Carbohydrate Polymers 157 (2017) 344–352

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Carbohydrate Polymers
journal homepage: [Link]/locate/carbpol

Flexible polypyrrole/copper sulfide/bacterial cellulose nanofibrous

composite membranes as supercapacitor electrodes
Shuo Peng a , Lingling Fan b,∗ , Chengzhuo Wei a , Xiaohong Liu a , Hongwei Zhang a ,
Weilin Xu a,b , Jie Xu a,∗
a
College of Materials Science & Engineering, State Key Lab for New Textile Materials & Advanced Processing Technology, Wuhan Textile University, 430200,
Wuhan, China
b
College of Textile Science & Engineering, Wuhan Textile University, 430200, Wuhan, China

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

Article history: Polypyrrole (PPy) and copper sulfide (CuS) have been successfully deposited on bacterial cellulose (BC)
Received 15 September 2016 membranes to prepare nanofibrous composite electrodes of PPy/CuS/BC for flexible supercapacitor appli-
Received in revised form 2 October 2016 cations. The introduction of CuS remarkably improves the specific capacitance and cycling stability of
Accepted 3 October 2016
BC-based electrodes. The specific capacitance of the supercapacitors based on the PPy/CuS/BC electrodes
Available online 4 October 2016
can reach to about 580 F g−1 at a current density of 0.8 mA cm−2 and can retain about 73% of their initial
value after 300 cycles, while the PPy/BC-based device could retain only 21.7% after 300 cycles. This work
Keywords:
provides a promising approach to fabricate cost-effective and flexible nanofibrous composite membranes
Polypyrrole
Copper sulfide
for high-performance supercapacitor electrodes.
Bacterial cellulose © 2016 Elsevier Ltd. All rights reserved.
Nanofibrous composite membranes
Flexible supercapacitor

1. Introduction tively small specific capacitance. The main electrode materials

used for pseudocapacitors are transition metal oxides/sulfides and
Recently, wearable electronics and their associated technolo- conducting polymers (CPs, e.g. polypyrrole (PPy), polyaniline, poly-
gies have been envisioned in an array of applications, thus greatly thiophene and their derivatives). Pseudocapacitor materials have
boosting the developments of flexible and wearable energy stor- relatively large capacitance values because the energy is stored
age systems (Jost, Dion, & Gogotsi, 2014). Flexible supercapacitors through a reversible redox reaction.
have received considerable attention due to their desirable advan- Among the abovementioned electrode materials, CPs have
tages, such as high energy density, good cycling stability, fast promised the most for high-performance flexible supercapacitor
charge/discharge rate, and environmental safety (Firoz Babu, Siva applications due to their high conductivity, high intrinsic flex-
Subramanian, & Anbu Kulandainathan, 2013; Liang et al., 2013; Xu ibility, various preparation methods and nontoxicity (Gholami,
et al., 2013; Li, Huang, Yang et al., 2014; Li, Huang, Zhang et al., 2014; Nia, & Alias, 2015; Liu, He, Fan, Miao, & Liu, 2014; Lü, Chen,
Liu, Yu, Yan, Li, & Zheng, 2015; Qin et al., 2015; Xu, Wang, & Fan, Lin, & Yu, 2015; Mensing, Wisitsoraat, Phokharatkul, Lomas, &
2015; Xu, Wang, Yuan, Wei, & Duan, 2015; Xu, Wang, Yuan, Wei, Tuantranont, 2015; Ramya, Sivasubramanian, & Sangaranarayanan,
& Gu, 2015; Zhu et al., 2014). On the basis of the energy-storage 2013; Snook, Kao, & Best, 2011; Wang, Li, Ni, Dai, & Lu, 2015).
mechanisms and the used electrode materials, supercapacitors can On the basis of low cost and environmental stability, PPy and
be divided into electrical double layer capacitors (EDLCs) and pseu- PPy-based composites used for flexible supercapacitors have been
docapacitors. The energy stored in EDLCs mainly results from the intensively studied. For example, Firoz Babu et al. (2013) inves-
charge separation at the electrode/electrolyte interface, and the tigated the influence of the fabric substrates on electrochemical
electrode materials used in EDLCs are carbon materials. Usually, performance and reported a specific capacitance of 235 F g−1 for
carbon materials have good rate capability but exhibit a rela- their viscose-based PPy electrode. Zhao and coworkers (Zhao, Shu,
Wang, Gambhir, & Wallace, 2015) demonstrated the performance
of PPy-graphene-coated nylon lycra textile electrode in superca-
∗ Corresponding authors. pacitor application, showing a specific capacitance of 114 F g−1 at a
E-mail addresses: hglingling@[Link] (L. Fan), xujie0@[Link] (J. Xu). scan rate of 5 mV s−1 . Liu, Cai, Zhao, Zhao, & Ge, 2016 fabricated a

[Link]
0144-8617/© 2016 Elsevier Ltd. All rights reserved.
 S. Peng et al. / Carbohydrate Polymers 157 (2017) 344–352 345

PPy/multi-walled carbon nanotube (MWCNT)/cotton flexible elec- 2. Experimental

trode, which exhibited a specific capacitance of 535 F g−1 at a very
low scan rate of 1 mV s−1 . Despite the attractive electrochemical 2.1. Materials
performance and potential of CNTs and graphene, the relatively
high price of CNTs and elaborate procedures to obtain graphene BC membranes (food-grade, degree of polymeriza-
would impede their further development in large-scale fabrication. tion ≈ 5.18 × 103 ) were purchased from Hainan Yide Foods
Transition metal sulfides (e.g., CuS, NiS, CoS, and VS) have been Co. Ltd. (China) and treated as the previous report (Xu et al., 2013).
considered as one of the most promising pseudocapacitor materi- Other chemicals were supplied by Sinopharm Chemical Reagent
als with respect to their specific capacitance and cost effectiveness Co. Ltd. (China) and used as received. Ultrapure water used in the
(Feng et al., 2011; Hsu, Chen, & Lin, 2014; Peng et al., 2015; Raj experiments with resistivity of 18 M cm was produced a Milli-Q
et al., 2014; S. Liu et al., 2015; Zhu, Xia, Zhou, & Lou, 2012;). In Advantage system.
the recent past, CuS have been extensively investigated due to
their good electronic conductivity and high energy capacitance. For 2.2. In situ synthesis of CuS on BC nanofibers
example, Zhu et al. (2012) utilized the template-engaged chemical
conversion route to prepare CuS nanoneedles on carbon nanotube In a typical procedure, the purified BC membrane (4 × 4 cm)
as electrode, which exhibited a specific capacitance of 122 F g−1 in were immersed into a beaker with a magnetic stirring bar con-
KOH electrolyte. More recently, Hsu et al. (2014) have fabricated taining 50 mL aqueous solution of copper sulfate pentahydrate
a CuS nanowire (NW) array with a hierarchical nanoarchitecture (CuSO4 ·5H2 O) for 8 h. Then it was taken out and soaked into a
on copper foil using a simple liquid-solid reaction, achieving a spe- 50 mL aqueous solution of sodium sulfide (Na2 S) with the same
cific capacitance of 305 F g−1 at a current density of 0.6 mA cm−2 . concentration as CuSO4 solution for 1 min. It was observed that the
Combining PPy with CuS to form composite electrode materials for BC membrane changed to a dark green color. Finally, the mem-
flexible supercapacitors is an effective route to further improve the brane was washed with pure water for several times and dried in
electrochemical properties of supercapacitors. However, to the best a vacuum oven at 60 ◦ C for 12 h. The BC membranes treated by the
of our knowledge, composite materials of PPy and CuS for flexible solutions of CuSO4 ·5H2 O with different concentrations of 10, 50,
supercapacitors have rarely been reported. 100 mM were named as CuS/BC-10, CuS/BC-50 and CuS/BC-100,
Bacterial cellulose (BC) is a fascinating natural nanofibrous respectively.
material with a three-dimensional and interconnected network
structure, which can be produced on industrial scales through 2.3. Fabrication of PPy/CuS/BC composite membranes
microbial fermentation process. The average diameter of its ribbon-
like fibrils is lower than 100 nm, while the length can be larger PPy was deposited on the CuS/BC membranes through in-situ
than 100 ␮m. The specific structure and numerous hydrogen bonds oxidative polymerization as previously reported (Xu et al., 2013).
endow BC with sufficient porosity and high specific surface area, The CuS/BC membranes were soaked in a pyrrole aqueous solu-
which can serve as a matrix to support other functionalized mate- tion (1.0 M) and stirred for 1 h. An aqueous solution of iron (III)
rials and a template to form different nanostructures (Hu, Chen, chloride hexahydrate (FeCl3 ·6H2 O, 0.5 M) was added to initiate
Yang, Zhe, & Wang, 2014; Tang, Han, Jiang, Chen, & Wang, 2015). the polymerization. After 2 h at 5 ◦ C, the obtained samples were
For example, CdS and CdSe nanoparticles have been prepared on cleaned thoroughly with alcohol and pure water and dried in a vac-
the BC nanofibers using in situ precipitation method (Li et al., uum oven at 40 ◦ C for 12 h. The composites prepared on different
2009; Yang et al., 2012). PPy (Müller, Rambo, Recouvreux, Porto, & CuS/BC membranes were coded as PPy/CuS/BC-10, PPy/CuS/BC-50
Barra, 2011; Müller, Rambo, Porto, Schreiner, & Barra, 2013; Wang, and PPy/CuS/BC-100, respectively. The control sample obtained by
Bian, Zhou, Tang, & Tang, 2013) and PANI (Lee, Chung, Kwon, Kim, using purified BC membrane without CuS was named as PPy/BC.
& Tze, 2012; Marins et al., 2011; Müller et al., 2012) nanopar-
ticles have been synthesized on the BC nanofibers via in-situ 2.4. Characterization
polymerization. Recently, Tang et al. prepared the polysiloxane-
coated PPy/BC nanocomposite membranes with amphiphobicity The mass of active materials was determined by the weight
by in situ oxidative polymerization of PPy and then infiltrated difference before and after the deposition of CuS and PPy. The
with polysiloxane solution (Tang et al., 2015). In our previous microscopic features of the samples were characterized on a JSM-
work (Xu et al., 2013), we have successfully fabricated the PPy/BC 6510LV scanning electron microscopy (SEM) microscope (JEOL,
nanofibrous membranes with core-sheath structure for the appli- Japan). Energy dispersive X-ray spectroscopy (EDS) was examined
cation of flexible supercapacitor electrodes, which exhibited an on a HORIBA X-ACT spectrometer. Fourier transform infrared (FTIR)
initial capacitance of 459.5 F g−1 at 0.16 A g−1 current density. More spectra were recorded by a TGA-FTIR spectrometer (Tensor 27,
recently, the PPy/NiS/BC membranes were prepared in our group Bruker, Germany) equipped with attenuated total reflectance (ATR)
(Peng et al., 2016), which had a relatively high initial capacitance cell. Thermal gravimetric analysis (TGA) was carried out under
of 713 F g−1 at 0.8 mA cm−2 current density. However, the capac- nitrogen atmosphere with a TG209F1 thermogravimetric analyzer
itance was decreased dramatically during the charge/discharge (NETZSCH, Germany) at a heating rate of 10 ◦ C min−1 . The surface
cycles, with the remaining capacitance of 258 F g−1 (only 36.2% of conductivity was measured by a digital four-point probe resistivity
the initial value) and 172 F g−1 (24.2%) after 100 and 300 cycles, measurement system (RTS-9, 4Probes Tech. Co., China) with copper
respectively. CuS could provide good cycling durability due to electrodes under a pressure of 5 N.
the crystallinity of CuS (Raj et al., 2014). To improve the cycling The electrochemical properties of the membrane electrodes
performance of the BC-based electrodes, herein, we report the were measured based on a symmetric two-electrode system with
fabrication of flexible PPy/CuS/BC nanofibrous composite mem- 2.0 M sodium chloride (NaCl) aqueous solution as electrolyte and
branes, which exhibited a high specific capacitance as high as a filter paper as separator. Cyclic voltammetry (CV) and electro-
580 F g−1 and good cycling performance (the retention 73% of ini- chemical impedance spectroscopy (EIS) were recorded with an
tial specific capacitance after 300 cycles) at a current density of Autolab PGSTAT302N electrochemical workstation (Metrohm AG,
0.8 mA cm−2 . Switzerland). The CV measurements were carried out from −0.9 V
346 S. Peng et al. / Carbohydrate Polymers 157 (2017) 344–352

Fig. 1. Optical images of BC, Cu2+/BC, CuS/BC and PPy/CuS/BC membranes.

to +0.9 V at various scan rates. The EIS tests were carried out in the it could be inferred that the CuS coatings on the BC was quite
frequency range from 0.01 Hz to 100 kHz using a sine wave with thin from the appearance of the typical peaks of cellulose in the
alternate signal amplitude of 5 mV. Galvanostatic charge-discharge spectrum of the CuS/BC membrane.
(GCD) cycling measurements were conducted over the potential As shown in Fig. 3b, TGA had been performed for BC, CuS/BC-10,
range from 0 to 0.8 V on a multichannel LAND CT2001A battery and CuS/BC-100 membranes. The weight loss had been monitored
testing device (Wuhan Land Electronics, China). as a function of temperature. For BC, the first period from 25 ◦ C
to 250 ◦ C with about 13% weight loss was attributed to the dehy-
dration of cellulose. The drastic weight loss in the second period
3. Results and discussion (250–380 ◦ C) was ascribed to the destruction of cellulose into d-
glucopyranose and free radical. The weight loss during the third
The images of BC and BC composites are shown in Fig. 1. Firstly, stage from 380 − 600 ◦ C was caused by the decarboxylation and
when the BC membrane was soaked in CuSO4 solution, the guest decarbonylation reactions. The CuS/BC composites underwent a
Cu2+ ions could infuse into the three-dimensional network struc- similar weight loss manner. However, the water loss in the com-
ture through the nanopores of BC to reach adsorption equilibrium. posite membranes was decreased with the introduction of CuS. In
The Cu2+ ions were anchored on the surface of the BC membrane addition, the onset temperature of the second stage for the CuS/BC
by the electrostatic interactions between Cu2+ and cellulose, since membranes was lower than that for pure BC, indicating that the
the oxygen atoms can bind Cu2+ by sharing a lone pair of electrons composite membranes are less thermally stable than pure BC. These
(Hu, Chen, Zhou, Wang, 2010). The free Cu2+ can be eliminated by results can be ascribed to that the hydrogen bonds in BC were prob-
washing in water. The BC membrane turned from white to light ably broken by the interaction between BC and CuS. The lower
green, suggesting the steady adsorption of Cu2+ on the membrane. weight loss of the composites than BC was due to the CuS residue.
As being dipped into the Na2 S solution, CuS was produced quickly The FTIR spectrum of PPy/CuS/BC-50 shown in Fig. 3a primarily
owing to the strong interaction between Cu2+ and S2− , and the color presented the typical peaks of PPy, revealing that the BC nanofibers
of the samples changed to dark green quickly. were entirely overlapped by PPy due to its high thickness (Peng
The microscopic features of the BC and CuS/BC membranes were et al., 2016). The peaks at 1524 cm−1 and 1435 cm−1 were attributed
investigated by SEM and the images are provided in Fig. 2. The to the C C and C N stretching vibrations in the pyrrole ring,
BC nanofibers have an average diameter less than 100 nm and are respectively. The peak at 1283 cm−1 corresponded to the C H and
cross-linked and overlapped, forming a porous three-dimensional N H in-plane deformation modes. The breathing vibration of the
network (Fig. 2a). The characteristic structure provides a valu- PPy ring appeared at 1130 cm−1 . The mode of in-plane deforma-
able feature for the adsorption and distribution of Cu2+ on the tion vibration of NH2 + groups derived from the protonated PPy
BC nanofibers. For the CuS/BC-10 membrane obtained with dilute chains was observed at 1084 cm−1 (Omastová, Trchová, Kovářová,
CuSO4 solution, the appearance of frequent grooves, wrinkles and & Stejskal, 2003). The peak at 1007 cm−1 was assigned to the C H
roughness on the surface and interspaces of the BC nanofibers and N H in-plane deformation vibrations. The C C and C H out-of-
indicated the successful deposition of CuS onto the BC membrane plane ring deformation modes were located at 959 and 764 cm−1 ,
(Fig. 2b). When the CuSO4 concentration increased, the aggregated respectively. Comparing to the FTIR spectrum of the PPy/BC mem-
CuS particles were observed on the BC membranes (Fig. 2c and brane reported previously (Xu et al., 2013), the characteristic peaks
2d). The EDS patterns of the CuS/BC-50 membrane (Fig. 2e) further of PPy shifted obviously to lower wavenumbers in the PPy/CuS/BC-
confirm the presence of CuS on the BC membrane. 50 composite possibly owing to the interaction between the PPy
The FTIR spectra of the BC, Cu2+ /BC-50 and CuS/BC-50 compos- chain and the CuS layer.
ites are plotted in Fig. 3a. For BC (Müller et al., 2013), the bands at The BC membrane is not conductive with a sheet resistance
3340 and 2895 cm−1 were attributed to the stretching vibration more than 1015  sq−1 ; however, the membrane could become
of hydroxyl groups and the asymmetrically stretching vibration conductive after the introduction of CuS, with the conductiv-
of C H and CH2 , respectively. The in-plane OH deformation and ity of about 0.5 S cm−1 . With the PPy coatings, the conductivity
bending vibrations were observed at 1647 and 1315 cm−1 , respec- of the composite membranes further increased to 8.2, 6.9, and
tively. The peak of the C O asymmetric bridge stretching situated 5.1 S cm−1 for PPy/CuS/BC-10, PPy/CuS/BC-50 and PPy/CuS/BC-100,
at 1159 cm−1 . The intensive bands at 1107 and 1055 cm−1 corre- respectively, which is even higher than those of PPy/BC membrane
sponded to the skeletal vibration of the C O and C O C functional (3.9 S cm−1 ) (Xu et al., 2013), pure PPy film (1.14 S cm−1 ) (Wang
groups of the pyranose ring. After the adsorption of Cu2+ , the bands et al., 2010), PPy-Cladophora cellulose composite paper (slightly
corresponding to the in-plane OH deformation and bending vibra- above 1 S cm−1 ) (Nyström, Razaq, Strømme, Nyholm, & Mihranyan,
tions became relatively strong in the spectrum of the Cu2+ /BC 2009), and PPy/graphene-coated cotton fabric (1.2 S cm−1 ) (Xu,
membrane. This observation pointed out that there was a stable Wang, Yuan, Wei, & Duan, 2015). The conductivity of the compos-
interaction between the OH groups and the Cu2+ ions and these ite membranes decreased with the increasing CuS concentration,
groups were the reactive position during in situ synthesis (Li et al., perhaps due to the relatively low conductivity of CuS as compared
2009). Since the ATR infrared light can penetrate only a filmy layer,
 S. Peng et al. / Carbohydrate Polymers 157 (2017) 344–352 347

Fig. 2. SEM images of (a) BC and CuS/BC membranes: (b) CuS/BC-10, (c) CuS/BC-50 and (d) CuS/BC-100; (e) EDS pattern of the CuS/BC-50 membrane.

with PPy. The high conductivity confirmed the possible application PPy nanosheath on the BC nanofibers and prevent the formation
of the composite membranes in flexible electronics. In addition, the of aggregates (Xu et al., 2013). Meanwhile, the CuS layer between
color of BC membranes changed from dark green to black after the the nanofibers was destroyed significantly by the growing of PPy.
polymerization (Fig. 1). The composite membranes were flexible enough to be bent by 180◦
The SEM images of the PPy/BC and PPy/CuS/BC samples are without breaking (shown in the inset of Fig. 4d), and be folded and
given in Fig. 4. For all the samples, the PPy nanoparticles were released for many times. The excellent flexibility of the resultant
mostly formed along the BC nanofibers to construct a continuous membranes and excellent adhesion of PPy is attributable to the for-
nanosheath structure as well as some aggregations. As the CuS layer mation of hydrogen bonding because of the effective interactions
on the nanofibers was rather flimsy and the nanofibers were not between the imine groups of PPy and the hydroxyl groups of cel-
entirely overlapped, it can be inferred that pyrrole could permeate lulose. The nanosheath structure, high conductivity and excellent
through the CuS layer and contact the nanofibers. The hydrogen flexibility make the PPy/CuS/BC composite membranes promising
bonds could act as a traction force to support the growing of the flexible electrode materials for supercapacitors.
348 S. Peng et al. / Carbohydrate Polymers 157 (2017) 344–352

(a) BC (b)
100

Cu2+/BC-50 80
Transmittance (%)

60

Mass (%)
45.58%
CuS/BC-50
40 32.46%
PPy/CuS/BC-50
BC
20
CuS/BC-10
CuS/BC-100
0.34%
0
4000 3500 3000 2500 2000 1500 1000 100 200 300 400 500 600

Wavenumber (cm ) -1 Temperature (°C)

Fig. 3. (a) FTIR spectra of BC, Cu2+ /BC-50, CuS/BC-50 and PPy/CuS/BC-50 membranes; (b) TG curves of pure BC, CuS/BC-10, and CuS/BC-100 membranes.

As a useful experimental tool with small potential variation, EIS deposition of less CuS. Such an increase in the electrical conduc-
is more reliable for characterizing the frequency response of the tivity of the BC-based supercapacitor can improve electrochemical
supercapacitor and it can provide the electronic/ionic conductivity performance, which can play a key role in enhancing the power
of the electrode materials during the charge-discharge progress. density. In the low frequency region, the impedance curves of the
Fig. 5a presents the Nyquist plots for the PPy/BC and PPy/CuS/BC PPy/CuS/BC-50 electrodes were less parallel to the imaginary axis
electrodes. All the impedance plots were featured by a semicir- as compared with the other electrodes, indicating the proper addi-
cle in the high frequency region and a linear portion in the low tion of CuS in the PPy/CuS/BC-50 electrodes was favorable for the
frequency region. The interception of the semicircle at the real infiltration of electrolyte ion to some extent (Yang et al., 2016).
axis in the high frequency region represents the internal resis- Fig. 5b shows the cyclic voltammetry (CV) curves for the PPy/BC
tance related to the intrinsic resistance of the active materials and and PPy/CuS/BC-50 membranes at a scan rate of 5 mV s−1 with the
the electrolytic resistance. The linear portion corresponds to the potential window ranging from −0.9 V to 0.9 V. Nearly rectangu-
diffusion-limited process, suggesting an ideal capacitive behav- lar shapes with large enclosed area were observed and there were
ior. The equivalent series resistance (Rs ) values for PPy/CuS/BC-10 no obvious redox peaks for the PPy/BC and PPy/CuS/BC-50 mem-
(9.5 ) and PPy/CuS/BC-50 (10.1 ) were slightly lower than that branes, indicating that the electrodes were charged and discharged
for PPy/BC (11.2 ) and PPy/CuS/BC-100 (12.1 ), revealing that at a pseudo-constant rate over the whole CV process. The devices
the electrical conductivity of overall electrode was reduced by the based on the PPy/CuS/BC-50 membranes had a higher area than

Fig. 4. SEM images of (a) PPy/BC and PPy/CuS/BC membranes: (b) PPy/CuS/BC-10, (c) PPy/CuS/BC-50 and (d) PPy/CuS/BC-100.
 S. Peng et al. / Carbohydrate Polymers 157 (2017) 344–352 349

12 6
(a) (b)
10 4

Current density (A g-1)

8 PPy/CuS/BC-10 2
PPy/CuS/BC-50
PPy/CuS/BC-100 PPy/CuS/BC-50
-Z'' (Ω)

6 0
PPy/BC PPy/BC

4 -2

2 -4

0 -6
8 10 12 14 16 18 20 22 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
Z' (Ω) Potential (V)

0.03
1000
(c) (d)
0.02
800

Specific capacitance (F g )
-1
0.01
Curremt (A)

600 PPy/CuS/BC-50
0.00 PPy/BC
5 mV s-1
400
-0.01 10 mV s-1
20 mV s-1
-1
-0.02 30 mV s 200
-1
40 mV s
50 mV s-1
-0.03
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 0
0 10 20 30 40 50
Potential (V) Scan rate (mV s-1)

Fig. 5. (a) Nyquist plots of the supercapacitors based on PPy/BC and PPy/CuS/BC electrodes; (b) CV curves of the supercapacitors based on PPy/CuS/BC-50 and PPy-BC
electrodes at a scan rate of 5 mV s−1 ; (c) CV curves of the supercapacitors based on PPy/CuS/BC-50 electrode at different scan rates; (d) Specific capacitance calculated from
CV curves for the supercapacitors based on PPy/CuS/BC-50 and PPy-BC electrodes at different scan rates.

the PPy/BC-based sample in the CV curves. In general, the enclosed importance in energy-storage devices as less energy will be wasted
area of the CV curve is proportional to the specific capacitance of to produce unwanted heat during GCD processes (Zhong et al.,
the electrode material. The CV curves for the PPy/CuS/BC-50 sample 2015). It can be found from Fig. 6a that the GCD curves were almost
at different scan rates are presented in Fig. 5(c). With the increased symmetrical at a current density of 0.8 mA cm−2 . The supercapac-
scan rates, the CV profiles for the samples deviated from rectangle- itors based on the PPy/CuS/BC electrodes had relatively smaller
like shape. Based on the CV curves, the specific capacitance (Csp ) IR drops than that based on the PPy/BC electrodes at the same
can be calculated by the following equation: current density, indicating that the supercapacitors based on the
 PPy/CuS/BC electrodes have better capacitive property. The gram-
IdV specific capacitance (Cm ) can be calculated from the GCD curves
Csp =
v × V × m with the following equation:
where I is the response current, v is the scan rate, V is the voltage I×t
window, and m is the mass of the active materials. The calculated Cm =
(V − IRdrop ) × m
Csp values for PPy/BC and PPy/CuS/BC-50 at different scan rates are
shown in Fig. 5(d). The Csp for the PPy/CuS/BC-50 and PPy/BC sam- where I is the constant charge/discharge current, t is the discharge
ples at the scan rate of 5 mV s−1 was 846 and 693 F g−1 , respectively. time, V is the potential window, IRdrop is the IR voltage drop, and
The capacitance of PPy/CuS/BC-50 was higher than that of PPy/BC m is the mass of electroactive material in the working electrode.
due to the synergetic contributions from the pseudocapacitance of The Cm values for PPy/CuS/BC-10, PPy/CuS/BC-50 and PPy/CuS/BC-
PPy and CuS. The Csp values decreased gradually with the increase 100 at a current density of 0.8 mA cm−2 were calculated to be
of scan rates because of the ion diffusion effect within the active about 530, 580 and 575 F g−1 , respectively, exceeding the value
materials and at the electrode/electrolyte interface (Wang et al., for PPy/BC (502 F g−1 ). The maximum value for PPy/CuS/BC-50 is
2012). even larger than the reported values of BC-based electrodes, such
The GCD curves of the supercapacitors based on the PPy/CuS/BC as PPy/BC/MWCNT (216.4 F g−1 ) (Li, Huang, Yang et al., 2014) and
and PPy-BC electrodes were tested at different current densities. An chemically bonded PPy/BC/graphene composites (556 F g−1 ) (Liu,
ideal supercapacitor will exhibit the symmetrical triangle shapes Zhou, Tang, & Tang, 2015). The mass loading of active materials
of the GCD curves with small IR drops, revealing that the redox for the PPy/BC membranes were significantly larger than that for
reaction is reversible. The IR drop is usually caused by the overall the composite membranes, leading to larger total capacitance and
internal resistance of the devices. Low internal resistance is of great consequently longer discharge time. However, the higher thick-
350 S. Peng et al. / Carbohydrate Polymers 157 (2017) 344–352

1.0 100

(a)
PPy/CuS/BC-10 (b)
PPy/CuS/BC-50
PPy/CuS/BC-100

Capacitance retention (%)

0.8 80
PPy/BC
73%

0.6 60
Voltage (V)

0.4
37%
40

PPy/CuS/BC-10 22%
0.2 20
PPy/CuS/BC-50
PPy/CuS/BC-100
PPy/BC
0.0 0
2000 3000 4000 5000 6000 7000 8000 0 50 100 150 200 250 300
Time (s)
Number of cycles
1000 300
(d)
(c) PPy/CuS/BC-50
PPy/CuS/BC-50 250 PPy/BC
PPy/BC
Specific capacitance (F g )

800
-1

Power density (W kg-1)

200

600 150

100

400
50

200 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 20 25 30 35 40 45 50 55 60 65 70 75

Discharge current density (mA cm )

-2
Energy density (Wh kg-1)

Fig. 6. (a) Galvanostatic charge-discharge profiles of the supercapacitors based on PPy/CuS/BC and PPy-BC electrodes at a current density of 0.8 mA cm−2 ; (b) Cycling stability
at a current density of 0.8 mA cm−2 ; (c) Specific capacitance of the supercapacitors based on PPy/CuS/BC-50 and PPy-BC electrodes at different current densities; (d) Ragone
plots of the supercapacitors based on PPy/CuS/BC-50 and PPy-BC electrodes.

ness of the PPy/BC membranes caused a decrease in flexibility as itance of the device based on PPy/CuS/BC-50 was retained 59.2%
compared with the composite membranes. Cycling performance when the current density increases from 0.2 A cm−2 to 1.6 A cm−2 .
of the electrodes was evaluated by long-term GCD, as shown in The specific capacitance of the device based on PPy/CuS/BC-50 at
Fig. 6b. The devices based on the PPy/CuS/BC-10, PPy/CuS/BC-50 the current density of 1.6 A cm−2 was still quite large, being about
and PPy/CuS/BC-100 electrodes could retain 73%, 73% and 37% of 481 F g−1 . The specific energy density (E) and power density (P) can
their initial Cm after 300 cycles, respectively, while the PPy/BC- be calculated by the following formulas (Xing et al., 2006):
based device could retain only 22% of its initial Cm after 300 cycles.
The remaining specific capacitance of 423 F g−1 for PPy/CuS/BC-50 E = (1/2)CV 2
is about 2.5 times of that for the recently proposed PPy/NiS/BC
(172 F g−1 ) after 300 cycles (Peng et al., 2016). The capacitance loss
P = E/t
of the PPy materials has been demonstrated to arise from the vol-
ume swelling and the structure relaxation of the materials caused
where C corresponds to the capacitance of the two-electrode capac-
by the intercalation and dissociation of dopant anions during the
itor, V is the potential window (excluding IR drop at the beginning of
long-time charge and discharge processes. The CuS layer served
the discharge), and t is the discharge time. The Ragone plots for the
as frameworks to stabilize the PPy layer and to limit the swelling
devices based on PPy/CuS/BC-50 and PPy-BC are shown in Fig. 6d. It
and shrinking of the PPy coating during the charge/discharge runs,
is obvious that the supercapacitor based on PPy/CuS/BC-50 exhib-
thus leading to an improved cycling stability. It is noteworthy that
ited better performances. The power density can reach to about
the device based on PPy/CuS/BC-100 had relatively poorer stability
253 W kg−1 , and the energy density can reach to about 71.0 Wh
than those based on PPy/CuS/BC-10 and PPy/CuS/BC-50 perhaps
kg−1 for the supercapacitor based on PPy/CuS/BC-50. However, the
due to the degradation of CuS layer in PPy/CuS/BC-100. Further
device based on PPy/BC had obviously small energy densities and
improvement on the cycling stability is needed for potential appli-
power densities due to the low Cm values and larger IR drops during
cations. Nevertheless, due to their low cost and facile fabrication,
the GCD process. The energy density in the present work is signif-
the PPy/CuS/BC composites show promising applications in wear-
icantly larger than the reported values for the devices using the
able electronics when apparel is changed frequently. The Cm values
PPy-coated fabrics (Liang et al., 2013; Xu, Wang, & Fan, 2015; Xu,
for the devices based on PPy/CuS/BC-50 and PPy/BC at different cur-
Wang, Yuan, Wei, & Gu, 2015; Zhu et al., 2014) and the PPy/RGO-
rent densities are shown in Fig. 6c. It can be found that the Cm values
coated fabrics (Xu, Wang, Yuan, Wei, & Duan, 2015) due to the
decreased with the increase of the current densities. The capac-
synergetic contributions from the pseudocapacitance of PPy and
 S. Peng et al. / Carbohydrate Polymers 157 (2017) 344–352 351

CuS. The data suggest that the PPy/CuS/BC membranes are expected Liu, C., Cai, Z., Zhao, Y., Zhao, H., & Ge, F. (2016). Potentiostatically synthesized
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Electrochimica Acta, 182, 361–367.
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sulfide/bacterial cellulose nanofibrous composite membranes for flexible
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and Hubei Province (No. 2012FFA098), Application and Founda- carbon nanofiber/ultrathin graphite hybrid for flexible solid-state
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tion Research Project of Wuhan Science and Technology Bureau
Raj, C. J., Kim, B. C., Cho, W. J., Lee, W. G., Seo, Y., & Yu, K. H. (2014). Electrochemical
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