Supporting Information

High Performance of Self-supported Flexible Supercapacitor Based

on Carbon Fibers Covalently Combined with

Monoaminophthalocyanine

Yan Luo1, Pengcheng Wu1, Jiangwei Li1, Shengchao Yang1, Keliang Wu1, Jianning

Wu1, Guihua Meng1*, Zhiyong Liu1*, Xuhong, Guo1

1 School of Chemistry and Chemical Engineering, Shihezi University/Key Laboratory for Green

Processing of Chemical Engineering of Xinjiang Bingtuan/Key Laboratory of Materials-Oriented

Chemical Engineering of Xinjiang Uygur Autonomous Region/Engineering Research Center of

Materials-Oriented Chemical Engineering of Xinjiang Bingtuan, Shihezi, Xinjiang 832003, PR

China

*Corresponding author：Guihua Meng, Ph.D.; Zhiyong Liu, Ph.D.

Email (G. H. Meng): mghua@shzu.edu.cn

Email (Z. Y. Liu): lzyongclin@sina.com

In order to study the effect of reaction time on graft rate of Pc-NH2, a controlled

experiment that reaction time was set as 1d, 2d, 3d and 4d was designed. With

increased reaction time, the surface morphology of carbon fibers is shown in figure

S1. It is clear to see that surface of carbon fiber changed the most obviously on the

third day. Stirring too long could cause exfoliation of GCC-PcNH2 from surface of

carbon fiber just as figure of 4 day.

Fig. S1 SEM images of GCC-PcNH2 with different reaction time.

To further determine the graft rate of PcNH2, XPS can be used to detect the

content of nitrogen element, which is only contained in phthalocyanine during the

whole reaction process. Therefore, the content of Pc-NH2 on the carbon fibers could

be reflected by the atomic percentages of nitrogen element. The content of N1

increased consistently until end of the third day, that up to 12.613%. On the fourth

day, the content of N1 decreased to 11.886% and the C1 and O1 increased obviously

as shown in table S1. It is consistent with our anticipation that excessive stirring could

result in shedding of graphene-like on the surface of carbon fibers and the best

reaction time is stirring for 3 days.

Table S1

Elemental composition of GCC-PcNH2 from XPS analyses.

Reation time (d) Atomic percentages [%]

C1 N1 O1

1 68.028 10.727 21.244

2 65.992 11.44 22.568

3 65.11 12.613 22.276

4 70.99 11.886 17,915To explore the effect of graft rate of Pc-NH2 on specific capacitance,

galvanostatic charge–discharge was adopted. Figure S2 show the GCD curves of

GCC-PcNH2 with different reaction time at an electrical current density 10 mA cm-2.

According the formula Eq 2, areal specific capacitances are 1.415 F cm-2 1.523 F cm-2

1.627 F cm-2 and 1.508 F cm-2 after reacting for 1d, 2d, 3d and 4d respectively.

Therefore, the content of Pc-NH2 could affect the areal specific capacitances and the

best graft rate shows the highest areal specific capacitances.

Fig. S2 GCD curve of GCC-PcNH2 with different reaction time.

Fig. S3 (a) EDX spectrum shows C, N and O elements’ characteristic peaks of GCC-

COOH; (b1) SEM of GCC-PcNH2; (b2) EDS of GCC-PcNH2; (b3), (b4) EDS of

GCC-PcNH2 for N and O respectively.

Figure S4. CV curves of SC under different bending conditions.

Figure S5. CVs curves of tandem devices with two and three SCs connected in series

Figure S6. The brightness of a LED powered by three supercapacitors changes over

time.

Table S2

Electrochemical performances of electrodes and devices compared to reported

literatures.

Materials Methods CN/CR Cm/ICD TD CD ED Year

s

Monoami

nophthalo

cyanine-

carbon

fiber

chemical

reaction

10000,

90.46%

2.425 F cm-

2/ 1 mA cm-2

Symmetric, all-solid-state

1.610 F

cm-2/1 mA

cm-2

1.651 × 10-4

W h cm-2/1

mA cm-2

This

work

graphene

sheets/car

bon cloth

Electrochemic

al exfoliation

and re-

deposition

3000,

95.7%

1.134 F cm-

2/ 2 mA cm-2

Symmetric,

all-solid-state

0.293 F

cm-2/2 mA

cm-2

9.15 × 10-5 W

h cm-2/2 mA

cm-2

2019

[S1]

Polyhydro

quinone/

graphite

electrochemic

al anodization

3000,

93%

0.378 F cm-

2/1 mA cm-2

Symmetric, all-solid-state

-- 8.4 × 10-6

Wh cm-2/1

mA cm-2

2019

[S2]

CO

F/carbon

mixture 4500,

76%

0.464 F cm-

2/0.5 mA

Symmetric, all-

0.167 F

cm-2/0.5

5.8 × 10-6

Wh cm-2/0.5

2019

[S3]

nanofiber cm-2 solid-state

mA cm-2 mA cm-2

Carbon

Felt

freeze-drying 4000,

95%

1.441 F cm-

2/0.5 mA

cm-2

Asymmetric, aqueous electrolytes

1.276 F

cm–2/0.3

mA cm–2

1.04 × 10-4

Wh cm–2/0.3

mA cm–2

2018

[S4]

Graphene

fiber

plasma

treatment

20000,

96.14%

0.363 F cm-

2/0.1 mA

cm-2

symmetric, all-solid-state

0.223 F

cm-2/0.1

mA cm-2

1.812 × 10-5

Wh cm-2/0.1

mA cm-2

2018

[S5]

Co(C

O3)0.5(O

H)·0.11H2

O@ZIF-

67

nanowire

s /carbon

cloth

Chemical

Vapor

Deposition

4000,

98.2%

1.22 F·cm-

2/0.5 mA

cm-2

-- -- -- 2018

[S6]

Na-Doped

MnO2

/Carbon

Nanotube

Fibers

hydrothermal

method and

plasma

treatment

5000,

90%

0.743 F cm-

2/1 mA cm-2

Asymmetric, all-solid-state

0.265 F

cm-2/1 mA

cm-2

1.784 × 10-5

Wh/cm-2/1

mA cm-2

2018

[S7]

N

Codoped

Carbon

low-temperature

solvothermal

route

10000,

100%

3.3 × 10-4 F

cm-2/ 5 mV

s-1

-- -- -- 2018

[S8]

TiN/MON

fiber

Anodization

and

hydrothermal

methods

8000,

84.5%

0.737 F cm-

2/10 mV s-1

Asymmetric, aqueous electrolytes

0.075 F

cm-2/10

mV s-1

2.37 × 10-5

Wh cm-2/10

mV s-1

2017

[S9]

NC: cycling number; CRR: capacitance retention; CSD: capacitance of single electrode; TD: type of device; CD: capacitance of device; ED: energy density

References[1] Z. J. Dou, Z.Y. Qin, Y. Y Shen, S. Hu, N. Liu, Y. W. Zhang, High–performance

flexible supercapacitor based on carbon cloth through in–situ electrochemical

exfoliation and re–deposition in neutral electrolyte, Carbon. 153 (2019) 617-624.

[2] V. K. A. Muniraj, P. K. Dwivedi, P. S.Tamhane, S. Szunerits, R. Boukherroub, M.

V. Shelke, High-Energy flexible supercapacitor-synergistic effects of

polyhydroquinone and RuO2. xH2O with microsized, few-layered, self-

supportive exfoliated-graphite sheets, ACS. Applied. materials & interfaces. 11

(2019) 18349-18360.

[3] A. K. Mohammed, V. Vijayakumar, A. Halder, M. Ghosh, M. Addicoat, U.

Bansode, et. al., Weak intermolecular interactions in covalent organic

framework-carbon nanofiber based crystalline yet flexible devices, ACS.

Applied. materials & interfaces. (2019).

[4] G. Lou, Y. Wu, X. Zhu, Y. Lu, S. Yu, C. Yang, et. al., Facile activation of

commercial carbon felt as a low-cost free-standing electrode for flexible

supercapacitors, ACS. Applied. materials & interfaces. 10 (2018) 42503-42512.

[5] J. Meng, W. Nie, K. Zhang, F. Xu, X. Ding, S. Wang, et. al., Enhancing

electrochemical performance of graphene fiber-based supercapacitors by plasma

treatment, ACS. Applied. materials & interfaces. 10 (2018) 13652-13659.

[6] C. Young, J. Wang, J. Kim, Y. Sugahara, J. Henzie, Y. Yamauchi. Controlled

chemical vapor deposition for synthesis of nanowire arrays of metal–organic

frameworks and their thermal conversion to carbon/metal oxide hybrid materials,

Chemistry. of. Materials. 30 (2018) 3379-3386.

[7] Q. Zong, Q. Zhang, X. Mei, Q. Li, Z. Zhou, D. Li, et. al., Facile synthesis of Na-

doped MnO2 nanosheets on carbon nanotube fibers for ultrahigh-energy-density

all-solid-state wearable asymmetric supercapacitors, ACS. Applied. materials &

interfaces. 10 (2018) 37233-37241.

[8] J. Zhou, L. Hou, S. Luan, J. Zhu, H. Gou, D. Wang, et. al., Nitrogen codoped

unique carbon with 0.4 nm ultra-micropores for ultrahigh areal capacitance

supercapacitors, Small. 14 (2018) e1801897.

[9] D. Ruan, R. Lin, K. Jiang, X. Yu, Y. Zhu, Y. Fu, et. al., High-performance porous

molybdenum oxynitride based fiber supercapacitors, ACS, Applied, materials &

interfaces. 9 (2017) 29699-29706.