Electrochimica Acta 69 (2012) 334–339

Contents lists available at SciVerse ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

A mesoscopic platinized graphite/carbon black counter electrode for a highly

efficient monolithic dye-sensitized solar cell
Guanghui Liu, Heng Wang, Xiong Li, Yaoguang Rong, Zhiliang Ku, Mi Xu, Linfeng Liu, Min Hu,
Ying Yang, Peng Xiang, Ting Shu, Hongwei Han ∗
Michael Grätzel Center for Mesoscopic Solar Cells, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, Hubei 430074, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A mesoscopic platinized graphite/carbon black counter electrode for monolithic dye-sensitized solar cell
Received 30 November 2011 (DSSC) is developed. Compared with the pure carbon electrode, its catalytic activity and charge trans-
Received in revised form 20 February 2012 fer rate are improved notably. The 0.5% Pt loading carbon electrode indicates an electrochemical active
Accepted 3 March 2012
surface of 109.37 m2 g−1 , which is higher than 86.58 m2 g−1 of the pure carbon electrode. As a result,
Available online 12 March 2012
high energy conversion efficiency up to 7.61% is obtained for monolithic DSSC based on this mesoscopic
platinized graphite/carbon black electrode. It could be expected that this low cost mesoscopic platinized
Keywords:
graphite/carbon black and simple manufacturing process would make the carbon catalyst-based mono-
Monolithic
Dye-sensitized solar cell
lithic DSSC available in practical application.
Mesoscopic © 2012 Elsevier Ltd. All rights reserved.
Counter electrode
Carbon

1. Introduction
Dye-sensitized solar cell (DSSC) has attracted widespread atten-
tion in the past decade as a promising renewable energy source,
because of its respectable high conversion efficiency and poten-
tially low-cost manufacture [1,2]. Up to now, the certified energy
conversion efficiency of DSSC has reached to 11.5%, making it a
credible alternative to conventional solar cells [3].
A typical DSSC is a sandwich structure based on two Fluorine-
doped Tin Oxide (FTO) glasses. One FTO glass acts as photocathode
and is coated with nanocrystalline metal dioxide semiconduc-
tor, such as TiO2 , which is sensitized with organic dye. The dye
absorbs visible light and releases electrons into the nanocrystalline
TiO2 film of photocathode, and then conduct to another FTO glass
naming as counter electrode. Normally, this counter electrode is
thermally decomposed Pt on FTO glass and presides over the reduc-
tion of the redox species, which serve as a mediator to regenerate
the sensitizer after electron injection. However, the typical design
seems to be difficult for practical solar cells of large surface area,
since the distance between photo- and counter electrode soon
becomes too large (>20 ␮m) due to the limited flatness of the sepa-
rate substrates, causing additional ohmic losses and even diffusion
limitation of the photocurrent in the electrolyte layer [4].
∗ Corresponding author. Tel.: +86 27 87793027.
E-mail address: hongwei.han@mail.hust.edu.cn (H. Han).
In 1996, Kay and Gratzel reported firstly a new low-cost type
of monolithic DSSC based on cheap graphite/carbon black elec-
trode and achieved an energy conversion efficiency of 6.7% [4].
Compared with the conventional DSSC, this monolithic DSSC
permits printing paste layer by layer on a single FTO glass sub-
strate by automatic machine, which offers more positive prospect
for commercial production as a result of lower material cost
and simpler manufacturing process since the FTO glass accounts
for most of its cost. Obviously, the counter electrode in mono-
lithic DSSC requires not only good electrochemical activity but
also high lateral conductivity, which is always negligible in the
sandwich DSSC. Though the carbon counter electrode on the con-
ductive glass has been investigated in the sandwich DSSC, this
carbon film without the conductive substrate cannot meet the
double demands of electrochemical activity and lateral conduc-
tivity within the monolithic DSSC [5,6]. Hence, this monolithic
DSSC still offers lower energy conversion efficiency and fill fac-
tor (FF) than that of the conventional sandwich structure DSSC,
because of the limitation of the ohmic resistance at the inter-
face between the electrolyte and the carbon counter electrode
[4,7–9]. Obviously, the catalytic activity and the lateral conduc-
tivity of carbon counter electrode should be improved, since this
carbon counter electrode serves for not only the redox of elec-
trolyte but also the conduction of charge within liquid monolithic
DSSC. In the previous work, it has been proved that the platiniza-
tion could increase the specific surface areas in the sandwich
DSSC. However, this platinized carbon black film without the

0013-4686/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2012.03.012
 G. Liu et al. / Electrochimica Acta 69 (2012) 334–339
Fig. 1. The XRD pattern (a) and TEM (b) image of the platinized carbon black.
conductive substrate cannot meet the demand of high lateral con-
ductivity within the monolithic DSSC. Moreover, the chemical
reduction methods used for platinization were complex and time-
consuming [8]. Recently, we reported a new simple method to
platinized carbon black which has been proved useful to improve
effectively the parameters of solid-stated monolithic DSSCs when
mixed with flake graphite [10,11]. Unfortunately, their electro-
chemical characterization and photoelectric behavior of liquid
version are still not investigated particularly. Here we character-
ized this mesoscopic platinized graphite/carbon black electrode
with cyclic voltammetry (CV) and electrochemical impedance spec-
troscopy (EIS). The results indicated the catalytic activity and
the lateral conductivity of the mesoscopic graphite/carbon black
counter electrode were improved by introducing trace of Pt. As a
result, high energy conversion efficiency up to 7.61% was obtained
for monolithic DSSC based on the mesoscopic platinized carbon
counter electrode.
2. Experimental
Platinized carbon paste was prepared as following: 2 g carbon
black powders (particle size: 30 nm) and H2 PtCl6 (Sigma) with a
predetermined Pt/carbon black weight ratio were added into 20 ml
isopropanol solution (Sigma) under continue stirring for 30 min,
and then the paste was sintered for 30 min at 380 ◦ C in furnace
to thermally deposit the Pt nanoparticles on the surface of car-
bon black, followed by mixing with graphite powders (particle
size: 1.3 ␮m) with a predetermined graphite/carbon black weight
ratio. Finally, 1 g of 20 nm ZrO2 nanopowders (Sigma) and 1 g of
hydroxypropyl cellulose (Sigma) were added into a 30 ml terpineol
solution. The platinized carbon material paste was obtained after
stirring vigorously using ball milling for 2 h.
CV was actualized in an Ar purged acetonitrile solution at a scan
rate of 100 mV s−1 . The platinized carbon paste was printed on FTO
glass with 0.36 cm2 and 50 ␮m, and then sintered at 400 ◦ C for
30 min, which acted as working electrode within CV testing. A large
Pt plate and Ag/AgCl electrode were used as counter electrode and
reference electrode, respectively. The electrolyte was acetonitrile
solution containing 0.1 M LiClO4 , 10 mM LiI and 1 mM I2 .
EIS was carried out with a dummy symmetric cell. Two identical
platinized carbon electrodes were sandwiched with a 100 ␮m film
of Surlyn and then heated for sealing. The electrolyte between these
two platinized carbon electrodes was the same within CV testing.
The EIS was characterized using a potentiostat (EG&G, M2273) with
the measured frequency range from 100 mHz to 1 MHz.
A dense TiO2 layer was deposited on FTO glass by spray
pyrolysis deposition with di-isopropoxytitanium bis(acetyl acet-
onate) solution. After that a 12 ␮m nanoporous TiO2 layer (PASOL
335
HPW-18NR TiO2 nanopowders, JGC Catalysts and Chemicals Ltd.,
Japan), a 3 ␮m light reflecting spacer layer contains 25 wt%
400 nm TiO2 nanopowders (JGC Catalysts and Chemicals Ltd.,
Japan) and 75 wt% 40 nm zirconia powder (Tosoh zirconia pow-
der TZ-3Y series, Tosoh Japan) and a 50 ␮m mesoscopic platinized
graphite/carbon black electrode were printed layer by layer. The
12 ␮m TiO2 layer and light reflecting spacer layer were sintered
for 30 min at 500 ◦ C and the platinized graphite/carbon black elec-
trode was sintered at 400 ◦ C for 30 min. All the thickness was
tested by four-probe method and the error is less than 1 ␮m.
Then, the substrate was sensitized with a 0.5 mM N719 solu-
tion. The cell was encapsulated by a 100 ␮m thick spacer of the
thermo-bonding polymer (Surlyn, DuPont) with sheet glass. After
sealing, the liquid electrolyte was injected through the hole in
the sheet glass, and then the hole was sealed with Surlyn poly-
mer and cover glass. The liquid electrolyte was composed of
0.6 M 1,2-dimethyl-3-propyl imidazolium iodide (DMPII), 0.1 M LiI,
0.05 M I2 , 0.5 M 4-tertbutylpyridine and 0.1 M guanidinium thio-
cyanate (GNCS) in 3-methoxypropionitrile solution. Photocurrent
density–voltage characteristics were measured with a Keithley
2400 source meter under illumination with an Oriel solar simu-
lator composed of a 1000 W xenon arc lamp and AM 1.5 G filters.
Light intensity was calibrated with a normative silicon cell. The area
of cell is 0.8 cm × 0.8 cm and the active area for the photocurrent
density–voltage characteristics is fixed to 0.13 cm2 with a mask.
3. Results and discussion
Fig. 1a shows the X-ray powder diffraction (XRD) pattern of
the platinized carbon black. The peaks at 39.8◦ , 46.24◦ , 67.48◦ and
81.24◦ corresponding to (1 1 1), (2 0 0), (2 2 0) and (3 1 1) of the face-
centered cubic (fcc) lattice of Pt were observed clearly. With the
Scherrer’s equation, the average size of Pt particle on the surface
of mesoscopic carbon black around was 23 nm calculated from the
broadening of the (1 1 1) XRD peak. This could be demonstrated
from the Transmission Electron Microscope (TEM) image of the pla-
tinized carbon black particles, which is presented in Fig. 1b. The
feature of platinized carbon black particles indicated that the Pt
particles with the size of 20–25 nm were homogeneously adsorbed
on the carbon black, which is similar to the result of XRD pattern.
The surface pattern of the mesoscopic platinized carbon film
is presented in Fig. 2 with the scanning electron microscopy
(SEM) image, exhibiting mesoscopic film with multi-pores. The
images of the mesoscopic carbon films containing 0 wt%, 1 wt%
and 2 wt% Pt were shown in the Supporting Information. The
Brunauer–Emmett–Teller (BET) test indicated that the surface area
of this porous layer is 91.08 m2 g−1 , the Barrett–Joyner–Halenda
(BJH) average pore diameter and pore volume are 14.7 nm and
336 G. Liu et al. / Electrochimica Acta 69 (2012) 334–339

Fig. 2. SEM images of mesoscopic platinized carbon electrode with 0.5 wt.% (a) and 3 wt.% (b).

0.33 cm3 g−1 , respectively. This means that a mesoscopic platinized
carbon layer of 1.2 cm2 geometric area and 50 ␮m thickness has
3825 cm2 of active surface area and a porosity of 24%. When the Pt
content is low (0.5%), the homogeneously dispersed Pt nanoparti-
cles and porous structure would ensure that this mesoscopic carbon
electrode supplies considerable quantities of catalytic active sites
to improve the process of electron exchange between electrode
and electrolyte. However, with Pt content increasing, it can be
found that the small Pt particles moved to the back-fence particles
and aggregated together to form a large bulk with the Pt percent
increase. At the same times, with the bulk growing up, some of the
pores in the mesoscopic carbon substrate were blocked. This phe-
nomenon can be seen in the case of 1 wt% (S1), 2 wt% (S2) and is
extremely prominent when Pt increases to 3 wt% (Fig. 2b).
It is well known that the sheet resistance of counter electrode in
DSSC will influence the FF parameter, which determines the shape
of the current–voltage characteristics and the maximum power
output of the device. In order to obtain high FF, the resistance of
counter electrode has to be as small as possible. Here the addition
of graphite and Pt particle in the carbon black paste is expected
to decrease the resistance of carbon electrode. Though the carbon
black nanoparticles exhibit high electrochemical activity, the film
comprised of only carbon black particles shows a cracked surface
resulting in a low lateral conductivity. Among the carbon materials,
the flake graphite is well known for the high lateral conductivity.
As shown in Fig. 3a, the sheet resistance of 50 ␮m film, tested by
four-probe method, increases obviously with an increase in the
ratio of graphite. The lowest sheet resistance of 5.5  square−1
appears at the largest ratio of graphite to carbon black. However,
the increase of the graphite affects not only the sheet resistance but
also the electrochemical activity, since the high oriented graphite
owns only a few active sites. To investigate the effect of graphite
on the electrochemical activity, the charge transfer resistance was
characterized by (EIS). Because several operational circuit elements
will contribute to the DSSC’s impedance, additional insight could
be obtained from analyzing separately the impedance behavior of
the counter electrode [12]. A typical impedance spectrum of the
dummy cell consisting of two identical mesoscopic carbon elec-
trodes is shown in Fig. 3b. In this model, the effect of the counter
electrode on the impedance of cell was ascertained. The charge-
transfer resistance (Rct ) at the interface between the mesoscopic
carbon electrode and electrolyte was calculated from the simu-
lated model of the equivalent circuit, which is presented in the inset
picture of Fig. 3b.
In the high frequency range, around 10 kHz, the impedance
is dominated by the ohmic serial resistance (Rs ) of the dummy
cell owing to the square resistance of FTO glass substrate, where
the phase is zero. In the case of overall impedance spectrum of
monolithic DSSC, the square resistance of mesoscopic platinized
graphite/carbon black electrode should be taken into account,
which is expected to be as low as possible. In the middle fre-
quency range, 100 Hz–10 kHz, the RC network of the electrode
and electrolyte interface consisting of the Rct and constant phase
element (CPE) dominates the impedance. The CPE reflects the
interfacial capacitance, taking into account the roughness of the
electrodes causing a depression of the semicircle to an ellipse in the

Fig. 3. (a) Sheet resistance and the charge transfer resistance of the film with different ratio of graphite to carbon black. (b) Nyquist plots of electrochemical cells consisting of
two identical platinized carbon coated FTO-glasses with various ratio of graphite to carbon black. (Inset) Equivalent circuit for the impedance spectrum, W: Nernst diffusion
impedance; Rct : charge-transfer resistance of one electrode; C: double layer capacity of one electrode; Rs : serial resistance.
 G. Liu et al. / Electrochimica Acta 69 (2012) 334–339 337

the lowest current density of redox reaction (1), indicating that

Fig. 4. CV curves of the platinized carbon electrodes with different Pt content load-
ing in 10 mM LiI, 1.0 mM I2 acetonitrile solution containing 0.1 M LiClO4 .
Nyquist plots. The impedance of CPE is expressed as ZCPE = A(jω)−˛
(0 ≤ ˛ ≤ 1). ˛ indicated the capacitance of CPE and the deviation
from the semicircle probably due to the porosity of electrode
surface. In the low frequency, the Nernst diffusion impedance
describes the diffusion of I3 − in the electrolyte. Due to the large
excess of I− relative to I3 − and the diffusion constant of I− and I3 −
being of the same order of magnitude, I− does not contribute to the
diffusion impedance.
Impedance values are summarized in Fig. 3a. The charge-
transfer resistance of the carbon film is a measure of its catalytic
activity for reducing the triiodide ion. Thus, the obvious increase of
Rct indicates the diminishment of the catalytic activity with the
increase of the ratio of graphite. Since the counter electrode of
monolithic DSSC requires both low sheet resistance and low charge
transfer resistance, the ratio of 3:1 for graphite to carbon black,
which owns the lowest total of sheet resistance and charge trans-
fer resistance, was chosen as the suitable ratio at the rest of this
work.
To distinguish the differences of catalytic activity before and
after depositing different Pt content on mesoscopic carbon elec-
trode, CV curves of the mesoscopic carbon electrodes with different
Pt percents were characterized at a scan rate of 100 mV s−1 and pre-
sented in Fig. 4. It could be found that there were two typical pairs
of redox waves. The more negative pair is assigned to redox reac-
tion (1) and the more positive one is appointed to redox reaction
(2)
I3 − + 2e− = 3I−
− −
3I2 + 2e = 2I3
the reduction of I3 − to I− has been greatly enhanced after doping
Pt nanoparticles on mesoscopic carbon electrode. It is well known
that the Pt has high electro catalytic activity for iodide/triiodide
redox couple. Generally, it could be expected that the percent of
Pt in carbon film should be as high as possible for higher catalytic
activity. However, in the case of the platinized carbon electrodes,
the electrode with 0.5% Pt loading shows the highest current den-
sity. When the percent of Pt in mesoscopic carbon film is increased
from 0.5% to 3%, the current density decreases slightly owing to
the decline of catalytic activity, particularly the decrease of overall
electrochemical active surface area.
EAS was employed frequently to characterize the catalysts in the
field of fuel cells [13]. Compared with the BET value, EAS is more
reasonable to calculate the actual catalytic active area of electrode
under working condition in DSSC. In Fig. 4, the large capacitance
current over the potential range is attributed to the contribution of
electrolytic double layer at the interface, indicating a large catalyst
surface area of the electrode. The EAS of the mesoscopic carbon
electrodes with different Pt content loading were calculated by the
Randles-Sevcik equation:
1/2
ip = (2.69 × 105 )n3/2 ADo Co∗ 1/2 (3)
where jp , n, A, Do , Co∗ and  represents the peak current of redox
reaction (1), number of transferred electrons, EAS, diffusion con-
stant of electrolyte, concentration of redox species and the scan
rate, respectively. As a result, the EAS of the mesoscopic carbon
electrode without Pt loading was 86.58 m2 g−1 , which is close to
the value from BET test of 91.08 m2 g−1 . When the content of Pt
reaches 0.5%, the EAS of mesoscopic platinized carbon electrode
was 109.36 m2 g−1 , about 26.3% larger than that of pure meso-
scopic carbon electrode. This suggests that the excessive EAS of
platinized carbon electrode is owing to the loading of Pt nanoparti-
cles. However, when the content of Pt within the mesoscopic carbon
electrode is over 0.5%, the EAS is decreased slightly but still larger
than the pure mesoscopic carbon electrode. This could be attributed
to the fact that the catalytic active site exposed in the electrolyte is
diminished with the increase of Pt content or some of the pore in
carbon substrate may be blocked by the Pt nanoparticles as shown
in SEM images. As a result, the mesoscopic carbon electrode with
0.5% Pt loading shows the largest EAS value, which means that the
mesoscopic carbon electrode with trace of Pt around 0.14 g m−2
could exhibit the largest catalytic activity.
The charge transfer process at the interface of electrode and
electrolyte was characterized with EIS (Fig. 5). Due to the consid-
(1) erable EAS and double layer capacitance between electrode and
(2)

The current density, peak current and electrochemical active sur-

face (EAS) of the mesoscopic carbon electrodes with different Pt
percents were calculated from the CV curves and summarized in
Table 1. Compared with the mesoscopic platinized carbon elec-
trodes, the pure mesoscopic carbon electrode without Pt shows

Table 1
The current density, peak current and EAS calculated from the CV curves for different
Pt content in mesoscopic carbon electrode. The size and thickness of the electrode
was 0.36 cm2 and 50 ␮m, respectively.

Pt percent Peak current A (cm2 ) EAS (m2 g−1 ) Current density

(wt%) (mA) (mA cm−2 )

0 0.763 1091 86.58 5.60E−03

0.5 0.963 1378 109.37 7.84E−03
1 0.888 1270 100.79 7.64E−03
2 0.798 1142 90.63 6.24E−03
Fig. 5. Nyquist plots of electrochemical cells consisting of two identical platinized
3 0.908 1299 101.95 7.08E−03
carbon coated FTO-glasses with various Pt loading.
338 G. Liu et al. / Electrochimica Acta 69 (2012) 334–339
Table 2
Photoelectric parameters of DSSCs based on the mesoscopic carbon counter electrodes with different content Pt loading and Impedance parameters for the mesoscopic
platinized carbon counter electrodes of various Pt loading estimated from impedance spectra and equivalent circuit.
Pt loading (wt%) Jsc (mA cm−2 ) Voc (mV)
0% 12.82 723.8
0.5% 13.89 723.6
1% 13.36 733.6
2% 13.06 721.4
3% 13.33 721.9
electrolyte, the charge transfer from electrode to triiodide was
accelerated. Table 2 shows the estimated values by fitting EIS spec-
tra with equivalent circuit. With the percent of Pt increases from 0%
to 0.5%, the Rct decreases drastically from 12.4 to 0.47  cm2 , lead-
ing to only 6.58 mV loss under a 14 mA cm−2 current flow. The Rct of
0.5% mesoscopic platinized carbon is even below that of commonly
Pt/FTO counter electrode 1.3  cm2 . The result indicates that the
catalysis is improved enormously with the addition of Pt. In other
words, the charge transfer reaction was accelerated at the appear-
ance of Pt loading on the mesoscopic carbon electrode. This could
be attributed to the enormous enhancement of EAS deliberated
above. However, the continued augment of percentage, from 0.5%
to 3%, does not conduce to sustaining decrease of Rct but increase
inversely to 2  cm2 and the frequency-independent parameter of
the CPE decreases from 0.86 to 0.76, correspondingly. It indicates
that the capacitance of CPE is decreased due to the decline of the
porosity of electrode surface. Nevertheless, the Rct is still smaller
than that of the pure mesoscopic carbon electrode because of the
abundant catalytic active sites of the Pt within mesoscopic carbon
electrode. This is in good accordance with the EAS value. As shown
in SEM images, when the percentage of Pt increases, the small Pt
nanoparticles aggregate together leading to diminished catalytic
active sites of Pt nanoparticles and some of the charge transfer
channel in the pore of mesoscopic carbon substrate is blocked by
the large bulks and not exposed to the electrolyte solution resulting
in the decrease of the active surface area of the carbon. There-
fore, the virtual catalytic active surface of the counter electrode is
decrease as the Pt increases from 0.5% to 3%, leading to the decline
of EAS and Rct .
Fig. 6 presents the photocurrent density–voltage charac-
teristics of monolithic DSSCs assembled by pure mesoscopic
graphite/carbon black electrode and the platinized graphite/carbon
black electrodes under standard simulated AM 1.5 illumination
of 100 mW cm−2 . The photovoltaic parameters are summared in
Table 2. Compared with the monolithic DSSC based on pure
Fig. 6. Photocurrent–voltage curves of monolithic DSSCs based on mesoscopic car-
bon counter electrodes with various Pt loading under one sun illumination (AM 1.5,
100 mW cm−2 ).
FF  CPE(CB):˛ Rct ( cm2 )
0.64 5.97 0.53 12.44
0.76 7.61 0.87 0.47
0.74 7.30 0.80 1.47
0.72 6.79 0.78 2.07
0.72 6.93 0.76 1.98
mesoscopic graphite/carbon black electrode, the device with the
mesoscopic platinized graphite/carbon black electrode exhibits
markedly better performance, which is in accord with the elec-
trochemical data. The results indicated that with the increase of Pt
content within the mesoscopic counter electrode, the open-circuit
voltage (Voc ) is affected slightly keeping in range of 720–734 mV,
but the short-circuit photocurrent (Jsc ) increase notably. The change
of Jsc can be explained by Eq. (4) [14]
RT
J= (4)
nFRct
where the J is inversely proportional to Rct . Hence, the cell with
pure mesoscopic graphite/carbon black electrode appears a rela-
tive low Jsc of 12.82 mA cm−2 , which possesses the largest Rct . After
replacing with mesoscopic platinized carbon electrode, a remark-
able increase in the Jsc is observed with the Rct decreasing. The
Jsc reaches the highest value of 13.89 mA cm−2 when 0.5% meso-
scopic platinized carbon electrode was used. When the content of
Pt within mesoscopic carbon electrode is over 0.5%, the Jsc decreases
to 13.33 mA cm−2 but still larger than that of the cell with pure
mesoscopic carbon electrode. In fact, with the increase of Pt con-
tent within mesoscopic graphite/carbon black electrode, the FF
of the device is remarkable improved, resulting in the obvious
enhancement of energy converson efficiency (). The FF was mainly
dominated by the value of the Rct . Since the charge-transfer resis-
tance influences particularly the I–V curves near the open circuit
potential, a relative low FF of 0.64 is obtained for the device with
pure mesoscopic graphite/carbon black electrode, which exhib-
ited the lowest  of 5.97%. As mentioned above, compared with
mesoscopic platinized carbon electrode, the pure mesoscopic car-
bon electrode shows the lowest EAS and the highest Rct , resulting
in the highest inner resistance and the relative low FF. However,
with the increase of Pt loading within mesoscopic graphite/carbon
black electrode, the FF of the devices are improved and that of
0.5% Pt loading exhibits the highest FF of 0.76, resulting in a high
efficiency up to 7.61% of monolithic DSSC based on mesoscopic
platinized graphite/carbon black electrode. This indicates that the
efficiency could be improved notably through introducing trace
of Pt. The relatively lower FF, 0.74 and 0.72, was also observed
at higher percentage of Pt loading, 1%, 2% and 3%, respectively.
These are in good accordance with the EIS analysis measured within
the symmetric sandwich-like cell, resulting in an efficiency of
lower than 7.3%.
4. Conclusions
Mesoscopic platinized carbon electrode for monolithic DSSC
was developed by thermal deposition. The CV curve and EIS spec-
tra shown that the EAS of the mesoscopic carbon electrode with
0.5% Pt loading are larger than that of pure carbon electrode and
the Rct dropped observably with the introduction of Pt, which indi-
cated that the catalytic activity and charge transfer rate of counter
electrode were enhanced remarkably by depositing Pt nanopar-
ticles onto the surface of the mesoscopic carbon electrode. As a
result, an energy conversion efficiency up to 7.61% was obtained
for the mesoscopic platinized carbon electrode based monolithic
 G. Liu et al. / Electrochimica Acta 69 (2012) 334–339
DSSC, which is higher than that of the pure graphite/carbon black
electrode based monolithic DSSC. It could be expected that the
low cost materials and simple manufacturing process would make
the mesoscopic platinized graphite/carbon black electrode based
monolithic DSSC available in practical application.
Acknowledgments
The authors acknowledge the financial support by the National
Natural Science Foundation of China (Grant No. 61106056), the
Nature Science Foundation of Hubei Province (2008CDA042), the
Scientific Research Foundation for Returned Scholars, Ministry of
Education of China (SRF for ROCS, SEM.), and the Fundamental
Research Funds for the Central Universities (Hust, 2011TS020). We
also thank the Analytical and Testing Center of HUST for SEM and
TEM testing.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.electacta.2012.03.012.
339
References
[1] B. Oregan, M. Gratzel, Nature 353 (1991) 737.
[2] C.Y. Chen, M.K. Wang, J.Y. Li, N. Pootrakulchote, L. Alibabaei, C.H. Ngoc-le, J.D.
Decoppet, J.H. Tsai, C. Gratzel, C.G. Wu, S.M. Zakeeruddin, M. Gratzel, ACS Nano
3 (2009) 3103.
[3] L.Y. Han, N. Koide, Y. Chiba, T. Mitate, Appl. Phys. Lett. 84 (2004) 2433.
[4] A. Kay, M. Gratzel, Sol. Energy Mater. Sol. Cells 44 (1996) 99.
[5] T.N. Murakami, S. Ito, Q. Wang, M.K. Nazeeruddin, T. Bessho, I. Cesar, P. Liska, R.
Humphry-Baker, P. Comte, P. Pechy, M. Gratzel, J. Electrochem. Soc. 153 (2006)
A2255.
[6] S.J. Thompson, N.W. Duffy, U. Bach, Y.B. Cheng, J. Phys. Chem. C 114 (2010)
2365.
[7] H. Pettersson, T. Gruszecki, R. Bernhard, L. Haggman, M. Gorlov, G. Boschloo, T.
Edvinsson, L. Kloo, A. Hagfeldt, Prog. Photovoltaics 15 (2007) 113.
[8] P.J. Li, J.H. Wu, J.M. Lin, M.L. Huang, Y.F. Huang, Q.G. Li, Sol. Energy 83 (2009)
845.
[9] K. Imoto, K. Takahashi, T. Yamaguchi, T. Komura, J. Nakamura, K. Murata, Sol.
Energy Mater. Sol. Cells 79 (2003) 459.
[10] H.W. Han, U. Bach, Y.B. Cheng, R.A. Caruso, C. MacRae, Appl. Phys. Lett. 94
(2009).
[11] H. Wang, G.H. Liu, X. Li, P. Xiang, Z.L. Ku, Y.G. Rong, M. Xu, L.F. Liu, M. Hu, Y.
Yang, H.W. Han, Energy Environ. Sci. 4 (2011) 2025.
[12] Q. Wang, J.E. Moser, M. Gratzel, J. Phys. Chem. B 109 (2005) 14945.
[13] K. Skupien, P. Putyra, J. Walter, R.H. Kozlowski, G. Khelashvili, A. Hinsch, U.
Wurfel, Prog. Photovoltaics 17 (2009) 67.
[14] L. Kavan, J.H. Yum, M. Gratzel, ACS Nano 5 (2011) 165.