Supporting Information

 Wiley-VCH 2014
69451 Weinheim, Germany

Platinum-Free Binary Co-Ni Alloy Counter Electrodes for Efficient

Dye-Sensitized Solar Cells**
Xiaoxu Chen, Qunwei Tang,* Benlin He, Lin Lin, and Liangmin Yu*
anie_201406982_sm_miscellaneous_information.pdf

Experimental Section
Preparation of binary CoNi alloy CEs: A mixing aqueous solution consisting of 5 mM Co(NO3)2,
20 mM Ni(NO3)2, and 2 ml of hydrazine hydrate (85 wt%) was made by agitating according to
various stoichiometric ratios [CoNi: 16 ml of Co(NO3)2 and 4 ml of Ni(NO3)2, CoNi0.50: 16 ml of
Co(NO3)2 and 2 ml of Ni(NO3)2, CoNi0.33: 24 ml of Co(NO3)2 and 2 ml of Ni(NO3)2, CoNi0.25: 16 ml
of Co(NO3)2 and 1 ml of Ni(NO3)2, CoNi0.20: 20 ml of Co(NO3)2 and 1 ml of Ni(NO3)2,]. After
vigorous agitation, the reactant was transferred into a Teflonlined autoclave and cleaned FTO glass
substrates (sheet resistance 12 sq1, purchased from Hartford Glass Co., USA) with FTO layer
downward were immersed in. After the reaction at 120 oC for 12 h, the FTO substrates were
thoroughly rinsed by deionized water and vacuumly dried at 50 oC. As references, the Coonly [24
ml of Co(NO3)2] and Nionly [24 ml of Ni(NO3)2] CEs were also prepared according to the same
procedures. The standard Pt CE (300~400 m in thickness) was purchased from Dalian
HepatChroma SolarTech Co. Ltd.
Assembly of DSSCs: A layer of TiO2 nanocrystal anode film with a thickness of 10 m and
active area of 0.25 cm2 was prepared by a solhydrothermal method and subsequently calcined at
450 oC for 30 min.[S1,S2] The resultant anodes were further sensitized by immersing into a 0.25 mM
ethanol solution of N719 dye. The DSSC was fabricated by sandwiching redox electrolyte between
dyesensitized TiO2 anode and FTO supported CoNi alloy CEs. 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 4tertbutylpyridine in 50 ml acetonitrile.
Electrochemical characterizations: The cyclic voltammetry (CV) curves were recorded on a
conventional CHI660E setup. Electrochemical impedance spectroscopy (EIS) measurements were

also carried out on the CHI660E Electrochemical Workstation in a frequency range of 0.01 Hz ~ 106
kHz and an ac amplitude of 10 mV at room temperature. Tafel polarization curves were recorded on
the same Workstation by assembling symmetric cell consisting of CE|redox electrolyte|CE.
Photovoltaic measurements: The photovoltaic test of the DSSC was carried out by measuring
the currentvoltage (JV) characteristic curves using the CHI660E Electrochemical Workstation
under irradiation of a simulated solar light from a 100 W Xenon arc lamp (XQ500 W) in ambient
atmosphere. The incident light intensity was controlled at 100 mW cm2 (AM1.5 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 DSSCs to avoid stray light completely. Each JV curve was measured at least five
times to eliminate experimental error and a compromise JV curve was employed.
Other characterizations: The morphologies of the binary CoNi alloy CEs were observed with a
scanning electron microscope (SEM, S4800). The XRD data were collected in a scan mode with a
scanning speed of 10 min1 in the 2 range of 20 ~ 80. XPS experiment was carried out on a RBD
upgraded PHI-5000C ESCA system (Perkin Elmer) with Mg K radiation (h = 1253.6 eV).

Supporting Figures

Co2p3/2: 778.32 eV
Ni2p 3/2: 853.12 eV

Intensity (a.u.)

C1s

Intensity (a.u.)

Sn3d
O1s

Co2p3/2

CoNi0.25 alloy particles

Ni2p3/2

FTO glass supported CoNi0.25 alloy

FTO glass supported CoNi0.25 alloy

CoNi0.25 alloy particles
0

200

400

600

800

1000

1200

750

800

Binding energy (eV)

850

900

Binding energy (eV)

Figure S1. XPS spectra of FTO glass supported CoNi0.25 and CoNi0.25 alloy particles.

CoNi0.25
CoNi0.33

14

CoNi0.50

12

CoNi
Co
Ni

10
8
6
4
2

-1.2

-0.8

-0.4

0.0

3
2

k at 1.3 4 V
Ox ida tion pea
k at 1.0 0 V
Ox ida tion pea

4
2

Reduction peak at 0.97 V

0
-2

Re duc tio n pea

k at -1.1 5 V

-4

10

11

12

Squre root of scan rate ( mV s

13

-1 1/2

-1

75 mV s
-1
100 mV s
-1
125 mV s
-1
150 mV s

-1
-2

0
-2
-1.2

6
-2

Peak current density

(mA cm

16

CoNi0.20

-2

-2

Current density (mA cm )

18

Current density (mA cm )

20

-0.8

-0.4

0.0

0.4

0.8

Potential (V vs Ag/AgCl)

1.2

1.6

-3
-1.2

-0.8

-0.4

0.0

0.4

0.8

1.2

1.6

Potential (V vs Ag/AgCl)

Figure S2. (a) CV curves of various CEs for I/I3 redox species recorded at a scan rate of 50 mV s1.
(b) CV curves of CoNi0.25 alloy CE for I/I3 redox species at different scan rates (from inner to outer:
75, 100, 125, and 150 mV s1), and the insert was relationship between peak current density and
square root of scan rates.

2
1

-2

Current density (mA cm )

-2

Current density (mAcm )

0.0

-0.5

-1.0

-1.5

-2.0
0

10

20

30

40

50

Cycles

st

th

th

th

th

th

1 , 10 , 20 , 30 , 40 , and 50 cycle
-1
-2
-1.2

-0.8

-0.4

0.0

0.4

0.8

1.2

1.6

Potential (V vs Ag/AgCl)

Figure S3. CV curves of CoNi0.25 CE for 50 cycles recorded at a scan rate of 50 mV s1, and the
insert represented relationship between peak current density and cycle number.

300
CPE1

CPE2

250
Rs
Rct2

Rct1

-Z'' ( cm )

200

150

CoNi
CoNi0.50

100

CoNi0.33
CoNi0.25

50

CoNi0.20

0
0

50

100

150

200

250

300

Z' ( cm )

Figure S4. Nyquist plots of the DSSCs employing various alloy CEs, and the insert was an
equivalent circuit.

References
[S1]

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

646651.

[S2]

P. P. Xu, Q. W. Tang, B. L. He, Q. H. Li, H. Y. Chen, Electrochim. Acta 2014, 134,

281286.