This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication.

Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available.

You can find more information about Accepted Manuscripts in the author guidelines.

Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the ethical guidelines, outlined in our author and reviewer resource centre, still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains.

Accepted Manuscript

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

View Article OnlineView Journal

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

This journal is © The Royal Society of Chemistry 20xx J. Mater. Chem. A, 2017, 00, 1-3 | 1

Please do not adjust margins

Please do not adjust margins

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:

chaogao@zju.edu.cn

† 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.

Page 1 of 5 Journal of Materials Chemistry A

Jour

nalo

fMat

eria

lsC

hem

istr

yA

Acc

epte

dM

anus

crip

t

Publ

ishe

d on

10

Oct

ober

201

7. D

ownl

oade

d by

Zhe

jiang

Uni

vers

ity o

n 11

/10/

2017

06:

23:4

3.

View Article OnlineDOI: 10.1039/C7TA07937K

COMMUNICATION Journal Name

2 | J. Mater. Chem. A, 2017, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

Please do not adjust margins

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)

Page 2 of 5Journal of Materials Chemistry A

Jour

nalo

fMat

eria

lsC

hem

istr

yA

Acc

epte

dM

anus

crip

t

Publ

ishe

d on

10

Oct

ober

201

7. D

ownl

oade

d by

Zhe

jiang

Uni

vers

ity o

n 11

/10/

2017

06:

23:4

3.

View Article OnlineDOI: 10.1039/C7TA07937K

Journal Name COMMUNICATION

This journal is © The Royal Society of Chemistry 20xx J. Mater. Chem. A, 2017, 00, 1-3 | 3

Please do not adjust margins

Please do not adjust margins

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.

Page 3 of 5 Journal of Materials Chemistry A

Jour

nalo

fMat

eria

lsC

hem

istr

yA

Acc

epte

dM

anus

crip

t

Publ

ishe

d on

10

Oct

ober

201

7. D

ownl

oade

d by

Zhe

jiang

Uni

vers

ity o

n 11

/10/

2017

06:

23:4

3.

View Article OnlineDOI: 10.1039/C7TA07937K

COMMUNICATION Journal Name

4 | J. Mater. Chem. A, 2017, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

Please do not adjust margins

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

Page 4 of 5Journal of Materials Chemistry A

Jour

nalo

fMat

eria

lsC

hem

istr

yA

Acc

epte

dM

anus

crip

t

Publ

ishe

d on

10

Oct

ober

201

7. D

ownl

oade

d by

Zhe

jiang

Uni

vers

ity o

n 11

/10/

2017

06:

23:4

3.

View Article OnlineDOI: 10.1039/C7TA07937K

Journal Name COMMUNICATION

This journal is © The Royal Society of Chemistry 20xx J. Mater. Chem. A, 2017, 00, 1-3 | 5

Please do not adjust margins

Please do not adjust margins

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).

References

1. X. Wang, X. Lu, B. Liu, D. Chen, Y. Tong and G. Shen, Adv. Mater.,

2014, 26, 4763-4782.

2. L. Dong, C. Xu, Y. Li, Z. Huang, F. Kang, Q. Yang and X. Zhao, J.

Mater. Chem. A, 2016, 4, 4659-4685.

3. H. Chen, F. Guo, Y. Liu, T. Huang, B. Zheng, N. Ananth, Z. Xu, W.

Gao and C. Gao, Adv. Mater., 2017, 29, 1605958.

4. W. Zeng, L. Shu, Q. Li, S. Chen, F. Wang and X. M. Tao, Adv.

Mater., 2014, 26, 5310-5336.

5. X. Xia, Y. Zhang, D. Chao, Q. Xiong, Z. Fan, X. Tong, J. Tu, H.

Zhang and H. Fan, Energy Environ. Sci., 2015, 8, 1559-1568.

6. D. Yu, Q. Qian, L. Wei, W. Jiang, K. Goh, J. Wei, J. Zhang and Y.

Chen, Chem. Soc. Rev., 2015, 44, 647-662.

7. J. Yan, Q. Wang, T. Wei and Z. Fan, Adv. Energy. Mater., 2014, 4,

1300816.

8. L. Zhang and X. S. Zhao, Chem. Soc. Rev., 2009, 38, 2520-2531.

9. H. Jiang, P. S. Lee and C. Li, Energy Environ. Sci., 2013, 6, 41-53.

10. X. Li and B. Wei, Nano Energy, 2013, 2, 159-173.

11. L. Kou, Z. Liu, T. Huang, B. Zheng, Z. Tian, Z. Deng and C. Gao,

Nanoscale, 2015, 7, 4080-4087.

12. T. Huang, S. Cai, H. Chen, Y. Jiang, S. Wang and C. Gao, J. Mater.

Chem. A, 2017, 5, 8255-8260.

13. T. Huang, B. Zheng, L. Kou, K. Gopalsamy, Z. Xu, C. Gao, Y. Meng

and Z. Wei, RSC Adv., 2013, 3, 23957-23962.

14. X. Zhao, B. Zheng, T. Huang and C. Gao, Nanoscale, 2015, 7,

9399-9404.

15. X. Yang, C. Cheng, Y. Wang, L. Qiu and D. Li, Science, 2013, 341,

534-537.

16. M. Beidaghi and C. Wang, Adv. Funct. Mater., 2012, 22, 4501-

4510.

17. S. Y. Yang, K. H. Chang, H. W. Tien, Y. F. Lee, S. M. Li, Y. S. Wang,

J. Y. Wang, C. C. M. Ma and C. C. Hu, J. Mater. Chem., 2011, 21,

2374-2380.

18. X. Huang, Z. Zeng, Z. Fan, J. Liu and H. Zhang, Adv. Mater. 2012,

24, 5979-6004.

19. M. Li, M. Zu, J. Yu, H. Cheng and Q. Li, Small, 2017, 13, 1602994.

20. B. Zheng, T. Huang, L. Kou, X. Zhao, K. Gopalsamy and C. Gao, J.

Mater. Chem. A, 2014, 2, 9736-9743.

21. V. Augustyn, P. Simon and B. Dunn, Energy Environ. Sci., 2014, 7,

1597-1614.

22. G. A. Snook, P. Kao and A. S. Best, J. Power Sources, 2011, 196,

1-12.

23. B. Wang, Q. Wu, H. Sun, J. Zhang, J. Ren, Y. Luo, M. Wang and H.

Peng, J. Mater. Chem. A, 2017, 5, 925-930.

24. Z. Xu and C. Gao, Nat. Commun., 2011, 2, 571.

25. Z. Xu and C. Gao, Acc. Chem. Res., 2014, 47, 1267-1276.

26. Z. Liu, Z. Li, Z. Xu, Z. Xia, X. Hu, L. Kou, L. Peng, Y. Wei and C. Gao,

Chem. Mater., 2014, 26, 6786-6795.

27. X. Zhao, Z. Xu, B. Zheng and C. Gao, Sci. Rep., 2013, 3, 3164.

28. X. Hu, Z. Xu and C. Gao, Sci. Rep.,2012, 2, 767.

29. L. Kou, T. Huang, B. Zheng, Y. Han, X. Zhao, K. Gopalsamy, H. Sun

and C. Gao, Nat. Commun., 2014, 5, 3754.

30. M. Beidaghi and C. Wang, Adv. Funct. Mater., 2012, 22, 4501-

4510.

31. J. H. Lee, N. Park, B. G. Kim, D. S. Jung, K. Im, J. Hur and J. W.

Choi, ACS nano, 2013, 7, 9366-9374.

32. Y. Huang, J. Liang and Y. Chen, small, 2012, 8, 1805-1834.

33. L. Zhang and X. Zhao, Chem. Soc. Rev., 2009, 38, 2520-2531.

34. Y. Zhou, S. L. Candelaria, Q. Liu, Y. Huang, E. Uchaker and G. CaO,

J. Mater. Chem. A, 2014, 2, 8472-8482.

35. G. Wang, L. Zhang and J. Zhang, Chem. Soc. Rev., 2012, 41, 797-

828.

36. H. Guo and Q. Gao, J. Power Sources, 2009, 186, 551-556.

37. S. P. Sasikala, K. E. Lee, J. Lim, H. J. Lee, S. H. Koo, I. H. Kim, H. J.

Jung and S. O. Kim, ACS nano, DOI: 10.1021/acsnano. 7b05029.

38. M. D. Stoller, S. Park, Y. Zhu, J. An and R. S. Ruoff, Nano Lett.,

2008, 8, 3498-3502.

39. S. Cho, M. Kim and J. Jang, ACS Appl. Mater. Interfaces, 2015, 7,

10213-10227.

40. J. Zhao, Y. Jiang, H. Fan, M. Liu, O. Zhuo, X. Wang, Q. Wu, L.

Yang, Y. Ma and Z. Hu, Adv. Mater., 2017, 29, 1604569.

41. G. Wu, P. Tan, X. Wu, L. Peng, H. Cheng, C. F. Wang, W. Chen, Z.

Yu and S. Chen, Adv. Funct. Mater. 2017, 27, 1702493.

42. J. Ren, W. Bai, G. Guan, Y. Zhang and H. Peng, Adv. Mater., 2013,

25, 5965-5970.

43. D. Yu, K. Goh, H. Wang, L. Wei, W. Jiang, Q. Zhang, L. Dai and Y.

Chen, Nat. Nanotechnol., 2014, 9, 555-562.

44. V. T. Le, H. Kim, A. Ghosh, J. Kim, J. Chang, Q. A. Vu, D. T. Pham,

J. H. Lee, S. W. Kim and Y. H. Lee, ACS Nano, 2013, 7, 5940-5947.

45. G. Qu, J. Cheng, X. Li, D. Yuan, P. Chen, X. Chen, B. Wang and H.

Peng, Adv. Mater., 2016, 28, 3646-3652.

46. X. Pu, L. Li, M. Liu, C. Jiang, C. Du, Z. Zhao, W. Hu and Z. L. Wang,

Adv. Mater., 2016, 28, 98-105.

47. Y. Meng, Y. Zhao, C. Hu, H. Cheng, Y. Hu, Z. Zhang, G. Shi and L.

Qu, Adv. Mater., 2013, 25, 2326-2331.

48. X. Ding, Y. Zhao, C. Hu, Y. Hu, Z. Dong, N. Chen, Z. Zhang and L.

Qu, J. Mater. Chem. A, 2014, 2, 12355-12360.

49. F. Zhang, M. Johansson, M. R. Andersson, J. C. Hummelen and O.

Inganas, Adv. Mater., 2002, 14, 662-665.

50. S. Park and R. S. Ruoff, Nature Nanotech., 2009, 4, 217-224.

51. D. Zhang, K. Ryu, X. Liu, E. Polikarpov, J. Ly, M. E. Tompson and

C. Zhou, Nano lett., 2006, 6, 1880-1886.

52. S. Chen, W. Ma, Y. Cheng, Z. Weng, B. Sun, L. Wang, W. Chen, F.

Li, M. Zhu and H. M. Cheng, Nano Energy, 2015, 15, 642-653.

Page 5 of 5 Journal of Materials Chemistry A

Jour

nalo

fMat

eria

lsC

hem

istr

yA

Acc

epte

dM

anus

crip

t

Publ

ishe

d on

10

Oct

ober

201

7. D

ownl

oade

d by

Zhe

jiang

Uni

vers

ity o

n 11

/10/

2017

06:

23:4

3.

View Article OnlineDOI: 10.1039/C7TA07937K