JP2011175940A - Dye-sensitized solar cell module and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell module having a simple structure, in which light receiving surfaces of the respective cells are located on the same side, and a superior electricity-conducting function and a stable spacer function are exhibited between the adjacent cells. <P>SOLUTION: Each cell 9 has a translucent conductive member 1, a catalyst layer 2, an electrolyte layer 3, a semiconductor layer 4, and a metal member 5 from a plate-like body A side toward a plate-like B side. In the dye-sensitized solar cell module, a partial surface (including the case where metal of a catalyst maternal is attached) of the translucent conductive member 1 constituting a counter electrode 20 of one cell and a surface of a thick-wall 52 of the metal member 5 having a thin-wall 51 and the thick-wall 52 constituting an optical electrode 40 of the other cell are laminated and brought into contact with each other between adjoining cells, thereby securing the electric conduction in series between the cells, and securing a gap between the counter electrode 20 and the optical electrode 40 with the thick-wall 52 of the metal member 5 as a spacer, and the counter electrodes 20 and the optical electrodes 40 of the adjoining cells are insulated from each other by insulating members 6A, 6B, respectively. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a module in which a plurality of dye-sensitized solar cells connected in series are incorporated between opposing insulating plate-like bodies, and a metal member is used for a photoelectrode.

  Conventionally, solar cells using mainly silicon as a photoelectric conversion element have been used. As a more economical next-generation solar cell, there is a “dye-sensitized solar cell”. Since the open-circuit voltage of the dye-sensitized solar cell is 1 V or less, the voltage tends to be insufficient to operate a general electronic device with a single cell. For this reason, the practical application of a dye-sensitized solar cell module in which a plurality of cells are connected in series has been studied.

  Patent Document 1 discloses a type of module (hereinafter referred to as “W-type module”) in which photoelectrodes and counter electrodes are alternately arranged on a substrate to form a series structure. However, in the case of the W-type module, half of the cells use incident light from the counter electrode side. When light enters from the counter electrode side, the intensity of light reaching the semiconductor layer is reduced by reflection at the counter electrode and absorption by the electrolytic solution, which causes a decrease in photoelectric conversion efficiency of the entire module.

  In Patent Document 2, a cell in which a photoelectrode constituent material, a porous insulating layer containing an electrolyte, and a counter electrode constituent material are stacked between a pair of substrates is formed, and a conductive member constituting the counter electrode has an intercell insulating layer. A module (hereinafter referred to as a “monolithic module”) having a structure in which it is overcome and connected to the photoelectrode of the adjacent cell is disclosed. The monolithic module is suitable for continuous production because it is laminated in order from a photoelectrode to a counter electrode on one substrate. However, since it is necessary to form a continuous layer so that the counter electrode member can get over the inter-cell insulating layer having a height of several tens of μm, an advanced lamination technique is required, and the manufacturing cost increases.

  In Patent Documents 3 to 6, in a module in which a photoelectrode and a counter electrode are on the same substrate side in each cell, a module of a type in which a photoelectrode and a counter electrode of adjacent cells are connected in series by inserting a conductive member (hereinafter referred to as a module). , "Z type module"). In the Z-type module, incident light from one substrate side can be used uniformly in each cell, so that the efficiency is not reduced as in the W-type module. However, it is necessary to insert a conductive member that connects the electrodes, and it is not always easy to achieve good conductivity in the energization path of the photoelectrode-conductive member-counter electrode, and sufficiently satisfactory conductivity is ensured. On the other hand, there has not yet appeared a product that has been reduced in production cost.

  In order to increase the output of the battery, it is advantageous to increase the area of one cell, but in that case, it is difficult to be deformed as a spacer for securing the space between the electrodes, and the strength is stably borne. It is desirable to apply what can be done. In particular, when the entire area of the module is large, it is necessary to provide a high-strength member having a spacer function also in a region between cells. However, since the proportion of the effective light receiving area decreases as the proportion of the inter-cell region increases, the conversion efficiency decreases. For this reason, it is desirable to make the inter-cell region as small as possible. In the structure between cells in the conventional Z-type module, it is difficult to stably perform an excellent spacer function with a small area.

JP 2007-18809 A JP 2008-16351 A JP 2001-357897 A Special Table 2002-535808 Special Table 2002-540559 JP 2007-18862 A

  An object of the present invention is to provide a dye-sensitized solar cell module having a simple structure in which the light receiving surface of each cell is on the same side and exhibits a good energization function and a stable spacer function between adjacent cells. .

The above object is a module in which a plurality of dye-sensitized solar cells connected in series are incorporated between an opposing insulating and translucent plate A and insulating plate B. Because
Each cell has a translucent conductive member, a catalyst layer, an electrolyte layer, a semiconductor layer, and a metal member from the plate A side to the plate B side, and the translucent conductive member and the catalyst layer The counter electrode is configured, the photoelectrode is configured by the semiconductor layer and the metal member,
Between adjacent cells, a part of the surface of the translucent conductive member constituting the counter electrode of one cell (including the case where the metal of the catalyst substance is attached) and the photoelectrode of the other cell The thin-walled portion and the thick-walled surface of the metal member having the thick-walled portion are stacked and brought into contact with each other to ensure serial continuity between the cells, and the thick-walled portion of the metal member is a spacer. As a gap between the photoelectrode and the counter electrode is secured,
This is achieved by a dye-sensitized solar cell module in which the photoelectrodes and the counter electrodes of adjacent cells are insulated from each other by an insulating member.

The metal member is formed by applying a technique of “masking with resist film → etching → removing resist film” to the metal sheet supported on the surface of the plate-like body B. be able to.
The material of the metal member may be derived from nickel, titanium, titanium alloy, chromium, aluminum, aluminum alloy, molybdenum, or steel sheet material. “Derived from sheet material” means a material obtained by processing a sheet material.

In particular, stainless steel can be adopted as the metal member. “Stainless steel” is an alloy steel that has improved corrosion resistance with a Cr content of 10.5 mass% or more and a C content of 1.2 mass% or less, as shown in the number 3801 of JIS G0203: 2009. is there. Specific stainless steel types include, for example, the following (A) or (B) if they are standard steel types. Examples of the content range of each component element include the following (C) or (D).
(A) Stainless steel that belongs to the ferritic steel types specified in JIS G4305: 2005, has a Cr content of 16 to 32 mass%, and a Mo content of 0.3 to 3 mass%.
(B) Stainless steel that belongs to the austenitic steel grade specified in JIS G4305: 2005, has a Cr content of 16 to 32% by mass, and a Mo content of 0.3 to 7% by mass.

(C) By mass% C: 0.0001 to 0.15%, Si: 0.001 to 1.2%, Mn: 0.001 to 1.2%, P: 0 to 0.04%, S: 0 to 0.03%, Ni: 0 to 0.6%, Cr: 16.0 to 35.0%, Mo: 0.3 to 3.0%, Cu: 0 to 1.0%, Nb: 0 ~ 1.0%, Ti: 0 to 1.0%, Al: 0 to 0.2%, N: 0 to 0.025% or less, B: 0 to 0.01%, remaining Fe and unavoidable impurities Ferritic stainless steel.

(D) By mass% C: 0.0001 to 0.15%, Si: 0.001 to 4.0%, Mn: 0.001 to 2.5%, P: 0 to 0.045%, S: 0 to 0.03%, Ni: 6.0 to 28.0%, Cr: 16.0 to 35.0%, Mo: 0.3 to 7.0%, Cu: 0 to 3.5%, Nb : 0 to 1.0%, Ti: 0 to 1.0%, Al: 0 to 0.1%, N: 0 to 0.3%, B: 0 to 0.01%, balance Fe and inevitable impurities Austenitic stainless steel consisting of

  In the above (C) and (D), the lower limit of the content is 0%, which means that the element is an optional element.

As a method for producing such a module, a plurality of dye-sensitized solar cells connected in series between an opposing insulating and translucent plate A and insulating plate B are provided. When manufacturing the embedded module,
[1] counter electrode side structure manufacturing process;
A plate-like body A having a translucent conductive member film on the surface is prepared,
Step of separating the translucent conductive members on both sides across the groove by forming a groove penetrating the film thickness in the translucent conductive member at a pitch equal to the cell pitch (see FIG. 2B) ,
A step of forming a catalyst layer on the surface portion of the translucent conductive member located in the region to be inside the cell (see FIG. 2C);
Inserting an insulating member into the groove to insulate adjacent translucent conductive members (see FIG. 2D);
Obtaining a counter electrode side structure by a procedure comprising:
[2] Photoelectrode side structure manufacturing process;
When a cell is constructed, a metal sheet having a thickness equal to or greater than [the distance between the plate A and the plate B] − [thickness of the translucent conductive member] is bonded to the surface of the plate B. Prepare something,
By the method of “masking with resist film → etching → resist film removal”, the surface portion of the metal sheet located in the area between adjacent cells is left as a thick part, and the metal sheet located in the area inside the cell is Etching the surface portion to form a thin wall portion (see FIGS. 3E and 3F),
The step of separating the metal sheets into individual metal members by forming grooves having a pitch equal to the cell pitch by the method of “masking with resist film → etching → resist film removal” (FIG. 3G) h)),
Forming a semiconductor layer on the thin portion (see FIG. 3I);
A step of carrying a sensitizing dye on the semiconductor layer (see FIG. 3 (j)),
Inserting an insulating member into the groove to insulate adjacent metal members from each other (see FIG. 3 (k));
Obtaining a photoelectrode-side structure by a procedure comprising:
[3] coalescence process;
The counter electrode side structure and the photoelectrode side structure are divided into a part of the surface of each of the former translucent conductive members (including the case where the metal of the catalyst substance is attached) and the latter thick wall. A step of sealing in a state in which the electrolyte layers are filled between the semiconductor layer and the catalyst layer, by combining the parts so that the parts are in contact with each other and overlapping
A method for producing a dye-sensitized solar cell module having the following formula is provided.

The present invention has the following merits.
(1) Since the photoelectrode is made of a metal material, the conductivity inside the battery is improved, which is advantageous for improving the photoelectric conversion efficiency.
(2) Since the conductor responsible for energization between the cells and the current collecting member of the photoelectrode are composed of one metal member, the structure of the module is simplified and the cost merit is excellent.
(3) Since the metal member can be directly formed on a metal sheet placed on a module substrate (insulating plate-like body) by using a photoetching technique, it has excellent dimensional accuracy. .
(4) Since the metal member functions as a spacer for securing a certain electrode interval between cells, other spacer members are unnecessary, and the area ratio occupied by the inter-cell region can be reduced. Thereby, the light incident on the module can be used effectively, leading to an improvement in photoelectric conversion efficiency.
(5) Since the spacer made of the metal member is hard to deform and can stably bear the strength, it is advantageous for the construction of a dye-sensitized solar cell module having a wide light receiving area.

The figure which illustrated typically the cross-section of the dye-sensitized solar cell module of this invention. The figure which illustrated typically the member section state in the counter electrode side structure fabrication process. The figure which illustrated typically the member cross-sectional state in the photoelectrode side structure preparation process.

  FIG. 1 schematically illustrates a cross-sectional structure of the dye-sensitized solar cell module 10 of the present invention. This figure is drawn with the thickness direction exaggerated, and does not reflect the actual dimensional shape of the module as it is. The insulative and translucent plate A and the insulative plate B are opposed to each other at a constant distance, and the translucent conductive member 1, catalyst layer 2, electrolyte layer 3, semiconductor layer 4 and A dye-sensitized solar cell 9 constituted by the metal member 5 is incorporated. A portion where cells are present when viewed in the thickness direction is called a cell region 100, and a portion between adjacent cells is called an inter-cell region 200. In each cell 9, the counter electrode 20 is configured by the translucent conductive member 1 and the catalyst layer 2, and the photoelectrode 40 is configured by the semiconductor layer 4 and the metal member 5. Between the cells, a partial surface of the translucent conductive member 1 constituting the counter electrode 20 of one cell and a partial surface of the metal member 5 constituting the photoelectrode 40 of the other cell overlap. Thereby, series connection between cells is realized. The metal member 5 responsible for series connection between cells has a thin portion 51 and a thick portion 52.

In the cell region 100, the semiconductor layer 4 is formed on the surface of the thin portion 51 of the metal member 5, and the photoelectrode 40 is configured.
In the inter-cell region 200, the surface of the thick portion 52 of the metal member 5 is in contact with the partial surface 11 of the translucent conductive member 1 in a stacked manner. As a result, conduction between adjacent cells is ensured, and the thick portion 52 functions as a spacer for maintaining the distance between the counter electrode 20 and the photoelectrode 40. The metal of the catalyst substance may adhere to the surface of the translucent conductive member 1 during the manufacturing process. There is no need for a catalyst function in this portion, but there is no problem that the metal of the catalyst material is attached. That is, the metal of the catalytic material may be interposed between the translucent conductive member 1 and the metal member 5 laminated in the inter-cell region 200 (in FIG. 1, the case where the metal is interposed). Exemplified) The opposing electrodes 20 and the photoelectrodes 40 of the adjacent cells 9 are insulated by insulating members 6A and 6B, respectively.

In each cell 9, when light incident from the plate-like body A side reaches the semiconductor layer 4, an electromotive force is generated between the photoelectrode 40 and the counter electrode 20, and electrons are “semiconductor layer 4 → metal member 5”. It moves along the route and goes out of the cell, and moves along the route “translucent conductive member 1 → catalyst layer 4 → electrolyte layer 3” and enters the cell. Each cell 9 is connected in series in the inter-cell region 200, and the metal member 5 in the cell 9 on the lowest potential side (rightmost cell in FIG. 1) and the cell 9 on the highest potential side (leftmost cell in FIG. 1). The voltage generated by the dye-sensitized solar cell module 10 is generated between the transparent conductive member 1 in FIG. When the circuit is configured by the conductive wire 8 and the load 7, power is consumed by the load 7.
FIG. 1 exemplifies the structure of a module in which three cells are arranged in series, but the number of cells arranged in series is actually set according to the required electromotive force.

[Metal members]
The dye-sensitized solar cell module of the present invention is characterized by the metal member 5 constituting the photoelectrode 40. Except for the cell on the lowest potential side, the metal member 5 used for each cell 9 has a thin portion 51 and a thick portion 52. These metal members 5 are basically plate-like members, and it can be understood that there are portions having different plate thicknesses in the plate surface. The difference in plate thickness between the thin portion 51 and the thick portion 52 may be about 20 to 100 μm, for example. The metal member 5 in the cell on the lowest potential side does not need to have the thick part 52 except when used as a spacer, and has a plate thickness corresponding to the thin part 51 of another cell in the cell region 200. ing. In this specification, the plate | board thickness part corresponded to the thin part 51 of the metal member 5 which does not have the thick part 52 is also called the thin part 51 for convenience. The photoelectrode 40 of each cell 9 is obtained by forming the semiconductor layer 4 on the surface of the thin portion 51. In the inter-cell region 200, the thick portion 52 functions as a spacer. The surface of the thick part 52 is laminated and contacted with a part of the surface 11 of the translucent conductive member 1 extending from the adjacent cell (including the case where the metal of the catalyst layer 2 is attached to the surface), The space between the plate-like bodies A and B is filled. In FIG. 1, although the dimension in the thickness direction of the module is exaggerated, the thick portion 52 is a plate-like metal body having a thickness in the thickness direction of the module. By laminating, the load applied between the plate-like bodies A and B can be stably borne. That is, the thick part 52 of the metal member 5 has a simple structure and simultaneously bears good conductivity and high strength.

  As the metal of the metal member 5, various metal materials can be applied as long as the material has corrosion resistance to the electrolytic solution used for the electrolyte layer 3. According to the study by the inventors, nickel, titanium, titanium alloy, chromium, aluminum, aluminum alloy, molybdenum, or steel can be used. When these metal materials are used, as will be described later, the formation of the thin portion 51 and the thick portion 52 and the adjacent metal members 5 of the adjacent cells using the method of “masking with a resist film → etching → removing the resist film” are used. It is possible to accurately form the grooves separating the two. The dye-sensitized solar cell module may be mounted on a relatively inexpensive device for personal use, and a metal material having an optimum corrosion resistance level may be selected in consideration of the service life of the device. In the above, examples of titanium and titanium alloys include those having the composition described in Table 2 of JIS H460: 2007. Examples of aluminum and aluminum alloys include those having the composition described in Table 2 of JIS H400: 2006.

  Stainless steel is a metal material that exhibits good corrosion resistance and is cheaper than noble metals and titanium alloys. Stainless steel is a suitable object as the material of the metal member 5 applied to the present invention. Among them, stainless steel having a Cr content of 16.0% by mass or more and a Mo content of 0.3% by mass or more exhibits excellent corrosion resistance with respect to an electrolyte solution of a dye-sensitized solar cell using iodine. Since the initial photoelectric conversion efficiency is maintained high over a long period of time, it is advantageous in constructing a dye-sensitized solar cell module with high durability. Specific stainless steel types include those shown in (A) to (D) above. In particular, the Cr content is more preferably 17.0% by mass or more, and the Mo content is more preferably 0.8% by mass or more.

  When stainless steel is used as the metal member 5, a large number of pits having edge-like boundaries can be formed on the surface of the thin portion 51 by etching. Such a roughened surface has a large surface area and excellent adhesion to the semiconductor layer, which is advantageous in obtaining excellent photoelectric conversion efficiency. A specific roughening method was disclosed in Japanese Patent Application No. 2009-191348 by the present applicant.

[Manufacture of modules]
In the dye-sensitized solar cell module of the present invention, for example, a “counter electrode side structure” based on the plate A and a “photo electrode side structure” based on the plate B are separately manufactured. Then, it can manufacture efficiently by the method of uniting these two members. Hereinafter, the manufacturing method will be exemplified.

[1] Counter electrode side structure manufacturing process FIG. 2 schematically shows a member cross-sectional state in a process for manufacturing the counter electrode side structure. This will be described based on the procedures (a) to (d) in FIG. In addition, this procedure is an illustration and is not necessarily limited to this.

(A) A plate-like body A having a translucent conductive member 1 film on the surface is prepared. The plate-like body A has translucency and insulation, and a glass plate or a translucent plastic sheet (acrylic sheet or the like) can be used. As the translucent conductive member 1, for example, an oxide conductive film such as ITO (indium-tin oxide), FTO (fluorine-doped tin oxide), TO (tin oxide), ZnO (zinc oxide) or the like can be used. The film thickness may be, for example, about 0.1 to 1.0 μm. It is desirable that the translucent conductive member 1 and the plate-like body A are joined so as not to easily peel off.

(B) In the translucent conductive member 1 on the plate A, grooves 61 penetrating the film thickness are formed at a pitch equal to the cell pitch. It is important to cut off the conduction between the translucent conductive members 1 on both sides by the groove 61. As the method, for example, a method of irradiating laser light using a laser torch 60 can be mentioned.

(C) The catalyst layer 2 is formed on the surface of each translucent conductive member 1 divided by the grooves 61. Platinum, nickel, polyaniline, polyethylene dioxythiophene, carbon, etc. can be applied as the catalyst material. In the case of a metal film such as platinum or nickel, it can be formed by sputtering, for example. According to the study by the inventors, it was confirmed that even when an extremely thin platinum film having an average film thickness of about 1 nm was formed, it functions as a battery. The average film thickness of the catalyst layer 2 may be about 1 to 300 nm, for example. In order to achieve both conversion efficiency stability and economic efficiency, it is more effective to control the range of 10 to 200 nm or 20 to 100 nm. It suffices that the catalyst layer 2 exists in a region (cell region 100 in FIG. 1) inside the cell, and the catalyst layer 2 is formed on a partial surface 11 of the region (inter-cell region 200 in FIG. 1) between cells. It is unnecessary. However, when the sputtering method is applied, the metal of the catalytic substance adheres to the portion of the partial surface 11 as long as it is not masked. Even if metal adheres to this portion, there is no particular problem.

(D) By inserting the insulating member 6 </ b> A into the groove 61, conduction between adjacent translucent conductive members 1 across the groove 61 is prevented. As the material of the insulating member 6B, for example, a thermosetting resin can be applied. In that case, the thermosetting resin can be cured in the coalescence process described later. When the thickness of the catalyst layer 2 is set to be thin in (c) above, it is possible to prevent conduction between the translucent conductive members 1 on both sides even if the metal material of the catalyst adheres to the groove 61 portion. Although it is possible, conduction between the translucent conductive members 1 can be completely avoided by inserting the insulating member 6A at a stage prior to the formation of the catalyst layer 2.

The procedure for performing the above (b) to (d) is in no particular order as long as (d) is after (b). For example, the groove formation in (b) may be performed after the formation of the catalyst layer 2 in (c). Further, as described above, the insulating member 6B of (d) may be inserted before the formation of the catalyst layer 2 of (c).
In this manner, the counter electrode side structure 70 is manufactured.

[2] Photoelectrode-side structure manufacturing process FIG. 3 schematically shows a member cross-sectional state in a process for manufacturing the photoelectrode-side structure. This will be described based on the procedures (e) to (k) in FIG. In addition, this procedure is an illustration and is not necessarily limited to this.

(E) A plate-like member in which the metal sheet 50 is bonded to the surface of the plate-like body B is prepared. Although the plate-like body B needs to have insulating properties, since it does not need translucency, various glasses, plastic sheets, and the like can be used. As described above, the metal sheet 50 is applicable to nickel, titanium, titanium alloy, chromium, aluminum, aluminum alloy, molybdenum, or steel sheet material, and is appropriate according to the service life of the device in which the module is mounted. A material having good corrosion resistance is selected. The thickness of the metal sheet 50 may be a thickness corresponding to [the distance between the plate A and the plate B] − [the thickness of the translucent conductive member] when the cell is constructed. It is also possible to prepare a thicker one and adjust the thickness by etching in a later step. As described above, when the metal of the catalytic substance adheres to a part of the surface 11 of the region between the cells of the translucent conductive member 1 (inter-cell region 200 in FIG. 1), the “corresponding thickness” described above. Is a thickness obtained by subtracting the thickness of the deposited catalyst layer. Specifically, for example, a metal sheet 50 of about 40 to 500 μm can be used. It is desirable that the metal sheet 50 and the plate-like body B are bonded with an adhesive or the like so that they are not easily peeled off. The resist film 63 is applied and masked except for the portion that becomes the thin portion 51.

(F) The metal sheet 50 is immersed in the etching solution 64 while being bonded to the plate-like body B, and a portion not masked by the resist film 63 is etched to form a thin portion 51 having a predetermined thickness. . The thickness of the thin portion 51 is, for example, 20 to 50 μm. When the metal sheet 50 is stainless steel, when an acid containing ferric chloride is used as an etchant, the surface of the metal sheet 50 becomes a roughened surface covered with pits having a high anchor effect, and photoelectric conversion is performed. This is advantageous for improving efficiency. After the thin portion 51 reaches a predetermined thickness, it is taken out from the etching solution 64 and the resist film 63 is removed.

(G) A resist film 63 is applied again on the surface of the metal sheet 50 on which the thin portion 51 is formed, except for a portion that becomes a groove for separating at a cell pitch.

(H) It is immersed again in the etching solution 64 to form grooves 65 having a pitch equal to the cell pitch, thereby dividing the metal sheet 50 into individual metal members 5. It is important that the adjacent metal members 5 are separated from each other by the groove 65 and do not have conduction. Each metal member 5 has a thin portion 51, and a portion of the metal member 5 that becomes the inter-cell region 200 in FIG. After the separation by the groove 65 is completed, the resist film 63 is removed from the etching solution 64.

(I) The semiconductor layer 4 is formed on the surface of the thin portion 51 of the metal member 5. The semiconductor layer 4 is a porous layer using semiconductor particles such as TiO ₂ having a large specific surface area. For example, the semiconductor layer 4 can be formed by applying and drying a paste containing TiO ₂ particles. If necessary, it is baked by heating to a temperature of about 400 to 500 ° C. When the paste is applied by a screen printing method, the semiconductor layer 4 can be accurately arranged in a predetermined range. The dry film thickness of the semiconductor layer 4 may be about 10 to 40 μm, for example.

(J) A sensitizing dye such as a ruthenium complex is supported on the semiconductor layer 4. As the method, a method of immersing the semiconductor layer 4 in a solution in which the sensitizing dye is dispersed while being mounted on the plate-like body B can be employed. When the sensitizing dye reaches the pores of the semiconductor layer 4 and then is pulled up from the solution and dried, the semiconductor layer 4 carrying the sensitizing dye is obtained.

(K) By inserting the insulating member 6 </ b> B into the groove 65, conduction between adjacent metal members 5 across the groove 65 is prevented. As the material of the insulating member 6B, for example, a thermosetting resin can be applied. In that case, the thermosetting resin can be cured in the coalescence process described later.

The procedure for performing the above (e) to (k) is as follows. (F) is after (e), (h) is after (g), and (i) is after (f) (h) etching. As long as (j) is after (i) and the insertion of the insulating member in (k) is after the formation of the groove in (h), the order is not specified. For example, the grooves (g) and (h) may be formed prior to the formation of the thin-walled parts (e) and (f), and the insulating member (k) may be inserted into the semiconductor layer (i). You may carry out before formation.
In this way, the photoelectrode side structure 80 is manufactured. Note that the above [1] and [2] are in no particular order.

[3] Combining Step The counter electrode side structure 70 and the photoelectrode side structure 80 obtained as described above are attached to a part of the surface 11 of each of the former translucent conductive members 1 (catalyst metal is attached). And the latter thick portions 52 are brought into contact with each other so as to overlap. At that time, sealing is performed with the electrolyte layer 3 filled between the catalyst layer 2 and the semiconductor layer 4. The electrolyte layer 3 can be composed of, for example, an electrolyte for a dye-sensitized solar cell containing iodine, or a medium in which ions can move by being impregnated with such an electrolyte. . In the case where a thermosetting resin is used as the insulating members 6A and 6B, heating is preferably performed at the sealing stage to cure the resin.
In this way, the dye-sensitized solar cell module 10 having a cross-sectional structure as shown in FIG. 1 is constructed.

  Using various metal materials as the metal member 5 constituting the photoelectrode 40, a dye-sensitized solar cell module in which 5 cells are arranged in series with the structure shown in FIG. 1 was produced, and the open circuit voltage of each module was evaluated. .

[Preparation of counter electrode structure]
As a light-transmitting substrate for the counter electrode, a material (manufactured by Asahi Glass Co., Ltd.) in which an FTO film having a thickness of about 1 μm was formed on a glass substrate was prepared (FIG. 2A). This glass substrate corresponds to the plate-like body A, and the FTO film corresponds to the translucent conductive member 1. By irradiating the translucent conductive member 1 with a YAG laser, grooves 61 penetrating the film thickness at a pitch equal to the cell pitch were formed (FIG. 2B). The catalyst layer 2 was formed by sputter-coating platinum as a catalyst material on the surface of each translucent conductive member 1 separated by the groove 61 (FIG. 2C). The catalytic material platinum is also attached to the partial surface 11 which becomes the inter-cell region 200 of FIG. It has been confirmed that there is no electrical continuity between the transparent conductive members 1 separated from each other. Thereafter, an insulating member 6A made of a thermosetting resin was injected into the groove 61. In this way, a counter electrode side structure 70 was obtained.

[Production of photoelectrode side structure]
As a material of the metal member 5, a sheet material of nickel, titanium, chromium, aluminum, and molybdenum (all of which are manufactured by Nilaco, purity; Three Nine), a cold-rolled steel plate SPCC defined in JIS G3141, and specified in JIS G4305 Cold rolled stainless steel sheet SUS447J1 (30% Cr-2% Mo ferritic steel) was prepared. Chromium has a plate thickness of 2.0 mm, and the others are metal sheets with a plate thickness of 0.1 mm. A PEN (polyethylene naphthalate) film (made by Teijin DuPont Films; Teonex) with a thickness of about 0.1 mm is fused to one side of each metal sheet using a thermoplastic resin film (Mitsui DuPont Chemicals; Surlyn). I let you. The PEN film and the fusion layer correspond to the plate-like body B in FIG.

A resist film (manufactured by Tokyo Ohka Kogyo Co., Ltd .; EPPR) 63 is applied to the surface of the metal sheet on the plate-like body B at an equal interval on a 2 mm wide portion that becomes the inter-cell region 200 using a photoresist device Masking was performed to expose a portion having a width of 10 mm to be the cell region 100 (FIG. 3E). This was immersed in an etching solution 64 of each metal to dissolve the metal in the exposed portion to a depth of 50 μm, thereby forming a thin portion 51 (FIG. 3F). The thickness of the thin portion 51 is 50 μm. Etching solution 64 is nitric acid for nickel, hydrofluoric acid for titanium, ferric chloride / hydrochloric acid mixture for chromium, aqueous sodium hydroxide solution for aluminum, nitric acid / sulfuric acid mixture for molybdenum, cold-rolled steel plate and A ferric chloride / hydrochloric acid mixture was used for the stainless steel plate. Next, after removing the resist film 63, a part with a width of 1 mm was left in a part of the thick part 52, and the other part was masked again with the resist film (FIG. 3G). This was again immersed in the etching solution 64, and the metal in the portion where the resist film was not applied was completely dissolved to form a groove 65 having a width of 1 mm (FIG. 3 (h)). As a result, the metal sheets were separated at the cell pitch and separated into adjacent metal members 5 that were not conductive. After removing the resist film 63, a TiO ₂ paste (manufactured by Solaronix; Ti-Nanoxide D / DP) is applied to the surface of the thin portion 51 of each metal member 5 by screen printing, and baked at 450 ° C. 4 was formed (FIG. 3 (i)). The average dry film thickness of the semiconductor layer 4 is about 10 μm. A ruthenium complex dye (manufactured by Solaronix; Ruthenium 535-bisTBA) was used as a sensitizing dye, and this was dispersed in a mixed solvent of acetonitrile and tert-butanol to obtain a dye solution 62. The semiconductor layer 4 was immersed in the dye solution 62 together with the plate-like body B to obtain the semiconductor layer 4 carrying the sensitizing dye (FIG. 3 (j)). Thereafter, an insulating member 6B made of a thermosetting resin was injected into the groove 65. Thus, the photoelectrode side structure 80 was obtained.

[Production of dye-sensitized solar cell module (merging process)]
The counter electrode side structure 70 and the photoelectrode side structure 80 obtained above were combined so that each of the former partial regions 11 and each of the latter thick portions 52 were in contact with each other and overlapped. At that time, the thermosetting resin of the insulating members 6A and 6B was cured by heating with a hot press machine. Thereafter, an electrolytic solution 3 containing iodine (manufactured by Pexel Technologies; PECE-K01) is injected from an electrolytic solution injection port previously provided in the counter electrode side structure 70, and the liquid is injected into the porous layer of the semiconductor layer 4. It filled between the counter electrode 20 and the photoelectrode 40 so that it might be impregnated. Sealed in this state, a dye-sensitized solar cell module composed of 5 cells of the type shown in FIG. 1 was constructed. Here, a metal (platinum) of a catalytic substance is interposed between the translucent conductive member 1 and the thick portion 52 of the metal member 5.

[Measurement of open circuit voltage V _OC ]
While irradiating pseudo solar light of AM 1.5, 100 mW / cm ² from the surface of the prepared dye-sensitized solar cell module on the plate A side using a solar simulator (Yamashita Denso Co., Ltd .; YSS-100). The open circuit voltage V _OC (V) of the module was measured with a source meter (manufactured by KEYTHLEY; Model 2400). The results are shown in Table 1.

  Since the open voltage of the single cell is 0.74V, the open voltage of each module in which 5 cells are connected in series is the sum of the open voltage of the single cells, and it is confirmed that the single cells are well connected in series. It was done.

  A cold-rolled annealed steel plate (2D finish) having a thickness of 0.1 mm made of each stainless steel type shown in Table 2 was produced by a general stainless steel plate production process, and this was used as a test material. In Table 2, in the structure column, “α” means ferrite and “γ” means austenite. The hyphen “-” in the table means that it is below the measurement limit by a normal analysis method in the steelmaking field.

Using these various stainless steel plates as the metal member 5 of the photoelectrode 40, a dye-sensitized solar cell module consisting of 5 cells was produced in the same manner as in Example 1. The short circuit current J _SC (mA / cm ² ) and the open circuit voltage V _OC (V) were measured with the source meter while irradiating the artificial sunlight in the same manner as in Example 1 for each module. Thereafter, each module was allowed to stand in a constant temperature bath at 85 ° C. for 100 hours, and then the short circuit current J _SC and the open circuit voltage V _OC were measured in the same manner. The results are shown in Table 3.

As can be seen from Table 3, the short circuit current J _SC and the good open circuit voltage V _OC were all shown immediately after the module was manufactured. After leaving at 85 ° C. for 100 hours, the short circuit current J _SC is not obtained in modules (No. 1 to 3, 21, and 22) in which the stainless steel type having no Mo added or Mo content of less than 0.3% by mass is used for the metal member 5. In addition, a decrease in the open circuit voltage V _OC was observed. This is considered to be mainly due to a decrease in conductivity due to the progress of corrosion of stainless steel. However, a low-cost module using such a stainless steel type can be useful for use in an inexpensive device with a relatively short service life.

  On the other hand, in modules (Nos. 4 to 9 and 23) using a stainless steel type containing Cr: 16.0% by mass or more and Mo: 0.30% by mass or more, even after being left at 85 ° C. for 100 hours, It was confirmed that the performance was maintained and it had high reliability.

A Insulating and translucent plate-like body B Insulating plate-like body 1 Translucent conductive member 2 Catalyst layer 3 Electrolyte layer 4 Semiconductor layer 5 Metal member 6A, 6B Insulating member 7 Load 8 Conductor 9 Dye-sensitized type Solar cell 10 Dye-sensitized solar cell module 11 Partial surface of translucent conductive member 20 Counter electrode 40 Photoelectrode 50 Metal sheet 51 Thin part 52 Thick part 60 Laser torch 61, 65 Groove 62 Dye solution 63 Resist film
64 Etching solution 70 Counter electrode side structure 80 Photo electrode side structure 100 Cell region 200 Inter-cell region

Claims (8)

A module in which a plurality of dye-sensitized solar cells connected in series are incorporated between the opposing insulating and translucent plate A and insulating plate B,
Each cell has a translucent conductive member, a catalyst layer, an electrolyte layer, a semiconductor layer, and a metal member from the plate A side to the plate B side, and the translucent conductive member and the catalyst layer The counter electrode is configured, the photoelectrode is configured by the semiconductor layer and the metal member,
Between adjacent cells, a part of the surface of the translucent conductive member constituting the counter electrode of one cell (including the case where the metal of the catalyst substance is attached) and the photoelectrode of the other cell The thin-walled portion and the thick-walled surface of the metal member having the thick-walled portion are stacked and brought into contact with each other to ensure serial continuity between the cells, and the thick-walled portion of the metal member is a spacer. As a gap between the photoelectrode and the counter electrode is secured,
A dye-sensitized solar cell module in which photoelectrodes and counter electrodes of adjacent cells are insulated from each other by an insulating member.   The metal member is formed by applying a technique of “masking with a resist film → etching → removing a resist film” on a metal sheet supported on the surface of the plate-like body B. Item 2. The dye-sensitized solar cell module according to Item 1.   The dye-sensitized solar cell module according to claim 1 or 2, wherein the metal member is derived from a sheet material of nickel, titanium, titanium alloy, chromium, aluminum, aluminum alloy, molybdenum, or steel.   The metal member belongs to a ferritic steel type defined in JIS G4305: 2005, and has a Cr content of 16.0 to 32.0 mass% and a Mo content of 0.3 to 3.0 mass%. The dye-sensitized solar cell module according to claim 1 or 2, comprising a certain stainless steel.   The metal member belongs to the austenitic steel grade specified in JIS G4305: 2005, and the Cr content is in the range of 16.0 to 32.0 mass% and the Mo content is in the range of 0.3 to 7.0 mass%. The dye-sensitized solar cell module according to claim 1 or 2, comprising a certain stainless steel.   The metal member is, by mass%, C: 0.0001 to 0.15%, Si: 0.001 to 1.2%, Mn: 0.001 to 1.2%, P: 0 to 0.04%, S: 0 to 0.03%, Ni: 0 to 0.6%, Cr: 16.0 to 35.0%, Mo: 0.3 to 3.0%, Cu: 0 to 1.0%, Nb : 0 to 1.0%, Ti: 0 to 1.0%, Al: 0 to 0.2%, N: 0 to 0.025% or less, B: 0 to 0.01%, balance Fe and inevitable The dye-sensitized solar cell module according to claim 1 or 2, wherein the dye-sensitized solar cell module is made of ferritic stainless steel made of impurities.   The metal member is C: 0.0001 to 0.15% by mass, Si: 0.001 to 4.0%, Mn: 0.001 to 2.5%, P: 0 to 0.045%, S: 0 to 0.03%, Ni: 6.0 to 28.0%, Cr: 16.0 to 35.0%, Mo: 0.3 to 7.0%, Cu: 0 to 3.5% Nb: 0 to 1.0%, Ti: 0 to 1.0%, Al: 0 to 0.1%, N: 0 to 0.3%, B: 0 to 0.01%, balance Fe and inevitable The dye-sensitized solar cell module according to claim 1 or 2, wherein the dye-sensitized solar cell module is made of an austenitic stainless steel made of natural impurities. When manufacturing a module in which a plurality of dye-sensitized solar cells connected in series are incorporated between the opposing insulating and translucent plate A and insulating plate B. ,
[1] counter electrode side structure manufacturing process;
A plate-like body A having a translucent conductive member film on the surface is prepared,
Separating the translucent conductive members on both sides across the groove by forming a groove penetrating the film thickness in the translucent conductive member at a pitch equal to the pitch of the cells;
Forming a catalyst layer on the surface portion of the translucent conductive member located in the region that is inside the cell;
Inserting an insulating member into the groove to insulate adjacent translucent conductive members;
Obtaining a counter electrode side structure by a procedure comprising:
[2] Photoelectrode side structure manufacturing process;
When a cell is constructed, a metal sheet having a thickness equal to or greater than [the distance between the plate A and the plate B] − [thickness of the translucent conductive member] is bonded to the surface of the plate B. Prepare something,
By the method of “masking with resist film → etching → resist film removal”, the surface portion of the metal sheet located in the area between adjacent cells is left as a thick part, and the metal sheet located in the area inside the cell is Etching the surface part into a thin part,
The step of separating the metal sheet by forming grooves having a pitch equal to the cell pitch by the method of “masking with resist film → etching → resist film removal” and dividing into individual metal members,
Forming a semiconductor layer on the thin portion;
Carrying a sensitizing dye on the semiconductor layer;
Inserting an insulating member into the groove portion to insulate adjacent metal members from each other;
Obtaining a photoelectrode-side structure by a procedure comprising:
[3] coalescence process;
The counter electrode-side structure and the photoelectrode-side structure are divided into a part of the surface of each of the former translucent conductive members (including the case where a catalyst metal is attached) and the latter thick wall. A step of sealing in a state in which the electrolyte layers are filled between the semiconductor layer and the catalyst layer, by combining the parts so that the parts are in contact with each other and overlapping
The manufacturing method of the dye-sensitized solar cell module in any one of Claims 1-7 which have these.