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Supporting Information for

Interconnected Carbon Nanosheets


Derived from Hemp for
Ultrafast Supercapacitors with High Energy

Huanlei Wang, †,‡ Zhanwei Xu, †,‡ Alireza Kohandehghan, †,‡ Zhi Li, †,‡,* Kai Cui, ‡

Xuehai Tan,†,‡ Tyler James Stephenson, †,‡ Cecil K. King’ondu, †,‡ Chris M. B. Holt,

†,‡
Brian C. Olsen, †,‡ Jin Kwon Tak, § Don Harfield, § Anthony O. Anyia, § and David

Mitlin,†,‡,*


Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G

2V4, Canada


National Institute for Nanotechnology (NINT), National Research Council of

Canada, Edmonton, Alberta T6G 2M9, Canada

§
Bioresource Technologies, Alberta Innovates - Technology Futures, Vegreville,

Alberta, T9C 1T4, Canada

*Address correspondence to lizhicn@gmail.com (L. Zhi); dmitlin@ualberta.ca (D.

Mitlin).
Figure S1. Photographic images of hemp bast fiber (a) before and (b) after

hydrothermal carbonization.

Figure S2. SEM images of (a) CNS-700 and (b) CNS-750.


a

Figure S3. TEM images of sample CNS-800.


a b

c d

e f

Figure S4. Annual dark-field images and EELS thickness curves (inset) of (a,b)

CNS-700, (c,d) CNS-750 and (e,f) CNS-800.


Table S1. Carbon, oxygen, and nitrogen contents in the studied samples obtained

from X-ray photoelectron spectroscopy


Samples CXPS (at%) NXPS (at%) OXPS (at%)
biochar 73.54 1.77 24.69
CNS-700 93.69 0.90 5.41
CNS-750 93.39 1.01 5.60
CNS-800 94.33 1.48 4.19
AC 95.35 - 4.65
CG 93.97 - 6.03

a b

Figure S5. (a) SEM micrograph of the carbon material obtained by direct

carbonization of hemp bast fiber. (b) SEM micrograph of the specimen after KOH

activation.
a Overall b Overall
Fitted G-band
Fitted G-band
Fitted D-band
Fitted D-band
Envelope
Envelope
Intensity (a.u.)

Intensity (a.u.)
1100 1200 1300 1400 1500 1600 1700 1100 1200 1300 1400 1500 1600 1700
-1 -1
Raman Shift (cm ) Raman Shift (cm )

c Overall d Overall
Fitted G-band Fitted G-band
Fitted D-band Fitted D-band
Envelope Envelope
Intensity (a.u.)

Intensity (a.u.)

1100 1200 1300 1400 1500 1600 1700 1100 1200 1300 1400 1500 1600 1700
-1
Raman Shift (cm ) Raman Shift (cm )
-1

e
Overall
Fitted G-band
Intensity (a.u.)

Fitted D-band
Envelope

1100 1200 1300 1400 1500 1600 1700


-1
Raman Shift (cm )

Figure S6. Raman spectra and fitted Raman curve of (a) CNS-700, (b) CNS-750, (c)

CNS-800, (d) AC, and (e) CG. (For simplicity, a two-symmetric-line fit (D and G

bands) using a Voigt function was applied to describe the Raman curves.1)
(002)

CNS-800 (100)

Intensity (a. u.)


CNS-750

CNS-700

20 30 40 50
2 theta (degree)

Figure S7. XRD patterns of the resultant carbon nanosheets.


a 1000 b 0.07
AC

dV/dD Pore Volume (cm g nm )


-1
0.06 AC
CG
Quantity Adsorbed (cm g )
800 CG
-1

-1
0.05
3

3
600 0.04

400 0.03

0.02
200
0.01

0 0.00
0.0 0.2 0.4 0.6 0.8 1.0 1 2 3 4 5 6 7 8 9 10
Relative Pressure (P/Po) Pore Size (nm)

c d
AC G-band
CG

Intensity (a.u.)
Intensity (a.u.)

D-band
CG

AC

20 30 40 50
1100 1200 1300 1400 1500 1600 1700
-1 2 theta (degree)
Raman Shift (cm )

Figure S8. (a) Nitrogen adsorption-desorption isotherms of commercial activated

carbon (AC), commercial graphene nanoplatelets (CG). (b) Pore size distributions

calculated from nitrogen adsorption isotherms using the DFT method. (c) Raman

spectra of baseline AC and CG. (d) XRD patterns of AC and CG. SEM micrographs of

(e) AC and (f) CG.


a 150
CNS-700 b
CNS-750 150 CNS-800
100 CNS-800
100
AC
Capacitance (F g )

Capacitance (F g )
-1

-1
50 CG 50
o o
0 C 20 C
0 0 o o
60 C 100 C
-50 -50

-100
-100
-150
-150
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Voltage (V) Voltage (V)

c 150 o d o
CNS-800, 0 C 150 CNS-800, 60 C
100 100
Capacitance (F g )
-1

Capacitance (F g )
-1
50 50 -1
0.1 V s
-1 0.1 V s
-1
0 0.2V s
-1 0.2V s
0 -1
0.5V s
-1 0.5V s
-50 -50 1.0 V s
-1

-100 -100
-150 -150
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Voltage (V) Voltage (V)

e 150 CNS-800, 100 C


o

100
Capacitance (F g )
-1

50 0.1 V s
-1

-1
0.2V s
0 -1
0.5V s
-1
-50 1.0 V s

-100

-150

0.0 0.5 1.0 1.5 2.0 2.5 3.0


Voltage (V)

Figure S9. (a) CV curves of resultant carbon nanosheets, commercial activated

carbon and commercial graphene nanoplatelets measured at 20 °C and 500 mV s-1. (b)

CV curves of CNS-800 tested at different temperatures using a scan rate of 500 mV

s-1. (c) CV curves of CNS-800 at scan rates from 0.1 to 0.5 V s-1, tested at 0°C. (d) CV

curves of CNS-800 at scan rates from 0.1 to 1 V s-1, tested at 60 °C. (e) CV curves of

CNS-800 at scan rates from 0.1 to 1 V s-1, tested at 100 °C.


a 3.0
CNS-700
2.5 CNS-750
CNS-800
AC
2.0
CG

Voltage (V)
1.5

1.0

0.5

0.0
0 100 200 300 400 500
Time (s)
3.0
b CNS-700
2.5 CNS-750
CNS-800
AC
2.0
CG
Voltage (V)

1.5

1.0

0.5

0.0
0 10 20 30 40
Time (s)

c 3.0
CNS-700
2.5 CNS-750
CNS-800
AC
2.0
CG
Voltage (V)

1.5

1.0

0.5

0.0
0 4 8 12 16 20
Time (s)

Figure S10. Galvanostatic charge-discharge profiles of carbon nanosheets,

commercial activated carbon and commercial graphene nanoplatelets at current

densities of (a) 1, (b) 10 and (c) 20 A g-1, tested at 20 °C.


60

50 CNS-700
CNS-750
40 CNS-800

-Z'' (ohm)
AC
30 CG

20

10

0
0 10 20 30 40 50 60
Z' (ohm)

Figure S11. Nyquist plots comparing carbon nanosheets, commercial activated

carbon and commercial graphene nanoplatelets, measured at 20 °C.

a 200 o
0 C CNS-700 b 200 o CNS-700 CNS-750 CNS-800
60 C
CNS-750 AC CG
Specific Capacitance (F g )

Specific Capacitance (F g )

CNS-800
-1

-1

150 AC 150
CG

100 100

50 50

0 0
0 10 20 30 40 0 20 40 60 80 100
-1 -1
Current Density (A g ) Current Density (A g )

c 200 100 C
o
CNS-700 CNS-750 CNS-800
AC CG
Specific Capacitance (F g )
-1

150

100

50

0
0 20 40 60 80 100
-1
Current Density (A g )

Figure S12. Specific capacitance versus current density, tested at (a) 0 °C, (b) 60 °C,

and (c) 100 °C.


100
a o
0 C
b 100
o
Energy Density (Wh kg ) 20 C

Energy Density (Wh kg )


-1

-1
10 10

1 36s 6s 3.6s 2s 1s 1 36s


PNGV 6s 3.6s 2s 1s PNGV
Power target CNS-700 AC Power target
CNS-700 AC
CNS-750 CG CNS-750 CG
CNS-800 CNS-800
0.1 0.1
100 1000 10000 100000 100 1000 10000 100000
-1 -1
Power Density (W kg ) Power Density (W kg )

100
c o
d 100
o
100 C
60 C
Energy Density (Wh kg )

Energy Density (Wh kg )


-1

-1
10 10

1 36s 6s 3.6s 2s 1s 1 36s 6s 3.6s 2s 1s


PNGV PNGV
CNS-700 AC Power target CNS-700 AC Power target
CNS-750 CG CNS-750 CG
CNS-800 CNS-800
0.1 0.1
100 1000 10000 100000 100 1000 10000 100000
-1 -1
Power Density (W kg ) Power Density (W kg )

Figure S13. Ragone Charts based on active materials comparing carbon nanosheets,

commercial activated carbon and commercial graphene nanoplatelets, evaluated at (a)

0 °C, (b) 20 °C, (c) 60 °C, and (d) 100 °C.


100

Capacitance Retention (%)


80

60

40

20

0
0 2000 4000 6000 8000 10000
Cycle Number

Figure S14. Capacitance retention versus the cycle number for CNS-800, measured at

10 A g-1 and 60 °C.

REFERENCES AND NOTES

1. Zickler, G. A.; Smarsly, B.; Gierlinger, N.; Peterlik, H.; Paris, O. A

Reconsideration of the Relationship between the Crystalline Size La of Carbons

Determined by X-Ray Diffraction and Raman Spectroscopy. Carbon 2006, 44,

3239-3246.