samples (Figure 4d). Thus, it can be seen
metry curves are depicted in Figure 5 and Figure S6a,b that the relaxation time constant, τ0 (the minimum
(SI). From these figures it can be seen that even at a time needed for all the energy to be discharged from
high scan rate of 200 mV s
1, the curves retain a perfect the supercapacitor cell with an efficiency >50%) de-
rectangular shape, which indicates pure EDLC behavior creases from 4.4 s (CK-750) to 1.9 s (CK-900). Impor-
and the rapid formation of the double-layer even at tantly, these values are considerably lower than those
high rates. Specific capacitances (for a single electrode) measured for microporous carbons with a granular
of ∼120
150 F g
1 are achieved at 1 mV s
1 and of morphology, such as the commercial activated carbon
∼80
120 F g
1 at 200 mV s
1 (see Figure S6c (SI)). Supra (8.5 s, see Figure 4d), advanced activated
As would be expected taking into account the similar- carbons37 and carbide-derived carbons (CDCs) in or-
ity of the electronic conductivity of CK-900 and the ganic electrolyte.6,41,42 These results clearly evidence
conductive additive Super P used in the preparation of the advantages of microporous carbon nanosheets
the electrodes, the behavior of the supercapacitors over granular carbons.
prepared with and without the conductive additive is In order to assess the energy and power character-
analogous (see Figure S6a,b (SI)). The surface area istics of PCNS-based supercapacitors, galvanostatic
normalized capacitance values (based on the BET sur- charge/discharge cycling experiments were per-
face area) at low sweep rates are 8.8, 6.8, 6.6, and formed at current densities of up to 40 A g
1 for CK-
6.1 μF cm
2 for CK-750, CK-800, CK-850, and CK-900, 750 and CK-800, and of up to 150 A g
1 for CK-850 and
respectively. These values are much higher than CK-900. Examples of the charge
discharge voltage
those determined for the activated carbon Supra profiles at different current densities are shown in
(∼5 μF cm
2) and are comparable or superior to Figure S7 (SI) for the CK-800 and CK-850-based super-
those achieved with advanced activated carbons.36
40 capacitors. At every current density, the voltage

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 ARTICLE
Figure 4. (a,b,c) Cyclic voltammograms at different scan rates in 1 M TEABF4/AN for the different PCNs, and (d) frequency
response of the PCNS and commercial activated carbon Supra.

Figure 5. (a) Charge/discharge voltage profile at 5 A g
1 (the voltage profiles of CK-850 and CK-900 have been displaced by 3 s
for clarity), (b) charge/discharge rate performance, and (c) Ragone plot of the PCNS samples and the activated carbon Supra in
1 M TEABF4/AN, and (d) cycling stability at different current densities (in A g
1) in the 0
2 V range for CK-850 and CK-900.

profiles are highly linear and symmetrical indicating which suggests that these materials exhibit an excel-
ideal EDLC behavior, in agreement with the results lent rate performance. This is confirmed by the results
obtained by cyclic voltammetry (see Figures 4a,b,c and in Figure 5b, which show the variation in specific
S5a (SI)). Interestingly, a small IR drop (almost negligi- capacitance with the current density. It can be seen
ble for CK-850 and CK-900) is observed even at a high that the samples synthesized at higher temperatures
discharge current density of 5 A g
1 (see Figure 5a), (i.e., CK-800, CK-850, and CK-900) have high specific

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 ARTICLE
capacitances (e.g., 121
134 F g
1 at 5 A g
1) and, more
importantly, excellent capacitance retention values,
which at a current density of 40 A g
1 are around
90%. These capacitance retention values are far super-
ior to those of microporous carbons37,43
45 and
remarkable even when compared to those of meso-
porous materials46,47 and carbon/graphene nano-
sheets.38,48
51 What is more, in the case of the
CK-800, CK-850, and CK-900 samples, the specific cap-
acitance remains almost constant in the 1
40 A g
1
range (<5% of capacitance loss). This contrasts with the
behavior observed for granular activated carbons
commonly used in commercial supercapacitors (e.g.,
Supra and YP-17D), which experience a remarkable
drop in specific capacitance with the increase in cur- Figure 6. Ragone plot of advanced porous carbon materials
rent density (see Figure 5b). An exceptionally good rate that can be found in the literature with outstanding beha-
performance is provided by the CK-850 and CK-900 vior as supercapacitor electrodes in organic electrolyte.
samples, which at the extremely high current density
of 150 A g
1 still retain a specific capacitance of 120 The stability of the CK-850- and CK-900-based
and 107 F g
1, respectively (their specific capacitance supercapacitors was evaluated by long-term charge

fades by only 15
18%). This behavior can be attrib- discharge cycling at several current densities (Figure 5d).
uted to the unique structural properties of the CK-850 It can be seen that after 10 000 cycles at 10 A g
1, the
and CK-900 samples, which combine a thin morphol- system still retains 90
94% of its initial capacitance
ogy (short ion diffusion paths), a bimodal microporos- (with no increase in the equivalent series resistance,
ity with interconnected narrow and wide micropores ESR), evidencing the superb robustness of the mate-
that improve the ion diffusion rates (vide supra), and a rials, even at high discharge rates. The CK-750 and
very good electronic conductivity (3.7 and 7.4 S cm
1 CK-800 samples exhibit similar cycling stabilities, as
at 7.1 MPa respectively), which provides high electron shown in Figure S9 (SI).
transport rates. Enlargement of the voltage window up to 2.7 V was
The Ragone plot in Figure 5c compares the PCNS tested in the supercapacitors after long-term cycling at
samples and the activated carbon Supra. The PCNS- 2 V. The cyclic voltammograms recorded at 20 mV s
1
based supercapacitors exhibit specific energies of (Figure S10a (SI)) showed no change in either the
13 Wh kg
1 (CK-750), 16 Wh kg
1 (CK-800 and cathodic or anodic currents when the voltage window
CK-900), and 18 Wh kg
1 (CK-850) at a specific power was enlarged, suggesting that the supercapacitors
of 2.5 kW kg
1, which contrasts with the low specific were stable over this voltage range. This was fur-
energy for activated carbon Supra (9 Wh kg
1). More ther confirmed by long-term cycling (5000 cycles) at
importantly, the specific energies of the PCNS samples 10 A g
1, after which only an 8
10% reduction in
are still in the 8
15 Wh kg
1 range at a high specific specific capacitance was observed (Figure S10b (SI)). In
power of 10 kW kg
1, indicating that ultrafast ion and this way, by using a voltage window of 2.7 V, it is possible
electron transport is taking place. This is particularly to almost double the amount of energy stored in these
relevant in the case of the CK-850 and CK-900 samples devices. Thus, a specific energy of around 26
34 Wh
that still possess a specific energy of 12 Wh kg
1 at kg
1 (depending on the type of PCNS) can be achieved
17 kW kg
1 and 19 kW kg
1, respectively, indicating that without compromising either the stability (Figure S10b
these samples can deliver a large amount of energy (SI)) or power performance (Figure 5c). As the carbon
very quickly (2.5 and 2.3 s, respectively). Figure S8 (SI) weight represents ∼30% of the total mass of a packaged
compares the Ragone plot of the PCNS with that of commercial EC,35 a specific energy of ∼8
11 Wh kg
1
Supra carbon in volumetric units. The PCNS synthe- is expected for a real packaged device, which is higher
sized at T e 850 °C store similar energy per unit volume than that of commercial AC-based supercapacitors.
(8
9 Wh L
1) to Supra carbon (9.6 Wh L
1) at low Furthermore, these PCNS-based supercapacitors are
discharge rates and surpass it for high discharge rates able to deliver 14
30 Wh kg
1 at a power density
(drain time <10 s). However, the volumetric energy- of 13 kW kg
1. Of particular interest are the results
power characteristics of the sample synthesized at the obtained with the CK-850- and CK-900-based super-
highest temperature (i.e., 900 °C) are inferior because capacitors, which can still deliver respectively ∼13 Wh
of its low packing density (0.27 g cm
3 at 7.1 MPa). kg
1 (5.2 Wh L
1) at a power density of 78 kW kg
1
Thereby, taking into account both the gravimetric and (31 kW L
1) and ∼14 Wh kg
1 (3.8 Wh L
1) at a power
volumetric energy-power characteristics, the best per- density of 112 kW kg
1 (30 kW L
1). Figure 6 provides
forming sample is CK-850. a comparison of the power and energy characteristics

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 ARTICLE
of the CK-850- and CK-900-based supercapacitors ranges of 0.7
0.85 nm and 0.95
1.6 nm. Furthermore,
with those of the most advanced porous carbon they exhibit good electronic conductivities, up to
materials that can be found in the literature,8,40,50,52,53 7.4 S cm
1 (load pressure: 7.1 MPa). These unique
confirming its high performance, especially in terms structural properties allow short diffusion paths and
of power handling (>20 kW kg
1). consequently the rapid transport of ions throughout
the carbonaceous matrix, as well as rapid electron
CONCLUSIONS transport, resulting in an excellent electrochemical
In summary, we have reported a novel and simple performance. In particular, the samples fabricated at
approach to produce 3D interconnected microporous 850 and 900 °C display a high specific capacitance at
carbon nanosheets. These carbon particles are pro- high discharge rates, an outstanding rate capability,
duced by the direct carbonization of potassium citrate and an excellent cycling stability in the 1 M TEABF4/
at temperatures in the 750
900 °C range. In this way, AN organic system. At a very high specific power of
the pyrolysis of the organic moiety and the activation 25
27 kW kg
1, their specific energy reaches 25 Wh kg
1.
of the carbonaceous material can be integrated in only These promising results reveal the development of a
one step. The interconnected carbon nanosheets have one-step, facile, cost-effective, and scalable synthesis
a thickness of <80 nm, and in addition, they possess strategy for the production of carbon materials that are
large specific surface areas (up to ∼2200 m2 g
1) and a highly suitable for the fabrication of top-performance
porosity made up of two micropore systems in the size supercapacitors.

EXPERIMENTAL SECTION active material and 10 wt % of PTFE. The electrochemical

measurements were performed in two-electrode Swagelok
Synthesis of Materials. In a typical synthesis procedure, 5 g of
type cells using stainless steel current collectors. Electrochemi-
potassium citrate (Aldrich) was heat-treated in a stainless steel
cal capacitors were built using two carbon electrodes of com-
reactor under nitrogen up to desired temperature (i.e., 750, 800,
parable mass, electrically isolated by glassy fibrous separator.
850, or 900 °C) at a heating rate of 3 °C/min and held at this
A 1 M tetraethylammonium tetrafluoroborate salt (TEABF4, electro-
temperature for 1 h. The black solid residue was then washed
chemical grade, Sigma-Aldrich) solution in acetonitrile (AN, 99.8%,
with HCl (10%). Finally, the solid was collected by filtration,
anhydrous, Sigma-Aldrich) was used as electrolyte. The electro-
washed with abundant distilled water, and dried at 120 °C for
chemical characterization was performed using a computer-con-
several hours. The carbon samples were denoted as CK-X, where
trolled potentiostat (Biologic VMP3 multichannel generator).
X is the reaction temperature (in °C).
Commercial activated carbon commonly used in commercial
Physical Characterization. Scanning electron microscopy (SEM)
supercapacitors (Supra DLC-50, Norit, SBET = 1890 m2 g
1, average
images were obtained on a Quanta FEG650 (FEI) instrument,
pore width ∼1.3 nm) was analyzed for comparison.
whereas transmission electron microscopy (TEM) images were
Cyclic voltammetry was conducted between 0 and 2
2.7 V
recorded on a JEOL (JEM 2100-F) apparatus operating at 200 kV.
at increasing sweep rates from 1 to 1000 mV s
1. The specific
The nitrogen sorption isotherms of the carbon samples were
gravimetric capacitance of a single electrode was calculated
measured at
196 °C using a Micromeritics ASAP 2020 sorpt-
from the area of the voltammograms by means of the following
ometer. The apparent surface area was calculated using the BET
formula:
method. An appropriate relative pressure range was selected to H
ensure that a positive line intersect of multipoint BET fitting I dV
C sp ¼ (1)
(C > 0) would be obtained and Vads(1
P/P0) would increase νm ΔV
with P/P0.54 The total pore volume was determined from the
where I = current (A), ν = scan rate (V/s), ΔV = voltage window
amount of nitrogen adsorbed at a relative pressure (P/P0) of
(V), and m = mass (grams) of carbon material in the working
0.95, whereas the micropore volume was determined using the
electrode.
Dubinin
Radushkevich equation.55 The average pore width, L0,
Galvanostactic charge/discharge cycling was also per-
was calculated by applying the equation proposed by Stoeckli
formed in the 0 to 2
2.7 V range at current densities in the
and Ballerini.56 The pore size distributions (PSD) were deter-
0.05
150 A g
1 range, based on the active mass of a single
mined by means of the Quench Solid State Density Functional
electrode. The specific gravimetric capacitance of a single
Theory (QSDFT) method for nitrogen.57,58 X-ray diffraction (XRD)
electrode determined from the galvanostatic cycles was calcu-
patterns were obtained on a Siemens D5000 instrument oper-
lated by means of the formula:
ating at 40 kV and 20 mA, using Cu KR radiation. The Raman
spectra were recorded on a Horiva (LabRam HR-800) spectro- 2I
meter. The source of radiation was a laser operating at a C sp ¼ (2)
(dV=dt)m
wavelength of 514 nm and at a power of 25 mW. X-ray
photoelectron spectroscopy (XPS) was carried out on a Specs
spectrometer, using Mg KR (1253.6 eV) radiation from a double where dV/dt = the slope of the discharge curve (V s
1).
anode at 150 W. Thermogravimetric analysis (TGA) curves were Electrochemical impedance spectroscopy (EIS) was per-
recorded on a TA Instruments Q600 TGA system. formed at open circuit voltage (i.e., 0 V) within the frequency
The dc electrical conductivity of the carbon powders was range of 1 mHz to 100 kHz and a 10 mV AC amplitude. Plots of
determined in a homemade apparatus (four-probe method) by the dependence of the capacitance on frequency were re-
pressing the powders between two plungers, into a hollow corded to characterize the impedance of the tested samples.
Nylon cylinder (inner diameter of 8 mm), and applying a The specific gravimetric capacitance of a single electrode, CEIS
pressure of 7.1 MPa. (F/g), was calculated according to the following formula and
Electrochemical Characterization. Electrodes were prepared by normalized with respect to the specific gravimetric capacitance
mixing 85 wt % of active material with 10 wt % of polytetra- at 1 mHz:
fluoroethylene (PTFE) binder (Aldrich, 60 wt % suspension in
2jIm(Z)j
water) and 5% Super P (Timcal). For CK-900, electrodes were C EIS ¼ (3)
also prepared without conductive additive by mixing 90 wt % of 2πf [(Im(Z))2 þ (Re(Z))2 ] 3 m

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www.acsnano.org
 ARTICLE
where f is the operating frequency (Hz), and Im(Z) and Re(Z) are with Tunable and Uniform Size. Angew. Chem., Int. Ed.
the imaginary and real components of the total device resis- 2010, 49, 7987–7991.
tance (Ohm). The relaxation time constant, τ0, which separates 11. Su, F.; Poh, C. K.; Chen, J. S.; Xu, G.; Wang, D.; Li, Q.; Lin, J.;
the capacitive behavior and the resistive behavior of the super- Lou, X. W. Nitrogen-Containing Microporous Carbon
capacitor, was deduced from the frequency f0 as follows: τ0 = 1/f0, Nanospheres with Improved Capacitive Properties. Energy
where f0 can be obtained from the real capacitance plot at Environ. Sci. 2011, 4, 717–724.
C0 = C1mHz/2 and from the imaginary capacitance plot where it 12. Chen, L.-F.; Zhang, X.-D.; Liang, H.-W.; Kong, M.; Guan, Q.-F.;
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To trace the Ragone plots, the specific energy (Wh kg
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calculated using the following formula: terial for Supercapacitors. ACS Nano 2012, 6, 7092–7102.
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1
E ¼ C cell ΔV d 2 (4) W.-C. Synthesis of Superior Carbon Nanofibers with Large
2 Aspect Ratio and Tunable Porosity for Electrochemical
where Ccell is the specific capacitance of the total cell (F g
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The specific power (kW kg
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the formula: Surfactant-Templated Assembly for Use as Anodes for
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Conflict of Interest: The authors declare no competing Carbon Spheres between Reduced Graphene Oxide
financial interest. Sheets for Preparing High-Rate Supercapacitor Electrodes.
Energy Environ. Sci. 2011, 4, 1866–1873.
17. Zhang, L. L.; Xiong, Z.; Zhao, X. S. Pillaring Chemically
Acknowledgment. This research work was supported by the Exfoliated Graphene Oxide with Carbon Nanotubes for
Spanish MINECO (MAT2012-31651). M.S. acknowledges the Photocatalytic Degradation of Dyes under Visible Light
award of a Ramón y Cajal contract. We thank Elena Fuertes for Irradiation. ACS Nano 2010, 4, 7030–7036.
the design of Scheme 1.
18. Wang, G.; Sun, X.; Lu, F.; Sun, H.; Yu, M.; Jiang, W.; Liu, C.;
Supporting Information Available: Thermogravimetric anal- Lian, J. Flexible Pillared Graphene-Paper Electrodes for
ysis curves, XPS spectra, same images, EELS spectrum, HRTEM High-Performance Electrochemical Supercapacitors.
images and FFT patterns, cyclic voltammograms and rate Small 2012, 8, 452–459.
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voltage profiles and long-term stability at different current Stephenson, T.; Mitlin, D. Electrochemical Supercapacitor
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