Supporting Information

Monolithic flexible supercapacitors drawn with nitrogen-doped

carbon nanotube-graphene ink

Sheng Zhu a, Jian Sheng a, Guodong Jia a, Zeyao Zhang a,d,e, Jia Guo a, Meng Wang a,

Jiangfeng Ni b,c,*, Yan Li a,d,*

a
Beijing National Laboratory for Molecular Sciences, Key Laboratory for the Physics and Chemistry of

Nanodevices, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of

Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

b
School of Physical Science and Technology, Center for Energy Conversion Materials & Physics

(CECMP), Jiangsu Key Laboratory of Thin Films, Soochow University, Suzhou 215006, China
c
Light Industry Institute of Electrochemical Power Sources, Suzhou 215699, China
d
Peking University Shenzhen Institute, Shenzhen 518057, China
e
PKU-HKUST ShenZhen-HongKong Institution, Shenzhen 518057, China

* Corresponding author, E-mail: yanli@pku.edu.cn (Y. Li); jeffni@suda.edu.cn (J. F. Ni)

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Figure S1. Photograph of the homogeneous NCNT/RGO ink (a) and features (school badge of
PKU ) (b, c) drawn on two sides of a piece of paper drawn by the ink. (d) Atomic force
microscopy image of the NCNT/RGO ink. (e) Raman spectra of the NCNTs, RGO, and
NCNT/RGO inks with different compositions.

Figure S2. (a) TEM image of CNT@polypyrrole core-shell nanostructure with the shell
thickness of 2-5nm. (b) TEM image of NCNT ink. (c) N 1s XPS spectrum of NCNTs.

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Figure S3. TEM images of RGO ink.

Figure S4. TEM images of various NCNT/RGO composite inks.

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Figure S5. (a) SEM image of commonly paper substrate. (b) SEM image of PMP substrate. (c)
The typical cross-sectional SEM image of PMP substrate.

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Figure S6. (a) Cross-sectional SEM image of PMP. Elemental mapping of C (b) and P (c)
elements.

Figure S7. (a) Wetting performance of CNTs ink (a) and NCNTs ink (b) droplet on PMP.

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Figure S8. Schematic illustration for the prepared process of the monolithic flexible paper SC.

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Figure S9. (a) GCD curves of typical NCNT/RGO SC under different current densities. (b)
Volumetric capacitance of various SCs under different current densities. (c) Specific capacitance
of various SCs at different frequencies.

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Figure S10. (a) GCD curves, (b) Specific capacitance, and (c) EIS data of various NCNT/RGO
SCs.

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Figure S11. (a) CV curves of as-constructed NMNS SC at various scan rates, (b) CV curves of
as-constructed NMNS SC under different bending angles.

Figure S12. Schematic diagram of the fabrication process for crimpling SCs product.

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Table S1 Capacitive properties of the NCNTs, RGO, and typical NCNT/RGO SCs.

Specific capacitance Areal capacitance Volumetric capacitance

(F g1) (mF cm2) (F cm3)
NCNTs 19.7 3.9 0.20
RGO 32.1 6.4 0.32
NCNT/RGO 45.2 9.0 0.45

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Table S2 Comparison of the properties of the typical NCNT/RGO-based paper SC with those

carbonaceous materials based flexible SCs in published papers.

Electrode Electrolyte C Emax Pmax Ref.

RGO H3PO4/PVA 2 2 2
0.54 mF cm 0.52 mWh cm 417 mW cm [1]
(500 mV s−1)
RGO H2SO4/PVA 0.95 mF cm2 / / [2]
(0.43 mA cm−2)
GO Na2SO4 0.51 mF cm2 0.43 mWh cm3 9.4 W cm3 [3]
(40 mV s−1)
Graphene H2SO4 3.67 mF cm2 1.36 mW cm3 20 W cm3 [4]
(1 A g−1)
Graphene H3PO4/PVA 1.7 mF cm2 0.34 μWh cm2 5.3 mW cm2 [5]
(20 mV s−1)
Graphene H2SO4/PVA 116 μF cm2 3.6 mWh cm3 1.27 kW cm3 [6]
(10 mV s−1)
Graphene LiCl/PVA 3.9 mF cm2 0.98 mWh cm3 0.3 W cm3 [7]
(0.1 mA cm−2)
Graphene H3PO4/PVA 9.09 μF cm2 727 nWh cm2 83.4 μW cm2 [8]
quantum dots (0.1 μA cm−2)
Boron-doped H2SO4/PVA 16.5 mF cm2 0.45 mWh cm3 / [9]
graphene (0.05 mA cm−2)
Graphene/CNT Na2SO4 2.16 mF cm2 0.16 mWh cm3 115 W cm3 [10]
s −3
(1 A cm )
RGO/CNTs H3PO4/PVA 6.1 mF cm2 0.68 mWh cm3 77 W cm3 [11]
(0.01 V s−1)
SWCNT@C H2SO4/PVA 37.1 mF cm2 3.29 μWh cm2 3.36 mW cm2 [12]
(0.05 mA cm−2)
CNT@carbon H3PO4/PVA 48 mF cm2 16 μWh cm2 3.6 mW cm−2 [13]
sheets (0.8 mA cm−2)
CNT fiber H3PO4/PVA 50 F cm3 4.5 mWh cm3 1.3 W cm3 [14]
(0.05 A cm−3)
Onion-like Et4NBF4/APC 0.9 mF cm2 10.0 mWh cm3 1.0 kW cm3 [15]
carbon (100 V s−1)
Active carbon Et4NBF4/APC 2.1 mF cm2 (1 / 44.9 mW cm2 [16]
mV s−1)
NCNT/RGO H3PO4/PVA 9.0 mF cm2 (0.1 0.80 μWh cm2 112.7 mW cm2 This
mA cm−2) study
0.45 F cm3 40.0 μWh cm 3
5.64 W cm 3

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Note that the volumetric values in this study were calculated using the volume of the entire

device.

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REFERENCES

[1] D. Qi, Z. Liu, Y. Liu, W. R. Leow, B. Zhu, H. Yang, J. Yu, W. Wang, H. Wang, S. Yin,
Suspended wavy graphene microribbons for highly stretchable microsupercapacitors, Adv.
Mater. 27 (2015) 5559-5566.
[2] Z. K. Wu, Z. Lin, L. Li, B. Song, K. S. Moon, S. L. Bai, C. P. Wong, Flexible micro-
supercapacitor based on in-situ assembled graphene on metal template at room temperature,
Nano Energy 10 (2014) 222-228.
[3] W. Gao, N. Singh, L. Song, Z. Liu, A. L. Reddy, M. L. Ci, R. Vajtai, Q. Zhang, B. Wei, P.
M. Ajayan, Direct laser writing of micro-supercapacitors on hydrated graphite oxide films, Nat.
Nanotechnol. 6 (2011) 496-500.
[4] M. F. El-Kady, V. Strong, S. Dubin, R. B. Kaner, Laser scribing of high-performance and
flexible graphene-based electrochemical capacitors, Science 335 (2012) 1326-1330.
[5] Y. Shao, J. Li, Y. Li, H. Wang, Q. Zhang, R. B. Kaner, Flexible quasi-solid-state planar
micro-supercapacitor based on cellular graphene films, Mater. Horiz. 4 (2017) 1145-1150.
[6] Z. S. Wu, K. Parvez, X. Feng, K. Müllen, Photolithographic fabrication of high-performance
all-solid-state graphene-based planar micro-supercapacitors with different interdigital fingers, J.
Mater. Chem. A 2 (2014) 8288-8293.
[7] B. Xie, Y. Wang, W. Lai, W. Lin, Z. Lin, Z. Zhang, P. Zou, Y. Xu, S. Zhou, C. Yang, F.
Kang, C. P. Wong, Laser-processed graphene based micro-supercapacitors for ultrathin, rollable,
compact and designable energy storage components, Nano Energy 26 (2016) 276-285.
[8] K. Lee, H. Lee, Y. Shin, Y. Yoon, D. Kim, H. Lee, Highly transparent and flexible
supercapacitors using graphene-graphene quantum dots chelate, Nano Energy 26 (2016) 746-
754.
[9] Z. Peng, R. Ye, J. A. Mann, D. Zakhidov, Y. Li, P. R. Smalley, J. Lin, J. M. Tour, Flexible
boron-doped laser-induced graphene microsupercapacitors, ACS Nano 9 (2015) 5868-5875.
[10] J. Lin, C. Zhang, Z. Yan, Y. Zhu, Z. Peng, R. H. Hauge, D. Natelson, J. M. Tour, 3-
dimensional graphene carbon nanotube carpet-based microsupercapacitors with high
electrochemical performance, Nano Lett. 13 (2012) 72-78.
[11] M. Beidaghi, C. Wang, Micro‐supercapacitors based on interdigital electrodes of reduced
graphene oxide and carbon nanotube composites with ultrahigh power handling performance,
Adv. Funct. Mater. 22 (2012) 4501-4510.
[12] Q. Meng, H. Wu, Y. Meng, K. Xie, Z. Wei, Z. Guo, High‐performance all‐carbon yarn
micro‐supercapacitor for an integrated energy system, Adv. Mater. 26 (2014) 4100-4106.

13
[13] P. He, Z. Ding, X. Zhao, J. Liu, Q. Huang, J. Peng, L. Z. Fan, Growth of carbon nanosheets
on carbon nanotube arrays for the fabrication of three-dimensional micro-patterned
supercapacitors, Carbon 155 (2019) 453-461.
[14] G. Wang, S. K. Kim, M. C. Wang, T. Zhai, S. Munukutla, G. S. Girolami, J. W. Lyding,
Enhanced electrical and mechanical properties of chemically cross-linked carbon-nanotube-
based fibers and their application in high-performance supercapacitors, ACS Nano 14 (2019)
632-639.
[15] D. Pech, M. Brunet, H. Durou, P. Huang, V. Mochalin, Y. Gogotsi, P. L. Taberna, P.
Simon, Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon, Nat.
Nanotechnol. 5 (2010) 651-654.
[16] D. Pech, M. Brunet, P. L. Taberna, P. Simon, N. Fabre, F. Mesnilgrente, V. Conédéra, H.
Durou, Elaboration of a microstructured inkjet-printed carbon electrochemical capacitor, J.
Power Sources 195 (2010) 1266-1269.

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