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ARTICLE

Performance of FTO-Free Conductive Graphene-Based Counter

Electrodes for Dye-Sensitized Solar Cells
Received 00th January 20xx,

RSC Advances Accepted Manuscript

a a, b,* a a a
Beili Pang , Lifeng Dong Shuai Ma , Hongzhou Dong , and Liyan Yu
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Accepted 00th January 20xx

DOI: 10.1039/x0xx00000x The attractiveness of graphene arises from its low cost, transparency, high electrical conductivity, chemical robustness,
and flexibility, as opposed to the rising cost and brittleness of FTO. In particular, graphene is emerging as a possible
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substitute for FTO in flexible displays, touch screens, and solar cells. The main goal of our work is to develop new
conductive oxide free graphene-based counter electrodes for dye sensitized solar cells (DSSCs). Graphene nanoplates are
modified by silane coupling agent to introduce vinyl groups, and then mixed with polyurethane adhesive and cast on glass
substrate. The film is irradiated by UV source and heat treated under Ar/H2. A network graphene film is formed and tightly
bonded on glass substrate with enhanced electrical conductivity. The structure of network graphene is investigated by
XPS, TGA and SEM. The DSSCs with network graphene counter electrode exhibit power conversion efficiencies of 9.33%,
much better than those with FTO electrodes (4.05%).

1. Introduction
Since the first archetype was proposed by O’Regan and cm2 V−1 s−1), large specific surface area (2600 m2 g−1), and
Gräzel in 1991, dye-sensitized solar cells (DSSCs) have outstanding thermal properties13-17. Furthermore, interconnected
attracted increasing attention due to their relatively high graphene can capture injected electrons and work as a
photoelectric conversion efficiency (PCE) and low-cost “speedway” to enhance electron transport rate18-20.
fabrication1. Typical DSSCs have a sandwich structure, However, there are only a few reports on a complete
including a photoanode, a counter electrode (CE), dye replacement of ITO/FTO as the DSSC CE with other
molecules, and redox electrolyte filling between electrodes. As materials21-23. For example, Veerappan et al. used a graphite
a crucial component, an ideal DSSC CE should possess high film as the CE with a PCE of 6.2%24. Chung et al. utilized
conductivity and superior catalytic properties2. ultraviolet oxidized multi-walled carbon nanotubes (MWCNTs)
Platinum (Pt) deposited on indium tin oxide (ITO) or and glycerol doped PEDOT: PSS films as the CE with PCEs of
fluorine doped tin oxide (FTO) substrates has been widely used 5.6% and 4.1%, respectively25. In this study, we developed a
as a standard counter electrode for DSSCs 3, 4. However, network structure graphene film to replace FTO film for the
ITO/FTO has many drawbacks such as brittleness, low DSSC counter electrode. For the preparation of network
adhesion to polymeric materials, a decrease in supply of structure graphene film, graphene oxide (GO) was modified by
indium, and the growing cost of indium metal, which have silane coupling agent to introduce vinyl group on graphene
restricted their further applications 5, 6. In addition, the surface. Polyurethane (PU) copolymer was used as adhesive to
ITO/FTO layer is usually fabricated via a rather expensive mix with modified graphene (mGr), and the mixture was spin
vacuum sputtering process. Thus, there is an imperative coated on glass substrates. Network structure graphene was
demand in finding new materials to replace the ITO/FTO film then formed and tightly adhered to the glass substrate after UV
as transparent conductive layers; in this regard, several irradiation, which were characterized by scanning electron
materials including conductive polymers7, carbon nanotubes microscopy (SEM), x-ray photoelectron spectroscopy (XPS)
(CNT)8, 9, graphene10,11, and metal grids12 have been proposed and thermogravimetric analysis (TGA). The DSSCs with
to substitute ITO/FTO films. For instance, graphene can be a network structure graphene as the CE exhibit an optimal PCE
promising candidate due to its high carrier mobility (>2×105 of 9.33%.

a.
College of Materials Science and Engineering, Qingdao University of Science and
Technology, Qingdao, 266042, P.R.China
b.
Department of Physics, Hamline University, Saint Paul, Minnesota 55104, USA (E-
mail: donglifeng@qust.edu.cn ldong03@hamline.edu )

See DOI: 10.1039/x0xx00000x

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Scheme1. Preparation of CE-1, CE-2, CE-3 and CE-4.

added into the dispersion (0.5 g of GO powder dispersed in 50

2. Experimental g of ethanol) followed by immediate adding 1 g of ammonia
solution (28%). Excess VTES was beneficial to a higher extent
2.1. Preparation of modified graphene (mGr) and reduced of condensation reaction between hydroxyl groups on GO
graphene (Gr) powder and methoxysilane groups of VTES. The solution was
stirred with 300 rpm at 60 °C for 6 h. 5 g of hydrazine hydrate
Graphene oxide (GO) was prepared by Hummers method26. was then added and the reaction was kept at 70 °C for 6 h. After
Briefly, 4.0 g of graphite was mixed with 4.0 g of NaNO 3 and washing with ethanol and distilled water for three times, the
184 mL of 95% H2SO4 and the mixture was stirred in an ice mGr was dried under vacuum.
bath. 24 g of KMnO4 was added slowly into the graphite Gr was prepared by GO and hydrazine hydrate. 0.5 g of
suspension while vigorous stirring and maintaining the GO was dispersed in 100 g of distilled water. Then 5 g of
temperature at 4 °C for 1 h. The graphite suspension was then hydrazine hydrate was added and the reaction was kept at 70 °C
stirred at 35 °C for 1 h. When 2 L of distilled water was added for 6 h to get reduced graphene nanosheets. After washing with
to the pasty graphitic suspension, the color of suspension distilled water for three times, the Gr was dried under vacuum.
changed to yellowish brown. After vigorous stirring at 98 °C
for 1 h, 20 mL of 35% H2O2 was added to the suspension 2.2. Preparation of counter electrodes
resulting in an immediate color change to golden yellow. The
oxidized product, GO, was washed several times with distilled As shown in scheme1, 1 g PU was mixed with 0.1 g mGr
water via centrifugation until the solution became acid free and 10 g ethyl acetate, and then stirred ultrasonically for 2 h to
followed by filtration and drying under vacuum. GO was finally get mGr/PU. The mGr/PU mixtures were spin coated on glass
obtained as gray powder. substrates at 1200 rpm for 20 s. Some samples were under UV
The silane coupling agent, triethoxyvinylsilane (VTES, irradiation for 30 min to get CE-1 and CE-4, and CE-2 was
98%), was purchased from Aladdin (China). 4 g of VTES was without UV irradiation. CE-3 was prepared by the Gr/PU which

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was mixed with 1 g PU, 0.1 g Gr and 10 g ethyl acetate and View Article Online
without UV irradiation. Then CE-1, CE-2, CE-3 and CE-4 were DOI: 10.1039/C6RA02854C
heat treated under Ar/H2 at 400 °C for 2 h to remove PU.
Except for CE-4, CE-1, CE-2 and CE-3 were drop-coated with
an isopropanol solution of 10 mM H2PtCl6, followed by a
treatment at 400 °C for 30 min. As a comparison, conventional
Pt electrodes were fabricated by drop-coating H2PtCl6 solution
on FTO substrate and treated at 400 °C for 30 min.

2.3. Characterization

The property of modified graphene was studied with

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Fourier transform infrared spectroscopy (FTIR, Nicolet iS5,
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USA). The chemical state of the samples was analyzed using

XPS with a spectrometer (EPMA-1600, Shimadzu, Japan)
equipped with Al Kα x-ray source. The morphology of the
samples was characterized using field-emission scanning
electron microscopy (FESEM, JEOL JSM 7000F, Japan). TGA Fig.1 FTIR spectra of VTES (a), mGr (b), and GO (c).
was conducted in a thermo-balance (TASDT Q600, Mettler-
Toledo, USA) with approximately 5 mg of sample weighed. 3. Results and discussion
The temperature was raised from 100 to 800 °C at a rate of 10
°C/min under a nitrogen flow to investigate main Silane coupling agent VTES can be anchored on the surface
decomposition behavior. of modified graphene (mGr) via condensation reactions
TiO2 photoanodes were supplied by Dalian Heptachroma between -COOH, -OH and epoxy groups present on the mGr
SolarTech Co., Ltd. They were soaked in an ethanol solution of surface and silanol groups formed by the hydrolysis of
0.5 mM ruthenium dye [N-719, cis-di(thiocyanato)-N,N- alkoxysilanes in VTES. The progress of condensation reaction
bis(2,2-bipyridyl-4-carboxylacid-4-tetrabutyl-ammonium can be identified by simultaneous disappearance of
carboxylate) ruthenium(II)] for 24 h, resulting in N-719 characteristic bands assigned to methoxysilane groups27.
sensitized TiO2 photoanode. The photoanode and various CEs Therefore, FTIR was used to understand the formation of
were assembled in sandwich-type cell. Liquid electrolyte DHS- anchored VTES on mGr surface and its chemical reduction via
E36 was injected into space between the two electrodes. Finally, hydrazine hydrate. Fig. 1 shows FTIR spectra of GO, mGr and
as prepared DSSCs (0.5cm2 in active area) were tested for VTES. As shown in Fig.1, characteristic GO absorption bands
photovoltaic characteristics (Scheme 2). (Curve c) appear at 3010–3680 cm-1 (–OH stretching), 1732
cm-1 (–C=O stretching), 1220 cm-1 (C(O)–OH bending), and
1045 cm-1 (C–O–C stretching), which provide evidence of
carboxylic acid, epoxide, and hydroxide functional groups28.
For the VTES (Curve a), absorption peaks at 2840 cm-1 and
2948 cm-1 correspond to stretching vibrations of -CH3 and -CH2,
respectively. The peak at 1076 cm-1 is related to Si-O-C2H5
linkages and disappeared after modified reaction (Curve b). The
stretching vibration of vinyl groups at 1602 cm-1 was observed
for the mGr (Curve b). On the other hand, C=O stretching
vibrations in carboxyl group of GO (Curve c) decreased after
chemical reduction (Curve b). After chemical reduction and
VTES addition, new absorptions appeared due to the
introduction of Si-O-Si groups (1169 cm-1) onto the mGr
surface, which indicates successful conduct of modified
reaction. As a result, VTES was linked to the surface of mGr
and resulted in UV curable vinyl groups on the mGr surface.

Scheme 2. Diagram of DSSC with graphene-based counter

electrode.

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Fig. 2 Images of mGr/PU (a, c) and Gr/PU (b, d) solutions before and after standing at room temperature for 24 h.

Reduced graphene flakes in polymer matrix tend to aggregate N 1s due to PU residues. The signals at 73 eV, 315–330 eV,
and stack in multi-layers due to van der Waals interactions. and 519 eV can be assigned to Pt 4f, Pt 4d and Pt 4p,
These aggregates usually have different physical and chemical respectively. In the survey spectrum of CE-1 and CE-2, the
properties from exfoliated monolayers29-31. As shown in Fig. 2, binding energy of 103 eV corresponds to Si 2p due to the
for reduced graphene solution (Gr/PU, Fig. 2b and 2d), Gr introduction of silane coupling agent.
aggregated and settled at the bottom of bottle (Fig.2d). In The C 1s spectrum of CE-2 (Fig. 3c) can be decomposed
contrast, no aggregations appeared for mGr solution (mGr/PU, into five components: C=C in aromatic rings (284.3 eV), C-C in
Fig. 2a and 2c) after standing for 24 h, which shows that mGr non-oxidized ring (284.5 eV), carbon in C–O bonds (286.1 eV),
can provide better dispersion in polymer matrix due to modified C=C vinyl group (284.6 eV) and C-C atoms in defective
functional groups on the mGr surface. The CEs were prepared structure of graphene lattice (285.6eV). In comparison, the
by these mixture solutions. As shown in Figure S1 and S2 in changes in the functional groups of the C 1s emission of CE-1
Supplementary Information, the film thickness of CE-1 is about can be seen in Fig. 3b. The C-C in aliphatic (284.8 eV) was
25 µm which is much thinner than that of CE-2 (49μm) and observed and the vinyl group disappeared after UV irradiation.
CE-3 (55μm). The photographs (Figure S3) show that the film This indicates that network structure graphene film was
of CE-1 was sufficiently transparent that the letters below the successfully formed on glass substrate from the vinyl group of
film could be seen clearly. However a lot of aggregations of mGr, which was shown in Figures S1, S2 (a), S3 (a, d) and
graphene layers appeared on the surface of CE-2 and CE-3, Figure 4(a). There are four components in C 1s spectrum of
which caused them to have low transparency. The surface of CE-3 (Fig. 3d), which include C=C in aromatic rings, C-C
CE-1 is rather uniform and tightly bonded on glass substrate, atoms in defective structure of graphene lattice, C-C in non-
even after immersing in acetonitrile solution for 24 h. oxidized ring (284.5 eV) and C-O(H) (288.5 eV). This indicates
XPS measurements were conducted to determine surface that Gr was effectively reduced during the reduction process.
chemical states, functional groups and elemental composition The atomic percentage of three samples is summarized in
of CE-1, CE-2 and CE-3 and to investigate the change of Table 1. The Pt percentage of CE-1 was much higher than those
functional groups induced by surface functionalization and UV- of CE-2 and CE-3, which suggests that network structure
curable treatment. As presented in Fig.3a, in the survey graphene can effectively enhance the deposition of more Pt
spectrum, the peaks centered on binding energies of 285 eV and nanoparticles into modified surface and prevent the aggregation
530 eV can be ascribed to C 1s and O 1s core-level emissions, of Pt nanoparticles32-35.
respectively. And the binding energy of 400 eV corresponds to

Table 1. Atomic percentages for CE-1, CE-2 and CE-3 as determined using XPS analyses.
Samples Atomic percentages (%)
C O Si Pt N
CE-1 80.57 5.35 0.73 2.30 11.05
CE-2 80.49 6.89 0.75 0.33 11.54
CE-3 85.45 5.26 - 0.26 9.03

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Fig. 3 (a) XPS survey spectra of CE-1, CE-2 and CE-3 film, and C 1s core level XPS spectrum of CE-1 film (b), CE-2 film (c) and
CE-3 film (d).

Fig.4 SEM images of the film surface of CE-1(a) and CE-3(b).

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As shown in Fig. 4, graphene sheets in Gr samples (CE-3,

Fig. 4b) physically assembled and the film was not uniformly
covered with graphene, which is undesirable for the deposition
of Pt particles and their catalytic activity36, 37. Instead, as given

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in Fig. 4a, graphene sheets in mGr samples (CE-1) exhibit
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much wrinkled surface and are connected to each other to form

network structure. The crumpled surfaces can provide more
sites for the deposition of Pt particles, and the network structure
can affiliate carrier transport during catalytic processes. This
clearly demonstrates that the introduction of silane coupling
agent and UV-curable process can effectively modify graphene
surfaces and result in the formation of network structure
graphene.
TGA was used to compare thermal decomposition
behavior of CE-1, CE-2, and CE-3. At 800°C, the residue of
CE-3 is about 91%, which is higher than that of CE-1 and CE-2.
Fig.6. Photovoltaic characterizations of DSSCs with different
It indicates that reduced graphene has high thermal resistance
counter electrodes.
due to sp2 structure. As given in Fig. 5, modified graphene
(mGr in CE-1 and CE-2) demonstrates an initial weight loss of Table 2 summarizes photovoltaic parameters, such as open-
2.5% and 2.3% between 100 and 400 °C, respectively, which circuit voltage (Voc), short-circuit current density (Jsc), fill
are higher than that of Gr (CE-3). These initial weight loss is factor (FF), and power conversion efficiencies (η) of all DSSCs
due to the presence of more functional groups on the surface of which were prepared in this work. The photocurrent density-
mGr. In comparison to CE-2, CE-1 shows higher thermal voltage (J–V) characteristics of the DSSCs with various CEs
stability from 400 to 800 °C. It was reported that network are shown in Figure 6.
structure of UV-curable films could improve thermal DSSCs made with bare FTO performed poorly owing to
resistance38, 39. Therefore, good thermal resistance of CE-1 the impotency of FTO substrate for I3- reduction. The Pt- and
indicates that network structure graphene can be formed via FTO-free CE-4 substrate shows a low resistivity of 0.74 Ω·cm
UV-curable treatment. (as measured by the four-point probe method), a good solar
conversion efficiency of 3.6% and fill-factor of 53.5%. This is
mainly due to that high specific surface area and many
chemical defects of network structure graphene can provide
high catalytic activity toward iodine reduction. On the other
hand, the relatively low solar conversion efficiency of 0.36%
and 0.13% obtained for CE-2 and CE-3 respectively is
attributed to two-dimensional surface structure of no-UV
curable graphene. The observations above indicate that the
optimal material for catalytic activity and conductivity is
network structure graphene, CE-4.
An improved efficiency of 9.33% was obtained by using
CE-1 which is higher than that of η=4.05% with Pt/FTO
electrode. As photovoltaic measurements were tested under the
same conditions and with the same photoanode, the increase in
Jsc can be ascribed to the network structure of CE-1 since the
network can serve as a conduction pathway. The large surface
Fig.5 TGA curve of CE-1, CE-2 and CE-3. area of CE-1 can result in high conductivity and improved
catalytic activity of the electrode40-42. In comparison to CE-4,
the increased efficiency of CE-1 can result from synergistic
effects of network structure graphene and Pt embedded within
graphene matrix (Figure S4).

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Table 2. Photovoltaic performance of DSSCs with different counter electrodes. Jsc: short-circuit current density, Voc: open-circuit
voltage, FF: fill factor, and η: photoelectric conversion efficiency.

Electrodes Jsc (mA cm-2 ) Voc (V) FF (%) η (%)

CE-1 25.46 0.632 58.0 9.33
CE-2 6.47 0.129 44.3 0.36
CE-3 2.56 0.193 26.3 0.13
CE-4 15.12 0.447 53.3 3.60
Pt/FTO 20.86 0.646 30.1 4.05
Bare FTO 1.7208 0.231 24.6 0.098

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Therefore, graphene structure can enhance active surface network structure graphene layers as a CE showed promising
area for electrochemical reactions and offer efficient channels results. The low-cost FTO-free graphene based counter
for electrolyte diffusion, meanwhile, an electronic conducting electrode optimized in the present work showed an energy
network created by graphene improves inter-layer conductive conversion efficiency of 9.33%.
connection, which is beneficial to electron transfer. It is clearly
found that the cells applying FTO as CE substrate generally
exhibit unsatisfactory photovoltaic performance mainly due to Acknowledgements
their low fill factor; instead, by applying graphene-based This work was partially supported by the International Science
substrate, the fill factor turns to be remarkably improved, the & Technology Cooperation Program of China (2014DFA60150)
photocurrent Jsc of CE-1 only shows minor increased compared and the National Natural Science Foundation of China
to those with FTO-based CE. Besides the advantages of (51172113 & 51373086). L. F. Dong thanks financial support
graphene discussed above, it is deduced that the superior band from the Malmstrom Endowed Fund.
matching of graphene coupled with CE of DSSCs can
contribute to the cell performance improvement. In general, the
work function of Pt and FTO is 5.65 eV and 4.4 eV, Notes and References
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DOI: 10.1039/C6RA02854C

Network structure graphene was used as an efficient counter electrode for DSSCs
which was generated from modified graphene after UV irradiation. The low-cost
FTO-free graphene based counter electrode demonstrates an energy conversion
efficiency of 9.33%.
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RSC Advances Accepted Manuscript