Ionics

https://doi.org/10.1007/s11581-017-2428-8

ORIGINAL PAPER

Biomass carbon/polyaniline composite and WO3 nanowire-based

asymmetric supercapacitor with superior performance
Haiping Wang 1 & Guofu Ma 2 & Yongchun Tong 1 & Zirong Yang 1

Received: 25 July 2017 / Revised: 16 December 2017 / Accepted: 26 December 2017

# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
The demand for advanced energy storage devices such as supercapacitors and lithium-ion batteries has been increasing to meet
the application requirements of hybrid vehicles and renewable energy systems. Here, high energy density aqueous asymmetric
supercapacitor (ASC) is assembled based on chestnut shell-based activated carbon (CAC)/PANI composite positive electrode
and tungsten trioxide (WO3) nanowires negative electrode. The CAC/PANI composite and WO3 nanowires were synthesized
through an interfacial polymerization method and a simple sodium sulfate assisted hydrothermal process, respectively. The CAC/
PANI//WO3 ASC device operates with a voltage of 1.5 V in 1 M H2SO4 electrolyte and achieved a high energy density of
15.4 Wh kg−1 at a power density of 252 W kg−1. Furthermore, the device shows an excellent cycling performance with
capacitance retention of 83% after 1500 cycles.

Keywords Chestnut shell . Polyaniline . Tungsten trioxide . Asymmetric supercapacitor

Introduction synthesize suitable materials, especially nanostructured mate-

rials, as a Faradic electrode; and to select a suitable electrolyte.
Supercapacitors or electrochemical capacitors have attracted Currently, activated carbon (AC) with a high specific surface
much attention because they can instantaneously provide area and moderate cost is the most widely used material for the
higher power density than batteries, and higher energy density capacitive electrode of asymmetric supercapacitors.
than conventional dielectric capacitors. However, they deliver Conducting polymers have been studied for their potential
lower energy density, which greatly restricts their application application as electrodes in energy storage devices [13–15].
[1–4]. An effective way is to develop hierarchical nanostruc- Among conducting polymers, polyaniline (PANI) has
tured or nanoporous materials to promote the specific capac- attracted interest due to its high specific capacitance, good
itance of electrodes [5–8] and another way is to explore asym- environmental stability, electroactivity, and doping-dedoping
metric supercapacitor (ASC), which integrates the different chemistry [16]. However, PANI exhibits the disadvantage of a
potential windows of capacitive and pseudocapacitive elec- low cycle life because swelling and shrinkage may occur dur-
trodes to increase the cell voltage [9–12]. The keys to achieve ing doping/dedoping processes, thus leading to mechanical
h i g h e n e rg y a n d p o w e r d e n s i t i e s o f as y m m e t r i c degradation of the electrodes and fading of electrochemical
supercapacitors are to use appropriate materials, usually car- performance. Interfacing other carbon materials with PANI
bon materials, as a capacitive electrode; to design and is one effective way to improve the electrochemical stability
of the composite. Previous reports have described that cou-
pling nanostructured PANI to carbonaceous materials can im-
* Haiping Wang
[email protected]
prove the utilization of PANI and provides a short transport
path for ion and electron. Therefore, composites based on the
1
appropriate stoichiometric combination of carbonaceous ma-
College of Chemistry and Chemical Engineering, Hexi University, terials and conducting polymers have been proven to be a
Zhangye 734000, China
2
potential breakthrough for a new generation of efficient
Key Laboratory of Eco-Environment-Related Polymer Materials of supercapacitors [17–19]. Hence, the research on the develop-
Ministry of Education, Key Laboratory of Polymer Materials of
Gansu Province, College of Chemistry and Chemical Engineering, ment of high-performance supercapacitors originating from
Northwest Normal University, Lanzhou 730070, China the synergistic combination of outstanding conducting
 Ionics

properties of carbonaceous materials and high The synthesis procedure of CAC/PANI composite is simi-
pseudocapacitance of conducting polymers is an ongoing in- lar to our previously reported [31]. Briefly, CAC (0.03 g) was
terest in nanotechnology [20–22]. added into a mixed solution of 50 mL of isopropyl alcohol and
Tungsten trioxide (WO3) attracts extensive attention be- 50 mL of 1 M H2SO4, and the mixture was sonicated for
cause of its distinctive physical and chemical properties, mak- 30 min to obtain a well-dispersed suspension. Then, ammoni-
ing it suitable for applications in electrochromic (EC) devices, um persulfate (APS, 0.76 g) was dissolved in the above solu-
photocatalysis, and gas sensing [23–26]. In the studies, WO3 tion to form a water phase. After that, the resulting solution
is also a promising electrode material due to its low cost, was cooled to 0 °C in an ice bath and the oil phase (aniline
simple synthesis, outstanding conductivity, and high theoreti- monomes (0.50 g) was dissolved in 100 mL of dichlorometh-
cal capacity [27]. Recently, Samu et al. reported tungsten tri- ane) cooled in advance was added drop-by-drop into the
oxide with nanoporous structures and studied their application above solution. The reaction was carried out with magnetic
as supercapacitor electrodes [28]. Wang et al. demonstrated stirring at 0 °C for 24 h; then, the resulting precipitate was
WO3@polypyrrole core-shell nanowires arrays with excellent washed several times with deionized water and ethanol, re-
supercapacitive performance [29]. CNT-WO3 hybrid elec- spectively. Finally, the product was dried at 60 °C for 12 h to
trodes have also been recognized as a potential candidate for obtain a dark green powder.
flexible asymmetric supercapacitor applications [30].
Here, we developed a novel asymmetric supercapacitor Synthesis of tungsten trioxide nanowires network
device using chestnut shell-based activated carbon (CAC)/
PANI composite and WO3 nanowires as the positive and neg- Tungsten trioxide (WO3) nanowire arrays were synthesized
ative electrodes, respectively. The as-fabricated CAC/PANI// by a sulfate-assisted hydrothermal method. Briefly, 3.29 g so-
WO3 asymmetric supercapacitor exhibits superior electro- dium tungstate powder was dissolved in 76 mL deionized
chemical properties in 1 M H2SO4 aqueous electrolyte, in- water, and a 3-M HCl aqueous solution was used to adjust
cluding wider operating voltage window (1.5 V), high energy the pH value to 2.0. Afterwards, ammonium sulfate (2.64 g)
density (15.4 W h kg−1), and outstanding cycle stability. was added to the reaction precursor to control the morphology
of the WO3 product. After stirring for 1 h, the clear solution
obtained was transferred into a 100-mL Teflon-lined stainless
steel autoclave and heated at 180 °C for 24 h. After cooled to
Experimental
room temperature naturally, the resulting precipitates of WO3
were collected by filtration, washed with distilled water and
Materials
absolute ethanol for several times to remove the residue of
reactants, and then dried in vacuum at 60 °C for 12 h.
Aniline (ANI, Shanghai Chemical Works, China) was distilled
under reduced pressure before used. Ammonium persulfate
Characterizations
(APS, Tianjing Damao Chemical Co., China) and sodium
tungstate dihydrate (Na2WO4∙2H2O, Aladdin Ltd. Shanghai
The as-prepared electrode materials were characterized by
China) solutions were prepared using deionized water. All
scanning electron microscopy (SEM, JSM-6701F, Japan) at
other chemical reagents were in analytical grade.
an accelerating voltage of 5.0 kV. X-ray diffraction (XRD)
of samples was performed on a diffractometer (D/Max-2400,
Synthesis of CAC/PANI composite Rigaku) advance instrument using Cu Kα radiation (k =
1.5418 Å) at 40 kV, 100 mA. The 2θ range used in the mea-
The chestnut shell-based activated carbon (CAC) was first surements was from 5 to 80°.
prepared from chestnut shells, which was performed by
mixing the dried chestnut shells with KOH solution at an Three-electrode cell fabrication
impregnation ratio of 5:2 (mass KOH/mass chestnut shells)
and stirring at 60 °C for 3 h. The resulting slurry was dried in For a conventional three-electrode system, a 3-mm-diameter
an oven for at least 24 h at 100 °C. The dried sample was glassy carbon electrode was used as the working electrode.
carbonized at 800 °C using a temperature ramp rate of The working electrodes were fabricated refers to ref. [32].
5 °C min−1 and then kept for 2.5 h under a flowing nitrogen Typically, 4 mg of electroactive material was ultrasonically
atmosphere in a tubular furnace. After being cooled to room dispersed in 400 μL of deionized water, and 4 μL of the
temperature, the carbide sample was washed repeatedly with polytetrafluoroethylene (PTFE) emulsion (60 wt%) was
0.5 M HCl until the pH of the washing solution reached 6.5. added to this dispersion. Two microliters of the above suspen-
Finally, the sample was washed with distilled water and dried sion was dropped onto the glassy carbon electrode using a
at 60 °C in ambient conditions for 24 h. pipet gun and dried at room temperature. The three-electrode
Ionics

system was tested in 1 M H2SO4 electrolyte; Platinum elec- the CAC electrode, which indicates the CAC possesses an
trode served as the counter electrode and saturated calomel electrical double-layer capacitance. However, the capacitance
electrode (SCE) as the reference electrode, respectively. characteristic of pure PANI or CAC/PANI composite is dis-
tinct from that of the CAC electrode close to the ideal rectan-
Two-electrode cell fabrication gular shape with pseudocapacitance characteristics. PANI or
CAC/PANI composite has three pairs of redox peaks: the first
The CAC/PANI//WO3 asymmetric supercapacitor was assem- couple of peaks (about 0.23 V/0.10 V) are attributed to the
bled in 1 M H2SO4 aqueous electrolyte using two electrodes redox transition of PANI between a semi-conducting state
into sandwich-type cells construction. The positive and nega- (leucoemeraldine form) and a conducting state
tive electrodes were pressed together and separated by a thin (polaronicemeraldine form); the second couple of peaks
polypropylene film. The working electrode was prepared by (about 0.47 V/0.43 V) are due to the transformation between
mixing the electroactive material with polyvinylidene fluoride the p-benzoquinone/hydroquinone couple because of the at-
(PVDF) and commercial carbon black (8:1:1) in N-methyl-2- tack by water; the third couple of peaks (about 0.73 V/0.70 V)
pyrrolidone (NMP) until it forms a homogeneous slurry. The are due to the formation/reduction of bipolaronic
obtained slurry was coated on stainless steel nets with a work- pernigraniline and protonated quinonediimine [32].
ing area of 1.0 cm2 and the electrodes were dried at 100 °C for However, the electrochemical performance of the CAC/
24 h and then weighted and pressed into sheets under 15 MPa. PANI composite is different from the pure PANI. The CV
To construct an ASC, the loading mass ratio of active mate- curve area of CAC/PANI is larger than that of pure PANI.
rials (m(CAC/PANI)/m(WO3)) was estimated to be 1.6 de- Furthermore, the first and the second couples of peaks of
pends on their specific capacitance and potential range for CAC/PANI composite are obviously higher than pure PANI
the charge/discharge process. at the same scan rate in 1 M H2SO4, and this verifies that the
CAC/PANI composite has a higher specific capacitance than
pure PANI, because of the linear relation between specific
Results and discussions capacitance and CV curve area. Figure 2b gives the galvano-
static charge/discharge curves of the CAC, pure PANI, and
Figure 1a shows the typical morphology of the as-synthesized CAC/PANI composite electrode at a current density of
CAC/PANI composite nanocones. Apparently, the nanocones 1 A g−1. The specific capacitance (Cm) can be calculated ac-
composite appears as random aggregation to form a reticular cording to the following equation: Cm = IΔt/mΔV, where I is
structure and such a structure with a porous network is favor- the current of discharge (A), Δt is the discharge time (s), ΔV is
able in supercapacitor applications [32]. The XRD pattern of the potential range during the discharge process, and m is the
CAC/PANI composite shows three characteristic peaks mass of active material within the electrode (g). According to
(Fig. 1b). The peaks at 2θ of 14.9 and 25.7° resulted from the above equation, the gravimetric capacitances are 207 F g−1
the periodicity both perpendicular and parallel to the polymer (CAC), 251 F g−1 (PANI), and 597 F g−1 (CAC/PANI), re-
chain, respectively. The peak at 2θ of 20.9° is caused by the spectively, which indicate that the specific capacitance of the
layers of polymer chains at alternating distances [33]. composite material (CAC/PANI) is obviously enhanced com-
Meanwhile, the diffraction peaks of chestnut shell-based acti- pared with the corresponding CAC and pure PANI. The larger
vated carbons at 44.3° cannot be obviously observed; maybe capacitance for CAC/PANI may be caused by the combination
the CAC particles interacted with PANI molecules and were of the electric double-layer capacitance of CAC and Faradaic
almost completely covered by PANI. The as-obtained WO3 pseudocapacitance of PANI. Moreover, the specific capaci-
nanostructures are mainly nanowires with a random arrange- tance of the CAC/PANI composite is superior to other com-
ment (Fig. 1c). The phase purity and crystal structure of the posite electrode materials, such as graphene oxide/polyaniline
WO3 nanowires were confirmed by XRD. As shown in (227 F g−1 at 2 A g−1) [35], grapheme/polyaniline nanofiber
Fig. 1d, all the diffraction peaks can be exclusively indexed (480 F g−1 at 0.1 A g−1) [20], and polyaniline/activated car-
to a pure hexagonal crystalline phase of WO3 with lattice bon/TiO2 (286 F g−1 at 1 A g−1) [36].
constants of a = 7.284 Å and c = 3.906 Å, which agrees well The electrochemical studies for the CAC/PANI composite
with the reported values of a = 7.298 Å, c = 3.899 Å, space and WO3 nanowires were performed in a three-electrode cell
group P6/mm from the JCPDS No. 33-1387 [34]. The strong using aqueous 1 M H2SO4 electrolyte. The performances of
and sharp diffraction peaks indicate good crystallinity of the electrode materials were analyzed using cyclic voltammetry
as-synthesized WO3 products. (CV) and galvanostatic charge/discharge (GCD) measure-
Figure 2a shows CV curves obtained in a three-electrode ments (Fig. 3). CV curves of the CAC/PANI composites at
cell for the CAC, pure PANI, and CAC/PANI composite elec- scan rates from 5 to 50 mV s−1 with the potential range of −
trodes under a scan rate of 5 mV s−1 in the potential window of 0.2 to 0.8 V are shown in Fig. 3a. The CAC/PANI composite
− 0.2–0.8 V. As can be seen, there is no peak originating from presents a couple of redox peaks attributed to the redox
 Ionics

Fig. 1 a SEM images of as-synthesized CAC/PANI. b XRD pattern of CAC/PANI composites. c SEM images of as-synthesized WO3. d XRD pattern of
WO3 nanowires

transition of PANI between a semiconducting state Fig. 3c, d, respectively. The GCD curves of the CAC/PANI
(leucoemeraldine form) and a conducting state (polaronic composite consist of two clear voltage stages: a fast potential
emeraldine form) [37], which results in the redox capacitance. drop (from 0.8 to 0.65 V) and a slow potential decay (from
Figure 3b shows the CV curves of WO3 nanowires, which 0.65 to 0 V) (Fig. 3c). The former, shorter discharge results
were measured from − 0.7 to 0 V with a change of scan rate from the electric double-layer capacitance of the electrode,
of 5 to 50 mV s−1. Characteristic redox peaks of WO3 elec- while the latter, longer discharge is ascribed to a combination
trodes were observed at about − 0.35 V of anodic scan and of electric double-layer capacitance and Faradaic capacitance,
about − 0.4 V of cathodic scan, respectively, which corre- representing the pseudocapacitive feature of the electrode.
sponds to the reversible intercalation/deintercalation of H+ Similarly, it should be noted that a characteristic
ions into/out of the WO3 host [38]. The electrochemical mech- pseudocapacitive behavior was observed for the WO3 elec-
anism of WO3 in H2SO4 electrolyte can be expressed as the trode (Fig. 3d). The steep increase in the potential above −
H+ insertion process takes place during the charge process, 0.1 V correlates with the observed decrease in the current in
and consequently the extraction process happens during the the CV curves of Fig. 3b. The specific capacitances were
discharge process: WO3 + xe− + xH+ ↔ HxWO3. In addition, measured from the discharging curves at different current den-
the current density became larger, and anode/cathode peak sities shown in Fig. 3e–f. For the discharging current densities
potentials moved to higher/lower voltage according to the from 1 to 5 A g−1, the specific capacitance values decreased
increase in scan rate, indicating the excellent electrochemical from 597 to 394 F g−1 (retained about 66%) for the CAC/
behavior. In addition, the obvious increase of current with PANI composite and decreased from 423 to 334 F g−1
scan rates means that the CAC/PANI composite and WO3 (retained about 79%) for WO3 nanowires, respectively.
nanowires electrode materials have good capacitance reten- Considering the high capacitance of the redox character
tion rates as the current density increases. Galvanostatic over the CAC/PANI composite and WO3 nanowires material,
charge/discharge (GCD) curves at different current densities an asymmetric supercapacitor was fabricated using these ma-
were measured to evaluate the specific capacitance of the terials as the positive and negative electrodes, respectively. To
CAC/PANI composite and WO3 nanowires, as shown in further evaluate the electrochemical properties and estimate
Ionics

Fig. 2 a CV curves of the CAC, pure PANI, and CAC/PANI composite at a scan rate of 5 mV s−1. b GCD curves of CAC, pure PANI, and CAC/PANI
composite at a current density of 1 A g−1

the stable potential windows of the CAC/PANI composite and materials are quite stable in a different range of potentials.
WO3 nanowires, we performed CV measurements on the two Consequently, if the total cell voltage can be expressed as
electrode materials in 1 M H2SO4 aqueous solution before the sum of the potential range for the CAC/PANI composite
evaluating the asymmetric cell, using a three-electrode system and WO3, it is possible to conclude that the cell potential can
with platinum as an auxiliary electrode and a saturated calo- be extended up to 1.5 V in 1 M H2SO4 aqueous solution for an
mel electrode (SCE) as a reference electrode. The CAC/PANI asymmetric supercapacitor. In order to obtain a capacitor op-
electrode was measured within a potential window of 0 to erating in a 1.5-V potential window, it is crucial to control the
0.8 V (vs. SCE), while WO3 was measured within a potential experimental conditions for the CAC/PANI to work in the
window of − 0.7 to 0 V (vs. SCE) at a scan rate of 5 mV s −1 potential range from 0 to 0.8 V and the AC electrode in the
(Fig. 4). Additionally, it can be observed that these two range from 0 to − 0.7 V.
 Ionics

the charge/discharge process (ΔV), and the mass of the elec-

trode (m) following the Eq. [39]:

q ¼ C m  ΔV  m

and in order to get q+ = q−, the mass balancing will follow the
Eq. [40]:

mþ =m− ¼ C m‐  ΔV − =C mþ  ΔV þ :

The mass ratio of m(CAC/PANI)/m(WO3) was estimated to be 1.6

from the specific capacitance calculated from their galvano-
static charge/discharge curves. Figure 5a shows the CV curves
of the CAC/PANI//WO3 asymmetric cell measured at various
scan rates of 15~50 mV s−1. The fabricated ASC demonstrates
Fig. 3 a, b CV curves of the CAC/PANI and WO3 electrodes at various
a typical capacitive behavior with distorted rectangular CV
scan rates performed in three electrode cells in 1 M H2SO4 electrolyte,
respectively. c, d Galvanostatic charge/discharge curves of CAC/PANI curves even with the high voltage of 1.5 V, indicating ideal
and WO3 electrodes at different current densities performed in three capacitive behavior and good reversibility. Meanwhile, when
electrode cells, respectively. e, f Specific capacitance of the CAC/PANI the scan rates are 15, 20, 40, and 50 mV s−1, the values of
and WO3 electrodes at different current densities, respectively
specific capacitance are calculated to be 300, 224, 107, and
82 F g−1. To further evaluate the performance of the asymmet-
As for a supercapacitor, the charge balance will follow the ric cell, we measured galvanostatic charge/discharge curves at
relationship q+ = q−. The charge stored by each electrode de- various current densities (Fig. 5b). According to the GCD
pends on the specific capacitance (Cm), the potential range for curves of the CAC/PANI//WO3 ASC were recorded with

Fig. 4 Comparative CV curves of CAC/PANI and WO3 electrodes performed in three electrode cells in 1 M H2SO4 electrolyte at a scan rate of 5 mV s−1
Ionics

the cycle number. The asymmetric cell exhibits excellent elec-

trochemical stability with only 5.6% deterioration of the initial
available specific capacitance after 600 cycles. It can be seen
that the asymmetric cell exhibits excellent cycling stability
with 83% capacitance of its initial value after 1500 cycles.
To further understand the resistive and capacitive behavior
of the CAC/PANI//WO3 ASC device, electrochemical imped-
ance spectroscopy (EIS) measurement was conducted with a
frequency range from 100 kHz to 0.01 Hz. As shown in Fig. 6,
the Nyquist plot of the CAC/PANI//WO3 ASC shows a small
semicircle in the high-frequency region and a greater than 45°
vertical curve in the low-frequency region, which results indi-
cating a low charge-transfer resistance in the electrochemical
system and a pronounced capacitive behavior with small dif-
Fig. 5 a CV curves of the CAC/PANI//WO3 ASC at different scan rates. fusion resistance, respectively [41, 42]. The obtained Nyquist
b GCD curves of the CAC/PANI//WO3 ASC at different current plot was further modeled and analyzed by the software of
densities. c GCD curves of the CAC/PANI//WO3 ASC at a current ZSimpWin on the basis of the electrical equivalent circuit
density of 0.5 A g−1. d Potential drop associated with CAC/PANI//WO3
ASC internal resistance (IR loss) vs. different discharge current densities.
(the inset of Fig. 6) [43], where Rs stands for a combined
e Ragone plot related to energy and power densities of the CAC/PANI// resistance of ionic resistance of the electrolyte, intrinsic resis-
WO3 ASC. f Cycling stability of the CAC/PANI//WO3 ASC test at a tance of the substrate, and contact resistance at the active
current density of 5 A g−1 material/current collector interface [44–46]. Rct is the charge
transfer resistance ascribed to the process occurring at the
various current densities, the specific capacitances of 274, electrode|electrolyte interface [44, 46–48]. Cdl is the electric
229, 203, and 173 F g−1 are obtained at current densities of double-layer capacitance, and CL is the limit capacitance [43].
0.5, 1, 1.5, and 2 A g−1. From the galvanostatic charge/ The slope of the 45° portion of the curve is called the Warburg
discharge curve of the asymmetric supercapacitor at a current resistance (W) and is a result of the frequency dependence of
density of 0.5 A g−1 (Fig. 5c), the discharge curve is almost ion diffusion/transport in the electrolyte to the electrode sur-
symmetric with its corresponding charge counterparts. In ad- face [49]. Based on the fitted impedance parameter values, the
dition, a good linear relation of charge/discharge potentials CAC/PANI//WO3 ASC not only has a low inner resistance
versus time is observed in the H2SO4 electrolyte, indicating (Rs, 8.5 Ω cm2), but also possesses a small interfacial charge
a rapid I-V response, small equivalent series resistance, and transfer resistance (Rct, 25.3 Ω cm2). Simultaneously, the
ideal capacitive characteristic, which are also confirmed by small Warburg coefficient (Aw, 0.8 Ω s-1/2 cm2) suggests that
CV curves (Fig. 5a). The internal resistance values were also a faster ion diffusion/transport to the electrode surface existed
determined from the slope and the initial voltage drops of the in the CAC/PANI//WO3 ASC system [50].
discharge curves at different discharge current densities
(Fig. 5d). The CAC/PANI//WO3 ASC has very little internal
resistance (IRdrop[V] = 0.0965 + 0.5126 I) from a linear fit to
the IR drop values, which favors high discharge power deliv-
ery in practical applications [40]. The Ragone plot of the de-
vice describing the relationship between energy density and
power density was obtained and is shown in Fig. 5e. The
energy and power densities were calculated from the dis-
charge curves at different current densities. The specific ener-
gy density (E, Wh kg−1) and power density (P, W kg−1) for a
supercapacitor cell can be calculated using the following
equations: E = 1/2 CΔV2 and P = E/t, where C is the specific
capacitance of the supercapacitor cell, ΔV is the scanned po-
tential window (excluding IR drop at the beginning of the
discharge process) in V, and t is the discharge time. It is obvi-
ous that the CAC/PANI//WO3 ASC exhibits the highest ener-
gy density of 15.4 Wh kg −1 with a power density of
Fig. 6 Nyquist plot of CAC/PANI//WO3 asymmetric supercapacitor for
252 W kg−1. Figure 5f shows the capacitance retention ratio
the two-electrode system; the inset shows an equivalent circuit used to fit
of the asymmetric capacitor charged at 1.5 V as a function of the Nyquist spectra
 Ionics

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Acknowledgements The research was financially supported by the poly (3, 4-ethylenedioxythiophene) nanocomposites for enhanced
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(NO.1308RJZA295, 1308RJZA265), the National Science Foundation https://doi.org/10.1016/j.jelechem.2017.08.012
of China (NO.21164009, 21174114), the program for Changjiang 14. Zhang SW, Yin BS, Liu C, Wang ZB, Gu DM (2017) Self-
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