JP4037618B2 - Dye-sensitized solar cell and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a dye-sensitized solar cell.
[0002]
[Prior art]
  In recent years, batteries called dye-sensitized solar cells have been developed. The dye-sensitized solar cell was developed in 1991 by Gretzer et al. At the University of Lausanne in Switzerland and is also called a Gretzell cell. This is because a light electrode having a light-transmitting substrate, a light-transmitting conductive layer laminated on the substrate, and a dye that emits electrons upon receiving light, and facing the light electrode at a predetermined interval. And a conductive counter electrode, and a fluid electrolyte layer disposed between the photoelectrode and the counter electrode. In general, a ruthenium complex is used as the dye, and an electrolytic solution containing iodine is used as the electrolyte layer. In the dye-sensitized solar cell described above, the phenomenon that electrons are emitted when the dye is excited by absorbing sunlight, and the holes that remain in the dye made of ruthenium complex oxidize iodine in the electrolyte layer are utilized. It has been reported in the literature.
[0003]
  Further, according to the published patent publication related to Japanese Patent Laid-Open No. 2000-173680, a solid body for sealing in which a photoelectrode and a counter electrode are combined so as to overlap each other and a sealing resin is applied between the photoelectrode and the counter electrode. A technique that intervenes is disclosed. According to the technology according to this publication, an epoxy resin or a silicone resin is used as a sealing resin.
[0004]
[Problems to be solved by the invention]
  However, when the battery seal portion is an epoxy resin, there is a problem in long-term corrosion resistance. In particular, good sealability cannot be ensured for a long period of time at the portion that is in direct contact with the electrolyte. This is because the degree of crosslinking decreases due to the reaction between the double bond portion in the resin skeleton and iodine in the electrolyte solution, and the battery seal portion swells due to the electrolyte solution. Further, when the battery seal portion is made of a silicone resin, there is a problem in the sealing performance of the electrolyte because it is easily swelled by the organic solvent in the electrolyte.
[0005]
  As a countermeasure, according to the technique disclosed in JP 2000-173680 described above, a solid material for sealing such as glass having high corrosion resistance is disposed between the photoelectrode and the counter electrode and sealed. In addition, since the above-described epoxy resin or the like is used for the adhesive layer between the solid material, the photoelectrode, and the counter electrode, the reliability in the sealing performance of the battery seal portion is not always sufficient.
[0006]
  This invention is made | formed in view of the above-mentioned situation, and makes it a subject to provide the dye-sensitized solar cell which can ensure favorable the sealing performance in a battery seal part over a long period of time, and its manufacturing method.
[0007]
[Means for Solving the Problems]
  (1) The inventor has been diligently developing a dye-sensitized solar cell. Then, attention was paid to the fact that the electrolyte layer in the dye-sensitized solar cell contains a halogen such as iodine. Halogen such as iodine is present in an ionized state in the electrolyte layer and has a property of easily reacting with a double bond portion in an organic substance. For this reason, a resin having a double bond in the skeleton such as an epoxy resin causes a reduction in the degree of crosslinking, and has low reliability against long-term electrolyte layer leakage.
[0008]
  As a result of studying the swelling property, adhesion, etc. of the battery seal portion of various materials with respect to the electrolyte layer, the polyisobutylene-based resin has been used as a material having high durability for the electrolyte layer containing a halogen such as iodine. I found it appropriate. The polyisobutylene-based resin is presumed to have no double bond in its basic skeleton, so that the reaction with a halogen such as iodine contained in the electrolyte layer can be suppressed.
[0009]
  (2) That is, the dye-sensitized solar cell according to the present invention includes a light-transmitting substrate, a transparent conductive layer, an N-type semiconductor layer, and a photoelectrode having a dye.
  A counter electrode facing the photoelectrode at a predetermined interval and having conductivity;
  An electrolyte layer enclosed between the photoelectrode and the counter electrode;
  In a dye-sensitized solar cell having a battery seal portion that seals against an electrolyte layer,
  ElectricThe repellent layer contains halogen, and the battery seal is formed using a polyisobutylene resin as a base material.And
  A plurality of counter electrodes are provided, and the plurality of counter electrodes share a light-transmitting substrate on the photoelectrode side. In parallel with each other at a predetermined interval,
The battery seal portion covers between the adjacent counter electrodes, and covers the surface opposite to the photoelectrode among the counter electrodes.It is characterized by this.
[0010]
  According to the dye-sensitized solar cell of the present invention, the electrolyte layer contains a halogen such as iodine or bromine. The battery seal portion is formed using a polyisobutylene resin as a base material. The polyisobutylene resin has high durability against halogens such as iodine and bromine. This is presumed to be because the basic skeleton does not have a double bond, so that the reaction with a halogen such as iodine can be suppressed. Furthermore, the polyisobutylene resin is excellent in barrier properties against moisture and gas. Adhesion to the transparent conductive layer and glass plate, which are the main constituent elements of the photoelectrode and counter electrode, is also high.
[0011]
  (3) A method for producing a dye-sensitized solar cell according to the present invention includes:A photoelectrode having a light-transmitting substrate, a transparent conductive layer, an N-type semiconductor layer, and a dye;
A counter electrode facing the photoelectrode at a predetermined interval and having conductivity;
An electrolyte layer containing halogen enclosed between the photoelectrode and the counter electrode;
A method for producing a dye-sensitized solar cell for producing a dye-sensitized solar cell comprising a battery seal portion formed using a polyisobutylene-based resin as a base material and sealing against an electrolyte layer,
  A battery element having a light-transmitting substrate, a transparent conductive layer, an N-type semiconductor layer, a photoelectrode having a dye, and a counter electrode having conductivity and facing the photoelectrode at a predetermined interval As well as
  Preparing a battery seal part having a base film and a coating material based on a polyisobutylene resin applied to one side of the base film;
  The process of bonding the battery seal portion to the battery element and curing the coating material with the coating material of the battery seal portion facing the counter electrode of the battery element.IncludingIt is characterized by.
[0012]
  According to the method for producing a dye-sensitized solar cell according to the present invention, the battery seal portion before being bonded to the battery element is mainly formed of a base film and a polyisobutylene-based resin laminated on one side of the base film. It has the coating material used as a seal part. Thereafter, in a state where the coating material of the battery seal portion is opposed to the counter electrode of the battery element, the battery seal portion is bonded to the battery element and the coating material is cured. Curing means to solidify the coating material. Therefore, the battery seal portion in the cured state has elasticity necessary for sealing.
[0013]
  By the way, the manufacturing method which adhere | attaches the coating material used as the main seal part which makes a polyisobutylene-type resin a base material directly on a battery element, without using a base film, and can seal is also considered. However, in this case, the amount of the coating material may vary depending on the part. In this regard, according to the method for producing a dye-sensitized solar cell according to the present invention, since a coating material based on a polyisobutylene resin is applied in advance to one side of a base film, a polyisobutylene resin is used as a substrate. This is advantageous for averaging the amount of the coating material. As a result, it is advantageous to suppress an excessive amount of the coating material serving as the main seal portion, and it is advantageous to suppress entry of the coating material component into the battery.
[0014]
  In addition, the battery seal part formed using the polyisobutylene-based resin as a base material has high adhesion to a counterpart material such as a transparent conductive layer or glass. When higher adhesion is required, primer treatment using a silane coupling agent or the like can be performed on the base material of the battery seal portion.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
  According to the dye-sensitized solar cell of the present invention, the battery seal portion is formed using a polyisobutylene resin as a base material. In this case, it may be formed of only polyisobutylene or a copolymer. A filler such as a glass filler may be blended in the polyisobutylene resin as necessary. An electrolyte solution can be used as the electrolyte layer. An electrolytic solution in which an electrolyte substance is dissolved in a solvent can be employed. As a solvent for the electrolytic solution, a nitrile compound such as acetonitrile, methoxyacetonitrile, propylonitrile, a solvent such as ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, or a mixed solvent thereof can be employed. . The electrolyte layer may be a solid electrolyte. Examples of the solid electrolyte include gels of the above electrolytic solutions, polymer electrolytes having iodine ion conductivity, inorganic electrolytes having iodine ion conductivity, and the like. The battery seal portion has a purpose of preventing leakage of an electrolyte layer such as an electrolyte solution inside the dye-sensitized solar cell and a purpose of preventing oxygen, water vapor, and the like from being mixed from the outside.
[0016]
  According to the technique relating to the dye-sensitized solar cell according to the present invention, a mode in which an injection port for injecting an electrolyte is provided can be employed. In this case, the battery seal part is composed of a main seal part formed using a thermosetting polyisobutylene resin surrounding the electrolyte layer as a base material, and an ultraviolet curable polyisobutylene resin sealing the inlet. It is possible to adopt a form having a secondary seal portion formed as:
[0017]
  According to the technique related to the dye-sensitized solar cell according to the present invention, a plurality of counter electrodes are arranged in parallel with a predetermined interval on a common photoelectrode.ButHiringHas been. In this case, the battery seal portion employs a configuration in which the counter electrodes adjacent to each other are covered and the surface opposite to the photoelectrode is covered among the counter electrodes.The
[0018]
  According to the dye-sensitized solar cell according to the present inventionProduction methodAccordingly, the battery seal portion can adopt a form having a base film and a main seal portion based on a polyisobutylene resin laminated on one side of the base film. In this case, it is possible to adopt a form in which the main seal portion covers between the adjacent counter electrodes and covers the surface of each counter electrode opposite to the photoelectrode. This is suitable when a plurality of counter electrodes are arranged in parallel.
[0019]
【Example】
  According to the present inventionReference prior to the description of the examplesAn example will be described. Figure 1referenceThe typical structure of the dye-sensitized solar cell which concerns on an example is shown. As shown in FIG. 1, this solar cell has a photoelectrode 1, a counter electrode 2, an electrolyte layer 3, and a battery seal portion 4. The light electrode 1 has a light incident surface 10 and a mounting surface 11 facing each other and a light transmitting glass substrate 13, and a mounting surface 11 on one side of the substrate 13 opposite to the light incident surface 10. A transparent conductive layer 15 having optical transparency laminated on the substrate, a porous N-type semiconductor layer 16 (titanium oxide layer) laminated on the transparent conductive layer 15, and a dye carried on the N-type semiconductor layer 16 18. The transparent conductive layer 15 is made of SnO doped with F or Sb.₂It is formed of a film or an ITO film. The dye 18 is a ruthenium complex and has an electron emission property associated with light reception.
[0020]
  The counter electrode 2 faces the photoelectrode 1 with a predetermined interval. The counter electrode 2 has a mounting surface 21 and a light-transmitting glass substrate 23, a conductive layer 25 laminated on the mounting surface 21 of the substrate 23, and a counter electrode catalyst 26 supported on the conductive layer 25. . Since the conductive layer 25 on the counter electrode 2 side is not required to transmit light, transparency is not particularly required. Therefore, the conductive layer 25 on the counter electrode 2 side can be formed of a metal having high corrosion resistance with respect to iodine and having conductivity. For example, titanium, tantalum, niobium, tungsten, platinum, or the like can be used. However, in order to make the parts common, in this embodiment, the photoelectrode 1 and the counter electrode 2 are the same.
[0021]
  The electrolyte layer 3 is disposed between the photoelectrode 1 and the counter electrode 2 and is formed of a fluid electrolyte. The electrolytic solution is obtained by dissolving an electrolyte in an organic solvent. As the electrolyte, iodine which is a halogen is adopted. Iodine exists as an ion. The counter electrode 2 is provided with an injection port 9 for injecting an electrolytic solution.
[0022]
  The battery seal portion 4 seals the electrolyte layer 3. The battery seal portion 4 is interposed between the photoelectrode 1 and the counter electrode 2 and has a main seal portion 5 having a frame shape formed using a thermosetting polyisobutylene resin as a base material, and an ultraviolet ray that blocks the injection port 9. The secondary seal portion 6 is formed with a curable polyisobutylene resin as a base material. The main seal portion 5 seals the periphery of the electrolyte layer 3.
[0023]
  In manufacturing the solar cell described above, a coating material based on a thermosetting polyisobutylene resin constituting the main seal portion 5 is disposed on at least one of the photoelectrode 1 and the counter electrode 2. Thereafter, the photoelectrode 1 and the counter electrode 2 are bonded so as to face each other. Thereafter, the thermosetting polyisobutylene resin is thermally cured by heat treatment to form the main seal portion 5. Thereafter, an electrolytic solution is injected from the inlet 9 of the counter electrode 2. Thereafter, a coating material having an ultraviolet curable polyisobutylene resin as a base material is disposed at the injection port 9 of the counter electrode 2, and this is irradiated with ultraviolet rays to be cured by ultraviolet rays, thereby forming the sub seal portion 6. In the ultraviolet curable polyisobutylene resin, an adhesive force can be instantaneously ensured by irradiation with ultraviolet rays, so that the electrolytic solution between the photoelectrode 1 and the counter electrode 2 can be quickly sealed.
[0024]
  When using the dye-sensitized solar cell described above, power is generated when light is incident on the light incident surface 10 of the photoelectrode 1. As a principle of power generation, electrons generated on the side of the N-type semiconductor layer 16 on the side of the photoelectrode 1 based on the dye 18 due to light incidence move to the counter electrode 2 side through the lead wire of the external circuit, It is generally considered that electricity is generated based on the fact that electrons are carried from the counter electrode 2 to the N-type semiconductor layer 16 by the oxidation-reduction reaction of iodine contained in the electrolyte solution of the electrolyte layer 3. For this reason, in order to ensure the durability of the dye-sensitized solar cell, it is essential to prevent leakage of the electrolyte solution constituting the electrolyte layer 3.
[0025]
  This exampleAccordingly, since the battery seal portion 4 is formed using a polyisobutylene resin as a base material, durability against iodine contained in the electrolyte solution of the electrolyte layer 3 is ensured, and the reliability of the battery seal portion 4 is ensured. improves. This has been confirmed by testing. It is presumed that the polyisobutylene-based resin does not have a double bond in its basic skeleton, and therefore can suppress reaction with halogen ions such as iodine ions contained in the electrolyte layer 3.
[0026]
  EspeciallyThis exampleAccording to the present invention, the battery seal portion 4 is interposed between the photoelectrode 1 and the counter electrode 2 and has a main seal portion 5 having a frame shape formed using a thermosetting polyisobutylene resin as a base material, and an injection port 9 and the sub-seal portion 6 which is formed using an ultraviolet curable polyisobutylene resin as a base material. Since the main seal portion 5 is cured before injecting the electrolytic solution, there is little demand for instantaneous curing, and therefore a thermosetting type is used. Since the secondary seal portion 6 is cured after injecting the electrolytic solution, there is a strong demand for instantaneous curing in order to prevent leakage of the electrolytic solution, so an ultraviolet curing type is used. For this reason, it is advantageous for preventing leakage of the electrolyte layer 3 accommodated between the photoelectrode 1 and the counter electrode 2 and suppressing the entry of gas such as air into the electrolyte layer 3.
[0027]
  (First test example)
  referenceA dye-sensitized solar cell according to an example was prepared as follows. First, a method for creating the photoelectrode 1 will be described. Transparent glass was used as the substrate 13 on the photoelectrode 1 side. The size of the transparent glass was 15 mm × 25 mm × 1.1 mm. The transparent conductive layer 15 laminated on the substrate 13 on the photoelectrode 1 side has a surface resistivity of 10Ω / □ and is Sn doped with F.₂A membrane was obtained. The surface resistivity is based on JIS-W7202. A titanium oxide paste 16c to be an N-type semiconductor layer 16 was laminated on the mounting surface 11 which is one side of the substrate 13 on the side of the photoelectrode 1 by screen printing a titanium oxide paste and baking at 450 ° C. The laminated titanium oxide layer 16c had an electrode area size of 6 mm × 20 mm and a thickness of 10 μm. By immersing the substrate 13 on the photoelectrode 1 side in an ethanol solution of ruthenium complex for a predetermined time (24 hours), the ruthenium complex functioning as the dye 18 is adsorbed on the surface of the titanium oxide layer 16c, and thus the photoelectrode 1 is attached. Created.
[0028]
  Next, creation of the counter electrode 2 will be described. As the substrate 23 on the counter electrode 2 side, the same transparent glass plate as that on the photoelectrode 1 side was used. A conductive layer 25 is laminated on the mounting surface 21 of the substrate 23. In order to inject the electrolytic solution, an injection port 9 having a diameter of about 1 mm was formed on the substrate of the counter electrode 2 by drilling. A Pt solution is applied to the surface of the conductive layer 25 on which the substrate 23 on the counter electrode 2 side is laminated by spin coating and baked at 400 ° C., thereby supporting Pt catalyst particles functioning as the counter electrode catalyst 26. A counter electrode 2 was formed.
[0029]
  Using the thus formed photoelectrode 1 and counter electrode 2, a main seal is formed by a dispenser at a position of about 2 mm outside the periphery of the N-type semiconductor layer 16 formed of the titanium oxide layer 16 c of the photoelectrode 1. A thermosetting polyisobutylene resin coating material to be part 5 was applied. The polyisobutylene resin used as the main seal portion 5 has a particle diameter of 50 μm in order to ensure electrical insulation between the photoelectrode 1 and the counter electrode 2 or to secure a storage chamber 35 for storing the electrolytic solution. A filler (for example, a glass filler) having a microsphere shape was added. Thereafter, the photoelectrode 1 and the counter electrode 2 were bonded together. In this case, after the photoelectrode 1 and the counter electrode 2 were bonded together, the polyisobutylene resin was thermally cured by heating at 100 ° C. for 30 minutes, and the main seal portion 5 was formed.
[0030]
  Next, in the state where the injection port 9 formed in the counter electrode 2 is immersed in the electrolytic solution, the inside of the storage chamber 35 between the photoelectrode 1 and the counter electrode 2 is removed by a vacuuming operation so that the electrolytic solution does not boil. Then, the electrolytic solution was injected into the storage chamber 35 by returning to atmospheric pressure. The electrolyte used was a solution in which iodine and lithium iodide were dissolved in propylene carbonate, which is an organic solvent.
[0031]
  After injecting the electrolytic solution into the storage chamber 35 as described above, a coating material of an ultraviolet curable polyisobutylene resin is applied to the injection port 9, and the spot is irradiated with ultraviolet rays, whereby the polyisobutylene resin is converted into ultraviolet rays. The secondary seal part 6 was formed by curing, and the electrolytic solution in the storage chamber 35 was sealed.
[0032]
  About the solar cell produced as mentioned above, the high temperature leaving test which is left to stand at 85 degreeC was performed for 100 hours, and the low temperature standing test to which it was left to stand at -40 degreeC was done for 100 hours. Even after the test, electrolyte leakage from the main seal portion 5 and the sub seal portion 6 did not occur. Since the glass transition temperature of the polyisobutylene resin is lower than −40 ° C., the necessary elasticity for sealing the main seal portion 5 and the sub seal portion 6 was ensured even in the low temperature test.
[0033]
  (No.1Example)
  According to the present invention1Examples will be described. 2 and 3 show the first1The typical structure of the dye-sensitized solar cell which concerns on an Example is shown. As shown in FIG. 2, this solar cell has a photoelectrode 1, a counter electrode 2B, a separator layer 7, an electrolyte layer 3, and a battery seal portion 4B. The photoelectrode 1 has a light incident surface 10 and a mounting surface 11 facing each other and has a light-transmitting glass substrate 13, and a light-transmitting transparent conductive layer laminated on the mounting surface 11 of the substrate 13. 15, a porous N-type semiconductor layer 16 (titanium oxide layer) laminated on the transparent conductive layer 15, and a dye 18 carried on the N-type semiconductor layer 16. The transparent conductive layer 15 has a groove 15m and is SnO doped with F or Sb.₂It is formed of a film or an ITO film. The dye 18 is a ruthenium complex. As shown in FIG. 2, a plurality of counter electrodes 2 </ b> B are arranged in series with respect to a common single light electrode 1. The counter electrode 2B is formed of a carbon film and has conductivity, durability against an electrolytic solution, and catalytic properties. Since no light is transmitted through the counter electrode 2B, transparency is not particularly required. A porous separator layer 7 is interposed between the photoelectrode 1 and the counter electrode 2B. The separator layer 7 blocks direct electrical conductivity between the photoelectrode 1 and the counter electrode 2B.
[0034]
  The electrolyte layer 3 is disposed between the photoelectrode 1 and the counter electrode 2B, and is formed of an electrolytic solution having fluidity. An inlet 9 for injecting an electrolytic solution is provided on the end side of the solar cell according to this example. The battery seal portion 4B seals the electrolyte layer 3. The battery seal portion 4B is interposed between the photoelectrode 1 and the counter electrode 2B, and seals the main seal portion 5B formed using a thermosetting polyisobutylene resin as a base material, the inlet 9, and an ultraviolet curable type. It is formed with the sub seal part 6B formed using polyisobutylene resin as a base material. As shown in FIG. 2, the main seal portion 5B seals the periphery of the electrolyte layer 3, an intermediate seal portion 5w that covers and covers the adjacent counter electrodes 2B, and the photoelectrode 1 of each counter electrode 2B. The outer surface seal portion 5x that covers the surface opposite to the outer surface and the outer edge seal portion 5y that seals the outer edge of the solar cell.
[0035]
  According to this examplereferenceSimilarly to the example, since the battery seal portion 4B is formed using a polyisobutylene resin as a base material, durability against iodine contained in the electrolytic solution is ensured, and the reliability of the battery seal portion 4B is improved. This has been confirmed by testing. In particular, according to the present embodiment, the battery seal portion 4B includes a main seal portion 5B interposed between the photoelectrode 1 and the counter electrode 2B and formed of a thermosetting polyisobutylene resin as a base material. The inlet 9 is closed and the sub seal portion 6B is formed with an ultraviolet curable polyisobutylene resin as a base material. As shown in FIG. 3, the sub seal portion 6 </ b> B is disposed along the outer end side of the substrate 13. Since the main seal portion 5B is cured before injecting the electrolytic solution, there is little demand for instantaneous curing, so a thermosetting type is used. Since the secondary seal portion 6B is cured after injecting the electrolytic solution, there is a strong demand for instantaneous curing, so an ultraviolet curing type is used. For this reason, it is advantageous for suppressing gas such as the atmosphere from entering the electrolyte layer 3 accommodated between the photoelectrode 1 and the counter electrode 2B.
[0036]
  (Second test example)
  First1The solar cell which concerns on an Example was created as follows. Transparent glass was used as the substrate 13 on the photoelectrode 1 side. The size of the transparent glass was 30 mm × 25 mm × 1.1 mm. The transparent conductive layer 15 laminated on the substrate 13 on the photoelectrode 1 side has a surface resistivity of 10Ω / □ and is Sn doped with F.₂A membrane was obtained. Further, a groove 15m was formed by scribing the transparent conductive layer 15 at a pitch of 7 mm, that is, cutting it off, thereby blocking the electrical conductivity of the adjacent conductive layer portion. Screen printing and baking at 450 ° C. are repeated on the transparent conductive layer 15 of the substrate on the side of the photoelectrode 1 to form a titanium oxide layer 16c to be an N-type semiconductor layer 16, a porous separator layer 7 and a counter electrode 2B. Carbon layers were laminated. After each layer is formed, the dye 18, that is, the ruthenium complex is adsorbed on the titanium oxide layer 16 c that becomes the N-type semiconductor layer 16 by immersing the substrate that becomes the photoelectrode 1 in an ethanol solution of ruthenium complex for a predetermined time (24 hours). I let you.
[0037]
  Next, a polyisobutylene-based resin coating material is applied to the substrate 13 on which the titanium oxide layer 16c, the porous separator layer 7, and the carbon layer serving as the counter electrode 2B are mounted. By doing so, the main seal portion 5B was formed. And the electrolyte solution was inject | poured into the solar cell from the injection port 9 by vacuum deaeration operation and immersion operation to electrolyte solution. After injecting the electrolytic solution, an ultraviolet curable polyisobutylene resin is applied to the injection port 9, and ultraviolet irradiation is applied to the injection port 9 to cure the ultraviolet ray, thereby forming an auxiliary seal portion 6B that closes the injection port 9 and electrolysis. The liquid was sealed.
[0038]
  About the solar cell produced as mentioned above, the high temperature leaving test which is left to stand at 85 degreeC was performed for 100 hours, and the low temperature standing test to which it was left to stand at -40 degreeC was done for 100 hours. Even after the test, electrolyte leakage from the main seal portion 5B and the sub seal portion 6B did not occur.
[0039]
  (No.2Example)
  According to the present invention2Examples will be described. 4-6 are the first2The typical structure of the dye-sensitized solar cell which concerns on an Example is shown. First2Examples are first1The configuration is basically the same as that of the embodiment, and the same effect is obtained. First1Parts common to the embodiments are denoted by common reference numerals. The following1A description will be given centering on differences from the embodiment. As shown in FIG. 4, this solar cell includes a photoelectrode 1, a counter electrode 2B, a separator layer 7, an electrolyte layer 3, and a battery seal portion 4C. The electrolyte layer 3 is disposed between the photoelectrode 1 and the counter electrode 2B, and is formed of an electrolytic solution having fluidity. The battery seal portion 4C seals the electrolyte layer 3. The battery seal portion 4C is interposed between the photoelectrode 1 and the counter electrode 2B, and closes the main seal portion 5C formed using a thermosetting polyisobutylene resin as a base material, the injection port 9, and an ultraviolet curable type. It is formed with the sub seal part 6C formed using polyisobutylene resin as a base material. The main seal portion 5C surrounds and seals the periphery of the electrolyte layer 3.
[0040]
  FIG. 6 shows the battery seal 4C before being bonded to the solar cell. The battery seal portion 4C before being bonded to the solar cell is a paste-like paste that becomes a main seal portion 5C having a base film 8 having flexibility and a polyisobutylene resin applied to one side of the base film 8 as a base material. It has a coating material 5H. The battery seal portion 4C before being attached to the battery element is provided with an inlet 9 for injecting an electrolyte so as to penetrate the battery seal portion 4C in the thickness direction.
[0041]
  Then, the step of bonding the coating material 5H of the battery seal portion 4C to the battery element is performed with the coating material 5H of the battery seal portion 4C facing the counter electrode 2B among the battery elements. In this case, the coating material 5H is pressurized and thermally cured to form the main seal portion 5C. As shown in FIG. 4, the thermoset main seal portion 5 </ b> C has an intermediate seal portion 5 w that covers and covers the adjacent counter electrodes 2 </ b> B, and a surface of each counter electrode 2 </ b> B opposite to the photoelectrode 1. It has an outer surface sealing portion 5x to be covered and an outer edge sealing portion 5y for sealing the outer edge of the solar cell.
[0042]
  According to the present embodiment, since the battery seal portion 4C is formed using a polyisobutylene resin as a base material, durability against iodine contained in the electrolytic solution is ensured, and the reliability of the battery seal portion 4C is improved. To do. This has been confirmed by testing. In particular, according to this embodiment, the battery seal portion 4C is interposed between the photoelectrode 1 and the counter electrode 2B, and is a main seal portion having a frame shape formed by using a thermosetting polyisobutylene resin as a base material. 5C and the sub seal part 6C formed by using an ultraviolet curable polyisobutylene resin as a base material while closing the injection port 9. Since the main seal portion 5C is cured before injecting the electrolytic solution, there is little demand for instantaneous curing, and therefore a thermosetting type is used. Since the sub seal portion 6C is cured after injecting the electrolytic solution, there is a strong demand for instantaneous curing in order to prevent leakage of the electrolytic solution, so an ultraviolet curing type is used. For this reason, it is advantageous for suppressing gas such as the atmosphere from entering the electrolyte layer 3 accommodated between the photoelectrode 1 and the counter electrode 2B.
[0043]
  According to the present embodiment, the base material 8 may be coated with the coating material 5H based on the polyisobutylene resin in an amount necessary for adhesion. For this reason, the amount of the coating material 5H applied to the base film 8 can be minimized. For this reason, it is advantageous to suppress the excessive coating material 5H from penetrating into the solar cell from the surface of the counter electrode 2B layer or the like. Therefore, it is advantageous to suppress a decrease in the performance of the solar cell. In addition, as a material of the base film 8, 1 type, such as a high density polyethylene, polyester, nylon, silicone, or the resin film which laminated | stacked these can be used. In some cases, a metal foil may be used as the base film 8. Moreover, as the base film 8, you may use what formed the metal thin film in the resin film.
[0044]
  (Third test example)
  A solar cell according to the third example was prepared as follows. This case is basically the same as the second test example. The size of the transparent glass forming the substrate 13 of the photoelectrode 1 was 30 mm × 25 mm × 1.1 mm. The transparent conductive layer 15 laminated on the substrate 13 on the photoelectrode 1 side has a surface resistivity of 10Ω / □ and is Sn doped with F.₂A membrane was obtained. Further, a groove 15m was formed by scribing the transparent conductive layer 15 at a pitch of 7 mm, that is, cutting it off, thereby blocking the electrical conductivity of the adjacent conductive layer portion. On the mounting surface 11 of the substrate 13 on the side of the photoelectrode 1, screen printing and baking at 450 ° C. are repeated to form a titanium oxide layer 16c that becomes an N-type semiconductor layer 16, a porous separator layer 7, and a counter electrode 2B. Each carbon layer was created. After forming each layer, the dye 18, that is, the ruthenium complex was adsorbed on the titanium oxide to be the N-type semiconductor layer 16 by immersing the substrate to be the photoelectrode 1 in an ethanol solution of the ruthenium complex for a predetermined time (24 hours). .
[0045]
  As shown in FIG. 6, a battery seal portion 4 </ b> C having a base film 8 and a coating material 5 </ b> H (target thickness: 10 μm) laminated on one surface of the base film 8 and using a polyisobutylene resin as a base material was used. Then, the step of bonding the coating material 5H of the battery seal portion 4C to the battery element was performed with the coating material 5H of the battery seal portion 4C facing the counter electrode 2B among the battery elements. Then, press bonding was performed using a hot roll device held in a warm state (150 ° C.), and the coating material 5H was pressurized and thermally cured to form a main seal portion 5C.
[0046]
  Then, electrolyte solution was inject | poured from the inlet 9 about 1 mm in diameter created beforehand so that it might penetrate to the battery seal part 4C in the thickness direction. After injecting the electrolytic solution, an ultraviolet curable polyisobutylene resin is applied to the injection port 9, and the ultraviolet ray is spot-irradiated to cure the polyisobutylene resin to form an auxiliary seal portion 6C. The electrolyte was sealed.
[0047]
  About the solar cell produced as mentioned above, the high temperature leaving test which is left to stand at 85 degreeC was performed for 100 hours, and the low temperature standing test to which it was left to stand at -40 degreeC was done for 100 hours. Even after the test, electrolyte leakage from the main seal portion 5C and the sub seal portion 6C did not occur.
[0048]
  Comparative Example A solar cell according to a comparative example was produced. The comparative example has the same configuration as that of the first embodiment. However, an epoxy resin was used as the material for the battery seal. About the solar cell created by the said method, the high temperature leaving test in 85 degreeC and the low temperature leaving test in -40 degreeC were each performed. As a result, after 100 hours passed in the high-temperature standing test at 85 ° C., liquid leakage from the sub-seal portion occurred. Moreover, after 100 hours passed in the low temperature standing test at −40 ° C., both the main seal portion and the sub seal portion were peeled off, and electrolyte leakage occurred.
[0049]
  (Other Examples) In addition, the present invention is not limited to the embodiments described above and shown in the drawings, and can be implemented with appropriate modifications within a range not departing from the gist.
[0050]
【The invention's effect】
  According to the dye-sensitized solar cell and the manufacturing method according to the present invention, the reliability for preventing leakage of the electrolyte layer can be improved. Therefore, the conversion efficiency in the solar cell can be maintained well over a long period. As a result, the environmental conditions in which the dye-sensitized solar cell can be used are expanded, and the application can be expected to expand.
[0051]
  According to the method for producing a dye-sensitized solar cell according to the present invention, an application material having a polyisobutylene resin as a base material may be applied to the base film in an amount necessary for adhesion. For this reason, the amount of the coating material applied to the base film can be minimized. For this reason, it becomes advantageous in suppressing that the excessive component of the coating material penetrates into the solar cell from the surface of the counter electrode layer or the like. Therefore, it is advantageous to suppress a decrease in the performance of the solar cell.
[Brief description of the drawings]
[Figure 1]referenceIt is a schematic sectional drawing which shows typically the dye-sensitized solar cell which concerns on an example.
FIG. 21It is a schematic sectional drawing which shows typically the dye-sensitized solar cell which concerns on an Example.
FIG. 31It is a schematic plan view which shows typically the dye-sensitized solar cell which concerns on an Example.
FIG. 42It is a schematic sectional drawing which shows typically the dye-sensitized solar cell which concerns on an Example.
FIG. 52It is a schematic plan view which shows typically the dye-sensitized solar cell which concerns on an Example.
FIG. 62It is a schematic sectional drawing which shows typically the battery seal part before bonding together to the dye-sensitized solar cell which concerns on an Example.
[Explanation of symbols]
  In the figure, 1 is a light electrode, 10 is a light incident surface, 13 is a substrate, 15 is a transparent conductive layer, 16 is a semiconductor layer, 18 is a dye, 2 is a counter electrode, 3 is an electrolyte layer, 4 is a battery seal portion, and 5 is A main seal portion 6 indicates a sub seal portion.

Claims (4)

A photoelectrode having a light-transmitting substrate, a transparent conductive layer, an N-type semiconductor layer, and a dye;
A counter electrode facing the photoelectrode at a predetermined interval and having conductivity;
An electrolyte layer enclosed between the photoelectrode and the counter electrode;
In a dye-sensitized solar cell having a battery seal part that seals against the electrolyte layer ,
With pre-Symbol electrolyte layer containing a halogen, the battery sealing portion is formed of polyisobutylene-based resin as a base material,
A plurality of the counter electrodes are provided, and the plurality of counter electrodes are arranged in parallel at a predetermined interval from each other with the substrate having light transmittance on the light electrode side in common.
The said battery seal part coat | covers between the said adjacent counter electrodes, and has coat | covered the surface on the opposite side to the said photoelectrode among each said counter electrodes, The dye-sensitized solar cell characterized by the above-mentioned . 2. The dye according to claim 1, wherein an injection port for injecting an electrolyte that forms the electrolyte layer enclosed between the photoelectrode and the counter electrode communicates with a storage chamber between the photoelectrode and the counter electrode. Provided in a sensitized solar cell , the battery seal portion closes the injection port and a main seal portion formed using a thermosetting polyisobutylene resin as a base material for sealing the periphery of the electrolyte layer A dye-sensitized solar cell, comprising: a sub-seal portion formed using an ultraviolet curable polyisobutylene resin as a base material. 3. The battery seal portion according to claim 1 , wherein the battery seal portion includes a base film and a main seal portion based on a polyisobutylene resin applied to one side of the base film, and the adjacent counter electrodes are adjacent to each other. A dye-sensitized solar cell, characterized in that the surface opposite to the photoelectrode is covered among the counter electrodes. A photoelectrode having a light-transmitting substrate, a transparent conductive layer, an N-type semiconductor layer, and a dye;
A counter electrode facing the photoelectrode at a predetermined interval and having conductivity;
An electrolyte layer containing halogen enclosed between the photoelectrode and the counter electrode;
A method for producing a dye-sensitized solar cell for producing a dye-sensitized solar cell comprising a battery seal portion that is formed using a polyisobutylene-based resin as a base material and seals the electrolyte layer,
Wherein with said light pole having said said substrate which transmits light wherein the transparent conductive layer and the N-type semiconductor layer dye, a conductive with facing at a predetermined interval with respect to the light pole While preparing a battery element having a counter electrode,
A step of preparing the cell sealing portion and a coating material for a polyisobutylene-based resin applied on one surface of the base film and the base film as a base material,
In a state of being opposed to the counter electrode of the battery element the coating material of the battery sealing portion, characterized in that it comprises a step of curing the coating material with bonding the battery sealing unit to the battery element method of manufacturing a color Motozo-sensitized solar cell.

Images