Composites: Part A 87 (2016) 256–262

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Multifunctional CuO nanowire embodied structural supercapacitor

based on woven carbon fiber/ionic liquid–polyester resin
Biplab K. Deka, Ankita Hazarika, Jisoo Kim, Young-Bin Park, Hyung Wook Park ⇑
Department of Mechanical Engineering, Ulsan National Institute of Science and Technology, UNIST-gil 50, Ulsan 44919, Republic of Korea

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

Article history: Novel structural supercapacitors based on CuO nanowires and woven carbon fiber (WCF) has been devel-
Received 30 December 2015 oped for the first time employing vacuum assisted resin transfer molding (VARTM) process. The growth of
Received in revised form 29 April 2016 CuO nanowires on WCF is an efficient process and can be used in structural capacitors which can trigger
Accepted 4 May 2016
the electric vehicle industries toward a new direction. The specific surface area of the carbon fiber was
Available online 7 May 2016
enhanced by NaOH etching (41.36 m2 g
1) and by growing CuO nanowires (132.85 m2 g
1) on the surface
of the WCF. The specific capacitance of the CuO–WCF based supercapacitor was 2.48 F g
1, compared
Keywords:
with 0.16 F g
1 for the bare WCF-based supercapacitor. The usage of ionic liquid and lithium salt
A. Carbon fibers
A. Polymer-matrix composites (PMCs)
improved the capacitance to 5.40 and 6.75 F g
1 with lowest ESR and Rp values of 133 and 1240 X along
B. Electrical properties with improving mechanical properties within an acceptable range. The energy and power densities were
E. Resin transfer molding (RTM) also increased up to 106.04 mW h kg
1 and 12.57 W kg
1. Thus, this study demonstrated that growing
CuO nanowires on the surface of WCF is a novel approach to improve multifunctionality that could be
exploited in diverse applications such as electric cars, unmanned aerial vehicles (UAVs), and portable
electronic devices.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Carbon fiber-based polymer composites are used extensively in
automotive, aerospace, and military applications because of their
light weights, high specific strengths and stiffnesses, impressive
thermal and electrical conductivities, and excellent corrosion resis-
tances [1,2]. Currently, optimizing the specific properties in terms
of weight and volume fractions is the primary goal of fiber-
reinforced composites. However, the interfacial interactions at
the fiber–matrix interface are equally important and govern the
overall performance of the composites [3]. The excellent interfacial
interaction leads to well dissipation of applied stress to the com-
posite that results improved specific properties. The enhancement
of the fiber surface area is considered to be one of the most promis-
ing methods to improve the interfacial interaction as it enhanced
the site of interaction with the matrix that results improved prop-
erties. Several methods have been used to accomplish this, e.g.,
KOH etching [4], nanofiber and nanotube growth [5], and surfac-
tant grafting. Recently, different metal oxide nanowires or nanor-
ods have been grown on the surface of carbon fibers; these have
been extensively used in different applications [6]. These nanorods
⇑ Corresponding author.
E-mail address: hwpark@unist.ac.kr (H.W. Park).
increased the surface of the fiber and triggers the interaction of the
fibers with the matrix.
The multifunctional aspect of a carbon fiber-reinforced polymer
composite relates to its structural and electrochemical energy stor-
age functions. Such multifunctionality has great potential in
mobile systems such as portable electronics, hybrid electric motor
vehicles, and certain aerospace applications [7–9]. It is a challeng-
ing task to develop a multifunctional composite material that can
simultaneously have outstanding structural and energy storage
capabilities. Previous researchers developed multifunctional struc-
tural supercapacitors using carbon fiber electrodes [10]. Others
have used woven carbon fiber (WCF) sizing with carbon nanotubes
[11] and monolithic carbon aerogels [12], but WCF supercapacitors
based on metal oxide nanowires have yet to be reported. A super-
capacitor has a longer cycle life, higher power density, and better
reversibility compared with a conventional battery [13]. Its energy
density is as high as that of dielectric capacitors [14].
Among different metal-oxide nanowires, CuO is considered as
one of the suitable materials due to its low cost, sufficient
resources, chemical stability, and eco-friendly synthesis methods
[15]. Owing to its large surface area and relatively high specific
capacitance (674 mA h g
1), CuO is a deserving candidate to be
used in electrochemical applications [16]. However, the develop-
ment of the polymer matrix is a challenging task for the research-

http://dx.doi.org/10.1016/j.compositesa.2016.05.007
1359-835X/Ó 2016 Elsevier Ltd. All rights reserved.
 B.K. Deka et al. / Composites: Part A 87 (2016) 256–262
ers as the mechanical properties and ionic conductivity of a poly-
mer electrolyte have so far been inversely proportional [17].
Although conventional carbon fiber polymer composite can
achieve highest degree of mechanical properties, the electrochem-
ical performances always showed lowest values. However, previ-
ous research has shown improvement in both the parameters
simultaneously by using some non-structural polymer like
polyethylene-oxide (PEO) and diglycidyl ether [18]. The ionic
movement in the supercapacitor was widely improved by incorpo-
rating the ionic liquid to the matrix [19]. Addition of some extra
amount of cationic salt has catalyzed the ionic transport process
[20]. However, the critical problem is that the matrix became com-
pliant with an increasing proportion of ionic liquid and can’t give
sufficient structural properties. Thus, it is a challenging task to
develop solid polymer electrolyte (SPE) which can give sufficient
ionic conductivity along with desirable mechanical properties [21].
In this study, CuO nanowires were grown on WCF and novel
multifunctional structural supercapacitors were developed using
vacuum-assisted resin transfer molding (VARTM). These results
have not been reported by any other researchers until now and it
is a quite efficient process compared to the previous reported work
of structural supercapacitors [10,11]. Moreover, VARTM is a simple,
reliable, economic, and time-efficient process. A new SPE synthe-
sized from an unsaturated polyester resin, an ionic liquid, and a
lithium salt had better load-bearing capacity than a traditional
SPE and was successfully formed into a supercapacitor using
VARTM.
2. Materials and methods
2.1. Materials
Structural supercapacitors samples were prepared by two sheets
of WCF (T-300, density 1.76 g cm
3, 3K plain weave, Amoco Corpo-
ration, Chicago, IL, USA) electrodes sandwiched with one woven
glass fiber (thickness  0.2 mm, plain weave, weight  200 g m
2)
supplied by JMC Corporation, Korea. The surface area of the WCF
electrodes was enhanced by growing CuO nanowires on them.
These nanowires were prepared from copper nitrate tetrahydrate
(Zn(NO3)23H2O) and hexamethylene tetramine (C6H12N4)
purchased from Sigma–Aldrich (St. Louis, MO, USA). The unsatu-
rated polyester resin (PES) (LSP-8020B) and methyl ethyl ketone
peroxide (MEKP) crosslinker used for the matrix development were
obtained from CCP Composites (Jeollabuk-do, Korea) and ARKEMA
(Kunsan city, Korea), respectively. The ionic liquid 1-ethyl-3-
methylimidazolium tetrafluoroborate (EMIMBF4; reagent-grade;
C–TRI, Chuncheon city, Korea) and the lithium salt lithium trifluo-
romethanesulfonate (LiTf) (Sigma–Aldrich, Seoul, Korea) were used
to increase the ionic conductivity of the matrix. Other reagents and
chemicals were of analytical grade.
2.2. Hydrothermal synthesis of CuO nanowires on WCF
The surface areas of the WCF electrodes were increased by
growing CuO nanowires on them using a hydrothermal process.
In this method, sufficient hexamethylenetetramine (HMTA) and
copper nitrate tetrahydrate solution precursors were mixed at a
1:1 M ratio. For the preparation of 60 mM of growth solution,
60 mM each of HMTA and copper nitrate were separately dissolved
in distilled water at room temperature over 10 min. The two solu-
tions were then combined and stirred for another 30 min at room
temperature. The pH of the final growth solution was maintained
at 6–8. The precursor solution was transferred to a stainless steel
autoclave and the WCF electrode samples were immersed in the
solution. The autoclave was kept inside heating oven at a fixed
257
temperature of 100 °C and atmospheric pressure. After eight hours,
the samples were washed with distilled water to remove any unre-
acted particles and dried at room temperature. The entire process
of growing CuO nanowires is described as follows [22]:
C6 H12 N4 þ 6H2 O $ 6HCHO þ 4NH3 ð1Þ


NH3 þ H2 O $ NHþ4 þ OH ð2Þ
2OH
þ Cu2þ $ CuðOHÞ2 ð3Þ
CuðOHÞ2 $ CuO þ H2 O ð4Þ
2.3. Preparation of the CuO nanowire–WCF/polyester composite
capacitor
The capacitor samples were prepared using vacuum-assisted
resin transfer molding (VARTM) [23]. In this process, the CuO
nanowire–embedded WCF and WGF samples were placed inside
the vacuum chamber. Basically, the structural supercapacitor con-
sists of two activated carbon based electrodes with high specific
surface area and the glass fiber layer as the electron insulation.
However, the ions can conduct easily from one side to other
(Fig. 1). The interface of the electrodes and electrolytes accumu-
lates the charges and the energy stored in the capacitor is highly
related to the available surface area of the electrodes, ion size
and concentration and the stability of the electrolyte during oxida-
tion and reduction reactions. Each sample was prepared at about
(70  70) cm2 in dimensions and the average of three samples
has been reported. Two copper wires were attached to the WCF
electrodes using a conductive epoxy glue prior to the VARTM.
One releasing medium followed by one resin transporting medium
were placed immediately above each ply. A pressure-resistant
plastic film was finally attached with adhesive tape. An inlet and
outlet were provided to enable vacuum and resin flow to the cham-
ber. The outlet was connected to vacuum pump to create ca. 60 kPa
of pressure inside the chamber. This reduced pressure assisted
resin flow into the chamber. After sufficient resin had been inlet,
the chamber was sealed for 48 h to allow the samples to cure.
The sample configurations and loading percentages of the ionic
liquid and the lithium salt are given in Table 1. In case of samples 1,
2, and 3, 100% (w/w) of polyester resin was used as electrolyte for
the supercapacitors. To prepare the ionic liquid and polyester resin
based polymer electrolyte (sample 4), 20% (w/w) of EMIMBF4 was
mixed with 80% (w/w) of polyester resin. The mixture was stirred
thoroughly to become homogeneous and infused to the VARTM
chamber. For the electrolyte preparation of sample 5, 10% (w/w)
of lithium salt was initially mixed with 20% of ionic liquid. The stir-
ring was continued until all salt is dissolved in the ionic liquid. This
salt and ionic liquid mixture were subsequently added to 70% of
polyester resin. After completion of mixing process, it was used
as electrolyte and inserted to the VARTM system.
3. Results and discussion
3.1. Surface area and morphology of the CuO nanowire–WCF
electrodes
The specific surface area and pore size distribution of the WCF
electrodes were measured using a Physisorption Analyzer
(ASAP2020 Analysis, Micromeritics, Norcross, GA, USA) in a pure
nitrogen atmosphere at 77 K following the Brunauer, Emmett and
Teller (BET) method. The BET surface area significantly increased
(to ca. 41 m2 g
1) after treatment of the fibers with a strong base
(Table 2). Shirshova et al. previously reported the enhancement
of the BET surface area of carbon fibers using various processes
[24]. However, this is the first report of improving the surface area
258 B.K. Deka et al. / Composites: Part A 87 (2016) 256–262

Fig. 1. Schematic diagrams of the WCF based structural supercapacitor with its structural components. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)

The WCF morphology was studied by scanning electron micro-

Table 1 scopy (SEM; Nanonova 230; FEI, Hillsboro, OR, USA). Fig. 2A shows
Supercapacitors formulation and codes along with the loading percentage.
SEM images of the bare WCF sample. The etching process carried
Sl Sample Sample code out by NaOH treatment generated mesopores on the surface, which
no. increased the surface area and the specific capacitance of the elec-
1 Woven carbon fiber/glass fiber/polyester resin (100%) WCF/GF/PES trode (Fig. 2B). The surface area and specific capacitance were fur-
2 NaOH activated-woven carbon fiber/glass fiber/ ac-WCF/GF/ ther enhanced after decorating the WCF surface with CuO
polyester resin (100%) PES
nanowires (Fig. 2C). The nanowires not only enhanced the electro-
3 CuO nanowire–woven carbon fiber/glass fiber/ CuO–WCF/
polyester resin (100%) GF/PES chemical properties but also increased contact with the multifunc-
4 CuO nanowire–woven carbon fiber/glass fiber/ionic CuO–WCF/ tional matrix. This improved surface contact should mitigate
liquid (20%)/polyester resin (80%) GF/IL/PES matrix-dominated failure processes, which is an issue of great con-
5 CuO nanowire–woven carbon fiber/glass fiber/ionic CuO–WCF/ cern for structural electrical applications. The hierarchical
liquid (20%)/lithium salt (10%)/polyester resin (70%) GF/IL/LiS/PES
microstructure of mesoporous ionic liquid/polyester matrix is pre-
sented by micrograph 2D. The presence of ionic liquid droplets seg-
regates in the continuous polyester affluent portion of the matrix.
Table 2
Inside the segregates, there are some bi-continuous networks con-
BET surface area determination of WCF, NaOH activated WCF, and CuO nanowire
grown WCF samples. nected to each other forming some spherical knots. The micropores
and gaps inside these knots are primarily responsible for the ionic
Sample BET surface area (m2/g) Pore volume (cm3/g) Pore size (nm)
conductivity of the matrix [19].
WCF 0.589 ± 0.002 0.0128 86.6
ac-WCF 41.365 ± 0.004 0.849 63.2
3.2. Electrochemical analysis
CuO–WCF 132.852 ± 0.001 0.726 65.8

The specific capacitance (C) of a composite sample was mea-

through the growth of CuO nanowires and applying these novel sured by cyclic voltammetry (NuVant Systems, Crown Point, IN,
materials in structural supercapacitors. Decorating with CuO nano- USA). A sample was tested in a three-electrode system consisting
wires enhanced the surface area to ca. 132 m2 g
1. The pore vol- of a silver–silver chloride reference electrode and a platinum coun-
ume increased from 0.0128 cm3 g
1 for the untreated WCF to ter electrode in a 3 M KCl solution. A composite sample was con-
0.849 cm3 g
1 after the fibers were treated with base, compared nected with copper wire to function as the working electrode.
with 0.726 cm3 g
1 for the CuO-nanowire–decorated WCF. The The electrochemical response was recorded using different sweep
weight percent of CuO nanowires grown on woven carbon fiber rates of 1, 5, 30, 60, and 100 mV s
1 within a voltage window of
was calculated from Thermogravimetric analysis (TGA, TA Instru-
0.5 to +0.5 V. The specific capacitance was calculated by the fol-
ments, USA) and its result was around 14%. Our previous research lowing equation [25]:
has shown that the surface area of carbon fiber increases with Z Vc
increasing the weight percent of CuO grown [6]. However, in this 1
C¼ Iv dV ð5Þ
study, one concentration of the nanowire has been considered. mv ðV c
V a Þ Va
 B.K. Deka et al. / Composites: Part A 87 (2016) 256–262 259

Fig. 2. SEM images of (A) WCF, (B) NaOH activated WCF, (C) CuO grown WCF samples and (D) microstructure of PES/IL/LiS matrix.

where C is the specific capacitance (F g
1), m is the active mass of
the electrodes (g), v is the scan rate (mV s
1), Iv is the voltammetric
current (A), and (Vc
Va) is the sweep potential range (V). Fig. 3A
shows the cyclic voltammograms of the WCF/PES composites at a
scan rate of 10 mV s
1. The curves had rectangular shapes, similar
to that of WCF [26]. As expected, the untreated WCF/PES composite
had a very small specific area and capacitance during charging and
discharging, indicating ideal pseudocapacitive behavior. The WCF
surface-activated by NaOH had a larger specific area
(41.37 m2 g
1) and specific capacitance (1.17 F g
1) (Fig. 4A) than
bare WCF (specific area ca. 0.59 m2 g
1, Csp ca. 0.15 F g
1). The
capacitance was further enhanced when CuO nanowires were
grown on the surface of the WCF (Csp ca. 2.48 F g
1). Previous
research reveals that CuO nanowires provide the reasonable
improvement of the surface area as well as high specific capacity
and outstanding mechanical properties in the composites [27].
Moreover, the high wettability provided by the CuO nanowires
increased the intimate contact of the electrodes with the elec-
trolyte, which boosted the electrochemical performance. Qian
et al. [12] applied a continuous carbon aerogel to a carbon fiber fab-
ric and thereby enhanced the surface area and the electrochemical
properties by almost 100-fold. In the work reported here, addition

Fig. 3. Cyclic voltammograms of (A) woven carbon fiber (WCF) and WCF based polyester composites at 10 mV/s scan rate and (B) CuO–WCF/IL/LiS/PES composite at different
scan rates. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
260 B.K. Deka et al. / Composites: Part A 87 (2016) 256–262
Fig. 4. Specific capacitance of (A) different WCF based samples at 10 mV s
1 scan
rate (black line) and (B) CuO–WCF/GF/IL/LiS/PES composite (blue line) at different
scan rates. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)
of an ionic liquid-based electrolyte increased the specific capaci-
tance of the CuO–WCF/PES composite to ca. 5.40 F g
1. An ionic liq-
uid provides a channel for ion movement inside a composite due to
formation of microporous structure inside the matrix as illustrated
by Fig. 2D and hence, it significantly improved the capacitance of
the supercapacitor [28]. The capacitance of the CuO–WCF compos-
ite increased still further when the lithium salt was added to the
polyester matrix (i.e., to Csp ca. 6.75 F g
1). Quantitative analysis
of the LiTf salt revealed that one-third of the Tf anions formed coor-
dination bonds with Li cations. The remaining two-thirds of the
anions remained free in the matrix. In contrast, two-thirds of the
BF4 anions of the EMIMBF4 ionic liquid were coordinately bound
with the Li cations. The anions remaining free in both cases were
expected to facilitate the ionic conductivity of the composite [29].
The cyclic voltammetry test was performed at different scan
rates to establish the rate capability of the composite samples
(Fig. 3B). At low scan rates, the composite samples displayed
rectangularly-shaped voltammograms, indicating ideal capacity.
As the scan rate increased, the voltammetric current that passed
through the samples also increased and the shape of the curve
deviated from its rectangular shape because of polarizations asso-
ciated with micropore blocking, ionic resistance, and ion depletion
[30]. The specific capacitances of the samples at different scan
rates can be estimated from Fig. 4B; the value for the CuO–WCF/
IL/LiS/PES composite at 100 mV s
1 was only 7.87% of that mea-
sured at 1 mV s
1 (Fig. 4B). At high scan rates, the availability of
ions near the electrode surfaces changed and the diffusion coeffi-
cient of ions decreased, driving the capacitances to lower values.
The equivalent series resistance (ESR) and polarization resis-
tance (Rp) were determined from electrochemical impedance spec-
troscopy (EIS) by using the same instrument (NuVant Systems,
Crown Point, IN, USA) and presented in Table 3. This table has
revealed that ESR as well as Rp values were decreased gradually
as the CuO nanowires were grown on WCF electrodes along with
ionic liquid and lithium salt added to the polyester resin. The ESR
of a supercapacitor depends on many factors, such as electrical
resistance of the electrodes and presence of active sites on it, ionic
resistance provide by the electrolyte and the existence of interfacial
resistance between the electrodes and electrolyte [31]. CuO nano-
wires grown on carbon fiber electrodes enhanced the surface area
as well as active sites and the complex of ionic liquids and lithium
salt increased conductivity between electrodes and electrolyte.
These low ESR and Rp values are very much important for the higher
performance of the supercapacitor. The low Rp values of some
supercapacitor samples may be obtained by the presence of leakage
in the device. The energy and power densities of the supercapacitor
have been calculated from the following equations [10],
1 2
E¼ CU ð6Þ
2 int
U2
P ¼ int ð7Þ
4Rs
R
where U int ¼ Rp þR
p
s
U appl .
Both energy and power densities have been significantly
improved after the electrodes modified by CuO nanowires growing
and using ionic liquid along with lithium salt in the polyester resin
matrix and presented in Table 3.
3.3. Tensile properties of the composites
Tensile testing was carried out according to the standard ASTM
D3039 using an Instron 5982 universal testing machine equipped
with a 10 kN load cell. Five specimens of each sample were tested
at a displacement rate of 2 mm min
1. The total volume fraction
(Vf), tensile strength and modulus values of bare WCF and CuO–
WCF composites with ionic liquid and lithium salt are presented
in Table 3. As expected, the bare WCF composite sample had the
lowest strength and modulus because of the absence of significant
interfacial interaction between the carbon fibers and the resin.
Increasing the surface area of the carbon fibers through treatment
with NaOH improved the interfacial interaction with the resin and
thereby increased the strength (by 56.6%) and modulus (by 49.2%)
of the composite. The CuO nanowire–decorated WCF samples
exhibited the greatest improvement in strength (80.6%) and mod-
ulus (77.1%). This behavior was similar to that reported for carbon
fiber/polymer composites where the carbon fibers were decorated
with metal oxide nanowires [32]. The growth of CuO nanowires on
the fiber surface facilitated load sharing and resulted in a higher
energy required to break the composite. Moreover, the increased
total volume fraction of WCF due to growth of CuO nanowire on
the fiber surface felicities the effective load sharing with the fiber,
hence required higher energy to break the composite. Furthermore,
the hydroxyl, carboxyl, and carbonyl functional groups on the sur-
face of the carbon fiber formed ionic bonds with the CuO nano-
wires and also bonded with the ester groups of the resin. This
extra bonding sequence increased the strength and modulus of
the composites. The ionic liquid incorporated into the resin occu-
pied some interfacial sites within the composites and reduced
the interfacial bonding area [33]. Therefore, a marked decline in
the mechanical properties (strength to 73.6%, modulus to 71.2%)
was observed. The number of interfacial interaction sites was fur-
ther decreased by the addition of the lithium salt: the strength
reduced to 68.2% and the modulus to 66.1%. The stress–strain
curves for the composites are shown in Fig. 5A. The elasticities of
the composites increased after activation of the fiber surface or
after growth of the CuO nanowires, which suggests better accom-
modation of an imposed strain.
3.4. In-plane shear testing
In-plane shear tensile testing was done according the standard
ASTM D3518/D3518M-13 using the same instrument and displace-
ment speed as used for the tensile testing. This test is typically
used to determine the in-plane uniaxial tensile stress–strain
response of ±45° composite materials reinforced by high-
modulus continuous fibers or woven fabrics. Five samples were
tested and the average values are reported. The shear strength
was calculated according to Eq. (8) [22];
Fm
sm12 ¼ ; ð8Þ
2bd
 B.K. Deka et al. / Composites: Part A 87 (2016) 256–262 261

Table 3
Mechanical and electrochemical performances of supercapacitors.

Sample no. WCF Vf (vol%) Tensile In-plane shear ESR Rp Energy density Power density

1
Strength (MPa) Modulus (GPa) Strength (MPa) Modulus (GPa) (X) (X) (mW h kg ) (W kg
1)
WCF/GF/PES 39.4 (±0.59) 149.640 (±4.489) 11.817 (±0.368) 57.914 (±1.158) 11.937 (±0.302) 730 1240 27.63 1.03
ac-WCF/GF/PES 40.1 (±0.46) 234.275 (±7.028) 17.638 (±0.469) 89.578 (±1.792) 18.072 (±0.386) 724 1150 36.86 2.52
CuO–WCF/GF/PES 45.6 (±0.84) 270.275 (±8.105) 20.912 (±0.627) 102.439 (±2.049) 21.584 (±0.261) 370 986 42.15 4.14
CuO–WCF/GF/IL/PES 44.8 (±0.73) 259.816 (±7.794) 20.183 (±0.315) 95.529 (±1.911) 19.682 (±0.615) 330 888 93.75 10.39
CuO–WCF/GF/IL/LiS/ 44.5 (±0.61) 251.758 (±7.553) 19.616 (±0.267) 92.464 (±1.849) 18.927 (±0.182) 130 674 106.04 12.57
PES

Fig. 5. (A) Tensile and (B) in-plane shear stress–strain curves of WCF and CuO–WCF/GF/IL/LiS/PES composites. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

where F m [N] is the maximum in-plane load, sm 12 [MPa] is the in- shear strength [34]. This work instead used the specific capacitance
plane shear strength, b [mm] is the specimen width, and d [mm] as a function of shear modulus for the same purpose. To find the
is the specimen thickness. Table 3 depicts the in-plane shear ideal performance value, the lower limit of the capacitance and
strength of bare WCF and surface modified WCF/polyester compos- modulus were connected and the intersection point was consid-
ites. It is evident that the shear strength of the supercapacitor ered as the ideal point; this location is indicated by an asterisk
increased with NaOH activation (by 54.6%) or CuO nanowire deco- (⁄) in the figure [35]. The composite approached the ideal point
ration (by 76.9%) of the WCF. The activation process or nanowire as its multifunctionality increased. Growing CuO nanowires on
growth increased the surface area of the WCF, which improved wet- the WCF surface improved the multifunctionality to a satisfactory
ting and enhanced the interaction of the carbon fiber with the level. The high wettability and improved surface area of the carbon
matrix. The stress–strain curves (Fig. 5B) show better elongation fiber after decorating with the CuO nanowires enhanced the inter-
at a given tensile stress for all of the modified composites, com-
pared with the WCF/PES control. This behavior is attributed to lar-
ger specific areas and reaction of the hydroxyl, carboxyl, and
carbonyl functional groups of the carbon fiber surfaces with the
ester linkages of the polyester resin. Furthermore, the Cu2+ ions
likely formed strong ionic bonds with the carboxylic functional
groups of the carbon fiber. However, the shear strength and strain
decreased after incorporating the ionic liquid (EMIMBF4) (to
64.9%) and lithium salt (LiTf) (to 59.6%) to the composite. The ionic
liquid and the salt interfered with the interfacial bonding of the
composite by blocking the interaction sites, as mentioned earlier.
These results clearly indicate that although the surface activation
of WCF by the base treatment and growth of nanowires enhanced
the mechanical performance, the ionic liquid and salt were unable
to adequately transfer the load from the matrix to fiber, thereby
degrading the mechanical properties.

3.5. Multifunctionality

Fig. 6 presents the multifunctionality of the CuO–WCF-based Fig. 6. Multifunctionality (modulus vs. specific capacitance) of various WCF/PES
structural supercapacitors. Previous researchers assessed multi- composites. (For interpretation of the references to color in this figure legend, the
functionality by measuring the energy density as a function of reader is referred to the web version of this article.)
262 B.K. Deka et al. / Composites: Part A 87 (2016) 256–262
facial contact of the fiber to the resin, which increased the multi-
functionality of the composite. Although incorporation of the
EMIMBF4 ionic liquid and the LiTf salt improved the specific capac-
itance, the mechanical performance was considered unsatisfactory.
Further research is planned to improve the balance of specific
capacitance and shear modulus toward the ideal value.
4. Conclusions
Structural supercapacitors based on CuO-nanowire–decorated
WCF were designed and fabricated using VARTM, an effective
and eco-friendly process. The surface area of the WCF was
increased by treatment with 4 M NaOH solution. Growing CuO
nanowires on the surface of the WCF also improved the specific
surface area. BET analysis revealed that the NaOH treatment
increased the surface area to ca. 41.4 m2 g
1 while the CuO-
nanowire–decorated WCF had an area of ca. 132.9 m2 g
1. These
areas are much greater than that of bare WCF (0.6 m2 g
1). Scan-
ning electron microscopy was used to study the NaOH etching
and the growth of the CuO nanowires. The specific capacitances
of the new supercapacitors were characterized by cyclic voltam-
metry, which revealed that the CuO decoration had increased the
capacitance to 2.48 F g
1. Adding the EMIMBF4 ionic liquid and
the LiTf salt further increased the specific capacitance to
5.40 F g
1 and 6.75 F g
1, respectively. However, the tensile and
in-plane shear strengths suffered. The ESR and Rp values drop to
130 and 674 X starting from 730 and 1240 X. The ionic liquid
and lithium salt based nanowires grown samples showed up to
106.04 mW h kg
1 of energy density and 12.57 W kg
1 of power
density values. Hence, the CuO nanowire decoration substantially
increased the multifunctionality of the supercapacitors. However,
it remains necessary to develop a multifunctional matrix that can
provide good electrical properties without compromising the
mechanical performance. Overall, eco-friendly CuO-nanowire/
WCF structural supercapacitors were developed cost-effectively
using VARTM. Related supercapacitors are expected to find uses
in applications such as energy storage in UAVs, aerospace, and
electric vehicles.
Acknowledgements
This work was supported by the 2016 Research Fund
(1.160005.01) of UNIST (Ulsan National Institute of Science and
Technology) and the Technology Innovation Program (10053248,
Development of Manufacturing System for CFRP (Carbon Fiber
Reinforced Plastics) Machining) funded by the Ministry of Trade,
industry & Energy (MOTIE, Korea).
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