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rsc.li/materials-a
Journal of Materials Chemistry AMaterials for energy and sustainabilitywww.rsc.org/MaterialsA
ISSN 2050-7488
Volume 4 Number 1 7 January 2016 Pages 1–330
PAPERKun Chang, Zhaorong Chang et al. Bubble-template-assisted synthesis of hollow fullerene-like MoS
2 nanocages as a lithium ion battery anode material
Journal of Materials Chemistry AMaterials for energy and sustainability
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This article can be cited before page numbers have been issued, to do this please use: S. Cai, T. Huang,
H. Chen, M. Salman, K. Gopalsamy and C. Gao, J. Mater. Chem. A, 2017, DOI: 10.1039/C7TA07937K.
Journal of Materials Chemistry A
COMMUNICATION
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MOE Key Laboratory of Macromolecular Synthesis and Functionalization,
Department of Polymer Science and Engineering, Key Laboratory of Adsorption
and Separation Materials & Technologies of Zhejiang Province, Zhejiang
University, 38 Zheda Road, Hangzhou 310027,P. R. China. Email:
† Electronic Supplementary Informa,on (ESI) available: [details of any supplementary information available should be included here]. See DOI: 10.1039/x0xx00000x
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Wet-spinning of ternary synergistic coaxial fibers for high
performance yarn supercapacitors
Shengying Cai, Tieqi Huang, Hao Chen, Muhammad Salman, Karthikeyan Gopalsamy and Chao Gao*
Graphene/CNTs/35%PEDOT:PSS@CMC (GCP-35@CMC) ternary
coaxial fibers are continuously prepared through coaxial wet-
spinning technology. The GCP-35@CMC-assembled flexible fiber-
shaped supercapacitors (FSCs) perform advanced area specific
capacitance (396.7 mF cm-2
at 0.1 mA cm-2
) and energy density
(13.8 µWh cm-2
). This performance is ascribed to the synergistic
effect of well-designed ternary system and special
microstructures.
The advent of next-generation wearable and flexible electronic
devices makes new requirements for energy storage systems,
typically batteries and supercapacitors.1-3 Different from traditional
bulky and heavy capacitors, the novel fiber supercapacitors (FSCs)
possess significant features of tiny volume and high flexibility,4
meeting the emerging demand well. The FSCs exhibit high power
density, long cycle life, excellent safety and wide operating
temperatures as well as its analogs.5 However, low energy density
seriously restricts its practical applications.6 A direct method to
promote the energy density of FSCs is to improve the capacitance.7
To address the problem, designing fiber-shaped electrodes with
specific structures is necessary.
Recent advances in supercapacitors have been focused on
nanostructured carbon materials, like carbon nanotubes (CNTs),
carbon onions, templated carbons and the new emerging
graphenes.8-12 Among all of them, graphene possesses the unique
properties of high theoretical surface area (2630 m2 g-1),
outstanding electrical conductivity and stability. Thus it is
recognized to be an ideal material for high performance
supercapacitors.13,14 However, the π-π restacking during
macroscopic assembling would intensely hinder electrolyte ions
transmission into the interlayer between graphene sheets, resulting
in low surface utilization efficiency and further unsatisfactory
electrochemical performance.15 To solve this problem, spacers have
been utilized to separate the adjacent graphene sheets, leading to
the increase of accessible specific area for ions.16-18 Even so, the
capacitance of FSCs based on pure electric double-layer capacitor
(EDLC) is still limited for their physical adsorption and desorption
under electrochemical cycling. On the contrary, pseudocapacitance
which mainly derived from transition metal oxides and conductive
polymers has a higher energy density than EDLC but are usually
limited by their intrinsic low electrical conductivity.19-23
Combination EDLC with pseudocapacitance seems to be a promising
strategy for high performance electrodes which possess the
advantages of both.
Facial yet green wet-spinning technology has been widely used to
prepare continuous graphene oxide (GO) based macroscopic
assembly,24-28 achieving continuous fabrication of tens of meters
long GO fibers (or films). Particularly, Kou and coworkers reported a
coaxial wet-spinning assembly approach to continuously spin
polyelectrolyte-wrapped graphene/carbon nanotube core-sheath
fibers. Spinnability of graphene oxide based solutions, especially
those composited with other component, will be improved due to
the constraint of polyelectrolyte layer. Moreover, the coaxial wet-
spinning process will render the pore structures of inner GO core
because of the uniform shrinkage force of the polyelectrolyte
sheath, leading to an outstanding electrochemical performance of
final FSCs.29
Here, novel ternary synergistic coaxial fibers (GCP@CMC)
composed of ternary core (graphene/CNTs/PEDOT:PSS) and CMC
(carboxyl methyl cellulose) sheath have been fabricated by coaxial
wet-spinning technology. In this ternary core, graphene assembly
acts as a conductive EDLC matrix both for electron transport and ion
adsorption. CNTs between graphene sheets are expected to
promote the diffusion process of electrolyte ions. The conductive
polymer PEDOT:PSS is introduced to contribute the extra
pseudocapacitance for higher energy density. Moreover, the PSS
chain segments of PEDOT:PSS possess good compatibility with
water and will optimize the wettability of electrodes, which is
beneficial for electrolyte ions diffusion. The CMC sheath is ionically
conductive while electrically insulative, which ensures electrodes
free of short circuit while allowing electrolyte ions to transport.
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0 15 30 45 600
15
30
45
60
RGO@CMCGC@CMCGP-35@CMCGCP-35@CMC
-Z"
( k)
Z' (k )
0 2 4 60
2
4
6
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
400
500
CA
(mF
cm
-2)
Current density (mAcm-2)
RGO@CMCGC@CMCGP-35@CMCGCP-35@CMC
0.0 0.2 0.4 0.6 0.8 1.0-5.0
-2.5
0.0
2.5
5.0
Curr
entdensity
(mA
cm
-2)
Potential (V)
RGO@CMCGC@CMCGP-35@CMCGCP-35@CMC
10 15 20 25 30 35 400
2
4
6
8
10
12
14
Inte
nsity
(a.u
.)
2-theta (degree)
RGO
CNTs
GC
GP-35
GCP-35
0 1000 2000 3000 4000 50000.0
0.5
1.0
1.5
Curr
entdensity
( mA
cm
-2)
Time (s)
RGO@CMCGC@CMCGP-35@CMCGCP-35@CMC
Thus electrodes of our FSCs can be intertwined as closely as
possible, which is beneficial to capacitive performance.
Furthermore, the addition of CNTs and PEDOT:PSS will attenuate
the interaction between graphene sheets, resulting in
unsatisfactory strength of ternary fiber and makes it hard to be
collected (especially in wet state). Therefore, the CMC is also
designed as a protect sheath to support the hybrid core. The
assembled FSCs delivered a relatively high area specific capacitance
(CA) of 396.7 mF cm-2 at a current density of 0.1 mA cm-2 and
showed good rate capability (71.8 % capacitance retention at 1.0
mA cm-2). No obvious decay of capacitance was observed after 5000
times of charge-discharge cycles. These excellent electrochemical
performances are attributed to the well-designed synergistic effect
of ternary system and special microstructures formed by the
shrinkage force of CMC during dried process.
Fig. 1 (a) Schematic representation for fabrication process and microscopic
structure of ternary coaxial fibers; (b-d) SEM images of GCP-35@CMC; (e)
Optical photograph of a half-meter long GCP-35@CMC; (f-i) EDX mapping of
the cross section of GCP-35@CMC.
Fig. 1a illustrates the fabrication process and microscopic
structure of ternary coaxial fibers. Typically, ternary dispersion and
CMC aqueous were transferred to two injection syringes, which
were connected with the inner and outer channel of specific
spinneret respectively. Continuous coaxial fibers were obtained by
simultaneously extruding two spinning solutions into a coagulation
bath, in which both of the graphene oxide and CMC will be
crosslinked respectively (the optical photos are showed in Fig. S1†).
Then the fibers were immersed in hydriodic acid ethanol/water
solution, converting GO to reduced graphene oxide (RGO). The
detailed experimental procedure is listed in supplementary
information.
The microscopic morphology of graphene/CNTs/35%PEDOT:PSS
coaxial fibers (GCP-35@CMC) was characterized by scanning
electron microscope (SEM), and the SEM images with different
magnifications are displayed in Fig. 1b-d. The ternary core which
consist of graphene, CNTs and PEDOT:PSS is tightly wrapped by
CMC sheath (Fig. 1b and c). The special highly wrinkled surface of
coaxial fibers is produced by the shrinkage of graphene sheets and
compression of CMC during drying process, to be beneficial to
electrochemical performance of FSCs.29 CNTs are uniformly
dispersed between the graphene sheets (Fig. 1d), as a good spacer
to eliminate the graphene sheets restacking.17,18,30 The optical
photograph of a half-meter long GCP-35@CMC coaxial fiber is
showed in Fig. 1e, indicating that the ternary coaxial fibers can be
fabricated continuously. The EDX mapping was carried out to
characterize the distribution of carbon, oxygen and sulfur elements
in GCP-35@CMC (Fig. 1f-i). Carbon and oxygen elements distribute
in both of the sheath and core of GCP-35@CMC (Fig. 1g and h),
stemmed from CMC, PEDOT:PSS and residual functional groups on
graphene sheets. However, sulphur element from PEDOT:PSS
mainly distributes in the core of GCP-35@CMC (Fig. 1i) and no
obvious distribution is found in CMC layer. It is demonstrated that
the electrochemical active PEDOT:PSS did not diffuse into CMC
layer during fabricate process and the definite core-shell structure
was formed.
Fig. 2 (a) X-ray diffraction (XRD) spectra; (b) CV curves at 10 mV s-1; (c)
Nyquist plots, the inset shows the high frequency behavior; (d) rate
performance while the current density increased from 0.1 mA cm-2 to 1.0
mA cm-2; (e) GCD tests at 0.1 mA cm-2; (f) the schematic of proposed charge
and discharge mechanism of GCP-35@CMC.
The crystal structure and interlayer spacing of graphene (RGO);
CNTs; graphene/CNTs (GC); graphene/35%PEDOT:PSS (GP-35) and
graphene/CNTs/35%PEDOT:PSS (GCP-35) are characterized by X-ray
diffraction (XRD), and the results are displayed in Fig. 2a. The RGO
fiber showed a 002 peak at 23.76o, corresponding to an interlayer
of 3.74 Å. This interlayer space is slightly larger than literature
reported before,21 which is beneficial to the performance of
(b) (a)
(c) (d) (e)
(f)
(a) (b)
(c)
(d)
(e)
(f) (g) (h) (i)
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supercapacitors.31, 32 While for GC fiber, a new peak which belongs
to CNTs appeared at 25.76o, and the original 002 peak of RGO was
indistinct and overlapped. It indicated that the original ordered π-π
stacking structure of graphene sheets was largely decimated by the
interlayer CNTs. The diffraction angle of RGO shifted from 23.76o to
17.26o and the peak shape become broad in GP-35, demonstrating
the interlayer spacing of graphene sheets increased from 3.74 Å to
5.13 Å after adding PEDOT:PSS. As for GCP-35, the XRD pattern
exhibited both broad peak at 17.26o as GP-35 and 25.76o peak
belongs to CNTs as GC, responding to a decreased restacking
structure and large interlayer spacing of graphene sheets, which is
beneficial to electrochemical performance.32
Considering that the surface hydrophilicity is crucial for the ions
connection with the electrodes,33-36 the contact angle measurement
was carried out to evaluate the wettability of our materials (Fig. S2†
). The contact angle of RGO is 72.7o, whereas GP-35 and GCP-35
showed a lower angle at 61.0o and 60.6o, respectively. It is indicated
that the wettability of graphene architectures has been promoted
by adding PEDOT:PSS. Similar phenomenon was observed in other
literature.37
The electrochemical performances of RGO@CMC, GC@CMC, GP-
35@CMC and GCP-35@CMC FSCs are displayed in Fig. 2b-e. As
shown in Fig. 2b, the CV curve of RGO@CMC changed from leaf to a
rectangular shape after combination with CNTs or PEDOT:PSS, which
reflects the typical behavior of EDLC and suggests excellent process
of charge propagation.38 This conversion is attributed to the
increased interlayer spacing of graphene sheets and the promoted
wettability of electrode, accelerating the diffusion process of
electrolyte ions and improve its responsiveness during charge and
discharge.37 No obvious redox peaks of GP-35@CMC can be seen in
its CV curve, but the redox peaks deriving from the fast faradaic
reactions are easily found in ternary GCP-35@CMC, indicating the
extra pseudocapacitance besides EDLC.39 This special phenomenon
will be explained subsequently. The electrochemical impedance
spectroscopy (EIS) was carried out to investigate the resistances of
electrodes from 0.1 to 100 kHZ (Fig. 2c). The low frequency portions
in Nyquist Plots of GC@CMC, GP-35@CMC and GCP-35@CMC are
more vertical to the axis of real component when compared with
RGO@CMC, indicating a better supercapacitor behavior and more
outstanding diffusion process of electrolyte ions.23 The equivalent
series resistance (ESR) of RGO@CMC, GC@CMC, GP-35@CMC and
GCP-35@CMC are 10.27 kΩ, 2.12 kΩ, 5.72 kΩ and 0.63 kΩ,
respectively. It is mainly composed of three parts: intrinsic ohmic
resistance Rs, interfacial charge transfer resistance Rct and warburg
diffusion resistance Rw.40 Compared with GP-35@CMC (5.72 KΩ),
GCP-35@CMC (after adding CNTs) performed much lower ESR (0.63
kΩ), which means that the charge transfer process of electrons and
ions in GCP-35@CMC is much more effective as it in GP-35@CMC.
Accordingly, the pseudocapacitance of PEDOT:PSS is utilized
efficiently in GCP-35@CMC but inefficiently in GP-35@CMC for its
magnitude larger ESR. The specific capacitance (CA) is calculated by
galvanostatic charge and discharge (GCD) measurements.
Accordingly, GCP-35@CMC displayed the best performance among
all samples: 396.7 mF cm-2 at 0.1 mA cm-2 and 285 mF cm-2 even at
1.0 mA cm-2 (Fig. 2d, 71.8 % capacitance retention). The energy
density of GCP-35@CMC reached 55.1 µWh cm-2 under the power
density of 0.1 mW cm-2 (based on individual electrode). The
electrochemical performance of our ternary GCP-35@CMC is at the
top class compared with other solid state FSCs: RGO+CNT@CMC
yarn (177 mF cm-2, 3.84 µWh cm-2),29 nitrogen doped fiber-shaped
micro-supercapacitors (1132 mF cm-2, 95.7 µWh cm-2),41
MWCNT/OMC FSCs (39.7 mF cm-2, 1.77 µWh cm-2),42 N-doped
RGO/SWNT FSCs (116 mF cm-2, 16.1 µWh cm-2),43 MWCNT/carbon
FSCs (86.8 mF cm-2, 9.8 µWh cm-2),44 hollow graphene/conducting
polymer FSCs (304.5 mF cm-2, 6.8 and 27.1 µWh cm-2),45 RGO-Ni-
yarn supercapacitor (72.1 mF cm-2, 1.60 µWh cm-2),46 GF@3D-G
core-sheath microfibers (1.2-1.7 mF cm-2, 0.04-0.17 µWh cm-2)47 and
graphene/polypyrrole composite FSCs (107.2 mF cm-2, 6.6-9.7 µWh
cm-2),48 etc. The detailed comparison was listed in table S1†. GCD
curves of all samples in Fig. 2e are close to a symmetric triangular,
indicating a relatively high Coulombic efficiency in low current
density. The charge and discharge curves of RGO@CMC, GC@CMC
and GP-35@CMC are all inclined to be straight responding to EDLC
behavior while GCP-35@CMC become distorted due to the high
level of fast faradaic reactions. The charge-discharge mechanism of
GCP-35@CMC is shown in Fig 2f, in which EDLC of RGO and CNTs are
well combined with the pseudocapacitance derived from PEDOT:PSS.
Fig. 3 SEM images of (a-c) GC@CMC; (e-f) GCP-25@CMC; (g-i) GCP-30@CMC
and (j-l) GCP-40@CMC coaxial fiber with different magnifications.
The mass ratio of PEDOT:PSS is also an important factor
influencing the electrochemical performance of ternary coaxial
fibers. Graphene/CNTs/25%PEDOT:PSS (GCP-25@CMC), graphene/
CNTs/30%PEDOT:PSS (GCP-30@CMC) and graphene/CNTs/40%
PEDOT:PSS (GCP-40@CMC) were further fabricated and assembled
by a similar way. The microscopic morphologies of these samples
were characterized by SEM (Fig. 3). All of them have a similar core-
sheath structure like GCP-35@CMC in Fig. 1b-d.
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0.0 0.2 0.4 0.6 0.8 1.0-4
-2
0
2
4
6
Curr
entdensity
(mA
cm
-2)
Potential (V)
GC@CMCGCP-25@CMCGCP-30@CMCGCP-35@CMCGCP-40@CMC
(a)
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
400
(c)
CA(m
F/c
m2)
Current density (mA/cm2)
GC@CMCGCP-25@CMCGCP-30@CMCGCP-35@CMCGCP-40@CMC
0 5 10 15 200
5
10
15
20(d)
GC@CMCGCP-25@CMCGCP-30@CMCGCP-35@CMCGCP-40@CMC
-Z"
(k)
Z' (k )
0 1 2 30
1
2
3
0 1000 2000 3000 4000 5000 60000.0
0.2
0.4
0.6
0.8
1.0
(b)
Pote
ntial(V
)Time (s)
GC@CMCGCP-25@CMCGCP-30@CMCGCP-35@CMCGCP-40@CMC
Fig. 4 Electrochemical performance of GC@CMC, GCP-25@CMC, GCP-
30@CMC, GCP-35@CMC and GCP-40@CMC, (a) CV tests at 10 mV s-1; (b)
GCD tests at 0.1 mA cm-2; (c) rate performance while the current density
increased from 0.1 to 1.0 mA cm-2; (d) Nyquist plots, the inset shows the
high frequency behavior.
The electrochemical performance of GC@CMC, GCP-25@CMC,
GCP-30@CMC and GCP-40@CMC was compared with GCP-
35@CMC in Fig. 4. When the amount of PEDOT:PSS is lower than
30%, GC@CMC and GCP-25@CMC just performed a typical EDLC
behaviour without obvious redox peaks or distortion of straight
lines in their CV and GCD curves (Fig. 4a and b), resulting low CA of
GC@CMC (203.6 mF cm-2) and GCP-25@CMC (265.6 mF cm-2).
When the amount of PEDOT:PSS was increased, the obvious
pseudocapacitance behaviour can be seen in CV and GCD curves of
GCP-30@CMC and GCP-40@CMC, and their CA reached to 282.9 mF
cm-2 and 348.7 mF cm-2, respectively. Interestingly, the CA of GCP-
40@CMC is lower than GCP-35@CMC, indicating that the excess
amount of PEDOT:PSS is unfavourable to the electrochemical
performance. This result can be explained below. The conductivity
of PEDOT:PSS49-51 is usually lower than graphene/CNTs composite
since the insulating PSS is incorporated. Thus the addition of
PEDOT:PSS reduces the conductivity of ternary system. The intrinsic
ohmic resistance (Rs) of GCP-35@CMC and GCP-40@CMC are
tested to be 430 Ω and 460 Ω, respectively, increasing with the
content of PEDOT:PSS indeed. Both of them have a higher value
than GC@CMC (360 Ω) in which PEDOT:PSS is absent (Fig. S5a†).
Besides, the low frequency portion in Nyquist Plots of GCP-
35@CMC (or GCP-25@CMC and GCP-30@CMC) is nearly vertical to
the axis of real component, whereas GCP-40@CMC is featured by a
gradual slope rather than a steep one in Fig. 4d and Fig. S5b†. It
seems that high fraction of conductive polymer (>35 wt%) may
block some pores in core and influence the ion diffusion process
although it still expands the interlayer space of graphene sheets
and improve the wettability as mentioned above.
Fig. 5 (a) The cycling stability of GCP-35@CMC after 5000 cycles at the
current density of 3.0 mA cm-2; (b) The bending stability tests, the insets
show the different bending states; (c) Ragone plots compared with the
selected fiber supercapacitors with solid electrolyte; (d) Photograph of three
bending FSCs assembled by GCP-35@CMC in series; (e) LED lighted by three
FSCs assembled by GCP-35@CMC in series.
The cycling performance of GCP-35@CMC FSCs was tested by
GCD. In Fig. 5a, the GCP-35@CMC showed 90.4% capacitance
retention within 5000 times of GCD cycles at the current density of
3.0 mA cm-2. The slightly decrease of capacitance may be caused by
evaporation of water in PVA gel during cycling.52 Furthermore, The
flexibility of assembled free standing FSCs was tested during
repeatedly bending cycles (Fig. 5b). The insets in Fig. 5b show the
different bending states from 0o to 180o. No obvious decay of
capacitance was observed after 10000 bending cycles,
demonstrating the good stability and flexibility of our GCP-35@CMC
assembly. Ragone plots was showed in Fig. 5c, both of the
performance based on individual electrode (55.1-39.6 µWh cm-2,
0.1-1.0 mW cm-2) and entire device (13.8-9.9 µWh cm-2, 0.025-0.255
mW cm-2) were compared, and the GCP-35@CMC FSCs displayed
advanced results. Additionally, three assembled free standing
flexible FSCs can be easily connected in series (Fig. 5d) and light up
a LED lamp for about one minute (Fig. 5e).
Conclusions
In summary, we have fabricated ternary graphene/CNTs/
PEDOT:PSS@CMC coaxial fibers continuously via coaxial wet-
spinning technology. Flexible GCP-35@CMC FSCs have been
assembled with high specific capacitance, good rate capability and
excellent flexible (396.7 mF cm-2 at 0.1 mA cm-2, 71.8 % capacitance
retention from 0.1-1.0 mA cm-2, 10000 times bending with no
obvious capacitance decrease). The outstanding performance is
ascribed to the unique synergistic effect of well-designed ternary
system and the combination of EDLC with suitable
pseudocapacitance. It is worth mentioning that the GCP-35@CMC is
at the top class when compared with other solid-state FSCs.30, 42-48
Our work paves a new way on preparation of wearable and high
performance flexible yarn supercapacitors for future applications.
(c) (d) (e)
(a) (b)
0.01 0.1 1 100.01
0.1
1
10
PA-entire
(mW cm-2)
EA
-entire (m
Wh c
m-2)E
A-indiv
idual (µµ µµW
h c
m-2)
PA-individual
(mW cm-2)
This
workThis
workRef. 47
Ref. 47
Ref. 44
Ref. 45
Ref. 45
Ref. 46
Ref. 42
Ref. 29
0.01 0.1 1 10
0.01
0.1
1
10
0 2000 4000 6000 8000 100000
50
100
150
200
250
300
350
CA (m
F c
m-2)
Bending cycle
0 1000 2000 3000 4000 50000
20
40
60
80
100
120
Capacitance rete
ntion / %
Cycle number
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Acknowledgements
This work is supported by MOST National Key Research and
Development Program (No. 2016YFA0200200), and the National
Natural Science Foundation of China (No.s 21325417 and
51533008).
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