TW201351673A - Silicon dioxide solar cell and glass plate having silicon dioxide solar cell structure - Google Patents

Abstract

To provide a silicon dioxide solar cell and a glass plate having a silicon dioxide solar cell structure that are easy to use. A silicon dioxide solar cell is configured by: arranging two electroconductive substrates so that the respective electroconductive surfaces face each other, where at least one of the substrates is a transparent light-entry-side substrate; and arranging a silicon dioxide particle compact on the substrate that is arranged so as to face the light-entry-side substrate. A porous titanium oxide sintered body is then arranged on the light-entry-side substrate. A glass plate having a silicon dioxide solar cell structure is configured by: arranging two electroconductive substrates so that the respective electroconductive surfaces face each other, where at least one of the substrates is a transparent light-entry-side substrate; and arranging a silicon dioxide particle compact on the substrate that is arranged so as to face the light-entry-side substrate. A porous titanium oxide sintered body is then arranged on the light-entry-side substrate. The liquid electrolyte is first injected when the cell is manufactured, and then removed. As a result, the electrolyte in liquid form is not present the cell, but some of the electrolyte component remains. This silicon dioxide solar cell and glass plate having a silicon dioxide solar cell structure do not involve use of a liquid electrolyte, and are therefore easy to use.

Description

Cerium dioxide solar cell and glass plate with erbium dioxide solar cell structure

The present invention relates to solar cells, and more particularly to a cerium oxide solar cell using cerium oxide and a glass plate having a cerium oxide solar cell structure.

Dry solar cells using semiconductors such as germanium have reached a practical stage. Semiconductor solar cells have high conversion efficiencies, but on the other hand they are at a high price because of the use of high purity materials.

A less expensive solar cell is a wet solar cell such as titanium dioxide (TiO ₂ ) and an electrolyte.

The structure of the titanium dioxide solar cell will be described using FIG.

In Fig. 1, (a) shows a titanium dioxide solar cell of a basic structure, and (b) shows a titanium dioxide solar cell which has been modified to be "dye-sensitized".

(a) A titanium dioxide solar cell having a basic structure shown in the drawings, a 1st-type glass substrate, in which a transparent conductive film 2 such as FTO is formed on one surface thereof to form a photoelectrode. A 3-series porous titanium oxide sintered body. The 4-system electrolyte is generally an iodine-based electrolyte in which iodine is dissolved in an aqueous solution of potassium iodide. A 5-series platinum counter electrode is formed on a glass substrate 7 on which a conductive film 6 such as FTO is formed. In addition, there are external loads such as 8-series sealing materials and 9-series resistors.

(b) A dye-sensitized titanium dioxide solar cell, a one-layer glass substrate, in which a transparent conductive film 2 such as FTO is formed on one surface thereof to form a photoelectrode. 10 is a porous titania sintered body to which a complex dye is attached. 4 series electrolyte, generally used in iodine An iodine-based electrolyte in which iodine is dissolved in an aqueous potassium solution. A 5-series platinum counter electrode is formed on a glass substrate 7 on which a conductive film 6 such as FTO is formed. In addition, there are external loads such as 8-series sealing materials and 9-series resistors.

The ultraviolet light that has passed through the transparent conductive film 2 on the glass substrate 1 and is incident is absorbed by the porous titanium oxide sintered body 3. The porous titanium oxide sintered body 3 which has been absorbed by light changes from an electronic ground state to an excited state, and the excited electrons are taken out from the transparent conductive film 2 to the outside by diffusion, and then introduced from the transparent conductive film 6 via the load 9. Platinum counter electrode 5.

Titanium dioxide has a photocatalytic function, and a material having photocatalytic function similar to that disclosed in Japanese Laid-Open Patent Publication No. 2004-290748 and No. 2004-290747 discloses fused silica treated with a hydrohalic acid.

Similarly, International Publication No. WO2005/089941, for materials having photocatalytic ability, discloses artificial crystals treated with hydrofluoric acid.

The artificial quartz photocatalyst has a function as a photocatalyst in a region of a wavelength of 200 to 800 nm which is wider than a photocatalyst, using fused silica as disclosed in JP-A-2004-290748 and JP-A-2004-290747.

The inventors of the present invention have found that the artificial crystal or fused silica belonging to the cerium oxide has a photovoltaic power generation capability, and the cerium oxide solar battery described in WO2011/049156 is proposed.

The solar cell described in International Publication WO2011/049156 will be described with reference to Fig. 2 .

In the figure, 11 and 17 are 30 mm × 30 mm glass substrates in which a transparent conductive layer FTO (fluorine-doped tin oxide) layer 12 and an FTO layer 16 are formed, and the size of the solar cell is 20 mm × 20 mm.

An n-type semiconductor layer 13 such as zinc oxide (ZnO) or titanium oxide (TiO ₂ ) is formed on the FTO layer on the light incident side, and a platinum film 15 is formed on the FTO layer 16 opposed to the FTO layer 12 on the light incident side.

Between the n-type semiconductor layer 13 and the platinum film 15, a glass containing SiO ₂ and a solar cell material 20 mixed with an electrolyte are sealed in a thickness of 0.15 to 0.20 mm.

In the solar cell material 20, particles of glass or the like containing SiO ₂ are immersed in a 5% hydrofluoric acid aqueous solution for 5 minutes, washed with water, dried, and pulverized so as to have a particle diameter of 0.2 mm or less.

The electrolyte was a liquid electrolyte in which 0.1 mol of LiI, 0.05 mol of I ₂ , 0.5 mol of 4-tert-butylpyridine, and 0.5 mol of tetrabutylammonium iodide were added to the solvent of acetonitrile.

Although the detailed mechanism of the photocell of cerium oxide is not clear, if it is irradiated with sunlight of a wavelength of 200 to 800 nm, it will be absorbed, and electrons will flow from the electrode on the side of the cerium oxide to the counter electrode via the load, in other words, from the counter electrode. A phenomenon in which an electric current flows toward an electrode on the ceria side.

Solar cell materials are most useful as artificial crystals, but fused silica glass, soda lime glass, alkali-free glass, and borosilicate glass can also generate electricity.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-290748

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-290747

[Patent Document 3] International Publication WO2005/089941

[Patent Document 4] International Publication WO2011/049156

The present inventors have found that artificial water crystal grains and fused silica grains treated with hydrohalic acid can exhibit more excellent solar cell functions by micronization.

The present inventors have found that artificial crystal or glass which is finely pulverized to a wavelength close to light will exhibit more excellent functions when used as a solar cell material.

The inventors have found that a cerium oxide solar cell generates electricity by using visible light to infrared light.

A glass plate is often used for lighting of buildings, lighting, warming of greenhouses for plant cultivation, dimming of lighting for stage/studios/shadows, and securing of sights for transportation devices such as automobiles.

The glass plates used in these devices will penetrate the necessary visible light, but will also penetrate ultraviolet light and infrared light other than visible light. Although the energy in sunlight is a small amount of 6%, an object irradiated by ultraviolet light having a short wavelength and high energy causes chemical changes, resulting in occurrence of adverse effects such as discoloration or embrittlement.

The energy in the sun also has 48% of infrared light. Because of the long wavelength and low energy, there are fewer cases of chemical changes to the illuminated object, but because it belongs to the hot line, it will cause the temperature of the object to be illuminated to rise.

In a cerium oxide solar cell, a titanium dioxide solar cell is combined in a series structure, and by taking an output from an electrode on the side of the solar cell of the cerium oxide and an electrode on the side of the TiO 2 solar cell, all of the light from ultraviolet light to infrared light is obtained. A solar cell that generates light by area light.

The ceria solar cell disclosed in the prior art International Publication No. WO 2011/049156 uses a liquid electrolyte. Further, the liquid electrolyte such as iodine which is most frequently used has a high reactivity, and if it is not completely sealed, it may be leaked by the liquid. The possibility of damage caused by damage to the surrounding machine caused by the machine or damage to the surrounding machine.

This phenomenon poses a major problem especially when blocking window glass of ultraviolet rays and infrared rays.

The inventors conducted further studies on the cerium oxide solar cell, and found that power can be generated even without using a liquid electrolyte.

This phenomenon is effective not only when used as a solar cell, but also when used in a window glass.

In light of this finding, it is an object of the present invention to provide a cerium oxide solar cell that does not use a liquid electrolyte.

Furthermore, it is an object of the present invention to provide a cerium oxide solar cell composite glass plate which does not use a liquid electrolyte.

In order to solve the problems, the cerium oxide solar cell provided by the present application is an artificial crystal granule which is treated with a hydrohalic acid and which is crystalline, or an amorphous glass which has been treated with a hydrohalic acid. , alkali-free glass, borosilicate glass, soda lime glass, etc., and no liquid electrolyte is used.

The solar cell further provided by the present application is an amorphous crystal particle treated by a hydrohalic acid or a quartz glass, an alkali-free glass, or a boron bismuth which has been treated with a halogen acid. In a cerium oxide solar cell comprising acid glass or soda lime glass, a titanium dioxide solar cell is combined in a series structure, and a liquid electrolyte is not used.

The solar cell further provided by the present application is an amorphous crystal particle treated by a hydrohalic acid or a quartz glass, an alkali-free glass, or a boron bismuth which has been treated with a halogen acid. Oxidation of acid glass, soda lime glass, etc. In the tantalum solar cell, a dye-sensitized titanium dioxide solar cell to which a complex pigment is attached is combined in a tandem structure, and a liquid electrolyte is not used.

The glass plate with the cerium oxide solar cell structure further provided by the present application is an artificial crystal granule which is treated with a hydrohalic acid and which is crystalline, or an amorphous glass which has been treated with a hydrohalic acid. , alkali-free glass, borosilicate glass, soda lime glass, etc., and no liquid electrolyte is used.

The glass plate with the cerium oxide solar cell structure further provided by the present application is an artificial crystal granule which is crystallized by hydrohalic acid or an amorphous quartz which has been treated with hydrohalic acid. In a cerium oxide solar cell comprising glass, alkali-free glass, borosilicate glass, soda lime glass, etc., a titanium dioxide solar cell is combined in a series structure, and a liquid electrolyte is not used.

The glass plate with the cerium oxide solar cell structure further provided by the present application is an artificial crystal granule which is crystallized by hydrohalic acid or an amorphous quartz which has been treated with hydrohalic acid. In a cerium oxide solar cell comprising glass, an alkali-free glass, a borosilicate glass, or a soda-lime glass, a dye-sensitized TiO 2 solar cell to which a ruthenium complex dye has been attached is combined in a tandem structure, and a liquid electrolyte is not used.

The specific features of the cerium oxide solar cell of the invention of the present application are as follows.

Two substrates having conductivity are disposed in a state of being opposed to each other, and at least one of the substrates is transparent and is a light incident side substrate, and the ceria particle formed body is disposed opposite to the light incident side substrate. On the configured substrate.

The two substrates having conductivity are disposed in opposite states according to the respective conductive surfaces, and at least one of the substrates is transparent and is set as a light incident side substrate, and the cerium oxide particles are disposed. The molded body is disposed on the substrate disposed to face the light incident side substrate, and the porous titanium oxide sintered body is disposed on the light incident side substrate.

Since the ceria solar cell and the ceria solar cell composite glass plate of the invention of the present application do not use a liquid electrolyte, there is no problem of liquid leakage.

1, 7, 11, 17‧‧‧ substrates

2, 6, 12, 16‧‧‧ transparent conductive film

3, 13‧‧‧ Porous titanium dioxide sintered body

4‧‧‧ Electrolytes

5, 15‧‧‧ counter electrode

8, 18‧‧‧ Sealing material

9, 19‧‧‧ external load

10, 23‧‧‧ Pigment-sensitized porous titanium oxide sintered body

13‧‧‧n type semiconductor layer

20‧‧‧Solar cell materials

21‧‧‧cerium oxide calcined body

1(a) and (b) are schematic views of a prior art porous titania solar cell and a dye-sensitized porous titania solar cell.

2 is a schematic diagram of a prior art cerium oxide solar cell.

3 is a schematic view of a glass having the cerium oxide solar cell of Example 1 and the cerium oxide solar cell structure of Example 2.

4 is a schematic view showing a glass having the solar cell using porous titania and ceria of Example 3 and the structure of the ceria solar cell of Example 4.

Fig. 5 is a schematic view showing a solar cell having the dye-sensitized porous titania and cerium oxide of Example 5 and a glass having a cerium oxide solar cell structure of Example 6.

Hereinafter, embodiments for carrying out the invention will be described with reference to the drawings.

[Example 1]

FIG. 3 shows the modified ceria solar cell and the ceria solar cell composite glass of the ceria solar cell shown in FIG. 2 as Example 1.

In the figure, 11 and 17 are glass substrates each having a transparent conductive film 12 such as FTO and a transparent conductive film 16 such as FTO, and the transparent conductive film 12 and the transparent conductive film 16 have electric power. Remove the function of the electrode. The glass substrates 11 and 12 are disposed in a state in which the transparent conductive film 12 on the glass substrate 11 and the FTO film 16 on the glass substrate 17 face each other.

21 is a cerium oxide (SiO ₂ ) fired body having a thickness of 0.15 to 0.20 mm, and is placed on a glass substrate 17 having no light incident side.

A platinum (Pt) film 15 as a charge extraction electrode is formed on the transparent conductive film 16 on the ceria side.

In addition, 18 series sealing material, 19 series external load.

The cerium oxide calcined body 21 is a glass granule such as quartz crystal, non-crystalline quartz glass, alkali-free glass, borosilicate glass or sodium calcium which is cerium oxide, and is immersed in a 5% hydrofluoric acid aqueous solution. After the minute, it was washed with water, dried, and then finely pulverized to a particle size of 500 nm or less.

The aqueous solution to be impregnated may be used as a hydrohalic acid in addition to hydrofluoric acid.

The liquid electrolyte is temporarily injected into the battery when the solar cell is manufactured, but since it is removed later, when the composite electrode is used as the ceria solar cell and the ceria solar cell, the liquid electrolyte is not present in the battery. However, there are some electrolyte components remaining.

The artificial crystal particles may also be used in a size of about 0.2 to 0.5 mm, or may be used without being calcined, but mixed with ethanol and coated on the platinum electrode 15 and then dried.

Light incident from the light incident side glass substrate 11 is incident on the ceria 21 and generates electricity.

The cerium oxide solar cell of the first embodiment can obtain a short-circuit current of 85 μA and an open voltage of 470 mV when the artificial crystal has a particle diameter of 0.2 mm or less, and a short-circuit current of 348 μA can be obtained when the particle diameter is 500 nm or less. , 620mV open voltage.

In addition, the inventors of the present invention have determined that the short-circuit current is measured by an illuminance of a 300 W white heat bulb that does not contain a component light source of the ultraviolet region, and an exposure time of 400 mV is observed for the artificial crystal solar cell belonging to the cerium oxide solar cell. The open voltage and the short-circuit current of 0.5 μA confirm that the cerium oxide solar cell can generate electricity even by using only infrared light.

From this phenomenon, it is known that the cerium oxide solar cell does not use a liquid electrolyte, and power can be generated even by using light that does not contain a component of the ultraviolet region.

[Embodiment 2]

The glass plate structure having the cerium oxide solar cell structure of the second embodiment is not changed as compared with the cerium oxide solar cell structure of the first embodiment, and thus the description thereof is omitted.

[Example 3]

The cerium oxide solar cell of Example 3 will be described with reference to Fig. 4 .

The solar cell of Example 3 was combined with the conventionally known titanium dioxide solar cell shown in Fig. 1 (a) in the ceria solar cell of Example 1.

In the figure, 11 is a transparent substrate made of glass or resin, and a transparent electrode film 12 such as FTO is formed on one surface thereof to form a light incident side electrode. The 13-series is made of solidified porous titanium dioxide by means of sintering or the like.

The 21-series artificial crystal particles having a particle diameter of 0.2 m or less are mixed with ethanol and applied to the electrode 15 made of platinum or the like, and dried.

A 16-series transparent electrode such as FTO, and 17 is a substrate made of glass or resin. In addition, 18 series sealing materials and 19 series external loads.

The ultraviolet light incident from the light incident side transparent substrate 11 is incident on the porous In the titanium dioxide 13 and generating electricity, ultraviolet light and visible light which do not contribute to power generation are incident on the cerium oxide 21 and generate electricity.

Accordingly, the ceria solar cell system of Example 3 can generate electricity by using light in the ultraviolet to visible light region.

A solar constant of 1 kw/1 m ^{2 was} irradiated to the ceria solar cell of Example 3 using a solar simulator to obtain a short-circuit current of 20 μA and an open voltage of 417 mV.

The liquid electrolyte is temporarily injected into the battery when the solar cell is manufactured, but since it is removed later, when the composite is used as a ceria solar cell and a ceria solar cell composite glass plate, there is no liquid electrolyte in the battery. However, there are some electrolyte components remaining.

[Example 4]

The glass plate structure having the cerium oxide solar cell structure of Example 4 is not changed as compared with the cerium oxide solar cell structure of Example 3, and thus the description thereof will be omitted.

[Example 5]

The cerium oxide solar cell of Example 5 will be described with reference to Fig. 5 .

In the ceria solar cell of Example 5, in the ceria solar cell of Example 3, the titanium oxide sintered body was attached to the solar cell of the complex dye.

In the figure, 11 is a transparent substrate made of glass or resin, and a transparent electrode film 12 such as FTO is formed on one surface thereof to form a light incident side electrode. In the case of the porous titania which is solidified by means of sintering or the like, a titanium oxide sintered body of a ruthenium complex dye is attached.

The 21-series artificial crystal particles having a particle diameter of 0.2 mm or less are mixed with ethanol and applied to the electrode 15 made of platinum or the like, and dried.

A 16-series transparent electrode such as FTO, and 17 is a substrate made of glass or resin. In addition, 18 series sealing materials and 19 series external loads.

The ultraviolet light incident from the light incident side transparent substrate 11 is incident on the porous titania 23 to generate electricity, and ultraviolet light and visible light which do not contribute to power generation are incident on the cerium oxide 21 and generate electricity.

Accordingly, the ceria solar cell system of Example 3 can generate electricity by using light in the ultraviolet to visible light region.

The liquid electrolyte is temporarily injected into the battery when the solar cell is manufactured, but since it is removed later, when the composite is used as a ceria solar cell and a ceria solar cell composite glass plate, there is no liquid electrolyte in the battery. However, there are some electrolyte components remaining.

[Embodiment 6]

The glass plate structure having the cerium oxide solar cell structure of Example 4 is not changed since the structure of the cerium oxide solar cell of Example 5, and thus the description is omitted.

Hereinafter, an alternative structure and material will be described.

[substrate]

In each of the examples, a container for accommodating a solar cell material and an electrolyte is made of a light-transmitting material on the light incident side, and a light-transmitting or opaque material is used for the light-incident side.

Glass, plastic, amorphous enamel, and polyester film can be used as the light transmissive material, and a metal plate such as stainless steel or nickel can be used as the opaque material.

[Transparent Conductor]

Glass and plastic used as light-transmitting materials are hardly conductive, and it is necessary to impart conductivity when using materials that are not electrically conductive. A light-transmitting and electrically conductive material is a carbon-based material such as AZO (Al-ZN-O), a carbon nanotube, or graphene, or a conductive PET, in addition to an oxide of tin such as FTO or ITO. ITO such as thin film; transparent conductive material such as carbon nanotubes and graphene, which is used for forming an electrode on a transparent body such as glass or plastic. The transparent electrode is disposed inside the solar cell.

On the opposite side of the light incident side of the solar cell storage container, when it is necessary to penetrate the light, a transparent electrode such as FTO, ITO, carbon nanotube, or graphene is formed on a transparent body such as glass or plastic. A metal plate in which a conductor for charge extraction such as a carbon nanotube or graphene is formed is used without passing light. The conductive system for charge extraction is disposed inside the solar cell.

By replacing the plastic with a conductive plastic, a transparent conductor may not be required.

[cerium oxide particles]

The crystalline artificial crystal particles or the amorphous glass particles treated with the hydrohalic acid are prepared as follows.

Crystallized artificial crystals of cerium oxide (SiO ₂ ) or glass particles of amorphous quartz glass, alkali-free glass, borosilicate glass, sodium calcium, etc., are immersed in an aqueous solution of hydrofluoric acid, followed by artificial crystal particles. Or the glass granules are washed with water, dried, and then made into a finely pulverized powder.

Hydrochloric acid may be used as the hydrohalic acid in addition to hydrofluoric acid, but is preferably hydrofluoric acid.

Furthermore, other hydrohalic acids can also be utilized.

In the case where the cerium oxide particles have not been treated with hydrohalic acid, the cerium oxide particle sample is micronized to an average particle diameter of several tens of nm.

The treatment of the cerium oxide particles by the hydrohalic acid may also be carried out not before the micronization, but after the micronization.

[Ceria layer]

The cerium oxide layer may also be a mixture of powders such as artificial crystals and platinum powder and ethanol, and calcined.

The particle size of the cerium oxide particle calcined body can be used up to about 0.5 mm.

[counter electrode]

As the semiconductor layer of the counter electrode, in addition to zinc oxide (ZnO), titanium oxide (TiO ₂ ), copper oxide (CuO), magnesium oxide (MgO), barium titanate (SrTiO ₃ ), carbon nitride can be used. , graphene, etc.

[incident side]

All of the examples described so far are those in which the cerium oxide calcined body is disposed on the light non-incident side. Since there is no absolute reason for such an arrangement, the cerium oxide calcined body can be disposed on the surface on the light incident side.

(industrial availability)

By using the invention of the present invention in which a tantalum dioxide solar cell is further combined in a tandem structure on a container of a titanium dioxide solar cell, it is possible to generate electricity by using all regions of the ultraviolet to infrared light to obtain a useful solar cell.

11, 17‧‧‧ substrate

12,16‧‧‧Transparent conductive film

15‧‧‧ counter electrode

18‧‧‧ Sealing material

19‧‧‧External load

21‧‧‧cerium oxide calcined body

Claims (6)

A cerium oxide solar cell is configured such that two conductive substrates are disposed such that respective conductive surfaces face each other, and at least one of the substrates is transparent and is a light incident side substrate; and two substrates are disposed between the two substrates The cerium oxide particle molded body is characterized in that the cerium oxide particle forming system is disposed on a substrate disposed opposite to the light incident side substrate; and the liquid electrolyte is not present in the cerium oxide solar cell, but Some of the electrolyte components remain. The cerium oxide solar cell according to the first aspect of the invention, wherein the porous titanium oxide sintered body is disposed on the light incident side substrate. A cerium oxide solar cell according to the second aspect of the invention, wherein the porous titanium oxide sintering system dye-sensitized porous titanium oxide sintered body. A glass plate having a structure of a cerium oxide solar cell, wherein two substrates having conductivity are disposed such that respective conductive surfaces face each other, and at least one of the substrates is transparent and is set as a light incident side substrate; A cerium oxide particle molded body is disposed between the substrates, wherein the cerium oxide particle forming system is disposed on a substrate disposed opposite to the light incident side substrate; and the cerium oxide solar cell composite glass plate is not disposed There is a liquid electrolyte, but there are some electrolyte components remaining. A glass plate having a cerium oxide solar cell structure according to the fourth aspect of the invention, wherein the porous titanium oxide sintered body is disposed on the light incident side substrate. A glass plate having a cerium oxide solar cell structure according to the fourth aspect of the invention, wherein the porous titanium oxide sintering system dye-sensitized porous titanium oxide sintered body.