Applied Surface Science 422 (2017) 975–984

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Applied Surface Science

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

Full length article

Free-standing graphene films prepared via foam film method for great
capacitive flexible supercapacitors
Yucan Zhu, Xingke Ye, Zhonghua Tang, Zhongquan Wan, Chunyang Jia ∗
State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Microelectronics and Solid-State Electronics, University of Electronic Science
and Technology of China, Chengdu 610054, PR China

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

Article history: Recently, graphene films have always attracted attention due to their excellent characteristics in energy
Received 6 March 2017 storage. In this work, a novel graphene oxide (GO) film with excellent mechanical properties, whose thick-
Received in revised form 31 May 2017 ness was regulated simply via changing the concentration of the surfactant, was successfully prepared
Accepted 6 June 2017
by foam film method. After chemical reduction, the reduced GO (rGO) films have excellent electrical
Available online 7 June 2017
conductivity of ∼172 S cm−1 . Moreover, the supercapacitors based on the rGO films exhibit satisfied
capacitive performance of ∼56 mF cm−2 at 0.2 mA cm−2 in 6 M KOH aqueous solution. Meanwhile, the
Keywords:
flexible all solid state supercapacitors (FSSCs) based on the rGO films also show great volumetric capac-
Foam film
Graphene oxide films
itance of ∼2810 mF cm−3 at 12 mA cm−3 (∼1607 mF cm−3 at 613 mA cm−3 ) with polyvinyl alcohol-KOH
Surfactant gel electrolyte. Besides, after 10000 cycles and continuously bent to 180◦ for 300 times, the volumetric
Flexible all solid state supercapacitors capacitance of the FSSC remains at 81.4% and 90.4% of its initial capacitance value, respectively. Therefore,
the free-standing rGO films prepared via foam film method could be considered as promising electrode
materials for high performance flexible supercapacitors.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction extensively, since it is one of the major factors that determines

Wearable electronic devices, such as pedometers, heat-rate
monitor, military garment devices and smartwatch, have attracted
increasing attention in the last few years, due to their applications
in fitness, medicare, military, information and so on [1–6]. How-
ever, the development of wearable electronics is always restricted
by the conventional power systems (e.g., batteries) which have
some drawbacks of small lifespan and low charge/discharge rates.
Even worse, they are too bulky and heavy to be considered as power
capacitance performance [11,12]. Among the electrode materi-
als, carbon materials (e.g., activated carbon, CNTs, black carbon,
graphene, ect.) have become typical promising electrode materi-
als due to their merits of high conductivity, widespread, stable
electrochemical property and so on [13]. In particular, graphene
possesses excellent properties of intrinsic physics and chemistry
[14,15]. For example, it has an excellent theoretical specific sur-
face area (2360 m2 g−1 ) [16], high intrinsic mobility (200000 cm2 v
−1 s −1 ) [17], as well as wonderful mechanical strength. What is

sources of flexible electronic devices [7,8]. Therefore, fabricating
the flexible power system with light weight, long lifespan and high
charge/discharge rates is critical for the development of wearable
electronics.
Electrochemical capacitors, which are also called supercapac-
itors (SCs), store energy by ion adsorption/desorption at the
interface of electrode and electrolyte or by redox reactions at
surface/near-surface of electrode materials [9,10]. In comparison
to conventional Li-ion batteries, SCs have higher security, longer
cycle life, higher power density and faster charge/discharge rates.
Thus SCs are more suitable for wearable electronics as power
system than batteries. In SCs, electrode materials are researched
∗ Corresponding author.
E-mail address: cyjia@uestc.edu.cn (C. Jia).
more, the intrinsic properties of graphene also endow graphene
films with outstanding mechanical strength and chemical stabil-
ity, indicating that their potential applications as flexible electrode
materials [18,19]. Effective efforts for preparing graphene films
were also reported in recent years. Chen et al. reported the chemi-
cal vapor deposition (CVD) prepared graphene films, which possess
high specific capacitance and electrical conductivity [20]. However,
CVD method requires harsh conditions and high-cost to be scaled
up. Many methods for preparing graphene films are therefore pro-
posed to prepare graphene oxide (GO) films. The typical methods
include vacuum filtration [21], spray-coating [22], spin-coating
[23], blade-casting technique [24]. The prepared GO films were
further reduced to the reduced GO (rGO) films by the reduction
process. These approaches for constructing free-standing ultrathin
GO films, however, have the cumbersome process for practical
application, which have to undergo the delamination of the films

http://dx.doi.org/10.1016/j.apsusc.2017.06.074
0169-4332/© 2017 Elsevier B.V. All rights reserved.
976 Y. Zhu et al. / Applied Surface Science 422 (2017) 975–984

from the substrate, and sometimes even need to apply electro-
chemical delamination or bubble delamination methods to obtain
high-integrity films [25–27].
In this work, ultrathin free-standing GO films were prepared
by the method of foam films without any substrates. This method
not only simplifies the process of fabricating free-standing films,
but also is a low-cost and facile operation. Furthermore, thick-
ness of the GO films also can be regulated by simply changing
the concentration of the surfactant. The prepared GO films have
excellent mechanical properties. The rGO films, obtained from the
GO films by chemical reduction process, also have extremely high
electrical conductivity. Meanwhile, the SCs based on the rGO films
exhibit excellent specific capacitance, and the flexible all solid state
supercapacitors (FSSCs) based on the rGO films also have impres-
sive capacitance performance, great electrochemical stability and
excellent mechanical flexibility.
2.4. Preparation of the FSSCs
PVA-KOH gel electrolyte was synthesized simply by a physical
mixing method. At first, 1 g PVA particles was added into 10 mL
deionized water. Subsequently, the mixture was stirred contin-
uously for 1 h at 85 ◦ C to form a clear solution. Then 1 g KOH
aqueous solution (6 M) was added into PVA solution and stirred
30 mins at room temperature to form PVA-KOH gel electrolyte.
The electrodes of devices were prepared through the rGO films
with 10 mm × 10 mm pressed on nickel foam by using pressure
of 20 MPa. Finally, PVA-KOH gel electrolyte was spread uniformly
on the electrodes. After evaporating for 1 h at room temperature,
two electrodes were completely overlapped and the system was
packaged by using polyethylene terephthalate (PET).
2.5. Material characterization

2. Materials and experimental Surface morphologies of the samples were investigated by

scanning electron microscope (SEM, JEOL JSM-7600F). Analysis of
2.1. Materials
element content was carried out by XPS measurements (Kratos
XSAM800). Structure of the samples was investigated via Raman
Natural graphite was purchased from Shanghai Hua Yi Group
spectroscope (WITec Alpha 300) using 532 nm laser and X-ray
Hua Yuan Chemical Industry Co. Ltd. (Shanghai, China). Hexadecyl
diffraction (SHIMADZU XRD-7000) using Cu Ka radiation. The sur-
trimethyl ammonium bromide (CTAB, 99%) was purchased from
face roughness and microstructure of samples were characterized
Aladdin Industrial Corporation. Polyvinyl alcohol (PVA, 98–99%
by atomic force microscope (AFM, Bruker instruments Dimension
hydrolyzed, medium molecular weight) was purchased from Alfa
Edge) with a silicon tip in tapping mode. Sheet resistance of the
Aesar (USA). Other chemical reagents were purchased from China
samples was tested by a standard four-point probe (MODEL 280)
as reagent grades and used without further purification.
method, and volume conductivity was calculated based on Eq.
2.2. Preparation of the GO films (1). Mechanical strength of the samples with rectangular strips of
5 mm × 20 mm was tested by using an INSTRON Universal Testing
The graphite oxide was synthesized from natural graphite via Machine with a constant loading rate of 0.5 mm min−1 .
1  
modified Hummers method [28]. Then graphite oxide was dis-
persed into deionized water and sonicated for 30 min at room ␴= Scm−1 (1)
Rs t
temperature to form GO suspension of 20 mg mL−1 .
Subsequently, 3 mL of CTAB (0.1 mg mL−1 ) was poured into where Rs is sheet resistance ( sq−1 ), t is thickness of the samples
20 mL GO suspension (20 mg mL−1 ). After the suspension was (cm).
stirred for 5 min, a small amount of GO suspension was spread onto
Teflon substrate by using dropper. Then copper circle was placed 2.6. Electrochemical measurements
on Teflon, followed by slowly move of copper circle parallel to the
substrate. After copper circle was moved from the suspension, a Electrochemical performance of the supercapacitors, such as
small amount of GO suspension was captured to the template of cyclic voltammetry (CV), galvanostatic charge-discharge (GCD),
copper circle. Finally, the GO films were obtained by evaporating and electrochemical impedance spectroscopy (EIS), were tested
the water of captured GO suspension in air at room temperature via electrochemical working station (CHI660E). Gravimetric capac-
(the preparation process as shown in Fig. 1a). Additionally, the GO itance (Cm ) of the rGO films was obtained from GCD curves by
films with different thicknesses can be obtained by adding different calculating based on Eq. (2). Areal capacitance (CA ) and volumetric
concentrations of CTAB into GO suspension in the above process. capacitance (Cv ) of the supercapacitors were obtained from GCD
curves by calculating based on Eq. (3) and (4), respectively. Energy
2.3. Preparation of the rGO films density (ED ) and power density (PD ) of the supercapacitors were
obtained via calculating based on Eqs. (5) and (6), respectively.
2.3.1. Vapor-phase reduction of the GO films
The GO films were putted into 300 mL sealed jar containing 3 mL 4It  
Cm = Fg −1 (2)
HI (57 wt% in H2 O) and 6 mL CH3 COOH (99.5 wt%) (HI/AcOH) and mV
then the sealed jar was placed into oven with 60 ◦ C for 10 h [29]. It  
At this point, the color of the GO films changed from golden yellow CA = Fcm−2 (3)
AV
to black, indicating that the GO films were reduced. Subsequently,
It  
the rGO films were rinsed with anhydrous ethanol for three times. Cv = Fcm−3 (4)
Finally vapor-phase reduced GO films (V-rGO) were dried at room VV
temperature. 2
Cv Vmax  
ED = Whcm−3 (5)
7200
2.3.2. Liquid-phase reduction of the GO films
3600ED  
The GO films were transferred into the mixture solution com- PD = Wcm−3 (6)
t
prised of 3 mL HI and 6 mL AcOH. Then the reaction system was
sealed and placed into oven with 60 ◦ C for 2 h. Subsequently, the where m is total mass of active material (g), A is area of device (cm2 ),
rGO films were rinsed with anhydrous ethanol for three times. The V is total volume of device (cm3 ), I is galvanostatic discharging cur-
final liquid-phase reduced GO films (L-rGO) were dried at room rent (A), t is discharging time (s), V is voltage window (V), Vmax
temperature. is operation potential (V).
 Y. Zhu et al. / Applied Surface Science 422 (2017) 975–984 977

Fig. 1. (a) Preparing procedure of the GO films. (b) Formation process of the free-standing ultrathin GO films. (c) Different shapes of the GO films. (d-f) Cross-sectional SEM
images of the GO films with different thicknesses.

3. Results and discussion
3.1. Preparation of the GO films
In this paper, the GO films were fabricated via foam film method
[30,31]. First, thin foam films, which are the sandwich structure
composed of the water core between amphipathic molecules with
hydrophobic groups outward, are obtained via the holes template
[31]. Then, the embedded water in the thin foam films is removed
via the evaporation in air, followed by the self-assembly of the
amphipathic molecules to form the dried foam films. However, for
GO flakes, which are 2D nanosheets with the amphiphilic charac-
ter, are different from conventional surfactant molecule composed
of hydrophilic and hydrophobic groups [32]. Thus a small amount
of surfactant is still added into GO suspension in order to boost
the stability of the bubble wall [33]. As shown in Fig. 1b, the GO
978 Y. Zhu et al. / Applied Surface Science 422 (2017) 975–984
Fig. 2. (a–c) Cross-sectional SEM image of the GO, L-rGO and V-rGO films. (d-f) SEM image of the GO, L-rGO and V-rGO films.
Table 1
Different concentrations of CTAB and the corresponding areal density of the rGO
films.
CTAB concentration (mg mL−1 ) Areal density (mg cm−2 )
0.1 1.07
0.3 0.84
0.5 0.45
films are formed via the evaporation caused self-assembly of the GO
flakes. The foam film method has some distinct advantages of low-
cost, low-energy consumption and facile operation. Meanwhile, we
can also prepare the GO films directly with the arbitrary shapes to
satisfy practical application (Fig. 1c and Fig. S1), and the holes tem-
plates can be reused for preparation of the same shape films. More
interestingly, the thickness of GO films were regulated by chang-
ing the concentration of CTAB ranging from 0.1 to 0.5 mg mL−1 . As
shown in Fig. 1d-f, the GO films fabricated with concentrations of
CTAB of 0.1, 0.3, and 0.5 mg mL−1 have the corresponding thick-
nesses of ∼4.5, ∼1.5 and ∼1.0 ␮m, respectively (areal densities of
the corresponding rGO films are presented in Table 1). This result
strongly suggests that the thickness of the GO films reduces with
the increasing concentration of CTAB within a certain range. In gen-
eral, surface tension of the solution decreases and the viscosity of
the solution increases with the increasing concentration of CTAB in
the studied range [34]. For this reason, the holes template captured
GO suspension reduced with the increasing concentration of CTAB
in a certain range, which eventually results in the decrease of the
GO film thickness.
3.2. Microstructure characterizations
Chemical reduction is a low-cost and effective method to reduce
the GO films. In this paper, the rGO films were obtained via reducing
GO films with HI/AcOH. The cross-sectional SEM images (Fig. 2a-c)
show that L-rGO and V-rGO films compared with GO films pos-
sess obvious hierarchical structure, which is beneficial to solution
Table 2
The element content and the ratio of carbon (C) and oxygen (O).
Samples C (%) O (%) C/O
GO 63.94 36.06 1.77
V-rGO 82.46 17.54 4.70
L-rGO 87.86 12.14 7.24
diffusion, since the diffusion layer thickness range from several
micrometers to dozens of micrometers in electrochemical reactions
[35]. Fig. 2d-f shows that the surface of GO film has numerous wrin-
kles, but the surface of rGO film emerges several ripples and slight
wrinkles. Meanwhile, the surface roughness of GO and rGO films
were also characterized by AFM, and the characterization results
show that the surface roughness of GO film is obvious higher than
that of rGO film (corresponding data and discussion were shown in
the Supplementary Materials). This phenomenon may be caused by
the decomposition of oxygen functional groups and the formation
of the structural defects [24,36–38].
XPS technique also provide the information of element content,
which is helpful for studying the reduction degree of the GO films.
Fig. 3a shows that intensity of C1 s peak in the GO films, which has
distinctly increased while intensity of O1 s peak decreased after the
reduction process. The ratio of carbon and oxygen (C/O) content
was obtained via calculating the ratio of C1 s and O1 s peak area,
as shown in Table 2. For the GO films, the ratio of C/O increases
from 1.77 to 4.70 after the vapor-phase reduction process, indi-
cating that some oxygen functional groups were removed [39].
Relative to vapor-phase reduction, the ratio of C/O increased to
7.24 via the liquid-phase reduction process, suggesting that the
reduction degree of the GO films by liquid-phase process is higher
than that of vapor-phase process. In addition, Fig. 3b shows that
high resolution C1 s peak of the GO films consist of two main
peaks at 284.5 eV and 286.8 eV, corresponding to C C/C C and
C O C/C OH, respectively [40]. After the reduction process, the
peak of C C/C C becomes the only main peak, suggesting the elimi-
 Y. Zhu et al. / Applied Surface Science 422 (2017) 975–984
Fig. 3. (a) XPS spectra of the GO, V-rGO and L-rGO films. (b) High-resolution C1 s spectra of the GO, V-rGO and L-rGO films. (c) XRD patterns of the GO, V-rGO and L-rGO
films. (d) Raman spectra of the GO, V-rGO and L-rGO films.
nation of some oxygen functional groups and the restoration of the
most of graphene networks. Moreover, the intensity of C C/C C
peak in L-rGO films is also higher than that of V-rGO films, demon-
strating that the reduction degree of liquid-phase process is higher
than that of vapor-phase process.
Because XPS technique can only detect a few nanometers depth
of the samples, the information of element content reveals only
the change of GO film surface [41]. Thus it is necessary to use XRD
technique to investigate the internal micro-structure of the sam-
ples. Fig. 3c shows that XRD pattern of the GO films presents an
obvious (001) peak at 8.96◦ corresponding to d-spacing of ∼9.86 Å,
whose interlayer spacing is distinctly larger than that of graphite
(d-spacing: ∼3.34 Å) due to the presence of the abundant oxygen
functional groups and the intercalated water molecules between
layers [29,42]. XRD pattern of V-rGO films not only has a (001) peak
at 10.18◦ (d-spacing: ∼8.68 Å), but also has an broad (002) peak at
24.56◦ (d-spacing: ∼3.62 Å), which indicating that the part decom-
position of oxygen functional groups of the GO films and results in
the different interlayer distances [41]. L-rGO films have only a broad
(002) peak at 24.68◦ corresponding to d-spacing of ∼3.6 Å, sug-
gesting that the GO films were deeply reduced. And the d-spacing
of L-rGO films is slightly larger than that of graphite due to the
residual oxygen functional groups or the structural defects [39]. In
addition, structural characterization of the GO and rGO films was
also investigated via Raman spectroscopy. Raman spectra (Fig. 3d)
of the GO films present two main peaks at ∼1344 and ∼1577 cm−1 ,
corresponding to D and G bands, respectively. After the chemical
reduction, the intensity ratio of D and G bands (ID /IG ) did increase
notably, suggesting that the increase of structural defects or degree
of disordered sp2 domains in the rGO films [35].
3.3. Mechanical strength and electrical conductivity
With the concentration of CTAB aqueous solution is
0.1 mg mL−1 , the GO films exhibit outstanding mechanical
979
properties, which can support a one-yuan coin (Fig. 4c). Fig. 4a-b
shows that stress-strain curves of the GO films and the correspond-
ing L-rGO films. The GO films possess greater Young’s modulus
(∼5.8 GPa) and tensile strength (∼96.4 MPa) than those of the
corresponding L-rGO films (Young’s modulus and tensile strength
of L-rGO films are ∼2.8 GPa and ∼54.7 MPa, respectively). The
reason of degraded mechanical properties of L-rGO films due to
the functional groups on the GO nanosheets can bind individual
sheets together, which leads that GO films are stiffer, denser
and stronger than rGO films [43]. In addition, the increase of
the structural defects also results in the decline of mechanical
properties of rGO films [44].
L-rGO films have excellent electrical conductivity of
∼172 S cm−1 , which is equivalent to the reported reduced graphene
oxide films [24,45,46]. For example, Kumar et al. reported that
reduced graphene oxide thin films exhibit electrical conductivity
of ∼152 S cm−1 [45] and flexible porous graphene film shows
electrical conductivity of 1.12 S cm−1 [46].
3.4. Electrochemical properties
3.4.1. Electrochemical properties of the SCs
Electrochemical properties of the rGO films in symmetrical SCs
were investigated using 6 M KOH aqueous solution as electrolyte.
First, capacitance performance of V-rGO films was investigated
with different thicknesses. Fig. 5a shows CA of the SCs based on
V-rGO films, which decreases with the increase of concentration
of CTAB. However, Cm of V-rGO films almost remain unchanged
(Fig. 5b). This phenomenon reveals that the thickness of the films
could be regulated by changing the concentrations of CTAB (Fig. 1d-
f). Meanwhile, there are almost no “dead weight” in electrode
materials for the SCs when thickness of the film increases in this
studied range.
980 Y. Zhu et al. / Applied Surface Science 422 (2017) 975–984

Fig. 4. (a–b) Stress-strain curves of the GO and L-rGO films. (c) Optical image of a one-yuan coin supported by the prepared GO films.

Based on the above results, it is clearly demonstrated that V-rGO
films with 0.1 mg mL−1 CTAB possess the best capacitance per-
formance among the different concentration of CTAB. In addition,
the GO films with 0.1 mg mL−1 CTAB possess excellent mechani-
cal strength that can withstand the liquid phase reduction process.
Thus we further investigated capacitance performance of the SCs
based on L-rGO films with 0.1 mg mL−1 CTAB. Fig. 5c shows that
the shape of CV curves of device based on L-rGO films is better
than that of the device based on V-rGO films, which is due to the
higher reduction degree of liquid-phase reduction compared to that
of vapor-phase reduction. Moreover, the CV curves are the near-
rectangular shapes with scan rates of 10, 20, 50, 100 and 200 mV s−1
at the potential window ranging from 0 to 1 V, indicating L-rGO
films possess the capacitance characteristic of electronic double
layer. In addition, the excellent current response rate to voltage
reversal at end potential of CV curves demonstrates that the low
internal resistance of the device, which can be attributed to the
high conductivity of the L-rGO films and the fast ion diffusion in
electrode material [47,48]. The shape of GCD curves is nearly sym-
metrical triangle, as shown in Fig. 5d, also suggesting that L-rGO
films exhibit ideal capacitive properties and high charge mobility.
In addition, EIS of the SCs based L-rGO films is also important for in-
depth research of electrochemical properties. Nyquist impedance
curve of the SCs based L-rGO films is comprised of a small semi-
circle in the high frequency region and a vertical line in the low
frequency region (Fig. 5e). The inset in Fig. 5e shows that the inter-
cept of real axis (Z’), corresponding to internal resistance of the SCs,
is ∼0.55 , which also demonstrates that L-rGO films possess excel-
lent electrical conductivity. The Warburg region of 0.68–12.1 Hz is
relatively short, indicating the fast ions diffusion in electrode mate-
rials, which is attributed to the presence of hierarchical structure.
As shown in Fig. 5f, CA of the SCs based on L-rGO films achieves
 Y. Zhu et al. / Applied Surface Science 422 (2017) 975–984 981

8
(a) 4 (b)
6
Current density (mA cm-2)
4

Current density (A g-1)

2
2
0 0
-2
-4 -2
-6 -1 -1
0.1 mg mL 0.1 mg mL
-8 -1
0.3 mg mL
-1 -4 0.3 mg mL
-1 -1
-10 0.5 mg mL 0.5 mg mL

1.0 0.8 0.6 0.4 0.2 0.0 1.0 0.8 0.6 0.4 0.2 0.0
Potential (V) Potential (V)

-2
1.0 (d)
(c) 0.2 mA cm
12 -2
0.4 mA cm
Current density (mA cm-2)

-2
8 1 mA cm
0.8 2 mA cm
-2

Potential (V)
4
0.6
0
10 mV s
-1 0.4
-4 -1
20 mV s
-1
-8 50 mV s 0.2
-1
100 mV s
-1
-12 200 mV s 0.0
1.0 0.8 0.6 0.4 0.2 0.0 0 100 200 300 400 500 600 700 800
Potential (V) Time (s)

400 60
)
-2

50 (f)
Capacitance (mF cm

(e) 30
40
25 30
300
20
20
-Z'' (ohms)

10
-Z'' (ohms)

15
0
200 0 2 4 6 8 10 12
10 -2
Current density (mA cm )
5 120
Capacitance (F g )

100
-1

100 0

0 5 10 15 20 25 30
80
Z' (ohms) 60
0 40
20
0 100 200 300 400 500
0
Z' (ohms) 0 1 2 3 4 5 6
-1
Current density (A g )

Fig. 5. (a–b) CV curves at 100 mV s−1 of the SC based on V-rGO films with different concentrations of CTAB. (c) CV curves of the SCs based on L-rGO films with potential
window ranging from 0–1 V at different scan rates. (d) GCD curves of the SC based on L-rGO films at different current densities. (e) Nyquist plot of the SC based on L-rGO
films. (f) CA and the Cm of the SC at different current densities.

∼56 mF cm−2 at 0.2 mA cm−2 , and still possesses ∼40 mF cm−2 curves of the FSSC with scan rates ranging from 10 to 200 mV s−1 at
at 10 mA cm−2 (Fig. 5f). It suggests that the devices possesses an the potential window of 0 ∼ 1 V are quasi-rectangular, as shown in
impressive rate capability. In addition, Cm of L-rGO films is also up Fig. 6a. Compared with the shape of CV curves at low scan rates, the
to ∼111 F g−1 at 0.1 A g−1 (∼80 F g−1 at 5 A g−1 ), which is even com- shapes of CV curves at high scan rates such as 200 mV s−1 distorts
parable with the reported literature for graphene-based composite slightly, which is due to the ions from the interface of the electrode
materials [35,49,50]. and electrolyte have sufficient time to infiltrate into the interlay-
ers of L-rGO films when scan rate is low. But when scan rates is
rising, the diffusion time of the ions was shortened, which causes
3.4.2. Electrochemical properties of the FSSCs
that some ions can’t migrate to the effective interlayers of the L-
For the reason of encapsulating difficulty and possible elec-
rGO films, eventually resulting in the distortion of CV curves shape
trolyte leakage of SCs with liquid electrolyte, the FSSCs were
and the slightly decrease of the device capacitance [47,48,51]. For
packaged by using PVA-KOH gel electrolyte in this work. The CV
982 Y. Zhu et al. / Applied Surface Science 422 (2017) 975–984

-3
0.6 (a) (b) 12 mA cm
Current density (mA cm-3) 1.0 25 mA cm
-3

-3
60 mA cm
0.4 -3
120 mA cm
0.8
0.2

Potential (V)
0.6
0.0

-0.2 -1
0.4
10 mV s
-1
20 mV s
-0.4 -1
50 mV s 0.2
-1
100 mV s
-0.6 200 mV s
-1

0.0
1.0 0.8 0.6 0.4 0.2 0.0 0 100 200 300 400 500 600
Potential (V) Time (s)

400 3000
(c) (d)
30

Specific capacitance (mF cm-3)

25 2500
300
20
-Z'' (ohms)

2000
-Z'' (ohms)

15

200 10 1500
5

0 1000
100
0 5 10 15 20 25 30
Z' (ohms) 500
0
0
0 100 200 300 400 500 0 100 200 300 400 500 600 700
Z' (ohms) Current density (mA cm-3)
0
10
(e)
(f)
100
Energy density (mWh cm-3)

Capacitance retention (%)

This work
80
Carbon fiber-FASC
ref.54
Carbon/MnO2-FSSC 60
ref.53

-1
10 Graphene-FSSC 40
ref.24

20

1 2 3
10 10 10 0
Power density (mW cm-3) 0 2000 4000 6000 8000 10000
Cycle numbers

Fig. 6. (a) CV curves of the FSSC based on L-rGO films at different scan rates. (b) GCD curves of the FSSC based on L-rGO films at different current densities. (c) Nyquist plot
of the FSSC based on L-rGO films. (d) Cv of the FSSC at different current densities. (e) Ragone plot of the FSSC. (f) Cycling performance of the FSSC.

the GCD curves of the devices (Fig. 6b), the charging curves and and Cv of the FSSCs still remain ∼1607 mF cm−3 at current den-
the discharging curves are almost symmetrical, exhibiting excel- sity of 613 mA cm−3 , indicating that the device possesses high rate
lent capacitive characteristics. In addition, according to EIS of FSSCs capability. Ragone plot is also great important for estimating over-
(Fig. 6c), the intercept of Nyquist impedance curves in real axis all performance of the FSSCs. As shown in Fig. 6e, ED of the FSSCs
shows that the internal resistance of the device is ∼1 , which is up to 0.39 mWh cm−3 with PD of 6.13 mW cm−3 , which is even
is higher than the internal resistance of the SCs with liquid elec- superior to the values reported for some solid-state SCs, such as
trolyte. This can be attributed to the tardy diffusion rate of the graphene paper-based FSSCs (0.12 mWh cm−3 ) [24], graphite/PANI
electrolyte in the solid-state device [51]. Moreover, the Warburg paper-based SCs (0.32 mWh cm−3 ) [52], carbon/MnO2 -based FSSCs
region (from 0.46 to 12.1 Hz) is slightly longer than that of the SCs (0.22 mWh cm−3 )[53] and H-TiO2 @MnO2 //H-TiO2 @C-based FASCs
with liquid electrolyte, also demonstrating that slower ions diffu- (0.3 mWh cm−3 ) [54]. What’s more, when PD of the FSSCs achieves
sion in the device with gel electrolyte. Fig. 6d shows Cv of the device 307 mW cm−3 , ED still remains at 0.22 mWh cm−3 . In addition,
at different current densities, which exhibits impressive specific the FSSCs has also excellent cycle stability performance and high
capacitance of ∼2810 mF cm−3 at current density of 12 mA cm−3 , degree reversibility according to the CV measurement with poten-
 Y. Zhu et al. / Applied Surface Science 422 (2017) 975–984
Fig. 7. (a) CV curves at 20 mV s−1 of the FSSC under the different bending angles. (b) Capacitance retention of the FSSC at different bending angles. (c) CV curves of the FSSC
after different bending cycles. (d) Capacitance retention of the FSSC after different bending cycles.
tial range of 0 ∼ 1 V at scan rate of 500 mV s−1 , which still possesses
high capacitance retention of 81.4% after 10000 cycles (Fig. 6f).
Considering the practicability of flexible devices, it is essential
that electrochemical properties of the devices remain unchanged
at the different bending states. Fig. 7a shows the CV curves of the
FSSCs under different bending states at scan rate of 20 mV s−1 ,
the shape of CV curves under different bending states exhibits
no obvious change. Interestingly, capacitance of the FSSCs has
slightly increased at bending angle of 100◦ (Fig. 7b), which may
be attributed to the convenient charge transfer because of the
decreased distance between two electrodes at bending state.
Furthermore, the flexibility of the FSSCs was further tested via
measuring capacitance retention of the FSSCs after repeated bend-
ing with bending angle of 180◦ . Fig. 7c shows that the shape
of CV curves is still basically superposition after different bend-
ing times. Moreover, capacitance retention of the FSSCs is up to
90.4% after continuous 300 times bending cycles (Fig. 7d), which
is slightly better than the values reported for flexible supercapaci-
tor, such as the CNT/PPy/HQ-based FSSC (90% after 100 cycles) [55],
graphene paper-based FSSCs (84.6% after 100 cycles) [24], conduc-
tive graphene-cotton fabric-based FSSCs (90.5% after 100 cycles)
[48]. These results demonstrate that the FSSCs possess great elec-
trochemical stability and excellent mechanical flexibility.
4. Conclusion
In summary, foam film technique was applied to prepare GO
films, whose thickness can be regulated by changing the con-
centration of CTAB. The prepared GO films possess excellent
983
mechanical strength (Young’s modulus and tensile strength are
5.8 GPa and 96.4 MPa, respectively). After liquid-phase reduction
process, L-rGO films exhibit electrical conductivity of ∼172 S cm−1 .
In addition, the SCs based on L-rGO films exhibit CA of ∼56 mF
cm−2 at 0.2 mA cm−2 , and Cm of L-rGO films is up to ∼111 F g−1
at 0.1 A g−1 . The FSSCs based on L-rGO films also show impressive
capacitance performance of ∼2810 mF cm−3 at 12 mA cm−3 . More
importantly, the capacitance value of FSSC still maintains 90.4% of
its initial capacity after bending 300 times bending cycles with
bending angle of 180◦ , demonstrating that the device possesses
strong practicability and reliability. Therefore, the FSSCs based on
the prepared rGO films via foam film method are well suited for
applications in wearable electronic as power system.
Acknowledgements
We are grateful to the National Natural Science Foundation
of China (Grant Nos. 21572030, 21272033, 21402023) and Tech-
nology Innovative Research Team of Sichuan Province of China
(No.2015TD0005) for financial support.
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