JP6412396B2 - Method for producing dye-sensitized solar cell - Google Patents

Description

  The present invention relates to a method for producing a dye-sensitized solar cell.

  The dye-sensitized solar cell employs a configuration in which an array of element arrays is formed on the substrate by patterning each functional film disposed on the substrate on the photoelectrode side for the purpose of improving power generation performance and the like. It has become so. Here, bonding (adhesion) between the photoelectrode substrate and the counter electrode substrate, separation between the arrayed elements formed on the substrate (partitions), retention of the electrolyte (electrolyte) inside the cell, and external atmosphere Intrusion suppression (sealing) or the like in the cell is performed by a sealing material disposed between a pair of substrates.

  Conventionally, as a method of arranging a sealing material between a pair of substrates, for example, a method of drawing and applying on a substrate by a dispenser using an adhesive (two-component mixed curing type, photocuring type, thermosetting type, etc.). For example, a method has been proposed in which hot melt adhesive is discharged from a nozzle and applied while forming a pattern on a substrate (see, for example, Patent Document 1).

  In addition, when manufacturing a dye-sensitized solar cell while bonding a pair of substrates together, as a method that can be produced by a roll-to-roll method conventionally employed, for example, a thermosetting resin is released as a desired shape. There has been proposed a technique for transferring a patterned adhesive using a sheet with an adhesive disposed on the sheet (see, for example, Patent Document 2).

JP 2011-183576 A International Publication No. 2014/112624

  Here, when applying an adhesive on a substrate using a dispenser as in the method described in Patent Document 1, in order to ensure adhesion and sealing between a pair of substrates, the start point and end point in the application pattern It is necessary to overlap with each other. However, when the start point and end point of the pattern are overlapped in this way, there is a problem that the thickness of this portion is not uniform compared to other portions.

  In addition, when applying an adhesive on a substrate using a dispenser, since the cross section of the application pattern is raised in a substantially convex shape, when thermocompression bonding, with respect to the center in the width direction of the pattern, In some cases, the shape may be irregularly shifted to either the left or right side. In order to suppress such a shift in shape to a minimum, for example, it is conceivable to increase the margin of the hot melt adhesive on the substrate. However, in this case, for example, if a large margin is secured on the electrode side, it is necessary to increase the amount of electrolyte contained more than necessary, or the gap between the electrode side and the adhesive side becomes large, and the air It is considered that there is a problem that it takes time to degas. Moreover, in the method using a dispenser like patent document 1, since it is difficult to translate a dispenser with the board | substrate drawn | fed out from a roll, for example, there exists a problem that the application to a roll to roll system is difficult.

  On the other hand, according to the technique described in Patent Document 2, the adhesive is attached to the substrate by pressing the sheet with the adhesive lightly against the substrate to such an extent that the shape of the adhesive does not collapse. However, in the method of preparing and transferring a patterned adhesive in advance as in Patent Document 2, there is concern about maintaining the accuracy of the pattern of the adhesive formed on the substrate and the transfer probability to the substrate. There was a problem from the viewpoint of stability and productivity.

  The present invention has been made in view of the above-mentioned problems, can be applied to a process of bonding a pair of substrates to each other by a roll-to-roll method, can appropriately control the application amount and the application pattern of the adhesive, An object of the present invention is to provide a method for producing a dye-sensitized solar cell capable of forming a pattern with high accuracy and high productivity.

Invention of Claim 1 is a manufacture of a dye-sensitized solar cell provided with a pair of board | substrate arrange | positioned facing each other, and the photoelectrode and counter electrode which are provided so that it may each oppose on this pair of board | substrate. A photoelectrode forming step of forming at least one or more photoelectrodes on either the one substrate or the other substrate of the pair of substrates continuously drawn out by a roll-to-roll method. A counter electrode forming step of forming a counter electrode at a position corresponding to the photoelectrode on the substrate opposite to the substrate on which the photoelectrode is formed, of the pair of substrates that are continuously drawn out, and a roller of a supporting step of supporting in a predetermined pattern of an adhesive to the surface, by contacting the rollers on one substrate of the pair of substrates, wherein the continuously fed, responsible to the surface of the roller The adhesive is in contact before Symbol hand on the substrate was coated, and the coating step for continuously forming the adhesive layer of the predetermined pattern, as a step after the coating step, the pair The substrates are stacked so that the photoelectrode and the counter electrode are sandwiched opposite to each other, and the pair of substrates are bonded to each other by the adhesive layer formed on the one substrate. And an adhesion step of adhering by pressing between and pressing .

  Invention of Claim 2 is a manufacturing method of the dye-sensitized solar cell of Claim 1, Comprising: The said carrying process uses the roller by which the said predetermined pattern was formed in the surface. .

  Invention of Claim 3 is a manufacturing method of the dye-sensitized solar cell of Claim 2, Comprising: The said roller is a roller main body, A predetermined pattern is formed in the surface, On the outer peripheral surface of the said roller main body And a thin plate-like plate member that can be detachably attached.

  Invention of Claim 4 is a manufacturing method of the dye-sensitized solar cell of Claim 2 or Claim 3, Comprising: The said coating process makes the said roller relatively with respect to said one board | substrate. The adhesive layer having the predetermined pattern is formed on the one substrate continuously or intermittently by moving and contacting.

  Invention of Claim 5 is a manufacturing method of the dye-sensitized solar cell as described in any one of Claims 2-4, Comprising: The said pattern of the surface of the said roller is formed in stripe form. It is characterized by comprising at least one of a groove portion, a groove portion formed in a lattice shape, and a hole portion formed in a dot shape.

  Invention of Claim 8 is a manufacturing method of the dye-sensitized solar cell of Claim 7, Comprising: The said adhesive agent consists of a hot-melt-type adhesive agent, The said adhesion process is a pair of said pressure roll. The pair of substrates is sandwiched between the pair of pressure rolls and pressed while heating the adhesive layer formed on the one substrate.

  The invention according to claim 9 is the method for producing the dye-sensitized solar cell according to claim 7, wherein the adhesive is made of a thermosetting adhesive, and the bonding step includes the pair of pressure rolls. The pair of substrates are sandwiched between the pair of pressure rolls and pressed while the adhesive layer formed on the one substrate is heated and cured.

  Invention of Claim 10 is a manufacturing method of the dye-sensitized solar cell of Claim 7, Comprising: The said adhesive agent consists of a photocurable adhesive agent, and the said adhesion process is light to the said adhesive bond layer. The pair of substrates are sandwiched between the pair of pressure rolls and pressed while being cured by irradiation.

  According to the method for producing a dye-sensitized solar cell according to the present invention, first, in the supporting step, after patterning and supporting the adhesive on the surface of the roller in advance, on one substrate in the coating step, Since it is a method of forming an adhesive layer having a predetermined pattern by transferring a patterned adhesive supported on the surface of the roller, it can easily cope with a process of bonding a pair of substrates to each other by a roll-to-roll method. In addition, the amount and pattern of the adhesive can be controlled appropriately, the pattern of the adhesive layer can be formed with high accuracy and high productivity, and the dye increase has excellent sealing properties and high battery characteristics. It becomes possible to manufacture a solar cell.

It is a schematic cross section explaining the dye-sensitized solar cell obtained by the manufacturing method of the dye-sensitized solar cell which is one Embodiment of this invention. It is a figure which illustrates typically the manufacturing method of the dye-sensitized solar cell which is one Embodiment of this invention, and is the schematic explaining the process of adhere | attaching continuously, extending | stretching a pair of board | substrates by a roll to roll system. is there. It is a figure which illustrates typically the manufacturing method of the dye-sensitized solar cell which is one Embodiment of this invention, (a) is a perspective view which shows the roller with which the adhesive agent is carry | supported previously, (b) is the outer periphery of a roller main body. It is a top view which shows the pattern of a groove part in the state which expand | deployed the thin plate-shaped plate member attached to a part. It is a figure which illustrates typically the manufacturing method of the dye-sensitized solar cell which is one Embodiment of this invention, and is a top view which shows the photoelectrode formed on one board | substrate before forming an adhesive bond layer. . It is a figure which illustrates typically the manufacturing method of the dye-sensitized solar cell which is one Embodiment of this invention, and also to FIG. 3 (a), (b) on one board | substrate with which the photoelectrode was formed. It is a top view which shows the state which formed the adhesive bond layer with the roller shown.

  Hereinafter, an embodiment of a method for producing a dye-sensitized solar cell according to the present invention will be described with reference to FIGS. Note that the drawings used in the following description may show the characteristic parts in an enlarged manner for the sake of convenience in order to make the characteristics easy to understand. There is. In addition, the materials and the like exemplified in the following description are examples, and the present invention is not limited to them, and can be appropriately modified and implemented without changing the gist thereof.

<Dye-sensitized solar cell>
As shown in FIG. 1, a dye-sensitized solar cell 1 obtained by the method for manufacturing a dye-sensitized solar cell according to this embodiment includes at least a pair of substrates 2 (2A, 2B) arranged to face each other. A photoelectrode 3 and a counter electrode 4 are provided on the pair of substrates 2A and 2B so as to face each other. In the dye-sensitized solar cell 1 shown in FIG. 1, the peripheral portions of the pair of substrates 2 </ b> A and 2 </ b> B are sealed with an adhesive layer 5. Further, the photoelectrode 3 and the counter electrode 4 are arranged so as to face each other so as to have a certain thickness dimension, and an electrolyte 6 is provided between them. It is sealed with the agent layer 5. Although not shown in FIG. 1, wiring patterns for collecting current generated between the photoelectrode 3 and the counter electrode 4 are formed on the pair of substrates 2A and 2B, respectively. (See the wiring pattern 33 shown in FIG. 4).
Hereinafter, each structure which comprises the dye-sensitized solar cell 1 obtained by the manufacturing method of this embodiment is explained in full detail.

(A pair of substrates)
In the pair of substrates 2A and 2B, as described above, one substrate 2A and the other substrate 2B are arranged to face each other. Further, a photoelectrode 3 is provided on one surface side of one substrate 2A disposed on the upper side in FIG. 1, and a counter electrode 4 is disposed on one surface side of the other substrate 2B disposed on the lower side in the drawing. Provided.

  One substrate 2A is a transparent member that functions as a photoelectrode substrate that supports the photoelectrode 3, has conductivity, and can be applied to the production and use of a photosensitized solar cell or the like using the photoelectrode and the photoelectrode. And if it is comprised with the material transparent with respect to visible light, the material etc. will not be specifically limited. For example, it is preferable to use a film base material made of a transparent conductive resin material as the one substrate 2A from the viewpoint of increasing the degree of freedom of installation in a place having a curved portion or an uneven portion. Although detailed illustration is omitted as such a resin material, for example, ITO (tin doped indium oxide), FTO (fluorine doped tin oxide), ATO (antimony doped tin oxide), GZO (gallium doped zinc oxide), Examples thereof include a conductive material layer made of AZO (aluminum-doped zinc oxide) formed on a transparent substrate made of a resin such as PET, PEN, polycarbonate, and acrylic.

  Further, as one substrate 2A, a metal or alloy such as silver, copper, aluminum, iron, titanium, stainless steel, nickel, manganese, zinc or the like is used as a conductive material layer in a mesh shape, and this is a transparent base made of the above resin. Examples thereof include a film formed on a material. By using the resin material as described above for one substrate 2A, it is possible to manufacture a dye-sensitized solar cell using a light, thin and flexible photoelectrode substrate.

  The other substrate 2B is a member that becomes a base (counter electrode substrate) of the counter electrode 4, and if it is made of a material applicable to the manufacture and use of the dye-sensitized solar cell 1, the material and the like are particularly Although it is not limited, it is made of a transparent member having conductivity as in the case of the one substrate 2A described above, and is transparent to visible light, from the viewpoint that both sides of the photoelectrode 3 and the counter electrode 4 can be received. A material is preferred. Further, as the other substrate 2B, although detailed illustration is omitted, as with the one substrate 2A on which the photoelectrode 3 is supported, from the point of increasing the degree of freedom of installation in a place having a curved portion or an uneven portion, etc. It is preferable to use a film substrate made of a transparent conductive resin material. For example, a conductive material layer made of ITO, FTO, ATO, GZO, or AZO is formed on a substrate made of a resin such as PET, PEN, polycarbonate, or acrylic. And those formed into a film.

  Moreover, as the other substrate 2B, a metal or alloy such as silver, copper, aluminum, iron, titanium, stainless steel, nickel, manganese, zinc or the like is used as a conductive material layer in a mesh shape. Examples thereof include a film formed above. By using the resin material as described above for the other substrate 2B, it becomes possible to manufacture a dye-sensitized solar cell using a light, thin and flexible counter electrode substrate.

  Further, the other substrate 2B is not necessarily required to have transparency, for example, metal such as iron, aluminum, stainless steel, copper, silver, titanium, platinum, gold, molybdenum, manganese, chromium, nickel, Alternatively, a conductive material layer made of an alloy is formed on a base material made of a resin such as PET, PEN, polycarbonate, or acrylic, or a metal foil made of the above metal material may be used instead of the other substrate 2B. it can.

(Photoelectrode)
As in the example shown in FIG. 1, the photoelectrode 3 is provided on one substrate 2 </ b> A, and although detailed illustration is omitted, a dye 32 is adsorbed and supported on the semiconductor layer 31. In the illustrated example, one substrate 2A of the photoelectrode 3 is disposed on the upper side. The photoelectrode 3 in the example shown in FIG. 1 is formed in the vicinity of the approximate center in the width direction of one substrate 2A.

The semiconductor layer 31 constituting the photoelectrode 3 is formed on one substrate 2A, and the material thereof is not particularly limited. Conventionally, the semiconductor layer 31 is used for a photoelectrode of a dye-sensitized solar cell capable of adsorbing a dye 32 described later. The semiconductor material used can be used without any limitation. As such a semiconductor material, for example, a porous material made of a metal oxide such as titanium oxide (TiO ₂ ), zinc oxide (ZnO), or strontium titanate (SrTiO ₃ ) can be used.

  When the semiconductor layer 31 is composed of metal oxide semiconductor fine particles, the semiconductor layer 31 may be formed by baking a known paste containing fine particles on one substrate 2A. Alternatively, the semiconductor layer 31 may be configured as a porous structure formed in a state where the fine particles of the metal oxide semiconductor are bonded to each other by spraying the fine particles of the metal oxide semiconductor onto the one substrate 2A. Examples of the method for forming the porous semiconductor layer 31 by spraying metal oxide semiconductor fine particles on one substrate 2A as described above include an aerosol deposition method (AD method).

  Here, the primary particle diameter of the metal oxide semiconductor fine particles constituting the semiconductor layer 31 may vary in a suitable range depending on the method of forming the fine particles on one substrate 2A. ˜500 μm is preferable, 1 nm to 250 μm is more preferable, 5 nm to 100 μm is further preferable, and 10 nm to 10 μm is particularly preferable. In addition, as a method for obtaining the primary particle diameter of the metal oxide semiconductor fine particles, for example, a method of determining from the peak value of the volume average diameter distribution obtained by measurement using a laser diffraction particle size distribution measuring device, or SEM Examples include a method of measuring the dimension in the major axis direction of a plurality of fine particles by observation and then calculating an average value thereof. Of these, the primary particle diameter of the metal oxide semiconductor fine particles is preferably measured by SEM observation.

  The semiconductor layer 31 preferably has a porous structure. As described above, at least the surface of the semiconductor layer 31 has a porous structure, so that an area capable of adsorbing the dye 32 (described later) on the semiconductor layer 31 is increased and the amount of the dye adsorbed can be increased. it can. Thereby, conversion efficiency improves and it becomes possible to obtain a high battery characteristic.

  The dye 32 is a layer made of a sensitizing dye formed so as to be adsorbed to the semiconductor layer 31 in the photoelectrode 3. The dye 32 has an action of being excited by emitted light and emitting electrons. The electrons emitted from the dye 32 are transferred to the semiconductor layer 31 having a wide band gap, and diffuse in the semiconductor layer 31 and smoothly move to the one substrate 2A.

  The dye 32 constituting the photoelectrode 3 is preferably provided so as to be adsorbed to the semiconductor layer 31, and formed so that the surface of the semiconductor layer 31 (including the inner surface) is covered with the dye 32. Is preferred.

  As described above, examples of the dye 32 that emits electrons by irradiated light include known organic dyes such as a ruthenium complex, cyanine, and chlorophyll.

(Counter electrode)
As in the example shown in FIG. 1, the counter electrode 4 is composed of a catalyst layer provided on the other substrate 2B, and in the illustrated example, the other substrate 2B is on the lower side. Further, the counter electrode 4 in the example shown in FIG. 1 is formed over almost the entire surface of the other substrate 2B.

  The catalyst layer constituting the counter electrode 4 is formed on the plate surface of the other substrate 2B by a known method such as a sputtering method or a printing method. As such a catalyst layer, a known material can be used. For example, a material having catalytic ability for the oxidation-reduction reaction of the electrolyte 6 can be selected.

  The other substrate 2B and the counter electrode 4 may not be transparent with respect to the light irradiated to the dye-sensitized solar cell, but are transparent from the viewpoint of ensuring the degree of freedom in the light irradiation direction, for example. It is preferable.

(Electrolytes)
The electrolyte 6 is filled in a space surrounded by the adhesive layer 5 between the photoelectrode 3 and the counter electrode 4. In the dye-sensitized solar cell 1, the electrolyte 6 is made of a substance including a redox pair that causes a redox reaction for continuously flowing electricity. Examples of such a redox pair include iodine redox. Examples of the electrolyte 6 containing iodine redox include non-aqueous solvents such as acetonitrile and propionitrile, or ionic liquids such as dimethylpropylimidazolium iodide and butylmethylimidazolium iodide, and lithium iodide and iodine. A solution in which is mixed is used. Further, the electrolyte 6 may contain other additives such as fillers and thickeners without departing from the spirit of the present invention.

  The concentration of the oxidation-reduction pair in the electrolyte 6 is not particularly limited. However, when the electrolyte 6 is a liquid electrolyte, it is preferably 0.1 to 10 mol / L, more preferably 0.2 to 2 mol / L. It is. Moreover, the preferable range of the density | concentration of an iodine in the case of adding an iodine in the solvent of the electrolyte 6 is 0.01-1 mol / L.

  In this embodiment, a semi-solid (gel) or solid material may be used for the electrolyte 6 instead of the liquid electrolyte. As such an electrolyte 6, for example, a gel electrolyte in which a gelling agent or a thickener is added to an electrolytic solution can be applied. Moreover, what was solidified by removing a solvent using the solution of a conventionally well-known p-type conductive polymer is applicable. Thus, the risk of leakage of the liquid electrolyte from the dye-sensitized solar cell 1 is eliminated by using the gel-like or solid electrolyte 6 instead of the liquid electrolyte.

(Adhesive layer)
The adhesive layer 5 provided in the dye-sensitized solar cell 1 of the present embodiment is formed by a manufacturing method described in detail later, and functions as a battery sealing material by bonding a pair of substrates 2A and 2B together. It is. The adhesive layer 5 is preferably a member that can hold the electrolyte 6 inside the battery. As such an adhesive layer 5, what consists of a conventionally well-known synthetic resin can be employ | adopted, for example, a hot-melt-type adhesive agent, a thermosetting adhesive agent, a photocurable adhesive agent, etc. without a restriction | limiting at all. Can be adopted.

  Among these, the thermoplastic resin used for the hot melt adhesive is not particularly limited, but preferably includes an ionomer resin excellent in heat sealability. The melting point of the hot melt resin is preferably not higher than the heat resistance temperature of the pair of substrates 2A and 2B made of a film substrate, specifically 150 ° C. or lower. The melt viscosity of the hot melt resin is preferably in the range of 100 to 100,000 mPa · s, and the viscosity may be adjusted by adding a solvent as necessary.

  Further, the thermosetting adhesive is not particularly limited, and preferably includes an epoxy thermosetting resin that does not produce a volatile substance as a by-product during curing and has excellent dimensional accuracy. In particular, a one-component type in which a main agent and a curing agent are mixed in advance is preferable, and various conventionally known one-component epoxy thermosetting resins can be used. The viscosity of the thermosetting adhesive is desirably in the range of 100 to 100,000 mPa · s, and the viscosity can be adjusted by adding a diluent or heating with a molten iron.

  Examples of the photocurable adhesive include acrylate radical polymerization resins and epoxy cationic polymerization resins. In addition, the photo-curing adhesive is preferably ultraviolet curable, is less susceptible to curing reaction inhibition by oxygen in the curing treatment atmosphere, and does not impair flexibility as a solar cell after curing. It is preferable to use a soft epoxy ultraviolet curing resin. Further, the viscosity of the photocurable adhesive is desirably in the range of 100 to 100,000 mPa · s, and the viscosity can be adjusted by blending conditions of the resin molecules or heating in a molten iron.

<Method for producing dye-sensitized solar cell>
Next, a method for producing the dye-sensitized solar cell 1 of the present embodiment will be described with reference to FIGS. 2 to 5 (see also FIG. 1 as appropriate). FIG. 2 is a schematic diagram for explaining a process of continuously bonding a pair of substrates 2A and 2B while being fed out by a roll-to-roll method. 3A is a perspective view showing the roller 13 on which the adhesive B is carried in advance, and FIG. 3B shows a thin plate member 13B attached to the outer peripheral portion of the roller body 13A of the roller 13. It is the top view which shows the pattern of the groove part 13b in the surface 13a in the state made. 4 is a plan view showing the photoelectrode 3 formed on one substrate A before the adhesive layer 5 is formed, and FIG. 5 is on the one substrate 2A on which the photoelectrode 3 is formed. 2 is a plan view showing a state in which the adhesive layer 5 patterned by the roller 13 is formed. A wiring pattern 33 for collecting current generated between the photoelectrode 3 and the counter electrode 4 shown in FIG. 1 is formed on one substrate A shown in FIGS.

The manufacturing method of the present embodiment includes a photoelectrode 3 and a counter electrode 4 provided on a pair of substrates 2 (2A, 2B) arranged to face each other as shown in FIG. This is a method for producing a sensitized solar cell 1. And the manufacturing method of this embodiment is a method provided with following each process (1) and (2) at least when the manufacturing apparatus 10 as shown in FIG. 2 is used.
(1) A carrying step of carrying the adhesive B on the surface 13a of the roller 13 in a predetermined pattern.
(2) The adhesive B carried on the surface 13a of the roller 13 is applied on one substrate 2A of the pair of substrates 2A and 2B so as to form an adhesive layer 5 having a predetermined pattern. Coating process.

  Furthermore, in the example described in the present embodiment, a photoelectrode forming step (A) in which at least one photoelectrode 3 is formed on one substrate 2A or the other substrate 2B of the pair of substrates 2A and 2B (A And a counter electrode forming step (B) of forming the counter electrode 4 at a position corresponding to the photoelectrode 3 on the substrate opposite to the substrate on which the photoelectrode 3 is formed, of the pair of substrates 2A and 2B. Is provided. In the present embodiment, an example in which the photoelectrode 3 is formed on one substrate 2A of the pair of substrates 2A and 2B and the counter electrode 4 is formed on the other substrate 2B will be described.

  Furthermore, in this embodiment, an electrolyte supply step (3) for supplying an electrolyte (not shown) to a region surrounded by the adhesive layer 5 formed on one substrate 2A, and a pair of substrates 2A and 2B, The photoelectrode 3 and the counter electrode 4 are overlapped so as to be opposed to each other, and a bonding step (4) is provided in which the pair of substrates 2A and 2B are bonded to each other by the adhesive layer 5 formed on one substrate 2A. It has been.

  In addition, in the manufacturing apparatus 10 in FIG. 2, the photoelectrode formation part 12 is provided between the 1st roll 11 and the line roll 11A in which a pair of board | substrate 2A is wound so that supply | payout is possible, and the other A counter electrode forming portion 17 is provided between the second roll 16 and the line roll 16A on which the substrate 2B is wound so as to be able to be fed. In the manufacturing method of the present embodiment, as shown in the illustrated example, by using the manufacturing apparatus 10 provided with the photoelectrode forming unit 12 and the counter electrode forming unit 17 described above, one substrate 2A to be transported or the other The photoelectrode 3 or the counter electrode 4 can be formed on the substrate 2B.

  Here, the photoelectrode formation step (A) may be provided at any stage as long as it is a step prior to the coating step (2), and the counter electrode formation step (B) ) May be provided at any stage as long as it is a process prior to the above-described bonding step (4). For this reason, in the detailed description of each step below, first, the photoelectrode formation step (A) and the counter electrode formation step (B) are described in detail, and then the steps (1) to (4) are described in detail. .

(A) Photoelectrode formation process In the manufacturing method of this embodiment, first, one substrate 2A to be a photoelectrode substrate is fed out from the first roll 11. The photoelectrode formation step (A) is a step performed before the coating step (2). In this step, one side of the one substrate 2A that has been fed out, in the manufacturing apparatus 10 in the illustrated example. A photoelectrode 3 as shown in FIG. 1 is formed on the lower surface side when being conveyed. In the photoelectrode formation process of this embodiment, as shown in FIG. 2, a photoelectrode is formed in the photoelectrode formation part 12 provided in the conveyance path | route of one board | substrate 2A.

In the photoelectrode formation step, the semiconductor layer 31 is formed by laminating TiO ₂ on one side of one substrate 2A, for example, by using the above-described AD method in the photoelectrode formation portion 12, as shown in FIG. After the formation, the photoelectrode 3 is formed by further adsorbing the dye 32 on the semiconductor layer 31 by a conventional method. One substrate 2A on which the photoelectrode 3 is formed is sequentially conveyed toward the roller 13 while being guided by a line roll 11A shown in FIG.

(B) Counter electrode forming step In the manufacturing method of the present embodiment, at least before the bonding step (4) described later, in the counter electrode forming step (B), one substrate 2A is formed on the other substrate 2B in advance. A counter electrode 4 is formed at a position corresponding to the photoelectrode 3 formed above (see FIG. 1). In the counter electrode forming process of the present embodiment, as shown in FIG. 2, in the counter electrode forming portion 17 provided in the transport path of the other substrate 2B, as shown in FIG. The counter electrode 4 is formed so as to cover the side.

  In the present embodiment, for example, the photoelectrode 3 is formed on one substrate 2A in advance and the counter electrode 4 is formed on the other substrate 2B so that each electrode is formed in advance. It is also possible to adopt a method in which the substrates 2A and 2B are fed out from each roll.

  Although detailed illustration is omitted in the counter electrode forming step, the counter electrode forming portion 17 forms a catalyst layer by stacking platinum (Pt) on one side of the other substrate 2B by using, for example, a sputtering method. Thus, the counter electrode 4 is formed. The other substrate 2B on which the counter electrode 4 is formed is joined and overlapped with the one substrate 2A on which the photoelectrode 3 is formed at the position of the line roll 16A, and bonded in the bonding step (4) described in detail later. Is done.

(1) Supporting Step The supporting step (1) provided in the manufacturing method of the present embodiment is a step of patterning and supporting the adhesive B on the surface 13a of the roller 13 as described above.
In the manufacturing apparatus 10 of the example shown in FIG. 2, the molten or dissolved adhesive B is stored in the melting tank 14, and a part of the roller 13 enters the inside through the opening 14 a of the melting tank 14 and is bonded. It is in a state immersed in the agent B. And the roller 13 is rotated centering on the axial part 13c (refer Fig.3 (a)), maintaining the state which controlled the adhesive agent B to the fixed temperature in the melting tank 14, and was heat-melted. At this time, by continuously winding the adhesive B on the surface of the roller 13, the adhesive B enters and is supported in the groove 13 b formed in a predetermined pattern on the surface 13 a. Further, the amount of the adhesive B wound up at this time is adjusted by a doctor blade 19 provided in the vicinity of the surface 13 a of the roller 13.

  As described above, in the carrying step (1), the adhesive B is carried on the groove portion 13b having a predetermined pattern formed on the surface 13a of the roller 13 in advance, so that the coating step (2), which is a subsequent step, is performed. ) And the coating amount and the coating pattern of the adhesive B can be appropriately controlled.

  The roller 13 used in the carrying step (1) is not particularly limited, and the groove 13b may be formed directly on the surface 13a of the roller body 13A of the roller 13 as in the example shown in FIG. Alternatively, as shown in FIGS. 3 (a) and 3 (b), a thin plate member 13B having a predetermined pattern formed on the outer surface of the roller body 13A is detachably attached. May be adopted. Here, the positions of the symbols AA ′ and BB ′ in the plate member 13B on the surface of the roller 13 shown in FIG. 3A are the symbols AA ′ in the plate member 13B shown in FIG. And BB ′, respectively.

  As described above, when the plate member 13B having a predetermined pattern formed on the surface is detachably attached to the roller body 13A, for example, when changing the pattern of the adhesive layer 5 on a model basis, Since only the plate member 13B is replaced, the workability in the process is improved.

  Moreover, it is more preferable that the surface 13a of the roller 13 is provided with an alignment mark for alignment with one substrate 2A to which the adhesive B is applied. Furthermore, the surface 13a of the roller 13 may be subjected to a coating process, a fine shape process, or the like.

  In the carrying step (1) of the present embodiment, the above-described pattern formed on the surface 13a of the roller 13 is described by taking as an example a configuration including groove portions 13b formed in a stripe shape. However, it is not limited to this. For example, the pattern for supporting the adhesive B formed on the surface of the roller used in the supporting step (1) may be a pattern composed of grooves formed in a lattice shape, or a hole formed in a dot shape. The pattern which consists of a part may be sufficient. Further, the cross-sectional shape of the groove 13b is not particularly limited, such as a U-groove or a V-groove in addition to a normal square groove.

  In this embodiment, even if the pattern shape of the roller surface is any of the above, for example, the adhesive B is patterned and supported in various shapes according to the specifications for each model of the dye-sensitized solar cell. The adhesive layer 5 can be formed in a pattern shape corresponding to this pattern.

  In the carrying step (1) of the present embodiment, as the adhesive B used in a molten or dissolved state, a hot melt adhesive, a thermosetting adhesive, a photocurable adhesive, or the like as described above is used. In the subsequent bonding step (4), a curing process according to the type of the adhesive B is performed.

(2) Coating step Next, in the coating step (2), the adhesive B carried on the surface 13a of the roller 13 is brought into contact with one substrate 2A, and this adhesive B is brought into contact with one substrate 2A. A patterned adhesive layer 5 is formed by coating and transferring the coating on the surface. In the present embodiment, a method of supplying a pair of substrates 2A and 2B by a roll-to-roll method as shown in FIG. 2 is adopted, and the roller 13 is brought into contact with one of the substrates 2A being conveyed in the coating process. Thus, the adhesive layer 5 is formed on one substrate 2 in a shape corresponding to a continuous and predetermined pattern.

At this time, for example, a pattern of the photoelectrode 3 as shown in FIG. 4 is formed on one substrate 2A. In FIG. 4, the patterns of a plurality of photoelectrodes 3 are sequentially arranged in the length direction of one substrate 2A.
Next, the adhesive layer 5 is continuously applied by applying the adhesive B in a pattern as shown in FIG. 3B on one substrate 2A on which the photoelectrode 3 as shown in FIG. 4 is formed. Form. Thereby, as shown in FIG. 5, the adhesive layer 5 is formed in a pattern surrounding the photoelectrode 3.

Thereafter, the one substrate 2A on which the adhesive layer 5 is formed is sequentially introduced into the dryer 15 to evaporate the solvent and the like contained in the original adhesive B.
And one board | substrate 2A is conveyed sequentially toward a pair of pressurization roll 18 (18A, 18B) side.

  Here, the carrying process (1) in which the adhesive B is carried on the roller 13 and the coating process (2) in which the adhesive B carried on the roller 13 is applied / transferred to one substrate 2A are the same. This is performed continuously using a roller 13. For this reason, first, the supporting process of the adhesive B is started in the supporting process (1), and after the adhesive B supported in the initial stage is applied to one substrate 2A, the supporting process (1) and A coating process (2) will be performed simultaneously.

Note that the pressing force of the roller 13 against the one substrate 2A when the adhesive B is applied / transferred to the one substrate 2A is not particularly limited as long as the shape and pattern arrangement of the adhesive layer 5 are not broken. Not. For example, the roller 13 can be pressed against one substrate 2 </ b> A with a low pressure that does not greatly deform or hardly deform the shape of the adhesive layer 5. As a result, the adhesive B carried in a predetermined pattern on the surface 13a of the roller 13 is applied and transferred to one side of the substrate 2A while maintaining almost the same pattern. At this time, by appropriately setting the coating conditions, it is possible to form the adhesive layer 5 on the one substrate 2A while maintaining the width and thickness (height) substantially uniformly.
That is, in this embodiment, by providing the above-described coating process, the pattern of the adhesive layer 5 can be made with higher accuracy in the process of continuously bonding the pair of substrates 2A and 2B to each other by the roll-to-roll method. It can be formed with high productivity.

  In the present embodiment, the method of carrying the adhesive B by one-step coating using only one roller 13 is described. However, the present invention is not limited to this. For example, a plurality of rollers 13 are arranged. Thus, it is also possible to adopt a method of forming the adhesive layer 5 by applying the adhesive B repeatedly or by applying it in a complicated pattern.

(3) Electrolyte Supply Process The adhesive layer 5 formed after coating is arranged in a dam shape so as to surround the photoelectrode 3 on one substrate 2A. In the electrolyte supply step, an electrolyte (not shown) is continuously supplied to a region surrounded by the adhesive layer 5. At this time, even if the electrolyte is a liquid electrolyte, the adhesive layer 5 leaks out to the outside.

  In addition, the supply timing of the electrolyte in this embodiment is not limited to the above. For example, a procedure for forming a through hole in one of the pair of substrates 2A and 2B, injecting an electrolyte from the through hole, and sealing the through hole after the adhesion step (4) as a subsequent step is completed. It is also possible to select as appropriate.

(4) Bonding Step Next, in the bonding step (4), the pair of substrates 2A and 2B are overlapped so that the photoelectrode 3 and the counter electrode 4 are sandwiched opposite to each other and placed on one substrate 2A. The pair of substrates 2A and 2B are bonded to each other by the formed adhesive layer 5. In the example described in the present embodiment, the counter electrode 4 (see FIG. 1) is formed so as to cover the one surface side (upper surface side) of the other substrate 2B in the counter electrode forming step (B). Therefore, the pair of substrates 2 </ b> A and 2 </ b> B are bonded to each other through the adhesive layer 5 and the counter electrode 4.

  In this bonding step (4), for example, first, the substrate 2A on which the photoelectrode 3 is formed and the other substrate 2B on which the counter electrode 4 is formed, which has passed through the dryer 15, are combined with the photoelectrode 3 While translating so as to face the counter electrode 4, they are superposed vertically on the line roll 16 </ b> A. At this time, the one substrate 2 </ b> A and the other substrate 2 </ b> B are not in contact with each other, and the gap between the two substrates can be controlled by the thickness (height) of the adhesive layer 5. Then, the pair of substrates 2A and 2B overlapped in this state are sequentially conveyed toward the pair of pressure rolls 18 (18A and 18B).

  The pair of stacked substrates 2A and 2B is sandwiched between a pair of pressure rolls 18A and 18B and pressed. At this time, the pair of pressure rolls 18A and 18B are provided with heating means (not shown), and the pair of pressure rolls 18A and 18B are heated to be sandwiched between the pair of substrates 2A and 2B. The adhesive layer 5 in a state is pressed while being heated. At this time, when the adhesive layer 5 is formed of a hot-melt adhesive, the pair of substrates 2A and 2B are uniformly bonded to each other by the heating and pressing described above. Thus, the photoelectrode 3 and the counter electrode 4 arranged so as to face each other between the pair of substrates 2A and 2B are sealed in cell units and connected in the length direction of the pair of substrates 2A and 2B. A dye-sensitized solar cell 1 is obtained.

  In addition, when a thermosetting adhesive is used for the adhesive layer 5, as described above, the adhesive layer 5 in a state of being sandwiched between the pair of substrates 2A and 2B is pressed while being heated. While the agent layer 5 is cured, the pair of substrates 2A and 2B can be bonded with high strength.

  Here, when a photocurable adhesive is used for the adhesive layer 5, for example, a light emitting means (not shown) is provided on the downstream side of the pair of pressure rolls 18 </ b> A and 18 </ b> B. By providing the pair of pressure rolls, the pair of substrates 2A and 2B are sandwiched between the two pairs of pressure rolls while being cured by irradiating the adhesive layer 5 with light. 2A and 2B can be bonded with high strength.

  And the dye-sensitized solar cell 1 connected by the elongate shape after sealing is wound around the product roll not shown and collect | recovered. Thereafter, the produced dye-sensitized solar cell 1 is appropriately cut according to the purpose and application thereof, whereby the dye-sensitized solar cell 1 including a plurality of cell units is obtained. As a cutting method at this time, for example, a method of burning off using laser irradiation and the like can be mentioned.

<Effect>
As described above, according to the method of manufacturing the dye-sensitized solar cell of the present embodiment, in the supporting step (1), after the adhesive B is patterned and supported on the surface 13a of the roller 13 in advance, In the process step (2), the adhesive B that is patterned and supported on the surface 13a of the roller 13 is transferred onto one substrate 2A, and the adhesive layer 5 having a predetermined pattern is formed. It is possible to easily cope with a process of bonding the substrates 2A and 2B to each other by a roll-to-roll method. Moreover, by providing said carrying | support process (1) and coating process (2), the application quantity and application | coating pattern of the adhesive agent B can be controlled appropriately, and the pattern of the adhesive bond layer 5 is highly accurate. Since it can be formed with high productivity, the dye-sensitized solar cell 1 having excellent sealing properties and high battery characteristics can be manufactured.

  Next, the present invention will be described in detail by the following examples, but the present invention is not limited only to these examples.

[Example 1]
In Example 1, a photoelectrode and a counter electrode were produced under the following conditions and procedures, and a dye-sensitized solar cell in which an electrolyte was filled between these electrodes was produced.

  First, a PEN film (thickness = 150 μm) having an ITO film as a transparent conductive layer on the surface is used as a base material (one substrate: photoelectrode substrate), and titanium oxide containing an average particle size of 50 nm is contained on the transparent conductive layer A paste (Peccell Technologies, Inc .: PECC-K01) was applied by screen printing to pattern a porous titanium oxide film. Furthermore, after forming a current collection wiring pattern by screen-printing nano silver paste (Mitsuboshi Belting Co., Ltd. product: MDot), it heat-processed in the 150 degreeC conveyor furnace. Thereafter, di-tetrabutylammonium cis-bis (isothiocyanato) bis (2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium (II) was added to an ethanol solution so that the concentration became 0.3 mM. The dye solution dissolved in (1) was applied to the portion where the porous titanium oxide film was formed and then dried to prepare a photoelectrode as shown in FIG.

Further, a hot melt adhesive was used as the adhesive. As this hot-melt type adhesive, an ionomer resin (DuPont: HiMilan 1557) to which 1 part by weight of SiO ₂ spacer beads having a diameter of ₂₀ μm was added was used, and a roll coater (melting temperature 140 ° C.) was used. An adhesive pattern was applied to the substrate to form an adhesive layer (see FIG. 5). At this time, the groove width is 1000 μm and the pitch is 500 μm for the purpose of holding the uniformly melted adhesive within the surface of the pattern portion of the roll plate on the outer periphery of the roll coater (see the hatched area shown in FIG. 3B). Concave grooves formed in a lattice shape were provided.

Next, a counter electrode substrate (the other substrate) in which a platinum film (thickness = 100 nm) is partially vapor-deposited on the PET film is overlaid on the above photoelectrode substrate, and then hot pressed (140 ° C., 0.1 MPa). Then, a pair of substrates were bonded together.
From the hole provided on the counter electrode substrate side, lithium iodide (0.1M), iodine (0.03M), dimethylpropylimidazolium iodide (0.6M), tert-butylpyridine (0.5M) After injecting an electrolyte solution in which γ-butyrolactone was dissolved in γ-butyrolactone, a hole was sealed using a UV curable resin, to prepare a dye-sensitized solar cell.

[Example 2]
In Example 2, as a hot melt type adhesive used for the adhesive layer, a solution obtained by dissolving 50% by weight of Aron Melt PES manufactured by Toa Gosei Co., Ltd. in an 8: 2 solvent of toluene: methyl ethyl ketone is heated and melted. Without applying a pattern using a roll coater, the solvent contained in the coating film was removed by drying with hot air at 80 ° C., and the pattern formation of the adhesive layer was carried out. A dye-sensitized solar cell was produced.

  The configurations and combinations thereof in the embodiments and examples described above are examples, and additions, omissions, substitutions, and other modifications of the configurations can be made without departing from the spirit of the present invention. . Moreover, this invention is not limited by each embodiment and each Example, It is limited only by a claim.

DESCRIPTION OF SYMBOLS 1 ... Dye-sensitized solar cell, 2 ... A pair of board | substrate, 2A ... One board | substrate, 2B ... The other board | substrate, 3 ... Photoelectrode, 4 ... Counter electrode, 5 ... Adhesive layer, 6 ... Electrolyte, 13 ... Roller, DESCRIPTION OF SYMBOLS 13A ... Roller main body, 13B ... Plate member, 13a ... Surface (roller), 13b ... Groove part, 18, 18A, 18B ... Pressure roll (a pair of pressure rolls), B ... Adhesive.

Claims (8)

A method for producing a dye-sensitized solar cell, comprising: a pair of substrates arranged to face each other; and a photoelectrode and a counter electrode provided on the pair of substrates so as to face each other,
A photoelectrode forming step of forming at least one photoelectrode on either the one substrate or the other substrate of the pair of substrates continuously drawn out by a roll-to-roll method;
A counter electrode forming step of forming a counter electrode at a position corresponding to the photo electrode on the substrate opposite to the substrate on which the photo electrode is formed, of the pair of substrates that are continuously drawn;
A supporting step of supporting the adhesive in a predetermined pattern on the surface of the roller;
By contacting the rollers on one substrate of the pair of substrates, wherein the continuously fed, and a coating in contact with the front Symbol hand on the substrate an adhesive is carried on the surface of the roller A coating step of continuously forming the adhesive layer of the predetermined pattern;
As a subsequent step of the coating step, the pair of substrates are overlapped so that the photoelectrode and the counter electrode are sandwiched opposite to each other, and the adhesive layer formed on the one substrate A bonding step in which a pair of substrates are bonded together by pressing between a pair of pressure rolls; and
A method for producing a dye-sensitized solar cell, comprising:   The method for producing a dye-sensitized solar cell according to claim 1, wherein a roller having a predetermined pattern formed on a surface thereof is used in the supporting step.   The said roller is provided with the roller main body and the thin plate-shaped plate member in which a predetermined pattern is formed in the surface, and can be attached to the outer peripheral surface of the said roller main body so that attachment or detachment is possible. A method for producing a dye-sensitized solar cell.   In the coating step, the roller is relatively moved and brought into contact with the one substrate, and the adhesive layer having the predetermined pattern is formed on the one substrate continuously or intermittently. The manufacturing method of the dye-sensitized solar cell of Claim 2 or Claim 3.   The pattern on the surface of the roller comprises at least one of a groove portion formed in a stripe shape, a groove portion formed in a lattice shape, and a hole portion formed in a dot shape. The manufacturing method of the dye-sensitized solar cell as described in any one of Claims 4. The adhesive comprises a hot melt adhesive,
In the bonding step, the pair of pressure rolls are heated, and the pair of substrates are sandwiched between the pair of pressure rolls while heating the adhesive layer formed on the one substrate. The method for producing a dye-sensitized solar cell according to any one of claims 1 to 5, wherein pressure is applied. The adhesive comprises a thermosetting adhesive,
In the bonding step, the pair of pressure rolls are heated, and the pair of substrates are moved by the pair of pressure rolls while the adhesive layer formed on the one substrate is heated and cured. The method for producing a dye-sensitized solar cell according to any one of claims 1 to 5 , wherein the pressure is applied while sandwiched. The adhesive comprises a photocurable adhesive,
6. The bonding process according to claim 1, wherein the bonding step includes pressing the pair of substrates between the pair of pressure rolls while irradiating and curing the adhesive layer with light . A method for producing a dye-sensitized solar cell according to one item .

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