Supporting Information

A Solar Cell That Is Triggered by Sun and Rain

Qunwei Tang,* Xiaopeng Wang, Peizhi Yang, and Benlin He
anie_201602114_sm_miscellaneous_information.pdf

Experimental Section
Synthesis of Pt3Ni, Co0.85Se, and Ni0.85Se CEs: The pristine Pt CE was commercially from
Yingkou OPV Tech New Energy Co., LTD. The feasibility of synthesizing Pt3Ni alloy CE was
electrodeposited on thoroughly cleaned ITO-PET flexible substrates by a cyclic voltammetry (CV)
technique. The typical precursor containing 30 mL of 1 mM chloroplatinic acid (H2PtCl6) solution
and 3 mL of 1 mM NiSO4 solutions. The electrodeposition was carried out on a three-electrode
system by scanning in a potential range of -0.6 ~ 0.8 V with a scan rate of 10 mV s-1. After
depositing for seven cycles, the as-prepared CEs were thoroughly rinsed with deionized water and
vacuum dried at 60 oC .
The transparent Co0.85Se and Ni0.85Se alloy CEs were confirmed by following experimental
procedures: A mixing aqueous solution consisting of 2 mM H2SeO3 and 100 mM LiCl was made by
agitating SeO2 ultrafine powders and anhydrous LiCl in deionized water. A mixture comprising of
10 mL of above solution and 10 mL of Co(NO3)2 or Ni(NO3)2 aqueous solution. The deposition of
metal selenide CEs on freshly cleaned ITO-PET substrate was carried out on a conversional
CHI660E setup comprising an Ag/AgCl reference electrode, a CE of platinum sheet, and a working
electrode of ITO/PEN substrate. A cyclic voltammetry mode was applied in a potential range of
0.9 ~ 1.4 V. The scan rate and scanning number were controlled at 10 mV s1 and 1 cycle,
respectively.

Synthesis of TiO2 Anodes: A TiO2 colloid was synthesized according to the procedures of our
previous report.[S1] A layer of TiO2 film with an average thickness of 10 m and active area of 0.25
cm2 was made by a doctor-blade method. Subsequently, the TiO2 film was heated at 60 oC for 5 h
and sensitized by 0.25 mmol dm-3 N719 ethanol solution for 24 h.
Fabrication of rGO Electrode: The rGO film was prepared by filtrating GO colloid prepared
by traditional hummers method, transferred to back side (PET layer) of ITO-PET substrate by a
heat-pressing method (at 40 C and 0.2 MPa for 10 min), and subsequently reduced with 5 wt% HI
ethanol solution for 10 h.
Assembly of Solar Cell: The bi-triggering solar cell was fabricated by sandwiching redox
electrolyte between a dye-sensitized TiO2 anode and a CE. A Surlyn film (30 m in thickness) was
utilized to seal the solar cell through hot-pressing. A redox electrolyte consisted of 100 mM of
tetraethylammonium

iodide,

100

mM

of

tetramethylammonium

iodide,

100

mM

of

tetrabutylammonium iodide, 100 mM of NaI, 100 mM of KI, 100 mM of LiI, 50 mM of I2, and 500
mM of 4-tert-butyl-pyridine in 50 ml acetonitrile.
Electrochemical Characterizations: The electrochemical performances were recorded on a
conventional CHI660E setup comprising an Ag/AgCl reference electrode, a CE of Pt sheet, and a
working electrode of ITO-PET supported CE. The CV curves were recorded in a supporting
electrolyte consisting of 50 mM M LiI, 10 mM I2, and 500 mM LiClO4 in acetonitrile. EIS
measurements were also carried out in a frequency range of 0.1 Hz ~ 105 kHz and an ac amplitude
of 10 mV at room temperature.
Photovoltaic Measurements: The photovoltaic test of the bi-triggering solar cell with an active
area of 0.25 cm2 was carried out by measuring the photocurrent-voltage (J-V) characteristic curves
using a CHI660E Electrochemical Workstation under irradiation of a simulated solar light from a

100 W Xenon arc lamp (XQ-500 W) in ambient atmosphere. The incident light intensity was
controlled at 100 mW cm-2 (calibrated by a standard silicon solar cell). A black mask with an
aperture area of around 0.25 cm2 was applied on the surface of solar cell to avoid stray light
completely.
Other Characterizations: The morphologies of the rGO film were observed on an SU8020
model scanning electron microscope (SEM, SU8020, Hitachi, Japan). X-ray diffraction (XRD)
profile of the rGO film was conducted on a Philips X-ray powder diffractometer with Cu K
radiation in the 2 range of 5 ~ 40 operating at 40 kV accelerating voltage and 40 mA current.
Fourier transform Raman spectrum measurement was performed on a Renishaw inVia Reflex
Raman Spectrometer.

Supporting Table and Figures

Table S1. The corresponding photovoltaic parameters for the flexible DSSCs. : power conversion
efficiency; Voc: open-circuit voltage; Jsc: short-circuit current density; FF: fill factor.
CEs
Pt
Pt3Ni
Co0.85Se
Ni0.85Se

Voc (V)
0.702
0.713
0.701
0.696

Jsc (mA cm-2)

12.86
13.82
8.98
8.62

(%)
5.98
6.53
4.26
4.09

FF (%)
66.2
66.3
67.7
68.2

Irradiation
front
front
rear
rear

Figure S1. The structures and components of the bi-triggering solar cells that can be excited by
sunlight and rain: (a) front irradiation, (b) rear irradiation.

30

Ox2, 2I3 - 2e = 3I2

Epp

Pt3Ni
Pt

25

Ox1, 3I - 2e = I3

20

-Z'' (ohm cm )

-2

Current density (mA cm )

Red2, 3I2 + 2e = 2I3

-3
-6

Red1, I3 + 2e = 3I

Pt3Ni alloy CE

CPE

15
10

Rs
W

Rct

Pt CE
0

-9
-0.6

0.0

0.6

Potential (V vs Ag/AgCl)

1.2

10

15

20

25

30

Z' (ohm cm )

Figure S2. (a) CV curves of Pt and Pt3Ni alloy CEs toward I-/I3- electrolyte recorded at a scan rate
of 50 mV s-1. (b) The Nyquist EIS plots for the symmetric dummy cells with two identical Pt or
Pt3Ni alloy CEs.

D band

Intensity (a.u.)

Intensity (a.u.)

G band

2D band

1000

1500

2000

2500

3000

-1

Raman shift ( cm )

3500

10

15

20

25

30

35

40

2theta (degree)

Figure S3. (a) Raman spectrum and (b) XRD pattern of the resultant rGO film.
The Raman spectrum of rGO shows two distinct and broad peaks at 1347 and 1594 cm-1, which
are the D and G Raman peaks of graphene, respectively. The peak at 1347 cm-1 (D band, the
breathing mode of k-point phonons of A1g symmetry) is usually associated with vibrations of carbon
atoms with dangling bonds in plane terminations of disordered graphite. The peak at 1594 cm-1 (G
band) corresponds to an E2g mode of graphene and is related to the vibration of sp2-bonded carbon
atoms. The second-order band (2D) is observed around 2930 cm-1. Although the D and 2D bands
can not be used to determine the number of layers, they are useful to investigate electronic defects.
In comparison with pristine graphene, the 2D mode becomes broader, suggesting a higher level of
disorder of the graphene layers and defects.

Figure S4. SEM photographs of rGO film at (a) low and (b) high magnifications.
The stacking architecture and scrolling nature are determined for the rGO film.

1.0

0.10

0.8

0.06

Voltage (V)

Current (A)

0.08

0.04

0.6

0.4

0.02

0.2

0.00

0.0
0

10

20

30

Time (s)

40

50

20

40

60

80

100

Time (s)

Figure S5. (a) Current and (b) voltage signals produced by dropping deionized water droplets on
rGO film at an injection velocity of 50 mL h-1. The lateral distance between dropping point and rGO
is 7.46 mm.

Figure S6. The contact angles (a) before and (b) after dropping 0.6 M NaCl droplets.

200

Voltage (V)

150

100

50

0
10

20

30

40

-1

Velocity (cm s )

Figure S7. The linear relationship between velocity of droplets and induced voltage.

0.8

-1

20 mL h

0.4

40

0.0
0.4

-1

50 mL h

0.2
0.0
0.3

Potential (V)

Current (A)

-1

20 mL h

80

-1

50 mL h

60
30
0

-1

-1

80 mL h

80 mL h

40

0.2

20

0.1
0.0

0
0

10

15

Time (s)

20

25

30

10

15

20

25

30

Time (s)

Figure S8. (a) Current and (b) voltage signals produced by dropping 1 M NaCl droplets on rGO
film at different injection velocities. The distance between droplets and rGO film is 7.46 mm.

-1

20 mL h

-1

20 mL h

0.0
0.4

-1

50 mL h

0.2
0.0

-1

80 mL h

0.4

Potential (V)

60

0.6

Current (A)

120

1.2

0
60

-1

50 mL h

30
0
80

-1

80 mL h

40

0.2

0.0

10

15

Time (s)

20

25

30

10

15

20

25

30

Time (s)

Figure S9. (a) Current and (b) voltage signals produced by dropping 2 M NaCl droplets on rGO
film at different injection velocities. The distance between droplets and rGO film is 7.46 mm.

Supporting References
[S1]

S. S. Yuan, Q. W. Tang, B. L. He, L. Men, H. Y. Chen, Electrochim. Acta, 2014, 125, 646.