C6RA02854C
C6RA02854C
C6RA02854C
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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 )
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1
2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
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
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ARTICLE
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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ARTICLE
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).
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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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8 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
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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