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Journal of Power Sources 274 (2015) 823e830

Contents lists available at ScienceDirect

Journal of Power Sources


journal homepage: www.elsevier.com/locate/jpowsour

High performance all-carbon thin film supercapacitors


Jinzhang Liu a, Francesca Mirri b, c, Marco Notarianni a, Matteo Pasquali b, c,
Nunzio Motta a, *
a
School of Chemistry, Physics, and Mechanical Engineering and Institute for Future Environments, Queensland University of Technology, Brisbane 4001,
QLD, Australia
b
Department of Chemical and Biomolecular Engineering, The Smalley Institute for Nanoscale Science and Technology, Rice University, 6100 Main Street,
Houston, TX 77005, United States
c
Department of Chemistry, The Smalley Institute for Nanoscale Science and Technology, Rice University, 6100 Main Street, Houston, TX 77005, United States

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Advance in supercapacitor technol-


ogy by materials engineering all
based on carbon.
 Our devices achieve volume energy
density comparable to Li-ion
batteries.
 Our devices achieve power density
better than laser-scribed-graphene
supercapacitors.

a r t i c l e i n f o a b s t r a c t

Article history: We fabricated high performance supercapacitors by using all carbon electrodes, with volume energy in
Received 9 September 2014 the order of 103 Whcm3, comparable to Li-ion batteries, and power densities in the range of 10 Wcm3,
Received in revised form better than laser-scribed-graphene supercapacitors. All-carbon supercapacitor electrodes are made by
10 October 2014
solution processing and filtering electrochemically-exfoliated graphene sheets mixed with clusters of
Accepted 16 October 2014
Available online 23 October 2014
spontaneously entangled multiwall carbon nanotubes. We maximize the capacitance by using a 1:1
weight ratio of graphene to multi-wall carbon nanotubes and by controlling their packing in the elec-
trode film so as to maximize accessible surface and further enhance the charge collection. This electrode
Keywords:
Graphene
is transferred onto a plastic-paper-supported double-wall carbon nanotube film used as current collector.
Supercapacitor These all-carbon thin films are combined with plastic paper and gelled electrolyte to produce solid-state
Carbon nanotubes bendable thin film supercapacitors. We assembled supercapacitor cells in series in a planar configuration
Gelled electrolyte to increase the operating voltage and find that the shape of our supercapacitor film strongly affects its
Electrochemical exfoliation capacitance. An in-line superposition of rectangular sheets is superior to a cross superposition in
maintaining high capacitance when subject to fast charge/discharge cycles. The effect is explained by
addressing the mechanism of ion diffusion into stacked graphene sheets.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction

Carbon nanomaterials have a unique place in nanoscience, due to


their excellent physical and chemical properties. Energy storage is one
* Corresponding author. Tel.: þ61 731385104.
of the important applications of carbon nanomaterials, because of
E-mail address: n.motta@qut.edu.au (N. Motta). their ability to trap charges coupled to a good conductivity. Electrodes

http://dx.doi.org/10.1016/j.jpowsour.2014.10.104
0378-7753/© 2014 Elsevier B.V. All rights reserved.
824 J. Liu et al. / Journal of Power Sources 274 (2015) 823e830

made of carbon nanostructures have been applied in fuel cells [1,2], DVD optical drive, and combined the laser-scribed graphene film and
lithium batteries [3], and supercapacitors [4]. Active-carbon-based gelled electrolyte to make solid-state supercapacitors with a capaci-
electrochemical supercapacitors are commercially available and tance of ~5 mFcm2 [24,25]. The primary step in the fabrication of
have wide applications in both energy storage and power supply. these supercapacitors is the preparation of GO, which uses many
Supercapacitors have been proposed to store extra energy from solar chemicals and is time-consuming. In this paper we explore a greener
panels and wind turbines [5]. Supercapacitors are superior to batte- way to produce graphene and a novel method to make solid-state thin
ries in power density, but inferior in energy density. The super- film supercapacitors with high performance.
capacitorebattery combination has been used in electrical vehicles, in The use of aqueous electrolyte containing SO2 4 ions to electro-
which the supercapacitor provided a peak power during acceleration chemically exfoliate graphite is simple and time-saving, and the
and hill-climbing, and it could be recharged by the battery during produced graphene is of high quality, comparable or even better than
regeneration braking [6]. Commercial supercapacitors are bulky, due rGO [26e28]. In comparison, the standard wet chemical preparation
to the strong encapsulation required for the liquid electrolyte. On the of GO and rGO includes several steps for chemical reaction and pu-
other hand, energy storage components have to be as small as possible rification. Here we produce graphene flakes by a fast electrochemical
for lightweight and portable gadgets. In this regard, the development exfoliation method with mild chemicals, typically NaSO4 in water, and
of solid-state thin film supercapacitors that use carbon nanomaterials blend them to multi-wall CNTs (MWCNTs) to make thin electrode
is highly desired. Research advancement in this area can also lead to films with high surface area for high-capacitance supercapacitors. We
novel design and manufacture of electrical vehicles: large-area thin use highly-conductive double-wall CNT (DWCNT) films coated onto
film supercapacitors, for example, could be stacked together and plastic papers as current collectors. Metal foils commonly used in
combined with strong composites to make vehicle's body panel with electrochemical supercapacitors account for 20e30% of the total
energy storage function. weight and have to undergo an anti-corrosion treatment. In our work,
In recent years, the use of carbon nanotubes (CNTs) and graphene the DWCNT film is flexible and lightweight, free from any corrosion
to make supercapacitors has attracted the attention of researchers problem. A gelled electrolyte is used to bind the two carbon-
since they have a higher specific capacitance than active carbon. nanomaterial layers to make a supercapacitor in the form of flexible
Research on CNT-based supercapacitors started before the isolation of film. We show that an in-plane assembly of supercapacitor cells in-
graphene in 2004. So far, either forest-like arrays [7,8] or networks [9] creases the voltage output.
of CNTs have been tested as supercapacitor electrodes. However, the
capacitance of these CNT-based supercapacitors is not satisfactory. A 2. Experimental
second approach is to use CNTs to support metal oxides [10,11] or
conductive polymers [12,13] to create high-capacitance pseudoca- 2.1. Ultrasound-assisted electrochemically exfoliation method to
pacitors, which exploit the oxidation-reduction process to charge and produce graphene
discharge. Yet, these structures are inherently three-dimensional;
thin-film supercapacitors have remained elusive because they We have previously reported the experimental details and char-
employ a liquid electrolyte for the redox reactions, which is not easily acterization of our graphene samples [27]. Briefly, a piece of highly
supported in a two-dimensional geometry. Compared to CNTs (either ordered pyrolytic graphite was immersed into an aqueous electrolyte
single-wall or multi-wall), graphene sheets have higher surface-to- containing 0.15 M NaSO4 and 0.01 M sodium dodecyl sulfate. The pH
volume ratio and result in higher capacitance when used as super- value of the solution was adjusted to ~2.0 by dropping sulfuric acid. A
capacitor electrodes. Composites of graphene or graphene oxide (GO) Pt wire was placed into the solution as cathode and the bias is set to
and other materials such as polyaniline [14], TiN [15], MnO2 [16], RuO2 5e6 V during the exfoliation process. The setup was placed into an
[17], and NiO [18] have been used as 3D-structured electrodes of ultrasonic bath, which speed up the exfoliation process and reduces
liquid-phase electrochemical supercapacitors; however, electrodes the overall thickness of the final graphene sheets. Within 1 h the
made out of sole-nanocarbon 2D structures are more interesting as graphite was totally exfoliated and dispersed into the electrolyte. The
they allow the use of a gelled electrolyte and the fabrication of metal- black solution was centrifuged to remove thick flakes. Few-layer
free and solid-state thin film supercapacitors. graphene with 54% bilayer sheets was obtained after the purifica-
Graphene used in supercapacitors is commonly produced by high- tion process and dispersed into DMF to form a stable suspension.
temperature catalytic growth or wet-chemical exfoliation of graphite.
Supercapacitors have been made [19] using the first method by 2.2. Mixing MWCNTs with graphene to make composite films
growing graphene sheets onto a nickel foam. The nickel foam acts as
both the catalyst to grow graphene sheets in a 3D structure and as MWCNTs purchased from ssnano.com are eCOOH functional-
current collector for the supercapacitor. Though high-temperature- ized and have outer diameters <8 nm and lengths of 5e20 mm.
grown graphene provides a clean surface and high conductivity, the MWCNTs and graphene sheets were respectively dispersed into
technique is costly and the yield of graphene is low. Many researchers DMF to form suspensions. The two solutions were mixed with
used reduced graphene oxide (rGO), mostly prepared by wet- controlled weight ratio of MWCNTs to graphene and undergone 1 h
chemical methods, to make supercapacitors. GO sheets can be ultrasound sonication upon the vacuum filtration process. This
mass-produced at low cost by using graphite powder and chemicals sonication process and the use of alumina membrane (Whatman
including oxidizing agents and acids, according to the Hummer's Co., pore size 20 nm) for filtration ensure uniformity of the com-
method [20]. Various wet-chemical methods have been developed to posite layer for capacitor electrode.
reduce GO, but the resistance of rGO is considerably higher than that
of pure graphene [21]. To make a supercapacitor electrode, the rGO 2.3. Preparation of conductive DWCNT films as supercapacitor
sheets were processed into 3D porous structure to improve their current collectors
capacitance [22]. Such an electrode is usually tens of microns in
thickness and is more suitable for liquid-electrolyte-based capacitors. The method for making highly conductive DWCNT film has been
Sheng et al. electrochemically reduced and deposited GO sheets from reported previously [29,30]. In brief, double-wall CNTs (purchased
an aqueous solution onto Au foils and made supercapacitors with from CCNI, batch X647H) were mixed with chlorosulfonic acid at
capacitance of 240e350 mFcm2 [23]. Kaner et al. developed a novel 2000 ppm with a speed-mixer (DAC 150.1 FV-K, Flak Tek Inc) for
technique to thermally reduce GO film by using the laser of a standard 20 min. Then the solution was diluted to 20 ppm to be used for
J. Liu et al. / Journal of Power Sources 274 (2015) 823e830 825

vacuum filtration. The DWCNT film on an alumina filter (Whatman 3. Results and discussion
Co., pore size 0.02 mm) was washed by chloroform to remove most
of the acid (film coagulation), followed by a drying process in air. To 3.1. Morphology of carbon films
transfer the DWCNT film on a PET substrate, the alumina mem-
brane covered with DWCNT film was floated onto the surface of 1 M Graphene sheets produced by our electrochemical exfoliation
NaOH aqueous solution in a petri dish. After etching away the method are usually composed of few carbon layers. We introduce ul-
membrane the DWCNT film was left floating on the solution sur- trasound assistance during the exfoliation process, which reduces the
face, then the NaOH solution was drained out and DI water was overall thickness of graphene flakes, producing a majority of bilayer
filled into the petri dish. This process was repeated three times to graphene flakes [27]. The MWCNTs used in this work are eCOOH
ensure the removal of sodium and hydroxide ions. To transfer the functionalized. The experimental process to make high-surface-area
film, a PET substrate was immersed into the water and the DWCNT graphene-MWCNT films for supercapacitors is illustrated in Fig. 1.
film landed onto the PET film by draining off the water. After drying, First, graphene and MWCNTs with the weight ratio of 1:1 are ultra-
the DWCNT film is tightly attached to the PET substrate. Similar sonically mixed in dimethylformamide (DMF) solution. The suspen-
transfer process was applied to attach the graphene-MWCNT sion is vacuum filtered onto a porous alumina membrane (purchased
electrode film to the DWCNT film. from Whatman Co., pore size 100 nm). The eCOOH functionalized
MWCNTs are entangled, forming micron-size clusters. The thickness of
the sole graphene film is 200e300 nm. The entangled MWCNTs
2.4. Fabrication of supercapacitors among stacked graphene sheets make the film surface rough.
When dried at 50  C in air, the filter-supported film contracts
To prepare the gelled electrolyte, 1 g PVA powder (molecular and detaches from the membrane, due to the evaporation of DMF
weight ~89,000e98,000, Sigma Aldrich) was added into a mixture and to the weak adhesion force between the graphene and the
solution of 10 ml DI water and 0.8 g concentrated phosphoric acid membrane. In order to make a very rough film, the free-standing
(85% solution in water). The solution was heated to 90  C under graphene-MWCNT mixture film is immersed again into DMF to
constant stirring in order to thoroughly dissolve PVA. Then the be shattered into tiny pieces by ultrasound sonication. A second
clear electrolyte was cooled down under ambient conditions. To filtration process is carried out to gather these pieces to form a
make a device, the PET paper covered with carbon nanomaterials loose and very rough film (the supercapacitor electrode). The
was cut into rectangular shapes. The electrolyte applied to two resulting film is transferred onto a felt-like DWCNT film supported
electrode films was allowed to naturally dry in air at room tem- by poly(ethylene terephthalate) (PET) plastic paper. The flexible
perature for 5 h. Then the two films were stacked together face-to- PET substrate (100-mm-thick) covered by the carbon materials can
face by mechanical pressure, and the overlapping area (typical be then cut into any shapes to make solid-state supercapacitors by
0.6  0.6 cm2) between two films is used to calculate the specific including a gelled electrolyte prepared using polyvinyl alcohol
areal capacitance. The gelled electrolyte acts as good binder and its (PVA) and phosphoric acid (Fig. 1).
thickness is about 15 mm. To study the in-plane assembly of two Field-emission scanning electron microscopy (FE-SEM, Zeiss
supercapacitors in series and to power a light-emitting diode by Sigma VP) was employed to examine the film morphology. The
four unit supercapacitors, we made the capacitor area of each unit DWCNT film attached to the PET plastic paper is about 500 nm in
as 1.0  0.8 cm2. thickness and 29 mgcm2 in weight per unit area. Without adding

Fig. 1. Illustration of the experimental process for the production of a rough electrode film consisting of graphene and MWCNTs. The sandwich structure of the device is shown.
826 J. Liu et al. / Journal of Power Sources 274 (2015) 823e830

MWCNTs, the graphene film shows a flat surface with creases The quasi-square shape of these CV curves indicates good capaci-
formed by folded graphene sheets (Fig. S1). With MWCNT clusters tive performance. Galvanostatic chargeedischarge (CD) curves of
protruding in stacked graphene sheets, the mixture film exhibits a the device measured at different current values are shown in
rough surface (Fig. S2). Compared to the flat graphene film, the Fig. 3b. The nearly triangular shape of the CD curve indicates stable
graphene-MWCNT mixture film has larger surface area due to the capacitance during the charge and discharge process; notably, CD
increased roughness, thus more ions from the electrolyte can be curves reported so far for similar supercapacitors based on gra-
received and the capacitance is improved. After shattering the phene/polyaniline or graphene/MnO2 mixtures are nonlinear and
mixture film and depositing the fragments onto a membrane again, asymmetric [11,12]. Fig. 3c shows the complex plot of impedance
the resultant film becomes rougher and looser, resulting in 40% data, measured in the frequency range of 0.04e1.0 MHz. The inset
increase in capacitance. By keeping the weight of the electrodes shows an expanded view for the high frequency region, revealing
constant, we found that the optimal ratio of graphene to MWCNT is that the series resistance of the device is about 30 U. This is
1:1 (Supplementary content). The surface-to-volume ratio of gra- attributed to the internal resistance of DWCNT film as current
phene sheets is higher than that of MWCNTs, so graphene sheets collector and the contact resistance between the DWCNT film and
exhibit higher capacitance than MWCNTs when used as capacitor the alligator clip. The dependence of the phase angle on frequency
electrodes. By inserting entangled MWCNTs in the form of porous is shown in Fig. 3d. The phase change is 80 at low frequency,
clusters into the stacked graphene sheets, the electrode film has not close to the ideal value of 90 . If we treat the capacitor as a parallel
only a rougher surface but also voids inside, thus more graphene RC circuit, the phase angle can be expressed as q ¼ tan1(Ic/IR),
sheets can be exploited to absorb ions from the electrolyte. We where Ic and IR are the current values through the capacitor and the
however have to keep enough graphene sheets to act as ion ab- resistor, respectively. Hence, the deviation of phase angle
sorbers. By increasing the percentage of MWCNTs over the 1:1 ra- from 90 is due to the current flowing through the gelled elec-
tio, the decreased amount of graphene sheets reduces the surface- trolyte. The areal capacitance can be deduced from the CV curves
to-volume ratio, resulting in a decreased capacitance. and the dependence of capacitance on voltage scan rate is plotted in
Fig. 2 shows the FE-SEM images of graphene-MWCNT mixture Fig. 3e. The capacitance gradually decreases with increasing the
films used as supercapacitor electrodes. In the titled-view images in scan rate, which is a common phenomenon among electrochemical
Fig. 2a and c, the film morphology can be depicted as mountainous capacitors. The higher the scan rate, the shorter time for the ions to
feature. The conductive DWCNT film used as current collector is diffuse into the electrode. Thus high scan rate leads to the decrease
beneath the coarse mixture film. It should be noted that the of the ions population in the electrode, accounting for the lower
adhesion force between graphene sheets and the DWCNT film is capacitance. The device stability was tested by repeatedly charging
strong enough to keep the electrode film attached to the base upon and discharging the capacitor at 100 mAcm2 for over 4500 cycles,
bending (Supplementary content). Fig. 2b was taken on a free providing a measure of the capacitance values at different cycles.
standing graphene-MWCNT film, showing that rolling hills and The capacitance retention against the number of CD cycles is shown
caves co-exist in the electrode film. Such a structure ensures a good in Fig. 3f. After continuously cycling the CD process for 3 days the
infiltration of gelled electrolyte into the film and increases the capacitor shows a retention of 92%.
capacitance of ions among graphene flakes and MWCNTs. The energy and power densities of the device are given by a
Ragone plot in Fig. 4. We believe our results are a breakthrough in
3.2. Supercapacitor performance the development of supercapacitors. For comparison, approximate
values of a thin-film Li battery and a supercapacitor based on laser-
Fig. 3a shows the currentevoltage (CV) curves of a typical device scribed graphene and PVA-H3PO4 gelled electrolyte, reported in
measured at different voltage scan rates with a range of 1.0e1.0 V. Ref. [30], are marked by two ellipse regions, respectively. It should

Fig. 2. FE-SEM images of the graphene-MWCNT blend film for the supercapacitor electrodes. (a) Tilted-view image of the electrode attached to a CNT film. (b) Plane-view of a free-
standing electrode film. (c) A high-magnification image showing the DWCNT film beneath the rough graphene-MWCNT mixture film.
J. Liu et al. / Journal of Power Sources 274 (2015) 823e830 827

Fig. 3. Performance of a typical supercapacitor. (a) Current-voltage curves measured in the range of 1.0 Ve1.0 V at different voltage scan rates. (b) Galvanostatic chargeedischarge
curves measured at different current densities. (c) Complex impedance spectrum of the device. The inset shows the magnified region at high frequencies. (d) Dependence of phase
change on frequency. (e) Dependence of capacitance on the voltage scan rate, extracted from the CV curves. (f) Stability of the device tested by cycling the chargeedischarge process
at 100 mAcm2 for three days.

be noted that the laser-scribed graphene film is about 20-mm-thick sandwich-structured solid state supercapacitors; (ii) to provide
and gives rise to ~5 mFcm2 [24], while in our work the rough Hþ ions that can penetrate deeper into the electrode layer, thanks
graphene-MWCNT film is < 5 mm in absolute thickness and shows a to their small size. For practical applications, multiple super-
specific capacitance as high as ~10 mFcm2. The high capacitance capacitors can be packaged in series, in parallel, or in
and narrow gap between the two opposite electrodes account for
the high energy density of our supercapacitors, which is
~103 Whcm3. Adding MWCNTs into the graphene film reduces
the sheet resistance (from 14 KUsq1 to 5 KUsq1); moreover the
DWCNT film used as current collector has a low sheet resistance of
6 Usq1. The low resistance of both graphene-MWCNT layer and
DWCNT film is essential to produce a high power output, as the
power density is inversely proportional to the resistance. The IR
drop in CD curves in Fig. 3b is too small to be noticed due to this
small resistance, and our device shows high power density in the
order of 10 Wcm3, similar to the commercialized Al electrolyte
capacitor [24].

3.3. In-plane assembly of supercapacitor cells for high operation


voltage

Electrochemical supercapacitors have the drawback of low


output voltage, and cannot compete with ionic batteries.
Although the use of ionic-liquid-based electrolyte can increase
the operating voltage window (from ~1 V to ~2.5 V) as well as the Fig. 4. The Ragone plot showing energy and power densities of the device. For com-
energy density [26], the PVA-acid electrolyte has a double parison, the values of Li thin film battery and a similar supercapacitor based on laser-
advantage: (i) acting as glue it binds two electrode films to make scribed graphene from Ref. [24,25] are roughly marked.
828 J. Liu et al. / Journal of Power Sources 274 (2015) 823e830

combinations of the two, in order to meet different energy and appropriate voltage output for touch-pad and flexible phone
power requirements. Thus, it is important to investigate the as- applications.
sembly of thin film supercapacitors in various configurations.
Herein, we use thin film supercapacitors with PVA-based gelled 3.4. The effect of 2D shape of sandwich-structured supercapacitor
electrolyte to create a device assembly for high voltage output. on the capacitance
Fig. 5a shows the optical photograph of two supercapacitor cells
sharing one DWCNT/PET film. Fig. 5b illustrates the device Kadhi et al. recently reported a consistent decrease of
structure and tandem connection of the two supercapacitors. CV capacitance by increasing the voltage scan rate or the CD current
curves measured at voltage scan rate of 100 mVs1 for a single in electrochemical supercapacitors developed by using laser-
device, two in series, and four in series are shown in Fig. 5c. The scribed graphene films as electrodes and various electrolytes,
operation voltage is multiplied by connecting supercapacitors in including aqueous solution, gelled PVA with acid, organic liquid
tandem, while both the total capacitance and the current in CV electrolyte, and ionic liquid [24,25]. This phenomenon seems to
loops are decreased. It should be noted that the current value at be inevitable among electrochemical capacitors. In order to
0 V is proportional to the capacitance. CD curves measured at reduce the capacitance loss at high voltage scan rate or CD cur-
50 mAcm2 for a single device, two and four devices in series, are rent, we studied the capacitance performance of single super-
shown in Fig. 5d. An optical photograph of four supercapacitors capacitors with square and rectangular shapes. We found that
connected in tandem is shown in Fig. 5e. The voltage output is the aspect ratio has a strong influence on the capacitance. Two
high enough to light up a red light-emitting diode (operating supercapacitors with identical area but different shapes (square
voltage range 2.5e5.0 V) (in web version), as shown in Fig. 5f. versus rectangular, width to length 5:1) were tested. Their
Our study reveals that multiple supercapacitor cells can be capacitance values extracted from CV curves and galvanostatic
assembled in-plane to increase the voltage output by sharing the CD curves are compared in Fig. 6a and b, respectively. At low scan
same DWCNT film as current collector, indicating the possibility rate or low discharge current, the capacitance values of the two
of making flat supercapacitors as thin as a paper but with devices are quite close. However, increasing the scan rate or the

Fig. 5. (a) An optical photograph demonstrating the in-plane assembly of two supercapacitors. The device structure and tandem connection are illustrated in (b). (c) CV curves
measured at 60 mVs1 for a single, two and four devices in series. (d) CD curves measured at 50 mAcm2 for a single device, two, and four devices in series. (e) and (f) Optical
photographs showing the connection of four supercapacitors in series and the capability of powering a LED.
J. Liu et al. / Journal of Power Sources 274 (2015) 823e830 829

Fig. 6. Capacitance comparison for two supercapacitors with different shapes: square and rectangular. (a) and (b) Variations of capacitance against voltage scan rate and CD current
value, respectively. (c) Top: plane-view outlines of the two devices; bottom: illustration showing the difference of the ions diffusing path in the square-shaped and rectangular-
shaped devices. For the right-hand device, the voltage drop along the DWCNT film leads to the horizontal movement of ions in the electrode layer, accounting for the increase
of capacitance.

CD current, the capacitance of the rectangular-shaped device is printing or brushing methods can be used to make the DWCNT
higher than that of the square-shaped one. In Fig. 6c, the plane- current collectors and graphene-MWCNT electrodes suitable for
view outlines of the two devices are given and the shape effect in-plane assembly of uniform unit cells.
on the capacitance is explained by using the two side-view il-
lustrations. In the square-shaped device, with bias on the CNT 4. Conclusion
film, the electric field is perpendicular to the substrate and the
ions in the gelled electrolyte move vertically into the electrode In conclusion we have fabricated highly efficient all-carbon-
layer. Likely, in this case the ions preferentially diffuse along the based thin film supercapacitors using conductive DWCNT films as
edges of stacked graphene sheets and those blocked by graphene current collectors and high surface area graphene-MWCNT mixture
sheets cannot infiltrate deeper. Only at low voltage scan rate or films as electrodes. These carbon films were coated onto flexible
low chargeedischarge current the ions have enough time to PET papers to make solid-state electrochemical supercapacitors
diffuse deeply into the electrode and spread into the interfaces of with gelled electrolyte. We developed a technique to increase the
stacked graphene sheets, reaching the maximum capacitance. For surface area as well as the capacitance of the electrode layer con-
the rectangular-shaped device, the current flowing along the CNT sisting of electrochemically-exfoliated graphene and eCOOH
film leads to a voltage drop. Therefore, the electric field across functionalized MWCNTs. Though the electrode film is few micro-
the electrolyte medium is slant and the ion movement would meters in thickness, it shows an areal specific capacitance as high as
have both vertical and horizontal vectors. The horizontal ~10 mFcm2. The volume energy and power densities of the device
component of the electric force facilitates the movement of ions are in the order of 103 Whcm3 and 10 Wcm3, respectively. We
into the interfaces of stacked graphene sheets, increasing the found that the aspect ratio of as-prepared film supercapacitor has
population of ions in the electrode layer. When the voltage scan an important effect on the capacitance. Rectangular shaped devices
rate or chargeedischarge current are very low, the effect of with high aspect ratio retain their capacitance more effectively in
aspect ratio on capacitance is minor because: (i) the voltage drop fast charge/discharge cycles, likely because of the voltage drop in
in the rectangular-shaped film is negligible at low current; (ii) strip-shaped DWCNT film as current collector. The in-plane as-
there is enough time for ions to diffuse along the edges and sembly of supercapacitors in series to increase the voltage output
surfaces of stacked graphene sheets to reach the saturation of will lead to space-saving integration of supercapacitor cells for
ions in the electrode. This means that the choice of the right practical applications.
aspect ratio is important to increase the capacitance of this kind
of devices. This finding will deeply influence the device design Acknowledgments
and assembly of unit cells in practical applications. Strip-shaped
supercapacitors would be more suitable to be aligned in parallel We thank the financial support of QUT through the Vice-Chan-
for achieving higher capacitance. In this work membranes are cellor’s Research Fellowship, and of ARC through the Discovery
consumed in the preparation of nanocarbon films. In the future project DP130102120 and the Welch Foundation grant C-1668. This
830 J. Liu et al. / Journal of Power Sources 274 (2015) 823e830

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