# A Study of Mixed Vegetable Dyes with Different Extraction Concentrations for Use as a Sensitizer for Dye-Sensitized Solar Cells

Authors: Kun-Ching Cho; Ho Chang; Chih-Hao Chen; Mu-Jung Kao; Xuan-Rong Lai
Journal: International Journal of Photoenergy
 (2014)

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## Abstract

Two vegetable dyes are used for the study: chlorophyll dye from sweet potato leaf extract and anthocyanin dye from extracts of blueberry, purple cabbage, and grape. The chlorophyll and anthocyanin dyes are blended in a cocktail in equal proportions, by volume. This study determines the effect of different extraction concentrations and different vegetable dyes on the photoelectric conversion efficiency of dye-sensitized solar cells. In order to make the electrode for the experiments, P25 TiO2 powder was coated on the ITO conducting surface, using a medical blade, to form a thin film with a thickness of around 35 μm. The experimental results show that the cocktail dye blended using extracts of sweet potato leaf and blueberries, in the volumetric proportion 1 : 1, at a weight concentration of 40%, using an extraction temperature of 50°C and an extraction heating time of 10 min produces the greatest photoelectric conversion efficiency (η) of up to 1.57%, an open-circuit voltage (VOC) of 0.61 V, and a short-circuit current density (JSC) of 4.75 mA/cm2.


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## Body

## 1. Introduction

Of the various renewable energy sources, wind power and solar energy have the greatest potential. Solar energy causes no public harm and can be used by anybody, without limits. Therefore, many countries are actively endeavoring to develop solar energy [1]. Dye-sensitized solar cells (DSSC) are increasingly used in conventional inorganic solid solar cells. TiO2 is the most promising electrode material for DSSCs because of its wide band gaps, which are suitable for interfacial electron transport. In the early 1990s, Grätzel et al. developed a new type of solar cell that absorbs incident solar light in the visible light wavelength zone of the dye with a high surface area of titanium dioxide (TiO2). The dye-sensitized TiO2 solar cell can be prepared in an ordinary environment, which significantly reduces its cost [2]. Currently, the most efficient dye-sensitized solar cell (DSSC), which uses Ru compound absorbed onto nanoscaleTiO2, has an efficiency of 11-12% [3, 4]. Although this type of DSSC is more efficient, its use of expensive metals, such as N3 and N719, has several drawbacks.Many inorganic, organic, and hybrid dyes have been employed as sensitizers [5–7]. Because ruthenium dyes, including N719 and N3, are very expensive and environmentally toxic, numerous metal-free organic dyes have been used in DSSCs [8, 9]. Recently, several natural organic dyes, such as anthocyanin, chlorophyll, tannin, and carotene, extracted from various plants, fruits, flowers, and leaves, have been successfully used as sensitizers in DSSCs [10–16]. Hao et al. extracted photosensitizer from the plants of black rice, capsicum, Erythrina variegata flower, Rosa xanthina, and kelp to serve as natural dyes. Black rice achieves the greatest photoelectric conversion efficiency of 0.327% [17]. Wongcharee et al. extracted natural pigments from rosella and blue pea and blended these two pigment dyes in equal proportions to determine the performance of the blended dye, which achieved a maximum photoelectric conversion efficiency of 0.37% [14]. In 2008, Calogero used the extracted fluid from red Sicilian orange and purple eggplant as a photosensitizer. The cell using red Sicilian orange juice as the sensitizer achieved the highest photoelectric conversion efficiency, with a maximum efficiency of 0.66% [18]. Thambidurai et al., 2011, have fabricated Ixora coccinea, Mulberry, and beetroot extract sensitized ZnO nanorod-based solar cells and have reported that the efficiencies are 0.33, 0.41, and 0.28%, respectively [19]. Park et al., 2013, have fabricated yellow Gardenia as natural photosensitizer and reported maximum power conversion efficiency of 0.35% [20]. Senthil et al., 2014, have fabricated DSSCs using natural dyes extracted from strawberry, which showed a maximum conversion efficiency of 0.49% [21]. The dye-sensitized solar cells (DSSC) fabricated using the predye treated and pure TiO2 nanoparticles sensitized by natural dye extract of Lawsonia inermis seed showed a promising solar light to electron conversion efficiency of 1.47% and 1%, respectively [22].This study uses a cocktail of dyes, which are extracted from four different kinds of vegetable dyes, in DSSCs, in order to reduce the cost of fabrication. The effect of different extraction concentrations and different vegetable dyes on the photoelectric conversion efficiency of dye-sensitized solar cells is also determined.


## 2. Experimental Details

Four types of single natural-dye materials were extracted from sweet potato leaf, blueberry, blue cabbage, grape, and eggplant. Using a cocktail blending method, chlorophyll dye and anthocyanin dye were blended in the volumetric proportion 1 : 1 to form four types of cocktail dyes. Anhydrous ethanol was used as the extraction solvent. They were heated by double-container boiling with different extracts, at weight concentrations of 10%, 20%, and 40%. The heating time for each extract was 10 minutes and the temperature used for each extract was 50°C.10 g of TiO2 powder in 67 mL of deionized water was violently stirred at room temperature, for 60 minutes and ultrasonically vibrated for 30 minutes. 3 g of polyoxyethylene (M.W. = 8000) was then added to the solution, which was stirred and heated, until it was completely dissolved. The solution was then ultrasonically vibrated for 30 minutes, to form a white gelatinous dispersion that served as a paste. The electrolyte was produced using 0.1 M of LiI, 0.05 M of I2, and 0.5 M of 4-tert-butylpyridine. The solvent used was acetonitrile (ACN), which served as the electrolyte for the cell.The photoelectrodes were soaked in N719 dye for 24 hours. The photoelectrodes and counter electrodes were tightly clamped to complete electrode packaging. The electrolyte was then added by capillary action, to reproduce completely assembled DSSCs. AnI-V curve analyzer (Keithley 2400) was used to measure the performance of the prepared DSSC. The open-circuit voltage VOC (V), the short-circuit current density   JSC (mA/cm2), the fill factor (FF), and the photoelectric conversion efficiency (η%) of each DSSC were also measured.


## 3. Results and Discussion

Figures1 and 2 show the morphology and cross-section of the fabricated TiO2 thin film. This study uses PEG to increase the specific area of the formed P25 TiO2 film, to increase the amount of dye absorbed and produce more electric current and to give a more complete TiO2 thin film.Figure 1
The FESEM image of the morphology of the TiO2 thin films.Figure 2
The FESEM image of the cross-section of the fabricated TiO2 thin film.Figure3 shows the absorption spectra for four natural dyes. The figure shows that the maximum absorption peaks for sweet potato leaf are at 665 and 434 nm, the ranges of absorption wavelength for the sweet potato leaf are 420~500 and 640~700 nm, the maximum absorption peak for grape is at 536 nm, the ranges of the absorption wavelength for grape are 545 nm and 470~700 nm, the maximum absorption peak for blueberry is at 541 nm, and the range of the absorption wavelength for blueberry is 460~700 nm. Figure 4 shows the absorption spectra for three types of cocktail dyes. Figure 4 shows that the cocktail dyes increase the range of the absorption wavelength and allows further absorption of more visible light, which increases the photoelectric conversion efficiency of a DSSSC.Figure 3
The absorption spectra for extracts of sweet potato leaf, grape, blueberry, and purple cabbage, in ethanol solution.Figure 4
The absorption spectra for extracts of the cocktail dyes.Table1 shows the photoelectrical parameters for a DSSC that is sensitized with different types of chlorophyll, anthocyanin, and cocktail dyes, at a weight concentration of 10%. The cocktail dye that is blended from extracts of sweet potato leaf and grape in a volumetric proportion of 1 : 1 produces the greatest photoelectric conversion efficiency of 0.17% and the highest short-circuit current of 0.53 mA/cm2. Sweet potato leaf dye produces the highest open-circuit voltage of 0.61 V. The cocktail dye that is blended from extracts of sweet potato leaf and grape in a volumetric proportion of 1 : 1 has the greatest fill factor of 60%.Table 1
The performance of DSSCs using natural dye at a weight concentration of 10%.
Dye
V
oc (V)
I
sc (mA/cm2)
FF (%)
η (%)
Sweet potato leaves
0.595
0.577
41
0.141
Blueberries
0.61
0.488
58
0.164
Purple cabbage
0.555
0.424
38
0.09
Grape
0.595
0.15
52
0.046
Sweet potato leaves and blueberries
0.53
0.096
39
0.02
Sweet potato leaves and purple cabbage
0.53
0.288
56
0.085
Sweet potato leaves and grape
0.537
0.53
60
0.17Figure5 and Table 2 show the photoelectrical parameters for a DSSC that is sensitized using different types of chlorophyll, anthocyanin, and cocktail dyes, at a weight concentration of 20%. Sweet potato leaf dye produces the greatest photoelectric conversion efficiency of 0.391% and the highest short-circuit current of 1.23 mA/cm2. Grape dye produces the highest open-circuit voltage of 0.71 V and blueberry dye produces the greatest fill factor of 61%.Table 2
The performance of DSSCs using natural dyes at a weight concentration of 20%.
Dye
V
oc (V)
I
sc (mA/cm2)
FF (%)
η (%)
Sweet potato leaf
0.645
1.23
49
0.391
Blueberries
0.67
0.532
61
0.218
Purple cabbage
0.64
0.642
55
0.226
Grape
0.71
0.503
45
0.16
Sweet potato leaf and blueberries
0.69
0.42
28
0.08
Sweet potato leaves and purple cabbage
0.645
0.534
60
0.207
Sweet potato leaf and grape
0.675
0.508
54
0.185Figure 5
The photocurrent-voltage curves for natural dyes at a weight concentration of 20%.Figure6 and Table 3 show the photoelectrical parameters for a DSSC that is sensitized using different types of chlorophyll, anthocyanin, and cocktail dyes, at a weight concentration of 40%. The cocktail dye that is blended using extracts of sweet potato leaf and blueberry in a volumetric proportion of 1 : 1 produces the highest photoelectric conversion efficiency of up to 1.57% and the highest short-circuit current of 4.75 mA/cm2. It can be seen that sweet potato leaf has higher absorption at wavelength of 420~450 nm and 650~690 nm. In addition, the blueberries have higher absorption at wavelength of 480~640 nm. Furthermore, the incident photon-electron conversion efficiency (IPCE) test shows that the cocktail dye blended by extracts of sweet potato leaf and blueberries has higher IPCE value at wavelength of 470~630 nm and 660~700 nm. Therefore, the cocktail dye that is blended using extracts of sweet potato leaf and blueberry produces the highest photoelectric conversion efficiency. All of the anthocyanins from purple cabbage produce the highest photoelectric conversion efficiency of 0.722%. Sweet potato leaf mixed with purple cabbage dye produces the highest open-circuit voltage of 0.615 V. Sweet potato leaf mixed with blueberry dye produces the greatest fill factor of 53%.Table 3
The performance of DSSCs using natural dyes at a weight concentration of 40%.
Dye
V
oc (V)
I
sc (mA/cm2)
FF (%)
η (%)
Sweet potato leaf
0.595
3.83
41
0.931
Blueberries
0.575
0.305
41
0.722
Purple cabbage
0.56
1.46
40
0.324
Grape
0.495
0.583
46
0.134
Sweet potato leaf and blueberries
0.61
4.75
53
1.57
Sweet potato leaf and purple cabbage
0.615
0.918
46
0.257
Sweet potato leaf and grape
0.515
1.35
37
0.256Figure 6
The photocurrent-voltage curves for natural dyes at a weight concentration of 40%.It can be seen from Tables1–3 that the photoelectric conversion efficiency increases with increasing in the weight concentration. This is because, after the higher weight concentration of cocktail dyes extract is adsorbed on the surface of TiO2 nanoparticles, the absorption intensity is higher and the absorption wavelength range is broader than in those lower weight concentrations of cocktail dyes extract. In addition, there is a higher interaction between TiO2 nanoparticles and the higher weight concentration of cocktail dyes extract, giving the produced DSSCs better charge transfer performance, which clearly improved efficiency. Further, due to the addition of the weight concentration of cocktail dyes extract, the total internal resistance value in the DSSC is decreased, thus leading to an increase of both the electron diffusion length and the effective electron diffusion coefficient, as well as strengthening of the electron transfer performance inside the DSSC.


## 4. Conclusions

The experimental results show that the cocktail dye that is blended using extracts of sweet potato leaf and blueberry in a volumetric proportion of 1 : 1, at a weight concentration of 40%, extracted at a temperature of 50°C and extracted using a heating time of 10 min produces the greatest photoelectric conversion efficiency (η) of up to 1.57%, the greatest open-circuit voltage (VOC) of 0.61 V, and the greatest short-circuit current density(JSC) of 4.75 mA/cm2. Chlorophyll dye that is extracted from sweet potato leaf also produces a photoelectric conversion efficiency (η) of 0.931%. Of all the anthocyanin dyes, the dye that is extracted from blueberry produces the greatest photoelectric conversion efficiency of 0.722%.



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*Source: 492747-2014-07-06.xml*