Supporting Information –

Flexible Boron-Doped Laser Induced

Graphene Microsupercapacitors

Zhiwei Peng,† Ruquan Ye,† Jason A. Mann,† Dante Zakhidov,† Yilun Li,† Preston R.

Smalley,†, ∞ Jian Lin‖* and James M. Tour†,‡,§,*

†
Department of Chemistry, ‡Smalley Institute for Nanoscale Science and Technology,
§
Department of Materials Science and NanoEngineering,

Rice University, 6100 Main Street, Houston, Texas 77005, USA

∞
Second Baptist School, 6410 Woodway Drive, Houston, Texas 77057, USA
‖
Department of Mechanical & Aerospace Engineering, University of Missouri, Columbia,

Missouri, 65211, USA

*Email: linjian@missouri.edu; tour@rice.edu

Calculation of parameters as indications for electrochemical performance of LIG

derived devices.

The specific areal capacitances (CA, in mF/cm2) and volumetric capacitances (CV, in F/m3)

from galvanostatic charge-discharge (CC) curves can be calculated by the following

equations:

I
CA  (1)
S  (dV / dt )

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 CA
CV  (2)
d

Where I is the discharge current (in amperes); dV/dt is the slope of galvanostatic

discharge curves; S is total area of active positive and negative electrodes. Considering

the dimensions of 12 such electrodes (5 mm in length and 1 mm in width), S is calculated

as 0.6 cm2. Whereas, for the calculation of volumetric capacitance, volumetric energy

density and volumetric power density, S is 0.8 cm2 which is calculated from the total

projected area of the devices including the gaps between the electrodes. d is the thickness

of active materials with 25 µm as revealed in Figure 1c inset.

The specific areal (EA, in µWh/cm2) and volumetric energy densities (EV, in Wh/m3) are

calculated using the following equations:

1 (V ) 2
EA   CA  (3)
2 3600

1 (V )2
EV   CV  (4)
2 3600

The specific areal (PA, in mW/cm2) and volumetric (PV, in W/cm3) power densities are

obtained from the following equations:

EA
PA   3600 (5)
t

EV
PV   3600 (6)
t

Where t is discharge time (in seconds).

For the bending experiment, the device was fixed on a platform by two screws at

different distances in which the bending radius can be calculated by the screw distance

and the curved height of the device:

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(7)
 𝒉𝟐 + 𝒅𝟐 ⁄𝟒
𝒓=
𝟐𝒉

Where r is the bending radius, h is the height of the curved device, and d is the distance

between the two screws.

Scheme S1. A scheme to show the calculation of bending radius from the measured

height of the curved device and the distance between the two screws.

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Supplementary figures

Figure S1. The FT-IR spectra of PAA sheet and PI sheet.

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Figure S2. Photograph of (a) PAA solution with 5 wt% of H3BO3. (b) Patterned B-LIG

on the PI/H3BO3 sheet after laser induction.

Figure S3. Cross-sectional SEM images of 5B-LIG on a PI sheet over a long distance.

The thickness of the 5B-LIG layer is uniform.

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Figure S4. Cross-sectional SEM images of xB-LIG layers on the PI sheet. (a) 0B-LIG.

(b) 1B-LIG. (c) 2B-LIG. (d) 8B-LIG.

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Figure S5. SEM EDAX elemental mapping of 5B-LIG. (a) SEM image of the

mapping area. (b) EDAX spectrum. (c) Boron mapping. (d) Carbon mapping. (e)

Oxygen mapping.

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Figure S6. High-resolution TEM images of 5B-LIG. Numerous graphene edges are

found on the surface of 5B-LIG flakes.

Figure S7. SEM images of LIG materials with different boron loadings. (a) 0B-LIG.

(b) 1B-LIG. (c) 2B-LIG. (d) 8B-LIG.

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Figure S8. TEM and HRTEM images of LIG materials with different boron

loadings. (a) and (e) 0B-LIG. (b) and (f) 1B-LIG. (c) and (g) 2B-LIG. (d) and (h) 8B-LIG.

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Figure S9. BET measurement of B-LIG material. The calculated surface area is 191

m2/g.

Figure S10. XPS survey spectra for (a) 5B-PI and (b) 5B-LIG.

Table S1. Comparison of areal capacitance from xB-LIG-MSCs.

H3BO3 Loadinga b
Areal Capacitancec
Sample Label B content (at%)
(wt%) (mF/cm2)
0B-LIG 0 0 2.34
1B-LIG 1 3.4 3.56
2B-LIG 2 4.0 4.93
5B-LIG 5 4.4 9.54
8B-LIG 8 6.2 6.72
a. H3BO3 loading amount is the mass percentage of H3BO3 over the weight of PAA.
b. B content is the atomic percentage of boron in xB-LIG powder from XPS elemental
spectra.
c. The average areal capacitance is calculated from charge-discharge curves of at least three
MSC devices for each xB-LIG at a current density of 1.0 mA/cm2.

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Figure S11. Additional electrochemical performance of 5B-LIG-MSC. (a) CV curves

of 5B-LIG-MSC at scan rates of 0.2, 0.5, 1.0 and 2.0 V/s. (b) CV curves of 5B-LIG-MSC

at scan rates of 5, 10, 15 and 20 V/s. (c) Galvanostatic CC curves of 5B-LIG-MSC at

current densities of 1.0, 2.0 and 5.0 mA/cm2. (d) Galvanostatic CC curves of 5B-LIG-

MSC at current densities of 10, 20 and 30 mA/cm2.

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Figure S12. Volumetric capacitance of 5B-LIG-MSC calculated from CC curves as a

function of current density. The red plot points (solid circles) were calculated using the

total projected area of the devices which includes the gaps between the electrodes,

whereas the black plot points (solid squares) were calculated using only the electrode

area.

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Figure S13. Impedance performances of LIG-MSC and 5B-LIG-MSC. The testing

frequency is ranging from 106 Hz to 0.01 Hz. This typical Nyquist plot shows a small

semicircle for both devices at a high frequency region, corresponding to a fast ionic

transport and low external resistance of devices. At the lower frequency region, the

Nyquist plot exhibits a linear part resulting from the interface between the electrolyte and

the electrode. This interface results in internal resistance of devices. From this Nyquist

plot we can see that 5B-LIG-MSC has both smaller external and internal resistances than

LIG-MSC. These results indicate faster ionic transport and better electrode-electrolyte

interface in 5B-LIG-MSC.

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Figure S14. CV curves of the 5B-LIG-MSC at different cycles during cycling test.

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Figure S15. (a) Volumetric Ragone plot of 5B-LIG-MSC and LIG-MSC calculated using

only the electrode area. (b) Areal Ragone plot of 5B-LIG-MSC and LIG-MSC calculated

using only the electrode area.

Table S2. Comparison of electrochemical performances of various MSCs.

Volumetric
Areal Capacitance Energy Density
Material Electrolyte Capacitance Ref
(mF/cm2) (mWh/cm3)
(F/cm3)
12.4 at 0.04
5.0 at 0.04 mA/cm2
5B-LIG a
H2SO4/PVA mA/cm2 (16.5 at 0.56 (0.74) -
(6.6 at 0.05 mA/cm2)
0.05 mA/cm2)
Onion 1 M Et4NBF4
1.7 at 1 V/s 1.3 at 1 V/s 1.7 1
Carbon in PC
Activated 1 M Et4NBF4
11.6 at 0.5 V/s 9.0 at 0.01 V/s 18 1
Carbon in PC
Activated 1 M Et4NBF4
2.1 at 1 mV/s 2.7 at 1 mV/s - 2
Carbon in PC
G/CNT 1 M Na2SO4 2.16 at 0.1 mV/s 1.08 at 0.1 mV/s 0.16 3
rGO/CNT 3 M KCl 5.1 at 3 mA/cm2 - 0.68 4
Graphene H2SO4/PVA 0.32 at 10 mV/s 72 at 10 mV/s 2.5 5
Porous
0.5 M H2SO4 - 7.6 at 3.1 mA/cm3 1 6
Carbon
LSG from 2.32 at 16.8
H2SO4/PVA 3.05 at 16.8 mA/cm3 ~0.6 7
GO mA/cm3
BNG H2SO4/PVA 0.39 at 10 mV/s 488 at 10 mV/s 16.9 8
RGO 1 M Na2SO4 ~1.0 ~3.1 0.43 9
2 2
LIG 0.5 M H2SO4 3.9 at 0.2 mA/cm 1.6 at 0.2 mA/cm ~0.15 10
8.0 at 0.03
LIG H2SO4/PVA 3.2 at 0.03 mA/cm2 0.45 11
mA/cm2
a
The areal capacitance, volumetric capacitance and energy density shown here from 5B-LIG
were calculated using the total projected area of the devices which includes the gaps between the
electrodes and electrode thickness. Note that the values in parentheses were calculated using only
the electrode area of the devices.

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