Advanced Energy Materials

Large-scale conductive yarns based on twistable Korean Traditional Paper (Hanji) for
supercapacitor applications: Towards high performance paper supercapacitors
--Manuscript Draft--

Manuscript Number: aenm.201801854R1

Full Title: Large-scale conductive yarns based on twistable Korean Traditional Paper (Hanji) for
supercapacitor applications: Towards high performance paper supercapacitors

Article Type: Full Paper

Section/Category:

Keywords: yarn-type paper supercapacitors; twistable energy storage electrodes; reduced

graphene oxide; carbon nanotube; solid-state supercapacitors

Corresponding Author: Le Hoang Sinh

Duy Tan University
Da Nang, VIET NAM

Additional Information:

Question Response

Please submit a plain text version of your June 12, 2018

cover letter here.
If you are submitting a revision of your
manuscript, please do not overwrite your twistable Korean Traditional Paper (Hanji) for supercapacitor applications: Towards
original cover letter. There is an
opportunity for you to provide your
responses to the reviewers later; please
do not add them here.
Dear Editor,
Attached herein is a manuscript entitled “Large-scale conductive yarns based on
high performance paper supercapacitors” by Young-Jung Heo, Ji Won Lee, Yeong-
Rae Son, Jong-Hoon Lee, Chang Su Yeo, Tran Dai Lam, Sang Yoon Park, Soo-Jin
Park, Le Hoang Sinh, and Min Kyoon Shin submitted for the publication in Advanced
Energy Materials as a Full Paper.
In this manuscript, we report a simple and scalable method to fabricate yarn type
supercapacitor with a large specific capacitance without the aid of traditional
pseudocapacitive electrode materials such as conducting polymers and metal oxides.
The yarn supercapacitors were made from twisting of reduced graphene oxide (rGO)
or/and single walled carbon nanotubes (SWNTs) coated on Korean traditional paper
(KTP). The yarn supercapacitor shows an excellent electrochemical performance with
a specific capacitance of 366 Fg-1 at scan rate of 25 mVs-1. Notably, a synergistic
effect between rGO and SWNTs were found, in which the supercapacitor coated of
both rGO and SWNT shows 500 times larger in specific capacitance than the
supercapacitor coated only rGO. The capacitance of rGO/SWNT@KTP yarn type is 7
times higher than that of sheet type supercapacitor at scan rate of 500 mVs-1.
Moreover, the supercapacitor shows high stability without any scarifying in electrical
performance up to 10,000 charge-discharge cycles.
Therefore, we strongly believe that the submitted manuscript would attract a great
attention in developing improved energy storage technologies. We hope that you will
find our manuscript as of particular interest to the readers of the Advanced Energy
Materials.
All the authors contributed to the work in this paper and all take responsibility for it.
Moreover, none of the work described in the manuscript has been published
elsewhere.
Thank you very much for your time spending on reading our manuscript.

Yours sincerely,
Dr. Min Kyoon Shin

Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation
 Advanced Institutes of Convergence Technology
Seoul National University
Suwon 443-270, Republic of Korea
Email: mkshin77@snu.ac.kr
Phone: +821029823265

Do you or any of your co-authors have a No. The authors declare no conflict of interest.
conflict of interest to declare?

Corresponding Author Secondary

Information:

Corresponding Author's Institution: Duy Tan University

Corresponding Author's Secondary

Institution:

First Author: Young-Jung Heo

First Author Secondary Information:

Order of Authors: Young-Jung Heo

Ji Won Lee

Yeong-Rae Son

Jong-Hoon Lee

Chang Su Yeo

Dai Lam Tran

Sang Yoon Park

Soo-Jin Park

Le Hoang Sinh

Min Kyoon Shin

Order of Authors Secondary Information:

Abstract: A simple and scalable method to fabricate a yarn type supercapacitor with a large
specific capacitance without the aid of traditional pseudocapacitive elecrode materials
such as conducting polymers and metal oxides is reported. The yarn supercapacitors
were made from twisting reduced graphene oxide (rGO) or/and single walled carbon
nanotubes (SWNTs) coated Korean traditional paper (KTP). The paper yarn
supercapacitor displays surprisingly enhanced electrochemical capacitance values,
showing synergistic effect between rGO and SWNTs (500 times larger than
performance of rGO coated paper yarn supercapacitors). Coating of rGO or/and
SWNTs on KTP gives good morphology and composite film, in which porosity
increases and mean pore diameter decreases. The rGO/SWNT paper yarn
supercapacitor shows good mechanical strength, high flexibility, excellent
electrochemical performance, and long-life operation. The paper yarn supercapacitor
gives an excellent electrochemical performance with a specific capacitance of 366 Fg-
1 at scan rate of 25 mVs-1 and, interestingly, high stability without any scarifying in
electrical performance up to 10,000 charge-discharge cycles. The capacitance of
rGO/SWNT@KTP yarn type is 7 times higher than that of sheet type supercapacitor at
scan rate of 500 mVs-1. Lighting a red LED is demonstrated by the paper yarn
supercapacitor without the use of supercapacitors connected in series.

Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation
Revised Manuscript

1
2 DOI: 10.1002/ ((please add manuscript number))
3 Article type: Full paper
4
5
6
7 Large-scale conductive yarns based on twistable Korean Traditional Paper (Hanji) for
8 supercapacitor applications: Towards high performance paper supercapacitors
9
10
11 Young-Jung Heo1, Ji Won Lee1, Yeong-Rae Son1, Jong-Hoon Lee1, Chang Su Yeo2, Tran Dai
12 Lam3, Sang Yoon Park4*, Soo-Jin Park1*, Le Hoang Sinh3*, Min Kyoon Shin4,a*
13
14 a
Representative Corresponding Author: Dr. Min Kyoon Shin
15
16
17 Y. -J. Heo, J. W. Lee, Y.-R Son, J. -H. Lee, Prof. S.-J. Park
1
18 Department of Chemistry, Inha University, Incheon 22212, Republic of Korea
19
20
21
C. S. Yeo,
2
22 Department of Physics, Sungkyunkwan University, Suwon, Republic of Korea
23
24 Prof. T. D. Lam, Dr. L. H. Sinh
25 3
Center for Advanced Chemistry, Institute of Research and Development, Duy Tan
26
27 University, 03 Quang Trung, Da Nang, Viet Nam
28
29 Prof. S. Y. Park, Dr. M. K. Shin
30 4
Advanced Institutes of Convergence Technology, Seoul National University, Suwon 443-
31
270, Republic of Korea
32
33
34 E-mail: mkshin77@snu.ac.kr, lehoangsinh@dtu.edu.vn, sjpark@inha.ac.kr,
35 yoonpark77@snu.ac.kr
36
37
38
Keywords: yarn-type paper supercapacitors, twistable energy storage electrodes, reduced
39 graphene oxide, carbon nanotube, solid-state supercapacitors
40
41
42
Abstract
43
44
45 A simple and scalable method to fabricate a yarn-type supercapacitor with a large specific
46
47 capacitance without the aid of traditional pseudocapacitive elecrode materials such as
48
49
50 conducting polymers and metal oxides is reported. The yarn-type supercapacitors were made
51
52 from twisting reduced graphene oxide (rGO) or/and single walled carbon nanotubes (SWNTs)-
53
54
55 coated Korean traditional paper (KTP). The yarn-type paper supercapacitor displays
56
57 surprisingly enhanced electrochemical capacitance values, showing synergistic effect between
58
59
60
rGO and SWNTs (500 times larger than performance of yarn-type rGO-coated paper
61
62 1
63
64
65
 supercapacitors). Coating of rGO or/and SWNTs on KTP gives good morphology to the
1
2 composite film, in which porosity increases and mean pore diameter decreases. The yarn-type
3
4
5 rGO/SWNT paper supercapacitor shows good mechanical strength, high flexibility, excellent
6
7 electrochemical performance, and long-life operation. The yarn-type paper supercapacitor has
8
9
10 an excellent electrochemical performance with a specific capacitance of 366 F g-1 at scan rate
11
12 of 25 mV s-1 and, interestingly, high stability without any degradation in electrical performance
13
14
15
up to 10,000 charge-discharge cycles. The average capacitance of rGO/SWNT@KTP yarn-type
16
17 supercapacitors is 7 times higher than that of sheet-type supercapacitors at scan rate of 500 mV
18
19 s-1. Lighting a red LED is demonstrated by the yarn-type paper supercapacitor without the use
20
21
22 of supercapacitors connected in series.
23
24
25
26
1. Introduction
27
28 Graphene is a promising material for application in supercapacitors thank to its outstanding
29
30 properties, i.e., excellent specific surface area (up to 2675 m2 g-1), high electrical conductivity,
31
32
33 good chemical stability, and high mechanical strength (~1 TPa).[1,2] For electrochemical
34
35 performance, the theoretical specific capacitance of single-layer-graphene is ~ 21 F cm-2 and
36
37
38 corresponding specific capacitance is ~550 F g-1 when entire surface area is fully utilized.[2]
39
40 However, the practical capacitive behavior of pure graphene is much lower than the theoretical
41
42
43 values due to the serious stacking of graphene sheets during both the preparation and operation
44
45 processes which leads to significant decrease of porosity of graphene-based electrodes.
46
47
48
Therefore, improving the overall electrochemical performance of graphene-based materials still
49
50 remains a great challenge. Besides stacking issue, the high hydrophobicity of pure graphene is
51
52 another critical issue for its supercapacitor application, which significantly decreases accessible
53
54
55 surface areas of electrode materials by common hydrophilic electrolytes, resulting in poor
56
57 electrochemical performance of supercapacitors. In this aspect, reduced graphene oxide (rGO),
58
59
60 a graphene derivative, exhibits some advantages over pure graphene. Although the electrical
61
62 2
63
64
65
 conductivity of rGO is lower in comparison with pure graphene, rGO contains a plenty of
1
2 oxygen-containing groups on the surface, which can be utilized for preparation of
3
4
5 functionalized rGO composites or tailoring the surface properties of rGO. Moreover, the
6
7 hydrophilicity of rGO can be adjusted by controlling the reduction degree. Back to the stacking
8
9
10 issue of rGO sheets, fiber-based materials have been introduced to rGO during solution process.
11
12 The fiber-based materials intercalate between rGO sheets to prevent their stacking, and lead to
13
14
15
improvements of both porosity and flexibility of rGO.[3–6] Among many kinds of fiber-based
16
17 materials, carbon nanotubes (CNTs) with nanoscale diameters have been considered as the most
18
19 promising candidate for flexible energy storage devices.[7,8] Many published works have been
20
21
22 done on rGO/CNTs composites, in which CNTs can effectively prevent stacking of rGO sheets
23
24 as well as improve electrical conductivity of rGO.[9–13] Cellulose fibers are another important
25
26
27 fiber-based material for this application.[14–20] Although the incorporation of cellulose fibers
28
29 into rGO-based electrodes leads to the increase of internal resistance of supercapacitors,
30
31
32
cellulose/rGO electrodes exhibit several advantages over pristine rGO electrodes: (i)
33
34 intercalation of cellulose nanofibers between rGO sheets prevents their stacking which results
35
36 in degradation of electrode porosity during supercapacitor operation; (ii) with super-hydrophilic
37
38
39 property, cellulose nanofibers play as nano/micro-capillaries for making the ions of electrolyte
40
41 pass easily through rGO electrodes; (iii) combination of cellulose nanofibers with rGO sheets
42
43
44 provide good flexibility of electrodes. Zheng et al. have reported on the freestanding cellulose
45
46 nanofibril-rGO-molybdenum oxynitride aerogel film electrode for all-solid-state
47
48
49 supercapacitors with ultrahigh energy density.[14] The film electrode showed an outstanding
50
51 specific capacitance of 680 F g-1 in an aqueous electrolyte and 518 F g-1 in an ionic liquid
52
53
54
electrolyte. Remarkably, the solid-state supercapacitor devices fabricated from the electrodes
55
56 gave an excellent energy density of 114 Wh kg-1. In this work, however, they did not show any
57
58 data related to mechanical strength of the film electrode. It is clear to see that cellulose
59
60
61 nanofibrils are short in fiber length, thus, they do not give a significant improvement of
62 3
63
64
65
 mechanical strength of the film electrode. Liu et al. have published a work related to three-
1
2 dimensional chemically bonded polypyrrole/bacterial cellulose/rGO for high-performance
3
4
5 supercapacitors.[18] The hybrid electrode showed a gravimetric capacitance of 492 F g-1 and
6
7 93.5% retention over 2000 recycling in a symmetric supercapacitor. Jiang et al. have made
8
9
10 successfully an in-situ grown bacterial nanocellulose/graphene oxide composite for flexible
11
12 supercapacitors.[19] The obtained electrode exhibited excellent electrochemical performance
13
14
15
with a gravimetric capacitance of 373 F g-1 at current density of 1 A g-1. However, these
16
17 electrodes are difficult to control porosity in whole electrodes and the preparation methods are
18
19 complex. Weng et al. have reported a simple method to make graphene-cellulose paper for
20
21
22 flexible supercapacitors from graphene suspension in N-methylpyrrolidone (NMP) and by the
23
24 filtration method.[15] The graphene sheets penetrated throughout the filter paper and formed a
25
26
27 continuous conducting network around the cellulose fibers. This structure helped the composite
28
29 paper to have excellent mechanical flexibility (94% retention in electric conductivity after being
30
31
32
bent 1000 times), good specific capacitance (120 F g-1), and energy storage performance (areal
33
34 energy density of 15 Wh cm-1). In comparison with commercial filter paper, Korean traditional
35
36
37 paper (KTP), which is made from mulberry bark with several superior properties, i.e., the
38
39 diameter of cellulose fibers in KTP was found around 11 m in this work, while that for
40
41
42 commercial filter paper is around 50 m.[21] Thus, KTP is expected to have better binding with
43
44 rGO sheets than commercial filter paper leading to increase of both performance and stability
45
46
47 of supercapacitors.
48
49 Graphene-based electrodes can be structured in several different shapes, i.e., the particles or
50
51
52
dots (0 dimension), fibers or yarns (1 dimension), films or sheets (2 dimensions), and foams (3
53
54 dimensions). The free-standing graphene-based paper electrodes have been attracted much
55
56 attention in last decade for flexible supercapacitors due to the tunable thickness, structural
57
58
59 flexibility, lightweight and easy assembly in to the device.[22,23] Although fast progress has been
60
61
62 4
63
64
65
 made in developing graphene-based paper supercapacitors, they usually do not allow sweat and
1
2 air from human body to pass through freely, thus they have limited wearability for potential
3
4
5 applications in wearable electronics.[24] In this context, graphene-based fiber and yarn
6
7 supercapacitors have a great application potential due to the combined merits of tiny volume,
8
9
10 high flexibility and weave-ability, which promise some applications in the next generation
11
12 supercapacitors for wearable and portable devices and electrical vehicles.[25] The macroscopic
13
14
15
fibers made of GO and rGO have been recently prepared by wet spinning.[26–28] These fibers
16
17 show remarkable mechanical properties, such as high modulus and tensile strength, which were
18
19 20-25 GPa and 400-440 MPa, respectively.[29] Moreover, after reduction, reduced graphene
20
21
22 oxide fiber exhibits a good electrical conductivity of 4000 S cm-1.[30] Unfortunately, these wet-
23
24 spun fibers exhibited low toughness, rough surfaces, and highly irregular cross sections. These
25
26
27 issues are very important in terms of the fiber/yarn-based supercapacitor performance. In
28
29 particular, the rough surface increases considerably the self-abrasion, while the irregular cross
30
31
32
section of the fibers results in unwanted stress concentration under mechanical loading, leading
33
34 them particularly susceptible to breaking. Moreover, irregular cross section also affects to the
35
36 electrical conductivity of the wet-spun fiber, which is limited by the smallest cross-sectional
37
38
39 area of fiber. Although these wet-spun fibers could exhibit relatively high Young’s modulus
40
41 and high tensile strength, they are found very brittle and easily breakable upon twisting,
42
43
44 knotting, and knitting.[31] This is the most disadvantages for knitted fabric wearable
45
46 supercapacitors.
47
48
49 Herein, we report new twisted yarn-type supercapacitors based on rGO or/and single walled
50
51 carbon nanotubes (SWNTs) coated on KTP which have outstanding mechanical and
52
53
54
electrochemical performances. Firstly, the highly ductile composite films were prepared by
55
56 using a scalable bar coating method of rGO, SWNT or rGO/SWNT solutions on KTP followed
57
58 by air drying at room temperature. These films were subsequently scrolled into fibers displaying
59
60
61 high toughness, outstanding ductility, and uniform circular cross sections. The effects of the
62 5
63
64
65
 carbon nanomaterials coating on porosity, mechanical properties, and electrochemical
1
2 performance of the supercapacitors were comprehensively investigated and presented in this
3
4
5 work.
6
7
8
9
10 2. Results and Discussion
11
12 2.1. Morphologies and textural properties of conductive composite film
13
14
15
The SWNT@KTP, rGO@KTP, and SWNT/rGO@KTP were prepared via the bar-coating
16
17 method. The apparatus for the bar-coating process is showed in Figure 1a. All solutions were
18
19
prepared at concentration of 1 mg mL-1. The gap between bar and substrate was fixed at 10 m.
20
21
22 The coating layers were selected at 1 to 10 layers in this work. After coating, the conductive
23
24 composite film was washed in deionized (DI) water three times to remove residual sodium
25
26
27 dodecylbenzene sulfonate (SDBS, surfactant) and any un-attached SWNT or/and rGO. The
28
29 resultant film was then dried in a vacuum oven at 60 oC for 10h. Figure 1b presents the optical
30
31
32 microscope images of pristine KTP (top image) and SWNT/rGO@KTP (bottom image). The
33
34 image of KTP exhibits highly uniform filaments with excellent entanglements between
35
36
37 filaments, which provide ductile property of KTP. The image of SWNT/rGO@KTP shows that
38
39 rGOs and SWNTs are adhesive well on KTP to obtain uniform coating in long range. The SEM
40
41
image of SWNT/rGO@KTP displays more clearly on dispersion of SWNTs and rGOs on KTP
42
43
44 and SWNTs and rGOs attached on KTP filaments as well in pores of KTP (Figure 1c). In high
45
46 magnification SEM image of SWNT/rGO@KTP in Figure 1d, we can clarify the SWNTs and
47
48
49 rGO flakes on a KTP filament. Thus, we expect that the porosity of KTP is enhanced by
50
51 introducing SWNT and rGO coatings. Figure 1e is XRD curves of pristine KTP and carbon
52
53
54 nanomaterials-coated KTP, which shows all characteristic peaks for cellulose crystal in KTP,
55
56 rGOs and SWNTs. In particular, two characteristic peaks of cellulose crystals in KTP were
57
58
59
found at 2θ of 15.2o and 23o.[32] The characteristic peaks for 002-plane of SWNT and MWNT
60
61 at 2θ of 25o were not be observed in XRD curves of SWNT@KTP, rGO/SWNT@KTP, and
62 6
63
64
65
 MWNT@KTP, which may be overlapped by high intense peak at 23o of cellulose crystals. The
1
2 peak for 002-plane of GO was found at 2θ of 11o. The slight shifting of peak for cellulose
3
4
5 crystals at 23o was found in rGO@KTP and rGO/SWNT@KTP because of its merging with
6
7 002-plane peak in rGO 2θ of 25o. Figure 1f gives the electrical resistance of rGO@KTP,
8
9
10 SWNT@KTP, rGO/SWNT@KTP, and a reference sample SWNT@commercial Double A
11
12 paper as a function of number of coating layers. The electrical conductivity of SWNT@KTP is
13
14
15
higher than that of SWNT@Double A paper, which implies that coating and penetration of
16
17 SWNT into KTP network are better than into Double A paper due to the highly porous structure
18
19 of KTP.
20
21
22 Figure 2 shows the effects of carbon materials coating on KTP. The SEM images display
23
24 clearly that SWNTs and rGOs were deposited on both filaments and micro-scale pores of KTP
25
26
27 (Figure 2a-h). The porosity of KTP was improved after coating with carbon nanomaterials
28
29 (Figure 2i). In particular, the porosities were 78.1, 80.5, 82.5 and 86.0 % for pristine KTP,
30
31
32
rGO@KTP, SWNT@KTP, and rGO/SWNT@KTP, respectively. The mean pore diameter of
33
34 KTP was also decreased due to the increase of the fraction of micropores when introducing of
35
36 carbon nanomaterials over nature macro-pores of pristine KTP. According to obtained data, the
37
38
39 mean pore diameters of pristine KTP, rGO@KTP, SWNT@KTP, and rGO/SWNT@KTP were
40
41 27.1, 15.5, 12.1, and 8.8 m. The highest porosity values of rGO/SWNT@KTP can be
42
43
44 explained by micro channels between cellulose and carbon materials and extra pores between
45
46 rGO and SWNT networks. The superior porosity and mean pore diameter of carbon
47
48
49 nanomaterials-coated KTP make them become excellent materials as electrodes for
50
51 supercapacitor. Based on the results, the structure of coated KTP can be illustrated as in Figure
52
53
54 2j, in which rGOs and SWNTs can adhere on both surface of KTP filaments as well inside the
55
56 pores of KTP. Data on morphologies and textural properties of KTP and conductive composite
57
58
59
films are summarized in Table 1.
60
61
62 7
63
64
65
 2.2. Water resistance of composite films
1
2 Coating carbon nanomaterials can enhance the water resistance of pristine KTP. Figure 3a
3
4
5 shows immediate contact angles of DI water solvent on pristine KTP and composite films and
6
7 decreased contact angles after 1 second (1s) and 60 seconds (60s). The pristine KTP exhibits
8
9
10 hydrophilic behavior with immediate and 1s contact angles of 65.3o and 33.2o, respectively. In
11
12 contrast, the composite films become more hydrophobicity with these values in range of 82.2-
13
14
15
117.2o and 46.8-114.8o for immediate and 60s contact angles, respectively. The contact angle
16
17 of rGO@KTP is lower than that of SWNT@KTP, which can be attributed to rGO has higher
18
19 hydrophilicity than SWNT due to residue of oxygen-containing groups. The highest coverage
20
21
22 on KTP filaments provides the best hydrophobic behavior of rGO/SWNT@KTP. To evaluate
23
24 the adhesive strength and stability of coating layers on KTP, the coated KTP and Double A
25
26
27 paper with rGO/SWNT were mechanical stirred in DI water for 30 min with 750 rpm. The
28
29 photographs of mechanical stirred samples are shown in Figure 3b. The coated layer on KTP
30
31
32
is still stable after stirred process; whereas the coated layer on Double A paper is mostly
33
34 detached from the surface of paper, which is indicated by changing color of the samples after
35
36 stirring. This is also proved by same resistivity of KTP before and after stirring process whereas
37
38
39 the resistivity value is increased in the case of Double A paper (Figure 3c).
40
41
42
43
44 2.3. Properties of twisted yarn fiber
45
46 The twisted yarn fibers from composite films were prepared by using mechanically scrolling.
47
48
49 The composite films were cut at specific widths and then were scrolled at fixed scrolling rate
50
51 of 180 rpm. To have successful scrolling, the composite films were wetted enough with DI
52
53
54
water. Finally, the twisted yarn fiber will be dried in air with fixing the ends of fiber. The
55
56 preparation of twisted fibers is illustrated in Figure 4a. The diameters of twisted yarn fibers are
57
58 controlled by varying widths of composite films, which increase linearly with the increase of
59
60
61 widths of composite films (Figure 4b). The images of twisted fiber are showed in Figure 4c.
62 8
63
64
65
 Figure 4d presents the mechanical properties of twisted fibers. According to the data,
1
2 rGO@KTP and rGO/SWNT@KTP twisted fibers exhibit the good mechanical strength with
3
4
5 maximum stress and elongation at break of 30 MPa and 8 %, respectively. Moreover,
6
7 SWNT@KTP twisted fiber shows more ductile behavior with maximum stress and elongation
8
9
10 at break of 20 MPa and 11%, respectively. Figure 4e provides a comparison on resistivity of
11
12 our twisted fibers with other published carbon-based fibers. Notably, SWNT@KTP and
13
14
15
rGO/SWNT@KTP twisted fibers show resistivity in comparable with carbon fiber bundles[33]
16
17 and even lower than that of pure rGO twisted fibers.[34] Furthermore, electrical resistivity values
18
19 of our twisted fibers exhibits a similar order of magnitude with those of wet-spun rGO/SWNT
20
21
22 fibers[35] and pristine MWCNT fibers[36], and are lower than that of wet spun SWNT fibers[37].
23
24 LED-activated tree from our conductive twisted fibers are illustrated and shown in Figure 4f.
25
26
27 The twisted fiber can be made in meter scale and connect together easily by knotting.
28
29
30
31
32 2.4. Electrochemical properties of yarn-type solid-state supercapacitor
33
34 Figures 5a and 5b illustrate fabrication of a yarn-type solid-sate supercapacitor from twisted
35
36 fibers (symmetric two electrodes). The composite films were scrolled around a nickel wire as
37
38
39 current collector. The resultant fibers were then coated with poly(vinyl alcohol) (PVA)
40
41 dissolved in 1 M sulfuric acid (H2SO4). The covered thin layer of protonated PVA can play a
42
43
44 significant role as both solid electrolyte and separator. Two fibers were twisted to make yarn-
45
46 type supercapacitors. Figure 5c gives the cyclic voltammetry (CV) curves of three types of
47
48
49 twisted fibers. The rGO/SWNT@KTP shows a superior electrochemical performance over
50
51 rGO@KTP and SWNT@KTP twisted fibers. This can be explained by high electrochemical
52
53
54
activity from rGO and good electrical conductivity of SWNTs, which cannot find in rGO@KTP
55
56 and SWNT@KTP twisted fibers. Moreover, this improvement also came from reducing the
57
58 restacking of rGO sheets by combination of rGO and SWNTs, which leads to the increase of
59
60
61 accessed area of active carbon materials to electrolyte. Figure 5d shows CV curves of
62 9
63
64
65
 rGO/SWNT@KTP yarn-type supercapacitor at difference scan rates of voltage. The inset figure
1
2 is plot of gravimetric specific capacitances of the supercapacitor as a function of scan rates of
3
4
5 voltage. The supercapacitor shows a remarkable specific capacitance of 366 F g-1 at scan rate
6
7 of 25 mV s-1. Notably, excellent electrochemical performance of our yarn-type supercapacitor
8
9
10 is obtained by using only carbon nanomaterials without employing pseudo capacitive materials
11
12 such as conducting polymers or metal oxides. Changing structure of supercapacitor from sheet
13
14
15
type to yarn-type is the key factor for this great achievement. There are several factors can
16
17 contribute to a superior electrochemical performance of the yarn-type solid state supercapacitor:
18
19 (i) high electrochemical activity of rGO; (ii) high electrical conductivity leading to decrease of
20
21
22 internal resistance of the supercapacitor, which is shown in Nyquist plot (Figure 5g); (iii) The
23
24 network of cellulose filaments of KTP plays as hydrophilic capillaries, which improves
25
26
27 diffusion of electrolyte through active material. The Figure 5e displays the capacitance
28
29 retention of the yarn-type supercapacitor up to 10,000 charge-discharge cycles. A slight
30
31
32
increase of capacitance of the yarn supercapacitor could be due to activation of the electrode
33
34 and more complete intercalation and de-intercalation of electrolytes when cycles of charge-
35
36 discharge increased, which has been reported.[38,39] More importantly, the yarn fiber does not
37
38
39 show any degradation in capacitance up to 10,000 charge-discharge cycles. This proves that our
40
41 yarn supercapacitor can be considered as a promising storage energy device. Yarn-type paper
42
43
44 supercapacitor electrodes with a Ni wire core shows higher specific capacitance than that of
45
46 yarn-type paper supercapacitor electrodes with a carbon fiber core (Figure 5f), which could be
47
48
49 explained by fact that Ni wire having a higher intrinsic electrical conductivity than carbon fibers
50
51 leads to lower equivalent series resistance (ESR). This is confirmed in the Nyquist plots of the
52
53
54
yarn supercapacitors with Ni wire core and carbon fiber core (Figure 5g).[40] In spite of
55
56 increased ESR, yarn-type paper supercapacitors with carbon fiber cores play a significant role
57
58 as metal free, lightweight, anti-corrosive wearable energy storage devices.
59
60
61
62 10
63
64
65
 The combination of energy storage and power densities for the complete supercapacitor
1
2 (including both electrodes of Ni wire cores and solid electrolyte) is indicated in the Ragone
3
4
5 plots of Figure 6, which compares performance with that for other micro-size energy storage
6
7 devices. The yarn-type paper supercapacitor had an average volumetric power density of
8
9
10 91 W cm−3. As a quantitative comparison, it is 9 of commercial 25 mF supercapacitors (~10
11
12 W cm−3)[41] and 5000 times of yarn-type supercapacitor based on RGO/CNT@CMC (0.018
13
14
15
W cm−3).[42] The yarn-type paper supercapacitor exhibited volumetric energy densities of up to
16
17 0.29 mWh cm−3, which is 1.3 times higher than that of yarn-type supercapacitor based on
18
19 carbon/MnO2 core-shell structure (0.22 mWh cm−3).[43] In addition, the yarn-type paper
20
21
22 supercapacitors have an average gravimetric power density of 3.7 kW kg-1 and maximum
23
24 gravimetric energy density of 11.7 mWh kg-1.
25
26
27 To illustrate advantages of yarn-type supercapacitor over sheet-type supercapacitor, Figure 7
28
29 shows a comparison on their specific capacitance. The CV curves of yarn-type and sheet-type
30
31
32
supercapacitors are shown in Figures 7a and 7b, respectively. Figure 7c presents specific
33
34 capacitance of both supercapacitors as a function of voltage scan rates. The specific
35
36 capacitances of yarn-type supercapacitor shows much higher than those of sheet-type capacitor.
37
38
39 The summarized data are shown in Table 2. Interestingly, the improvement is more significant
40
41 when voltage scan rates increase. In particular, at scan rate of 500 mV s-1, yarn-type
42
43
44 supercapacitor gives a specific capacitance higher than 7 times that of sheet-type supercapacitor.
45
46 This can be explained by shortening of conductive pathways in yarn-type supercapacitor
47
48
49 compare with sheet-type supercapacitor, which leads to lower ESR in yarn-type supercapacitor
50
51 than that of sheet-type supercapacitor. Moreover, winkling and increasing packing density of
52
53
54
yarn-type supercapacitor during twisting can also contribute in this improvement. To support
55
56 our suggesting, the Nyquist plots of both supercapacitors were evaluated and are shown in
57
58 Figure 7d. The ESR of yarn-type supercapacitor was 6.5 Ω, which is much lower than that of
59
60
61 sheet-type supercapacitor (125.4 Ω).
62 11
63
64
65
 1
2 3. Conclusion
3
4
5 The yarn-type paper supercapacitors were fabricated by simply twisting rGO or/and SWNT-
6
7 coated KTP films. These composite films were made by using a scalable bar coating process.
8
9
The yarn-type supercapacitors show large scale production, good mechanical stability, and
10
11
12 excellent electrochemical performance. In particular, the supercapacitor can give a maximum
13
14 gravimetric specific capacitance of 366 F g-1. Interestingly, the average capacitance of
15
16
17 rGO/SWNT@KTP yarn-type supercapacitors is 7 times higher than that of sheet-type
18
19 supercapacitors at scan rate of 500 mV s-1. More importantly, the supercapacitor exhibits
20
21
22 excellent long-term stability up to 10,000 charge-discharge cycles. The obtained results suggest
23
24 that our yarn-type supercapacitors have great potential applications as wearable energy-storage
25
26
27
devices.
28
29
30
31 4. Experimental Section
32
33
34 Materials
35
36 Korean traditional paper (KTP) was purchased from Ajhanji Company. rGO (high porosity)
37
38
39 was purchased from graphene supermarket, and SWNT was purchased from OCSiAl company.
40
41 Sodium dodecylbenzenesulfonate (SDBS), sulfuric acid (H2SO4, 95 wt%) and poly(vinyl
42
43
44 alcohol) (PVA) (MW 85,000-124,000; 99+%, hydrolyzed) was purchased from Aldrich
45
46 Chemicals. All other reagents were of analytical grade.
47
48
49
50 Preparation of rGO, SWNT, and rGO/SWNT solutions
51
52 rGO and SWNT ink solution were prepared by dispersing 20 mg of rGOs and SWNTs with 20
53
54
55
mg of SDBS surfactant in 20 mL of deionized water, respectively. rGO and SWNT powder
56
57 with SDBS in water dispersions were prepared using homogenization and ultra-sonication (tip
58
59 probe sonicator). rGO/SWNT solution was prepared by mixing the rGO and SWNT solution.
60
61
62 12
63
64
65
 1
2 Bar coating of conductive solutions on KTP
3
4
5 Highly porous KTP (~10 gsm (gram per square meter), thickness 60 μm) was used as substrates
6
7 to apply the dispersion coatings, by using a laboratory scale PI-1210 auto film applicator (Tester
8
9
10 Sangyo co., LTD). Conductive sheets were prepared by bar coating the dispersed solutions on
11
12 KTP with a micrometer adjustable film applicator (thickness 10 m) operating under controlled
13
14
15 bar moving speed of 10 mm s-1, so that the ink can be sufficiently absorbed into the KTP to
16
17 proceed the coating. After coating, the coated sheets were washed three times with ethanol and
18
19
20
water. The loaded material weights were determined by thermogravimetric analysis (TGA).
21
22
23
24 Fabrication of twisted yarn and yarn-type single electrode
25
26
27 Twisting yarns were prepared by scrolling mechanically. In order to have a successful scrolling,
28
29 the sheet must be left to wet. One end of a strip of 10 cm in length is tightly attached to the
30
31
32 electric motor, then, the conductive sheet was slowly twisted using the electric motor to
33
34 introduce 92 to 735 turns per meter of inserted twist per yarn length. After twisting process,
35
36
37 both ends of the twisted yarn were fixed to the glass slide and the twisted yarn was dried at 40
38
o
39 C with vacuum condition. Depending upon the width of the conductive sheets, the resulting
40
41
yarn diameter ranged from ~0.25 to ~2 mm. Metal core sheath structured yarn is illustrated in
42
43
44 Figure 4a. The core material, which is a 0.2 mm diameter nickel (Ni) wire, is pulled out to
45
46 merge with the conductive sheet. The twisting process of the spindle at the right-hand side
47
48
49 causes the Ni wire and the conductive sheet to rotate together, resulting in the wrapping of the
50
51 conductive sheet around the wire to form a metal core sheath structured yarn as single electrode.
52
53
54
55
56 Characterizations
57
58
59
Surface morphology of KTP sheets and twisting yarns were characterized using high resolution
60
61 scanning electron microscopy (HR-SEM, SU-8010, Hitachi Co.). Structural properties of the
62 13
63
64
65
 prepared materials were examined using X-ray diffraction (XRD, D2 PHASER, Bruker Co.).
1
2 TGA was carried out on Pyris 1 (Perkin elmer Co.) at a heating rate of 10 °C min-1 from 50 to
3
4
5 900 °C under a N2 atmosphere. The resistance of conductive papers and yarns was measured
6
7 by using the four-point probe technique (EDTM). The tensile strength and Young’s modulus of
8
9
10 the twisted yarns were measured by using a universal testing machine (UTM, LR5KPlus,
11
12 LLOYD Instruments Ltd.) at a loading rate of 2 mm min−1 with a gauge length of 25 mm. Cyclic
13
14
15 voltammetry and electrochemical impedance spectroscopy (EIS) measurement were
16
17 investigated using electrochemical analyzer (IviumStat electrochemical workstation). Textural
18
19
20 properties of pristine KTP and carbon nanomaterials coated on KTP films were evaluated by
21
22 using a high-pressure mercury porosimeter (Micromeritics AutoPore IV 9500) with range of
23
24
25
pressure from 0.1 to 60,000 psia. The pore diameter can be calculated by Washburn equation:
26
1
27 𝐷 = (𝑃) 4𝛾 𝑐𝑜𝑠𝜑 (1)
28
29
30 Where P is the applied pressure, γ is the surface tension of mercury, and φ is the contact angle
31
32
33 between of the mercury and the sample. Mean pore diameter in range of measurement can be
34
35 calculated from pore diameter of initial pressure (Di) to pore diameter of final pressure (Dj) as
36
37 (Dj-Di)/2.
38
39
40 Porosity (%) can be calculated by the equation:
41
42 𝑉
43 𝑃𝑜𝑟𝑜𝑠𝑖𝑡𝑦(%) = 𝑉𝑣 𝑥100% (2)
𝑇
44
45
46
Where Vv is the void volume, which occupied by mercury; VT is total volume of sample.
47
48
49
50 Preparation of solid electrolyte and construction of supercapacitor
51
52
53 Gel electrolyte was prepared by mixing 1M H2SO4 with PVA powder. This solution was stirred
54
55 vigorously throughout the mixing process and then continuously heated to 85 ° C until the
56
57
58 solution was clear. For-solid state capacitor, two such yarn-type electrodes were first
59
60 individually wetted with 1M H2SO4/PVA gel electrolyte. The electrolyte wetted electrodes
61
62 14
63
64
65
 were placed in parallel and dried until gel solidification at room temperature. By rotating
1
2 process, the two yarn electrodes will be plied together to form a two-ply yarn supercapacitor.
3
4
5
6 Acknowledgements
7
8 This work was supported by the National Research Foundation of Korea (NRF) grant funded
9
10
11 by the Korea government (MSIP, Ministry of Science, ICT & Future Planning) (No.
12
13 2016M3A7B4910458 and 2016M3A7B4910457).
14
15
16 This research was supported by Traditional Culture Convergence Research Program through
17
18 the National Research Foundation of Korea(NRF) funded by the Ministry of Science, ICT &
19
20
21 Future Planning (2016M3C1B5952897) and the Technology Innovation Program (or Industrial
22
23 Strategic Technology Development Program (10080293, Development of carbon-based non
24
25
phenolic electrode materials with 3,000m2/g grade surface area for energy storage device)
26
27
28 funded By the Ministry of Trade, Industry & Energy(MOTIE, Korea).
29
30
31
32
33 Received: ((will be filled in by the editorial staff))
34 Revised: ((will be filled in by the editorial staff))
35 Published online: ((will be filled in by the editorial staff))
36
37
38
39 References
40
41 [1] T. J. Booth, P. Blake, R. R. Nair, D. Jiang, E. W. Hill, U. Bangert, A. Bleloch, M.
42
43
44 Gass, K. S. Novoselov, M. I. Katsnelson, A. K. Geim, Nano Lett. 2008, 8, 2442.
45
46 [2] J. Xia, F. Chen, J. Li, N. Tao, Nat. Nanotechnol 2009, 4, 505.
47
48
49 [3] B. You, L. Wang, L. Yao, J. Yang, Chem. Commun. 2013, 49, 5016.
50
51 [4] Z. U. Khan, A. Kausar, H. Ullah, Polym. - Plast. Technol. Eng. 2016, 55, 559.
52
53
54
[5] X. Zang, Q. Zhou, J. Chang, Y. Liu, L. Lin, Microelectron. Eng. 2015, 132, 192.
55
56 [6] X. Huang, X. Qi, F. Boey, H. Zhang, Chem. Soc. Rev. 2012, 41, 666.
57
58 [7] J. Ren, Y. Zhang, W. Bai, X. Chen, Z. Zhang, X. Fang, W. Weng, Y. Wang, H. Peng,
59
60
61 Angew. Chemie - Int. Ed. 2014, 53, 7864.
62 15
63
64
65
 [8] Y. Zhang, W. Bai, X. Cheng, J. Ren, W. Weng, P. Chen, X. Fang, Z. Zhang, H. Peng,
1
2 Angew. Chemie - Int. Ed. 2014, 53, 14564.
3
4
5 [9] D. Yu, L. Dai, J. Phys. Chem. Lett. 2010, 1, 467.
6
7 [10] G. Sun, X. Zhang, R. Lin, J. Yang, H. Zhang, P. Chen, Angew. Chemie - Int. Ed. 2015,
8
9
10 54, 4651.
11
12 [11] Z.-D. Huang, B. Zhang, S.-W. Oh, Q.-B. Zheng, X.-Y. Lin, N. Yousefi, J.-K. Kim, J.
13
14
15
Mater. Chem. 2012, 22, 3591.
16
17 [12] Z. Fan, J. Yan, L. Zhi, Q. Zhang, T. Wei, J. Feng, M. Zhang, W. Qian, F. Wei, Adv.
18
19 Mater. 2010, 22, 3723.
20
21
22 [13] P. Chen, Y. Xu, S. He, X. Sun, S. Pan, J. Deng, D. Chen, H. Peng, Nat. Nanotechnol.
23
24 2015, 10, 1077.
25
26
27 [14] Q. Zheng, A. Kvit, Z. Cai, Z. Ma, S. Gong, J. Mater. Chem. A 2017, 5, 12528.
28
29 [15] Z. Weng, Y. Su, D. W. Wang, F. Li, J. Du, H. M. Cheng, Adv. Energy Mater. 2011, 1,
30
31
32
917.
33
34 [16] L. Valentini, M. Cardinali, E. Fortunati, L. Torre, J. M. Kenny, Mater. Lett. 2013, 105,
35
36 4.
37
38
39 [17] W. Ouyang, J. Sun, J. Memon, C. Wang, J. Geng, Y. Huang, Carbon 2013, 62, 501.
40
41 [18] Y. Liu, J. Zhou, J. Tang, W. Tang, Chem. Mater. 2015, 27, 7034.
42
43
44 [19] Q. Jiang, C. Kacica, T. Soundappan, K. Liu, S. Tadepalli, P. Biswas, S. Singamaneni,
45
46 J. Mater. Chem. A 2017, 5, 13976.
47
48
49 [20] X. Du, Z. Zhang, W. Liu, Y. Deng, Nano Energy 2017, 35, 299.
50
51 [21] L. Jiang, G. W. Nelson, H. Kim, I. N. Sim, S. O. Han, J. S. Foord, ChemistryOpen
52
53
54
2015, 4, 586.
55
56 [22] H. Gwon, H.-S. Kim, K. U. Lee, D.-H. Seo, Y. C. Park, Y.-S. Lee, B. T. Ahn, K. Kang,
57
58 Energy Environ. Sci. 2011, 4, 1277.
59
60
61 [23] G. Eda, M. Chhowalla, Nano Lett. 2009, 9, 814.
62 16
63
64
65
 [24] D. Yu, Q. Qian, L. Wei, W. Jiang, K. Goh, J. Wei, J. Zhang, Y. Chen, Chem. Soc. Rev.
1
2 2015, 44, 647.
3
4
5 [25] D. Yu, Q. Qian, L. Wei, W. Jiang, K. Goh, J. Wei, J. Zhang, Y. Chen, Chem. Soc. Rev.
6
7 2015, 44, 647.
8
9
10 [26] Z. Xu, C. Gao, Nat. Commun. 2011, 2, 571.
11
12 [27] H.-P. Cong, X.-C. Ren, P. Wang, S.-H. Yu, Sci. Rep. 2012, 2, 613.
13
14
15
[28] J. Sun, Y. Li, Q. Peng, S. Hou, D. Zou, Y. Shang, Y. Li, P. Li, Q. Du, Z. Wang, Y. Xia,
16
17 L. Xia, X. Li, A. Cao, ACS Nano 2013, 7, 10225.
18
19 [29] R. Jalili, S. H. Aboutalebi, D. Esrafilzadeh, R. L. Shepherd, J. Chen, S. Aminorroaya-
20
21
22 Yamini, K. Konstantinov, A. I. Minett, J. M. Razal, G. G. Wallace, Adv. Funct. Mater.
23
24 2013, 23, 5345.
25
26
27 [30] Z. Xu, H. Sun, X. Zhao, C. Gao, Adv. Mater. 2013, 25, 188.
28
29 [31] S. Seyedin, M. S. Romano, A. I. Minett, J. M. Razal, Sci. Rep. 2015, 5, 14946.
30
31
32
[32] S. Park, J. O. Baker, M. E. Himmel, P. A. Parlla, D. K. Johnson, Biotechnol. Biofuels.
33
34 2010, 3, 10.
35
36 [33] F. Lundström, K. Frogner, M. Andersson, Compos. Part B Eng. 2018, 140, 204
37
38
39 [34] R. Cruz-Silva, A. Morelos-Gomez, H. I. Kim, H. K. Jang, F. Tristan, S. Vega-Diaz, L.
40
41 P. Rajukumar, A. L. Elías, N. Perea-Lopez, J. Suhr, M. Endo, M. Terrones, ACS Nano
42
43
44 2014, 8, 5959.
45
46 [35] D. Yu, K. Goh, H. Wang, L. Wei, W. Jiang, Q. Zhang, L. Dai, Y. Chen, Nat.
47
48
49 Nanotechnol. 2014, 9, 555.
50
51 [36] J. Foroughi, G. M. Spinks, D. Antiohos, A. Mirabedini, S. Gambhir, G. G. Wallace, S.
52
53
54
R. Ghorbani, G. Peleckis, M. E. Kozlov, M. D. Lima, R. H. Baughman, Adv. Funct.
55
56 Mater. 2014, 24, 5859.
57
58 [37] B. Vigolo, A. Pénicaud, C. Coulon, C. Sauder, R. Pailler, C. Journet, P. Bernier, P.
59
60
61 Poulin, Science 2000, 290, 1334.
62 17
63
64
65
 [38] H.-C. Chen, C.-C. Wang, S.-Y. Lu, J. Mater. Chem. A 2014, 2, 16955.
1
2 [39] S. Aloqayli, C. K. Ranaweera, Z. Wang, K. Siam, P. K. Kahol, P. Tripathi, O. N.
3
4
5 Srivastava, B. K. Gupta, S. R. Mishra, F. Perez, X. Shen, R. K. Gupta, Energy Storage
6
7 Mater. 2017, 8, 68.
8
9
10 [40] V. Ganesh, S. Pitchumani, V. Lakshminarayanan, J. Power Sources 2006, 158, 1523.
11
12 [41] D. Pech, M. Brunet, H. Durou, P. Huang, V. Mochalin, Y. Gogotsi, P. L. Taberna, P.
13
14
15
Simon, Nat. Nanotechnol. 2010, 5, 651.
16
17 [42] L. Kou, T. Huang, B. Zheng, Y. Han, X. Zhao, K. Gopalsamy, H. Sun, C. Gao, Nat.
18
19 Commun. 2014, 5, 3754.
20
21
22 [43] X. Xiao, T. Li, P. Yang, Y. Gao, H. Jin, W. Ni, W. Zhan, X. Zhang, Y. Cao, J. Zhong,
23
24 L. Gong, W. C. Yen, W. Mai, J. Chen, K. Huo, Y. L. Chueh, Z. L. Wang, J. Zhou, ACS
25
26
27 Nano 2012, 6, 9200.
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 18
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45 Figure 1. Conformal coating of carbon solutions on KTP sheet. a) Bar coating of
46
47
rGO/SWNT on KTP paper. b) Microscope images of pristine KTP and rGO/SWNT coated KTP,
48 inset indicated KTP has light and air permeability. (c,d) Surface morphology of rGO/SWNT on
49 KTP, inset shows the networks between rGO and SWNT on KTP. e) XRD curves of pristine
50 KTP and carbon nanomaterials coated KTP. f) Sheet resistances of carbon inks on KTP and
51 Double A paper. Their concentration are 1 mg/mL as same.
52
53
54
55
56
57
58
59
60
61
62 19
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 Figure 2. Morphologies and textural properties of conductive KTP sheets depending on
31 coating carbon solutions. SEM images of (a,e) neat KTP , (b,f) rGO on KTP, (c,g) SWNT on
32
33 KTP and (d,h) rGO/SWNT on KTP with different magnifications. i) Porosity and mean pore
34 diameter changes as function of carbon materials. j) Schematic illustration showing the
35 structures of conductive KTP sheets as function of carbon materials.
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 20
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 Figure 3. Water resistance of pristine KTP and composite films. a) Immediate and 1s (for
33 KTP) and 60s (for composite films) contact angles. b) Photograph of coated KTP and Double
34 A paper after mechanical stirred in DI water for 30 min. c) Sheet resistance of coated KTP and
35
36 Double A paper after mechanical stirred in DI water for 30 min.
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 21
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43 Figure 4. Fabrication of twisted yarns using conductive KTP sheets. a) Schematic
44 illustration showing the fabrication of a twisted yarn. b) The dependence of fiber diameter on
45
46 paper width. c) SEM image of twisted yarn with knot architectures. d) Stress-strain curves for
47 twisted yarns as function of carbon materials. Inset shows tensile strength and Young’s modulus
48 of twisted yarns. e) Comparison of the fiber resistances of our twisted yarns with other reports
49 conductive fibers. f) Photographs of LED-activated tree through conductive yarns.
50
51
52
53
54
55
56
57
58
59
60
61
62 22
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46 Figure 5. Electrochemical properties of yarn-type solid-state supercapacitor a) Schematic
47
48
illustration showing the fabrication of yarn-type single electrode. b) Schematic illustration of
49 the structure and cross-section of biscrolled electrodes. c) Comparison of cyclic voltammetry
50 curves of the SWNT, rGO and rGO/SWNT on KTP twisted yarns. d) Cyclic voltammetry at
51 different voltage scan rates of rGO/SWNT on KTP twisted yarn. e) Cycling retention of
52 rGO/SWNT on KTP twisted yarns. Inset shows yarn-type solid-state supercapacitor used to
53
54 repeatedly light up a red LED. f) Cyclic voltammetry of rGO/SWNT@KTP twisted yarn
55 supercapacitors with different conducting cores at 100 mV s-1 (black line: Ni wire, red line:
56 carbon fibers). g) Nyquist plots for paper yarn supercapacitor electrodes with Ni wires (filled
57 black circles) and carbon fibers (filled red circles) as cores, showing the imaginary part versus
58
the real part of impedance. Inset: magnified diagram for high frequencies.
59
60
61
62 23
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16 Figure 6. Ragone plots of yarn-type solid-state supercapacitor. a) Comparing gravimetric
17
18
energy density and gravimetric power density. b) Comparing volumetric energy density and
19 volumetric power density.
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 24
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 Figure 7. Electrochemical performance comparison between yarn-type and sheet-type. a)
33 Cyclic voltammetry of yarn-type supercapacitor (inset: structure of yarn-type supercapacitor).
34 b) Cyclic voltammetry of sheet-type supercapacitor (inset: structure of sheet-type
35
36
supercapacitor). c) Specific capacitance of yarn-type and sheet-type supercapacitors as a
37 function of voltage scan rates. d) Nyquist plots of yarn-type and sheet-type supercapacitors.
38 Inset: magnified diagram for high frequencies.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 25
63
64
65
 Table 1. Textural properties of KTP samples.
1
2 Specimens Total pore area Average Bulk Apparent Porosity
3
4 (m2 g-1) pore density at (skeletal) (%)
5 diameter 0.23 psi density
6 (um) (g mL-1) (g mL-1)
7 Neat KTP 0.886 27.1 0.141 0.914 78.1
8
9
rGO@KTP 1.690 15.5 0.154 1.796 80.5
10 SWNT@KTP 2.836 12.1 0.141 1.114 82.5
11 rGO/SWNT@KTP 2.198 8.8 0.175 1.114 86.0
12
13
14
15 Table 2. Comparing specific capacitance of yarn-type and sheet-type supercapacitors at
16 difference voltage scan rates.
17
18
19
Scan rates Volumetric capacitance (mF cm- Gravimetric capacitance (F g-1)
20 (mVs-1) 3)

21 Yarn type Sheet type Yarn type Sheet type

22 25 1198.2 549.4 366.2 211.9
23
50 904.6 421.3 285.9 158.3
24
25 100 753.0 307.6 255.1 121.0
26 250 455.34 127.7 166.9 50.7
27 500 322.2 45.9 119.3 19.3
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 26
63
64
65
 A simple and scalable method to fabricate of yarn-type supercapacitor from rGO or/and
1 SWNT coated Korean traditional paper (KTP) is reported. The supercapacitor shows
2 good mechanical strength, excellent electrochemical performance with maximum gravimetric
3
4
specific capacitance of 366 F g-1 and without any scarifying in electrochemical performance
5 up to 10,000 charge-discharge cycles.
6
7 Keyword: yarn-type paper supercapacitors, twistable energy storage electrodes, reduced
8 graphene oxide, carbon nanotube, solid-state supercapacitors
9
10
11 Young-Jung Heo1, Ji Won Lee1, Yeong-Rae Son1, Jong-Hoon Lee1, Chang Su Yeo2, Tran Dai
12 Lam3, Sang Yoon Park4*, Soo-Jin Park1*, Le Hoang Sinh3*, Min Kyoon Shin4,a*
13
14
15
Large-scale conductive yarns based on twistable Korean Traditional Paper (Hanji) for
16 supercapacitor applications: Towards high performance paper supercapacitors
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 27
63
64
65
Supporting Information

Click here to access/download

Supporting Information
Supporting Information.docx
Full manuscript

Click here to access/download

Production Data
Full manuscript_aenm.201801854R1.docx
short summary

Click here to access/download

Production Data
short summary.docx
Table of contents

Click here to access/download

Production Data
TOC.tif
Supporting Information

Click here to access/download

Production Data
Supporting Information_100.docx