# Performance Degradation of Dye-Sensitized Solar Cells Induced by Electrolytes

Authors: Ru-Yuan Yang; Huang-Yu Chen; Fu-Der Lai
Journal: Advances in Materials Science and Engineering
 (2012)

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## Abstract

We investigated the change of the electric characteristics in dye-sensitized solar cell (DSSC) when the electrolyte has been injected and measured initially and lately for a period of time. It was found that the short-circuit current density decreased from 9.799 mA/cm2 to 7.056 mA/cm2 and the fill factor increased from 0.406 to 0.559 when the cell had stood for an hour, while the open-circuit photovoltage did not change due to fixed difference between the Fermi level of TiO2 and the oxidation-reduction potential of electrolyte. The results can be explained by using the variation of the series resistance in the equivalent circuit of the DSSC.


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## Body

## 1. Introduction

Dye-sensitized solar cells (DSSC) have attracted much attention ever since Grätzel et al. demonstrated the possibility to convert solar energy to electricity with a photoelectro-chemical dye-sensitized device [1]. The DSSC provides a technically and economically credible alternative concept to present day p-n junction photovoltaic devices. The development of these new types of solar cell is promoted by the increasing public awareness that the earth’s oil reserves will run out during this century. Because the energy needs of the planet will at least double within the next 50 years, the stage is set for a major shortage of energy supply unless renewable sources can cover the substantial deficit that fossil fuels can no longer furnish.This accomplishes the optical absorption and charge separation processes by the association of a sensitizer as a light-absorbing material with a wide-band-gap semiconductor of mesoporous or nanocrystalline morphology [1–3]. It also offers the prospect of very low cost fabrication without expensive and energy-intensive high-temperature and high-vacuum processes, compatibility with flexible substrates, and variety of presentations and appearances to facilitate market entry, both for domestic devices and in architectural or decorative applications. Generally, the semiconductor, which accepts the electron from the sensitizer and transfers it to the electrode, is nanocrystalline anatase TiO2 which is mesoporous because of high surface area. High surface area of TiO2 thin film improves the adsorption of sensitizer and hence increases the light-harvesting capacity of the mesoporous film. However, the electrolyte may penetrate into the mesoporous film and contact the dye-free TiO2 and the electrode surface, resulting in the increase of the reverse saturation current. On the other hand, it also increases the contact area between the electrolyte and the sensitizer so that facilitates the reduction of I3- by the combination of the hole. It was found that the short-circuit photocurrent decreased and the fill factor of the dye-sensitized solar cell increased as time goes on.In this study, the change of the electric characteristics in dye-sensitized solar cell (DSSC) when the electrolyte has been injected and measured initially and lately for a period of time was investigated. The short-circuit photocurrent density (Jsc) and the fill factor (F.F.) were varied and the results can be explained by using the variation of the series resistance in the equivalent circuit of the DSSC.


## 2. Experimental Apparatus and Procedure

### 2.1. Preparing the Working Electrode

A TiO2 thin-film electrode was designed and fabricated for use in a dye-sensitized solar cell. This TiO2 thin-film was deposited on the top of an FTO-glass (Fluorine doped tin oxide, SnO2:F) substrate, which has a size of 20 × 20 × 3 mm and a sheet resistance of 8 Ω/sq. The TiO2 particles (P-25) are composed of 30% rutile and 70% anatase, with a particle size range (<100 nm).Figure1 shows the procedure of preparing the working electrode of DSSC with a layer of TiO2 particles and the steps are described as follows. (1) Diluting 40 μL of acetylacetone in 1 mL of de-ionic (DI) water; (2) mixing 1 g of TiO2 particles with the diluted acetylacetone, and stir well to make the colloid of TiO2 particles; (3) adjusting the glutinosity of the colloid of TiO2 particles by adding 1.5 mL of DI water and 40 μL of surfactant (Triton-100, C8H17C6H4(OCH2CH2)nOH), and then homogenize the colloid of TiO2 particles for 30 minute in a mortar; (4) dropping the quantitative colloid of TiO2 particles on the top of the F:SnO2 (FTO) glass substrate, and then spin coat the working electrode with rotational speed of 3000 rpm; (5) drying the working electrode with a layer of TiO2 particles at room temperature for 10 minute, and then sinter this working electrode at 500°C for 30 minutes in a high-temperature furnace; (6) immersing the FTO-glass substrate with a layer of TiO2 particles into the (3 × 10−4mol/L) solution of N-719 dye (Ruthenium, RuL2(NCS)2) and ethyl alcohol (CH3CH2OH, 95%) for 24 hours at room temperature. A conventional working electrode with a layer of nanocrystalline TiO2 on the FTO-glass substrate was fabricated using above procedures to demonstrate the feasibility and advantages of the working electrode with a layer of TiO2 particles. An α-step (Dekeak 6 M) surface profiler was utilized to obtain the surface profile of the thin film and the average thickness of the thin film on the FTO-glass substrate of the working electrode. The thickness of the TiO2 thin films was about 10 μm. Figure 2 shows the practical working electrode.Figure 1
The procedure of preparing the working electrode.Figure 2
The photograph of the working electrode.


### 2.2. Assembling the DSSC

Figure3 shows the schematic of the DSSC. The thin film on the FTO-glass substrate of the working electrode was fringed using the Scotch magic transparent tape (3 M). Then, the working electrode and the counter electrode that a thin film of platinum was deposited on the FTO-glass substrate using a ion sputter (Hitachi E-1010) were fitted together, such that the space between the two electrodes was adjusted to approximately 160 μm for embarking the liquid electrolyte. After sealing, the liquid electrolyte, which was composed of 0.5 M lithium iodine (LiI) and 0.05 M iodine (I2) in 3-methoxypropionitrile, was injected into the cell through a hole on the cell that was prepared in advance.Figure 3
Schematic of the dye-sensitized solar cell.


### 2.3. Testing

A home-madeI-V measurement system was adopted to measure the open-circuit photovoltage and short-circuit photocurrent of the DSSC. A solar simulator with a 500 W halogen lamp and a light intensity of 100 mW/cm2, was employed to illuminate the DSSC. In addition, the power conversion efficiency η of the DSSC was determined by
(1)η(%)=VocJscFFPin×100.In (1), Voc, Jsc, and Pin represent the open-circuit voltage, the short-circuit current density, and the incident light power (100 mw/cm2), respectively. Moreover, the fill factor FF is given by
(2)FF=Vmax⁡Jmax⁡VocJsc.In (2), Vmax and Imax represent the voltage and the current at the maximum output power point, respectively. The I-V characteristics of the prepared DSSC were measured at initial assembling stage and at one hour lately.


## 2.1. Preparing the Working Electrode

A TiO2 thin-film electrode was designed and fabricated for use in a dye-sensitized solar cell. This TiO2 thin-film was deposited on the top of an FTO-glass (Fluorine doped tin oxide, SnO2:F) substrate, which has a size of 20 × 20 × 3 mm and a sheet resistance of 8 Ω/sq. The TiO2 particles (P-25) are composed of 30% rutile and 70% anatase, with a particle size range (<100 nm).Figure1 shows the procedure of preparing the working electrode of DSSC with a layer of TiO2 particles and the steps are described as follows. (1) Diluting 40 μL of acetylacetone in 1 mL of de-ionic (DI) water; (2) mixing 1 g of TiO2 particles with the diluted acetylacetone, and stir well to make the colloid of TiO2 particles; (3) adjusting the glutinosity of the colloid of TiO2 particles by adding 1.5 mL of DI water and 40 μL of surfactant (Triton-100, C8H17C6H4(OCH2CH2)nOH), and then homogenize the colloid of TiO2 particles for 30 minute in a mortar; (4) dropping the quantitative colloid of TiO2 particles on the top of the F:SnO2 (FTO) glass substrate, and then spin coat the working electrode with rotational speed of 3000 rpm; (5) drying the working electrode with a layer of TiO2 particles at room temperature for 10 minute, and then sinter this working electrode at 500°C for 30 minutes in a high-temperature furnace; (6) immersing the FTO-glass substrate with a layer of TiO2 particles into the (3 × 10−4mol/L) solution of N-719 dye (Ruthenium, RuL2(NCS)2) and ethyl alcohol (CH3CH2OH, 95%) for 24 hours at room temperature. A conventional working electrode with a layer of nanocrystalline TiO2 on the FTO-glass substrate was fabricated using above procedures to demonstrate the feasibility and advantages of the working electrode with a layer of TiO2 particles. An α-step (Dekeak 6 M) surface profiler was utilized to obtain the surface profile of the thin film and the average thickness of the thin film on the FTO-glass substrate of the working electrode. The thickness of the TiO2 thin films was about 10 μm. Figure 2 shows the practical working electrode.Figure 1
The procedure of preparing the working electrode.Figure 2
The photograph of the working electrode.


## 2.2. Assembling the DSSC

Figure3 shows the schematic of the DSSC. The thin film on the FTO-glass substrate of the working electrode was fringed using the Scotch magic transparent tape (3 M). Then, the working electrode and the counter electrode that a thin film of platinum was deposited on the FTO-glass substrate using a ion sputter (Hitachi E-1010) were fitted together, such that the space between the two electrodes was adjusted to approximately 160 μm for embarking the liquid electrolyte. After sealing, the liquid electrolyte, which was composed of 0.5 M lithium iodine (LiI) and 0.05 M iodine (I2) in 3-methoxypropionitrile, was injected into the cell through a hole on the cell that was prepared in advance.Figure 3
Schematic of the dye-sensitized solar cell.


## 2.3. Testing

A home-madeI-V measurement system was adopted to measure the open-circuit photovoltage and short-circuit photocurrent of the DSSC. A solar simulator with a 500 W halogen lamp and a light intensity of 100 mW/cm2, was employed to illuminate the DSSC. In addition, the power conversion efficiency η of the DSSC was determined by
(1)η(%)=VocJscFFPin×100.In (1), Voc, Jsc, and Pin represent the open-circuit voltage, the short-circuit current density, and the incident light power (100 mw/cm2), respectively. Moreover, the fill factor FF is given by
(2)FF=Vmax⁡Jmax⁡VocJsc.In (2), Vmax and Imax represent the voltage and the current at the maximum output power point, respectively. The I-V characteristics of the prepared DSSC were measured at initial assembling stage and at one hour lately.


## 3. Results and Discussion

Figure4 shows I-V characteristics of the DSSC when the electrolyte is just injected into the space between the working electrode and the counter electrode. The measured Voc, Jsc, and F.F. are 9.799 mA/cm2, 0.658 V, and 0.406, respectively. Figure 5 shows I-V characteristics of the dye-sensitized solar cell after the electrolyte has been injected and stay for one hour. The measured Voc, Jsc, and F.F. are 7.056 mA/cm2, 0.668 V, and 0.559, respectively. as Comparing Figure 4 to Figure 5, it is found that the Jsc decreases from 9.799 mA/cm2 to 7.056 mA/cm2 and F.F increases from 0.406 to 0.559. The Voc does not change due to the fixed difference between the Fermi level of TiO2 and the oxidation-reduction potential of electrolyte. To understand the difference in their Jsc for the measurement at initial assembling stage and at one, two, three and so forth hours lately. We conduct the standard I-V curve of the solar cell and discuss the change of the series resistance and the shunt resistance.Figure 4
I-V curve of DSSC when the electrolyte is just injected.Figure 5
I-V curve of DSSC when the electrolyte has been injected and stay for one hour.It has been known that the tangent slope of vertical part (nearVoc) is proportional to the reciprocal of the series resistance (1/Rs) and the tangent slope of transverse part (near Jsc) is proportional to the reciprocal of the shunt resistance (1/Rsh). When Rsh increase or/and Rs decrease, F.F. will become better. The tangent slope of Voc part in Figure 5 is larger than that in Figure 4, which means Rs decreases as time goes on. However, the tangent slope of Isc does not change obviously so that Rsh is almost the same. We thus discuss the factor that affects the series resistance Rs and ignores the shunt resistance Rsh.The series-internal resistance of DSSCs was investigated by some researchers based on an equivalent circuit of DSSCs [4, 5]. It was found that series-internal resistance correlates with the charge-transfer at Pt counter electrode, TCO substrate resistance, and Nernstian diffusion in the electrolyte. According to these, the equivalent circuit of DSSCs is constructed as shown in Figure 6. The series resistance is the sum of the charge transfer resistance at Pt/electrode interface (R1), the diffusion resistance of I3- ions in electrolyte (R2), and the sheet resistance of TCO (Rh). Because R1 and Rh relate to the property of the material, they cannot change as time goes on. We think the major factor that influences Rs must be R2. The probable explanation is that the electrolyte only contacts the top surface of TiO2 thin film when the electrolyte is just injected. However, the electrolyte may permeate into the mesoporous film after an hour and the contact area with dye-adsorbed TiO2 will increase, so the charge-transfer from the electrolyte to the oxidized dye will be accelerated. The large contact area between the electrolyte and the dye-adsorbed TiO2 film improve the rate of I3- reduction and hence decrease Rs.Figure 6
Equivalent circuit based on current-voltage characteristics of DSSCs. The sum ofR1, R2, and Rh corresponds closely to the series resistance of DSSCs. C1 is capacitance elements.According to the diode equation that correlates with Figure6:
(3)I=Iph-Io{exp⁡[q(V+IRs)nkT]-1}-V+IRsRsh,
where Iph is the ideal photocurrent, I0 is the reverse saturation current, n is the ideality factor whose value is between 1 and 2 for the DSSC, Rs is the series resistance which is the sum of R1, R2, and Rh, and Rsh is the shunt resistance. The gain in open circuit voltage can be calculated from (3):
(4)Voc=nkTqln⁡[IIo-VocIoRsh+1].
As Rsh increase, Voc will also increase. as comparing Figure 4 to Figure 5, it is found that Voc does not change obviously. Since 1/Rs is unchanged, it confirms that the shunt resistance in DSSCs is almost the same as time goes on.The short circuit current can be obtained from (3) when V=0, and it can be found that Isc will increase as Rs decreases. However, Jsc decreases from 9.799 mA/cm2 in Figure 4 to 7.056 mA/cm2 in Figure 5. It must be the influences of the dark current which correlates with the recombination of charge carriers by reduction of I3- at dye-free TiO2 surface and bare FTO surface exposed to electrolyte through porous electrode [6]. As we discussed before, the electrolyte will permeate into the mesoporous film when DSSC has been staid for an hour. It may apply the electrolyte to contact the dye-free TiO2 surface and even the FTO surface, so that accelerates the recombination of the charge carriers from the conduct band of TiO2 to the electrolyte and produces the reverse saturation current. The increase of the dark current lowers Isc seriously so that it is important to modify the working electrode surface to decrease the reverse charge flow.Based on the above discussion, it is known how to improve the performance of DSSCs by modifying the interface between the working electrode and the electrolyte, as investigated by some research workers [7–9]. Su et al. fabricated layer-by-layer Au nanoparicles, which were prepared using chemical reduction method, onto the working electrode as a Schottky barrier in a water-based DSSC [10]. It was found that an interfacial blocking layer could suppress the interfacial recombination between TiO2 and excited dye molecules or I−/I3- couple, which led to an improvement on cell performance [7–9]. Moreover, in order to improve the performance of DSSCs, it is also necessary to suppress the dark current. The reverse charge flow, recapture of the electron by the electrolyte, could be impaired by judicious design of the sensitizer. It can also form a tightly packed insulating monolayer blocking the dark current. Consequently, decreasing the recombination of charges in the dye or electrolyte is one of the important issues to increase the conversion efficiency of DSSC and is worthy of ongoing study.


## 4. Conclusion

In this study, we discussed the change of the current-voltage characteristics in DSSCs as time goes on and found that fill factor (F.F) got better but short circuit current densityJsc decreased. The results were explained by using the variation of the series resistance in the equivalent circuit of the DSSC. The increase of F.F. may result from the decrease of series resistance Rs due to the electrolyte permeating into the mesoporous working electrode and hence increase the contact area with the dye-adsorbed TiO2. However, it also applies the electrolyte to contact the dye-free TiO2 surface and even the FTO surface, so that accelerates the recombination of the charge carriers from the conduct band of TiO2 to the electrolyte and produces the reverse saturation current.



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*Source: 902146-2012-09-09.xml*