Supporting Information

High Performance Solid-State Asymmetric Supercapacitor using Green

Synthesized Graphene-WO3 Nanowires Nanocomposite

Arpan Kumar Nayak, Ashok Kumar Das, and Debabrata Pradhan*

Materials Science Centre, Indian Institute of Technology, Kharagpur 721 302, W.B., India

Total Number of Pages – 6

Figure S1: Page S2
Figure S2: Page S3
Figure S3: Page S4
Figure S4: Page S5
Figure S5 and S6: Page S6

S1
Figure S1. HR-TEM image of a WO3 nanowire in 10-graphene-WO3 nanowires nanocomposite.

S2
 (a)
Counts per sec

(i) 10-Graphene-WO3

O 1s

W 4f
W 4d
O KLL

W 4p

C 1s
(ii) WO3

1200 1000 800 600 400 200 0

Binding energy (eV)
(b) W 4f (c) O 1s
Counts per sec

W 4f7/2
Counts per sec

WO3 nanowires

WO3 nanowires
W 4f5/2
531.9 eV

530.4 eV
35.6 eV
37.7 eV

42 40 38 36 34 534 532 530 528

Binding energy (eV) Binding energy (eV)

Figure S2. (a) Survey XPS spectra of (i) 10 graphene-WO3 nanowires nanocomposite and (ii)
WO3 nanowires. Region (b) W 4f and (c) O 1s XPS spectra of WO3 nanowires.

S3
 8 15

Current density (A g )

Current density (A g )
−1 (a) WO3 (b) 2-Graphene-WO3

−1
10
4
5
0 (i) 0 (i)
(ii) 0.1 M H2SO4 (ii)
-4 (iii) −1
-5 (iii) 0.1 M H2SO4
Scan rate (mV S ) (iv) −1
(iv) Scan rate (mV S )
(i) 1, (ii) 5, (iii) 10 -10 (v)
-8 (v) (iv) 20, (v) 40, (vi) 60 (vi) (i) 1, (ii) 5, (iii) 10
-15 (iv) 20, (v) 40, (vi) 60
(vi) (vii) 80, and (viii) 100 (vii)
(vii) (vii) 80, and (viii) 100
-12 (viii) (viii)
-20
-0.4 -0.2 0.0 0.2 0.4 0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
Potential (V vs SCE) Potential (V vs SCE)
Current density (A g )

Current density (A g )
5-Graphene-WO3 10-Graphene-WO3
(c) 20 (d)
−1

−1
10
10
0 (i)
(ii) 0 (i)
(iii) 0.1 M H2SO4 (ii)
-10 (iv) 0.1 M H2SO4
Scan rate (mV S )
−1
-10 (iii)
−1
Scan rate (mV S )
(v) (i) 1, (ii) 5, (iii) 10 (iv)
-20 (vi)
(i) 1, (ii) 5, (iii) 10
(iv) 20, (v) 40, (vi) 60 -20 (v)
(vii) (iv) 20, (v) 40, (vi) 60
(viii)
(vii) 80, and (viii) 100 (vi)
(vii) (viii) (vii) 80, and (viii) 100
-30
-0.4 -0.2 0.0 0.2 0.4 0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
Potential (V vs SCE) Potential (V vs SCE)
Current density (A g )

(e)
−1

15-Graphene-WO3

10

0 (i)
(ii)
(iii) 0.1 M H2SO4
-10 (iv) Scan rate (mV S )
−1

(v) (i) 1, (ii) 5, (iii) 10

(vi) (iv) 20, (v) 40, (vi) 60
-20 (vii) (vii) 80, and (viii) 100
(viii)

-0.4 -0.2 0.0 0.2 0.4 0.6

Potential (V vs SCE)

Figure S3. Cyclic voltammograms at different scan rates, (a) WO3 nanowires, (b) 2-graphene-
WO3, (c) 5-graphene-WO3, (d) 10-graphene-WO3, and (e) 15-graphene-WO3 nanowires
nanocomposite.

S4
 0.6 0.6
(a) WO3 (b)
Potential (V vs SCE)

Potential (V vs SCE)
2-Graphene-WO3
−1
0.4 (i) 1 Ag 0.4 −1
−1 (i) 1 Ag
(ii) 2 Ag −1
−1 (ii) 2 Ag
0.2 (iii) 3 Ag 0.2 −1
−1 (iii) 3 Ag
(iv) 4 Ag −1
−1 (iv) 4 Ag
0.0 (v) 5 Ag 0.0 −1
−1 (v) 5 Ag
(vi) 6 Ag −1
−1 (vi) 6 Ag
-0.2 (vii) 7 Ag -0.2 −1
(vii) 7 Ag
-0.4 (vii)(vi)(v)(iv) (iii) (ii) -0.4
(i) (vii)(vi)(v)(iv)(iii) (ii) (i)

0 100 200 300 0 100 200 300 400

Time (s) Time (s)
0.6 5-Graphene-WO3
0.6 10-Graphene-WO3
(c) (d)
Potential (V vs SCE)

Potential (V vs SCE) −1
0.4 −1 0.4 (i) 1 Ag
(i) 1 Ag −1
−1 (ii) 2 Ag
(ii) 2 Ag −1
0.2 −1 0.2 (iii) 3 Ag
(iii) 3 Ag −1
−1 (iv) 4 Ag
(iv) 4 Ag −1
0.0 −1 0.0 (v) 5 Ag
(v) 5 Ag −1
−1 (vi) 6 Ag
(vi) 6 Ag −1
-0.2 −1 -0.2 (vii) 7 Ag
(vii) 7 Ag

-0.4 (vii)(vi)(v)(iv) (iii) (ii) (i) -0.4 (vii)(vi)(v)(iv)(iii) (ii) (i)

0 100 200 300 400 500 0 200 400 600 800

Time (s) Time (s)
0.6 15-Graphene-WO3
(e)
Potential (V vs SCE)

−1
(i) 1 Ag
0.4 −1
(ii) 2 Ag
−1
(iii) 3 Ag
0.2 −1
(iv) 4 Ag
−1
(v) 5 Ag
0.0 −1
(vi) 6 Ag
−1
(vii) 7 Ag
-0.2

-0.4 (vii)(vi)(v)(iv) (iii) (ii) (i)

0 200 400 600 800

Time (s)

Figure S4. Galvanostatic charge/discharge plots of at different current densities, (a) WO3
nanowires, (b) 2-graphene-WO3 nanowires nanocomposite, (c) 5-graphene-WO3 nanowires
nanocomposite, (d) 10-graphene-WO3 nanowires nanocomposite, and (e) 15-graphene-WO3
nanowires nanocomposite.

S5
 0.8

Potential (V vs SCE)
0.6 } } IR drop

0.4

0.2 10-Graphene-WO3

15-Graphene-WO3

0.0 Current density 1 A g

−1

0.1 M H2SO4
-0.2
400 500 600
Time (s)

Figure S5. Galvanostatic charge/discharge plots of (a) 10-graphene-WO3 nanowires

nanocomposite and (b) 15-graphene-WO3 nanowires nanocomposite showing the IR drop.

(a)
60
(b)
C
Z'' (ohm)

40 Rs

RCT
W

20
(a) 10-Graphene-WO3 (Before stability)
(b) 10-Graphene-WO3 (After stability)

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

Figure S6. (a) Nyquist plots of 10-graphene-WO3 nanowires nanocomposite (a) before and (b)
after 2000 cycles of stability test. Inset shows an equivalent circuit model to fit the Nyquist plots.

S6