Method for producing perovskite solar cell, and perovskite solar cell

Abstract

In order to provide a method for producing a perovskite solar cell that can be used even in an environment in which salt damage is predicted, this method for producing a perovskite solar cell includes a step for forming a coating layer by applying, on a perovskite sheet formed of a plurality of layers including a perovskite crystal structure, an adsorption material having a layered double hydroxide represented by chemical formula: M2+ 1-xM3+ x(OH)2(NO3 -)x / n·mH2O (where M2+ represents a divalent metal, M3+ represents a trivalent metal, and n represents a natural number).

Description

Method for manufacturing perovskite solar cell and perovskite solar cell

[0001] The present invention relates to a method for manufacturing a perovskite solar cell and a perovskite solar cell.

[0002] In recent years, perovskite solar cells using organic materials have been researched as solar cells with high photoelectric conversion efficiency. A basic perovskite solar cell comprises a substrate and a first electrode (positive electrode), a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode (negative electrode) stacked in this order. It has also been proposed to inexpensively manufacture perovskite solar cells using roll-to-roll (R2R) manufacturing (see Patent Document 1, etc.). A demonstration experiment has also been proposed to install perovskite solar cells in port facilities susceptible to salt damage and investigate the durability of the perovskite solar cells.

[0003] Special Publication No. 2022-534602

[0004] However, no specific proposals have been made on how to improve the durability of perovskite solar cells in environments where salt damage is expected.

[0005] Therefore, an object of the present invention is to provide a method for manufacturing a perovskite solar cell and a perovskite solar cell that can be used even in environments where salt damage is expected.

[0006] The method for producing a perovskite solar cell according to claim 1 comprises adding a compound represented by the chemical formula M to a perovskite sheet formed from a plurality of layers including a perovskite crystal structure. 2+ 1-x M 3+ x (OH)2(NO3 - ) x / n Layered double hydroxide (M 2+ is a divalent metal, M 3+ The perovskite solar cell according to claim 7 includes a step of applying an adsorbent having a perovskite-type crystal structure (wherein n represents a trivalent metal and n is a natural number) to form a coating layer. 2+1-x M 3+ x (OH)2(NO3 - ) x / n Layered double hydroxide (M 2+ is a divalent metal, M 3+ represents a trivalent metal, and n is a natural number.

[0007] According to the method for producing a perovskite solar cell of claim 1, 2+ 1-x M 3+ x (OH)2(NO3 - ) x / n Layered double hydroxide (M 2+ is a divalent metal, M 3+ represents a trivalent metal, and n is a natural number) is converted to chloride ions (Cl - According to the seventh aspect of the present invention, the perovskite solar cell has a chemical formula of M 2+ 1-x M 3+ x (OH)2(NO3 - ) x / n Layered double hydroxide (M 2+ is a divalent metal, M 3+ represents a trivalent metal, and n is a natural number) is converted to chloride ions (Cl - ), making it possible to use perovskite solar cells even in environments where salt damage is expected.

[0008] FIG. 2 is a perspective view showing a state in which a protective net equipped with perovskite solar cells has been installed on temporary scaffolding. FIG. 3 is a perspective view showing a protective net equipped with perovskite solar cells. FIG. 4 is a cross-sectional view taken along arrows A-A in FIG. 2. FIG. 5 is a schematic diagram showing a manufacturing line for protective nets equipped with perovskite solar cells according to a first embodiment. FIG. 6 is a block diagram of a manufacturing line 50. FIG. 7 is a schematic diagram showing a manufacturing line for protective nets equipped with perovskite solar cells according to a second embodiment.

[0009] First Embodiment Hereinafter, a first embodiment will be described in detail with reference to FIGS. 1 to 5. In this first embodiment, chloride ions (Cl - The present invention relates to a perovskite solar cell 10 having a coating layer 30 (described in detail below) that adsorbs a cellulose acylate (C1) and a method for manufacturing the same. In the first embodiment, the following description will be given taking as an example a protective net 20 that includes perovskite solar cells 10 and that protects a building under construction near a port.

[0010] Figure 1 is a perspective view showing a state in which a protective net 20 equipped with perovskite solar cells 10 (see Figure 2) is installed on temporary scaffolding 1. In Figure 1, the vertical direction is the Z-axis direction, the short side direction of the temporary scaffolding 1 is the Y-axis direction, and the direction perpendicular to the Y-axis direction in a horizontal plane is the X-axis direction.

[0011] The temporary scaffolding 1 is made by assembling a large number of single pipes (tubular members) 2 using various types of fastening fittings (joints) 3 and installing them on the ground via base fittings 4. Scaffolding boards 5 and ladders and stairs (not shown) are installed on the temporary scaffolding 1, and workers perform various tasks related to the building (repairs, painting, construction, etc.) while moving on the scaffolding boards 5, etc. Note that the temporary scaffolding 1 may also use bitie scaffolding instead of the single pipes 2.

[0012] As a safety measure for nearby pedestrians, a protective net 20 equipped with perovskite solar cells 10 is provided on the -Y side (outside) of the temporary scaffolding 1 as a site sheet to prevent tools and other objects from falling and as a protective net. The perovskite solar cells 10 will be described later.

[0013] The protective net 20 is tied to the single pipes 2 of the temporary scaffolding 1 via binding members 6 and is suspended outside the temporary scaffolding 1. The lower end or other parts of the protective net 20 may be fixed to part of the temporary scaffolding 1 via binding members 6.

[0014] Figure 2 is a perspective view showing a protective net 20 equipped with perovskite solar cells 10. As shown in Figure 2, the protective net 20 has perovskite solar cells 10 joined in the form of strips along the X-axis direction to the surface of a mesh 16, which is the base material of the protective net 20. If perovskite solar cells 10 were joined to the entire surface of the mesh 16, the breathability that is one of the functions of the protective net 20 would be lost. For this reason, in the first embodiment, the perovskite solar cells 10 are joined only partially to the mesh 16. When the protective net 20 is provided on the temporary scaffolding 1, the perovskite solar cells 10 may be provided along the X-axis direction or the Z-axis direction.

[0015] The mesh 16 has multiple meshes and is made of a resin material (e.g., polyester) that is resistant to rain, heat, and the like. To minimize the effects of wind, the mesh 16 preferably has a porosity of 10% to 55%, or in other words, a solidity of 45% to 90%. Furthermore, the mesh 16 can have a mesh spacing of 0.5 mm to 5 mm, more preferably a mesh spacing (grid spacing) of 1 mm to 3 mm, to prevent foreign matter from passing through. Note that minute foreign matter passing through a mesh spacing of 0.5 mm or 1 mm is virtually void of any problem.

[0016] In the first embodiment, the porosity of the mesh 16 may be set according to the area of ​​the mesh 16 covered by the perovskite solar cells 10. For example, suppose that the porosity of a conventional protective net not provided with perovskite solar cells 10 is 20%. Here, if the perovskite solar cells 10 cover 50% of the area of ​​the mesh 16, then by using a mesh 16 with a porosity of 35% to 45%, preferably 40%, it is possible to ensure breathability of the protective net 20 as a whole.

[0017] Furthermore, although details will be described later, the mesh 16 is coated with a thermally conductive agent for conducting heat from the perovskite solar cell 10 to the mesh 16, forming a thermally conductive portion 17 (see Figure 3). Since the power generation efficiency of the perovskite solar cell 10 decreases when the temperature becomes too high, the heat from the perovskite solar cell 10 is transferred to the mesh 16 side, thereby preventing a decrease in the power generation efficiency of the perovskite solar cell 10.

[0018] FIG. 3 is a cross-sectional view taken along the line A-A in FIG. 2 . Note that FIG. 3 illustrates the configuration of the perovskite solar cell 10 in an easy-to-understand manner, and therefore differs from the actual dimensions. As shown in FIG. 3 , the perovskite solar cell 10 includes a first electrode 11 (positive electrode in this first embodiment), a hole transport layer 12, a perovskite layer 13, an electron transport layer 14, a second electrode 15 (negative electrode in this first embodiment), and a coating layer 30 stacked in this order on a mesh 16, which is a base material, via a thermal conductive portion 17. Note that it is preferable to provide a transparent protective layer on the surface of the second electrode 15, and it is preferable to perform a water-repellent treatment on this protective layer and then form the coating layer 30.

[0019] If the proportion of the area of ​​the perovskite solar cell 10 in the area of ​​the mesh 16 increases, the amount of power generated by the perovskite solar cell 10 will increase, but the breathability of the mesh 16 will decrease, and there is a risk that the breathability required of the protective net 20 will no longer be met.

[0020] Therefore, in this first embodiment, the ratio of the area of ​​the perovskite solar cells 10 to the area of ​​the mesh 16 is set to 15% to 75%, preferably 25% to 65%, and more preferably 35% to 50%. The ratio of the area of ​​the perovskite solar cells 10 to the area of ​​the mesh 16 may be determined based on the power required for construction of the building protected by the protective net 20. Because the perovskite solar cells 10 generate electricity regardless of the position of the sun and even on cloudy days, they can be installed on four sides of the building (east, west, south, and north). Furthermore, as the building becomes taller, the temporary scaffolding 1 also becomes taller, and the number of protective nets 20 used and the area of ​​the protective nets 20 also increase. Therefore, a sufficient power generation area for generating electricity using the perovskite solar cells 10 can be secured in proportion to the size of the building.

[0021] Furthermore, because winds are stronger on higher floors than on lower floors, the breathability of the protective net 20 on higher floors needs to be higher than that of the protective net 20 on lower floors. As mentioned above, during construction of lower floors, power is generated by perovskite solar cells 10, and the power generation area is smaller than during construction of higher floors. For this reason, the area of ​​the perovskite solar cells 10 in the protective net 20 for lower floors may be larger than the area of ​​the perovskite solar cells 10 in the protective net 20 for higher floors. Furthermore, the area of ​​the perovskite solar cells 10 in the protective net 20 for middle floors may be smaller than the area of ​​the perovskite solar cells 10 in the protective net 20 for lower floors, but larger than the area of ​​the perovskite solar cells 10 in the protective net 20 for higher floors.

[0022] Furthermore, if there are no high-rise buildings around the port where the building of this first embodiment is to be constructed, the higher floors of the building will be exposed to wind with a higher salt concentration than the lower floors. For this reason, in this first embodiment, the chemical formula of the coating layer 30 of the protection net 20 on the higher floors is M 2+ 1-x M 3+ x (OH)2(NO3 - ) x / nIt is desirable that the content of the layered double hydroxide expressed as mH2O is greater than the content of the layered double hydroxide contained in the coating layer 30 of the protection net 20 on the lower floors. 2+ 1-x M 3+ x (OH)2(NO3 - ) x / n The layered double hydroxide represented by mH2O will be described later.

[0023] Figure 4 is a schematic diagram showing a production line 50 for protective nets 20 equipped with perovskite solar cells 10, and Figure 5 is a block diagram of the production line 50. Below, we will continue to explain the production line 50 for protective nets 20 equipped with perovskite solar cells 10 of the first embodiment using Figures 4 and 5. The production line 50 mainly comprises a thermal conductive agent applicator 54 that applies a thermal conductive agent, an adhesive applicator 55 that applies an adhesive, a coating device 70, a cutting device 60, a memory 61 that stores programs for driving the production line 50, and a control device 62 that has a CPU and controls the entire production line 50.

[0024] The control device 62 rotates a pair of transport rolls 53 using a motor (not shown) to unwind the mesh sheet 52 wound around the mesh roll 51 in the +X-axis direction.

[0025] The transport roll 53 is a cylindrical member that is driven by a motor (not shown) and in the first embodiment, unwinds the mesh sheet 52 wound around the mesh roll 51 in the +X-axis direction.

[0026] The control device 62 applies a thermal conductive agent to the mesh sheet 52 unwound in the +X-axis direction using the thermal conductive agent applicator 54. In the first embodiment, the thermal conductive agent applicator 54 is a device that applies a heat-dissipating grease such as silicone grease. Silicon grease has a thermal conductivity of approximately 3 W / mK to 5 W / mK, and is able to conduct heat from the perovskite solar cell 10 to the mesh 16. In the first embodiment, a carbon paste made by adding carbon particles to a resin may also be used as the thermal conductive agent.

[0027] 4 shows one thermal conductive agent applicator 54, multiple thermal conductive agent applicators 54 may be provided along the direction perpendicular to the paper surface. Furthermore, if the thermal conductive agent applicator 54 is provided with a pressing mechanism and a drive mechanism that drives the pressing mechanism several millimeters to several tens of millimeters along the direction perpendicular to the paper surface, the thermal grease can be applied uniformly to the mesh sheet 52. Furthermore, a pressing roll may be provided downstream of the thermal conductive agent applicator 54 (in the +X-axis direction) to apply the thermal grease uniformly to the mesh sheet 52.

[0028] As mentioned above, the power generation efficiency of the perovskite solar cell 10 decreases when the temperature becomes too high, so in the first embodiment, a thermal conductive agent is applied to the mesh sheet 52 in order to transfer the heat of the perovskite solar cell 10 to the mesh 16, which is the base material.

[0029] The control device 62 causes the adhesive applicator 55 to apply an adhesive to the mesh sheet 52, which has been coated with the thermal conductive agent, in order to bond the mesh sheet 52 to the perovskite solar cell 10. The adhesive applicator 55 applies the adhesive to the upper surface of the mesh sheet 52, for example, by a spray method. As the adhesive, an emulsion adhesive, a pressure-sensitive adhesive, or a hot-melt adhesive can be used as appropriate.

[0030] In the first embodiment, the thermal conductive agent applicator 54 applies the thermal conductive agent to the entire upper surface of the mesh sheet 52, whereas the adhesive applicator 55 applies the adhesive to the portion of the upper surface of the mesh sheet 52 to which the battery sheet 57 is joined. Therefore, the position of the adhesive applicator 55 in the Z-axis direction can be adjusted so that the spray width of the spray nozzle of the adhesive applicator 55 matches the dimension of the battery sheet 57 in the direction perpendicular to the paper surface (the dimension in the Y-axis direction).

[0031] Furthermore, instead of or in addition to adjusting the installation position of adhesive applicator 55, a masking member that prevents adhesive from being applied to mesh sheet 52 may be provided in the space between the upper surface of mesh sheet 52 and adhesive applicator 55. By providing the masking member, it is possible to prevent adhesive from being applied to portions of the upper surface of mesh sheet 52 to which battery sheet 57 is not joined.

[0032] In order to avoid applying adhesive to the upper surface of the mesh sheet 52 before the thermal conductive agent has dried, the production line 50 may ensure a distance in the X-axis direction between the thermal conductive agent application device 54 and the adhesive application device 55, control the conveying speed of the conveying roll 53, or provide a drying device (not shown) between the thermal conductive agent application device 54 and the adhesive application device 55.

[0033] Furthermore, if a heat-dissipating adhesive such as an epoxy adhesive or an acrylic adhesive is used as the thermal conductive agent, either the thermal conductive agent applicator 54 or the adhesive applicator 55 can be omitted, simplifying the production line 50. Epoxy adhesives have a thermal conductivity of 0.1 W / mK to 0.8 W / mK, and recently some have a thermal conductivity of 3 W / mK, allowing them to conduct heat from the perovskite solar cell 10 to the mesh 16. Acrylic adhesives have a thermal conductivity of 1.7 W / mK to 2.2 W / mK, allowing them to conduct heat from the perovskite solar cell 10 to the mesh 16.

[0034] Since the thermal conductivity of water at room temperature is 0.597 W / mK, in this first embodiment, it is preferable to use a thermal conductive agent with a thermal conductivity of 0.4 W / mK or higher. While there is no particular upper limit on the thermal conductivity, considering availability and cost, it is preferable to use a thermal conductive agent with a thermal conductivity of 5.0 W / mK or lower in this first embodiment. If, for example, a heat-dissipating adhesive is used and the heat-conducting agent applicator 54 is omitted, the adhesive applicator 55 can simply apply the heat-dissipating adhesive to the entire upper surface of the mesh sheet 52. This eliminates the need for a masking member when applying the heat-dissipating adhesive using the adhesive applicator 55, thereby simplifying the production line 50.

[0035] The control device 62 rotates the transport roll 58 using a motor (not shown) to unwind the battery sheet 57 wound around the battery roll 56 in the +X-axis direction. While one battery roll 56, one battery sheet 57, and one transport roll 58 are shown in Figure 4, four battery rolls 56, four battery sheets 57, and four transport rolls 58 are provided along the direction perpendicular to the page. This allows four perovskite solar cells 10 to be arranged in a strip shape on the mesh 16, as shown in Figure 2.

[0036] As described above, in the first embodiment, the bonding area of ​​the battery sheet 57 bonded to the mesh sheet 52 differs between the protective net 20 for low floors and the protective net 20 for high floors. Therefore, for example, when manufacturing the protective net 20 for high floors, the number of battery rolls 56, battery sheets 57, and transport rolls 58 can be reduced to three. Alternatively, or in combination with this, the Y-direction dimension of the battery sheet 57 can be made shorter than the Y-direction dimension of the battery sheet 57 of the protective net 20 for low floors. In this way, the configuration of the production line 50 of the first embodiment can be changed and the dimensions of the battery sheet 57 can be changed depending on the specifications of the protective net 20.

[0037] The battery sheet 57 is manufactured by the method described in, for example, Japanese Patent Publication No. 2022-534602 or the method described in the British Swedish オ The battery sheet 57 can be produced by a process such as the R2R process developed at the SPECIFIC Innovation and Knowledge Centre at the University of England, and is wound up into a battery roll 56. The battery sheet 57 is cut using a cutting device 60, which will be described later, to produce the perovskite solar cell 10.

[0038] The coating layer 30 is formed on the second electrode 15, which is one of the functional layers, in order to prevent the battery sheet 57 from being deteriorated by the influence of salt. In the first embodiment, the coating layer 30 has an inner container, and the inner container contains a transparent resin and a compound having the chemical formula M 2+ 1-x M 3+ x(OH)2(NO3 - ) x / n The layered double hydroxide represented by mH2O is contained. A plurality of film forming devices 70 are provided in the direction perpendicular to the paper surface, corresponding to the number of battery rolls 56.

[0039] Here, the coating layer 30 of the first embodiment and the chemical formula contained in this coating layer 30 are M 2+ 1-x M 3+ x (OH)2(NO3 - ) x / n ・We will explain layered double hydroxides represented by mH2O.

[0040] (Coating Layer) The coating agent of the first embodiment contains a resin that functions as a binder and a layered double hydroxide. Alternatively, the coating agent may be prepared by mixing a layered double hydroxide with a paint containing a resin, or by mixing a layered double hydroxide with a paint that does not contain a resin.

[0041] The resin may be a curable liquid resin that can coat the battery sheet 57 and prevent external moisture, chlorine, and the like from coming into contact with the coated surface. Examples of resins that can be used include epoxy resins, acrylic resins, and urethane resins. These resins may be used alone or in combination. The resin may be a one-component resin or a two-component resin.

[0042] (Epoxy Resin) Examples of epoxy resins that can be used include bisphenol A epoxy resins, halogenated bisphenol A epoxy resins, bisphenol F epoxy resins, novolac epoxy resins, and cresol novolac epoxy resins.

[0043] Examples of bisphenol A epoxy resins include condensation polymers of bisphenol A diglycidyl ethers such as bisphenol A diglycidyl ether, bisphenol A polypropylene oxide diglycidyl ether, bisphenol A ethylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol A propylene oxide diglycidyl ether. These epoxy resins can be used alone or in combination of two or more.

[0044] A reactive diluent can also be added to and blended with the epoxy resin. Such a reactive diluent is effective in reducing the viscosity of the composition. Examples of such a reactive diluent include compounds having one epoxy group in the molecule, such as phenyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, styrene oxide, and octylene oxide. The amount of such a reactive diluent can be preferably 45% by weight or less, and more preferably 25% by weight or less, based on the base resin.

[0045] Furthermore, epoxy resins can also be blended with additives that do not contain epoxy groups but can react with curing agent components (such as amine compounds). Examples of such compounds include isocyanates such as hexamethylene diisocyanate and tolylene diisocyanate, as well as α,β-unsaturated carbonyl compounds that undergo a Michael addition reaction with amine compounds, such as acrylic esters and acrylamide derivatives. Acrylic esters are effective in improving low-temperature curing properties, while acrylamide derivatives are effective in improving thixotropy or adhesive properties. Such additives can be blended in amounts of preferably 30% by weight or less, more preferably 20% by weight or less, based on the base resin.

[0046] The epoxy resin may also contain other components such as plasticizers, dyes, organic pigments, inorganic fillers, polymeric compounds, antioxidants, ultraviolet absorbers, coupling agents, and surfactants.

[0047] (Acrylic Resin) Examples of the acrylic resin include polymers of acrylic monomers and copolymers of acrylic monomers with other monomers. Examples of the acrylic monomer include (meth)acrylic acid, C1-10 alkyl (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, and hexyl (meth)acrylate, C3-12 cycloalkyl (meth)acrylate esters such as cyclohexyl (meth)acrylate, aryl (meth)acrylate esters such as phenyl (meth)acrylate, aralkyl (meth)acrylate esters such as benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxyethyl (meth)acrylate, and the like. hydroxy C2-6 alkyl (meth)acrylates such as hydroxypropyl (meth)acrylate; alkylamino-alkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl (meth)acrylate; (meth)acrylamides or derivatives thereof such as (meth)acrylamide, N-methyl(meth)acrylamide, methylol (meth)acrylamide, and alkoxymethyl (meth)acrylamide; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate; and (meth)acrylonitrile.

[0048] Examples of monomers copolymerizable with the acrylic monomer include aromatic vinyl monomers such as styrene, α-methylstyrene, p-t-butylstyrene, and vinyltoluene, fatty acid vinyl ester monomers such as vinyl propionate, esters of unsaturated polycarboxylic acids such as maleic anhydride, maleic acid, fumaric acid, and itaconic acid, or esters of unsaturated polycarboxylic acid derivatives such as dimethyl maleate and diethyl fumarate, N-substituted maleimides such as N-phenylmaleimide, and olefin monomers such as ethylene and propylene. These monomers may be used alone or in combination of two or more.

[0049] (Urethane Resin) As the urethane resin, for example, a urethane prepolymer having a free isocyanate group obtained by reacting a polyol with a polyisocyanate can be used.

[0050] As the polyol, polyether polyol, polyolefin polyol, or the like can be used.

[0051] Suitable examples of polyether polyols include polyalkylene polyols having 2 to 4 hydroxyl groups (active hydrogen groups) in the molecule, which are obtained by addition polymerization of a polyol having 2 to 8 carbon atoms and having two or more, preferably 2 to 6, hydroxyl groups, such as ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanediol, hexanetriol, glycerin, trimethylolpropane, or pentaerythritol, with an alkylene oxide having preferably 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran, in the presence of an alkali catalyst.

[0052] Suitable polyolefin polyols include polydiene polyols having 2 to 4 hydroxyl groups per molecule, which are obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran with diene compounds such as butadiene and isoprene. Suitable polyisocyanates are compounds having two or more, preferably two to three, isocyanate groups per molecule.

[0053] Specific examples of polyisocyanates include isocyanate compounds such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diphenyl diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; biuret polyisocyanate compounds such as Sumidur N (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.); Desmodur IL, HL (trade name, manufactured by Bayer A.G.), and Coronate E.H. (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) and other polyisocyanate compounds having an isocyanate ring; and adduct polyisocyanate compounds such as Sumidur L (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.) and Coronate HL (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) These polyisocyanates can be used alone or as a mixture of two or more.

[0054] (Layered double hydroxide) Layered double hydroxide is a compound having the chemical formula M 2+ 1-x M 3+ x (OH)2(NO3 - ) x / n mH2O, where M 2+ is a divalent metal, M 3+ represents a trivalent metal, and n is a natural number. Also, x is a number in the range of 0<x<1, and generally in the range of 1 / 6<x<1 / 3. m is a number greater than 0. This layered double hydroxide is sometimes called a hydrotalcite-like compound. Divalent metal ions (M 2+ ) for example, Mg 2+ , Fe 2+ , Zn 2+ , Li 2+ , Ni 2+ , Co 2+ , Cu 2+ In addition, trivalent metal ions (M3+ ) is, for example, Al 3+ , Fe 3+ , Cr 3+ , Mn 3+ The divalent metal ions (M 2+ ) and trivalent metal ions (M 3+ ) does not have to be of one type, and may include multiple types.

[0055] Nitrate ions NO3 between the layers of layered double hydroxide - The nitrate ions are exchanged with other anions that have a higher affinity with the layered double hydroxide. The layered double hydroxide containing nitrate ions as in this embodiment is called a nitric acid type layered double hydroxide. The nitric acid type layered double hydroxide is a type of layered double hydroxide that does not contain chloride ions (Cl - ) and instead absorbs nitrate ions NO3 - As a result, chloride ions (Cl ) are released into the battery sheet 57 (particularly the perovskite layer 13). - ) can be prevented from entering, and chloride ions (Cl - ) to suppress deterioration of the battery sheet 57.

[0056] The layered double hydroxide according to this embodiment may contain, for example, a divalent metal ion (M 2+ ) is Mg 2+ and trivalent metal ions (M 3+ ) is Al 3+ Mg 2+ 1-x Al 3+ x (OH)2(NO3 - ) x / n ・mH2O (Mg-Al type) and divalent metal ions (M 2+ ) is Mg 2+ and trivalent metal ions (M 3+ ) is Fe 3+ Mg 2+ 1-x Fe 3+ x (OH)2(NO3 - ) x / n ・mH2O (Mg-Fe type) and divalent metal ions (M 2+ ) is Fe 2+and trivalent metal ions (M 3+ ) is Fe 3+ Fe 2+ 1-x Fe 3+ x (OH)2(NO3 - ) x / n ・mHO (Fe-Fe type). Note that the Mg-Fe type is superior to the Mg-Al type in that it has a high specific gravity, making it easy to separate by sedimentation, and it can reduce raw material costs.

[0057] Furthermore, the layered double hydroxide according to this embodiment preferably has a crystallite size of 20 nm or less, more preferably 10 nm or less. For example, if the crystallite size of the layered double hydroxide is 20 nm or less, the specific surface area can be increased to 20 m. 2 / g or more, and the adsorption performance can be improved.

[0058] The layered double hydroxide is synthesized by mixing an acidic solution containing divalent metal ions and trivalent metal ions with an alkaline solution. The smaller the crystallite size of the layered double hydroxide synthesized here, the larger its specific surface area can be. Therefore, the shorter the aging time after synthesis, the better, and after mixing the acidic solution and the alkaline solution, it is better to neutralize them within at least 120 minutes, preferably within 60 minutes, and more preferably simultaneously with mixing. Details of the method for synthesizing layered double hydroxides are described in JP 2021-195276 A.

[0059] The nitric acid type layered double hydroxide is preferably contained in the resin or paint in a weight ratio of 1 to 10%, preferably 1 to 5%. This is because if the content of the nitric acid type layered double hydroxide is low, chloride ions (Cl - ), and if the content of the nitric acid type layered double hydroxide is high, the manufacturing cost for forming the coating layer 30 increases.

[0060] Furthermore, it is desirable to increase the content of the nitrate type layered double hydroxide when the perovskite solar cell 10 is used on a higher floor compared to when the perovskite solar cell 10 is used on a lower floor. For example, the content of the nitrate type layered double hydroxide may be 1% to less than 3% on the lower floors and 3% to 6% on the higher floors.

[0061] Furthermore, when the perovskite solar cell 10 is used in a heavily salt-damaged region within 200 to 500 meters from the coast, the content of the nitric acid-type layered double hydroxide is desirably higher than when the perovskite solar cell 10 is used in a salt-damaged region within 500 to 2,000 meters from the coast. Thus, the content of the nitric acid-type layered double hydroxide is desirably set in inverse proportion to the distance from the coast. The resin and paint are preferably transparent so as not to block sunlight from reaching the perovskite layer 13 of the perovskite solar cell 10, and for example, resin and paint with a visible light transmittance of 70% or more are preferred. Mixing the nitric acid-type layered double hydroxide into the resin or paint does not affect the visible light transmittance of the resin or paint.

[0062] 4 , the control device 62 bonds the mesh sheet 52 coated with adhesive to the battery sheet 57 transported above the mesh sheet 52 by the transport rolls 58 by pressing them together with a pair of pressure rolls 59. In the first embodiment, four pairs of pressure rolls 59 are provided along the direction perpendicular to the paper surface according to the positions where the battery sheet 57 is pressed, but the number of pairs of pressure rolls 59 is not limited to this.

[0063] The control device 62 cuts the joined mesh sheet 52 and battery sheet 57 to a predetermined length using the cutting device 60. This produces a perovskite solar cell 10 having a coating layer 30 containing the nitrate-type layered double hydroxide formed thereon, and ultimately a protective net 20.

[0064] In the production line 50 of the first embodiment, a mechanism for providing grommets for fastening the binding members 6 may be added, or a mechanism for performing wiring processing for the battery sheet 57 may be added. In addition, in the production line 50 of the first embodiment, a mechanism for providing a human presence sensor for detecting a worker on the temporary scaffolding 1 or a sensor for detecting the environment (temperature, humidity, noise) around the temporary scaffolding 1 may be added.

[0065] In the R2R process, after forming the perovskite layer 13, which is part of the functional layer, the coating layer 30 may be formed on the perovskite layer 13, or the coating layer 30 may be formed on the electron transport layer 14.

[0066] According to the first embodiment, a coating layer 30 containing a nitrate-type layered double hydroxide is formed on part of a perovskite solar cell 10 formed from multiple layers, thereby improving the durability of the perovskite solar cell 10 and enabling the perovskite solar cell 10 to be used even in environments where salt damage is expected. It also makes it possible to construct a solar power generation facility using solar power generation panels other than the perovskite solar cell 10 in salt damage areas or areas prone to severe salt damage. In this case, it is desirable to form a coating layer 30 containing a nitrate-type layered double hydroxide on the mounting frame that supports the solar panel in addition to the solar power generation panel.

[0067] Second Embodiment A second embodiment will be described below with reference to Fig. 6. The same components as those in the first embodiment are denoted by the same reference numerals, and their description will be omitted or simplified. In the second embodiment, the coating layer 30 is made up of multiple layers with a peelable film 72 interposed therebetween.

[0068] Figure 6 is a schematic diagram showing a production line 50 for a protective net 20 equipped with perovskite solar cells 10 according to the second embodiment. The production line 50 of the second embodiment is configured by adding a film roll 71, a film 72, an adhesive applicator 73 that applies a peelable adhesive, a second transport roll 58, and a second coating device 70 to the production line 50 of Figure 4. The production line 50 of the second embodiment also operates under the control of a control device 62.

[0069] The film roll 71 is a cylindrical member that is driven by a motor (not shown), and in this second embodiment, the film 72 wound around the film roll 71 is unwound in the −X-axis direction. In this second embodiment, the number of film rolls 71 is the same as the number of battery rolls 56.

[0070] The film 72 is a sheet that covers the battery sheet 57 on which the coating layer 30 is formed, and is preferably a transparent film having a visible light transmittance of, for example, 70% or more. The film 72 can be made of a cellulose-based resin, a polyolefin-based resin, an acrylic resin, or the like, and the thickness of the film 72 is preferably 10 μm to 50 μm.

[0071] The adhesive applicator 73 applies an adhesive to the joining surface of the film 72 in order to releasably join the battery sheet 57 and the film 72. For this reason, the adhesive strength of the adhesive applicator 73 is weaker than that of the adhesive applicator 55. In the second embodiment, the adhesive applicator 73 preferably applies an acrylic adhesive, a hot melt adhesive, a water-based adhesive, or a silicone adhesive.

[0072] A pair of conveying rolls 58 presses the battery sheet 57 on which the coating layer 30 is formed and the film 72 on which the adhesive is applied to join them together, and conveys the joined battery sheet 57 and film 72 in the −Z-axis direction in FIG. 6 .

[0073] The mesh sheet 52 to which adhesive has been applied by the adhesive applicator 55 and the joined battery sheet 57 and film 72 are pressed and joined by a pair of pressure rolls 59 .

[0074] The coating layer 30 is formed by a coating device 70 provided after the pair of pressure rolls 59 applying a nitric acid type layered double hydroxide mixed with a resin or paint onto the upper surface of the film 72 .

[0075] After the second coating layer 30 is formed, the joined mesh sheet 52, battery sheet 57, and film 72 are cut to a predetermined length by a cutting device 60. In this way, a perovskite solar cell 10 having a plurality of coating layers 30 containing nitrate-type layered double hydroxide formed thereon, and ultimately a protective net 20, are manufactured.

[0076] In the second embodiment, the second coating layer 30 is formed on the peelable film 72, so that, for example, the nitric acid type layered double hydroxide of the coating layer 30 does not react with chloride ions (Cl - When the film 72 can no longer adsorb chloride ions (Cl), the coating layer 30 formed on the battery sheet is exposed by peeling off the film 72. This exposed coating layer 30 adsorbs chloride ions (Cl - ), the durability of the perovskite solar cell 10 is improved and the service life can be extended even in environments where salt damage is expected.

[0077] In the second embodiment, three or more coating layers 30 may be formed. In addition, in order to make the film 72 easier to turn over, it is preferable to form a tab on the film 72 for turning over the film 72.

[0078] In the first and second embodiments described above, the adsorbent is applied to the upper surface of the battery sheet 57 by the film forming device 70. However, it is also possible to provide a peelable film 72 on the upper surface of the battery sheet 57, and apply the adsorbent to this film 72 by the film forming device 70.

[0079] The above-described embodiment is a preferred example of the present invention. However, the present invention is not limited to this, and various modifications are possible within the scope of the present invention. For example, the coating layer 30 of this embodiment may be used for buildings in salt-damaged areas, rather than in ports. Furthermore, if the coating layer 30 of this embodiment is used for solar panels or their mountings, solar panels can be installed in ports and salt-damaged areas. In this case, the amount of nitrate-type layered double hydroxide to be added can be determined depending on the distance from the sea and the presence or absence of surrounding buildings.

[0080] REFERENCE SIGNS LIST 10 Perovskite solar cell 16 Mesh 17 Heat conductive portion 18 Pattern portion 19 Wiring portion 20 Protective net 30 Coating layer 50 Production line 52 Mesh sheet 54 Heat conductive agent application device 55 Adhesive application device 57 Battery sheet 62 Control device 70 Coating formation device 72 Film 73 Adhesive application device

Claims

1. A perovskite sheet formed from multiple layers containing a perovskite crystal structure has the chemical formula M 2+ 1-x M 3+ x (OH)2(NO3 - ) x / n Layered double hydroxide (M 2+ is a divalent metal, M 3+ represents a trivalent metal, and n is a natural number) to form a coating layer.

2. The method for producing a perovskite solar cell according to claim 1, wherein the adsorbent is a mixture of the layered double hydroxide and a resin or paint.

3. The method for producing a perovskite solar cell according to claim 2, wherein the adsorbent is transparent.

4. The method for producing a perovskite solar cell according to claim 2, wherein the layered double hydroxide is contained in an amount of 1% to 10% by weight relative to the resin or paint.

5. A method for producing a perovskite solar cell according to claim 1, comprising the step of forming a plurality of said coating layers.

6. A method for manufacturing a perovskite solar cell according to any one of claims 1 to 5, wherein the coating layer is formed into a peelable film.

7. A perovskite sheet formed of a plurality of layers including a perovskite crystal structure; 2+ 1-x M 3+ x (OH)2(NO3 - ) x / n Layered double hydroxide (M 2+ is a divalent metal, M 3+ represents a trivalent metal, and n is a natural number.

8. The perovskite solar cell according to claim 7, wherein the coating layer is transparent.

9. The perovskite solar cell according to claim 7, wherein the layered double hydroxide is mixed into a resin or paint.

10. The perovskite solar cell according to claim 9, wherein the layered double hydroxide is contained in an amount of 1% to 10% by weight of the resin or paint.

11. The perovskite solar cell according to claim 7, wherein a plurality of said coating layers are formed.

12. The perovskite solar cell according to any one of claims 7 to 11, wherein the coating layer is formed into a peelable film.

Images