WO2009064100A2 - Lifetime extension method and apparatus for dye-sensitized solar cell - Google Patents

Lifetime extension method and apparatus for dye-sensitized solar cell Download PDF

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Publication number
WO2009064100A2
WO2009064100A2 PCT/KR2008/006634 KR2008006634W WO2009064100A2 WO 2009064100 A2 WO2009064100 A2 WO 2009064100A2 KR 2008006634 W KR2008006634 W KR 2008006634W WO 2009064100 A2 WO2009064100 A2 WO 2009064100A2
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WIPO (PCT)
Prior art keywords
electrolyte
dye
solar cell
negative electrode
sensitized solar
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PCT/KR2008/006634
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French (fr)
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WO2009064100A3 (en
Inventor
Ho-Gi Bae
Chong-Chan Lee
Jong-Bok Kim
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Dongjin Semichem Co., Ltd.
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Publication of WO2009064100A2 publication Critical patent/WO2009064100A2/en
Publication of WO2009064100A3 publication Critical patent/WO2009064100A3/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention relates to a method and an apparatus for extending lifetime of dye-sensitized solar cell. Specifically, the present invention relates to a method and apparatus for extending lifetime of dye-sensitized solar cell that can achieve durable lifetime of dye-sensitized solar cell equal to or longer than that of silicon solar cell, thus enabling long-term stabilization and practical use of dye-sensitized solar cell.
  • Background Art
  • a dye-sensitized solar cell is a photoelectrochemical solar cell using a photosensitive dye molecule capable of absorbing visible rays to produce electron-hole pairs and an oxide semiconductor electrode consisting of titanium oxide which transfers produced electrons.
  • a photosensitive dye molecule capable of absorbing visible rays to produce electron-hole pairs
  • an oxide semiconductor electrode consisting of titanium oxide which transfers produced electrons.
  • solar energy absorption process and electromotive force production process by separation of electron-hole pairs occur simultaneously in silicon semiconductor
  • dye-sensitized solar cells solar energy absorption process and electric charge transfer process are separately conducted.
  • dye-sensitized solar cells dye absorbs solar energy, and semiconductor transfers electric charge.
  • the dye-sensitized solar cell has advantages in that manufacture cost is low compared to the existing silicon solar cells, it is pro-environmental and it can be manufactured flexibly. However, it has a limitation in terms of practical use because of its low energy conversion efficiency.
  • dye-sensitized solar cells of the prior art include a dye- sensitized solar cell announced by Gratzel et al., Swiss, 1991.
  • the dye-sensitized solar cell suggested by Gratzel et al. is a photoelectrochemical solar cell using a photosensitive dye molecule and an oxide semiconductor consisting of titanium oxide nanoparticles, which consists of a nanoparticle oxide semiconductor negative electrode, platinum positive electrode, dye absorbed into the negative electrode, and oxidation/reduction electrolyte using an organic solvent, and has advantage in that manufacture cost is low compared to the existing silicon solar cells.
  • an electrolyte obtained from an organic solvent generally comprises volatile materials for improvement of energy efficiency, which cause volatilization of an electrolyte solvent from solar cells when temperature outside of solar cell increases by solar rays, thus decreasing energy efficiency.
  • the present invention provides a method for extending lifetime of dye-sensitized solar cell which comprises a negative electrode comprising semiconductor particles, a positive electrode facing the negative electrode, dye absorbed into the negative electrode, an electrolyte filled between the negative electrode and the positive electrode, and a frame surrounding them, said method comprising the step of i) supplementing to the electrolyte an electrolyte or insufficient component of the electrolyte, or ii) exchanging the electrolyte.
  • the present invention also provides an apparatus for extending lifetime of dye- sensitized solar cell, said apparatus comprising: a dye-sensitized solar cell which comprises a negative electrode comprising semiconductor particles, a positive electrode facing the negative electrode, dye absorbed into the negative electrode, an electrolyte filled between the negative electrode and the positive electrode, and a frame surrounding them, and has an inlet stage and outlet stage connected to the electrolyte- filled part; a means for supplying an electrolyte or dye, connected to the inlet stage; and a means for recovering an electrolyte or dye, connected to the outlet stage.
  • a dye-sensitized solar cell which comprises a negative electrode comprising semiconductor particles, a positive electrode facing the negative electrode, dye absorbed into the negative electrode, an electrolyte filled between the negative electrode and the positive electrode, and a frame surrounding them, and has an inlet stage and outlet stage connected to the electrolyte- filled part; a means for supplying an electrolyte or dye, connected to the inlet stage; and a
  • FIG. 1 is a conceptual drawing of one example of solar cell applied for the lifetime extension method of dye- sensitized solar cell according to the present invention.
  • FIG. 2 is a conceptual drawing of another example of solar cell applied for the lifetime extension method of dye-sensitized solar cell according to the present invention.
  • FIG. 3 is a conceptual drawing of one example of the lifetime extension apparatus and solar cell applied for the lifetime extension method of dye-sensitized solar cell according to the present invention.
  • FIG. 4 is a conceptual drawing of one example of circulation structure of the lifetime extension apparatus and solar cell applied for the lifetime extension method of dye- sensitized solar cell according to the present invention.
  • FIG. 5 is a conceptual drawing of another example of circulation structure of the lifetime extension apparatus and solar cell applied for the lifetime extension method of dye-sensitized solar cell according to the present invention.
  • FIG. 6 is a conceptual drawing of one example of circulation structure of the lifetime extension apparatus and solar cell applied for the lifetime extension method of dye- sensitized solar cell according to the present invention, further comprising a gas circulation means.
  • the present invention relates to a method for extending lifetime of dye-sensitized solar cell. Specifically, the present invention relates to a method for extending lifetime of dye-sensitized solar cell(lOO) which comprises a negative electrode(l ⁇ ) comprising semiconductor particles, a positive electrode(20) facing the negative electrode, dye absorbed into the negative electrode(l ⁇ ), an electrolyte(30) filled between the negative electrode(l ⁇ ) and the positive electrode (20), and a frame(40) surrounding them, said method comprising the step of i) supplementing to the electrolyte an electrolyte or insufficient component of the electrolyte, or ii) exchanging the electrolyte.
  • Lifetime of dye- sensitized solar cell is determined by decrease of energy efficiency due to volatilization of volatile materials comprised in an electrolyte.
  • volatile component in case such a problem occurs, insufficient component among the components of electrolyte, preferably volatile component can be supplemented to improve electrolyte properties, thus prolonging lifetime of solar cell.
  • electrolyte itself can be supplemented.
  • insufficient part of the electrolyte previously filled in solar cell can be filled by supplementing new electrolyte.
  • One example of the structure of dye-sensitized solar cell for this is as shown in Fig. 1.
  • existing electrolyte can be exchanged with new electrolyte, or, the existing electrolyte can be extracted and insufficient component can be added thereto, impurities can be removed therefrom, or insufficient amount can be supplemented thereto to replace the existing electrolyte, so that the solar cell may show energy efficiency similar to new solar cell, thereby prolonging lifetime of solar cell.
  • One example of the structure of dye-sensitized solar cell for this is as shown in Fig. 2.
  • an electrolyte can be exchanged by the steps of a) discharging the electrolyte filled between the negative electrode and positive electrode, b) injecting dye into the solar cell and then optionally circulating it so as to induce absorption, and then discharging remaining dye, and c) injecting an electrolyte between the negative electrode and positive electrode into the solar cell.
  • the step of drying inside of the solar cell may be further comprised between the steps a) and b) or between the steps b) and c). Since deterioration of solar cell is caused by deterioration of electrolyte and desorption of dye, in order to prevent this, dye absorption step may be further comprised.
  • electrolyte is discharged from the existing solar cell, and if necessary, inert gas or nitrogen gas, etc. (if necessary, heated high temperature gas can be used) is circulated for removal of electrolyte remaining in the cell so as to conduct drying process, and then, dye (dye can be used alone, or dispersion of dye in a solvent can be used for smooth supply of dye) is injected in the solar cell, and maintained for a time or continuously circulated (circulation is preferable because it can increase absorption efficiency) so that dye may be absorbed into particles of negative electrode (mainly nanoparticles of titanium oxide), and thereafter, remaining dye is removed by discharge, and then, if necessary, the above-explained drying process (for inducing dye absorption) or common washing process (for removal of remaining dye) is optionally and repeatedly (alternatively) conducted, and then, new electrolyte (including electrolyte prepared by adding insufficient components to the existing electrolyte as well as new electrolyte) is injected in the cell.
  • electrolyte comprising dye which is prepared by mixing dye with new electrolyte (including electrolyte prepared by adding insufficient components to existing electrolyte as well as new electrolyte), is injected in the cell, so that dye absorption process and new electrolyte filling process can be conducted by one process .
  • the process is substantially a two-step process comprising discharge of electrolyte and injection of electrolyte comprising dye. Absorption of dye is continuously conducted during the operation of solar cell and thus separate process is not required, and injection of new electrolyte is completed in the above process.
  • the process can be conducted as follows: previously filled electrolyte is discharged, and, the electrolyte comprising dye, which is prepared by mixing dye with new electrolyte (including electrolyte prepared by adding insufficient components to existing electrolyte as well as new electrolyte), is injected in the cell, and maintained for a time or circulated so as to induce absorption of dye, and then, gas-tighted as it is.
  • passing circulation is preferable because it increases absorption opportunity to increase absorption efficiency.
  • the above process may further comprise, after the step b'), the step c') discharging the electrolyte comprising dye, and injecting electrolyte which does not comprise dye between the negative electrode and positive electrode in the solar cell.
  • new electrolyte can be filled in the cell in order to increase energy efficiency of the electrolyte.
  • the above process may further comprise the step of drying inside of the solar cell between the steps a') and b') or between the steps b') and c'). Thereby, remaining substances can be removed, or absorption efficiency can increase.
  • washing step may be further comprised together with the drying step, or drying and washing steps can be alternately conducted.
  • the present invention also provides a lifetime extension apparatus for conducting the above-explained life time extension method, said apparatus comprising a dye- sensitized solar cell(lOO) which comprises a negative electrode(l ⁇ ) comprising semiconductor particles, a positive electrode(20) facing the negative electrode, dye absorbed into the negative electrode(l ⁇ ), an electrolyte(30) filled between the negative electrode(l ⁇ ) and the positive electrode (20), and a frame(40) surrounding them, and has an inlet stage(50) and outlet stage(60) connected to the electrolyte-filled part(30); a means for supplying an electrolyte or dye(200), connected to the inlet stage(50); and a means for recovering an electrolyte or dye(300), connected to the outlet stage(60).
  • a dye- sensitized solar cell(lOO) which comprises a negative electrode(l ⁇ ) comprising semiconductor particles, a positive electrode(20) facing the negative electrode, dye absorbed into the negative electrode(l ⁇ ), an electrolyte(30) filled between the negative
  • the apparatus in order to exchange electrolyte, is equipped with electrolyte recovery means (recovery bath) connected to the outlet stage of solar cell for discharge of electrolyte previously filled in the solar cell, and it is equipped with electrolyte supply means consisting of an electrolyte storage bath, a pump which supplies electrolyte from the storage bath, and supply line which connects the pump to the inlet stage of the solar cell, for supply of new electrolyte.
  • electrolyte recovery means recovery bath
  • electrolyte supply means consisting of an electrolyte storage bath, a pump which supplies electrolyte from the storage bath, and supply line which connects the pump to the inlet stage of the solar cell, for supply of new electrolyte.
  • the storage bath in Fig. 3 can be an electrolyte storage bath, dye storage bath or a storage bath of electrolyte comprising dye.
  • the supply means can be an electrolyte supply means or dye supply means according to the type of storage means
  • the recovery means can be an electrolyte recovery means or dye recovery means according to discharged materials.
  • the electrolyte supply means (200) and recovery means (300) are connected to each other so as to have circulation structure. Examples of this structure are as shown in Figs. 4 to 6. Specifically, discharged materials are re-treated or circulated as it is so that recovered materials in the recovery bath can be supplied to the storage bath in the supply means. Storage and recovery bath in Figs. 4 and 5 represents this.
  • Fig. 4 shows one example of W type cell/module or Z type cell/module
  • Fig. 5 shows current collector grid type cell/module.
  • existing electrolyte is discharged and recovered in storage and recovery bath, where insufficient components are added, impurities are removed, or new electrolyte is added, thus new electrolyte is stored, and the new electrolyte is supplied to a pump so that the electrolyte can be exchanged with new electrolyte.
  • a storage bath for supplying of new electrolyte can be further equipped, separately from the recovery and storage bath.
  • supply and recovery connection parts can be respectively connected to the inlet stage(50) and outlet stage(60), and a gas circulation means(400) which circulates gas (preferably inert gas or nitrogen gas, more preferably heated) in the solar cell, as shown in Fig. 6, and, although not shown, a washing solution circulation means can be further equipped.
  • gas circulation means(400) which circulates gas (preferably inert gas or nitrogen gas, more preferably heated) in the solar cell, as shown in Fig. 6, and, although not shown, a washing solution circulation means can be further equipped.
  • solid line arrows indicate liquid flow
  • dot line arrows indicate gas flow.
  • the storage and recovery bath can be divided into electrolyte, dye and mixture (mixture of electrolyte and dye), through which the above explained lifetime extension method can be variously composed and conducted as required.
  • the lifetime extension apparatus may further comprise electrolyte monitoring means or solar cell monitoring means so that deterioration of electrolyte or solar cell energy efficiency decrease can be monitored and the lifetime extension apparatus can be operated when required.

Abstract

The present invention relates to a method and apparatus for extending lifetime of dye-sensitized solar cell. Specifically, the present invention relates to a method for extending lifetime of dye-sensitized solar cell which comprises a negative electrode comprising semiconductor particles, a positive electrode facing the negative electrode, dye absorbed into the negative electrode, an electrolyte filled between the negative electrode and the positive electrode, and a frame surrounding them, said method comprising the step of i) supplementing to the electrolyte an electrolyte or insufficient component of the electrolyte, or ii) exchanging the electrolyte; and an apparatus for conducting the lifetime extension method of dye-sensitized solar cell. According to the present invention, durable lifetime of dye-sensitized solar cell equal to or longer than that of silicon solar cell can be achieved, thus enabling long-term stabilization and practical use of a solar cell.

Description

Description
LIFETIME EXTENSION METHOD AND APPARATUS FOR DYE-SENSITIZED SOLAR CELL
Technical Field
[1] The present invention relates to a method and an apparatus for extending lifetime of dye-sensitized solar cell. Specifically, the present invention relates to a method and apparatus for extending lifetime of dye-sensitized solar cell that can achieve durable lifetime of dye-sensitized solar cell equal to or longer than that of silicon solar cell, thus enabling long-term stabilization and practical use of dye-sensitized solar cell. Background Art
[2] A dye-sensitized solar cell is a photoelectrochemical solar cell using a photosensitive dye molecule capable of absorbing visible rays to produce electron-hole pairs and an oxide semiconductor electrode consisting of titanium oxide which transfers produced electrons. In the existing silicon solar cells, solar energy absorption process and electromotive force production process by separation of electron-hole pairs occur simultaneously in silicon semiconductor, while in dye-sensitized solar cells, solar energy absorption process and electric charge transfer process are separately conducted. Specifically, in dye-sensitized solar cells, dye absorbs solar energy, and semiconductor transfers electric charge.
[3] The dye-sensitized solar cell has advantages in that manufacture cost is low compared to the existing silicon solar cells, it is pro-environmental and it can be manufactured flexibly. However, it has a limitation in terms of practical use because of its low energy conversion efficiency.
[4] Therefore, in order to increase energy conversion efficiency of dye-sensitized solar cells, increasing the absorption of solar rays, increasing dye absorption amount thus increasing electron production amount, or preventing the extinction of the excited electrons by electron-hole recombination, etc. may be required.
[5] Thus, in order to increase dye absorption amount per unit area, a method of preparing oxide semiconductor particles with a few nanometer size, a method of increasing reflectivity of platinum electrode so as to increase absorption of solar rays, a method of mixing a few micro size semiconductor oxide light scatterer, etc. are now under development.
[6] Representative examples of dye-sensitized solar cells of the prior art include a dye- sensitized solar cell announced by Gratzel et al., Swiss, 1991. The dye-sensitized solar cell suggested by Gratzel et al. is a photoelectrochemical solar cell using a photosensitive dye molecule and an oxide semiconductor consisting of titanium oxide nanoparticles, which consists of a nanoparticle oxide semiconductor negative electrode, platinum positive electrode, dye absorbed into the negative electrode, and oxidation/reduction electrolyte using an organic solvent, and has advantage in that manufacture cost is low compared to the existing silicon solar cells.
[7] However, an electrolyte obtained from an organic solvent generally comprises volatile materials for improvement of energy efficiency, which cause volatilization of an electrolyte solvent from solar cells when temperature outside of solar cell increases by solar rays, thus decreasing energy efficiency.
[8] In addition, long-term operation of dye- sensitized solar cells may cause separation of the absorbed dye from oxide semiconductor particles thus decreasing energy efficiency.
[9] Accordingly, since deterioration of dye-sensitized solar cells shortens lifetime of dye- sensitized solar cells compared to silicon solar cells, and it adversely affects its long term stability and practical use, the development of dye-sensitized solar cells capable of solving the above problems and achieving durable lifetime equal to or longer than silicon solar cells is urgently needed. Disclosure of Invention Technical Problem
[10] In order to solve the above problems of the prior art, it is an object of the present invention to provide a method and apparatus for extending lifetime of dye-sensitized solar cells that can achieve durable lifetime of dye-sensitized solar cells equal to or more than that of silicon solar cells, thus securing its long term stability and practical use. Technical Solution
[11] In order to solve the above objet, the present invention provides a method for extending lifetime of dye-sensitized solar cell which comprises a negative electrode comprising semiconductor particles, a positive electrode facing the negative electrode, dye absorbed into the negative electrode, an electrolyte filled between the negative electrode and the positive electrode, and a frame surrounding them, said method comprising the step of i) supplementing to the electrolyte an electrolyte or insufficient component of the electrolyte, or ii) exchanging the electrolyte.
[12] The present invention also provides an apparatus for extending lifetime of dye- sensitized solar cell, said apparatus comprising: a dye-sensitized solar cell which comprises a negative electrode comprising semiconductor particles, a positive electrode facing the negative electrode, dye absorbed into the negative electrode, an electrolyte filled between the negative electrode and the positive electrode, and a frame surrounding them, and has an inlet stage and outlet stage connected to the electrolyte- filled part; a means for supplying an electrolyte or dye, connected to the inlet stage; and a means for recovering an electrolyte or dye, connected to the outlet stage.
Advantageous Effects
[13] According to the method and apparatus for extending lifetime of dye-sensitized solar cells, deterioration of an electrolyte and insufficiency of absorbed dye, etc. which shorten lifetime of dye-sensitized solar cells and decrease energy efficiency, can be prevented, thereby achieving durable lifetime extension of dye-sensitized solar cell from about 5 years of the existing dye-sensitized solar cells to equal to or longer than (about 20 years or more) about 10 to 15 years of silicon solar cells.
[14] And, in case a device for monitoring deterioration of electrolyte is equipped and the monitoring is conducted, a lifetime extension method can be conducted when deterioration is detected, thereby maximizing energy efficiency of solar cells. Brief Description of the Drawings
[15] Fig. 1 is a conceptual drawing of one example of solar cell applied for the lifetime extension method of dye- sensitized solar cell according to the present invention.
[16] Fig. 2 is a conceptual drawing of another example of solar cell applied for the lifetime extension method of dye-sensitized solar cell according to the present invention.
[17] Fig. 3 is a conceptual drawing of one example of the lifetime extension apparatus and solar cell applied for the lifetime extension method of dye-sensitized solar cell according to the present invention.
[18] Fig. 4 is a conceptual drawing of one example of circulation structure of the lifetime extension apparatus and solar cell applied for the lifetime extension method of dye- sensitized solar cell according to the present invention.
[19] Fig. 5 is a conceptual drawing of another example of circulation structure of the lifetime extension apparatus and solar cell applied for the lifetime extension method of dye-sensitized solar cell according to the present invention.
[20] Fig. 6 is a conceptual drawing of one example of circulation structure of the lifetime extension apparatus and solar cell applied for the lifetime extension method of dye- sensitized solar cell according to the present invention, further comprising a gas circulation means.
[21] * Explanations for reference numerals of drawings
[22] 10: negative electrode
[23] 20: positive electrode
[24] 30: electrolyte or electrolyte-filled part
[25] 40: frame
[26] 50: inlet stage [27] 60: outlet stage
[28] 100: solar cell
[29] 200: supplying means
[30] 300: recovering means
[31] 400: gas circulation means
Mode for the Invention
[32] The present invention will now be explained in detail.
[33] The present invention relates to a method for extending lifetime of dye-sensitized solar cell. Specifically, the present invention relates to a method for extending lifetime of dye-sensitized solar cell(lOO) which comprises a negative electrode(lθ) comprising semiconductor particles, a positive electrode(20) facing the negative electrode, dye absorbed into the negative electrode(lθ), an electrolyte(30) filled between the negative electrode(lθ) and the positive electrode (20), and a frame(40) surrounding them, said method comprising the step of i) supplementing to the electrolyte an electrolyte or insufficient component of the electrolyte, or ii) exchanging the electrolyte.
[34] Lifetime of dye- sensitized solar cell is determined by decrease of energy efficiency due to volatilization of volatile materials comprised in an electrolyte. Thus, in case such a problem occurs, insufficient component among the components of electrolyte, preferably volatile component can be supplemented to improve electrolyte properties, thus prolonging lifetime of solar cell.
[35] In addition to supplementing insufficient component of the electrolyte, electrolyte itself can be supplemented. Specifically, insufficient part of the electrolyte previously filled in solar cell can be filled by supplementing new electrolyte. One example of the structure of dye-sensitized solar cell for this is as shown in Fig. 1.
[36] Besides, existing electrolyte can be exchanged with new electrolyte, or, the existing electrolyte can be extracted and insufficient component can be added thereto, impurities can be removed therefrom, or insufficient amount can be supplemented thereto to replace the existing electrolyte, so that the solar cell may show energy efficiency similar to new solar cell, thereby prolonging lifetime of solar cell. One example of the structure of dye-sensitized solar cell for this is as shown in Fig. 2.
[37] The exchange of the electrolyte can be conducted by the following methods.
[38] First, an electrolyte can be exchanged by the steps of a) discharging the electrolyte filled between the negative electrode and positive electrode, b) injecting dye into the solar cell and then optionally circulating it so as to induce absorption, and then discharging remaining dye, and c) injecting an electrolyte between the negative electrode and positive electrode into the solar cell. And, the step of drying inside of the solar cell may be further comprised between the steps a) and b) or between the steps b) and c). Since deterioration of solar cell is caused by deterioration of electrolyte and desorption of dye, in order to prevent this, dye absorption step may be further comprised. Specifically, previously filled electrolyte is discharged from the existing solar cell, and if necessary, inert gas or nitrogen gas, etc. (if necessary, heated high temperature gas can be used) is circulated for removal of electrolyte remaining in the cell so as to conduct drying process, and then, dye (dye can be used alone, or dispersion of dye in a solvent can be used for smooth supply of dye) is injected in the solar cell, and maintained for a time or continuously circulated (circulation is preferable because it can increase absorption efficiency) so that dye may be absorbed into particles of negative electrode (mainly nanoparticles of titanium oxide), and thereafter, remaining dye is removed by discharge, and then, if necessary, the above-explained drying process (for inducing dye absorption) or common washing process (for removal of remaining dye) is optionally and repeatedly (alternatively) conducted, and then, new electrolyte (including electrolyte prepared by adding insufficient components to the existing electrolyte as well as new electrolyte) is injected in the cell. Thereby, previously desorbed dye is removed, insufficient absorption dye is supplemented by the above absorption process, and new electrolyte with insufficient components added is filled in the cell, thereby improving energy efficiency of solar cell thus prolonging lifetime of dye-sensitized solar cell.
[39] Besides, the process can be more simplified as follows: a') electrolyte filled between the negative electrode and positive electrode is discharged, and b') electrolyte comprising dye is injected and then, optionally circulated, thereby prolonging lifetime of solar cell.
[40] Specifically, previously filled electrolyte is discharged, and the electrolyte comprising dye, which is prepared by mixing dye with new electrolyte (including electrolyte prepared by adding insufficient components to existing electrolyte as well as new electrolyte), is injected in the cell, so that dye absorption process and new electrolyte filling process can be conducted by one process . The process is substantially a two-step process comprising discharge of electrolyte and injection of electrolyte comprising dye. Absorption of dye is continuously conducted during the operation of solar cell and thus separate process is not required, and injection of new electrolyte is completed in the above process. Alternatively, the process can be conducted as follows: previously filled electrolyte is discharged, and, the electrolyte comprising dye, which is prepared by mixing dye with new electrolyte (including electrolyte prepared by adding insufficient components to existing electrolyte as well as new electrolyte), is injected in the cell, and maintained for a time or circulated so as to induce absorption of dye, and then, gas-tighted as it is. In this case, passing circulation is preferable because it increases absorption opportunity to increase absorption efficiency.
[41] Moreover, the above process may further comprise, after the step b'), the step c') discharging the electrolyte comprising dye, and injecting electrolyte which does not comprise dye between the negative electrode and positive electrode in the solar cell. Namely, new electrolyte can be filled in the cell in order to increase energy efficiency of the electrolyte.
[42] Preferably, the above process may further comprise the step of drying inside of the solar cell between the steps a') and b') or between the steps b') and c'). Thereby, remaining substances can be removed, or absorption efficiency can increase. And, washing step may be further comprised together with the drying step, or drying and washing steps can be alternately conducted.
[43] The present invention also provides a lifetime extension apparatus for conducting the above-explained life time extension method, said apparatus comprising a dye- sensitized solar cell(lOO) which comprises a negative electrode(lθ) comprising semiconductor particles, a positive electrode(20) facing the negative electrode, dye absorbed into the negative electrode(lθ), an electrolyte(30) filled between the negative electrode(lθ) and the positive electrode (20), and a frame(40) surrounding them, and has an inlet stage(50) and outlet stage(60) connected to the electrolyte-filled part(30); a means for supplying an electrolyte or dye(200), connected to the inlet stage(50); and a means for recovering an electrolyte or dye(300), connected to the outlet stage(60).
[44] One example of the apparatus is as shown in Fig. 3. Specifically, in order to exchange electrolyte, the apparatus is equipped with electrolyte recovery means (recovery bath) connected to the outlet stage of solar cell for discharge of electrolyte previously filled in the solar cell, and it is equipped with electrolyte supply means consisting of an electrolyte storage bath, a pump which supplies electrolyte from the storage bath, and supply line which connects the pump to the inlet stage of the solar cell, for supply of new electrolyte.
[45] Especially, in case dye absorption is conducted together with electrolyte exchange, the storage bath in Fig. 3 can be an electrolyte storage bath, dye storage bath or a storage bath of electrolyte comprising dye. Thus, the supply means can be an electrolyte supply means or dye supply means according to the type of storage means, and the recovery means can be an electrolyte recovery means or dye recovery means according to discharged materials.
[46] Preferably, the electrolyte supply means (200) and recovery means (300) are connected to each other so as to have circulation structure. Examples of this structure are as shown in Figs. 4 to 6. Specifically, discharged materials are re-treated or circulated as it is so that recovered materials in the recovery bath can be supplied to the storage bath in the supply means. Storage and recovery bath in Figs. 4 and 5 represents this.
[47] Fig. 4 shows one example of W type cell/module or Z type cell/module, and Fig. 5 shows current collector grid type cell/module. In case only electrolyte exchange is conducted through this, existing electrolyte is discharged and recovered in storage and recovery bath, where insufficient components are added, impurities are removed, or new electrolyte is added, thus new electrolyte is stored, and the new electrolyte is supplied to a pump so that the electrolyte can be exchanged with new electrolyte.
[48] In case inducing of dye absorption is conducted together and an electrolyte comprising dye is used, existing electrolyte is recovered in storage and recovery bath, where insufficient components are added, impurities are removed, or new electrolyte is added, and dye is added thus new electrolyte is stored, and the new electrolyte comprising dye is supplied to a pump so that the electrolyte can be exchanged with new electrolyte.
[49] And, in case an electrolyte which does not comprise dye is finally filled, a storage bath for supplying of new electrolyte can be further equipped, separately from the recovery and storage bath.
[50] In case inducing of dye absorption is conducted together and dye is used for absorption, existing electrolyte is recovered in storage and recovery bath, where insufficient components are added, impurities are removed, or new electrolyte is added, thus new electrolyte is stored, and a storage bath for supplying of dye is separately equipped so that dye absorption process and new electrolyte supply process can be separately conducted.
[51] Furthermore, in case drying process is further conducted, supply and recovery connection parts can be respectively connected to the inlet stage(50) and outlet stage(60), and a gas circulation means(400) which circulates gas (preferably inert gas or nitrogen gas, more preferably heated) in the solar cell, as shown in Fig. 6, and, although not shown, a washing solution circulation means can be further equipped. In Fig. 6, solid line arrows indicate liquid flow, and dot line arrows indicate gas flow.
[52] And, as shown in Fig. 6, the storage and recovery bath can be divided into electrolyte, dye and mixture (mixture of electrolyte and dye), through which the above explained lifetime extension method can be variously composed and conducted as required.
[53] Moreover, the lifetime extension apparatus may further comprise electrolyte monitoring means or solar cell monitoring means so that deterioration of electrolyte or solar cell energy efficiency decrease can be monitored and the lifetime extension apparatus can be operated when required.
[54] The present invention is not limited to the foregoing examples and drawings attached hereto, and various modification or alteration can be made by a person of ordinary skill in the art without departing from the aspect and scope of the present invention as described in the claims appended hereto. Industrial Applicability
[55] According to the method and apparatus for extending lifetime of dye-sensitized solar cells, deterioration of an electrolyte and insufficiency of absorbed dye, etc. which shorten lifetime of dye-sensitized solar cells and decrease energy efficiency, can be prevented, thereby achieving durable lifetime extension of dye-sensitized solar cell from about 5 years of the existing dye-sensitized solar cells to equal to or longer than (about 20 years or more) about 10 to 15 years of silicon solar cells.
[56] And, in case a device for monitoring deterioration of electrolyte is equipped and the monitoring is conducted, a lifetime extension method can be conducted when deterioration is detected, thereby maximizing energy efficiency of solar cells.

Claims

Claims
[1] A method for extending lifetime of dye-sensitized solar cell which comprises a negative electrode comprising semiconductor particles, a positive electrode facing the negative electrode, dye absorbed into the negative electrode, an electrolyte filled between the negative electrode and the positive electrode, and a frame surrounding them, said method comprising the step of i) supplementing to the electrolyte an electrolyte or insufficient component of the electrolyte, or ii) exchanging the electrolyte.
[2] The method according to claim 1, wherein the electrolyte is exchanged by a) discharging the electrolyte filled between the negative electrode and the positive electrode, b) injecting dye into the solar cell and optionally circulating it so as to induce absorption, and then discharging remaining dye, and c) injecting an electrolyte between the negative electrode and positive electrode into the solar cell.
[3] The method according to claim 2, further comprising the step of drying the inside of the cell between the steps a) and b) or between the steps b) and c).
[4] The method according to claim 1, wherein the electrolyte is exchanged by a') discharging the electrolyte filled between the negative electrode and positive electrode, and b') injecting an electrolyte comprising dye and then optionally circulating it.
[5] The method according to claim 4, further comprising after the step b'), the step c') discharging the electrolyte comprising dye, and injecting an electrolyte which does not comprise dye between the negative electrode and positive electrode into the cell.
[6] The method according to claim 4 or 5, further comprising the step of drying the inside of the cell between the steps a') and b') or between the steps b') and c').
[7] An apparatus for extending lifetime of dye- sensitized solar cell, said apparatus comprising: a dye-sensitized solar cell which comprises a negative electrode comprising semiconductor particles, a positive electrode facing the negative electrode, dye absorbed into the negative electrode, an electrolyte filled between the negative electrode and the positive electrode, and a frame surrounding them, and has an inlet stage and outlet stage connected to the electrolyte-filled part; a means for supplying an electrolyte or dye, connected to the inlet stage; and a means for recovering an electrolyte or dye, connected to the outlet stage.
[8] The apparatus according to claim 7, wherein the electrolyte supplying means and the electrolyte recovering means are connected to each other so as to form a cir- culation structure.
[9] The apparatus according to claim 7 or 8, wherein supply and recovery connection parts are respectively connected to the inlet stage and the outlet stage, and the apparatus further comprises a means for circulating gas in the solar cell.
PCT/KR2008/006634 2007-11-14 2008-11-11 Lifetime extension method and apparatus for dye-sensitized solar cell WO2009064100A2 (en)

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