WO2017006839A1 - Perovskite solar cell - Google Patents

Abstract

The purpose of the present invention is to solve problems such as the optical degradation of sensitizing dye which is a concern of a dye-sensitized solar cell, the volatilization of electrolyte solution, low durability due to leakage, and high manufacturing cost which is a concern in silicon solar cells and compound-semiconductor solar cells. Provided is a perovskite solar cell in which a negative electrode, a hole block layer, a perovskite layer, a hole transport layer, and a positive electrode are sequentially formed. The perovskite solar cell is characterized in that: the negative electrode comprises at least one type of material selected from a group including metal titanium, titanium alloy, metal titanium subjected to surface treatment, and titanium alloy subjected to surface treatment; and the positive electrode is irradiated with light.

Description

Perovskite solar cell

The present invention relates to a method for manufacturing a photoelectric conversion element using a metal titanium material and using an organic / inorganic perovskite compound as a photoelectric conversion layer, and a perovskite solar cell manufactured by the manufacturing method.

Photoelectric conversion elements are widely used in single crystal silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, solar cells using non-silicon compound semiconductors, and the like.

However, these solar cells need to be manufactured under a high vacuum, and there is a problem that the manufacturing cost becomes high.

Organic solar cells that can be manufactured at low cost are expected as next-generation solar cells that replace these solar cells. As one of the organic solar cells, a dye-sensitized solar cell has been proposed.

The dye-sensitized solar cell has (i) a layer of titanium dioxide nanoparticles formed on a conductive substrate, a photoelectrode on which the sensitizing dye is adsorbed, and (ii) a conductive substrate. And (iii) a structure in which an electrolyte solution is injected between the substrates and the electrolyte solution is sealed. The dye-sensitized solar cell has a simple manufacturing process and can be manufactured at low cost.

However, in the conventional dye-sensitized solar cell, since a liquid such as an organic solvent is used as an electrolytic solution, it is required to improve durability. Further, the dye-sensitized solar cell is also required to be improved in that the conversion efficiency is lower than that of a silicon solar cell or the like.

In order to solve the above problems, Patent Document 1 discloses a new solar cell using a glass plate or plastics material coated with a transparent conductive film as a negative electrode substrate, and using organic or inorganic perovskite crystals as a sensitizer. Proposed. This is called a perovskite solar cell.

Perovskite solar cells have higher conversion efficiency than dye-sensitized solar cells, higher utilization efficiency of visible light than silicon solar cells, thin-film solar cells that can be made flexible, There is an advantage such as low cost, and it is attracting attention.

However, in the conventional perovskite solar cell, since the electrical resistance of the transparent conductive film is large, there is a demand for improvement in that the photoelectric conversion efficiency is lowered when the area is increased.

JP 2014-72327 A

The present invention is concerned with photosensitizing dyes that are concerned about dye-sensitized solar cells, that the electrolyte solution is volatilized, that durability due to leakage is low, silicon-based solar cells, and compound semiconductor-based solar cells. It aims at solving the problems such as the high manufacturing cost.

In the present invention, titanium metal is used for the negative electrode substrate, and an organic / inorganic perovskite compound is used for the photoelectric conversion layer.

The inventors of the present invention have intensively studied to solve the problems of the prior art and found that a perovskite solar cell having a specific structure can achieve the above object.

That is, the present invention is the following perovskite solar cell.

Item 1.
A perovskite solar cell in which a negative electrode, a hole blocking layer, a perovskite layer, a hole transport layer and a positive electrode are formed in order,
The negative electrode is composed of at least one material selected from the group consisting of titanium metal, titanium alloy, surface-treated metal titanium, and surface-treated titanium alloy,
A perovskite solar cell, which is irradiated with light from the positive electrode side.

Item 2.
2. The perovskite solar cell according to item 1, wherein a mesoporous metal oxide layer is formed between the hole blocking layer and the perovskite layer.

Item 3.
The hole blocking layer has a thickness of 1 to 500 nm, and the hole blocking layer is composed of at least one material selected from the group consisting of an n-type semiconductor, an electron transporting conductive polymer, and an electron transporting inorganic salt. Item 3. The perovskite solar cell according to Item 1 or 2, wherein

Item 4.
The hole blocking layer is made of at least one material selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, aluminum oxide, cesium carbonate, fullerene derivatives, graphene derivatives, and perylene derivatives. 4. The perovskite solar cell according to any one of Items 1 to 3.

Item 5.
Item 5. The perovskite solar cell according to Item 4, wherein the titanium oxide is titanium oxide prepared by surface-treating metal titanium or a titanium alloy.

Item 6.
Item 6. The perovskite solar cell according to Item 5, wherein the surface treatment is at least one surface treatment selected from the group consisting of atmospheric oxidation treatment and anodization treatment of titanium metal or a titanium alloy.

Item 7.
Item 7. The perovskite type according to any one of Items 4 to 6, wherein the titanium oxide is titanium oxide prepared by hydrolysis and heat treatment of a titanium alkoxide compound that is a titanium oxide precursor. Solar cell.

Item 8.
Item 8. The perovskite solar cell according to any one of Items 4 to 7, wherein the titanium oxide is titanium oxide prepared by further performing a surface treatment using a titanium tetrachloride aqueous solution.

Item 9.
The mesoporous metal oxide layer has a thickness of 5 to 5,000 nm, and the mesoporous metal oxide layer is composed of at least one material selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, and niobium oxide. The perovskite solar cell according to Item 2, wherein the perovskite solar cell is characterized.

Item 10.
The perovskite layer has a thickness of 5 to 10,000 nm, and the perovskite layer is RNH ₃ PbX ₃ , R (NH ₂ ) ₂ PbX ₃ , RNH ₃ SnX ₃ and R (NH ₂ ) ₂ SnX ₃ (R is an alkyl group) Wherein X is at least one kind of material selected from the group consisting of Cl, Br and I selected from the group consisting of Cl, Br and I. The perovskite solar cell according to any one of the above.

Item 11.
The RNH ₃ PbX ₃ (R is an alkyl group, X is at least one halogen selected from the group consisting of Cl, Br and I) is CH ₃ NH ₃ PbI ₃ , Item 11. A perovskite solar cell according to Item 10.

Item 12.
RNH ₃ PbX ₃ (R is an alkyl group, X is at least one halogen selected from the group consisting of Cl, Br and I), but CH ₃ NH ₃ PbI _3-n Cl _n (n is 0 to 0) 3. The method for producing a perovskite solar cell according to Item 10, wherein:

Item 13.
Item 13. The perovskite solar cell according to any one of Items 1 to 12, wherein the hole transport layer has a thickness of 1 to 5,000 nm, and the hole transport layer is made of a p-type semiconductor. battery.

Item 14.
The hole transport layer is composed of at least one material selected from the group consisting of a spiro-OMeTAD derivative, molybdenum oxide, vanadium oxide, copper iodide, copper thiocyanate, polythiophene, and polytriphenylamine. 14. The perovskite solar cell according to any one of Items 1 to 13.

Item 15.
The hole transport layer is a hole transport layer prepared by doping with at least one material selected from the group consisting of oxygen, lithium compounds, cobalt compounds, vanadium compounds, and molybdenum compounds. 15. The perovskite solar cell according to any one of Items 1 to 14,

Item 16.
The positive electrode is selected from the group consisting of gold, silver, aluminum, tin-doped indium oxide, fluorine-doped tin oxide, tin oxide, indium zinc oxide, zinc oxide, aluminum-doped zinc, PEDOT: PSS, graphene, polyaniline, and carbon nanotubes Item 16. The perovskite solar cell according to any one of Items 1 to 15, wherein the positive electrode has a thin film shape, a nanowire shape, or a grid shape.

Item 17.
Item 18. The perovskite solar cell according to any one of Items 1 to 16, wherein a negative electrode, a hole blocking layer, a perovskite layer, a hole transport layer, a positive electrode, and an antireflection film are sequentially formed. Perovskite solar cell.

Item 18.
Item 18. The perovskite solar cell according to Item 17, wherein the antireflection film is made of at least one material selected from the group consisting of molybdenum oxide, magnesium fluoride, and lithium fluoride.

Item 19.
Item 19. The perovskite solar cell according to any one of Items 1 to 18, wherein the condensing device is disposed on the positive electrode side.

Item 20.
Item 20. The perovskite solar cell according to any one of Items 1 to 19, wherein a power storage device is disposed.

The perovskite solar cell of the present invention can exhibit high photoelectric conversion characteristics even in a large-area solar cell by using titanium or a titanium alloy as a negative electrode substrate.

It is the schematic (sectional drawing) which shows one Embodiment of the perovskite type solar cell of this invention. Specifically, a negative electrode, a hole blocking layer, a mesoporous metal oxide layer, a perovskite layer, a hole transport layer, and a positive electrode are formed in order, and a schematic diagram showing that light irradiation is performed from the positive electrode side (cross-sectional view) It is.

The present invention will be described in detail below.

Perovskite solar cell The perovskite solar cell of the present invention is composed of the following members.

In the perovskite solar cell of the present invention, a negative electrode, a hole blocking layer, a perovskite layer, a hole transport layer, and a positive electrode are formed in this order, and the negative electrode is made of metal titanium, titanium alloy, and surface-treated metal titanium. And at least one material selected from the group consisting of surface-treated titanium alloys, and light irradiation is performed from the positive electrode side.

In the present specification, a material selected from the group consisting of titanium metal, titanium alloy, surface-treated metal titanium, and surface-treated titanium alloy may be simply referred to as titanium material.

(1) Negative electrode The negative electrode is composed of at least one material selected from the group consisting of titanium metal, titanium alloy, surface-treated metal titanium, and surface-treated titanium alloy. Metal titanium materials such as metal titanium and titanium alloys, and materials obtained by surface treatment of these metal titanium materials can be used.

When titanium alloy material is used, the type is not particularly limited. As the titanium alloy, Ti-6Al-4V, Ti-4.5Al-3V-2Fe-2Mo, Ti-0.5Pd and the like are preferable.

As the titanium material, a material obtained by mirror-treating metal titanium or titanium alloy material by buffing or electrolytic polishing is more preferable.

The thickness of the negative electrode substrate is usually preferably about 0.01 to 10 mm, more preferably about 0.01 to 5 mm, and further preferably about 0.05 to 1 mm.

Titanium material has a lower electrical resistance value than a negative electrode on which a conventional transparent conductive film is formed. Therefore, compared with a perovskite solar cell using a conventional transparent conductive film, the titanium material has a large photoelectric conversion efficiency for a large cell area, and as a result, high power can be generated.

In conventional perovskite solar cells, light irradiation is performed from a negative electrode on which a transparent conductive film is formed.

In the perovskite solar cell of the present invention, since the titanium material used for the negative electrode does not have light transmittance, it is characterized in that light irradiation is performed from the positive electrode.

Further, it is preferable to carry out a surface treatment such as a physical polishing such as a mirror surface treatment or a chemical polishing such as chemical etching on titanium metal or a titanium alloy.

(2) Hole blocking layer The hole blocking layer does not move holes generated by charge separation in the organic-inorganic perovskite compound of the photoelectric conversion layer to the negative electrode side, but only electrons that have been charge separated move to the negative electrode side. It becomes a layer that plays an important role.

In order to prevent the holes generated by the charge separation from moving to the negative electrode side and move only the electrons to the negative electrode substrate side, a dense hole blocking layer is required.

The hole blocking layer preferably has a thickness of about 1 to 500 nm. The thickness of the hole blocking layer is more preferably about 1 to 100 nm.

The hole blocking layer is preferably composed of at least one material selected from the group consisting of an n-type semiconductor, an electron transporting conductive polymer, and an electron transporting inorganic salt. The hole blocking layer is preferably an n-type semiconductor.

The hole blocking layer is preferably composed of at least one material selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, aluminum oxide, cesium carbonate, fullerene derivatives, graphene derivatives, and perylene derivatives.

The titanium oxide is preferably titanium oxide prepared by surface treatment of titanium metal or a titanium alloy.

The surface treatment is preferably at least one surface treatment selected from the group consisting of atmospheric oxidation treatment and anodization treatment for titanium metal or titanium alloy.

The hole blocking layer is preferably a titanium oxide layer formed by subjecting titanium metal to an oxidation treatment such as atmospheric oxidation treatment or anodizing treatment. The atmospheric oxidation treatment temperature is preferably about 300 to 700 ° C. It is preferable to carry out atmospheric oxidation treatment at about 400 to 600 ° C.

As anodizing treatment, anodic oxidation is performed in an electrolytic solution containing at least one acid selected from the group consisting of inorganic acids and organic acids that do not have an etching action on metal titanium and a salt compound thereof. It is a process of forming an oxide film of titanium.

Since the voltage value at the time of anodization and the thickness of the titanium oxide film are proportional, it is preferable because the thickness of the hole blocking layer can be easily controlled by controlling the applied voltage. The anodization voltage is preferably about 1 to 200V, more preferably about 10 to 100V.

The electrolytic solution having no etching action on titanium is an electrolytic solution containing at least one compound selected from the group consisting of inorganic acids, organic acids and salts thereof (hereinafter also referred to as inorganic acids). Is preferred.

The electrolyte solution containing the inorganic acid or the like is preferably a dilute aqueous solution of phosphoric acid or phosphate. As the organic acid having no etching action on titanium, acetic acid, adipic acid, lactic acid and the like are preferable. Further, salts of these acids such as sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydrogen carbonate, sodium acetate, potassium adipate, sodium lactate and the like can also be used.

In addition, it is preferable to use an electrolytic solution containing an electrolyte such as sodium sulfate, potassium sulfate, magnesium sulfate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate.

As the inorganic acid, phosphoric acid and phosphate are most preferable.

The electrolytic solution is preferably a dilute aqueous solution such as an inorganic acid. The concentration of the inorganic acid or the like in the electrolytic solution is preferably in the range of about 1% by weight for reasons such as economy. For example, in an electrolytic solution containing phosphoric acid, a concentration range of about 0.01 to 10% by weight is preferable, a concentration range of about 0.1 to 10% by weight is more preferable, and a concentration range of about 1 to 3% by weight is more preferable.

These acids may be used alone or in combination of any two or more of these acids regardless of whether they are organic acids or inorganic acids. As an example of the preferable aspect of the electrolyte solution containing 2 or more types of acids, the aqueous solution containing a phosphate and phosphoric acid is mentioned.

The blending ratio of the acid in the electrolytic solution varies depending on the type of acid and acid salt to be used, anodization conditions, etc., but is generally preferably about 0.01 to 10% by weight, preferably 0.1 to 10% by weight in terms of the total amount of the acid. % Is more preferable, and about 1 to 3% by weight is more preferable.

The titanium oxide is preferably titanium oxide prepared by subjecting a titanium alkoxide compound, which is a titanium oxide precursor, to hydrolysis treatment and heat treatment. The hole blocking layer may be formed by coating a titanium alkoxide compound, which is a titanium oxide precursor, on a material not treated with titanium metal, followed by hydrolysis and heat treatment.

The titanium oxide is preferably titanium oxide prepared by surface treatment with an aqueous titanium tetrachloride solution. By subjecting the titanium oxide layer obtained by the oxidation treatment to surface treatment with an aqueous solution of titanium tetrachloride, a denser hole blocking layer is formed, and the hole blocking effect is enhanced.

The hole blocking layer is preferably made of at least one material selected from the group consisting of electron transporting conductive polymers such as fullerene derivatives and electron transporting inorganic salts such as cesium carbonate.

Further, in addition to titanium oxide, it may be composed of inorganic n-type semiconductors such as zinc oxide, zirconium oxide, aluminum oxide and cesium carbonate, and organic n-type semiconductors such as fullerene derivatives, graphene derivatives and perylene derivatives.

(3) Mesoporous metal oxide layer In a perovskite solar cell, a mesoporous metal oxide layer is preferably formed between the hole blocking layer and the perovskite layer.

The mesoporous metal oxide layer has a porous structure with fine pores. For this reason, it is preferable to support the organic-inorganic perovskite compound, which is a photoelectric conversion layer, evenly in the mesoporous metal oxide layer.

The thickness of the mesoporous metal oxide layer is preferably about 5 to 5,000 nm, and more preferably about 100 to 500 nm. In this mesoporous metal oxide, the mesoporous metal oxide layer is preferably composed of at least one material selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide and niobium oxide.

A paste prepared by mixing a powder of titanium oxide, aluminum oxide, zirconium oxide, niobium oxide or the like having an average particle diameter of preferably about 1 to 1,000 nm, more preferably about 10 to 50 nm, with a solvent such as ethanol or isopropanol. It is preferable to prepare an agent.

Next, the paste is preferably heat-treated at 100 to 600 ° C. after coating treatment such as spin coating, dip coating, screen printing, and air spraying.

In addition, a hole blocking layer can be obtained by heat treating the titanium oxide, aluminum oxide, zirconium oxide, and niobium oxide powder pastes by spin coating, dip coating, screen printing, air spraying, etc., followed by heat treatment at 100-600 ° C. It is also possible to form a mesoporous metal oxide between the perovskite layer and the perovskite layer.

(4) Perovskite layer The perovskite layer is a charge separation layer. The thickness of the perovskite layer is preferably about 5 to 10,000 nm, and more preferably about 50 to 500 nm.

The perovskite layer is composed of RNH ₃ PbX ₃ , R (NH ₂ ) ₂ PbX ₃ , RNH ₃ SnX ₃ and R (NH ₂ ) ₂ SnX ₃ (R is an alkyl group, X is a group consisting of Cl, Br and I. It is preferably made of at least one material selected from the group consisting of at least one selected halogen.

R in RNH ₃ PbX ₃ , R (NH ₂ ) ₂ PbX ₃ , RNH ₃ SnX ₃ and R (NH ₂ ) ₂ SnX ₃ is an alkyl group, and preferably has a linear or branched structure. Examples of R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a dodecyl group.

X in RNH ₃ PbX ₃ , R (NH ₂ ) ₂ PbX ₃ , RNH ₃ SnX ₃ and R (NH ₂ ) ₂ SnX ₃ is a halogen, preferably a halogen selected from the group consisting of Cl, Br and I; A combination of a plurality of selected halogens is preferred.

RNH ₃ PbX ₃ (R is an alkyl group and X is at least one halogen selected from the group consisting of Cl, Br and I) is preferably CH ₃ NH ₃ PbI ₃ . The perovskite layer is more preferably dark brown and CH ₃ NH ₃ PbI ₃ that absorbs all visible light from 300 nm to 800 nm.

RNH ₃ PbX ₃ (R is an alkyl group, X is at least one halogen selected from the group consisting of Cl, Br and I), but CH ₃ NH ₃ PbI _3-n Cl _n (n is 0 to 3 It is preferable that More preferably, the use of CH ₃ NH ₃ PbI _3-n Cl _n (where n is from 0 to 3) not only simplifies the coating technique, but also diffuses electrons and holes generated in the perovskite crystal due to light absorption. The length is increased and the photoelectric conversion efficiency is improved.

In order to form an organic / inorganic perovskite layer, first, an alkylamine halide, lead halide, and tin halide are dissolved in a solvent. Halogen is at least one halogen selected from the group consisting of Cl, Br and I. Subsequently, it is preferable that the dissolved material is coated by a spray method, a spin coating method, a dip coating method, a die coating method or the like and then dried. Alternatively, it is possible to form a perovskite layer which is a charge separation layer formed by vapor deposition.

Examples of the solvent include esters such as γ-butyllactone, methyl formate, and ethyl acetate; ketones such as acetone and dimethyl ketone; ethers such as diethyl ether and diisopropyl ether; alcohols such as methanol and ethanol; Halogenated hydrocarbons such as ethylene chloride and chloroform; nitrile solvents such as acetonitrile and propionitrile; N, N-dimethylformamide, dimethyl sulfoxide and the like can be preferably used.

(5) Hole transport layer The hole transport layer is important for moving the holes to the positive electrode side without moving the electrons generated by the charge separation with the organic / inorganic perovskite compound in the photoelectric conversion layer to the positive electrode. A layer that plays a role.

The hole transport layer is preferably a p-type semiconductor, and the thickness thereof is preferably about 1 to 5,000 nm, more preferably about 1 to 300 nm.

The hole transport layer is preferably composed of a p-type semiconductor.

The hole transport layer is preferably composed of at least one material selected from the group consisting of spiro-OMeTAD derivatives, molybdenum oxide, vanadium oxide, copper iodide, copper thiocyanate, polythiophene and polytriphenylamine.

Spiro-OMeTAD derivatives are 2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenylamino) -9,9'-spirobifluorene and derivatives of the same compound.

It is preferable to use a material doped with a hole transport layer.

The hole transport layer is preferably a hole transport layer prepared by doping with at least one material selected from the group consisting of oxygen, lithium compounds, cobalt compounds, vanadium compounds and molybdenum compounds. More preferably, the material to be doped is at least one material selected from the group consisting of vanadium compounds and molybdenum compounds.

In order to form the hole transport layer, the component in which the component for forming the hole transport layer is dissolved in a solvent is coated by a spray method, a spin coating method, a dip coating method, etc. and then dried. It is preferable to form a transport layer.

Examples of the solvent include esters such as γ-butyllactone, methyl formate, and ethyl acetate; ketones such as acetone and dimethyl ketone; ethers such as diethyl ether and diisopropyl ether; alcohols such as methanol and ethanol Halogenated hydrocarbons such as ethylene chloride and chloroform; nitrile solvents such as acetonitrile and propionitrile; hydrocarbon solvents such as chlorobenzene, dichlorobenzene and toluene can be preferably used.

(6) Positive electrode Positive electrode is gold, silver, aluminum, tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), tin oxide (SnO ₂ ), indium zinc oxide (IZO), zinc oxide (ZnO), It is preferably composed of at least one material selected from the group consisting of aluminum-doped zinc (AZO), PEDOT: PSS, graphene, carbon nanotubes, and polyaniline.

PEDOT: PSS is a mixture obtained by adding poly (ethylene sulfonic acid) (PSS), which is a polymer electrolyte, to PEDOT (poly -3-4- ethylenedioxythiophene) exhibiting good conductive properties.

The positive electrode preferably has a thin film shape, a nanowire shape, or a grid shape.

The thickness of the positive electrode is preferably about 1 to 1,000 nm, more preferably about 1 to 300 nm.

As the positive electrode film forming method, it is preferable to coat by vapor deposition, sputtering, spray method, spin coating method, dip coating method or the like.

Since the perovskite solar cell of the present invention uses a titanium material having no optical transparency for the negative electrode, light irradiation is performed from the positive electrode side.

Since the light is irradiated from the positive electrode, the positive electrode preferably has an opening. The area of the opening of the positive electrode is preferably about 50 to 99%, more preferably about 90 to 99% with respect to the area of the positive electrode.

(7) Antireflection film The perovskite solar cell is preferably subjected to antireflection film processing in order to improve light transmittance. In the perovskite solar cell, a negative electrode, a hole blocking layer, a perovskite layer, a hole transport layer, a positive electrode, and an antireflection film are preferably formed in this order.

The antireflection film is preferably made of at least one material selected from the group consisting of molybdenum oxide (MoOx), magnesium fluoride (MgF ₂ ), and lithium fluoride (LiF).

As a method for forming the antireflection film, coating is preferably performed by vapor deposition, sputtering, spraying, spin coating, dip coating, or the like.

(8) Concentrator The perovskite solar cell of the present invention performs light irradiation from the positive electrode side. The perovskite solar cell preferably has a condensing device arranged on the positive electrode side. In the perovskite solar cell, it is preferable that the condensing device is disposed on the positive electrode or antireflection film side. Furthermore, high power generation corresponding to high photoelectric conversion efficiency is possible.

The light irradiation means is arranged from the positive electrode or the antireflection film side through the light collecting device. By installing a condensing device between the positive electrode and the light source, light that is wasted is collected, and high power corresponding to high photoelectric conversion efficiency is achieved.

The condensing rate when the incident light is converged by using a condensing device is preferably about 110 to 5,000%, more preferably about 200 to 4,000%, further preferably about 300 to 3,000%, and about 500 to 900%. Particularly preferred. For example, setting the condensing rate to 500% means converging the original incident light by five times using the condensing device.

The condensing device is not particularly limited, but a condensing lens such as a linear Fresnel lens made of transparent plastics such as glass, PMMA (Polymethyl methacrylate), PET (Polyethylene terephthalate), PEN (Polyethylene naphthalate) is used. It is preferable to use it.

(9) Power storage device The perovskite solar cell preferably includes a power storage device.

By storing a large amount of DC power generated by the perovskite solar cell in the storage battery, it is possible to ensure the achievement of stable power. By using the solar battery and the storage battery function together, it is possible to prevent the power generation amount from being greatly influenced by the weather, time, or the like, which is a problem in the conventional solar battery.

A secondary battery that uses lead dioxide (PbO ₂ ) for the positive electrode, lead (Pb) for the negative electrode, and dilute sulfuric acid (H ₂ SO ₄ ) for the electrolyte, as a storage battery that stores DC power generated by the perovskite solar cell. Lead-acid battery; nickel oxyhydroxide (NiOOH) for the positive electrode, hydrogen storage alloy for the negative electrode, nickel-metal hydride battery that uses an alkaline aqueous solution of potassium hydroxide for the electrolyte; lithium-containing metal oxide for the positive electrode; Lithium battery, which is a secondary battery using a carbon material such as graphite, and an organic electrolyte as an electrolyte; NAS battery, which is a secondary battery using sulfur as a positive electrode, sodium as a negative electrode, and β-alumina as an electrolyte; It is preferable to select arbitrarily.

It is preferable to store the electric power generated in the perovskite solar cell by converting it into hydrogen by electrolysis of water. The characteristics of hydrogen that can be easily stored and transported can be utilized.

Hereinafter, the present invention will be described with reference to examples. The present invention is not limited to these examples.

[Example 1]
(1) As a negative electrode , a titanium material (25 mm × 25 mm × 1 mm) obtained by mirror-treating metallic titanium was ultrasonically cleaned with acetone for 15 minutes. Subsequently, it was ultrasonically washed with ethanol for 15 minutes and then dried. Next, oxygen flow (0.05 MPa, 5 minutes) was performed in a UV ozone cleaner UV253S (manufactured by Filgen). UV irradiation was then performed for 30 minutes followed by a nitrogen flow (0.2 MPa, 7.5 minutes).

(2) Preparation of hole blocking layer 10 μL of titanium tetrapropoxide (manufactured by Wako Pure Chemical Industries) prepared in a glove box (manufactured by Miwa Seisakusho) was dissolved in 1 mL of ethanol (manufactured by Wako Pure Chemical Industries). Next, this solution was coated with a hole blocking layer on a titanium material using a spin coater (manufactured by Mikasa, MS-A100).

Spin coating conditions were as follows: 50 μL of titanium tetrapropoxide ethanol solution was dropped onto the titanium material and then coated at 1,000 rpm for 40 seconds using a spin coater. Next, an operation of drying at 125 ° C. for 1 minute was performed 5 times. Subsequently, it heat-processed for 20 minutes at 500 degreeC, and produced the positive hole block layer.

(3) Preparation of mesoporous metal oxide layer Titanium oxide paste (Dyesol 18NR-T) was dispersed in ethanol at a weight ratio of 2: 7. Next, 50 μL of this solution was dropped on the titanium material on which the hole blocking layer was formed, and coating was performed at 3,000 rpm for 40 seconds using a spin coater. Next, heat treatment was performed at 500 ° C. for 15 minutes to produce a mesoporous metal oxide layer.

(4) Preparation of perovskite layer 400 mg of lead iodide PbI ₂ (Aldrich) was dissolved in 1 mL of dimethylformamide (DMF Wako Pure Chemical Industries). Subsequently, this solution was dripped so that it might spread over the titanium material in which the above-mentioned mesoporous metal oxide layer was formed. Next, coating was performed at 3,000 rpm for 40 seconds using a spin coater. Subsequently, it was dried at 70 ° C. for 30 minutes.

Next, hydrogen iodide (30 mL, 0.227 mol, 57 wt% aqueous solution, manufactured by Aldrich) and methylamine (27.8 mL, 0.273 mol, 40% methanol solution, manufactured by Tokyo Chemical Industry) were stirred at 0 ° C. for 2 hours. The solvent was then evaporated and the product was dissolved in ethanol. Next, methylamine iodide was obtained by recrystallization from diethyl ether.

10 mg of methylamine iodide CH ₃ NH ₃ I obtained by the above treatment was dissolved in 1 mL of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.). Next, 150 μL of this solution was dropped, and after standing for 30 seconds, coating was performed at 3,000 rpm for 40 seconds using a spin coater. Then, it dried at 70 degreeC for 30 minutes, and produced the perovskite layer.

(5) Preparation of hole transport layer 2,2 ', 7,7'-Tetrakis (N, N-di-p-methoxyphenylamino) -9,9'-spirobifluorene (spiro-OMeTAD, manufactured by Merck) A chlorobenzene solution (80 mg / mL) was prepared. As additives, 17.5 μL of lithium bistrifluoromethanesulfonylimide (Li-TFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) acetonitrile (Aldrich) solution (520 mg / mL) and 28.8 μL of tert-butylpyridine (Aldrich) were added.

A Spiro-OMeTAD chlorobenzene solution was dropped over the titanium material on which the perovskite layer was formed, and then coated at 3,000 rpm for 40 seconds using a spin coater. Thereafter, it was left for 12 hours in the presence of oxygen.

(6) Production of positive electrode On the titanium material on which the above-described hole transport layer was formed, gold was deposited to a thickness of 25 nm using a vapor deposition apparatus (MSVDE-YSS, manufactured by Miwa Seisakusho), and a perovskite solar cell was produced.

(7) Evaluation results The perovskite solar cell produced by the above procedure was equipped with a 0.05 cm ² optical mask using a solar simulator (Yamashita Denso, YSS-80) and IV measuring instrument (spectrometer). The results of examining the photoelectric conversion efficiency of the solar cell are shown in Table 1.

[Example 2]
(1) As a negative electrode , a titanium material (25 mm × 25 mm × 1 mm) obtained by mirror-treating metallic titanium was ultrasonically cleaned with acetone for 15 minutes. Subsequently, it was ultrasonically washed with ethanol for 15 minutes and then dried. Next, oxygen flow (0.05 MPa, 5 minutes) was performed in a UV ozone cleaner UV253S (manufactured by Filgen). UV irradiation was then performed for 30 minutes followed by a nitrogen flow (0.2 MPa, 7.5 minutes).

(2) Preparation of hole blocking layer The above titanium material was heat-treated at 500 ° C. for 20 minutes (atmospheric oxidation) to prepare a hole blocking layer.

(3) Preparation of mesoporous metal oxide layer Titanium oxide paste (Dyesol 18NR-T) was dispersed in ethanol at a weight ratio of 2: 7. Next, 50 μL of this solution was dropped on the titanium material on which the hole blocking layer was formed, and an operation of coating with a spin coater at 3,000 rpm for 40 seconds was performed. Next, heat treatment was performed at 500 ° C. for 20 minutes to produce a mesoporous metal oxide layer.

(4) Preparation of perovskite layer 400 mg of PbI ₂ was dissolved in 1 mL of dimethylformamide (DMF). This solution was dropped over the titanium material on which the above-mentioned mesoporous metal oxide layer was formed, and then coated with a spin coater at 3,000 rpm for 40 seconds, and then at 70 ° C. for 30 minutes. Dried.

Next, hydrogen iodide (30 mL, 0.227 mol, 57 wt% aqueous solution, manufactured by Aldrich) and methylamine (27.8 mL, 0.273 mol, 40% methanol solution, manufactured by Tokyo Chemical Industry) were stirred at 0 ° C. for 2 hours. The solvent was then evaporated and the product was dissolved in ethanol. Next, methylamine iodide was obtained by recrystallization from diethyl ether.

10 mg of CH ₃ NH ₃ I obtained by the above treatment was dissolved in 1 mL of 2-propanol. Next, 300 μL of this solution was dropped, and after standing for 30 seconds, coating was performed at 3,000 rpm for 40 seconds using a spin coater. Then, it dried at 70 degreeC for 30 minutes, and produced the perovskite layer.

(5) Preparation of hole transport layer 2,2 ', 7,7'-Tetrakis (N, N-di-p-methoxyphenylamino) -9,9'-spirobifluorene (spiro-OMeTAD, manufactured by Merck) A chlorobenzene solution (80 mg / mL) was prepared. As additives, 17.5 μL of lithium bistrifluoromethanesulfonylimide (Li-TFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) acetonitrile (Aldrich) solution (520 mg / mL) and 28.8 μL of tert-butylpyridine (Aldrich) were added.

A Spiro-OMeTAD chlorobenzene solution was dropped over the titanium material on which the perovskite layer was formed, and then coated at 3,000 rpm for 40 seconds using a spin coater.

Thereafter, molybdenum oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was vapor-deposited to a thickness of 10 nm (dope) in order to improve the hole transport efficiency using a vapor deposition apparatus and to prevent the perovskite layer from deteriorating, thereby producing a hole transport layer.

(6) Production of positive electrode Silver was deposited to a thickness of 10 nm using a vapor deposition device on the titanium material on which the hole transport layer was formed. Next, 20 nm of molybdenum oxide was deposited as an antireflection film to produce a perovskite solar cell.

(7) Evaluation results The perovskite solar cell produced by the above procedure was equipped with a 0.05 cm ² optical mask using a solar simulator (Yamashita Denso, YSS-80) and IV measuring instrument (spectrometer). The results of examining the photoelectric conversion efficiency of the solar cell are shown in Table 2.

Compared with Example 1, in Example 2, the hole blocking layer was produced by a simple technique in which a mirror-treated metal titanium was heated at 500 ° C. for 20 minutes.

Nevertheless, a photoelectric conversion efficiency more than twice that of Example 1 was obtained. Improvement by photoelectric conversion efficiency by depositing molybdenum oxide on hole transport layer, changing gold to silver as counter electrode, changing film thickness of deposition, depositing molybdenum oxide as antireflection film, etc. Was recognized.

[Example 3]
(1) As a negative electrode , a titanium material (25 mm × 25 mm × 1 mm) obtained by mirror-treating metallic titanium was ultrasonically cleaned with acetone for 15 minutes. Subsequently, it was ultrasonically washed with ethanol for 15 minutes and then dried. Next, oxygen flow (0.05 MPa, 5 minutes) was carried out in a UV ozone cleaner UV253S (manufactured by Philgen). UV irradiation was then performed for 30 minutes followed by a nitrogen flow (0.2 MPa, 7.5 minutes).

(2) Production of hole blocking layer The above titanium material was heat-treated (atmospheric oxidation) at 500 ° C. for 20 minutes to produce a hole blocking layer.

(3) Preparation of Mesoporous Metal Oxide Layer An Al ₂ O ₃ 2-propanol dispersion (manufactured by Aldrich) was dispersed in 2-propanol at a volume ratio of 1: 2. Next, 50 μL of this solution was dropped onto the titanium material on which the hole blocking layer was formed, and coating was performed at 3,000 rpm for 40 seconds using a spin coater. Next, it heat-processed for 10 minutes at 100 degreeC, and produced the metal oxide layer.

(4) Preparation of perovskite layer Hydrogen iodide (30mL, 0.227mol, 57wt% aqueous solution, manufactured by Aldrich) and methylamine (27.8mL, 0.273mol, 40% methanol solution, manufactured by Tokyo Kasei) were stirred at 0 ° C for 2 hours. . After evaporating the solvent, the product was dissolved in ethanol. Then, methyl iodide was obtained by recrystallization from diethyl ether. Next, a dimethylformamide (DMF) solution of PbCl ₂ (manufactured by Aldrich) (245 mg) and CH ₃ NH ₃ I (420 mg) obtained by the above treatment was prepared.

This solution was dropped over the titanium material on which the metal oxide layer was formed, and then coated at 3,000 rpm for 80 seconds using a spin coater. Then, it was dried at 80 ° C. for 30 minutes. Next, heat treatment was performed at 100 ° C. for 90 minutes to produce a perovskite layer.

(5) Preparation of hole transport layer 2,2 ', 7,7'-Tetrakis (N, N-di-p-methoxyphenylamino) -9,9'-spirobifluorene (spiro-OMeTAD, manufactured by Merck) A chlorobenzene solution (80 mg / mL) was prepared. As additives, 17.5 μL of lithium bistrifluoromethanesulfonylimide (Li-TFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) acetonitrile (Aldrich) solution (520 mg / mL) and 28.8 μL of tert-butylpyridine (Aldrich) were added.

A Spiro-OMeTAD chlorobenzene solution was dropped over the titanium material on which the perovskite layer was formed, and then coated at 3,000 rpm for 40 seconds using a spin coater.

Thereafter, using a vapor deposition apparatus, molybdenum oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was vapor-deposited by 10 nm in order to prevent the perovskite layer from deteriorating in order to improve the hole transport efficiency, and a hole transport layer was produced.

(6) Production of positive electrode On the titanium material on which the above-described hole transport layer was formed, silver was deposited to a thickness of 10 nm using a vapor deposition apparatus. Next, 20 nm of molybdenum oxide was deposited as an antireflection film to produce a perovskite solar cell.

(7) Evaluation results The perovskite solar cell produced by the above procedure was equipped with a 0.05 cm ² optical mask using a solar simulator (Yamashita Denso, YSS-80) and IV measuring instrument (spectrometer). Table 3 shows the results of examining the photoelectric conversion efficiency of the solar cell.

[Example 4]
(1) As a negative electrode , a titanium material (25 mm × 25 mm × 1 mm) obtained by mirror-treating metallic titanium was ultrasonically cleaned with acetone for 15 minutes. Further, it was ultrasonically washed with ethanol for 15 minutes and then dried. Next, oxygen flow (0.05 MPa, 5 minutes) was performed in a UV ozone cleaner UV253S (manufactured by Filgen). UV irradiation was then performed for 30 minutes followed by a nitrogen flow (0.2 MPa, 7.5 minutes).

(2) Production of hole blocking layer The above titanium material was heat-treated (atmospheric oxidation) at 500 ° C. for 20 minutes to produce a hole blocking layer.

(3) Preparation of perovskite layer Hydrogen iodide (30mL, 0.227mol, 57wt% aqueous solution, manufactured by Aldrich) and methylamine (27.8mL, 0.273mol, 40% methanol solution, manufactured by Tokyo Chemical Industry) were stirred at 0 ° C for 2 hours. . After evaporating the solvent, the product was dissolved in ethanol. Then, methyl iodide was obtained by recrystallization from diethyl ether. 245 mg of PbCl ₂ (manufactured by Aldrich) and 420 mg of CH ₃ NH ₃ I obtained by the above treatment were dissolved in 1 mL of dimethylformamide (DMF).

After dripping this solution over the titanium material on which the above metal oxide layer was formed, it was coated at 3,000 rpm for 80 seconds using a spin coater, and then dried at 80 ° C. for 30 minutes. I let you. Next, heat treatment was performed at 100 ° C. for 90 minutes to produce a perovskite layer.

(4) Preparation of hole transport layer 2,2 ', 7,7'-Tetrakis (N, N-di-p-methoxyphenylamino) -9,9'-spirobifluorene (spiro-OMeTAD, Merck) A chlorobenzene solution (80 mg / mL) was prepared. As additives, 17.5 μL of lithium bistrifluoromethanesulfonylimide (Li-TFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) acetonitrile (Aldrich) solution (520 mg / mL) and 28.8 μL of tert-butylpyridine (Aldrich) were added.

A Spiro-OMeTAD chlorobenzene solution was dropped over the titanium material on which the perovskite layer was formed, and then coated at 3,000 rpm for 40 seconds using a spin coater.

Thereafter, molybdenum oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was vapor-deposited to a thickness of 10 nm using a vapor deposition device to prevent the perovskite layer from deteriorating to produce a hole transport layer.

(5) Production of positive electrode On the titanium material on which the above-described hole transport layer was formed, silver was vapor-deposited to 10 nm using a vapor deposition apparatus. Next, 20 nm of molybdenum oxide was deposited as an antireflection film to produce a perovskite solar cell.

(6) Evaluation results The perovskite solar cell produced by the above procedure was equipped with a 0.05 cm ² optical mask using a solar simulator (Yamashita Denso, YSS-80) and IV measuring instrument (spectrometer). The results of examining the photoelectric conversion efficiency of the solar cell are shown in Table 4. Example 4 does not include a mesoporous layer.

[Example 5]
(1) As a negative electrode , a titanium material (25 mm × 25 mm × 1 mm) obtained by mirror-treating metallic titanium was ultrasonically cleaned with acetone for 15 minutes. Further, it was ultrasonically washed with ethanol for 15 minutes and then dried. Next, oxygen flow (0.05 MPa, 5 minutes) was performed in a UV ozone cleaner UV253S (manufactured by Filgen). UV irradiation was then performed for 30 minutes followed by a nitrogen flow (0.2 MPa, 7.5 minutes).

(2) Production of hole blocking layer The above titanium material was heat-treated at 700 ° C. for 20 minutes (atmospheric oxidation) to produce a hole blocking layer.

(3) Preparation of perovskite layer Hydrogen iodide (30mL, 0.227mol, 57wt% aqueous solution, manufactured by Aldrich) and methylamine (27.8mL, 0.273mol, 40% methanol solution, manufactured by Tokyo Chemical Industry) were stirred at 0 ° C for 2 hours. . The solvent was then evaporated and the product was dissolved in ethanol. Next, methyl iodide was obtained by recrystallization from diethyl ether. A dimethylformamide (DMF) solution of PbCl ₂ (manufactured by Aldrich) (245 mg) and CH ₃ NH ₃ I (420 mg) obtained by the above treatment was prepared.

This solution was dropped over the titanium material on which the metal oxide layer was formed, and then coated at 2,000 rpm for 80 seconds using a spin coater. Then, it was dried at 80 ° C. for 30 minutes. Next, heat treatment was performed at 100 ° C. for 90 minutes to produce a perovskite layer.

(4) Preparation of hole transport layer 80 mg of spiro-OMeTAD was dissolved in 1 mL of chlorobenzene. 17.5 μL of a solution in which 520 mg of Li-TFSI was dissolved in 1 mL of acetonitrile and 28.8 μL of tert-butylpyridine were added. Next, this solution was dropped over the titanium material on which the perovskite layer was formed, and then coated at 3,000 rpm for 40 seconds using a spin coater.

Thereafter, in order to improve the hole transport efficiency, molybdenum oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was vapor-deposited by 10 nm to prevent deterioration of the perovskite layer by using a vapor deposition apparatus, thereby preparing a hole transport layer.

(5) Production of positive electrode Silver was deposited to a thickness of 10 nm on the titanium material on which the hole transport layer was formed using a vapor deposition device. Thereafter, a perovskite solar cell was fabricated by depositing molybdenum oxide as an antireflection film to a thickness of 20 nm.

(6) Evaluation results The perovskite solar cell produced by the above procedure was equipped with a 0.05 cm ² optical mask using a solar simulator (Yamashita Denso, YSS-80) and IV measuring instrument (spectrometer). The results of examining the photoelectric conversion efficiency of the solar cell are shown in Table 5. Example 5 does not include a mesoporous layer.

[Example 6]
(1) As a negative electrode , a titanium material (25 mm × 25 mm × 1 mm) obtained by mirror-treating metallic titanium was ultrasonically cleaned with acetone for 15 minutes. Further, it was ultrasonically washed with ethanol for 15 minutes and then dried. Next, oxygen flow (0.05 MPa, 5 minutes) was performed in a UV ozone cleaner UV253S (manufactured by Filgen). UV irradiation was then performed for 30 minutes followed by a nitrogen flow (0.2 MPa, 7.5 minutes).

(2) Production of hole blocking layer The above titanium material was heat-treated (atmospheric oxidation) at 300 ° C. for 20 minutes to produce a hole blocking layer.

(3) Preparation of perovskite layer Hydrogen iodide (30mL, 0.227mol, 57wt% aqueous solution, manufactured by Aldrich) and methylamine (27.8mL, 0.273mol, 40% methanol solution, manufactured by Tokyo Chemical Industry) were stirred at 0 ° C for 2 hours. . The solvent was then evaporated and the product was dissolved in ethanol. Then, methyl iodide was obtained by recrystallization from diethyl ether. Next, a dimethylformamide (DMF) solution of PbCl ₂ (manufactured by Aldrich) (245 mg) and CH ₃ NH ₃ I (420 mg) obtained by the above treatment was prepared.

This solution was dropped over the titanium material on which the metal oxide layer was formed, and then coated at 2,000 rpm for 80 seconds using a spin coater. Then, it was dried at 80 ° C. for 30 minutes. Next, heat treatment was performed at 100 ° C. for 90 minutes to produce a perovskite layer.

(4) Preparation of hole transport layer 2,2 ', 7,7'-Tetrakis (N, N-di-p-methoxyphenylamino) -9,9'-spirobifluorene (spiro-OMeTAD, Merck) A chlorobenzene solution (80 mg / mL) was prepared. As additives, 17.5 μL of lithium bistrifluoromethanesulfonylimide (Li-TFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) acetonitrile (Aldrich) solution (520 mg / mL) and 28.8 μL of tert-butylpyridine (Aldrich) were added.

This solution was dropped over the titanium material on which the perovskite layer was formed, and then coated at 3,000 rpm for 40 seconds using a spin coater.

Thereafter, using a vapor deposition apparatus, molybdenum oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was vapor-deposited by 10 nm in order to prevent the perovskite layer from deteriorating in order to improve the hole transport efficiency, and a hole transport layer was produced.

(5) Production of positive electrode On the titanium material on which the above-described hole transport layer was formed, silver was vapor-deposited to 10 nm using a vapor deposition apparatus. Thereafter, a perovskite solar cell was fabricated by depositing molybdenum oxide as an antireflection film to a thickness of 20 nm.

(6) Evaluation results The perovskite solar cell produced by the above procedure was equipped with a 0.05 cm ² optical mask using a solar simulator (Yamashita Denso, YSS-80) and IV measuring instrument (spectrometer). The results of examining the photoelectric conversion efficiency of the solar cell are shown in Table 6. Example 6 does not include a mesoporous layer.

[Example 7]
(1) As a negative electrode , a titanium material (25 mm × 25 mm × 1 mm) obtained by mirror-treating metallic titanium was ultrasonically cleaned with acetone for 15 minutes. Further, it was ultrasonically washed with ethanol for 15 minutes and then dried. Subsequently, oxygen flow (0.05 MPa, 5 minutes) was performed in a UV ozone cleaner UV253S (manufactured by Filgen), followed by ultraviolet irradiation for 30 minutes, and then nitrogen flow (0.2 MPa, 7.5 minutes).

(2) Preparation of hole blocking layer The titanium material was anodized at 10 V, 30 V, 50 V, 100 V or 150 V in 1 wt% phosphoric acid for 10 minutes, respectively, to form a titanium oxide layer on the surface of the titanium material. . Next, the substrate was washed with 0.04M TiCl ₄ aqueous solution, allowed to stand at 80 ° C. for 30 minutes, and then washed with pure water and ethanol.

(3) Preparation of mesoporous metal oxide layer 50 μL of a solution of titanium oxide paste (Dyesol 18NR-T) dispersed in ethanol at a weight ratio of 2: 7 was applied onto the titanium material on which the hole blocking layer was formed. The solution was dropped and coated using a spin coater at 3,000 rpm for 40 seconds. Next, heat treatment was performed at 500 ° C. for 20 minutes to produce a mesoporous metal oxide layer.

(4) Preparation of perovskite layer Hydrogen iodide (30mL, 0.227mol, 57wt% aqueous solution, manufactured by Aldrich) and methylamine (27.8mL, 0.273mol, 40% methanol solution, manufactured by Tokyo Kasei) were stirred at 0 ° C for 2 hours. . The solvent was then evaporated and the product was dissolved in ethanol. Next, methylamine iodide was obtained by recrystallization from diethyl ether. A dimethylformamide (DMF) solution of PbCl ₂ (manufactured by Aldrich) (245 mg) and CH ₃ NH ₃ I (420 mg) obtained by the above treatment was prepared.

This solution was dropped over the titanium material on which the metal oxide layer was formed, and then coated at 2,000 rpm for 80 seconds using a spin coater. Then, it was dried at 80 ° C. for 30 minutes. Next, heat treatment was performed at 100 ° C. for 90 minutes to produce a perovskite layer.

(5) Preparation of hole transport layer 2,2 ', 7,7'-Tetrakis (N, N-di-p-methoxyphenylamino) -9,9'-spirobifluorene (spiro-OMeTAD, manufactured by Merck) A chlorobenzene solution (80 mg / mL) was prepared. As additives, 17.5 μL of lithium bistrifluoromethanesulfonylimide (Li-TFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) acetonitrile (Aldrich) solution (520 mg / mL) and 28.8 μL of tert-butylpyridine (Aldrich) were added.

A Spiro-OMeTAD chlorobenzene solution was dropped over the titanium material on which the perovskite layer was formed, and then coated at 3,000 rpm for 40 seconds using a spin coater.

Thereafter, in order to improve the hole transport efficiency, molybdenum oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was vapor-deposited by 10 nm to prevent deterioration of the perovskite layer by using a vapor deposition apparatus, thereby preparing a hole transport layer.

(6) Production of positive electrode On the titanium material on which the above-described hole transport layer was formed, silver was deposited to a thickness of 10 nm using a vapor deposition apparatus. Thereafter, a perovskite solar cell was fabricated by depositing molybdenum oxide as an antireflection film to a thickness of 20 nm.

(7) Evaluation results The perovskite solar cell produced by the above procedure was equipped with a 0.05 cm ² optical mask using a solar simulator (Yamashita Denso, YSS-80) and IV measuring instrument (spectrometer). Table 7 shows the results of examining the photoelectric conversion efficiency of the solar cell.

[Example 8]
(1) As a negative electrode , a titanium material (25 mm × 25 mm × 1 mm) obtained by mirror-treating metallic titanium was ultrasonically cleaned with acetone for 15 minutes. Further, it was ultrasonically washed with ethanol for 15 minutes and then dried. Next, oxygen flow (0.05 MPa, 5 minutes) was performed in a UV ozone cleaner UV253S (manufactured by Filgen). UV irradiation was then performed for 30 minutes followed by a nitrogen flow (0.2 MPa, 7.5 minutes).

(2) Production of hole blocking layer The titanium material was anodized in 1% by weight phosphoric acid at 10V or 30V for 10 minutes, respectively, to form a titanium oxide layer on the surface of the titanium material.

(3) Preparation of mesoporous metal oxide layer Titanium oxide paste (Dyesol 18NR-T) was dispersed in ethanol at a weight ratio of 2: 7. 50 μL of this solution was dropped onto the titanium material on which the hole blocking layer was formed, and an operation of coating with a spin coater at 3,000 rpm for 40 seconds was performed.

Next, heat treatment was performed at 500 ° C. for 20 minutes to produce a mesoporous metal oxide layer. Next, the substrate washed with 0.04M TiCl ₄ aqueous solution was left at 80 ° C. for 30 minutes, and then washed with pure water and ethanol.

(4) Preparation of perovskite layer Hydrogen iodide (30mL, 0.227mol, 57wt% aqueous solution, manufactured by Aldrich) and methylamine (27.8mL, 0.273mol, 40% methanol solution, manufactured by Tokyo Kasei) were stirred at 0 ° C for 2 hours. . The solvent was then evaporated and the product was dissolved in ethanol. Next, methylamine iodide was obtained by recrystallization from diethyl ether. Next, a dimethylformamide (DMF) solution of PbCl ₂ (manufactured by Aldrich) (245 mg) and CH ₃ NH ₃ I (420 mg) obtained by the above treatment was prepared.

This solution was dropped over the titanium material on which the metal oxide layer was formed, and then coated at 2,000 rpm for 80 seconds using a spin coater. Then, it was dried at 80 ° C. for 30 minutes. Next, heat treatment was performed at 100 ° C. for 90 minutes to produce a perovskite layer.

(5) Preparation of hole transport layer 2,2 ', 7,7'-Tetrakis (N, N-di-p-methoxyphenylamino) -9,9'-spirobifluorene (spiro-OMeTAD, manufactured by Merck) A chlorobenzene solution (80 mg / mL) was prepared. As additives, 17.5 μL of lithium bistrifluoromethanesulfonylimide (Li-TFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) acetonitrile (Aldrich) solution (520 mg / mL) and 28.8 μL of tert-butylpyridine (Aldrich) were added.

A Spiro-OMeTAD chlorobenzene solution was dropped over the titanium material on which the perovskite layer was formed, and then coated at 3,000 rpm for 40 seconds using a spin coater.

After that, using a vapor deposition apparatus, molybdenum oxide (manufactured by Wako Pure Chemical Industries) was vapor-deposited by 10 nm in order to improve the hole transport efficiency and to prevent the perovskite layer from deteriorating, thereby preparing a hole transport layer.

(6) Production of positive electrode Silver was deposited to a thickness of 10 nm using a vapor deposition device on the titanium material on which the hole transport layer was formed. Thereafter, a perovskite solar cell was fabricated by depositing molybdenum oxide as an antireflection film to a thickness of 20 nm.

(7) Evaluation results The perovskite solar cell produced by the above procedure was equipped with a 0.05 cm ² optical mask using a solar simulator (Yamashita Denso, YSS-80) and IV measuring instrument (spectrometer). Table 8 shows the results of examining the photoelectric conversion efficiency of the solar cell.

DESCRIPTION OF SYMBOLS 1 Negative electrode 2 Hole block layer 3 Mesoporous metal oxide layer 4 Perovskite layer 5 Hole transport layer 6 Positive electrode 7 Light

Claims (20)

A perovskite solar cell in which a negative electrode, a hole blocking layer, a perovskite layer, a hole transport layer and a positive electrode are formed in order,
The negative electrode is composed of at least one material selected from the group consisting of titanium metal, titanium alloy, surface-treated metal titanium, and surface-treated titanium alloy,
A perovskite solar cell, which is irradiated with light from the positive electrode side. The perovskite solar cell according to claim 1, wherein a mesoporous metal oxide layer is formed between the hole blocking layer and the perovskite layer. The hole blocking layer has a thickness of 1 to 500 nm, and the hole blocking layer is composed of at least one material selected from the group consisting of an n-type semiconductor, an electron transporting conductive polymer, and an electron transporting inorganic salt. The perovskite solar cell according to claim 1, wherein the perovskite solar cell is formed. The hole blocking layer is made of at least one material selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, aluminum oxide, cesium carbonate, fullerene derivatives, graphene derivatives, and perylene derivatives. The perovskite solar cell according to any one of claims 1 to 3. The perovskite solar cell according to claim 4, wherein the titanium oxide is titanium oxide prepared by surface-treating metal titanium or a titanium alloy. 6. The perovskite solar cell according to claim 5, wherein the surface treatment is at least one surface treatment selected from the group consisting of atmospheric oxidation treatment and anodization treatment of titanium metal or a titanium alloy. The perovskite type according to any one of claims 4 to 6, wherein the titanium oxide is titanium oxide prepared by subjecting a titanium alkoxide compound, which is a titanium oxide precursor, to hydrolysis treatment and heat treatment. Solar cell. The perovskite solar cell according to any one of claims 4 to 7, wherein the titanium oxide is titanium oxide prepared by further surface-treating with an aqueous titanium tetrachloride solution. The mesoporous metal oxide layer has a thickness of 5 to 5,000 nm, and the mesoporous metal oxide layer is composed of at least one material selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, and niobium oxide. The perovskite solar cell according to claim 2, wherein The perovskite layer has a thickness of 5 to 10,000 nm, and the perovskite layer is RNH ₃ PbX ₃ , R (NH ₂ ) ₂ PbX ₃ , RNH ₃ SnX ₃ and R (NH ₂ ) ₂ SnX ₃ (R is an alkyl group) And X is at least one material selected from the group consisting of Cl, Br and I selected from the group consisting of Cl, Br and I). The perovskite solar cell according to any one of the above. The RNH ₃ PbX ₃ (R is an alkyl group, X is at least one halogen selected from the group consisting of Cl, Br and I) is CH ₃ NH ₃ PbI ₃ , Item 11. A perovskite solar cell according to Item 10. RNH ₃ PbX ₃ (R is an alkyl group, X is at least one halogen selected from the group consisting of Cl, Br and I), but CH ₃ NH ₃ PbI _3-n Cl _n (n is 0 to 0) The method for manufacturing a perovskite solar cell according to claim 10, wherein The perovskite solar system according to any one of claims 1 to 12, wherein the hole transport layer has a thickness of 1 to 5,000 nm, and the hole transport layer is made of a p-type semiconductor. battery. The hole transport layer is composed of at least one material selected from the group consisting of a spiro-OMeTAD derivative, molybdenum oxide, vanadium oxide, copper iodide, copper thiocyanate, polythiophene, and polytriphenylamine. The perovskite solar cell according to any one of claims 1 to 13. The hole transport layer is a hole transport layer prepared by doping with at least one material selected from the group consisting of oxygen, lithium compounds, cobalt compounds, vanadium compounds, and molybdenum compounds. The perovskite solar cell according to any one of claims 1 to 14. The positive electrode is selected from the group consisting of gold, silver, aluminum, tin-doped indium oxide, fluorine-doped tin oxide, tin oxide, indium zinc oxide, zinc oxide, aluminum-doped zinc, PEDOT: PSS, graphene, polyaniline, and carbon nanotubes The perovskite solar cell according to any one of claims 1 to 15, wherein the positive electrode has a thin film shape, a nanowire shape, or a grid shape. The perovskite solar cell according to any one of claims 1 to 16, wherein a negative electrode, a hole blocking layer, a perovskite layer, a hole transport layer, a positive electrode, and an antireflection film are formed in this order. Perovskite solar cell. The perovskite solar cell according to claim 17, wherein the antireflection film is made of at least one material selected from the group consisting of molybdenum oxide, magnesium fluoride, and lithium fluoride. The perovskite solar cell according to any one of claims 1 to 18, wherein the condensing device is disposed on the positive electrode side. The perovskite solar cell according to any one of claims 1 to 19, wherein a power storage device is disposed.

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