WO2014115763A1 - Film-forming method, porous film, photo-electrode, and dye-sensitized solar cell - Google Patents
Film-forming method, porous film, photo-electrode, and dye-sensitized solar cell Download PDFInfo
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- WO2014115763A1 WO2014115763A1 PCT/JP2014/051253 JP2014051253W WO2014115763A1 WO 2014115763 A1 WO2014115763 A1 WO 2014115763A1 JP 2014051253 W JP2014051253 W JP 2014051253W WO 2014115763 A1 WO2014115763 A1 WO 2014115763A1
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- particles
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention includes a film forming method for forming a porous film made of the particles on the substrate by spraying the particles onto the substrate, the porous film formed by the film forming method, and the porous film. And a dye-sensitized solar cell including the photoelectrode.
- a paste in which titanium oxide particles are mixed with a binder such as a polymer is applied on a substrate, and this is fired to form a porous film.
- This method has an advantage that a porous film can be easily obtained.
- the substrate material is required to have heat resistance, there is a problem that the substrate to be used is substantially limited to the glass substrate. Then, it replaces with the method of baking a paste, and the method of spraying a titanium oxide particle on a board
- AD method aerosol deposition method
- Patent Documents 1 to 3 can be cited as conventional AD methods.
- the titanium oxide particles to be sprayed (ultrafine particle brittle material)
- secondary particles aggregated to about 50 nm to 1 ⁇ m by firing primary particles having a particle size of about several tens of nm are used.
- the secondary particles have a characteristic that they are easily broken and crushed from the interface by an impact sprayed on the substrate. For this reason, according to the AD method of Patent Document 1, a dense film-formed body (dense film) having a theoretical density of 95% or more is obtained.
- Patent Documents 2 to 3 propose an AD method for obtaining a porous film instead of a dense film by changing the method for producing secondary particles used in the AD method of Patent Document 1. Specifically, first, primary particles are dispersed in a solution having a binder such as a high molecular polymer, and an aggregate obtained by drying and solidifying the primary particles is obtained. Is sintered strongly to obtain a porous sintered body in a large lump. Next, this sintered body is crushed with a mortar and further passed through a 25 ⁇ m mesh to obtain secondary particles adjusted to a size of about 20 ⁇ m that can be sprayed. It is reported that a porous film can be obtained by spraying the secondary particles so as to collide with the substrate at an angle of 60 °.
- a binder such as a high molecular polymer
- the present invention has been made in view of the above circumstances, and a film forming method capable of forming a thick porous film more easily than the conventional one, a porous film manufactured by the film forming method, and the porous film And a dye-sensitized solar cell provided with the photoelectrode.
- a solvent containing a raw material compound the fine particles of the inorganic substance using the raw material compound as a raw material are synthesized and aggregated particles obtained by aggregating the fine particles are used.
- a film forming method comprising forming a porous film made of the inorganic substance on the substrate. That is, in the solvent containing the raw material compound, the fine particles of the inorganic material using the raw material compound as a raw material are synthesized and the aggregated particles obtained by aggregating the fine particles are used to bond the fine particles in the aggregated particles.
- the inorganic particles are formed on the base material by spraying the porous particles produced through the strengthening process onto the base material, thereby joining the base material and the porous particle and joining the porous particles to each other.
- a film forming method comprising forming a porous film made of a substance.
- [3] In the step of strengthening the bonding between the fine particles, by firing at a temperature range of a temperature at which the fine particles are in contact with each other by a solid-phase reaction and a temperature range that can be bonded to the melting point of the inorganic substance.
- a reactive compound containing a metal or a semiconductor constituting the fine particles and the aggregated particles are mixed, and the fine particles are chemically bonded via the reactive compound.
- the film forming method according to any one of [1] to [3], wherein the film is bonded to the substrate.
- porous film is a porous film for a photoelectrode of a dye-sensitized solar cell.
- porous film formed by the film forming method according to any one of [1] to [8].
- a photoelectrode comprising the porous film according to [9].
- a dye-sensitized solar cell comprising the photoelectrode according to [10].
- primary particles fine particles
- secondary particles aggregated particles obtained by aggregating the primary particles are used.
- Aggregated particles having a uniform particle diameter can be obtained by growing the fine particles while stirring in the reaction solution for liquid phase synthesis and further aggregating the fine particles.
- Aggregated particles are in a porous state in which fine particles are partially bonded. Even if the porous particles obtained through the bonding step for strengthening the bonding between the fine particles collide with the substrate, the porous particles can be maintained. As a result, a porous film having a high porosity can be obtained.
- the porous particles have the same particle size as the aggregated particles, large particles are not mixed in the sprayed particles, and the blasting effect hardly occurs, so that a thick porous film is efficiently formed. be able to. Further, even when a thick porous film is formed, the porosity of the region close to the substrate and the region away from the substrate can be made the same, and the porosity of the entire film can be made uniform.
- the porous film of the present invention has high structural strength because the entire film is formed of porous particles having a uniform particle size. Furthermore, it has a high porosity throughout the membrane. For this reason, the photoelectrode which increased dye adsorption amount than before is obtained. As a result, the photoelectrode and dye-sensitized solar cell provided with the porous film of the present invention have excellent photoelectric conversion efficiency.
- the fine particles mean particles (primary particles) made of an inorganic substance.
- Aggregated particles refer to particles formed by agglomerating the fine particles.
- the porous particles are particles obtained by firing the aggregated particles.
- the film forming method according to the first embodiment of the present invention synthesizes fine particles (primary particles) made of an inorganic substance using a raw material compound as a raw material in a solvent containing the raw material compound (in a liquid phase raw material). Aggregated particles obtained by aggregating the fine particles are used.
- the agglomerated particles may be synthesized by a conventionally known hydrothermal synthesis method, or commercially available products may be used.
- a commercial product of the aggregated particles can be purchased from, for example, Teika Corporation.
- As a conventionally known hydrothermal synthesis method a method in which a solid reactant and a solvent or an aqueous solution acting as a reactant are placed in an autoclave and treated under high temperature and high pressure conditions can be applied. By this treatment, the solid reactants dissolve and react with each other or react with the components of the aqueous solution, whereby the target fine particles can be precipitated.
- the liquid phase raw material includes a solvent and a raw material compound to be dissolved or dispersed in the solvent.
- the raw material compound is a compound containing an inorganic substance constituting the fine particles.
- fine particles comprising titanium oxide and aggregated particles in which the fine particles are aggregated can be obtained by a hydrothermal synthesis method using water as the solvent and TiCl 4 as the raw material compound.
- the said inorganic substance is not restrict
- the material of the porous film which comprises the photoelectrode of a conventionally well-known dye-sensitized solar cell is mentioned. Specific examples include metals or semiconductors such as titanium and zinc, salts of the metals or semiconductors, and halides of the metals or semiconductors.
- the average particle size (average of major axis) of the fine particles (primary particles) constituting the aggregated particles is not particularly limited, but is preferably 1 nm to 100 nm, more preferably 5 nm to 70 nm, and further preferably 10 nm to 40 nm.
- the average particle diameter of the fine particles is 1 nm or more, porous aggregated particles can be easily obtained, and a porous film having a specific surface area sufficient for adsorbing the sensitizing dye can be formed.
- the average particle size of the fine particles is 100 nm or less, the bonding force between the fine particles constituting the aggregated particles can be increased, and aggregated particles having high physical strength can be obtained.
- the method for obtaining the average particle diameter of the fine particles includes a method of measuring and averaging the long diameters of a plurality of fine particles by SEM observation. The larger the number of measurements when calculating the average, the better. However, for example, with respect to 30 to 100 aggregated particles, there is a method in which the average value is calculated by measuring the major axis of about 10 fine particles each.
- the agglomerated particles are secondary particles obtained by further agglomerating fine particles obtained by the liquid phase synthesis method.
- the average particle diameter (average of the major axis) of the aggregated particles is not particularly limited, but is preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 0.2 ⁇ m to 2 ⁇ m, still more preferably 0.5 ⁇ m to 1.5 ⁇ m.
- the average particle diameter of the aggregated particles is 0.1 ⁇ m or more, a structurally strong porous film different from the green compact can be easily obtained. That is, a sufficient film forming effect can be easily obtained.
- the average particle size of the aggregated particles is 5 ⁇ m or less, it is possible to sufficiently suppress the blasting effect of scraping the porous film formed by the previously sprayed aggregated particles with the aggregated particles sprayed later.
- a method for obtaining the average particle size of the aggregated particles for example, a method of determining the peak value of the volume average particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring device or the major axis of a plurality of aggregated particles by SEM observation.
- the method of measuring and averaging is mentioned. The larger the number of measurements when calculating the average, the better. However, for example, there is a method of calculating the average value by measuring the major axis of 30 to 100 aggregated particles.
- the particle size of the aggregated particles is preferably measured by the SEM observation.
- a bonding process for strengthening the bonding between the fine particles constituting the aggregated particles is performed.
- this bonding treatment it is preferable to sinter the aggregated particles without using a binder containing a high molecular polymer as in Patent Documents 2 to 3, and only the aggregated particles are baked (only the aggregated particles are It is more preferable to fire alone.
- the high molecular polymer means a polymer having a molecular weight (Mw) of 1000 or more. Since the firing in the present embodiment is performed for the purpose of strengthening the bonding between the already aggregated fine particles, it is not necessary to perform the firing in a state where the aggregated particles are closely packed.
- agglomerated particles in order to prevent unnecessary bonding between the agglomerated particles, it is preferable to fire in a state where the agglomerated particles are not closely packed. Specifically, it is preferable to perform firing in a state where the density of the aggregated particles is 3.7 to 4.1 g / cm 3 . This is particularly important and will be explained in more detail below.
- the binder used in conventional baking is used for the purpose of aggregating particles that are not yet bonded. Furthermore, in order to ensure the aggregation state of the particles, it is necessary to densely pack the particles to which the binder is attached before firing. The binder burns out after firing and has a function of assisting strong sintering of the particles. However, it is extremely difficult to control the size of the sintered body (large lump) obtained after firing. For this reason, the process which crushes a sintered compact and arranges (classifies) further to a desired size using a filter etc. is indispensable. On the other hand, the agglomerated particles in the present embodiment do not require the binder because the fine particles, which are primary particles, are already bonded before firing.
- the agglomerated particles By firing the agglomerated particles without using the binder, the agglomerated particles are bonded together more firmly without binding the agglomerated particles, and the structural strength of the agglomerated particles is increased. Enhanced porous particles can be obtained.
- the binder since the binder is not used, a large lump (sintered body) formed by firmly bonding the aggregated particles (secondary particles) to each other is not formed.
- the conventional sintered body needs to be crushed later, but this trouble does not occur in this embodiment.
- the temperature range of the baking is not particularly limited as long as it is a temperature capable of strengthening the bonding between the fine particles, but the temperature is higher than the temperature at which the portion where the fine particles are in contact with each other by a solid-phase reaction, and the inorganic A temperature range below the melting point of the substance is preferred.
- solid phase reaction refers to a location where the fine particles are in contact with each other in a temperature range below the melting point temperature of the fine particles, where atom diffusion and recombination occur at the locations where the fine particles are in contact with each other. Refers to the reaction of binding.
- the calcination temperature is preferably 400 to 1000 ° C, more preferably 500 to 800 ° C, and further preferably 500 to 600 ° C.
- the firing time is preferably 1 hour to 24 hours, more preferably 3 hours to 12 hours, and even more preferably 5 hours to 12 hours.
- the average particle diameter of the porous particles is preferably substantially the same as that of the aggregated particles. As described above, even if the aggregated particles are fired, the aggregated particles are hardly bound to each other as long as the binder is not used and the firing temperature and the firing time are as described above. Further, even if the aggregated particles are attached to each other by the firing, the adhesion is not strong, and therefore it can be easily returned to the original size of the aggregated particles by lightly understanding.
- the density of the porous particles is not particularly limited but is preferably 3.3 ⁇ 4.2g / cm 3, more preferably 3.5 ⁇ 4.2g / cm 3, is 3.7 ⁇ 4.1g / cm 3 Further preferred. When the density is in the above range, a porous film having a high porosity can be easily obtained.
- the Mohs hardness of the porous particles is preferably in the range of 5.5 to 6.0.
- the porous particles can be suppressed from being pulverized by spraying, and a porous film maintaining the porosity of the porous particles can be easily formed.
- bonding by chemical treatment can be performed instead of the firing as a treatment for strengthening the bonding between the fine particles constituting the agglomerated particles.
- a reactive compound containing a metal or a semiconductor constituting the fine particles is used, the reactive compound is mixed with the aggregated particles, and the fine particles are chemically bonded via the reactive compound. can do.
- the reactive compound a compound whose reaction is accelerated by light or heat can be used.
- examples of the reactive compound include TiCl 4 .
- an aqueous solution of TiCl 4 having a concentration of 0.05 to 0.1 mol / L for 30 minutes and heating at 60 to 100 ° C. for 30 minutes to 2 hours (or irradiating with UV light together with heating) The bond between the fine particles in the aggregated particles can be strengthened. In this case, it is possible to prevent the agglomerated particles from being joined by heating the aqueous solution while stirring so that the agglomerated particles are not bonded to form a large lump.
- FIG. 1 is a configuration diagram of a film forming apparatus 60 applicable to the present embodiment.
- the film forming apparatus used in the film forming method of the present embodiment is not limited to the configuration shown in FIG. 1 as long as it is an apparatus capable of spraying the porous particles, which are the raw material of the porous film, onto the base material.
- the film forming apparatus 60 includes a gas cylinder 55, a transfer pipe 56, a nozzle 52, a base 63, and a film forming chamber 51.
- the gas cylinder 55 is filled with a gas for accelerating the porous particles 54 and spraying it on the base material 53 (hereinafter referred to as a carrier gas).
- a carrier gas a gas for accelerating the porous particles 54 and spraying it on the base material 53 (hereinafter referred to as a carrier gas).
- One end of a transfer pipe 56 is connected to the gas cylinder 55.
- the carrier gas supplied from the gas cylinder 55 is supplied to the carrier pipe 56.
- the transport pipe 56 is provided with a mass flow controller 57, an aerosol generator 58, a disintegrator 59 and a classifier 61 that can appropriately adjust the dispersion degree of the porous particles 54 in the transport gas, in order from the front side. It has been.
- the crusher 59 By the crusher 59, the state in which the porous particles 54 adhere to each other due to moisture or the like can be solved. Further, even if there are porous particles that have passed through the crusher 59 in an attached state, the particles can be removed by the classifier 61.
- the mass flow controller 57 can adjust the flow rate of the carrier gas supplied from the gas cylinder 55 to the carrier pipe 56.
- the aerosol generator 58 is loaded with porous particles 54.
- a sensitizing dye may be adsorbed in advance on the porous particles 54 before spraying.
- the porous particles 54 are dispersed in the carrier gas supplied from the mass flow controller 57 and conveyed to the crusher 59 and the classifier 61.
- the nozzle 52 is arranged so that an opening (not shown) faces the base material 53 on the base 63.
- the other end of the transport pipe 56 is connected to the nozzle 52.
- the carrier gas containing the porous particles 54 is injected from the opening of the nozzle 52 onto the base material 53.
- the base material 53 is placed on the upper surface 73 of the base 63 so that one surface 72 of the base material 53 comes into contact therewith. Further, the other surface 71 (film forming surface) of the substrate 53 faces the opening of the nozzle 52.
- the collision energy between the porous particles 54 is appropriately controlled on the film forming surface 71 according to the average particle diameter, hardness, and spraying speed of the porous particles 54. It is preferable that it consists of a material. With such a member, the adhesion of the porous particles 54 to the film-forming surface 71 is improved, and the porous particles 54 to be deposited are easily joined together, so that a porous film having a high porosity can be easily formed. It can be formed into a film.
- the base material 53 is preferably made of a material that allows the sprayed porous particles 54 to bite into the film-forming surface 71 and to adhere to the porous particles 54 without penetrating.
- a substrate 53 include a resin film (resin sheet). Since the film can be formed at room temperature according to the AD method, the substrate 53 is not required to have high heat resistance. More specific selection of the base material 53 may be appropriately performed according to the material of the porous particles 54, the film forming conditions such as the spraying speed, and the use of the porous film.
- the film forming chamber 51 is provided for film formation in a reduced pressure atmosphere.
- a vacuum pump 62 is connected to the film forming chamber 51, and the inside of the film forming chamber 51 is depressurized as necessary.
- the film forming chamber 51 is provided with a base exchange means (not shown).
- the vacuum pump 62 is operated to depressurize the film forming chamber 51.
- the pressure in the film forming chamber 51 is not particularly limited, but is preferably set to 5 to 1000 Pa. By reducing the pressure to this extent, convection in the film forming chamber 51 is suppressed, and it becomes easy to spray the porous particles 54 onto predetermined positions on the film forming surface 71.
- the carrier gas is supplied from the gas cylinder 55 to the carrier pipe 56, and the flow rate and flow rate of the carrier gas are adjusted by the mass flow controller 57.
- the carrier gas for example, a general gas such as O 2 , N 2 , Ar, He, or air can be used. What is necessary is just to set suitably the flow velocity and flow volume of carrier gas according to the material of the porous particle 54 sprayed from the nozzle 52, average particle diameter, flow velocity, and flow volume.
- the porous particles 54 are loaded into the aerosol generator 58, and the porous particles 54 are dispersed in the carrier gas flowing in the carrier pipe 56 and accelerated.
- the porous particles 54 are ejected from the opening of the nozzle 52 at a subsonic to supersonic speed, and are laminated on the film forming surface 71 of the substrate 53.
- the spraying speed of the porous particles 54 onto the film forming surface 71 can be set to 10 to 1000 m / s, for example.
- the speed is not particularly limited, and may be set as appropriate according to the material of the base material 53.
- the porous particles 54 are successively applied to the porous particles 54 that have digged into the film forming surface 71 of the substrate 53. Colliding with each other, a new surface is formed on the surfaces of the porous particles 54 by the collision of the porous particles 54, and the porous particles 54 are joined to each other on the new surface.
- a temperature rise that causes the entire porous particles 54 to melt does not occur. Therefore, a glassy grain boundary layer is hardly formed on the new surface.
- the spraying of the porous particles 54 from the nozzle 52 is stopped.
- a porous film having a predetermined film thickness made of porous particles 54 is formed on the film forming surface 71 of the substrate 53.
- the film forming method by the AD method is exemplified above, the film forming method of the present invention is not limited to the AD method. Even if a porous film is formed by spraying the porous particles onto a substrate using a conventionally known powder spraying method, such as a spray method, a cold spray method, an electrostatic spray method, or a spraying method. Good.
- a conventionally known powder spraying method such as a spray method, a cold spray method, an electrostatic spray method, or a spraying method. Good.
- the porous film of the second embodiment of the present invention is a porous film formed on a substrate by the film forming method of the first embodiment.
- This porous film has high structural strength because the entire film is formed of porous particles having a uniform particle diameter. Furthermore, it has a high porosity throughout the membrane. For this reason, the photoelectrode which increased dye adsorption amount than before is obtained. As a result, the photoelectrode and dye-sensitized solar cell provided with the porous film of the present invention have excellent photoelectric conversion efficiency.
- the use of the porous film of the present embodiment is not limited to the photoelectrode, but can be widely applied to the use of substance adsorption and substance support using a porous structure.
- the photoelectrode of the third embodiment of the present invention is a photoelectrode in which a sensitizing dye is adsorbed on the porous film of the second embodiment.
- the kind of sensitizing dye is not particularly limited, and conventionally known dyes can be applied.
- the porous film is preferably formed on a transparent conductive substrate.
- the photoelectrode of the third embodiment can be manufactured by a conventional method except that the porous film of the second embodiment is used.
- the dye-sensitized solar cell according to the fourth embodiment of the present invention includes the photoelectrode according to the third embodiment, a counter electrode, and an electrolytic solution or an electrolyte layer.
- the electrolytic solution is preferably sealed with a sealing material between the photoelectrode and the counter electrode.
- a resin film or resin sheet having a transparent conductive film formed on the surface can be used.
- the resin (plastic) those having visible light permeability are preferable, and examples thereof include polyacryl, polycarbonate, polyester, polyimide, polystyrene, polyvinyl chloride, and polyamide.
- polyester, particularly polyethylene terephthalate (PET) is produced and used in large quantities as a transparent heat-resistant film.
- electrolytic solution an electrolytic solution used in a conventionally known dye-sensitized solar cell can be applied.
- a redox couple (electrolyte) is dissolved in the electrolytic solution.
- the electrolyte solution may contain other additives such as fillers and thickeners without departing from the spirit of the present invention.
- an electrolyte layer (solid electrolyte layer) may be applied instead of the electrolytic solution.
- the electrolyte layer has a function similar to that of the electrolytic solution, and is in a gel or solid state.
- the electrolyte layer for example, a solution obtained by gelling or solidifying the electrolyte solution by adding a gelling agent or a thickener to the electrolyte solution and removing the solvent as necessary can be applied.
- a gel or solid electrolyte layer there is no possibility of the electrolyte solution leaking from the dye-sensitized solar cell.
- the dye-sensitized solar cell of the fourth embodiment can be manufactured by a conventional method except that the photoelectrode of the third embodiment is used.
- the porous film of the second embodiment constituting the photoelectrode of the third embodiment has a structural strength, structural uniformity, porosity, porosity that is higher than that of a porous film formed by a conventional powder spraying method. Excellent uniformity and dye adsorption. As a result, the durability and photoelectric conversion efficiency of the photoelectrode of the third embodiment and the dye-sensitized solar cell of the fourth embodiment can be improved.
- Example 1 Commercially available agglomerated particles made of TiO 2 aggregated until fine particles having an average primary particle size of about 15 nm were about 1 ⁇ m were purchased and used. The aggregated particles were washed with purified water or the like, spread on a bat and dried so that the aggregated particles were not packed closely. The dried aggregated particles having an average particle diameter of about 1 ⁇ m were put in a reagent bottle and temporarily stored. Next, 10 g of the dried powdery agglomerated particles was put in an alumina container having a volume of 150 cm 3 . At this time, no pressure was applied to the powder, and a certain amount of gaps were included between the particles. At this time, no binder is used.
- porous particles made of TiO 2 having an average particle diameter of about 1 ⁇ m, which was the same as the aggregated particles.
- the density of the obtained porous particles was 3.8 g / cm 3 .
- the porous particles were sprayed onto the PEN substrate on which ITO was formed by AD method to form a porous film made of TiO 2 .
- the film thickness could be arbitrarily adjusted in the range of 0.1 ⁇ m to 30 ⁇ m.
- Example 2 Commercially available agglomerated particles made of TiO 2 aggregated until fine particles having an average primary particle diameter of about 30 nm were about 1 ⁇ m were purchased and used. The aggregated particles were washed with purified water or the like, spread on a bat and dried so that the aggregated particles were not packed closely. The dried aggregated particles having an average particle diameter of about 1 ⁇ m were put in a reagent bottle and temporarily stored. Next, 10 g of the dried powdery agglomerated particles was put in an alumina container having a volume of 150 cm 3 . At this time, no pressure was applied to the powder, and a certain amount of gaps were included between the particles. At this time, no binder is used.
- porous particles made of TiO 2 having an average particle diameter of about 1 ⁇ m, which was the same as the aggregated particles.
- the density of the obtained porous particles was 4.0 g / cm 3 .
- the porous particles were sprayed onto the PEN substrate on which ITO was formed by AD method to form a porous film made of TiO 2 .
- the film thickness could be arbitrarily adjusted in the range of 0.1 ⁇ m to 30 ⁇ m.
- Example 3 Commercially available agglomerated particles made of TiO 2 aggregated until fine particles having an average primary particle size of about 15 nm were about 1 ⁇ m were purchased and used. The aggregated particles were washed with purified water or the like, spread on a bat and dried so that the aggregated particles were not packed closely. The dried aggregated particles having an average particle diameter of about 1 ⁇ m were put in a reagent bottle and temporarily stored. Next, 10 g of the dried powdery agglomerated particles was put in an alumina container having a volume of 150 cm 3 . At this time, no pressure was applied to the powder, and a certain amount of gaps were included between the particles. At this time, no binder is used.
- porous particles made of TiO 2 having an average particle diameter of about 1 ⁇ m, which was the same as the aggregated particles.
- the density of the obtained porous particles was 3.7 g / cm 3 .
- the porous particles were sprayed onto the PEN substrate on which ITO was formed by AD method to form a porous film made of TiO 2 .
- the film thickness could be arbitrarily adjusted in the range of 0.1 ⁇ m to 30 ⁇ m.
- the porosity of the porous film decreases, and in an extreme case, it becomes a dense film.
- the collision energy also depends on the size of the particles to be sprayed and the material (hardness) of the substrate. Thus, it is not impossible to adjust the porosity only by the strength of the collision energy, but it is very difficult.
- the porous particles were sprayed onto a PEN substrate on which ITO was formed by AD method to form a film (film thickness: 1.8 ⁇ m) made of TiO 2 . Subsequently, an attempt was made to form a porous film having a thickness of 10 ⁇ m or more. However, a large number of large-diameter particles exceeding 10 ⁇ m were mixed in the particles to be sprayed, and the blasting action was dominant. Cann't get.
- a plurality of porous films having different film thicknesses were produced by the film forming methods of Example 1, Example 2, and Comparative Example 1, and the porosities thereof were compared.
- the comparison of the porosity was evaluated by comparing the dye adsorption amount. Specifically, each porous film is immersed in a solution containing N719 dye to adsorb the dye, and then the porous film is immersed in another solvent to remove the dye adsorbed on the porous film. Released. The amount of the desorbed dye was measured, and the porosities were compared by calculating the dye adsorption amount (dye adsorption density) per unit volume of each porous film. The result is shown in FIG.
- the dye adsorption density did not change even when the film thickness changed, and was almost constant. This indicates that the porosity is constant even when the thickness of the porous film is changed.
- the porous membrane of Example 1 has a higher dye adsorption density and a larger specific surface area than Example 2. This indicates that the specific surface area is increased because the average particle diameter of the primary particles used in the film forming method of Example 1 is smaller than that of Example 2. Therefore, it was shown that the porosity of the obtained porous film can be controlled by adjusting the average particle diameter of the primary particles used in the film forming method of the present invention.
- the solar cell using the porous film of Example 1 and Example 2 showed higher photoelectric conversion efficiency than the solar cell using the porous film of Comparative Example 1.
- This result is considered to reflect that the dye adsorption density (porosity) of the porous films of Example 1 and Example 2 is higher than that of Comparative Example 1.
- the porous film of Comparative Example 3 was thin, the photoelectric conversion efficiency was low. From this result, it was shown that the porous film obtained by the film forming method of the present invention is useful as a photoelectrode of a dye-sensitized solar cell.
- Example 1 in which the average particle diameter of primary particles used for film formation is smaller has a larger specific surface area than Example 2, by reducing the average particle diameter of primary particles, It was found that the specific surface area can be increased.
- a thick porous film was obtained as in Examples 1 and 2, but the specific surface area was smaller than that in Example and the photoelectric conversion efficiency ⁇ was also inferior.
- the average particle size of the particles to be sprayed is about 10 ⁇ m, and particles larger than 10 ⁇ m were also mixed in the particles to be sprayed, so that the film-forming effect and the blast effect antagonized during film formation, and the film growth stopped. It is thought that this is because it has been. In addition, depending on the film forming conditions, a phenomenon that the film breaks in the middle was also observed.
- the film forming method, the porous film, the photoelectrode provided with the porous film, and the dye-sensitized solar cell using the photoelectrode are widely applicable in the field of solar cells.
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Abstract
Description
本願は、2013年1月22日に、日本に出願された特願2013-009210号に基づき優先権を主張し、その内容をここに援用する。 The present invention includes a film forming method for forming a porous film made of the particles on the substrate by spraying the particles onto the substrate, the porous film formed by the film forming method, and the porous film. And a dye-sensitized solar cell including the photoelectrode.
This application claims priority on January 22, 2013 based on Japanese Patent Application No. 2013-009210 filed in Japan, the contents of which are incorporated herein by reference.
そこで、ペーストを焼成する方法に代えて、酸化チタン粒子を基板に吹き付けて酸化チタンからなる製膜体を得る方法も検討されている。このような方法としては、スプレー法、コールドスプレー法、静電スプレー法、溶射法、エアロゾルデポジション法(AD法)などが挙げられる。 As a method of forming a porous film that constitutes the photoelectrode of a dye-sensitized solar cell, a paste in which titanium oxide particles are mixed with a binder such as a polymer is applied on a substrate, and this is fired to form a porous film. How to do is known. This method has an advantage that a porous film can be easily obtained. However, since the substrate material is required to have heat resistance, there is a problem that the substrate to be used is substantially limited to the glass substrate.
Then, it replaces with the method of baking a paste, and the method of spraying a titanium oxide particle on a board | substrate and obtaining the film forming body which consists of titanium oxide is also examined. Examples of such a method include a spray method, a cold spray method, an electrostatic spray method, a thermal spray method, and an aerosol deposition method (AD method).
すなわち、原料化合物を含有する溶媒中において、前記原料化合物を原料とする無機物質の微粒子を合成するとともに前記微粒子を凝集させてなる凝集粒子を用いて、前記凝集粒子内の前記微粒子同士の結合を強化する工程を経て作製された多孔質粒子を基材に吹き付けて、前記基材と前記多孔質粒子とを接合させると共に、前記多孔質粒子同士を接合させることによって、前記基材上に前記無機物質によって構成された多孔質膜を製膜することを特徴とする製膜方法。
[2] 前記微粒子同士の結合を強化する工程において、前記凝集粒子を密に充填しないことにより、前記凝集粒子内の前記微粒子同士を接合させることを特徴とする前記[1]に記載の製膜方法。
前記微粒子同士の結合を強化する工程において、前記凝集粒子を密に充填しないことにより、前記凝集粒子同士を接合させずに、前記凝集粒子内の前記微粒子同士のみを接合させることを特徴とする前記[1]に記載の製膜方法。
[3] 前記微粒子同士の結合を強化する工程において、固相反応によって前記微粒子同士が接触している箇所を接合可能な温度以上、前記無機物質の融点以下、の温度域で焼成することにより前記微粒子同士を接合することを特徴とする前記[1]又は[2]に記載の製膜方法。
[4] 前記微粒子同士の結合を強化する工程において、前記微粒子を構成する金属又は半導体が含まれる反応性化合物と前記凝集粒子とを混合し、前記反応性化合物を介して前記微粒子同士を化学的に接合することを特徴とする[1]~[3]の何れか一項に記載の製膜方法。
[5] 前記凝集粒子及び前記多孔質粒子の平均粒径が200nm~2μmであることを特徴とする前記[1]~[4]の何れか一項に記載の製膜方法。
[6] 前記微粒子の平均粒径が10nm~100nmであることを特徴とする前記[1]~[5]の何れか一項に記載の製膜方法。
[7] 前記基材に吹き付けられる前記多孔質粒子の中に、粒径が5μm以上の多孔質粒子を含まないことを特徴とする前記[1]~[6]の何れか一項に記載の製膜方法。
すなわち、前記吹き付ける多孔質粒子の中に、粒径が5μm以上の多孔質粒子を含まないことを特徴とする前記[1]~[6]の何れか一項に記載の製膜方法。[8] 前記多孔質膜が色素増感太陽電池の光電極用の多孔質膜であることを特徴とする前記[1]~[7]の何れか一項に記載の製膜方法。
[9] 前記[1]~[8]の何れか一項に記載の製膜方法によって製膜された多孔質膜。
[10] 前記[9]に記載の多孔質膜を備えたことを特徴とする光電極。
[11] 前記[10]に記載の光電極を備えたことを特徴とする色素増感太陽電池。 [1] In a solvent containing a raw material compound, the fine particles of the inorganic substance using the raw material compound as a raw material are synthesized and aggregated particles obtained by aggregating the fine particles are used. By producing porous particles through a step of strengthening bonding, spraying the porous particles on a base material, joining the base material and the porous particles, and joining the porous particles to each other, A film forming method comprising forming a porous film made of the inorganic substance on the substrate.
That is, in the solvent containing the raw material compound, the fine particles of the inorganic material using the raw material compound as a raw material are synthesized and the aggregated particles obtained by aggregating the fine particles are used to bond the fine particles in the aggregated particles. The inorganic particles are formed on the base material by spraying the porous particles produced through the strengthening process onto the base material, thereby joining the base material and the porous particle and joining the porous particles to each other. A film forming method comprising forming a porous film made of a substance.
[2] In the step of strengthening the bonding between the fine particles, the fine particles in the aggregated particles are bonded to each other by not packing the aggregated particles closely, and the film formation according to the above [1] Method.
In the step of strengthening the bonding between the fine particles, the fine particles in the aggregated particles are bonded together without bonding the aggregated particles by not packing the aggregated particles closely. The film forming method according to [1].
[3] In the step of strengthening the bonding between the fine particles, by firing at a temperature range of a temperature at which the fine particles are in contact with each other by a solid-phase reaction and a temperature range that can be bonded to the melting point of the inorganic substance. The film forming method according to [1] or [2], wherein the fine particles are bonded to each other.
[4] In the step of strengthening the bonding between the fine particles, a reactive compound containing a metal or a semiconductor constituting the fine particles and the aggregated particles are mixed, and the fine particles are chemically bonded via the reactive compound. The film forming method according to any one of [1] to [3], wherein the film is bonded to the substrate.
[5] The film forming method according to any one of [1] to [4], wherein an average particle diameter of the aggregated particles and the porous particles is 200 nm to 2 μm.
[6] The film forming method according to any one of [1] to [5], wherein an average particle size of the fine particles is 10 nm to 100 nm.
[7] The porous particles to be sprayed onto the base material do not include porous particles having a particle size of 5 μm or more, according to any one of [1] to [6], Film forming method.
That is, the film forming method according to any one of [1] to [6], wherein the porous particles to be sprayed do not contain porous particles having a particle size of 5 μm or more. [8] The film forming method according to any one of [1] to [7], wherein the porous film is a porous film for a photoelectrode of a dye-sensitized solar cell.
[9] A porous film formed by the film forming method according to any one of [1] to [8].
[10] A photoelectrode comprising the porous film according to [9].
[11] A dye-sensitized solar cell comprising the photoelectrode according to [10].
なお本明細書において、微粒子とは無機物質からなる粒子(一次粒子)のことをいう。凝集粒子とは、前記微粒子が凝集して形成された粒子のことをいう。多孔質粒子とは、前記凝集粒子を焼成して得られる粒子のことをいう。
《製膜方法》
本発明の第一実施形態の製膜方法は、原料化合物を含有する溶媒中(液相原料中)において、前記原料化合物を原料とする、無機物質からなる微粒子(1次粒子)を合成するとともに前記微粒子を凝集させてなる凝集粒子を用いる。 Hereinafter, the present invention will be described with reference to the drawings based on preferred embodiments, but the present invention is not limited to such embodiments.
In the present specification, the fine particles mean particles (primary particles) made of an inorganic substance. Aggregated particles refer to particles formed by agglomerating the fine particles. The porous particles are particles obtained by firing the aggregated particles.
<Film forming method>
The film forming method according to the first embodiment of the present invention synthesizes fine particles (primary particles) made of an inorganic substance using a raw material compound as a raw material in a solvent containing the raw material compound (in a liquid phase raw material). Aggregated particles obtained by aggregating the fine particles are used.
前記無機物質は特に制限されないが、例えば、従来公知の色素増感太陽電池の光電極を構成する多孔質膜の材料が挙げられる。具体的には、チタン、亜鉛等の金属若しくは半導体、その金属若しくは半導体の塩、又はその金属若しくは半導体のハロゲン化物等が例示できる。 The liquid phase raw material includes a solvent and a raw material compound to be dissolved or dispersed in the solvent. The raw material compound is a compound containing an inorganic substance constituting the fine particles. For example, fine particles comprising titanium oxide and aggregated particles in which the fine particles are aggregated can be obtained by a hydrothermal synthesis method using water as the solvent and TiCl 4 as the raw material compound.
Although the said inorganic substance is not restrict | limited in particular, For example, the material of the porous film which comprises the photoelectrode of a conventionally well-known dye-sensitized solar cell is mentioned. Specific examples include metals or semiconductors such as titanium and zinc, salts of the metals or semiconductors, and halides of the metals or semiconductors.
本実施形態における焼成は、既に凝集している微粒子同士の結合を強化する目的で行うため、前記凝集粒子同士を密に充填させた状態で焼成する必要はない。むしろ、凝集粒子同士の不要な結合を防止するためには、前記凝集粒子同士を密に充填させない状態で焼成することが好ましい。具体的には、凝集粒子の密度が3.7~4.1g/cm3の状態で焼成することが好ましい。このことは特に重要なので、以下に更に詳細に説明する。 In the present embodiment, in order to increase the structural strength of the aggregated particles, a bonding process for strengthening the bonding between the fine particles constituting the aggregated particles is performed. As this bonding treatment, it is preferable to sinter the aggregated particles without using a binder containing a high molecular polymer as in Patent Documents 2 to 3, and only the aggregated particles are baked (only the aggregated particles are It is more preferable to fire alone. Here, the high molecular polymer means a polymer having a molecular weight (Mw) of 1000 or more.
Since the firing in the present embodiment is performed for the purpose of strengthening the bonding between the already aggregated fine particles, it is not necessary to perform the firing in a state where the aggregated particles are closely packed. Rather, in order to prevent unnecessary bonding between the agglomerated particles, it is preferable to fire in a state where the agglomerated particles are not closely packed. Specifically, it is preferable to perform firing in a state where the density of the aggregated particles is 3.7 to 4.1 g / cm 3 . This is particularly important and will be explained in more detail below.
一方、本実施形態における前記凝集粒子は、1次粒子である微粒子同士が焼成前に既に結合しているため、前記バインダーは必要ない。前記バインダーを使用せずに前記凝集粒子を焼成することにより、前記凝集粒子同士を結着させずに、前記凝集粒子を構成する微粒子同士をより強固に接合し、前記凝集粒子の構造的強度を高めた多孔質粒子を得ることができる。この際、前記バインダーを使用していないので、前記凝集粒子(2次粒子)同士が強固に結合して形成される大きな塊(焼結体)は形成されない。従来の焼結体は、後で解砕する必要があるが、本実施形態ではこの手間が生じない。本実施形態では、前記バインダーを使用しないことにより、焼成後においても前記凝集粒子と同様に粒径が揃った多孔質粒子を得ることができる。 The binder used in conventional baking is used for the purpose of aggregating particles that are not yet bonded. Furthermore, in order to ensure the aggregation state of the particles, it is necessary to densely pack the particles to which the binder is attached before firing. The binder burns out after firing and has a function of assisting strong sintering of the particles. However, it is extremely difficult to control the size of the sintered body (large lump) obtained after firing. For this reason, the process which crushes a sintered compact and arranges (classifies) further to a desired size using a filter etc. is indispensable.
On the other hand, the agglomerated particles in the present embodiment do not require the binder because the fine particles, which are primary particles, are already bonded before firing. By firing the agglomerated particles without using the binder, the agglomerated particles are bonded together more firmly without binding the agglomerated particles, and the structural strength of the agglomerated particles is increased. Enhanced porous particles can be obtained. At this time, since the binder is not used, a large lump (sintered body) formed by firmly bonding the aggregated particles (secondary particles) to each other is not formed. The conventional sintered body needs to be crushed later, but this trouble does not occur in this embodiment. In the present embodiment, by not using the binder, it is possible to obtain porous particles having a uniform particle size even after firing, similarly to the aggregated particles.
前記凝集粒子が酸化チタンからなる場合、前記焼成温度は400~1000℃が好ましく、500~800℃がより好ましく、500~600℃が更に好ましい。この焼成温度において、焼成時間は、1時間~24時間が好ましく、3時間~12時間がより好ましく、5時間~12時間が更に好ましい。 The temperature range of the baking is not particularly limited as long as it is a temperature capable of strengthening the bonding between the fine particles, but the temperature is higher than the temperature at which the portion where the fine particles are in contact with each other by a solid-phase reaction, and the inorganic A temperature range below the melting point of the substance is preferred. Here, the term “solid phase reaction” refers to a location where the fine particles are in contact with each other in a temperature range below the melting point temperature of the fine particles, where atom diffusion and recombination occur at the locations where the fine particles are in contact with each other. Refers to the reaction of binding.
When the aggregated particles are made of titanium oxide, the calcination temperature is preferably 400 to 1000 ° C, more preferably 500 to 800 ° C, and further preferably 500 to 600 ° C. At this firing temperature, the firing time is preferably 1 hour to 24 hours, more preferably 3 hours to 12 hours, and even more preferably 5 hours to 12 hours.
上記範囲の密度であると、多孔度の高い多孔質膜を容易に得ることができる。 The density of the porous particles is not particularly limited but is preferably 3.3 ~ 4.2g / cm 3, more preferably 3.5 ~ 4.2g / cm 3, is 3.7 ~ 4.1g / cm 3 Further preferred.
When the density is in the above range, a porous film having a high porosity can be easily obtained.
上記範囲のモース硬度であると、吹き付けによって多孔質粒子が粉砕されることを抑制し、多孔質粒子の多孔度を維持した多孔質膜を容易に形成することができる。 When the porous particles are made of titanium oxide, the Mohs hardness of the porous particles is preferably in the range of 5.5 to 6.0.
When the Mohs hardness is in the above range, the porous particles can be suppressed from being pulverized by spraying, and a porous film maintaining the porosity of the porous particles can be easily formed.
具体的には、例えば、前記微粒子を構成する金属又は半導体を含む反応性化合物を用い、前記反応性化合物を前記凝集粒子と混合し、前記反応性化合物を介して前記微粒子同士を化学的に接合することができる。前記反応性化合物として、光又は熱によって反応が促進される化合物を用いることができる。 In order to increase the structural strength of the agglomerated particles, bonding by chemical treatment can be performed instead of the firing as a treatment for strengthening the bonding between the fine particles constituting the agglomerated particles.
Specifically, for example, a reactive compound containing a metal or a semiconductor constituting the fine particles is used, the reactive compound is mixed with the aggregated particles, and the fine particles are chemically bonded via the reactive compound. can do. As the reactive compound, a compound whose reaction is accelerated by light or heat can be used.
以下、本発明の第一実施形態である多孔質膜の製膜方法を、図1を参照して説明する。
尚、以下の説明で用いる図面は模式的なものであり、長さ、幅、及び厚みの比率等は実際のものと同一とは限らず、適宜変更できる。 <Film formation by AD method>
Hereinafter, a method for forming a porous membrane according to a first embodiment of the present invention will be described with reference to FIG.
The drawings used in the following description are schematic, and the length, width, thickness ratio, and the like are not necessarily the same as the actual ones, and can be changed as appropriate.
製膜装置60は、ガスボンベ55と、搬送管56と、ノズル52と、基台63と、製膜室51と、を備えている。
ガスボンベ55には、多孔質粒子54を加速させて基材53に吹き付けるためのガス(以下、搬送ガスという)が充填されている。
ガスボンベ55には、搬送管56の一端が接続されている。ガスボンベ55から供給される搬送ガスは、搬送管56に供給される。 <Film forming device>
The
The
One end of a
また、製膜室51には図示略の基台交換手段が備えられている。 The
The
以下、多孔質粒子54の吹き付け方法の一例を説明する。
まず、真空ポンプ62を稼動させて製膜室51内を減圧する。製膜室51内の圧力は特に制限されないが、5~1000Paに設定することが好ましい。この程度に減圧することにより、製膜室51内の対流を抑制し、多孔質粒子54を製膜面71の所定の箇所に吹き付けることが容易になる。 <Blowing method>
Hereinafter, an example of a method for spraying the
First, the
搬送ガスの流速及び流量は、ノズル52から吹き付ける多孔質粒子54の材料、平均粒径、流速及び流量に応じて適宜設定すればよい。 Next, the carrier gas is supplied from the
What is necessary is just to set suitably the flow velocity and flow volume of carrier gas according to the material of the
以上の工程により、基材53の製膜面71の上に多孔質粒子54からなる所定の膜厚の多孔質膜が製膜される。 When the porous film of the
Through the above steps, a porous film having a predetermined film thickness made of
本発明の第二実施形態の多孔質膜は、第一実施形態の製膜方法により基材上に形成された多孔質膜である。この多孔質膜は、膜全体が均一な粒径の多孔質粒子によって形成されているため、構造的強度が高い。更に、膜全体に亘って高い多孔度を有する。このため、色素吸着量を従来よりも増加させた光電極が得られる。この結果、本発明の多孔質膜を備えた光電極及び色素増感太陽電池は、優れた光電変換効率を有する。
本実施形態の多孔質膜の用途は、光電極に限られず、多孔質構造を利用した物質吸着や物質担持の用途に広く適用できる。 <Porous membrane>
The porous film of the second embodiment of the present invention is a porous film formed on a substrate by the film forming method of the first embodiment. This porous film has high structural strength because the entire film is formed of porous particles having a uniform particle diameter. Furthermore, it has a high porosity throughout the membrane. For this reason, the photoelectrode which increased dye adsorption amount than before is obtained. As a result, the photoelectrode and dye-sensitized solar cell provided with the porous film of the present invention have excellent photoelectric conversion efficiency.
The use of the porous film of the present embodiment is not limited to the photoelectrode, but can be widely applied to the use of substance adsorption and substance support using a porous structure.
本発明の第三実施形態の光電極は、第二実施形態の多孔質膜に増感色素を吸着させた光電極である。増感色素の種類は特に制限されず、従来公知の色素が適用できる。第三実施形態において、多孔質膜は透明導電基板上に形成されていることが好ましい。 << Photoelectrode >>
The photoelectrode of the third embodiment of the present invention is a photoelectrode in which a sensitizing dye is adsorbed on the porous film of the second embodiment. The kind of sensitizing dye is not particularly limited, and conventionally known dyes can be applied. In the third embodiment, the porous film is preferably formed on a transparent conductive substrate.
本発明の第四実施形態の色素増感太陽電池は、第三実施形態の光電極と、対向電極と、電解液若しくは電解質層とを備えている。電解液は、光電極と対向電極の間において封止材によって封止されていることが好ましい。 《Dye-sensitized solar cell》
The dye-sensitized solar cell according to the fourth embodiment of the present invention includes the photoelectrode according to the third embodiment, a counter electrode, and an electrolytic solution or an electrolyte layer. The electrolytic solution is preferably sealed with a sealing material between the photoelectrode and the counter electrode.
1次粒径の平均が約15nmの微粒子が約1μmになるまで凝集したTiO2からなる市販の凝集粒子を購入して使用した。この凝集粒子を精製水等により洗浄し、凝集粒子同士が密に充填されないようにバット上に広げて乾燥させた。乾燥した粉状の約1μmの平均粒径の前記凝集粒子を試薬瓶に入れて一時保管した。
次に、その乾燥した粉状の凝集粒子10gを体積150cm3のアルミナ製の容器に入れた。この際、粉体に圧力をかけることは行わず、粒子間にある程度の隙間が含まれる状態とした。また、この際、バインダーは使用していない。
この状態で、空気雰囲気で500℃で5時間焼成し、平均粒径が前記凝集粒子と同様の約1μmに揃ったTiO2からなる多孔質粒子を得た。
得られた多孔質粒子の密度は、3.8g/cm3となった。
この多孔質粒子をAD法によって、ITOが製膜されたPEN基板上に吹き付けて、TiO2からなる多孔質膜を製膜した。膜厚は0.1μm~30μmの範囲で任意に調整することが可能であった。 [Example 1]
Commercially available agglomerated particles made of TiO 2 aggregated until fine particles having an average primary particle size of about 15 nm were about 1 μm were purchased and used. The aggregated particles were washed with purified water or the like, spread on a bat and dried so that the aggregated particles were not packed closely. The dried aggregated particles having an average particle diameter of about 1 μm were put in a reagent bottle and temporarily stored.
Next, 10 g of the dried powdery agglomerated particles was put in an alumina container having a volume of 150 cm 3 . At this time, no pressure was applied to the powder, and a certain amount of gaps were included between the particles. At this time, no binder is used.
In this state, calcination was performed at 500 ° C. for 5 hours in an air atmosphere to obtain porous particles made of TiO 2 having an average particle diameter of about 1 μm, which was the same as the aggregated particles.
The density of the obtained porous particles was 3.8 g / cm 3 .
The porous particles were sprayed onto the PEN substrate on which ITO was formed by AD method to form a porous film made of TiO 2 . The film thickness could be arbitrarily adjusted in the range of 0.1 μm to 30 μm.
1次粒径の平均が約30nmの微粒子が約1μmになるまで凝集したTiO2からなる市販の凝集粒子を購入して使用した。この凝集粒子を精製水等により洗浄し、凝集粒子同士が密に充填されないようにバット上に広げて乾燥させた。乾燥した粉状の約1μmの平均粒径の前記凝集粒子を試薬瓶に入れて一時保管した。
次に、その乾燥した粉状の凝集粒子10gを体積150cm3のアルミナ製の容器に入れた。この際、粉体に圧力をかけることは行わず、粒子間にある程度の隙間が含まれる状態とした。また、この際、バインダーは使用していない。
この状態で、空気雰囲気で500℃で5時間焼成し、平均粒径が前記凝集粒子と同様の約1μmに揃ったTiO2からなる多孔質粒子を得た。
得られた多孔質粒子の密度は、4.0g/cm3となった。
この多孔質粒子をAD法によって、ITOが製膜されたPEN基板上に吹き付けて、TiO2からなる多孔質膜を製膜した。膜厚は0.1μm~30μmの範囲で任意に調整することが可能であった。 [Example 2]
Commercially available agglomerated particles made of TiO 2 aggregated until fine particles having an average primary particle diameter of about 30 nm were about 1 μm were purchased and used. The aggregated particles were washed with purified water or the like, spread on a bat and dried so that the aggregated particles were not packed closely. The dried aggregated particles having an average particle diameter of about 1 μm were put in a reagent bottle and temporarily stored.
Next, 10 g of the dried powdery agglomerated particles was put in an alumina container having a volume of 150 cm 3 . At this time, no pressure was applied to the powder, and a certain amount of gaps were included between the particles. At this time, no binder is used.
In this state, calcination was performed at 500 ° C. for 5 hours in an air atmosphere to obtain porous particles made of TiO 2 having an average particle diameter of about 1 μm, which was the same as the aggregated particles.
The density of the obtained porous particles was 4.0 g / cm 3 .
The porous particles were sprayed onto the PEN substrate on which ITO was formed by AD method to form a porous film made of TiO 2 . The film thickness could be arbitrarily adjusted in the range of 0.1 μm to 30 μm.
1次粒径の平均が約15nmの微粒子が約1μmになるまで凝集したTiO2からなる市販の凝集粒子を購入して使用した。この凝集粒子を精製水等により洗浄し、凝集粒子同士が密に充填されないようにバット上に広げて乾燥させた。乾燥した粉状の約1μmの平均粒径の前記凝集粒子を試薬瓶に入れて一時保管した。
次に、その乾燥した粉状の凝集粒子10gを体積150cm3のアルミナ製の容器に入れた。この際、粉体に圧力をかけることは行わず、粒子間にある程度の隙間が含まれる状態とした。また、この際、バインダーは使用していない。
この状態で、空気雰囲気で300℃で5時間焼成し、平均粒径が前記凝集粒子と同様の約1μmに揃ったTiO2からなる多孔質粒子を得た。
得られた多孔質粒子の密度は、3.7g/cm3となった。
この多孔質粒子をAD法によって、ITOが製膜されたPEN基板上に吹き付けて、TiO2からなる多孔質膜を製膜した。膜厚は0.1μm~30μmの範囲で任意に調整することが可能であった。 [Example 3]
Commercially available agglomerated particles made of TiO 2 aggregated until fine particles having an average primary particle size of about 15 nm were about 1 μm were purchased and used. The aggregated particles were washed with purified water or the like, spread on a bat and dried so that the aggregated particles were not packed closely. The dried aggregated particles having an average particle diameter of about 1 μm were put in a reagent bottle and temporarily stored.
Next, 10 g of the dried powdery agglomerated particles was put in an alumina container having a volume of 150 cm 3 . At this time, no pressure was applied to the powder, and a certain amount of gaps were included between the particles. At this time, no binder is used.
In this state, calcination was performed at 300 ° C. for 5 hours in an air atmosphere to obtain porous particles made of TiO 2 having an average particle diameter of about 1 μm, which was the same as the aggregated particles.
The density of the obtained porous particles was 3.7 g / cm 3 .
The porous particles were sprayed onto the PEN substrate on which ITO was formed by AD method to form a porous film made of TiO 2 . The film thickness could be arbitrarily adjusted in the range of 0.1 μm to 30 μm.
公知の火炎溶融法によって作製された、1次粒径の平均が約15nmのTiO2粒子および1次粒径の平均が2μmのTiO2粒子を10:90(体積比)で混合した粒子を焼成せずに用い、AD法によって、ITOが製膜されたPEN基板上に前記混合した粒子を吹き付けて、TiO2からなる多孔質膜を製膜した。膜厚は0.1μm~30μmの範囲で任意に調整することが可能であった。
しかしながら、1次粒子のTiO2粒子を結着させずにそのまま吹き付けて製膜しているので、得られた多孔質膜におけるTiO2粒子同士の接合は、吹き付け時の衝突エネルギーにのみ依存している。このため、充分な衝突エネルギーを得るために強く吹き付ける必要がある。しかし、強く吹き付けると多孔質膜の多孔度が下がり、極端な場合には緻密膜になってしまう。また、衝突エネルギーは、吹き付ける粒子の大きさや基板の材質(硬度)によっても左右される。このように、衝突エネルギーの強さだけで多孔度を調整することは不可能ではないが、非常に困難である。 [Comparative Example 1]
Produced by a known flame fusion method, an average primary particle size calcined particles with an average of TiO 2 particles and the primary particle size of about 15nm was mixed TiO 2 particles 2μm 10:90 (volume ratio) The porous particles made of TiO 2 were formed by spraying the mixed particles on the PEN substrate on which ITO was formed by using the AD method. The film thickness could be arbitrarily adjusted in the range of 0.1 μm to 30 μm.
However, since the film as it is sprayed without binding the TiO 2 particles of primary particles, the bonding of the TiO 2 particles are in the obtained porous film, depending only on the collision energy at the time of spraying Yes. For this reason, it is necessary to spray strongly in order to obtain sufficient collision energy. However, when strongly sprayed, the porosity of the porous film decreases, and in an extreme case, it becomes a dense film. The collision energy also depends on the size of the particles to be sprayed and the material (hardness) of the substrate. Thus, it is not impossible to adjust the porosity only by the strength of the collision energy, but it is very difficult.
公知の火炎溶融法によって作製された1次粒径の平均が15nmのTiO2粒子を用いて、この粒子を焼成せずに用い、AD法によって、ITOが製膜されたPEN基板上に前記粒子を吹き付けて、TiO2からなる多孔質膜の製膜を試みた。しかし、構造的に脆弱な圧粉体しか得られなかった。 [Comparative Example 2]
Using TiO 2 particles having an average primary particle diameter of 15 nm prepared by a known flame melting method, the particles are used without firing, and the particles are formed on the PEN substrate on which ITO is formed by AD method. To make a porous film made of TiO 2 . However, only a structurally fragile green compact was obtained.
公知の火炎溶融法によって作製された1次粒径の平均が15nmのTiO2粒子と、バインダーであるポリエチレングリコール(PEG)(Mw:6000):を97:3(重量比)で混合した。この混合物を室温で乾燥固化させて、1次粒子が凝集した凝集体を得た。この凝集体を500℃で5時間焼成したのち、得られた焼結体の塊を乳鉢によって解砕し、25μmのメッシュに通すことにより、TiO2からなる多孔質粒子を作製した。
得られた多孔質粒子の平均粒径は約10μmであった。この多孔質粒子を用いて、AD法によって、ITOが製膜されたPEN基板上に前記多孔質粒子を吹き付けてTiO2からなる膜(膜厚1.8μm)を製膜した。
続いて10μm以上の厚みを有する多孔質膜の製膜を試みたが、吹き付ける粒子中に10μmを超える大径の粒子が多数混在しており、ブラスト作用が優勢であったため、厚い多孔質膜を得ることができなかった。 [Comparative Example 3]
TiO 2 particles having an average primary particle diameter of 15 nm prepared by a known flame melting method and polyethylene glycol (PEG) (Mw: 6000): as a binder were mixed at 97: 3 (weight ratio). This mixture was dried and solidified at room temperature to obtain an aggregate in which primary particles were aggregated. After this aggregate was fired at 500 ° C. for 5 hours, the resulting sintered mass was crushed with a mortar and passed through a 25 μm mesh to produce porous particles made of TiO 2 .
The average particle diameter of the obtained porous particles was about 10 μm. Using the porous particles, the porous particles were sprayed onto a PEN substrate on which ITO was formed by AD method to form a film (film thickness: 1.8 μm) made of TiO 2 .
Subsequently, an attempt was made to form a porous film having a thickness of 10 μm or more. However, a large number of large-diameter particles exceeding 10 μm were mixed in the particles to be sprayed, and the blasting action was dominant. Couldn't get.
実施例1、実施例2および比較例1の製膜方法により、膜厚の異なる複数の多孔質膜を作製し、その多孔度を比較した。多孔度の比較は、色素吸着量を比較することにより評価した。具体的には、各多孔質膜をN719色素が含まれる溶液に浸漬し、色素を吸着させた後、別の溶媒に多孔質膜を浸漬して、多孔質膜に吸着していた色素を脱離させた。この脱離した色素量を測定し、各多孔質膜の単位体積あたりの色素吸着量(色素吸着密度)を算出することにより、多孔度を比較した。その結果を図2に示す。 <Measurement of specific surface area>
A plurality of porous films having different film thicknesses were produced by the film forming methods of Example 1, Example 2, and Comparative Example 1, and the porosities thereof were compared. The comparison of the porosity was evaluated by comparing the dye adsorption amount. Specifically, each porous film is immersed in a solution containing N719 dye to adsorb the dye, and then the porous film is immersed in another solvent to remove the dye adsorbed on the porous film. Released. The amount of the desorbed dye was measured, and the porosities were compared by calculating the dye adsorption amount (dye adsorption density) per unit volume of each porous film. The result is shown in FIG.
実施例1、実施例2、比較例1及び比較例3の製膜方法により得た多孔質膜を色素増感太陽電池の光電極として用い、その変換効率を測定した。対極として、片面にプラチナの付いたガラス基板を用いた。色素としてN719を用い、電解液としてAN50(ソラロニクス社製)を用いて、常法により太陽電池セルを作製した。各多孔質膜を備えた各太陽電池セルの光電変換効率を、市販のソーラーシミュレータを用いて測定した。この結果を表1に示す。 <Measurement of photoelectric conversion efficiency η>
The porous film obtained by the film forming method of Example 1, Example 2, Comparative Example 1 and Comparative Example 3 was used as a photoelectrode of a dye-sensitized solar cell, and its conversion efficiency was measured. A glass substrate with platinum on one side was used as the counter electrode. Using N719 as the dye and AN50 (manufactured by Solaronics) as the electrolyte, solar cells were produced by a conventional method. The photoelectric conversion efficiency of each solar battery cell provided with each porous film was measured using a commercially available solar simulator. The results are shown in Table 1.
実施例1及び2の製膜方法によって膜厚の厚い多孔質膜が得られた。その比表面積が大きく、色素吸着量が多いため、高い光電変換効率ηを示した。また、製膜に使用する1次粒子の平均粒径が小さい実施例1の方が、実施例2よりも大きい比表面積を有することから、1次粒子の平均粒径を小さくすることにより、その比表面積を大きくすることが可能であることがわかった。
比較例1の製膜方法でも実施例1及び2と同様に膜厚の厚い多孔質膜が得られたが、その比表面積は実施例よりも小さく、光電変換効率ηも劣っていた。また、前述したように、吹き付ける粒子同士の衝突エネルギーのみで多孔質膜の多孔度を制御しているため、吹き付けの条件検討に多大な労力を要した。
比較例2では、平均粒径が小さい15nmの粒子のみを吹き付けたため、粒子が堆積しただけの圧粉体となった。圧粉体の構造は基板から容易に剥がれ落ちるほど脆弱であり、色素増感太陽電池の多孔質膜として使用可能な強度はなかった。
比較例3では、1次粒子をバインダーで固めて焼結させた塊を更に解砕して得た粒子で製膜したため、厚い多孔質膜が得られなかった。この理由として、吹き付ける粒子の平均粒径が約10μmであり、この吹き付け粒子中に10μmよりも大きい粒子も混在していたため、製膜中に製膜効果とブラスト効果が拮抗し、膜成長が止まってしまったためであると考えられる。また、製膜条件によっては膜が途中で割れてしまう現象も見られた。 [Summary of Examples and Comparative Examples]
A thick porous film was obtained by the film forming methods of Examples 1 and 2. Since the specific surface area was large and the amount of dye adsorption was large, a high photoelectric conversion efficiency η was exhibited. Moreover, since Example 1 in which the average particle diameter of primary particles used for film formation is smaller has a larger specific surface area than Example 2, by reducing the average particle diameter of primary particles, It was found that the specific surface area can be increased.
In the film forming method of Comparative Example 1, a thick porous film was obtained as in Examples 1 and 2, but the specific surface area was smaller than that in Example and the photoelectric conversion efficiency η was also inferior. In addition, as described above, since the porosity of the porous film is controlled only by the collision energy between the particles to be sprayed, much labor has been required for examining the spraying conditions.
In Comparative Example 2, since only particles with a small average particle diameter of 15 nm were sprayed, a green compact with only particles deposited was obtained. The structure of the green compact was so weak that it easily peeled off from the substrate, and there was no strength that could be used as a porous film of a dye-sensitized solar cell.
In Comparative Example 3, since a film obtained by further pulverizing a lump obtained by solidifying primary particles with a binder and sintering the film was formed, a thick porous film could not be obtained. The reason is that the average particle size of the particles to be sprayed is about 10 μm, and particles larger than 10 μm were also mixed in the particles to be sprayed, so that the film-forming effect and the blast effect antagonized during film formation, and the film growth stopped. It is thought that this is because it has been. In addition, depending on the film forming conditions, a phenomenon that the film breaks in the middle was also observed.
Claims (11)
- 原料化合物を含有する溶媒中において、前記原料化合物を原料とする無機物質の微粒子を合成するとともに前記微粒子を凝集させてなる凝集粒子を用いて、前記凝集粒子に含まれる前記微粒子同士の結合を強化する工程を経て多孔質粒子を作製し、前記多孔質粒子を基材に吹き付けて、前記基材と前記多孔質粒子とを接合させると共に、前記多孔質粒子同士を接合させることによって、前記基材上に前記無機物質によって構成された多孔質膜を製膜することを含むことを特徴とする製膜方法。 In the solvent containing the raw material compound, the fine particles of the inorganic substance using the raw material compound as a raw material are synthesized and the aggregated particles obtained by aggregating the fine particles are used to strengthen the bonding between the fine particles contained in the aggregated particles. The porous substrate is produced through the step of performing, the porous particle is sprayed on the base material, the base material and the porous particle are joined together, and the porous particles are joined together to form the base material. A film forming method comprising forming a porous film composed of the inorganic substance on the film.
- 前記微粒子同士の結合を強化する工程において、前記凝集粒子を密に充填しないことにより、前記凝集粒子内の前記微粒子同士を接合させることを特徴とする請求項1に記載の製膜方法。 The film forming method according to claim 1, wherein, in the step of strengthening the bonding between the fine particles, the fine particles in the aggregated particles are bonded together by not packing the aggregated particles closely.
- 前記微粒子同士の結合を強化する工程において、固相反応によって前記微粒子同士が接触している箇所を接合可能な温度以上、前記無機物質の融点以下、の温度域で焼成することにより前記微粒子同士を接合することを特徴とする請求項1又は2に記載の製膜方法。 In the step of strengthening the bonding between the fine particles, the fine particles are baked at a temperature range from a temperature at which the fine particles are in contact with each other by a solid-phase reaction to a temperature above the melting point of the inorganic substance and below. The film forming method according to claim 1, wherein bonding is performed.
- 前記微粒子同士の結合を強化する工程において、前記微粒子を構成する金属又は半導体が含まれる反応性化合物と前記凝集粒子とを混合し、前記反応性化合物を介して前記微粒子同士を化学的に接合することを特徴とする請求項1~3の何れか一項に記載の製膜方法。 In the step of strengthening the bonding between the fine particles, a reactive compound containing a metal or a semiconductor constituting the fine particles and the aggregated particles are mixed, and the fine particles are chemically bonded via the reactive compound. The film forming method according to any one of claims 1 to 3, wherein:
- 前記凝集粒子及び前記多孔質粒子の平均粒径が200nm~2μmであることを特徴とする請求項1~4の何れか一項に記載の製膜方法。 5. The film forming method according to claim 1, wherein an average particle diameter of the aggregated particles and the porous particles is 200 nm to 2 μm.
- 前記微粒子の平均粒径が10nm~100nmであることを特徴とする請求項1~5の何れか一項に記載の製膜方法。 6. The film forming method according to claim 1, wherein the average particle diameter of the fine particles is 10 nm to 100 nm.
- 前記基材に吹き付けられる前記多孔質粒子の中に、粒径が5μm以上の多孔質粒子を含まないことを特徴とする請求項1~6の何れか一項に記載の製膜方法。 The film forming method according to any one of claims 1 to 6, wherein the porous particles sprayed onto the substrate do not contain porous particles having a particle size of 5 µm or more.
- 前記多孔質膜が色素増感太陽電池の光電極用の多孔質膜であることを特徴とする請求項1~7の何れか一項に記載の製膜方法。 The film forming method according to any one of claims 1 to 7, wherein the porous film is a porous film for a photoelectrode of a dye-sensitized solar cell.
- 請求項1~8の何れか一項に記載の製膜方法によって製膜された多孔質膜。 A porous film formed by the film forming method according to any one of claims 1 to 8.
- 請求項9に記載の多孔質膜を備えたことを特徴とする光電極。 A photoelectrode comprising the porous film according to claim 9.
- 請求項10に記載の光電極を備えたことを特徴とする色素増感太陽電池。 A dye-sensitized solar cell comprising the photoelectrode according to claim 10.
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JP2020152951A (en) * | 2019-03-19 | 2020-09-24 | 積水化学工業株式会社 | Forming method for ceramic film, manufacturing apparatus for ceramic film, and film type flexible solar battery |
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JP2003208901A (en) * | 2002-01-16 | 2003-07-25 | Nissan Motor Co Ltd | Porous oxide film, its manufacturing method and cell of fuel cell using the same |
JP2004039286A (en) * | 2002-06-28 | 2004-02-05 | Toto Ltd | Method for manufacturing optical semiconductor electrode and photoelectric conversion element |
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JP2020152951A (en) * | 2019-03-19 | 2020-09-24 | 積水化学工業株式会社 | Forming method for ceramic film, manufacturing apparatus for ceramic film, and film type flexible solar battery |
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