sensors

Article
Multifunctional Graphene-Based Composite Sponge
Xu Cui 1 , Jiayu Tian 2 , Yin Yu 2 , Aron Chand 2 , Shuocheng Zhang 2 , Qingshi Meng 2 ,
Xiaodong Li 2, * and Shuo Wang 2, *
1 College of Civil Aviation, Shenyang Aerospace University, Shenyang 110136, China; cuixu@sau.edu.cn
2 College of Aerospace Engineering, Shenyang Aerospace University, Shenyang 110136, China;
tianjiayu@email.sau.edu.cn (J.T.); yuyin@email.sau.edu.cn (Y.Y.); aaronchand714@yahoo.com (A.C.);
zhangshuocheng@email.sau.edu.cn (S.Z.); mengqingshi@sau.edu.cn (Q.M.)
* Correspondence: lixiaodong@sau.edu.cn (X.L.); shuowang@sau.edu.cn (S.W.)




Received: 14 October 2019; Accepted: 2 January 2020; Published: 7 January 2020


Abstract: Although graphene has been widely used as a nano-filler to enhance the conductivity of
porous materials, it is still an unsatisfactory requirement to prepare graphene-based sponge porous
materials by simple and low-cost methods to enhance their mechanical properties and make them
have good sensing and capacitive properties. Graphene platelets (GnPs) were prepared by the
thermal expansion method. Graphene-based sponge porous materials were prepared by a simple
method. A flexible sensor was formed and supercapacitors were assembled. Compared with other
graphene-based composites, the graphene-based composite sponge has good electrical response
under bending and torsion loading. Under 180◦ bending and torsion loading, the maximum resistance
change rate can reach 13.9% and 52.5%, respectively. The linearity under tension is 0.01. The
mechanical properties and capacitance properties of the sponge nanocomposites were optimized
when the filler fraction was 1.43 wt.%. The tensile strength was 0.236 MPa and capacitance was
21.4 F/g. In cycles, the capacitance retention rate is 94.45%. The experimental results show that
the graphene-based sponge porous material can be used as a multifunctional flexible sensor and
supercapacitor, and it is a promising and multifunctional porous nanocomposite material.

Keywords: graphene; sponge porous materials; multifunctional; flexible sensor; supercapacitor

1. Introduction
In recent years, porous materials have been widely used in superhydrophobic materials, adsorption
materials, electronics, and other fields owing to their porous, loose, and flexible characteristics [1–3].
Conductive porous materials have unique porous structure and demonstrate excellent electrical
conductivity, enabling them to have a broad prospective application in various fields such as flexible
sensing, electrochemistry, and supercapacitors [4–6]. However, conductive porous materials have
their own limitations such as uneven pore size distribution and weak adhesion between the filler and
pore structure. The porous materials prepared by pyrolysis [7], polymer solidification [8], or aerogel
preparation [9] will produce low porosity and weak adhesion [10–12]. The preparation process of
porous materials is complex, and their properties may be unstable. Compared with other porous
materials, the pore distribution of sponge is uniform and its structure is stable [13].
In order to improve the conductivity and capacitance of porous sponge materials, conductive fillers
are needed [14,15]. Among the commonly used carbon-based conductive fillers, graphene has been the
most preferable nanofiller and has been extensively studied for its excellent electrical, mechanical [16–18],
and capacitive properties [19–21]. Graphene has also exhibited excellent compatibility with polymers,
making it one of the most promising candidates as nanofiller [22,23]. Graphene oxide and reduced
graphene oxide can improve their dispersion in solvents by modifying the surface of graphene

Sensors 2020, 20, 329; doi:10.3390/s20020329 www.mdpi.com/journal/sensors

Sensors 2020, 20, 329 2 of 13

with functional groups, but their conductivity and structural stability are weaker than pristine
graphene [24–27]. Compared with graphene, carbon nanotubes generally have the disadvantage of
relatively weak ionic carrying capacity, which makes it difficult to improve the capacitive performance
of polymers [28]. Therefore, graphene is an ideal conductive filler for porous materials. It is worth
mentioning that graphene improves the capacitive properties of polymer very well. Graphene is
a monoatomic layer of SP2 carbon atom with two-dimensional hexagonal crystal structure (HCC).
Graphene is an ideal conductive filler for active materials of supercapacitors because of its strong ability
to carry ions, hence it has attracted extensive research interest in the field of supercapacitors [29–31].
The combination of porous materials and fillers will greatly improve the mechanical properties,
electrical conductivity and capacitance performance, which is worthy of further exploration [32–34].
However, there are still some unresolved problems. Some experiments have not studied the electrical
responses of porous nanocomposites under tension, compression, bending, and torsion [35,36]. Yu
Zhao et al. prepared flexible epoxy/Graphene platelets composite film using flexible curing agent J2000.
The film has high tensile sensitivity, but the electric response under bending load is relatively weak, and
the resistance change rate is 2% [37]. Yin Cheng, et al. developed a highly sensitive graphene-based
fiber, which can be used to detect tensile strain, bending and torsion. The maximum resistance
change rate of the graphene fiber can reach 140% when it is twisted in the anticlockwise direction, but
the maximum resistance change rate is 40% when it is twisted in the clockwise direction [38]. The
electrical response sensitivity of other types of graphene-based composite under bending and torsion
loading may be weaker than that of graphene sponge. In situ polymerization of graphene sponge
with manganese dioxide, poly (3,4-ethylenedioxythiophene), and carbon nanotubes can obtain high
specific capacitance. However, the specific capacitance of pure graphene sponge obtained by relevant
research is 9.78 F/g, so there is room for further improvement, and the study of capacitance properties
of graphene sponge with different filler components was lacking [39–41]. In this experiment, these
problems have been solved to a certain extent.
In this paper, a multifunctional flexible and conductive graphene-based sponge composite
material is introduced. GnPs were prepared by thermal-sonication approach. The effects of different
filler fractions on the mechanical and capacitive properties of nanocomposites were studied. The
electrical responses of nanocomposites under different loading conditions such as tension, compression,
bending, and torsion were tested. The electrical response of graphene sponge was measured when
the temperature changed. GnPs synthesized by thermal expansion method are cheap and have
good conductivity. The prepared sponge has good strength, sensing performance, and capacitance
parameters. Graphene-based sponge composites have broad application prospects in multi-functional
sensors and supercapacitors owing to their good versatility, easy production, and low cost.

2. Experimental Materials and Experimental Methods

2.1. Experimental Materials and Instruments

Asbury Carbons (Asbury, NJ, USA) kindly supplied graphite intercalation compound (GIC, 1721).
The sponge made of melamine with the density of 15–17 kg/m3 was provided by Xijie Co (Wuhan,
Hubei, China). The porosity was 88.725% ± 0.53%. Na2SO4 was purchased from Tianjin Hengxing
Chemical Reagent Manufacturing Co., Ltd. (Tianjin, China). All chemicals were used as received
without any further purification.
Scanning electron microscope (SEM) images of the graphene sponge were obtained by SU8010
(Tokyo, Japan). Transmission electron microscope (TEM) images of the GnPs were obtained by
JEOL JEM-2100 (Tokyo, Japan). Raman spectra of GnPs were characterized by Raman spectrometer
Avantes AvaRaman (The Netherlands). Tensile test measurement was performed using a uniaxial
tensile loading machine LTD GX-SF001 (Shenzhen, Guangdong, China). Fluke 2638A Hydra Series
III Data Acquisition System (Everett, WA, USA) constantly monitored the resistance of the graphene
sponge under different conditions. AnKe GDJS-408L high and low temperature test equipment is
Sensors 2020, 20, x FOR PEER REVIEW 3 of 13

responsible for providing temperature environment for the change of resistance of graphene sponge
Sensors 2020, 20, 329
with temperature. 3 of 13
Capacitive properties of graphene sponge were analyzed using an electrochemical
workstation ChenHua CHI660E B19038 (Shanghai, China).
responsible for providing temperature environment for the change of resistance of graphene sponge
2.2. Experimental Methods
with temperature. Capacitive properties of graphene sponge were analyzed using an electrochemical
A pieceChenHua
workstation of spongeCHI660E
(rectangular cuboids
B19038 of 6.0 cm
(Shanghai, × 2.0 cm × 0.3 cm) was used as the matrix of the
China).
composite material. Figure 1 shows the preparation method of 1.43 wt.% graphene sponge
2.2. Experimental Methods
nanocomposites. GnPs were added to acetone to form a colloidal solution, which was then
ultrasonicated
A piece offor 3 h, resulting
sponge (rectangularin the formation
cuboids of 6.0ofcm
a homogeneous
× 2.0 cm × 0.3GnPs solution.
cm) was Afterwards,
used as the matrixthe
of
sponge was soaked into the solution and simultaneously ultrasonicated for 10
the composite material. Figure 1 shows the preparation method of 1.43 wt.% graphene sponge h in order for the GnPs
to permeate completely
nanocomposites. GnPsinto weretheadded
spongetoskeleton.
acetoneThe composite
to form spongesolution,
a colloidal was driedwhich
in an oven
was at 80
then
°C for 5 h.
ultrasonicated for 3 h, resulting in the formation of a homogeneous GnPs solution. Afterwards,
Two sponge
the sponge electrodes
was soaked into the(6.0 cm × 2.0
solution andcm × 0.3 cm) were
simultaneously immersed infor1 10
ultrasonicated M hNa SO4 solution
in2order for the
overnight. Then, a sandwich structure was created by combining the two electrode
GnPs to permeate completely into the sponge skeleton. The composite sponge was dried in an oven sponges, two
at
pieces
◦ of platinum
80 C for 5 h. sheets as the current collectors, and a piece of filter paper as the separator.

Figure 1. The fabrication of multifunctional graphene sponge nanocomposites.

Figure 1. The fabrication of multifunctional graphene sponge nanocomposites.
Two sponge electrodes (6.0 cm × 2.0 cm × 0.3 cm) were immersed in 1 M Na2 SO4 solution
3. Results and
overnight. Then,Discussion
a sandwich structure was created by combining the two electrode sponges, two pieces
of platinum sheets as the current collectors, and a piece of filter paper as the separator.
3.1. Morphology of Graphene-Based Composite Sponges
3. Results and Discussion
Heat treatment of graphite intercalation compounds (GICs) to produce thermal shock will
immediately
3.1. Morphology convert the intercalants
of Graphene-Based into Sponges
Composite a large amount of gas, resulting in volume expansion.
Figure 2 shows the expansion process from graphite intercalation compounds to the TEM image of
Heat platelets.
graphene treatmentTheof graphite intercalation compounds
graphite intercalation compoundswere (GICs) to produce
heat-treated in thermal
a muffleshock will
furnace at
immediately convert the intercalants into a large amount of gas, resulting in volume
700 °C for about 1 min. This rapid thermal expansion converts the dense, disk-like graphite GICs into expansion.
Figure
worm-like2 shows the expansion
expanded graphiteprocess
flakes from graphite
consisting of intercalation compounds
loosely jointed, thin GnPs to the TEM
[42]. image of
Subsequent
graphene platelets. The graphite intercalation compounds were heat-treated in a muffle
processing such as ultrasonication separates stacked graphene layers until a few layers remain, which furnace at
700 ◦ C for about 1 min.
is specifically known as This rapid
GnPs. TEM thermal
image expansion
shows thatconverts the dense, disk-like
the microstructures of GnPsgraphite
have a GICs
large
into worm-like expanded graphite flakes consisting of loosely jointed, thin GnPs [42].
specific area and the platelets stack upon each other to promote electrical and thermal conduction. SubsequentIn
processing
addition, thesuch as ultrasonication
platelet separates stacked
edges are featureless and verygraphene layers
thin, thus until a few
possessing thelayers remain, which
characteristics of a
is specifically
monolayer known as GnPs. TEM image shows that the microstructures of GnPs have a large
graphene.
specific area and the platelets stack upon each other to promote electrical and thermal conduction.
In addition, the platelet edges are featureless and very thin, thus possessing the characteristics of a
monolayer graphene.
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Figure
Figure 2. Schematic of
2. Schematic of thermal
thermal expansion
expansion process
process of
of graphite
graphite intercalation
intercalation compounds. TEM,
compounds. TEM,
transmission electron microscope.
transmission electron microscope.

In Figure 3, GnPs demonstrate obvious absorptions at 1359 cm −1 , 1584 cm−1 , and 2723 cm−1 ,
In Figure 3, GnPs demonstrate obvious absorptions at 1359 cm−1, 1584 cm −1, and 2723 cm−1, which
2 resonance on an ordered
which correspond to D, G, and 2D bands, respectively. G band refers to sp
correspond to D, G, and 2D bands, respectively. G band refers to sp resonance on an ordered
2
graphitic lattice, while D band is activated from the first order scattering process of sp22 carbons owing
graphitic lattice, while D band is activated from the first order scattering process of sp carbons owing
to the presence of in-plane defects such as substitutional hetero-atoms, vacancies, grain boundaries, or
to the presence of in-plane defects such as substitutional hetero-atoms, vacancies, grain boundaries,
other defects, which might be sp3 hybridized carbon structure associated with the quantity of impurity
or other defects, which might be sp3 hybridized carbon structure associated with the quantity of
or oxidation degree.
impurity or oxidation degree.

G 2D
Relative intensity

ID/IG = 0.07

1400 1600 2400 2600 2800

Raman, cm-1

Figure 3. Raman Spectra of graphene platelets (GnPs).

Figure 4 shows a comparison of scanning electron microscopic images of different sponges.

The interconnected pores and Figurethe3.network structure
Raman Spectra of the sponge
of graphene is(GnPs).
platelets clearly visible in Figure 4(a1,a2).
Figure 4(a2) presents an extremely smooth surface which poses no barriers during GnPs’ deposition and
Figure 4morphology
the primary shows a comparison
of the spongeof scanning
structureelectron
remainsmicroscopic
unchanged after images of different
coating. Figure sponges. The
4(b1,b2,c1,c2)
interconnected
show the sponge pores and the network
morphology at fillerstructure
fraction of the1.43sponge
wt.%. isTheclearly visible sponges
graphene in Figureshown
4(a1,a2).
in
Figure 4(a2) presents
4(b1,b2) were an extremely
subjected to smooth
ultrasonicsurface
shock which poses for
treatment no barriers during4(b2)
10 h. Figure GnPs’ deposition
enlarges the
and the primary
representative areasmorphology
of Figure 4(b1)of the
at asponge structure remains
high magnification. The SEMunchanged
micrographsafter of
coating. Figure
the graphene
4(b1,b2,c1,c2)
sponge show
in Figure theshow
4(b2) sponge morphologydispersion
a homogeneous at filler fraction
of GnPsofon1.43the wt.%.
spongeTheporegraphene
surface, sponges
forming
shown in Figure 4(b1,b2) were subjected to ultrasonic shock treatment for 10
continuous electron pathways, which is essential for high performance electrodes. The quality ofh. Figure 4(b2) enlarges
the representative
GnPs’ coating can be areas of Figure
further improved4(b1)byatsonication
a high magnification.
during the dippingThe SEM micrographs
process. of the
The graphene
graphene
sponge sponge
shown in Figure
in Figure 4(c1)4(b2)
was show a homogeneous
subjected to ultrasonicdispersion of GnPs
shock treatment foron5 h.theThe
sponge
coating pore
of
surface, forming continuous electron pathways, which is essential for high performance
graphene platelets on the sponge skeleton in Figure 4(b2) is more uniform than that in Figure 4(c1), electrodes.
The the
and quality of GnPs’
amount coating platelets
of graphene can be further improved
attached by sonication
to the sponge skeleton during
is alsothe dipping
greater. Thisprocess. The
is because
graphene
the sponge
ultrasonic showntime
vibration in Figure
of the 4(c1) was subjected
graphene sponge shown to ultrasonic
in Figureshock4(c1) treatment
is shorter for
than5 that
h. The
in
coating of graphene platelets on the sponge skeleton in Figure 4(b2) is more
Figure 4(b2). It is difficult to make more graphene platelets adhere to the sponge skeleton with uniform than that in
Figure 4(c1), and the amount of graphene platelets attached to the sponge skeleton is also greater.
 Sensors 2020, 20, x FOR PEER REVIEW 5 of 13
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This is because the ultrasonic vibration time of the graphene sponge shown in Figure 4(c1) is shorter
than that in Figure 4(b2). It is difficult to make more graphene platelets adhere to the sponge skeleton
shorter ultrasonic concussion time, and the uniformity of coating is poor. The graphene sponge shown
with shorter ultrasonic concussion time, and the uniformity of coating is poor. The graphene sponge
in Figure
shown 4(c2) was subjected
in Figure 4(c2) was to ultrasonic
subjected shock treatment
to ultrasonic for 15 h.
shock treatment forIn
15Figure 4(c2), 4(c2),
h. In Figure the adhesion
the
and coating
adhesionuniformity
and coatingof graphene
uniformity of platelets
graphene on the sponge
platelets skeleton
on the sponge are also
skeleton are not
also as
notgood as as
as good that in
Figure 4(b2).
that This is
in Figure because
4(b2). the
This is graphene
because sponge insponge
the graphene Figurein4(c2) has4(c2)
Figure undergone a longer
has undergone ultrasonic
a longer
ultrasonic
vibration vibration
treatment than treatment than 4(b2).
that in Figure that inLong
Figure
time4(b2). Long time
ultrasound mayultrasound
lead to themay lead to the
exfoliation of some
exfoliation of some graphene platelets that have been coated on the skeleton.
graphene platelets that have been coated on the skeleton. Therefore, in this experiment, we chooseTherefore, in this
experiment,
10 h as we choose
the ultrasonic 10 h astime
treatment the ultrasonic treatment
of the graphene time of the graphene sponge.
sponge.

Figure 4. Scanning electron microscopic (SEM) images of the (a1,a2) pure sponge, (b1,b2) graphene
Figure
sponge with4. ultrasonic
Scanning electron microscopic
vibration for 10 h, (SEM)
(c1) images of the
graphene (a1,a2)with
sponge pure ultrasonic
sponge, (b1,b2) graphene
vibration for 5 h,
sponge with ultrasonic vibration for 10 h, (c1) graphene sponge with ultrasonic vibration for 5 h, and
and (c2) graphene sponge with ultrasonic vibration for 15 h.
(c2) graphene sponge with ultrasonic vibration for 15 h.
3.2. Mechanical Property
The tensile strength and elongation at break of sponges with different filler fractions are tested.
Figure 5a demonstrates changes in tensile strength of sponge nanocomposites with the increase of
GnPs filler fractions ranging from 0 wt.% to 2.32 wt.%. The maximum tensile strength of graphene
sponge has reached 0.236 MPa at 1.43 wt.% filler fraction, depicting an increase by 45% as compared
 specific surface area and interfacial structure, which can effectively prevent stress concentrations and
facilitate stress transfer across the interface under loading. However, the maximum tensile strength
at 2.32 wt.% filler fraction is 8.47% lower than that at 1.43 wt.% of filler fraction. This may be because
of the aggregation of graphene platelets with the increase of filler fraction, which leads to the decrease
of the structural and mechanical properties of the attached sponge skeleton, thus reducing the
Sensors 2020, 20, 329 6 of 13
maximum tensile strength of the graphene sponge.
As shown in Figure 5b, the elongation at break of sponge nanocomposites decreases with the
increase of graphene filler fraction. When the graphene filler fraction is 2.32 wt.%, the elongation at
with that of the pure sponge. This increment is the result of the ability of the GnPs to provide more
break of the sponge nanocomposites decreases by about 79.9%. This is attributed to the enhancement
specific surface area and interfacial structure, which can effectively prevent stress concentrations and
effect of graphene on the sponge matrix, which experienced hardening and toughening effects during
facilitate stress transfer
the accumulation ofacross the interface
nano-fillers. underGnPs
In conclusion, loading. However,
increase the strength
the tensile maximum andtensile strength
decrease the at
2.32 wt.% filler fraction is 8.47% lower
elongation of sponge nanocomposites. than that at 1.43 wt.% of filler fraction. This may be because of
the aggregation
By testing the mechanical properties, it was found that the sample with 1.43 wt.% filler fraction of
of graphene platelets with the increase of filler fraction, which leads to the decrease
the structural
obtained and mechanical
the best properties
tensile strength andofpreferable
the attached sponge Therefore,
elongation. skeleton, thus
1.43 reducing the maximum
wt.% samples were
selected
tensile strengthas the representative
of the graphene of the follow-up series of experiments.
sponge.

22

0.25
(a) 20

18
(b)

Breaking elongation (%)

Tensile strength (MPa)

16

14
0.20
12

10

8
0.15 6

0.10 0
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
Filler fraction (wt.%)
GnPs content (wt.%)

Figure 5. (a)5. The

Figure tensile
(a) The strength
tensile strengthunder
underdifferent
different filler fractions.(b)(b)
filler fractions. The
The breaking
breaking elongation
elongation with with
different fillerfiller
different fractions.
fractions.

As
3.3. shown in Figure 5b, the elongation at break of sponge nanocomposites decreases with the
Tensile Linearity
increase of graphene filler
Signal linearity is fraction. When
an important the graphene
parameter filler when
to measure fraction is 2.32 wt.%,
determining the the elongation
sensitivity of at
breakmaterials.
of the sponge nanocomposites decreases by about 79.9%. This is attributed to
The cross-sectional area of graphene sponge decreases during tension, but owing to thethe enhancement
effectspecial
of graphene on the
high elastic spongestructure
skeleton matrix, ofwhich experienced
sponge, the distancehardening
between and toughening
conductive paths effects during
decreases
the accumulation
and the paths of nano-fillers.
become In the
denser in conclusion,
process ofGnPs increase the
cross-sectional tensile These
shrinkage. strength andlead
factors decrease
to a the
decrease
elongation of in the resistance
sponge of graphene sponges during stretching.
nanocomposites.
By testing the mechanicalthe
As shown in Figure 6, strain increases
properties, it wasfrom
found0% that
to 15.27% and thewith
the sample rate of
1.43change
wt.%infiller
relative
fraction
resistance decreases uniformly with the increase of strain, which indicates that
obtained the best tensile strength and preferable elongation. Therefore, 1.43 wt.% samples were the material has a
selected
good linear response. The sensitivity coefficient (slope) is 0.01. On the basis of the aforementioned
as the representative of the follow-up series of experiments.
analysis, it can be highlighted that conductivity of the nanocomposite sponge is inversely related to
the cross-sectional
3.3. Tensile Linearity area of the specimen.
Signal linearity is an important parameter to measure when determining the sensitivity of materials.
The cross-sectional area of graphene sponge decreases during tension, but owing to the special high
elastic skeleton structure of sponge, the distance between conductive paths decreases and the paths
become denser in the process of cross-sectional shrinkage. These factors lead to a decrease in the
resistance of graphene sponges during stretching.
As shown in Figure 6, the strain increases from 0% to 15.27% and the rate of change in relative
resistance decreases uniformly with the increase of strain, which indicates that the material has a
good linear response. The sensitivity coefficient (slope) is 0.01. On the basis of the aforementioned
analysis, it can be highlighted that conductivity of the nanocomposite sponge is inversely related to
the cross-sectional area of the specimen.
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0.00 1.43wt%
0.00 1.43wt%
-0.05
-0.05

ΔR/R
-0.10

ΔR/R
-0.10

-0.15
-0.15
Slope：-0.01
Slope：-0.01
-0.20
-0.20

-0.25
-0.25-2 0 2 4 6 8 10 12 14 16
-2 0 2 4 Strain
6 8(%)10 12 14 16
Strain (%)
Figure 6. The stretch linearity at filler fraction of 1.43 wt.%.
Figure 6.
Figure Thestretch
6. The stretchlinearity
linearityat
atfiller
filler fraction
fraction of
of 1.43
1.43 wt.%.
wt.%.

3.4.
3.4.Electrical
ElectricalResponse
ResponsetotoBending
Bendingand andTorsion
Torsion
3.4. Electrical Response to Bending and Torsion
The
The produced
produced graphene-based
graphene-basedsponge spongealsoalsopossesses
possessesthethe ability
ability ofof sensing
sensing deformations
deformations such such
The produced graphene-based sponge also possesses the ability of sensing deformations such
as
as bending
bending and and twisting.
twisting. Figure
Figure77shows showsthe thechange
changein inresistance
resistanceat at different
different bending
bending angles
angles and
and
as bending and twisting. Figure 7 shows the change in resistance at different bending angles and
twist
twistangles.
angles.From
FromFigure
Figure7,7,ititcan
canbebeseen
seenthat
thatresistance
resistancechanges
changesat atlarge
largeangles
anglesare
are more
more sensitive
sensitive
twist angles. From Figure 7, it can be seen that resistance changes at large angles are more sensitive
than
than those
those atat small
small angles,
angles, whether
whether in in torsion
torsion or
or bending.
bending. This
Thismay
maybe bebecause
becauseof ofthe
the reduction
reduction in in
than those at small angles, whether in torsion or bending. This may be because of the reduction in
cross-sectional
cross-sectionalarea,area,enabling
enablingthe thegraphene
graphenesponge
spongestructure
structureto to become
become denser
denser as
as the
the bending
bending andand
cross-sectional area, enabling the graphene sponge structure to become denser as the bending and
twisting
twistingangle
angleincreases,
increases,which
whichmakes makesthe thesponge
spongesensitive
sensitivetowards
towardsdetecting
detectingangular
angulardeformations.
deformations.
twisting angle◦
increases, which makes the sponge sensitive towards detecting angular deformations.
Under
Under180°180 bending
bendingand andtorsion
torsionloading,
loading,the themaximum
maximumresistance
resistancechange
changerate ratecan
canreach
reach13.9%
13.9% and
and
Under 180° bending and torsion loading, the maximum resistance change rate can reach 13.9% and
52.5%,
52.5%,respectively.
respectively. Whether
Whetherthe thetwo
twoloads
loadsareare applied
applied clockwise
clockwise or or counter
counter clockwise,
clockwise, thethe electric
electric
52.5%, respectively. Whether the two loads are applied clockwise or counter clockwise, the electric
response
responseresults
results are
are consistent.
consistent. ItItcan
canbebeseen
seenthat
thatthe
thegraphene
graphenesponge
spongehas hasgood
goodelectrical
electricalresponse
response
response results are consistent. It can be seen that the graphene sponge has good electrical response
performance bendingand
performance under bending andtorsion.
torsion.ThisThischaracteristic
characteristic raises
raises thethe possibility
possibility of application
of application for
for this
performance under bending and torsion. This characteristic raises the possibility of application for
this graphene-based
graphene-based sponge
sponge in sensor
in the the sensor and material
and material healthhealth detection,
detection, especially
especially whenwhen the sensor
the sensorneeds
this graphene-based sponge in the sensor and material health detection, especially when the sensor
needs
to facetobending
face bending and torsion
and torsion and other and complex
other complex
loadingloading methods.
methods.
needs to face bending and torsion and other complex loading methods.
255
255
280
280

240 240
(Ω)
(Ω)

240 240
Resistance(Ω)
Resistance(Ω)

Resistance
Resistance

200
200
225
225

160
160

210
210 (a)
(a) 120
120
(b)
(b)
-20 0 20 40 60 80 100 120 140 160 180 200 -20 0 20 40 60 80 100 120 140 160 180 200
-20 0 20 40 60 80 100 120 140 160 180 200
Bending angle (°) -20 0 20 40 Twist
60 80angle
100 (°)
120 140 160 180 200
Bending angle (°) Twist angle (°)
(a)The
Figure7.7.(a)
Figure Theresistance
resistancevariations
variationswith
withdifferent
differentbending
bendingangles;
angles;(b)
(b)The
Theresistance
resistancevariations
variationswith
with
Figure 7. (a)
different Theangles.
twist resistance variations with different bending angles; (b) The resistance variations with
different twist angles.
different twist angles.
3.5. Pressure Sensitivity
Figure 8a shows the reaction time of the composite material under 4.9 KPa. It can be seen that
the composite material has a relatively short reaction time to pressure and has a certain pressure
sensitivity. Further, the loads of 2.45 KPa, 4.9 KPa, and 12.25 KPa were applied to the graphene
3.5. Pressure Sensitivity
Figure 8a shows the reaction time of the composite material under 4.9 KPa. It can be seen that
the composite material has a relatively short reaction time to pressure and has a certain pressure
sensitivity.
Sensors 2020, 20,Further,
329 the loads of 2.45 KPa, 4.9 KPa, and 12.25 KPa were applied to the graphene
8 of 13
sponge, respectively, and the corresponding resistance changes were tested. As shown in Figure 8b,
the resistance of the graphene sponge decreases under pressure. This is attributed to the compactness
sponge, respectively, and the corresponding resistance changes were tested. As shown in Figure 8b, the
of the sponge’s skeleton and the denser GnPs, resulting in more conductive channels and lower
resistance of the graphene sponge decreases under pressure. This is attributed to the compactness of
resistance under compression. Resistance variation reaches a maximum at 12.25 KPa load. It is worth
the sponge’s skeleton and the denser GnPs, resulting in more conductive channels and lower resistance
mentioning that the resistance value after unloading is close to the original resistance value, which
under compression. Resistance variation reaches a maximum at 12.25 KPa load. It is worth mentioning
reflects the good piezoelectric properties of graphene sponge and its application prospect as a
that the resistance value after unloading is close to the original resistance value, which reflects the
pressure sensor.
good piezoelectric properties of graphene sponge and its application prospect as a pressure sensor.

0.2
400
Response time of 4.9KPa
350
0.0

300

Resistance (Ω)
-0.2
250
ΔR/R

0.423s 0.353s 200

-0.4
150

-0.6 100

-0.8 (a) 50

0
(b)
0 5 10 15 20 25 30 35
10 20 30 40
Time (second) Time (second)

Figure 8.
Figure (a) Compression
8. (a) Compression response
response time;
time; (b)
(b) The
The pressure
pressure sensitivity
sensitivity testing
testing of
of the
the GnPs
GnPs sponge.
sponge.
3.6. Temperature Influence
3.6. Temperature Influence
Temperature is one of the factors that affect the conductivity of nanocomposites. The change
Temperature is one of the factors that affect the conductivity of nanocomposites. The change of
of ambient temperature will cause the change of semiconductor or conductor sensing parameters.
ambient temperature will cause the change of semiconductor or conductor sensing parameters.
Therefore, it is necessary to study the electrical response of graphene sponge under temperature
Therefore, it is necessary to study the electrical response of graphene sponge under temperature
change. In this experiment, the temperature range was 25 ◦ C~80 ◦ C, and the temperature rise rate of
change. In this experiment, the temperature range was 25 °C~80 °C, and the temperature rise rate of
the composite was 50 s/◦ C. It can be seen from Figure 9 that the resistance changes greatly with the
the composite was 50 s/°C. It can be seen from Figure 9 that the resistance changes greatly with the
increase of temperature in the process of temperature rise below 50 ◦ C. However, in the process of
increase of temperature in the process of temperature rise below 50 °C. However, in the process of
temperature rising above 50 ◦ C, the change of resistance is relatively gentle. It can be seen that the
temperature rising above 50 °C, the change of resistance is relatively gentle. It can be seen that the
sensitivity of the graphene sponge to temperature is relatively high in a specific temperature range,
sensitivity of the graphene sponge to temperature is relatively high in a specific temperature range,
which2020,
Sensors
may bex FOR
because of the porous heat conduction structure formed by the graphene sponge. The
which may20,be PEER of
because REVIEW
the porous heat conduction structure formed by the graphene sponge. 9 ofThe
13
electrical response of the graphene sponge at temperature needs further study.
electrical response of the graphene sponge at temperature needs further study.
800

700

600
Resistance (Ω)

500

400

300

200
20 30 40 50 60 70 80 90
Temperature (℃)
Figure 9. Change of resistance with temperature.
Figure 9. Change of resistance with temperature.

3.7. Supercapacitor
The mechanical robustness and the distinctively porous structure of the graphene sponge imply
that they have the potential to be used as electrodes for supercapacitor. The electrochemical
performances of graphene sponge were studied using cyclic voltammetry (CV) and the galvanostatic
Sensors 2020, 20, 329 9 of 13

Sensors
3.7. 2020, 20, x FOR PEER REVIEW
Supercapacitor 10 of 13

Thecapacitance
specific mechanical robustness
obtained fromand the
the distinctively
CV curve, which porous structurewith
increases of the
thegraphene
decreasesponge imply rate,
in scanning that
they have the potential to be used as electrodes for supercapacitor. The electrochemical
the specific capacitance obtained from the GCD curve also increases with the decrease in current performances of
graphene
density. Thesponge were studied
increments using cyclic
of capacitance with voltammetry
the decrease(CV) and the
in either scangalvanostatic charge/discharge
rates or current densities are
(GCD) technique. All electrochemical measurements used two-electrode
caused by the time-dependent ion diffusions in the electrode materials [44]. configuration, which can
measure the cell performance more accurately.
The cyclic stability was measured for these graphene sponge electrodes. The capacitance decay
was Figure
examined10a shows
betweenthe 0CV graphs
and 0.8 Vofatthe0.5
graphene
A/g forsponge
20,000electrodes at a scan
cycles. Figure 10drate of 50that
shows mV/scapacity
within
0–0.8 V. For the pure sponge with GnPs filler fractions of 0 wt.%, CV curve is a straight
retentions are 94.45% for graphene sponge at 1.43 wt.%. Specific capacitance gradually decreases and line, implying
no electrochemical
remains relatively capacitance.
stable after Inthecomparison,
initial 2000the graphene
cycles. This sponge
can be shows a near
attributed torectangular shape,
porous structure
implying a relatively
evolved through highfew
the first current
cyclesresponse
to obtainfor double-layer
a stable capacitancecapacitance behavior.cycles.
for the following This should be
The cyclic
contributed by the GnPs that have feature high electrical conductivity. Therefore,
testing shows high stability for all the samples, which would be caused by the high structural the mechanisms
of the supercapacitive
integrity of graphene performance can be classified
[45]. The fabricated grapheneassponges
electrochemical
have thedouble layertocapacitances
potential be used as
(EDLCs) [43].
electrodes for various energy storage devices.

0.2
(a) 50 mV/s 0.3
(b) 1.43 wt.% GnPs Sponge
Current Density (A/g)

Current Density (A/g) 0.2

0.1

0.0 0.0

-0.1

1.43 wt.%
-0.2
0.94 wt.% 100 mV/s
-0.2 0.47 wt.% 50 mV/s
0 wt.% -0.3
20 mV/s
0.0 0.2 0.4 0.6 0.8 0.0 0.2 0.4 0.6 0.8
Pontential (V) Pontential (V)

30

(d)
1.0

(c) 1.43 wt.% GnPs Sponge

Specific Capacitance (F/g)

25
0.8
Potential (V)

20
0.6

0.5 A/g 15
0.4 1 A/g
3 A/g
5 A/g 10 1.43 wt.% GnPs Sponge
0.2

5
0.0

0
0 10 20 0 100 200 300 400 500 5,000 10,000 15,000 20,000
Time (Sec) Cycle Number

Figure 10. Electrochemical

Figure 10. Electrochemical characterization
characterization of
of supercapacitors
supercapacitors based
based on
on graphene
graphene sponge
sponge containing
containing
1.43
1.43 wt.%, 0.94 wt.%, 0.47 wt.%, and 0 wt.% GnPs. (a) Cyclic voltammetry (CV) curves obtained at at
wt.%, 0.94 wt.%, 0.47 wt.%, and 0 wt.% GnPs. (a) Cyclic voltammetry (CV) curves obtained 50
50 mV/s. (b) CV curves at various scan rates. (c) Galvanostatic charge/discharge (GCD) curves of the
mV/s. (b) CV curves at various scan rates. (c) Galvanostatic charge/discharge (GCD) curves of the 1.43
1.43 wt.% graphene sponge. (d) Cyclic stability.
wt.% graphene sponge. (d) Cyclic stability.

The CV curve of the 1.43 wt.% graphene sponge is much closer to the rectangle-like shape than
4. Conclusions
the curve of the other two, and thus the curve has a larger area, representing the highest specific
In conclusion,
capacitance. GnPs were
This is because synthesized
of the by thermal
fact that sponges expansion
with high and peeling.
GnPs fractions haveAmore
multifunctional
conducting
graphene-based
channels sponge nanocomposite
and inter-particle pores. was prepared by a simple method. By studying and
optimizing the composition of graphene filler, it was found that the mechanical properties and
supercapacitance of sponge nanocomposites were the best when the filler composition was 1.43 wt.%.
Under 180° bending and torsion loading, the maximum resistance change rate can reach 13.9% and
52.5%, respectively. The tensile linearity is 0.01488. The maximum tensile strength was 0.236 MPa
and the maximum capacitance was 21.4 F/g. The sponge nanocomposites developed have good
Sensors 2020, 20, 329 10 of 13

EDLCs take important role in capacitance enhancement for the 1.43 wt.% graphene sponge. The
specific capacitance values calculated from CV curves are 12.1, 13.8, and 16.7 F/g for the graphene
sponge containing 0.47 wt.%, 0.94 wt.%, and 1.43 wt.% GnPs, respectively. The specific capacitance
increases with GnPs filler fraction, because more GnPs create more electron pathways in the graphene
sponge, leading to transfer of more electrons for electrochemical double layer capacitances.
The performance of the 1.43 wt.% graphene sponge was specifically investigated at 20–100 mV/s.
In Figure 10b, the CV curves of graphene sponge electrodes maintain similar shapes at different
scan rates, indicating remarkable electrochemical performance. The specific capacitances calculated
from the CV curves are 12, 16.7, and 21.4 F/g when the scan rates increases from 20 mV/s to 100
mV/s, respectively. With the decrease of scanning speed, the specific capacitance of the graphene
sponge increases slightly. This inter-testing rate capability is caused by the interconnected holes in the
electrodes that affect the diffusion of electrolyte ions.
Figure 10c contains the GCD curves of the graphene sponge tested at 0.5, 1, 3, and 5 A/g. These
graphene sponges show specific capacitance at 19.7, 16.5, 14.1, and 10.3 F/g of different current density
from 0.5 to 5 A/g. It can be seen that the specific capacitance calculated from CV and GCD curves are
similar. The GCD curves of 1.43 wt.% are almost linear and symmetrically mirrored to its discharge
counterparts, which indicates a perfect electrochemical capacitive behavior. Similar to the specific
capacitance obtained from the CV curve, which increases with the decrease in scanning rate, the specific
capacitance obtained from the GCD curve also increases with the decrease in current density. The
increments of capacitance with the decrease in either scan rates or current densities are caused by the
time-dependent ion diffusions in the electrode materials [44].
The cyclic stability was measured for these graphene sponge electrodes. The capacitance decay
was examined between 0 and 0.8 V at 0.5 A/g for 20,000 cycles. Figure 10d shows that capacity
retentions are 94.45% for graphene sponge at 1.43 wt.%. Specific capacitance gradually decreases and
remains relatively stable after the initial 2000 cycles. This can be attributed to porous structure evolved
through the first few cycles to obtain a stable capacitance for the following cycles. The cyclic testing
shows high stability for all the samples, which would be caused by the high structural integrity of
graphene [45]. The fabricated graphene sponges have the potential to be used as electrodes for various
energy storage devices.

4. Conclusions
In conclusion, GnPs were synthesized by thermal expansion and peeling. A multifunctional
graphene-based sponge nanocomposite was prepared by a simple method. By studying and optimizing
the composition of graphene filler, it was found that the mechanical properties and supercapacitance of
sponge nanocomposites were the best when the filler composition was 1.43 wt.%. Under 180◦ bending
and torsion loading, the maximum resistance change rate can reach 13.9% and 52.5%, respectively.
The tensile linearity is 0.01488. The maximum tensile strength was 0.236 MPa and the maximum
capacitance was 21.4 F/g. The sponge nanocomposites developed have good sensitivity and electrical
response under bending, torsion, and compression loads. It shows good performance in flexible
sensor and supercapacitor applications. The electrical response of graphene sponge at different
temperatures was investigated. There are no expensive materials or complex equipment used in the
whole manufacturing process of nanocomposites. It is believed that this material has broad application
prospects in engineering, electronics, and other fields.

Author Contributions: X.C. and X.L. conceived and designed the experiments; S.W. supervised the entire project;
J.T., Y.Y., and X.C. performed the experiments; X.C., J.T., Q.M., and S.W. analyzed the data; X.C., J.T., S.Z., and
A.C. contributed reagents/materials/analysis tools; X.C. and J.T. wrote the paper; S.W., X.L., X.C., J.T., Y.Y., A.C.,
S.Z., and Q.M. participated in a full and extensive discussion. All authors have read and agreed to the published
version of the manuscript.
Sensors 2020, 20, 329 11 of 13

Funding: Q.M. thanks Asbury Carbons (Asbury, NJ, USA) for providing the graphite intercalation compounds
(1721). This work was financially supported by the Natural Science Foundation of Liaoning Province—China [grant
number 2019-ZD-0246], the Foreign Training Program of Liaoning Higher Education Institutions [grant number
2018LNGXGJWPY-YB008], the National Natural Science Foundation (51973123), Natural Science Foundation of
Liaoning Province—China (2019-MS-256), Aeronautical Science Foundation of China (2018ZF54036), and China
Postdoctoral Science Foundation (2019M651151).
Conflicts of Interest: The authors declare no conflict of interest.

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