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Solar Energy 84 (2010) 12941300 www.elsevier.com/locate/solener

Study the performance of photogalvanic cells for solar energy conversion and storage: Rose BengalD-XyloseNaLS system
K.M. Gangotri a,*, Mahesh Kumar Bhimwal b,1
b a Department of Chemistry, Jai Narain Vyas University, Jodhpur, Rajasthan 342 033, India Solar Energy Laboratory, Department of Chemistry, Jai Narain Vyas University, Jodhpur, Rajasthan 342 033, India

Received 21 November 2009; received in revised form 3 April 2010; accepted 10 April 2010 Available online 14 May 2010 Communicated by: Associate Editor Nicola Romeo

Abstract The Rose Bengal is used as photosensitizer with D-Xylose as reductant and sodium lauryl sulphate (NaLS) as surfactant for the enhancement of the conversion eciency and storage capacity of photogalvanic cell for its commercial viability. The observed value of the photogeneration of photopotential was 885.0 mV and photocurrent was 460.0 lA whereas maximum power of the cell was 407.10 lW. The observed power at power point was 158.72 lW and the conversion eciency was 1.52%. The ll factor 0.3151 was experimentally determined at the power point of the cell. The rate of initial generation of photocurrent was 63.88 lA min1. The photogalvanic cell so developed can work for 145.0 min in dark on irradiation for 165.0 min, i.e. the storage capacity of the photogalvanic cell is 87.87%. A simple mechanism for the photogeneration of photocurrent has also been proposed. 2010 Elsevier Ltd. All rights reserved.
Keywords: Rose Bengal; D-Xylose; Sodium lauryl sulphate; Conversion eciency; Storage capacity; Photocurrent

1. Introduction The development of viable and long-term solution to meet our energy needs, that also maintains the quality of our environment which remains one of the most critical challenge is being facing by the scientic community. The solution of this challenge increasingly depend on electrochemical processes in solids. The solar energy is easily available, cheaper, environmental friendly source and has the potential to provide energy with almost zero emission. The novel approach for renewable sources of energy has led to an increasing interest in photogalvanic cells because of their reliable solar energy conversion and storage capacity. In present work, the photons of sunlight are used as
* Corresponding author. Address: C-38, University Jaswant Campus, Jodhpur, Rajasthan 342 001, India. Tel.: +91 291 251 3899; fax: +91 2912614162. E-mail addresses: k.mgangotri@yahoo.co.in (K.M. Gangotri), bhim wal08@gmail.com (M.K. Bhimwal). 1 Tel.: +91 9460435421; fax: +91 2912614162.

driving force for the conversion and storage of sunlight in photogalvanic cell. The photogalvanic eect was rst of all observed by Rideal and Williams (1925) but it was systematically investigated by Rabinowitch (1940a,b) and later on Clark and Eckert (1975), and Hall et al. (1977). Wildes (1977), Murthy et al. (1980), Suda et al. (1978), Dixit and Mackay (1982), Hamdi and Aliwi (1996) and Bayer et al. (2001) have reported the various systems in photogalvanic cell for solar energy conversion and storage. Jinting et al. (2008) have observed the performance of dye-sensitized solar cells based on nanocrystals TiO2 lm prepared with mixed template method. The performance of photogalvanic cells for the conversion of solar energy into electrical energy and storage capacity depends on the photochemistry of the cell. According to Albery and Archer (1977), the conversion eciency of the photogalvanic cell could be as large as 18% but it is unlikely that all the necessary conditions can be met. A more reliable estimate of the maximum power conversion eciency that could be achieved from a photogalvanic cell is between 5% and 9%. Memming (1980) and

0038-092X/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.solener.2010.04.006

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Bhardwaj et al. (1981) have suggested the process of solar energy conversion by photoelectrochemical process and chloroplast photoelectrochemical cells, respectively. Groenen et al. (1984) have observed micelles eect in the ferrous/thionine photogalvanic cell. Recently the photogalvanic eects have been observed in various systems by Dube and Sharma (1994), Dube (2007), Lal (2007), Pramila and Gangotri (2007), Kumari et al. (2009), Genwa et al. (2009), Gangotri and Bhimwal (in press), Gangotri and Gangotri (2009) and Gangotri and Indora (2010) for solar energy conversion and storage in photogalvanic cells. They have used dierent photosensitizers, micellar species and reductants in photogalvanic system, but no attention has been paid to use of the Rose BengalD-XyloseNaLS system to enhance the electrical output i.e. 460.0 lA and storage capacity i.e. 87.87% of the photogalvanic cells and to reduce the cost of the cell to gain commercial viability. Therefore, the present work was undertaken and the variation of the power output with the concentrations of the reductant, surfactant, sodium hydroxide, variation of diffusion length and other parameters of the cell is found to be quite sensitive. 2. Experimental method A glass tube of H-shape was used containing known amount of the solutions of the photosensitizer Rose Bengal (Merck) with reductant-D-Xylose (Loba), surfactantsodium lauryl sulphate (s.d. ne) and sodium hydroxide (Merck) in the present work. The total volume of the mixture was always kept 25.0 ml making up by doubly distilled water. All the solutions were kept in amber coloured containers to protect them from sunlight. A platinum electrode (1.0 1.0 cm2) was dipped in one limb having a window

and a saturated calomel electrode (SCE) was immersed in another limb of the H-tube. The terminals of the electrode were connected to a digital pH meter (Systronics model335) and the whole cell was placed in the dark. The potential (mV) was measured in dark when the photogalvanic cell attained a stable potential. Then, the limb containing platinum electrode was exposed to a 200 W tungsten lamp (Sylvania) as light source. Employing lamps of dierent wattage varies the light intensity. A water lter was placed between the illuminated chamber and the light source to cut-o infrared radiations. On illumination, the photochemical bleaching of Rose Bengal was studied potentiometrically. The photopotential and photocurrent generated by the system was measured with the help of the digital pH meter and microammeter (Ruttonsha Simpson), respectively. The currentvoltage characteristics of photogalvanic cell have been studied by applying an external load with the help of a carbon pot (log 470 K) connected in the circuit through a key to have close circuit and open circuit device. The experimental set-up of photogalvanic cell is given in Fig. 1. 3. Results and discussion 3.1. Eect of variation of photosensitizer (Rose Bengal) concentration on the system With the increase in concentration of the photosensitizer (Rose Bengal) in present system, the photopotential and photocurrent were found to increase until it reaches a maximum value. On further increase in concentration of photosensitizer a decrease in electrical output of the cell was found. The eect of variation of Rose Bengal concentration on photopotential and photocurrent are reported in Table 1.

Fig. 1. Experimental set-up of photogalvanic cell.

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Table 1 Eect of variation of photosensitizer (Rose Bengal) concentration on the system. Concentration of photosensitizer (Rose Bengal 105 M) 9.52 9.68 9.84 10.00 10.16 Rose BengalD-XyloseNaLS system Photopotential (mV) 792.0 828.0 885.0 836.0 802.0 Photocurrent (lA) 335.0 390.0 460.0 378.0 352.0 Power (lW) 265.32 322.92 407.10 316.00 282.00 Conversion eciency (%) 0.93 1.37 1.52 1.34 1.26 Storage capacity in dark (min) 65.0 75.0 145.0 90.0 70.0

[D-Xylose] = 1.20 103 M; light intensity = 10.4 mW cm2; [NaLS] = 6.80 103 M; temperature = 299 K; pH = 12.83.

On the lower side of the concentration range of photosensitizer, there are a limited number of photosensitizer molecules to absorb the major portion of the light in the path and, therefore, there is low electrical output, whereas higher concentration of the photosensitizer does not permit the desired light intensity to reach the molecules near the electrodes and hence, there is corresponding fall in the power of the cell. 3.2. Eect of variation of reductant (D-Xylose) concentration on the system With the increase in concentration of the reductant (DXylose) in present system, the photopotential was found to increase till it reaches a maximum value. On further increase in concentration of reductant, a decrease in the electrical output of the cell was observed. The eect of variation of reductant concentration on the photopotential and photocurrent of system are reported in Table 2. The fall in power output was also resulted with decrease in concentration of reductant due to less number of molecules available for electron donation to the cationic form of dye. On the other hand, the movement of dye molecules may be hindered by the higher concentration of reductant to reach the electrode in the desired time limit and it will also result into a decrease in electrical output. 3.3. Eect of variation of surfactant (NaLS) concentration on the system The eect of surfactant-sodium lauryl sulphate (NaLS) concentration was also investigated in the present system.
Table 2 Eect of variation of reductant (D-Xylose) concentration on the system. Concentration of reductant (D-Xylose 103 M) 0.98 1.08 1.20 1.31 1.42 Rose BengalD-XyloseNaLS system Photopotential (mV) 795.0 825.0 885.0 812.0 780.0

The surfactant was used to increase the solubility of photosensitizer. It was observed that electrical output of the cell was found to increase on increasing the concentration of surfactant reaching a maximum value. On further increase in their concentrations, a fall in photopotential, photocurrent and power of the photogalvanic cell was observed. The results are reported in Table 3. 3.4. Eect of pH on the system The photogalvanic system is quite sensitive for pH variation. The electrical output of the photogalvanic cell was changed by the variation of pH on the system. It can be observed from the Table 4 that there is an increase in electrical output of the cell with the increase in pH values. At pH 12.83 a maxima was obtained. On further increase in pH, there was a decrease in photopotential and photocurrent. Thus, photogalvanic cells containing the Rose BengalD-XyloseNaLS system were found to be quite sensitive to the pH of the solutions. The eect of variation of pH on photopotential and photocurrent are reported in Table 4. 3.5. Eect of diusion length on the system The eect of variation of diusion length (distance between the two electrodes i.e. saturated calomel electrode and Pt electrodes) on the current parameters of the photogalvanic cell was studied using H-cells of dierent dimensions. It was observed that there was a sharp increase in photocurrent (imax) in the rst few minutes of illumination and then, there was a gradual decrease to a stable value of

Photocurrent (lA) 348.0 386.0 460.0 378.0 340.0

Power (lW) 276.66 318.45 407.10 306.93 265.20

Conversion eciency (%) 1.14 1.52 1.52 1.15 1.11

Storage capacity in dark (min) 60.0 65.0 145.0 70.0 80.0

[Rose Bengal] = 9.84 105 M; light intensity = 10.4 mW cm2; [NaLS] = 6.80 103 M; temperature = 299 K; pH = 12.83.

K.M. Gangotri, M.K. Bhimwal / Solar Energy 84 (2010) 12941300 Table 3 Eect of variation of surfactant (NaLS) concentration on the system. Concentration of surfactant (NaLS 103 M) 6.48 6.64 6.80 6.96 7.12 Rose BengalD-XyloseNaLS system Photopotential (mV) 792.0 822.0 885.0 834.0 785.0 Photocurrent (lA) 348.0 382.0 460.0 378.0 342.0 Power (lW) 275.61 314.00 407.10 315.25 268.47 Conversion eciency (%) 1.23 1.09 1.52 1.14 0.87

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Storage capacity in dark (min) 60.0 75.0 145.0 60.0 70.0

[Rose Bengal] = 9.84 103 M; light intensity = 10.4 mW cm2; [D-Xylose] = 1.20 103 M; temperature = 299 K; pH = 12.83. Table 4 Eect of variation of pH on the system. pH Rose BengalD-XyloseNaLS system Photopotential (mV) Photocurrent (lA) Power (lW) Conversion eciency (%) 1.00 1.06 1.52 1.24 1.07 Storage capacity in dark (min) 55.0 65.0 145.0 80.0 65.0

12.79 12.81 12.83 12.85 12.87

790.0 845.0 885.0 822.0 790.0

352.0 405.0 460.0 382.0 335.0

278.08 342.22 407.10 314.00 264.65

[Rose Bengal] = 9.84 103 M; light intensity = 10.4 mW cm2; [DXylose] = 1.20 103 M; temperature = 299 K; [NaLS] = 6.80 103 M.

photocurrent. This photocurrent at equilibrium is represented as (ieq). This kind of photocurrent behaviour is due to an initial rapid reaction followed by a slow ratedetermining step at a later stage. On the basis of the eect of diusion path length on the current parameters, as investigated by Kaneko and Yamada (1977), it may be concluded that the leuco or semi reduced form of dyes, and the dyes itself are the main electroactive species at the illuminated and the dark electrodes, respectively. However, the reducing agents and their oxidized products behave as the electron carriers in the cell diusing through the path. The results are graphically represented in Fig. 2. 3.6. Eect of light intensity on the system We have used dierent light intensity sources for change in the intensity of light and it was found that photocurrent showed a linear increasing behaviour with the increase in light intensity whereas photopotential increases in a logarithmic manner. Whereas, the light intensity was measured in term of mW cm2 with the help of solarimeter (CEL Model SM 203). The results are graphically represented in Fig. 3. 3.7. Currentvoltage (iV) characteristics of the photogalvanic cell The short circuit current (isc) and open circuit voltage (Voc) of the photogalvanic cells were measured with the

Fig. 2. Variation of current parameters with diusion length on the system.

Fig. 3. Variation of photocurrent and log V with light intensity.

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help of a microammeter (keeping the circuit closed) and with a digital pH meter (keeping the other circuit open), respectively. The current and potential values in between these two extreme values were recorded with the help of a carbon pot (log 470 K) connected in the circuit of microammeter, through which an external load was applied. The CurrentVoltage (iV) characteristics of the photogalvanic cell containing Rose BengalD-XyloseNaLS system is graphically represented in Fig. 4. It was observed that iV curve deviated from their regular rectangular shapes. A point in iV curve, called power point (pp) is determined where the product of current and potential was maximum and the ll factor is calculated using the following formula: V pp ipp 1 Fill factorg V oc isc where as Vpp and ipp represent the value of photopotential and photocurrent at power point, respectively and Voc, isc represent open circuit voltage and short circuit current, respectively. The value of ll factor (g) = 0.3151 was obtained and the power point of cell (pp) = 158.72 lW was determined on the system. 3.8. Storage capacity of the photogalvanic cell The storage capacity of the photogalvanic cell was observed by applying an external load (necessary to have current at power point) after termination the illumination as soon as the potential reaches a constant value. The storage capacity was determined in terms of t1/2, i.e., the time required in fall of the electrical output (power) to its half at power point in dark. It was observed that the photogalvanic cell can be used in dark for 145.0 min on irradiation for 165.0 min, so observed storage capacity is 87.87%. The results are graphically represented in Fig. 5. 3.9. Conversion eciency of the photogalvanic cell The conversion eciency of system containing Rose Bengal as photosensitizer is calculated using the electrical

Fig. 5. Storage capacity of the photogalvanic cell.

output at power point and the power of incident radiations. The conversion eciency of the photogalvanic cell is determined as 1.52% using the following formula. Conversion efficiency V pp ipp 100% 2 10:4 mW cm2 Electrode area cm2 The systems (at the optimum conditions) were also exposed to sunlight, and the conversion eciency and sunlight conversion data for this system are reported in Table 5. 3.10. The performance of photogalvanic cell The overall performance of the photogalvanic cell was observed and reached to remarkable level in the performance of photogalvanic cells with respect to electrical output, initial generation of photocurrent, conversion eciency and storage capacity of the photogalvanic cell. The results so obtained in Rose BengalD-XyloseNaLS system are summarized in Table 6. 4. Mechanism On the basis of these observations, a mechanism has been suggested for the generation of photocurrent in the photogalvanic cell as given below.
Table 5 Conversion eciency of the photogalvanic cell. Concentration of photosensitizer (Rose Bengal 105 M) 9.52 9.68 9.84 10.00 10.16 Rose BengalD-XyloseNaLS system Fill factor (g) 0.3037 0.3062 0.3151 0.3093 0.3061 Conversion eciency (%) 0.93 1.37 1.52 1.34 1.26 Sunlight conversion data Photopotential (mV) 1980.0 2070.0 2210.0 2090.0 2005.0 Photocurrent (lA) 840.0 980.0 1150.0 945.0 880.0

Fig. 4. Currentvoltage (iV) curve of the photogalvanic cell.

[Rose Bengal] = 9.84 103 M; light intensity = 10.4 mW cm2; [DXylose] = 1.20 103 M; temperature = 299 K; [NaLS] = 6.80 103 M.

K.M. Gangotri, M.K. Bhimwal / Solar Energy 84 (2010) 12941300 Table 6 The performance of photogalvanic cell. S.N. 1 2 3 4 5 6 7 8 9 10 Parameters Dark potential Open circuit voltage (VOC) Photopotential (DV) Initial generation of photocurrent Equilibrium photocurrent (ieq) Maximum photocurrent (imax) Time of illumination Storage capacity (t1/2) Conversion eciency (CE) Fill factor (g) Observed results 210.0 mV 1095.0 mV 885.0 mV 63.88 lA min1 460.0 lA 575.0 lA 165.0 min 145.0 min 1.52% 0.3151

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light intensity = 10.4 mW cm2; [Rose Bengal] = 9.84 105 M; [D-Xylose] = 1.20 103 M; temperature = 299 K; [NaLS] = 6.80 103 M; pH = 12.83.

4.1. Illuminated chamber On irradiation, dye molecules get excited. RB ! RB

hm

photogalvanic systems i.e. DSS/CTAB/Triton X-100RohodamineOxalic acid system by Genwa and Genwa (2008) and Brij-35-DTPA system by Genwa and Khatri (2009). They have reported conversion eciency is 0.24 0.86% and 0.27070.643% respectively, in comparison to the present photogalvanic system consisting of Rose BengalD-XyloseNaLS, the conversion eciency is 1.52% and the storage capacity of the cell is 145.0 min on the irradiation for 165.0 min in the so developed photogalvanic systems. In view of these observations, it can be concluded that Rose Bengal is better photosensitizer with D-Xylose as reductant and sodium lauryl sulphate as surfactant in photogalvanic cell for solar energy conversion and storage. However, the considerable research and development for further improvement in results for solar energy conversion and storage is still need. Acknowledgement

The excited dye molecules accept an electron from reductant and converted into semi or leuco form of dye, and the reductant into its oxidized form RB R ! RB semi or leuco R 4

The authors are thankful to Professor P.K. Sharma (M), Head, Department of Chemistry, J.N.V. University, Jodhpur for providing all necessary facilities. One of the author (Mahesh Kumar Bhimwal) is thankful to Indian government for providing nancial assistance for the research purpose. References
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4.1.1. At platinum electrode The semi or leuco form of dye loses an electron to electrode and converted into original dye molecule. RB ! RB e

4.2. Dark chamber 4.2.1. At counter electrode Dye molecules accept an electron from electrode and converted in semi or leuco form. RB e ! RB semi or leuco 6 Finally leuco/semi form of dye and oxidized form of reductant combine to give original dye and reductant molecule and the cycle will go on RB R ! RB R 7 where RB, RB, RB, R and R+ are the dye (Rose Bengal), excited form of dye, semi or leuco form of dye, reductant and oxidized form of the reductant, respectively. 5. Conclusion The photogalvanic cells have the promising storage capacity. In present research work the Rose Bengal as photosensitizer, D-Xylose as reductant and sodium lauryl sulphate as surfactant have been used in the system and the higher values of conversion eciency and storage capacity have been observed in comparison to earlier reported

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