WO2012066922A1

WO2012066922A1 - Gas manufacturing apparatus, gas manufacturing method, and gas manufacturing apparatus array

Info

Publication number: WO2012066922A1
Application number: PCT/JP2011/074971
Authority: WO
Inventors: 正樹加賀; 吉田　章人; 宮西　晋太郎; 弘松原
Original assignee: シャープ株式会社
Priority date: 2010-11-16
Filing date: 2011-10-28
Publication date: 2012-05-24
Also published as: JP5676218B2; JP2012107280A

Abstract

This gas manufacturing apparatus is characterized in being provided with a photoelectric conversion section, which has the light receiving surface and the rear surface thereof, and first and second electrodes for electrolysis, said electrodes being arranged on the rear surface and respectively having surfaces that can be in contact with the electrolyte solution. The gas manufacturing apparatus is also characterized in that the first and the second electrodes for electrolysis are provided such that, at the time when the first and the second electrodes for electrolysis are in contact with the electrolyte solution, the first and the second electrodes decompose the electrolyte solution by electrolysis using an electromotive force generated when the photoelectric conversion section receives light, and respectively generate a first gas and a second gas, and that the first electrode for electrolysis and the second electrode for electrolysis respectively have tilt angles different from each other, said tilt angles being formed between the surfaces that can be in contact with the electrolysis solution and the horizontal reference surface when the light receiving surface of the photoelectric conversion section is horizontally set.

Description

Gas production apparatus, gas production method, and gas production apparatus array

The present invention relates to a gas production apparatus, a gas production method, and a gas production apparatus array.

In recent years, the use of renewable energy is desired from the viewpoint of depletion of fossil fuel resources and the suppression of global warming gas emissions. There are a wide variety of renewable energy sources such as sunlight, hydropower, wind power, geothermal power, tidal power, and biomass. Among them, sunlight has a large amount of available energy, and there are geographical restrictions on other renewable energy sources. Because of the relatively small amount, early development and popularization of technology that can efficiently use energy from sunlight is desired.

Possible forms of energy generated from sunlight include electrical energy produced using solar cells and solar thermal turbines, thermal energy by collecting solar energy in a heat medium, and other types of sunlight. Examples include storable fuel energy such as liquid fuel and hydrogen by substance reduction. Many solar cell technologies and solar heat utilization technologies have already been put into practical use, but the energy utilization efficiency is still low, and the cost of producing electricity and heat is still high. Technology development is underway. Furthermore, while these forms of electricity and heat can be used to supplement short-term energy fluctuations, it is extremely difficult to supplement long-term fluctuations such as seasonal fluctuations, It is a problem that there is a possibility that the operating rate of the power generation equipment may be reduced due to the increase in power generation. On the other hand, storing energy as a substance, such as liquid fuel and hydrogen, is extremely effective as a technology that efficiently supplements long-term fluctuations and increases the operating rate of power generation facilities. It is an indispensable technology to raise and reduce carbon dioxide emissions thoroughly.

The types of fuel that can be stored are roughly divided into liquid fuels such as hydrocarbons, gaseous fuels such as biogas and hydrogen, solid pellets such as biomass-derived wood pellets and metals reduced by sunlight. it can. In terms of ease of infrastructure development and energy density, liquid fuel, gaseous fuel including hydrogen in terms of total utilization efficiency improvement with fuel cells, etc., solid fuel in terms of storability and energy density, Although each form has advantages and disadvantages, a hydrogen production technique by decomposing water with sunlight has attracted particular attention from the viewpoint that water that can be easily obtained as a raw material can be used.

As a method of producing hydrogen using solar energy using water as a raw material, platinum is supported on a photocatalyst such as titanium oxide, and this substance is put in water to perform light separation in a semiconductor, and an electrolytic solution. The water is decomposed directly at high temperature using the photolysis method by reducing protons and oxidizing water, or by using thermal energy such as a high-temperature gas furnace, or indirectly by coupling with redox of metals, etc. Pyrolysis method that uses the metabolism of microorganisms that use light such as algae, water electrolysis method that combines electricity generated by solar cells and water electrolysis hydrogen production equipment, photoelectric conversion used in solar cells Examples of the method include a photovoltaic method in which electrons and holes obtained by photoelectric conversion are used in a reaction by a hydrogen generation catalyst and an oxygen generation catalyst by supporting a hydrogen generation catalyst and an oxygen generation catalyst on the material. Among these, the one that has the possibility of producing a small hydrogen production device by integrating the photoelectric conversion unit and the hydrogen generation unit is considered to be a photolysis method, a biological method, a photovoltaic method, From the viewpoint of the conversion efficiency of solar energy, the photovoltaic method is considered to be one of the technologies closest to practical use.

Until now, the example of the hydrogen production apparatus which integrated photoelectric conversion and hydrogen generation by the photolysis method or the photovoltaic method has been disclosed. In the photolysis method, for example, according to Patent Document 1, a titanium oxide photocatalyst electrode on which a ruthenium complex is adsorbed and a platinum electrode, an apparatus using oxidation reduction of iodine or iron is disclosed. According to Patent Documents 2 and 3, an integrated structure is adopted by connecting two layers of photocatalysts in tandem, connecting a platinum counter electrode, and sandwiching an ion exchange membrane therebetween. On the other hand, in the photovoltaic method, a concept of a hydrogen production apparatus in which a photoelectric conversion unit, a hydrogen generation unit, and an oxygen generation unit are integrated has been announced (Non-Patent Document 1). According to this, charge separation is performed by using a photoelectric conversion unit, and hydrogen generation and oxygen generation are performed using corresponding catalysts. The photoelectric conversion part is made of a material used for solar cells. For example, in Non-Patent Document 2, after charge separation is performed with three silicon pin layers, a platinum catalyst is responsible for hydrogen generation and ruthenium oxide is responsible for oxygen generation. Further, in Non-Patent Document 3, a multi-junction photoelectric conversion material that absorbs light of different wavelengths is used by using Pt as a hydrogen generation catalyst and RuO ₂ as an oxygen generation catalyst to achieve high efficiency. In Patent Document 4 and Non-Patent Document 3, a hydrogen generation catalyst (NiFeO) and three layers of silicon pin are stacked in parallel on a substrate, and an oxygen generation catalyst (Co-Mo) is further formed on the silicon layer. ) To produce an integrated hydrogen production apparatus.

JP 2006-89336 A Special table 2003-504799 gazette JP-T-2004-504934 JP 2003-288955 A

However, in the gas manufacturing apparatus using the electromotive force generated by receiving light by the conventional photoelectric conversion device, the gas generated from the electrode for electrolysis is recovered as bubbles in the electrolytic solution, so that two gases generated from the two electrodes for electrolysis are used. The recovery ports are close to each other, and the piping is complicated.
This invention is made | formed in view of such a situation, and provides the gas manufacturing apparatus which can collect | recover the generated gas with the simplified piping.

The present invention includes a photoelectric conversion unit having a light receiving surface and a back surface thereof, and first and second electrodes for electrolysis that are provided side by side on the back surface and each have a surface that can contact an electrolytic solution, When the first and second electrolysis electrodes come into contact with the electrolytic solution, the first and second electrolysis electrodes use the electromotive force generated by the photoelectric conversion unit to receive light to electrolyze the electrolytic solution, respectively. When the light receiving surface of the photoelectric conversion unit is leveled, the first electrolysis electrode and the second electrolysis electrode are horizontal with the surface that can come into contact with the electrolytic solution. Provided is a gas production apparatus characterized in that an inclination angle with respect to a reference plane is different.

According to the present invention, the first and second electrolysis electrodes are configured to electrolyze the electrolytic solution using the electromotive force generated by the light received by the photoelectric conversion unit to generate the first gas and the second gas, respectively. Since it is provided, the first gas can be generated on the surface of the first electrolysis electrode, and the second gas can be generated on the surface of the second electrolysis electrode.
According to the present invention, since the first electrolysis electrode and the second electrolysis electrode are provided on the back surface of the photoelectric conversion portion, light can be incident on the light receiving surface of the photoelectric conversion portion without passing through the electrolyte solution. It is possible to prevent absorption of incident light and scattering of incident light. As a result, the amount of incident light to the photoelectric conversion unit can be increased, and the light use efficiency can be increased.
According to the present invention, since the first electrolysis electrode and the second electrolysis electrode are provided on the back surface of the photoelectric conversion unit, the light incident on the light receiving surface is generated from the first and second electrolysis electrodes, respectively. It is not absorbed or scattered by the first gas and the second gas. As a result, the amount of incident light to the photoelectric conversion unit can be increased, and the light use efficiency can be increased.

According to the present invention, the first electrolysis electrode and the second electrolysis electrode have different inclination angles between the surface that can come into contact with the electrolytic solution and the horizontal reference surface, so that the first gas rises as bubbles. A surface that can contact the electrolyte solution of the first electrolysis electrode that sometimes becomes the guide surface, and a surface that can contact the electrolyte solution of the second electrolysis electrode that becomes the guide surface when the second gas rises as bubbles. It can be shifted. Accordingly, a pipe for recovering the first gas provided close to the upper end of the first electrolysis electrode and a pipe for recovering the second gas provided close to the upper end of the second electrolysis electrode Can be provided without overlapping, and piping can be simplified. In particular, when the gas production apparatus is provided with a plurality of at least one of the first electrolysis electrode and the second electrolysis electrode, or when a plurality of gas production apparatuses are installed side by side, a plurality of first gas recovery ports are provided. The piping for connecting and the piping for connecting the plurality of second gas recovery ports can be provided without overlapping, and the piping can be simplified. Thereby, the installation cost when providing piping for recovering the first gas and the second gas can be reduced, and piping connection errors and the like can be prevented. In addition, the first electrolysis electrode and the second electrolysis electrode have different inclination angles between the surface that can contact the electrolytic solution and the horizontal reference surface, so that the light receiving surface of the photoelectric conversion unit is substantially horizontal. It is also possible to install so that the installation cost can be reduced. Moreover, it becomes possible to install a gas production apparatus on the surface of a pond or the sea.

It is a schematic plan view which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. FIG. 2 is a schematic cross-sectional view of the gas production apparatus taken along one-dot chain line AA in FIG. FIG. 2 is a schematic cross-sectional view of the gas production apparatus taken along a dotted line BB in FIG. FIG. 2 is a schematic cross-sectional view of a gas production apparatus taken along a dotted line CC in FIG. It is a schematic back view which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic sectional drawing which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. It is a schematic plan view which shows the structure of the gas manufacturing apparatus of one Embodiment of this invention. FIG. 18 is a schematic cross-sectional view of the gas production apparatus taken along dotted line AA in FIG. It is a schematic plan view which shows the structure of the gas manufacturing apparatus array of one Embodiment of this invention.

The gas production apparatus of the present invention includes a photoelectric conversion unit having a light receiving surface and a back surface thereof, first and second electrodes for electrolysis that are provided side by side on the back surface and each have a surface that can contact an electrolyte solution When the first and second electrolysis electrodes are in contact with the electrolytic solution, the first and second electrolysis electrodes electrolyze the electrolytic solution using electromotive force generated by the photoelectric conversion unit receiving light. The first electrolysis electrode and the second electrolysis electrode can contact the electrolyte when the first gas and the second gas are generated, respectively, and the light receiving surface of the photoelectric conversion unit is horizontal. The inclination angle between the surface and the horizontal reference surface is different.

In the present invention, the inclination angle is an inclination angle with respect to a horizontal reference plane, and is an angle in a range of 0 degrees to 180 degrees. When comparing two surfaces with an inclination angle, if one surface has an inclination angle of x degrees greater than 0 degrees and less than 90 degrees and the other surface has an inclination angle of (180-x) degrees, The inclination angles of these two surfaces are different.
In the present invention, the first electrode and the second electrode are electrodes for outputting photovoltaic power of the photoelectric conversion unit, and the first electrolysis electrode and the second electrolysis electrode are for electrolyzing the electrolytic solution. Electrode.
In the gas production apparatus of the present invention, when the light receiving surface of the photoelectric conversion unit is leveled, a first gas discharge port provided close to the upper end of the surface of the first electrolysis electrode that can contact the electrolytic solution; A second gas discharge port provided close to the upper end of the surface of the second electrolysis electrode that can contact the electrolyte, and the first electrolysis electrode collects the first gas from the first gas discharge port. The second electrolysis electrode may have a surface that can contact the electrolyte solution that is inclined so that the second gas can be recovered from the second gas discharge port. preferable.
According to such a configuration, the first gas can be recovered from the first gas outlet, and the second gas can be recovered from the second gas outlet.
In the gas manufacturing apparatus of the present invention, the photoelectric conversion unit has a rectangular light receiving surface, and the first and second gas discharge ports are provided close to opposite sides of the light receiving surface of the photoelectric conversion unit, respectively. Preferably. According to such a configuration, the first gas outlet and the second gas outlet can be provided on both sides of the photoelectric conversion unit, and the pipe for recovering the first gas and the pipe for recovering the second gas Can be simplified.

In the gas production apparatus of the present invention, at least one of the first and second electrolysis electrodes has a plurality of surfaces that can contact the strip-shaped electrolyte solution, and the long sides of the surfaces are adjacent to each other. It is preferable that they are provided alternately.
According to such a configuration, the distance between the portion where the reaction generating the first gas occurs and the portion where the reaction generating the second gas occurs can be shortened, and the ion concentration generated in the electrolyte can be reduced. Imbalance can be reduced. Moreover, the 1st gas and 2nd gas can be collect | recovered easily by making the surface which can contact electrolyte solution into strip | belt shape.
In the gas manufacturing apparatus of the present invention, the first mold part and the second electrolysis electrode provided between the first electrolysis electrode and the back surface of the photoelectric conversion unit and the back surface of the photoelectric conversion unit are provided. The first mold part and the second mold part have a horizontal reference with a surface that can contact the electrolyte of the first electrolysis electrode when the light receiving surface of the photoelectric conversion unit is horizontal. It is preferable that the tilt angle between the reference surface and the tilt angle between the surface and the reference surface is different from the tilt angle between the second electrolysis electrode and the electrolyte.
According to such a configuration, the inclination angle between the surface of the first electrolysis electrode that can contact the electrolytic solution and the horizontal reference surface, the surface of the second electrolysis electrode that can contact the electrolytic solution, and the reference The inclination angle between the surfaces can be easily made different.

In the gas production apparatus of the present invention, the first mold part and the second mold part are preferably made of a solid resin.
According to such a configuration, the first mold part and the second mold part can be easily molded.
In the gas production apparatus of the present invention, it is preferable that a first conductive part is further provided between the first mold part and the first electrolysis electrode or between the second mold part and the second electrolysis electrode.
According to such a configuration, when the electromotive force generated by the photoelectric conversion unit receiving light is output to the first and second electrolysis electrodes, the internal resistance can be further reduced.
In the gas production apparatus of the present invention, each of the first and second electrolysis electrodes preferably has a groove-like depression extending in an inclined direction on a surface that can contact the electrolytic solution.
According to such a configuration, the first gas and the second gas can be raised as bubbles along the groove-shaped depression, and the first gas and the second gas can be separated and recovered. Moreover, according to this structure, the partition provided between the electrode for 1st electrolysis and the electrode for 2nd electrolysis is also omissible.

In the gas production apparatus of the present invention, when the light receiving surface of the photoelectric conversion unit is horizontal, the first electrolysis electrode can contact an electrolytic solution having an inclination angle of 1 degree to 60 degrees with the horizontal reference plane It is preferable that the second electrolysis electrode has a surface that can contact an electrolytic solution having an inclination angle of 120 degrees or more and 179 degrees or less with respect to the reference surface.
According to such a configuration, a recovery port for recovering the first gas and a recovery port for recovering the second gas can be provided on both sides of the gas production device, respectively, in order to recover the first gas. And a pipe for recovering the second gas can be provided on both sides of the gas production apparatus.
In the gas manufacturing apparatus of the present invention, the photoelectric conversion unit receives light to generate an electromotive force between the light receiving surface and the back surface, and the first electrolysis electrode is electrically connected to the back surface of the photoelectric conversion unit. And it is preferable that the 2nd electrode for electrolysis is electrically connected with the light-receiving surface of the said photoelectric conversion part.
According to such a structure, the thing of a laminated structure can be utilized for a photoelectric conversion part.

In the gas production apparatus of the present invention, it is preferable that the gas production apparatus further includes a first electrode that contacts the light receiving surface of the photoelectric conversion unit.
According to such a configuration, the internal resistance can be reduced.
In the gas manufacturing apparatus of the present invention, it is preferable to further include a second conductive part that electrically connects the first electrode and the second electrolysis electrode.
According to such a structure, the light-receiving surface of a photoelectric conversion part and the 2nd electrode for electrolysis can be electrically connected.
In the gas manufacturing apparatus of the present invention, it is preferable that the second conductive portion is provided in a contact hole that penetrates the photoelectric conversion portion.
According to such a configuration, the wiring distance between the light receiving surface of the photoelectric conversion unit and the second electrolysis electrode can be shortened, and the internal resistance can be reduced.

The gas manufacturing apparatus of the present invention includes a second mold part provided between the second electrolysis electrode and the back surface of the photoelectric conversion part, the second mold part having insulating properties, and the photoelectric conversion unit. It is preferable that the second conductive portion is provided on a portion of the second mold portion that covers the side surface of the photoelectric conversion portion.
According to such a configuration, the second conductive portion can be provided with a small number of steps, and the manufacturing cost can be reduced.
The gas manufacturing apparatus of the present invention includes a second mold part provided between the second electrolysis electrode and the back surface of the photoelectric conversion part, the second mold part having insulating properties, and the photoelectric conversion unit. The second electrolysis electrode is preferably provided on a portion of the second mold part that covers the side surface of the photoelectric conversion unit, and is in contact with the first electrode.
According to such a configuration, the first electrode and the second electrolysis electrode can be electrically connected without providing the second conductive portion.

In the gas manufacturing apparatus of the present invention, the first mold part provided between the first electrolysis electrode and the back surface of the photoelectric conversion unit, and the second electrolysis electrode and the back surface of the photoelectric conversion unit are provided. A second electrode provided between the back surface of the photoelectric conversion unit and the first mold unit and between the back surface of the photoelectric conversion unit and the second mold unit. Is preferred.
According to such a configuration, when the electromotive force generated when the photoelectric conversion unit receives light is output to the first and second electrolysis electrodes, the internal resistance between the back surface of the photoelectric conversion unit and the first electrolysis electrode Can be made smaller.
In the gas manufacturing apparatus of the present invention, it is preferable to further include a third conductive part that electrically connects the second electrode and the first electrolysis electrode.
According to such a structure, the back surface of a photoelectric conversion part and the 1st electrode for electrolysis can be electrically connected.

In the gas manufacturing apparatus of the present invention, it is preferable that the third conductive portion is provided so as to cover the side portion of the first mold portion and is in contact with the second electrode.
According to such a structure, the back surface of a photoelectric conversion part and the 1st electrode for electrolysis can be electrically connected easily.
In the gas manufacturing apparatus of the present invention, the photoelectric conversion unit generates a potential difference between the first and second areas on the back surface by receiving light, the first area is electrically connected to the first electrolysis electrode, The second area is preferably electrically connected to the second electrolysis electrode.
According to such a configuration, an electromotive force can be generated between the first area and the second area in the photoelectric conversion unit.

In the gas manufacturing apparatus of the present invention, the photoelectric conversion part is made of at least one semiconductor material having an n-type semiconductor part and a p-type semiconductor part, and one of the first and second areas is the n-type semiconductor part. It is preferable that the other part is a part of the p-type semiconductor part.
According to such a configuration, an electromotive force can be generated between the first and second areas on the back surface of the photoelectric conversion unit when the photoelectric conversion unit receives light.
In the gas manufacturing apparatus of the present invention, it is preferable that a translucent substrate is further provided, and the photoelectric conversion unit is provided on the translucent substrate.
According to such a structure, a photoelectric conversion part can be formed on a translucent board | substrate.

The gas manufacturing apparatus of the present invention further includes a translucent substrate, the photoelectric conversion unit is provided on the translucent substrate, and the translucent substrate has a light receiving surface of the photoelectric conversion unit horizontally. Then, the inclination angle between the surface of the first electrolysis electrode that can contact the electrolytic solution and the horizontal reference surface, and the surface between the surface of the second electrolysis electrode that can contact the electrolytic solution and the reference surface. It is preferable that it is formed so as to have a different inclination angle.
According to such a configuration, the first and second electrolysis electrodes are provided so that the inclination angles of the surfaces of the first and second electrolysis electrodes that can contact the electrolytic solution differ depending on the shape of the translucent substrate. Can do.
In the gas production apparatus of the present invention, it is preferable that the second electrolysis electrode is provided on the back surface of the photoelectric conversion unit via an insulating unit.
According to such a configuration, it is possible to prevent a leak current from occurring.
In the gas production apparatus of the present invention, it is preferable that the photoelectric conversion unit has a photoelectric conversion layer including a p-type semiconductor layer, an i-type semiconductor layer, and an n-type semiconductor layer.
According to such a configuration, an electromotive force can be generated by causing light to enter the photoelectric conversion unit.

In the gas production apparatus of the present invention, the photoelectric conversion unit includes a plurality of photoelectric conversion layers connected in series, and the plurality of photoelectric conversion layers generate electromotive force generated by receiving light in the first electrolysis electrode and the second electrolysis. It is preferable to supply it to the electrode for use.
According to such a configuration, a high voltage electromotive force can be easily output to the first and second electrolysis electrodes.
In the gas manufacturing apparatus of the present invention, each photoelectric conversion layer is preferably connected in series by a fourth conductive portion.
According to such a configuration, the photoelectric conversion layers can be provided side by side.
In the gas production apparatus of the present invention, one of the first electrolysis electrode and the second electrolysis electrode is a hydrogen generation unit that generates H ₂ from the electrolytic solution, and the other is oxygen generation that generates O ₂ from the electrolytic solution. It is preferable that the hydrogen generation unit and the oxygen generation unit include a catalyst for a reaction in which H ₂ is generated from the electrolytic solution and a catalyst for a reaction in which O ₂ is generated from the electrolytic solution, respectively.
According to such a configuration, hydrogen serving as a fuel for the fuel cell can be produced.

In the gas production apparatus of the present invention, it is preferable that at least one of the hydrogen generation unit and the oxygen generation unit has a catalyst surface area larger than an area of the light receiving surface.
According to such a configuration, hydrogen and oxygen can be produced more efficiently.
In the gas production apparatus of the present invention, it is preferable that at least one of the hydrogen generation part and the oxygen generation part is a porous conductor carrying a catalyst.
According to such a configuration, the catalyst area of the reaction in which hydrogen or oxygen is generated can be increased.
In the gas production apparatus of the present invention, it is preferable that the hydrogen generation unit includes at least one of Pt, Ir, Ru, Pd, Rh, Au, Fe, Ni, and Se as a hydrogen generation catalyst.
According to such a configuration, hydrogen can be efficiently generated from the electrolytic solution.

In the gas production apparatus of the present invention, it is preferable that the oxygen generation unit includes at least one of Mn, Ca, Zn, Co, and Ir as an oxygen generation catalyst.
According to such a configuration, oxygen can be efficiently generated from the electrolytic solution.
The gas manufacturing apparatus of the present invention further includes a light-transmitting substrate and an electrolyte chamber, and the photoelectric conversion unit is provided on the light-transmitting substrate, and includes a first electrolysis electrode and a second electrolysis electrode. It is preferable that a top plate is further provided, and the electrolytic solution chamber is provided between the first electrolysis electrode and the second electrolysis electrode and the top plate.
According to such a configuration, the surface of the first electrolysis electrode that can contact the electrolyte solution and the surface of the second electrolysis electrode that can contact the electrolyte solution can be provided facing the electrolyte chamber, The first and second electrodes for electrolysis can be brought into contact with the electrolytic solution.

In the gas production apparatus of the present invention, it is preferable that the gas production apparatus further includes a partition partitioning the electrolyte chamber between the first electrolysis electrode and the top plate and the electrolyte chamber between the second electrolysis electrode and the top plate. .
According to such a configuration, the first gas and the second gas can be separated by the partition wall.
In the gas production apparatus of the present invention, the partition preferably includes an ion exchanger.
According to such a structure, the imbalance of the ion concentration which arises in electrolyte solution can be eliminated easily.
Moreover, this invention installs the gas manufacturing apparatus of this invention so that the light-receiving surface of the said photoelectric conversion part may become substantially horizontal, The said gas manufacturing apparatus has the 1st gas exhaust port which discharges | emits 1st gas, The second electrolysis chamber is provided with a second gas exhaust port for discharging the second gas, and an electrolytic solution chamber. The electrolytic solution is introduced into the electrolytic solution chamber, and sunlight is incident on the light receiving surface of the photoelectric conversion unit. A gas production method is also provided in which the first gas and the second gas are generated from the electrode for electrode and the electrode for second electrolysis, respectively, and the first gas and the second gas are discharged from the first gas outlet and the second gas outlet, respectively. .
According to the gas production method of the present invention, the first gas and the second gas can be produced by allowing light to enter the photoelectric conversion unit, and the first gas and the second gas can be easily recovered.

The present invention further includes a plurality of the gas production apparatuses of the present invention, a first gas discharge path, and a second gas discharge path, and each gas production apparatus includes a first gas discharge port and a first gas discharge port for discharging the first gas. A second gas discharge port for discharging two gases, the first gas discharge path is electrically connected to the first gas discharge port of each gas production apparatus, and the second gas discharge path is a second gas of each gas production apparatus. A gas production device array in communication with the outlet is also provided.
According to the gas production device array of the present invention, the generation amounts of the first gas and the second gas can be increased, and the first gas and the second gas are recovered from the first gas discharge path and the second gas discharge path, respectively. can do. Moreover, the 1st gas exhaust path and the 2nd gas exhaust path can be simplified and provided.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings. The configurations shown in the drawings and the following description are merely examples, and the scope of the present invention is not limited to those shown in the drawings and the following description.

Diagram 1 of a gas producing device is a schematic plan view showing the configuration of a gas producing device according to an embodiment of the present invention. 2 to 4 are schematic cross-sectional views of the gas production apparatus taken along one-dot chain line AA, dotted line BB, and dotted line CC in FIG. 1, respectively. FIG. 5 is a schematic back view showing the configuration of the gas production apparatus according to one embodiment of the present invention. 6 to 16 are schematic cross-sectional views showing the configuration of the gas production apparatus according to the embodiment of the present invention. 6, 13, and 15 correspond to the sectional view of the gas production apparatus taken along the dotted line BB in FIG. 1, and the sectional views of FIGS. 7, 8, 11, 12, 14, and 16 are 9 and 10 correspond to the cross-sectional view of the gas production apparatus taken along one-dot chain line AA in FIG.

The gas production apparatus 23 according to the present embodiment includes a photoelectric conversion unit 2 having a light receiving surface and a back surface thereof, and a surface that is provided side by side on the back surface of the photoelectric conversion unit 2 and that can contact an electrolytic solution. 1 and

second electrolysis electrodes

8 and 7, and when the first and

second electrolysis electrodes

8 and 7 are in contact with the electrolytic solution, the first and

second electrolysis electrodes

8 and 7 are connected to the photoelectric conversion unit 2. The electrolysis solution is electrolyzed using the electromotive force generated by receiving the light to generate the first gas and the second gas, respectively, and when the light receiving surface of the photoelectric conversion unit 2 is leveled, the first electrolysis The electrode for electrode 8 and the electrode for second electrolysis 7 are characterized in that the inclination angles between the surface that can contact the electrolyte and the horizontal reference surface are different.
Moreover, the gas manufacturing apparatus 23 of the present embodiment may include the translucent substrate 1.
Hereinafter, the gas manufacturing apparatus of this embodiment is demonstrated.

1. Translucent substrate The translucent substrate 1 may be provided in the gas manufacturing apparatus 23 of the present embodiment. Moreover, the photoelectric conversion part 2 may be provided on the translucent board | substrate 1 so that a light-receiving surface may become the translucent board | substrate 1 side. In addition, when the photoelectric conversion part 2 consists of semiconductor substrates etc. and has fixed intensity | strength, the translucent board | substrate 1 can be abbreviate | omitted. Moreover, when the photoelectric conversion part 2 can be formed on a flexible material such as a resin film, the translucent substrate 1 can be omitted.

Moreover, the translucent board | substrate 1 is a member used as the foundation for comprising this gas manufacturing apparatus. Moreover, in order to receive sunlight with the light-receiving surface of the photoelectric conversion unit 2, it is preferable to be transparent and have a high light transmittance. However, as long as the light can be efficiently incident on the photoelectric conversion unit 2. There is no limit to the light transmittance.
As a substrate material having a high light transmittance, for example, a transparent rigid material such as soda glass, quartz glass, Pyrex (registered trademark), or a synthetic quartz plate, or a transparent resin plate or film material is preferably used. In view of chemical and physical stability, it is preferable to use a glass substrate.
On the surface of the translucent substrate 1 on the photoelectric conversion unit 2 side, a fine uneven structure can be formed so that incident light is effectively irregularly reflected on the surface of the photoelectric conversion unit 2. This fine concavo-convex structure can be formed by a known method such as reactive ion etching (RIE) treatment or blast treatment.

Further, when the light-receiving surface of the photoelectric conversion unit 2 is leveled, the translucent substrate 1 has an inclination angle between the surface of the first electrolysis electrode 8 that can contact the electrolytic solution and a horizontal reference surface, You may shape | mold so that the inclination angle between the surface which can contact the electrolyte solution of the electrode 7 for 2 electrolysis and a horizontal reference plane differs. By providing the photoelectric conversion unit 2 and the first and

second electrolysis electrodes

8 and 7 on the translucent substrate 1 formed in this manner, the surface of the first electrolysis electrode 8 that can contact the electrolytic solution and The tilt angle between the horizontal reference plane and the tilt angle between the horizontal reference plane and the plane that can contact the electrolytic solution of the second electrolysis electrode 7 can be different. For example, the gas manufacturing apparatus of the present embodiment can have a cross section as shown in FIGS. 6 is a cross-sectional view corresponding to the cross-sectional view taken along the dotted line BB in FIG. 1, and FIG. 7 is a cross-sectional view corresponding to the cross-sectional view taken along the dotted line CC in FIG. By using the translucent substrate 1 as shown in FIGS. 6 and 7, it is possible to provide different inclination angles of the surfaces of the first and

second electrolysis electrodes

8 and 7 that can come into contact with the electrolytic solutions, The first gas recovery port 20 and the second gas recovery port 19 can be provided on both sides of the gas production apparatus. Thereby, the piping for recovering the first gas and the piping for recovering the second gas can be simplified.
Such a molded translucent substrate 1 may be formed by pouring glass or the like into a mold, may be formed by deforming a plate-like substrate, or may be formed by combining plate-like substrates. May be.

2. First Electrode, Second Conductive Part The first electrode 4 can be provided on the translucent substrate 1 and can be provided in contact with the light receiving surface of the photoelectric conversion part 2. Moreover, the 1st electrode 4 may have translucency. Moreover, the 1st electrode 4 may be directly provided in the light-receiving surface of the photoelectric conversion part 2, when the translucent board | substrate 1 can be abbreviate | omitted. The first electrode 4 can be electrically connected to the second electrolysis electrode 7. By providing the first electrode 4, the current flowing between the light receiving surface of the photoelectric conversion unit 2 and the second electrolysis electrode 7 can be increased. Further, when the photoelectric conversion unit 2 generates an electromotive force between the first area and the second area on the back surface of the photoelectric conversion unit 2 as shown in FIGS. 14 to 16, the first electrode 4 is unnecessary.
The first electrode 4 may be electrically connected to the second electrolysis electrode 7 through the second conductive portion 10 as shown in FIGS. 4, 7, 8, and 11, and as shown in FIG. It may be in contact with the electrode 7.
The first electrode 4 may be made of a transparent conductive film such as ITO or SnO _2, or may be made of a metal finger electrode such as Ag or Au.

A case where the first electrode 4 is a transparent conductive film will be described below.
The transparent conductive film is used to facilitate contact between the light receiving surface of the photoelectric conversion unit 2 and the second electrolysis electrode 7.
What is generally used as a transparent electrode can be used. Specifically, In—Zn—O (IZO), In—Sn—O (ITO), ZnO—Al, Zn—Sn—O, SnO _{2 and the} like can be given. The transparent conductive film preferably has a sunlight transmittance of 85% or more, particularly 90% or more, and particularly 92% or more. This is because the photoelectric conversion unit 2 can absorb light efficiently.
As a method for producing the transparent conductive film, a known method can be used, and examples thereof include sputtering, vacuum deposition, sol-gel method, cluster beam deposition method, and PLD (Pulse Laser Deposition) method.

The second conductive portion 10 can be provided so as to contact the first electrode 4 and the second electrolysis electrode 7 respectively. By providing the second conductive portion 10, the first electrode 4 and the second electrolysis electrode 7 that are in contact with the light receiving surface of the photoelectric conversion portion 2 can be easily electrically connected.

Moreover, the 2nd electroconductive part 10 may be provided in the contact hole which penetrates the photoelectric conversion part 2 or the 2nd type | mold part 12 like FIG. Thus, the current path between the light receiving surface of the photoelectric conversion unit 2 and the second electrolysis electrode 7 can be shortened, and the first gas and the second gas can be generated more efficiently. In addition, the contact hole provided with the second conductive portion 10 may be one or more, and may have a circular cross section.
Moreover, the 2nd electroconductive part 10 may be provided so that the side surface of the photoelectric conversion part 2 may be covered like FIG.

The material of the second conductive portion 10 is not particularly limited as long as it has conductivity. A paste containing conductive particles, for example, a carbon paste, an Ag paste or the like applied by screen printing, an inkjet method, etc., dried or baked, a method of forming a film by a CVD method using a raw material gas, a PVD method, Examples thereof include a vapor deposition method, a sputtering method, a sol-gel method, and a method using an electrochemical redox reaction.

3. Photoelectric Conversion Unit The photoelectric conversion unit 2 has a light receiving surface and a back surface, and a first electrolysis electrode 8 and a second electrolysis electrode 7 are provided on the back surface of the photoelectric conversion unit 2. The light receiving surface is a surface that receives light for photoelectric conversion, and the back surface is the back surface of the light receiving surface. Moreover, the photoelectric conversion part 2 can be provided on the translucent substrate 1 provided with the first electrode 4 with the light receiving surface facing down. For example, the photoelectric conversion unit 2 may generate an electromotive force between the light receiving surface and the back surface as shown in FIGS. 2 to 4 and 6 to 13, and the first area on the back surface as shown in FIGS. And an electromotive force may be generated between the first area and the second area. The photoelectric conversion unit 2 as shown in FIGS. 14 to 16 can be formed by a semiconductor substrate on which the n-type semiconductor region 37 and the p-type semiconductor region 36 are formed. Moreover, when the translucent board | substrate 1 has a part from which an inclination angle differs like FIG.6, 7, the photoelectric conversion part 2 is formed on the part from which an inclination angle differs, respectively, and these photoelectric conversion parts are made into You may connect electrically.
Although the shape of the photoelectric conversion part 2 is not specifically limited, For example, it can be set as a square shape.
The photoelectric conversion unit 2 is not particularly limited as long as it can separate charges by incident light and generates an electromotive force. For example, the photoelectric conversion unit using a silicon-based semiconductor or the photoelectric conversion unit using a compound semiconductor A photoelectric conversion part using a dye sensitizer, a photoelectric conversion part using an organic thin film, and the like.

When the first gas and the second gas are hydrogen and oxygen, the photoelectric conversion unit 2 is necessary for generating hydrogen and oxygen in the first electrolysis electrode 8 and the second electrolysis electrode 7 by receiving light. It is necessary to use a material that generates an electromotive force. The potential difference between the first electrolysis electrode 8 and the second electrolysis electrode 7 needs to be larger than the theoretical voltage (1.23 V) for water decomposition, and for this purpose, a sufficiently large potential difference needs to be generated in the photoelectric conversion unit 2. There is. Therefore, it is preferable that the photoelectric conversion unit 2 connects two or more junctions in series such as a pn junction to generate an electromotive force. For example, as shown in FIG. 16, it can have a structure in which photoelectric conversion layers provided in parallel are connected by the fourth conductive portion 42.

Examples of materials that perform photoelectric conversion include silicon-based semiconductors, compound semiconductors, and materials based on organic materials, and any photoelectric conversion material can be used. In order to increase the electromotive force, these photoelectric conversion materials can be stacked. In the case of stacking, it is possible to form a multi-junction structure with the same material, but stacking multiple photoelectric conversion layers with different optical band gaps and complementing the low sensitivity wavelength region of each photoelectric conversion layer mutually By doing so, incident light can be efficiently absorbed over a wide wavelength region. The plurality of photoelectric conversion layers preferably have different band gaps. According to such a configuration, the electromotive force generated in the photoelectric conversion unit 2 can be increased, and the electrolytic solution can be electrolyzed more efficiently.

Moreover, it is possible to interpose a conductor such as a transparent conductive film between the layers in order to improve the serial connection characteristics between the photoelectric conversion layers and to match the photocurrent generated in the photoelectric conversion unit 2. Thereby, it becomes possible to suppress deterioration of the photoelectric conversion unit 2.
An example of the photoelectric conversion unit 2 will be specifically described below. The photoelectric conversion unit 2 may be a combination of these. Moreover, as long as there is no contradiction, the example of the following photoelectric conversion parts 2 can also be made into a photoelectric converting layer.

3-1. Photoelectric conversion part using a silicon-based semiconductor Examples of the photoelectric conversion part 2 using a silicon-based semiconductor include a single crystal type, a polycrystalline type, an amorphous type, a spherical silicon type, and combinations thereof. Any of them can have a pn junction in which a p-type semiconductor and an n-type semiconductor are joined. Further, a pin junction in which an i-type semiconductor is provided between a p-type semiconductor and an n-type semiconductor may be provided. Further, it may have a plurality of pn junctions, a plurality of pin junctions, or a pn junction and a pin junction.
The silicon-based semiconductor is a semiconductor containing silicon, such as silicon, silicon carbide, or silicon germanium. In addition, silicon or the like in which n-type impurities or p-type impurities are added is included, and crystalline, amorphous, or microcrystalline silicon is also included.
In addition, the photoelectric conversion unit 2 using a silicon-based semiconductor may be a thin film or a thick photoelectric conversion layer formed on the translucent substrate 1, or a pn junction or a wafer such as a silicon wafer. A pin junction may be formed, or a thin film photoelectric conversion layer may be formed on a wafer having a pn junction or a pin junction.

An example of forming the photoelectric conversion unit 2 using a silicon-based semiconductor is shown below.
A first conductivity type semiconductor layer is formed on the first electrode 4 laminated on the translucent substrate 1 by a method such as a plasma CVD method. As the first conductive type semiconductor layer, a p + type or n + type amorphous Si thin film doped with a conductivity type determining impurity atom concentration of about 1 × 10 ¹⁸ to 5 × 10 ²¹ / cm ³ , a polycrystalline or A microcrystalline Si thin film is used. The material of the first conductivity type semiconductor layer is not limited to Si, and it is also possible to use a compound such as SiC, SiGe, or Si _x O _1-x .

On the first conductivity type semiconductor layer thus formed, a polycrystalline or microcrystalline crystalline Si thin film is formed as a crystalline Si photoactive layer by a method such as plasma CVD. The conductivity type is the first conductivity type having a lower doping concentration than the first conductivity type semiconductor, or the i conductivity type. The material for the crystalline Si-based photoactive layer is not limited to Si, and it is also possible to use a compound such as SiC, SiGe, or Si _x O _1-x .

Next, in order to form a semiconductor junction on the crystalline Si-based photoactive layer, a second conductivity type semiconductor layer having a conductivity type opposite to the first conductivity type semiconductor layer is formed by a method such as plasma CVD. As the second conductive type semiconductor layer, an n + type or p + type amorphous Si thin film doped with about 1 × 10 ¹⁸ to 5 × 10 ²¹ / cm ³ of a conductivity type determining impurity atom, or a polycrystalline or microscopic A crystalline Si thin film is used. The material of the second conductivity type semiconductor layer is not limited to Si, and it is also possible to use a compound such as SiC, SiGe, or Si _x O _1-x . In order to further improve the bonding characteristics, it is possible to insert a substantially i-type non-single-crystal Si-based thin film between the crystalline Si-based photoactive layer and the second conductive type semiconductor layer. In this manner, one photoelectric conversion layer closest to the light receiving surface can be stacked.

Next, a second photoelectric conversion layer is formed. The second photoelectric conversion layer includes a first conductive semiconductor layer, a crystalline Si-based photoactive layer, and a second conductive semiconductor layer, and each layer corresponds to the first photoelectric conversion layer. The first conductive type semiconductor layer, the crystalline Si-based photoactive layer, and the second conductive type semiconductor layer are formed. When a potential sufficient for water splitting cannot be obtained with a two-layer tandem, it is preferable to take a three-layer structure or more. However, the volume crystallization fraction of the crystalline Si photoactive layer of the second photoelectric conversion layer is preferably higher than that of the first crystalline Si photoactive layer. Similarly, when three or more layers are laminated, the volume crystallization fraction is preferably increased as compared with the lower layer. This increases the absorption in the long wavelength region, shifts the spectral sensitivity to the longer wavelength side, and can improve the sensitivity in a wide wavelength region even when the photoactive layer is configured using the same Si material. This is because. That is, by using a tandem structure with Si having different crystallization rates, the spectral sensitivity is widened, and light can be used with high efficiency. At this time, if the low crystallization rate material is not on the light receiving surface side, high efficiency cannot be achieved. Further, when the crystallization rate is lowered to 40% or less, the amorphous component increases and deterioration occurs.

Next, the example of formation of the photoelectric conversion part 2 using a silicon substrate is shown below.
As the silicon substrate, a single crystal silicon substrate, a polycrystalline silicon substrate, or the like can be used, and may be p-type, n-type, or i-type. An n-type semiconductor region 37 is formed by doping an n-type impurity such as P into a part of the silicon substrate by thermal diffusion or ion implantation, and a p-type impurity such as B is heated on the other part of the silicon substrate. The p-type semiconductor region 36 can be formed by doping by diffusion or ion implantation. Thus, pn junction in the silicon substrate, pin junction can be formed and npp ⁺ junction or pnn ⁺ junction, it is possible to form a photoelectric conversion unit 2.

Each of the n-type semiconductor region 37 and the p-type semiconductor region 36 can be formed on the silicon substrate as shown in FIGS. 14 to 16, and one of the n-type semiconductor region 37 and the p-type semiconductor region 36 is formed. A plurality of can be formed. In addition, as shown in FIG. 16, the photoelectric conversion unit 2 can be formed by arranging the silicon substrates on which the n-type semiconductor region 37 and the p-type semiconductor region 36 are arranged side by side and connecting them in series by the fourth conductive unit 42.
Note that, although described with reference to a silicon substrate, pn junction, pin junction, may use other semiconductor substrate or the like can be formed npp ⁺ junction or pnn ⁺ junction. In addition, as long as the n-type semiconductor region 37 and the p-type semiconductor region 36 can be formed, the semiconductor layer is not limited to the semiconductor substrate and may be a semiconductor layer formed on the substrate.

3-2. Photoelectric conversion part using a compound semiconductor The photoelectric conversion part using a compound semiconductor is, for example, GaP, GaAs, InP, InAs, or IId-VI elements composed of group III-V elements, CdTe / CdS, Examples thereof include those in which a pn junction is formed using CIGS (Copper Indium Gallium DiSelenide) composed of the I-III-VI group.

An example of a method for manufacturing a photoelectric conversion unit using a compound semiconductor is shown below. In this manufacturing method, all film-forming processes are continuously performed using a metal organic chemical vapor deposition (MOCVD) apparatus. Done. As a group III element material, for example, an organic metal such as trimethylgallium, trimethylaluminum, or trimethylindium is supplied to the growth apparatus using hydrogen as a carrier gas. For example, a gas such as arsine (AsH ₃ ), phosphine (PH ₃ ), and stibine (SbH ₃ ) is used as the material of the group V element. As a dopant of p-type impurities or n-type impurities, for example, diethyl zinc for p-type conversion, monosilane (SiH ₄ ), disilane (Si ₂ H ₆ ), hydrogen selenide (H ₂ Se) for n-type conversion, for example. Etc. are used. These source gases can be thermally decomposed by supplying them onto a substrate heated to, for example, 700 ° C., and a desired compound semiconductor material film can be epitaxially grown. The composition of these growth layers can be controlled by the gas composition to be introduced, and the film thickness can be controlled by the gas introduction time. When multi-junction laminating these photoelectric conversion parts, it is possible to form a growth layer with excellent crystallinity by adjusting the lattice constant between layers as much as possible, and to improve the photoelectric conversion efficiency. Become.

In addition to the portion where the pn junction is formed, for example, a known window layer on the light receiving surface side or a known electric field layer on the non-light receiving surface side may be provided to improve carrier collection efficiency. Further, a buffer layer for preventing diffusion of impurities may be provided.

3-3. Photoelectric conversion part using a dye sensitizer The photoelectric conversion part using a dye sensitizer is mainly composed of, for example, a porous semiconductor, a dye sensitizer, an electrolyte, a solvent, and the like.
As a material constituting the porous semiconductor, for example, one or more kinds of known semiconductors such as titanium oxide, tungsten oxide, zinc oxide, barium titanate, strontium titanate, cadmium sulfide can be selected. As a method for forming a porous semiconductor on a substrate, a paste containing semiconductor particles is applied by a screen printing method, an ink jet method and the like, dried or baked, a method of forming a film by a CVD method using a raw material gas, etc. , PVD method, vapor deposition method, sputtering method, sol-gel method, method using electrochemical oxidation-reduction reaction, and the like.

As the dye sensitizer adsorbed on the porous semiconductor, various dyes having absorption in the visible light region and the infrared light region can be used. Here, in order to firmly adsorb the dye to the porous semiconductor, the carboxylic acid group, carboxylic anhydride group, alkoxy group, sulfonic acid group, hydroxyl group, hydroxylalkyl group, ester group, mercapto group, phosphonyl in the dye molecule It is preferable that a group or the like is present. These functional groups provide an electrical bond that facilitates electron transfer between the excited state dye and the conduction band of the porous semiconductor.

Examples of dyes containing these functional groups include ruthenium bipyridine dyes, quinone dyes, quinone imine dyes, azo dyes, quinacridone dyes, squarylium dyes, cyanine dyes, merocyanine dyes, and triphenylmethane dyes. Xanthene dyes, porphyrin dyes, phthalocyanine dyes, berylene dyes, indigo dyes, naphthalocyanine dyes, and the like.

Examples of the method of adsorbing the dye to the porous semiconductor include a method of immersing the porous semiconductor in a solution in which the dye is dissolved (dye adsorption solution). The solvent used in the dye adsorption solution is not particularly limited as long as it dissolves the dye, and specifically, alcohols such as ethanol and methanol, ketones such as acetone, ethers such as diethyl ether and tetrahydrofuran. Nitrogen compounds such as acetonitrile, aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as benzene, esters such as ethyl acetate, water, and the like.

The electrolyte is composed of a redox pair and a solid medium such as a liquid or polymer gel holding the redox pair.
In general, iron- and cobalt-based metals and halogen substances such as chlorine, bromine, and iodine are preferably used as the redox pair, and metal iodides such as lithium iodide, sodium iodide, and potassium iodide and iodine are used. The combination of is preferably used. Furthermore, imidazole salts such as dimethylpropylimidazole iodide can also be mixed.

Examples of the solvent include carbonate compounds such as propylene carbonate, nitrile compounds such as acetonitrile, alcohols such as ethanol and methanol, water, aprotic polar substances, and the like. Of these, carbonate compounds and nitrile compounds are preferred. Used.

3-4. Photoelectric conversion part using organic thin film Photoelectric conversion part 2 using an organic thin film is an electron hole transport layer composed of an organic semiconductor material having electron donating properties and electron accepting properties, or an electron transport layer having electron accepting properties. And a hole transport layer having an electron donating property may be laminated.
The electron-donating organic semiconductor material is not particularly limited as long as it has a function as an electron donor, but it is preferable that a film can be formed by a coating method, and among them, an electron-donating conductive polymer is preferably used. The

Here, the conductive polymer refers to a π-conjugated polymer, which is composed of a π-conjugated system in which double bonds or triple bonds containing carbon-carbon or hetero atoms are alternately connected to single bonds, and exhibits semiconducting properties. Point.

Examples of the electron-donating conductive polymer material include polyphenylene, polyphenylene vinylene, polythiophene, polycarbazole, polyvinyl carbazole, polysilane, polyacetylene, polypyrrole, polyaniline, polyfluorene, polyvinyl pyrene, polyvinyl anthracene, and derivatives, Examples thereof include a polymer, a phthalocyanine-containing polymer, a carbazole-containing polymer, and an organometallic polymer. Of these, thiophene-fluorene copolymer, polyalkylthiophene, phenylene ethynylene-phenylene vinylene copolymer, fluorene-phenylene vinylene copolymer, thiophene-phenylene vinylene copolymer and the like are preferably used.

The electron-accepting organic semiconductor material is not particularly limited as long as it has a function as an electron acceptor. However, it is preferable that a film can be formed by a coating method, and among them, an electron-donating conductive polymer is preferably used. The
Examples of the electron-accepting conductive polymer include polyphenylene vinylene, polyfluorene, and derivatives and copolymers thereof, or carbon nanotubes, fullerene and derivatives thereof, CN group or CF ₃ group-containing polymers, and —CF Examples thereof include _3- substituted polymers.

In addition, an electron-accepting organic semiconductor material doped with an electron-donating compound, an electron-donating organic semiconductor material doped with an electron-accepting compound, or the like can be used. Examples of the electron-accepting conductive polymer material doped with the electron-donating compound include the above-described electron-accepting conductive polymer material. As the electron-donating compound to be doped, for example, a Lewis base such as an alkali metal such as Li, K, Ca, or Cs or an alkaline earth metal can be used. The Lewis base acts as an electron donor. Examples of the electron-donating conductive polymer material doped with the electron-accepting compound include the above-described electron-donating conductive polymer material. As the electron-accepting compound to be doped, for example, a Lewis acid such as FeCl ₃ , AlCl ₃ , AlBr ₃ , AsF ₆ or a halogen compound can be used. In addition, Lewis acid acts as an electron acceptor.

In the photoelectric conversion unit 2 shown above, it is assumed that sunlight is received and photoelectric conversion is primarily performed. However, it is emitted from a fluorescent lamp, an incandescent lamp, an LED, or a specific heat source depending on the application. It is also possible to perform photoelectric conversion by irradiating artificial light such as light.

4). Second Electrode, Third Conductive Part The second electrode 5 can be provided between the back surface of the photoelectric conversion unit 2 and the first mold unit 11 and between the back surface of the photoelectric conversion unit 2 and the second mold unit 12. . The second electrode 5 can be electrically connected to the first electrolysis electrode 8. By providing the second electrode 5, it is possible to reduce ohmic cross between the back surface of the photoelectric conversion unit 2 and the first electrolysis electrode 8. The second electrode 5 may be electrically connected to the first electrolysis electrode 8 through the third conductive portion 17 as shown in FIGS. 3 and 13, or may be in contact with the first electrolysis electrode 8. Good. The third conductive part 17 may be provided in a contact hole provided in the first mold part 11 as shown in FIG. 3 so as to cover the side part of the first mold part 11 as shown in FIG. It may be provided.
6 and 7, the second electrode 5 is provided between the back surface of the photoelectric conversion unit 2 and the insulating unit 21 and between the back surface of the photoelectric conversion unit 2 and the first electrolysis electrode 8. Also good.
Moreover, it is preferable that the 2nd electrode 5 has the corrosion resistance with respect to electrolyte solution, and the liquid shielding property with respect to electrolyte solution. Thereby, corrosion of the photoelectric conversion part 2 by electrolyte solution can be prevented.
Although it will not specifically limit if the 2nd electrode 5 has electroconductivity, For example, it is a metal thin film, for example, is thin films, such as Al, Ag, Au. These can be formed by, for example, sputtering. Further, for example, a transparent conductive film such as In—Zn—O (IZO), In—Sn—O (ITO), ZnO—Al, Zn—Sn—O, and SnO ₂ is used.

The material of the third conductive portion 17 is not particularly limited as long as it has conductivity. A paste containing conductive particles, for example, a carbon paste, an Ag paste or the like applied by screen printing, an inkjet method, etc., dried or baked, a method of forming a film by a CVD method using a raw material gas, a PVD method, Examples thereof include a vapor deposition method, a sputtering method, a sol-gel method, and a method using an electrochemical redox reaction.

5. 1st type | mold part, 2nd type | mold part, 1st electroconductive part The 1st type | mold part 11 can be provided between the back surface of the photoelectric conversion part 2, and the electrode 8 for 1st electrolysis, The 2nd type | mold part 12 is It can be provided between the back surface of the photoelectric conversion unit 2 and the second electrolysis electrode 7. Further, the first mold part 11 and the second mold part 12 are arranged between a surface that can contact the electrolytic solution of the first electrolysis electrode 8 and a horizontal reference surface when the light receiving surface of the photoelectric conversion unit 2 is leveled. And the inclination angle between the surface of the second electrolysis electrode 7 that can contact the electrolytic solution and the horizontal reference surface may be different. By providing the first mold part 11 and the second mold part 12 formed in this way, the inclination angle between the surface of the first electrolysis electrode in contact with the electrolytic solution and the surface of the second electrolysis electrode in contact with the electrolytic solution. Can be adjusted.

Moreover, the 1st type | mold part 11 and the 2nd type | mold part 12 may have a groove-shaped hollow like FIG. By forming the first electrolysis electrode 8 on the first mold part 11 and the second electrolysis electrode 7 on the second mold part 12, the electrolytic solution of the first electrolysis electrode 8 is formed. Groove-shaped depressions can be formed on the surface that can be contacted with each other and the surface that can be contacted with the electrolytic solution of the second electrolysis electrode 7.

Further, the first mold part and the second mold part may have electrical insulation. As a result, leakage current can be reduced. Further, in this case, the second mold part 12 can be provided so as to cover the side surface of the photoelectric conversion part 2 as shown in FIGS. 11 and 12, and the second mold part 12 covering the side surface of the photoelectric conversion part 2 can be provided. The second conductive portion 10 or the second electrolysis electrode 7 can be provided thereon. Thus, leakage current can be prevented and the second electrolysis electrode 7 and the first electrode 4 can be electrically connected.
The first mold part 11 and the second mold part 12 can be formed from, for example, a solid resin. By using a solid resin, the first mold part 11 and the second mold part 12 having a desired shape can be formed.
The first mold part 11 may be made of a conductive material. Thereby, the back surface of the photoelectric conversion unit 2 and the first electrolysis electrode 8 can be electrically connected via the first mold unit.

Further, the first conductive part 9 can be provided between the first mold part 11 and the first electrolysis electrode 8 or between the second mold part 12 and the second electrolysis electrode 7. By providing the first conductive portion 9, it is possible to reduce internal resistance when the electromotive force generated by the photoelectric conversion portion 2 receiving light is output to the first electrolysis electrode 8 and the second electrolysis electrode 7. .
The first conductive portion 9 can be provided between the second mold portion 12 and the second electrolysis electrode 7 as shown in FIGS. 8, 11, 14, and 16, for example. Thus, it can be provided between the first mold part 11 and the first electrolysis electrode 8.
Although it will not specifically limit if the 1st electroconductive part 11 has electroconductivity, For example, it is a metal thin film, for example, is thin films, such as Al, Ag, Au. These can be formed by, for example, sputtering. Further, for example, a transparent conductive film such as In—Zn—O (IZO), In—Sn—O (ITO), ZnO—Al, Zn—Sn—O, and SnO ₂ is used.

6). Insulating part The insulating part 21 can be provided in order to prevent the occurrence of leakage current. For example, when the second conductive portion 10 is provided in a contact hole penetrating the photoelectric conversion portion 2 as shown in FIGS. 4, 7, and 8, the insulating portion 21 can be provided on the side wall of the contact hole. Moreover, when not providing the 2nd type | mold part 12 like FIG. 7, it can provide between the electrode 7 for 2nd electrolysis and the back surface of the photoelectric conversion part 2. FIG. Moreover, when the 2nd type | mold part 12 has electroconductivity, the insulating part 21 can also be provided between the 2nd type | mold part 12 and the back surface of the photoelectric conversion part 2. FIG.

The insulating part 11 can be used regardless of an organic material or an inorganic material. For example, polyamide, polyimide, polyarylene, aromatic vinyl compound, fluorine polymer, acrylic polymer, vinylamide polymer, etc. Examples of organic polymers and inorganic materials include metal oxides such as Al ₂ O ₃ , SiO ₂ such as porous silica films, fluorine-added silicon oxide films (FSG), SiOC, HSQ (Hydrogen Silsesquioxane) films, SiN _x , It is possible to use a method of forming a film by dissolving silanol (Si (OH) ₄ ) in a solvent such as alcohol and applying and heating.

As a method for forming the insulating portion 11, a film containing a paste containing an insulating material is applied by a screen printing method, an ink jet method, a spin coating method, etc., dried or baked, or a CVD method using a source gas is used. And a method using a PVD method, a vapor deposition method, a sputtering method, a sol-gel method, and the like.

7. First Electrolysis Electrode, Second Electrolysis Electrode The first electrolysis electrode 8 and the second electrolysis electrode 7 are respectively provided on the back surface of the photoelectric conversion unit 2, and the back surface side surface of the photoelectric conversion unit 2 Each has a surface which is the back surface and can contact the electrolyte. Thus, the first electrolysis electrode 8 does not block light incident on the photoelectric conversion unit 2.
In addition, when the first electrolysis electrode 8 and the second electrolysis electrode 7 are in contact with the electrolytic solution, the electrolysis solution is electrolyzed by using the electromotive force generated by the photoelectric conversion unit 2 receiving light, and the first gas is obtained. And a second gas is generated. For example, when an electromotive force is generated between the light receiving surface and the back surface when the photoelectric conversion unit 2 receives light, the first electrolysis electrode 8 is connected to the back surface of the photoelectric conversion unit 2 as shown in FIGS. The second electrolysis electrode 7 can be electrically connected to the light receiving surface of the photoelectric conversion unit 2 as shown in FIGS. 4, 7, 8, 11, and 12. In addition, when an electromotive force is generated between the first area and the second area on the back surface of the photoelectric conversion unit 2 by receiving light, the first electrolysis electrode 8 is connected to the first area and the second area as shown in FIGS. The second electrolysis electrode 7 can be electrically connected to one of the two areas and the other of the first and second areas.

In addition, the first electrolysis electrode 8 and the second electrolysis electrode 7 include a surface that can contact the electrolytic solution of the first electrolysis electrode 8 and a horizontal reference surface when the light receiving surface of the photoelectric conversion unit 2 is horizontal. And the inclination angle between the surface of the second electrolysis electrode 7 that can come into contact with the electrolytic solution and the horizontal reference surface are different. Thus, when the first gas rises in the electrolyte as bubbles, the surface of the first electrolysis electrode 8 that can be in contact with the electrolyte, and the second gas rises in the electrolyte as bubbles. Sometimes, the surface of the second electrolysis electrode 7 that becomes the guide surface can be shifted from the surface that can contact the electrolyte.
The difference between the inclination angles of the first electrolysis electrode 8 and the second electrolysis electrode 7 is, for example, that the first gas outlet 20 and the second gas outlet 19 for recovering the first gas and the second gas are photoelectrically converted. The difference may be shifted up and down when the light receiving surface of the portion 2 is leveled. Further, for example, as shown in FIG. 1, the first electrolysis electrode 8 is formed such that the first gas discharge port 20 is formed on one of the both sides of the gas production apparatus 23 and the second gas discharge port 19 is formed on the other side. And the difference of the inclination angle of the electrode 7 for 2nd electrolysis may be given.

When the light receiving surface of the photoelectric conversion unit 2 is leveled, the surface of the first electrolysis electrode 8 that can come into contact with the electrolytic solution may have, for example, an inclination angle of 1 to 60 degrees, preferably 5 degrees. It may be 30 degrees or less. Further, at this time, the surface of the second electrolysis electrode 7 that can come into contact with the electrolytic solution may have an inclination angle of 120 degrees or more and 179 degrees or less, preferably 150 degrees or more and 175 degrees or less. . Thus, the first gas can be discharged from one of the two sides of the gas production device 23, the second gas can be discharged from the other, and a pipe for collecting the first gas and the second gas can be provided. It can be simplified.

A method for making a difference between the inclination angle of the surface of the first electrolysis electrode 8 that can contact the electrolytic solution and the inclination angle of the surface of the second electrolysis electrode 7 that can contact the electrolytic solution is not particularly limited. As shown in FIGS. 2 to 4 and 8 to 16, the first mold part 11 and the second mold part 12 may be provided to provide a difference in inclination angle. For example, as shown in FIGS. You may give the difference of an inclination angle by shape | molding.
It should be noted that the surface of the first electrolysis electrode 8 and the second electrolysis electrode 7 that can contact the electrolytic solution is a guide surface when the first gas or the second gas rises as bubbles in the electrolytic solution. For example, it may be a flat surface or a curved surface. Moreover, when the surface which can contact electrolyte solution is a curved surface and the inclination angle changes with places, the inclination angle of this curved surface means the average inclination angle.

The first electrolysis electrode 8 and the second electrolysis electrode 7 can each have a groove-like recess extending in an inclined direction on a surface that can contact the electrolytic solution. Thus, the first gas or the second gas can be raised as bubbles in the electrolytic solution along the groove-like depression, and the first gas and the second gas can be easily separated. Moreover, the partition wall 13 formed between the first electrolysis electrode 8 and the second electrolysis electrode 7 can be omitted by forming such a groove-like depression. For example, as shown in FIG. 9, one groove-like depression may be formed on each surface of the first electrolysis electrode 8 and the second electrolysis electrode 7 that can come into contact with the electrolytic solution. A plurality of electrodes may be formed on the surfaces of the electrode for electrolysis 8 and the electrode for second electrolysis 7 that can contact the electrolytic solution.

At least one of the first electrolysis electrode 8 and the second electrolysis electrode 7 has a plurality of surfaces, each of which has a surface that can contact the strip-shaped electrolyte solution, and the long sides of the surfaces are adjacent to each other It may be provided alternately. FIG. 17 is a schematic plan view of the gas production apparatus of the present embodiment, and FIG. 18 is a schematic cross-sectional view of the gas production apparatus taken along the dotted line AA in FIG. The cross-sectional view of the gas production device 23 in the direction perpendicular to the dotted line AA has a cross section as shown in FIGS. In this way, by providing the first electrolysis electrode 8 and the second electrolysis electrode 7, the distance between the portion where the reaction generating the first gas occurs and the portion where the reaction generating the second gas occurs is increased. It can be shortened, and the ion concentration imbalance generated in the electrolyte can be reduced. Moreover, the 1st gas and 2nd gas can be collect | recovered easily by making the surface which can contact electrolyte solution into strip | belt shape. Moreover, the some 1st gas exhaust port 20 can be formed in one among the both sides of the gas manufacturing apparatus 23, and the some 2nd gas exhaust port 19 can be formed in the other. As a result, the first gas discharge path 25 for recovering the first gas and the second gas discharge path 26 for recovering the second gas can be provided on both sides of the gas production device 23, thereby simplifying the piping. be able to. Alternatively, even if the first gas discharge path 25 and the second gas discharge path 26 are not provided, the gas discharged from the first gas discharge port 20 or the second gas discharge port 19 is replaced with water through a gas collecting unit (not shown). It is possible to collect gas by a method such as a method.

Moreover, it is preferable that at least one of the first electrolysis electrode 8 and the second electrolysis electrode 7 has a catalyst surface area larger than the area of the light receiving surface. According to such a configuration, the first gas or the second gas can be generated more efficiently by the electromotive force generated in the photoelectric conversion unit 2.
In addition, at least one of the first electrolysis electrode 8 and the second electrolysis electrode 7 is preferably a porous conductor carrying a catalyst. According to such a configuration, the surface area of at least one of the first electrolysis electrode 8 and the second electrolysis electrode 7 can be increased, and the first gas or the second gas can be generated more efficiently. Can do. Further, by using a porous conductor, it is possible to suppress a change in potential due to a current flowing between the photoelectric conversion unit 2 and the catalyst, and to generate the first gas or the second gas more efficiently. Can be made.
One of the first electrolysis electrode 8 and the second electrolysis electrode 7 may be a hydrogen generation unit, and the other may be an oxygen generation unit. In this case, one of the first gas and the second gas is hydrogen, and the other is oxygen.

9. Hydrogen generating part The hydrogen generating part is a part for generating H ₂ from the electrolytic solution, and is one of the first electrolysis electrode 8 and the second electrolysis electrode 7.
Further, the hydrogen generation unit may include a catalyst for a reaction in which H ₂ is generated from the electrolytic solution. Thereby, the reaction rate of the reaction in which H ₂ is generated from the electrolytic solution can be increased. The hydrogen generation part may consist only of a catalyst for the reaction in which H ₂ is generated from the electrolytic solution, or this catalyst may be supported on a support. Further, the hydrogen generation unit may have a catalyst surface area larger than the area of the light receiving surface of the photoelectric conversion unit 2. Thereby, the reaction in which H ₂ is generated from the electrolytic solution can be set to a faster reaction rate. The hydrogen generation part may be a porous conductor carrying a catalyst. This can increase the catalyst surface area. In addition, a change in potential due to a current flowing between the light receiving surface or the back surface of the photoelectric conversion unit 2 and the catalyst included in the hydrogen generation unit can be suppressed. Furthermore, the hydrogen generation unit may include at least one of Pt, Ir, Ru, Pd, Rh, Au, Fe, Ni, and Se as a hydrogen generation catalyst. According to such a configuration, hydrogen can be generated at a higher reaction rate by the electromotive force generated in the photoelectric conversion unit 2.

The catalyst for the reaction of generating H ₂ from the electrolyte (hydrogen generation catalyst) is a catalyst that promotes the conversion of two protons and two electrons into one molecule of hydrogen, is chemically stable, and generates hydrogen overvoltage. Can be used. For example, platinum group metals such as Pt, Ir, Ru, Pd, Rh, and Au, which have catalytic activity for hydrogen, and alloys or compounds thereof, Fe, Ni, and Se that constitute the active center of hydrogenase that is a hydrogen-producing enzyme. An alloy or a compound, a combination thereof, or the like can be preferably used. Among them, a nanostructure containing Pt and Pt has a small hydrogen generation overvoltage and can be suitably used. Materials such as CdS, CdSe, ZnS, and ZrO ₂ whose hydrogen generation reaction is confirmed by light irradiation can also be used.

The hydrogen generating catalyst can be supported on the conductor. Examples of the conductor carrying the catalyst include metal materials, carbonaceous materials, and conductive inorganic materials.
As the metal material, a material having electronic conductivity and resistance to corrosion in an acidic atmosphere is preferable. Specifically, noble metals such as Au, Pt, Pd, metals such as Ti, Ta, W, Nb, Ni, Al, Cr, Ag, Cu, Zn, Su, Si, and nitrides and carbides of these metals, Examples of the alloy include stainless steel, Cu—Cr, Ni—Cr, and Ti—Pt. It is more preferable that the metal material contains at least one element selected from the group consisting of Pt, Ti, Au, Ag, Cu, Ni, and W from the viewpoint that there are few other chemical side reactions. These metal materials have a relatively small electric resistance, and can suppress a decrease in voltage even when a current is extracted in the surface direction. Further, when using a metal material having poor corrosion resistance in an acidic atmosphere such as Cu, Ag, Zn, etc., noble metals and metals having corrosion resistance such as Au, Pt, Pd, carbon, graphite, glassy carbon, A metal surface having poor corrosion resistance may be coated with a conductive polymer, a conductive nitride, a conductive carbide, a conductive oxide, or the like.

As the carbonaceous material, a chemically stable and conductive material is preferable. Examples thereof include carbon powders and carbon fibers such as acetylene black, vulcan, ketjen black, furnace black, VGCF, carbon nanotube, carbon nanohorn, and fullerene.

Examples of the inorganic material having conductivity include In—Zn—O (IZO), In—Sn—O (ITO), ZnO—Al, Zn—Sn—O, SnO ₂ , and antimony oxide-doped tin oxide. .

In addition, examples of the conductive polymer include polyacetylene, polythiophene, polyaniline, polypyrrole, polyparaphenylene, polyparaphenylene vinylene, and the like, and examples of the conductive nitride include carbon nitride, silicon nitride, gallium nitride, indium nitride, and nitride. Germanium, titanium nitride, zirconium nitride, thallium nitride, etc. are listed, and conductive carbides include tantalum carbide, silicon carbide, zirconium carbide, titanium carbide, molybdenum carbide, niobium carbide, iron carbide, nickel carbide, hafnium carbide, tungsten carbide. , Vanadium carbide, chromium carbide, and the like. Examples of the conductive oxide include tin oxide, indium tin oxide (ITO), and antimony oxide-doped tin oxide.

The structure of the conductor supporting the hydrogen generation catalyst includes a plate shape, a foil shape, a rod shape, a mesh shape, a lath plate shape, a porous plate shape, a porous rod shape, a woven fabric shape, a nonwoven fabric shape, a fiber shape, and a felt shape. It can be used suitably. Further, a grooved conductor in which the surface of the felt-like electrode is pressure-bonded in a groove shape is preferable because the electric resistance and the flow resistance of the electrode liquid can be reduced.

10. Oxygen generating portion The oxygen generating portion is a portion that generates O ₂ from the electrolytic solution, and is one of the first electrolysis electrode 8 and the second electrolysis electrode 7.
Further, the oxygen generation unit may include a catalyst for a reaction in which O ₂ is generated from the electrolytic solution. Thereby, the reaction rate of the reaction in which O ₂ is generated from the electrolytic solution can be increased. Further, the oxygen generation part may consist only of a catalyst for the reaction that generates O ₂ from the electrolytic solution, or the catalyst may be supported on a carrier. Further, the oxygen generation unit may have a catalyst surface area larger than the area of the light receiving surface of the photoelectric conversion unit 2. Thereby, the reaction in which O ₂ is generated from the electrolytic solution can be set to a faster reaction rate. The oxygen generation part may be a porous conductor carrying a catalyst. This can increase the catalyst surface area. In addition, a change in potential due to a current flowing between the light receiving surface or the back surface of the photoelectric conversion unit 2 and the catalyst included in the oxygen generation unit can be suppressed. Furthermore, the oxygen generation unit may include at least one of Mn, Ca, Zn, Co, and Ir as an oxygen generation catalyst. According to such a configuration, oxygen can be generated at a higher reaction rate by the electromotive force generated in the photoelectric conversion unit.

The catalyst for the reaction of generating O ₂ from the electrolyte (oxygen generating catalyst) is a catalyst that promotes the conversion of two water molecules into one molecule of oxygen, four protons, and four electrons, and is chemically stable. In addition, a material having a small oxygen generation overvoltage can be used. For example, oxides or compounds containing Mn, Ca, Zn, Co, which are active centers of Photosystem II, which is an enzyme that catalyzes the reaction of generating oxygen from water using light, and platinum such as Pt, RuO ₂ , IrO ₂ It is possible to use compounds containing group metals, oxides or compounds containing transition metals such as Ti, Zr, Nb, Ta, W, Ce, Fe, Ni, and combinations of the above materials. Among these, iridium oxide, manganese oxide, cobalt oxide, and cobalt phosphate can be suitably used because they have low overvoltage and high oxygen generation efficiency.

The oxygen generating catalyst can be supported on the conductor. Examples of the conductor carrying the catalyst include metal materials, carbonaceous materials, and conductive inorganic materials. These explanations apply as long as there is no contradiction in the explanation of the hydrogen generation catalyst described in “9.
When the catalytic activity of the hydrogen generating catalyst and the oxygen generating catalyst alone is small, a promoter can be used. Examples thereof include oxides or compounds of Ni, Cr, Rh, Mo, Co, and Se.

The method for supporting the hydrogen generating catalyst and the oxygen generating catalyst can be applied directly to a conductor or semiconductor, PVD methods such as vacuum deposition, sputtering, and ion plating, dry coating methods such as CVD, The method can be appropriately changed depending on the material such as an analysis method. A conductive material can be appropriately supported between the photoelectric conversion unit and the catalyst. Also, when the catalytic activity for hydrogen generation and oxygen generation is not sufficient, the reaction surface area is increased by supporting it on porous materials such as metals and carbon, fibrous materials, nanoparticles, etc., and the hydrogen and oxygen generation rates are improved. It is possible to make it.

11. Top Plate, Electrolyte Chamber The top plate 14 can be provided on the first electrolysis electrode 8 and the second electrolysis electrode 7 so as to face the translucent substrate 1. The top plate 14 can be provided such that a space is provided between the first electrolysis electrode 8 and the second electrolysis electrode 7 and the top plate 14. This space can be used as the electrolytic solution chamber 15, and the first electrolytic electrode 8 and the second electrolytic electrode 7 can be brought into contact with the electrolytic solution by introducing the electrolytic solution into the electrolytic solution chamber 15. Moreover, when using a box-shaped thing for a top plate, the top plate 14 may be the bottom part of a box.

Further, the top plate 14 is a material that constitutes the electrolytic solution chamber 15 and confines the generated first gas and second gas, and a highly confidential substance is required. It is not particularly limited whether it is transparent or opaque, but it is preferably a transparent material in that it can be visually confirmed that the first gas and the second gas are generated. . The transparent top plate is not particularly limited, and examples thereof include a transparent rigid material such as quartz glass, Pyrex (registered trademark), and a synthetic quartz plate, a transparent resin plate, and a transparent resin film. Among them, it is preferable to use a glass material because it is a gas that is not chemically permeable and is chemically and physically stable.

12 Partition Wall The partition wall 13 can be provided so as to partition the first electrolysis electrode 8 and the second electrolysis electrode 7. The partition wall 13 includes an electrolytic solution chamber 15 that is a space between the first electrolysis electrode 8 and the top plate 14 and an electrolytic solution chamber 15 that is a space between the second electrolysis electrode 7 and the top plate 14. It can provide so that it may partition. As a result, the first gas and the second gas generated by the first electrolysis electrode 8 and the second electrolysis electrode 7 can be prevented from mixing, and the first gas and the second gas can be separated. It can be recovered.
The partition wall 13 may include an ion exchanger. As a result, the ion concentration that is unbalanced between the electrolytic solution in the space between the first electrolysis electrode 8 and the top plate 14 and the electrolytic solution in the space between the second electrolysis electrode 7 and the top plate 14 is obtained. Can be kept constant.

For the partition wall 13, for example, an inorganic film such as porous glass, porous zirconia, or porous alumina or an ion exchanger can be used.
As the ion exchanger, any ion exchanger known in the art can be used, and a proton conductive membrane, a cation exchange membrane, an anion exchange membrane, or the like can be used.
The material of the proton conductive film is not particularly limited as long as it is a material having proton conductivity and electrical insulation, and a polymer film, an inorganic film, or a composite film can be used.

Examples of the polymer membrane include Nafion (registered trademark) manufactured by DuPont, Aciplex (registered trademark) manufactured by Asahi Kasei Co., and Flemion (registered trademark) manufactured by Asahi Glass Co., Ltd., which are perfluorosulfonic acid electrolyte membranes. Examples thereof include membranes and hydrocarbon electrolyte membranes such as polystyrene sulfonic acid and sulfonated polyether ether ketone.

Examples of the inorganic film include films made of phosphate glass, cesium hydrogen sulfate, polytungstophosphoric acid, ammonium polyphosphate, and the like. Examples of the composite membrane include a membrane made of a sulfonated polyimide polymer, a composite of an inorganic material such as tungstic acid and an organic material such as polyimide, and specifically, Gore Select membrane (registered trademark) or pores manufactured by Gore. Examples thereof include a filling electrolyte membrane. Furthermore, when used in a high temperature environment (for example, 100 ° C. or higher), sulfonated polyimide, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), sulfonated polybenzimidazole, phosphonated polybenzimidazole, sulfuric acid Examples include cesium hydrogen and ammonium polyphosphate.

The cation exchange membrane may be any solid polymer electrolyte that can move cations. Specifically, fluorine ion exchange membranes such as perfluorocarbon sulfonic acid membranes and perfluorocarbon carboxylic acid membranes, polybenzimidazole membranes impregnated with phosphoric acid, polystyrene sulfonic acid membranes, sulfonated styrene / vinylbenzene copolymers Examples include membranes.
When the anion transport number of the supporting electrolyte solution is high, it is preferable to use an anion exchange membrane. As the anion exchange membrane, a solid polymer electrolyte capable of transferring anions can be used. Specifically, a polyorthophenylenediamine film, a fluorine-based ion exchange film having an ammonium salt derivative group, a vinylbenzene polymer film having an ammonium salt derivative group, a film obtained by aminating a chloromethylstyrene / vinylbenzene copolymer, etc. Can be mentioned.

13. Sealing material The sealing material 16 adheres the translucent substrate 1 and the top plate 14, and seals the electrolyte flowing in the gas production device 23 and the first gas and the second gas generated in the gas production device 23. Material. When using a box-shaped thing for the top plate 14, the sealing material 16 is used in order to adhere | attach this box and the translucent board | substrate 1. FIG. As the sealing material 16, for example, an ultraviolet curable adhesive, a thermosetting adhesive, or the like is preferably used, but the type thereof is not limited. UV curable adhesives are resins that undergo polymerization when irradiated with light having a wavelength of 200 to 400 nm and undergo a curing reaction within a few seconds after light irradiation, and are classified into radical polymerization type and cationic polymerization type. Examples of the polymerization type resin include acrylates, unsaturated polyesters, and examples of the cationic polymerization type include epoxy, oxetane, and vinyl ether. Examples of the thermosetting polymer adhesive include organic resins such as phenol resin, epoxy resin, melamine resin, urea resin, and thermosetting polyimide. The thermosetting polymer adhesive is heated and polymerized in a state where pressure is applied at the time of thermocompression bonding, and then cooled to room temperature while being pressurized. I don't need it. In addition to the organic resin, a hybrid material having high adhesion to the glass substrate can be used. By using a hybrid material, mechanical properties such as elastic modulus and hardness are improved, and heat resistance and chemical resistance are dramatically improved. The hybrid material is composed of inorganic colloidal particles and an organic binder resin. For example, what is comprised from inorganic colloidal particles, such as a silica, and organic binder resin, such as an epoxy resin, a polyurethane acrylate resin, and a polyester acrylate resin, is mentioned.

Here, the sealing material 16 is described. However, the sealing material 16 is not limited as long as it has a function of bonding the translucent substrate 1 and the top plate 14, and a member such as a screw is externally used using a resin or metal gasket. It is also possible to appropriately use a method of applying pressure physically to increase confidentiality.

14 Electrolytic Solution Chamber The electrolytic solution chamber 15 can be a space between the first electrolysis electrode 8 and the top plate 14 and a space between the second electrolysis electrode 7 and the top plate 14. Further, the electrolyte chamber 15 can be partitioned by the partition wall 13.
For example, a pump or a fan that circulates the electrolyte in the electrolyte chamber 15 so that the generated bubbles of the first gas and the second gas are efficiently separated from the first electrolysis electrode 8 or the second electrolysis electrode 7. It is also possible to provide a simple device such as a heat convection generator.

15. Water supply port, first gas discharge port, second gas discharge port, first gas discharge channel and second gas discharge channel The water supply port 18 is a part of the sealing material 16 included in the gas production device 23 or the top plate 14. It can be provided by making an opening in a part or the like. The water supply port 18 is arranged to replenish the electrolytic solution decomposed into the first gas and the second gas, and the arrangement location and shape of the water supply port 18 can be efficiently supplied to the gas production apparatus. For example, there is no particular limitation.

The first gas outlet 20 is provided close to the upper end of the surface of the first electrolysis electrode 8 that can come into contact with the electrolytic solution when the light receiving surface of the photoelectric conversion unit 2 is leveled upward. it can. Further, the second gas discharge port 19 is provided close to the upper end of the surface of the second electrolysis electrode 7 that can come into contact with the electrolytic solution when the light receiving surface of the photoelectric conversion unit 2 is leveled upward. it can. As a result, when the gas production device 23 is installed so that the light receiving surface of the photoelectric conversion unit 2 is horizontal, the first gas generated by the first electrolysis electrode 8 is used as bubbles in the electrolytic solution. Can be recovered from the first gas discharge port 20, and the second gas generated in the second electrolysis electrode 7 can be raised as bubbles to rise in the electrolytic solution and recovered from the second gas discharge port 19. .

Further, the first gas discharge port 20 can be connected to the first gas discharge passage 25, and the second gas discharge port 19 can be connected to the second gas discharge passage 26. In addition, the first gas exhaust path 25 can be electrically connected to the plurality of first gas exhaust ports 20, and the second gas exhaust path 26 can be electrically connected to the plurality of second gas exhaust ports 19. As a result, the first gas and the second gas generated by the gas production device 23 can be recovered.

16. Electrolytic Solution The electrolytic solution is not particularly limited as long as it is a raw material for the first gas and the second gas. For example, the electrolytic solution is an aqueous solution containing an electrolyte, for example, an electrolytic solution containing 0.1 M H ₂ SO ₄ , 0.1M potassium phosphate buffer. In this case, hydrogen and oxygen can be produced from the electrolytic solution as the first gas and the second gas.

Gas manufacturing method The gas manufacturing method of this embodiment installs the gas manufacturing apparatus 23 so that the said light-receiving surface becomes substantially horizontal, and the said gas manufacturing apparatus discharges | emits 1st gas, 1st gas discharge port, The second electrolysis chamber is provided with a second gas exhaust port for discharging the second gas, and an electrolytic solution chamber. The electrolytic solution is introduced into the electrolytic solution chamber, and sunlight is incident on the light receiving surface of the photoelectric conversion unit. A first gas and a second gas are generated from the first electrode and the second electrolysis electrode, respectively, and the first gas and the second gas are discharged from the first gas outlet and the second gas outlet, respectively.
Thereby, the first gas and the second gas can be produced.

Gas Manufacturing Device Array The gas manufacturing device array of the present embodiment includes a plurality of gas manufacturing devices 23 of the present embodiment, a first gas discharge path 25, and a second gas discharge path 26. The first gas discharge port 20 for discharging the first gas and the second gas discharge port 19 for discharging the second gas are provided, and the first gas discharge path 25 is the first gas discharge port 20 of each gas production device 23. The second gas discharge path 26 is connected to the second gas discharge port 19 of each gas production device 23. For example, as shown in FIG. 19, the gas production apparatus array can be formed by arranging the gas production apparatuses. In this case, the first gas discharge path 25 and the second gas discharge path 26 are connected to each gas production apparatus 23. Since it can provide in both sides, piping can be simplified.

1: Copper substrate 2: Photoelectric conversion part 4: First electrode 5: Second electrode 7: Second electrolysis electrode 8: First electrolysis electrode 9: First electroconductive part 10: Second electroconductive part 11: First type part 12: Second mold part 13: Bulkhead 14: Top plate 15: Electrolyte chamber 16: Sealing material 17: Third conductive part 18: Water supply port 19: Second gas outlet 20: First gas outlet 21: Insulating part 23: Gas production apparatus 25: First gas discharge path 26: Second gas discharge path 28: Photoelectric conversion layer 33: Third conductive part 35: Semiconductor region 36: p-type semiconductor region 37: n-type semiconductor region 40: Isolation 42: 4th conductive part 43: 5th conductive part 45: Gas production device array

Claims

A photoelectric conversion unit having a light receiving surface and a back surface thereof, and first and second electrodes for electrolysis that are provided side by side on the back surface and each have a surface that can come into contact with an electrolytic solution,
When the first and second electrolysis electrodes are in contact with the electrolytic solution, the first and second electrolysis electrodes use the electromotive force generated by the photoelectric conversion unit to receive light to electrolyze the electrolytic solution, respectively. 1 gas and a second gas are provided to be generated,
When the light receiving surface of the photoelectric conversion unit is horizontal, the first electrolysis electrode and the second electrolysis electrode have different inclination angles between a surface that can contact the electrolytic solution and a horizontal reference surface. Gas production equipment.
An electrolyte chamber containing the electrolyte solution;
When the light receiving surface of the photoelectric conversion unit is leveled, the electrolyte chamber is a first gas exhaust port provided close to the upper end of the surface that can contact the electrolyte of the first electrolysis electrode, or second A second gas outlet provided close to the upper end of the surface of the electrode for electrolysis that can contact the electrolyte;
The electrode for first electrolysis has a surface that can contact the inclined electrolyte so that the first gas can be recovered from the first gas outlet,
2. The apparatus according to claim 1, wherein the second electrolysis electrode has a surface that can contact the inclined electrolyte so that the second gas can be recovered from the second gas discharge port.
The photoelectric conversion unit has a rectangular light receiving surface,
The device according to claim 2, wherein the first and second gas discharge ports are provided in proximity to opposing sides of the light receiving surface of the photoelectric conversion unit.
At least one of the first and second electrolysis electrodes has a plurality of surfaces, each of which has a surface that can come into contact with the strip-shaped electrolyte solution, and the long sides of the surfaces are alternately provided so as to be adjacent to each other. The device according to any one of claims 1 to 3.
A first mold part provided between the first electrolysis electrode and the back surface of the photoelectric conversion part; and a second mold part provided between the second electrolysis electrode and the back surface of the photoelectric conversion part. ,
When the light receiving surface of the photoelectric conversion unit is leveled, the first mold part and the second mold part have an inclination angle between a surface that can contact the electrolytic solution of the first electrolysis electrode and a horizontal reference surface, The apparatus according to any one of claims 1 to 4, wherein the second electrolysis electrode is formed so that an inclination angle between a surface that can come into contact with the electrolytic solution and the reference surface is different.
The apparatus according to claim 5, wherein the first mold part and the second mold part are made of a solid resin.
The apparatus according to claim 5 or 6, further comprising a first conductive part between the first mold part and the first electrolysis electrode or between the second mold part and the second electrolysis electrode.
The device according to any one of claims 1 to 7, wherein each of the first and second electrolysis electrodes has a groove-like recess extending in an inclined direction on a surface that can contact the electrolytic solution.
When the light receiving surface of the photoelectric converter is leveled,
The first electrolysis electrode has a surface that can contact an electrolytic solution having an inclination angle of 1 degree to 60 degrees with respect to a horizontal reference surface, and the second electrolysis electrode is between the reference surface and the reference surface. The apparatus according to any one of claims 1 to 8, wherein the apparatus has a surface that can contact an electrolytic solution having an inclination angle of not less than 120 degrees and not more than 179 degrees.
The photoelectric conversion unit generates an electromotive force between the light receiving surface and the back surface by receiving light,
The first electrolysis electrode is electrically connected to the back surface of the photoelectric conversion unit,
The apparatus according to any one of claims 1 to 9, wherein the second electrolysis electrode is electrically connected to a light receiving surface of the photoelectric conversion unit.
The apparatus according to any one of claims 1 to 10, further comprising a first electrode in contact with a light receiving surface of the photoelectric conversion unit.
The apparatus according to claim 11, further comprising a second conductive portion that electrically connects the first electrode and the second electrolysis electrode.
The device according to claim 12, wherein the second conductive portion is provided in a contact hole penetrating the photoelectric conversion portion.
A second mold part provided between the second electrolysis electrode and the back surface of the photoelectric conversion part;
The second mold part has insulating properties and is provided so as to cover the side surface of the photoelectric conversion part,
The device according to claim 12, wherein the second conductive portion is provided on a portion of the second mold portion that covers a side surface of the photoelectric conversion portion.
A second mold part provided between the second electrolysis electrode and the back surface of the photoelectric conversion part;
The second mold part has insulating properties and is provided so as to cover the side surface of the photoelectric conversion part,
The device according to claim 11, wherein the second electrolysis electrode is provided on a portion of the second mold part that covers a side surface of the photoelectric conversion unit and is in contact with the first electrode.
A first mold part provided between the first electrolysis electrode and the back surface of the photoelectric conversion part; and a second mold part provided between the second electrolysis electrode and the back surface of the photoelectric conversion part. Prepared,
16. The method according to claim 1, further comprising a second electrode provided between the back surface of the photoelectric conversion unit and the first mold unit and between the back surface of the photoelectric conversion unit and the second mold unit. The device described.
The apparatus according to claim 16, further comprising a third conductive portion that electrically connects the second electrode and the first electrolysis electrode.
The device according to claim 17, wherein the third conductive portion is provided so as to cover a side portion of the first mold portion and is in contact with the second electrode.
The photoelectric conversion unit generates a potential difference between the first and second areas of the back surface by receiving light,
The first area is electrically connected to the first electrolysis electrode;
The apparatus according to any one of claims 1 to 9, wherein the second area is electrically connected to the second electrolysis electrode.
The photoelectric conversion part is made of at least one semiconductor material having an n-type semiconductor part and a p-type semiconductor part,
20. The device of claim 19, wherein one of the first and second areas is part of the n-type semiconductor part and the other is part of the p-type semiconductor part.
A translucent substrate;
The apparatus according to any one of claims 1 to 20, wherein the photoelectric conversion unit is provided on the translucent substrate.
A translucent substrate;
The photoelectric conversion unit is provided on the translucent substrate,
When the light-receiving surface of the photoelectric conversion unit is leveled, the translucent substrate has an inclination angle between a surface that can contact the electrolytic solution of the first electrolysis electrode and a horizontal reference surface, and a second electrolysis substrate. The apparatus according to any one of claims 1 to 6, wherein the device is shaped so that an inclination angle between a surface of the electrode that can contact the electrolyte and the reference surface is different.
23. The apparatus according to claim 22, wherein the second electrolysis electrode is provided on the back surface of the photoelectric conversion unit via an insulating unit.
The apparatus according to any one of claims 1 to 23, wherein the photoelectric conversion unit includes a photoelectric conversion layer including a p-type semiconductor layer, an i-type semiconductor layer, and an n-type semiconductor layer.
The photoelectric conversion unit includes a plurality of photoelectric conversion layers connected in series,
The apparatus according to any one of claims 1 to 24, wherein the plurality of photoelectric conversion layers supply an electromotive force generated by receiving light to the first electrolysis electrode and the second electrolysis electrode.
26. The apparatus according to claim 25, wherein each photoelectric conversion layer is connected in series by a fourth conductive portion.
Of the first electrolysis electrode and the second electrolysis electrode, one is a hydrogen generation unit that generates H 2 from the electrolytic solution, and the other is an oxygen generation unit that generates O 2 from the electrolytic solution,
The hydrogen generation unit and the oxygen generation unit each include a catalyst for a reaction for generating H 2 from the electrolytic solution and a catalyst for a reaction for generating O 2 from the electrolytic solution, respectively. apparatus.
28. The apparatus according to claim 27, wherein at least one of the hydrogen generation part and the oxygen generation part has a catalyst surface area larger than an area of the light receiving surface.
29. The apparatus according to claim 27 or 28, wherein at least one of the hydrogen generator and the oxygen generator is a porous conductor carrying a catalyst.
The apparatus according to any one of claims 27 to 29, wherein the hydrogen generation unit includes at least one of Pt, Ir, Ru, Pd, Rh, Au, Fe, Ni, and Se as a hydrogen generation catalyst.
The apparatus according to any one of claims 27 to 30, wherein the oxygen generation unit includes at least one of Mn, Ca, Zn, Co, and Ir as an oxygen generation catalyst.
A translucent substrate and an electrolyte chamber;
The photoelectric conversion unit is provided on the translucent substrate,
A top plate is further provided on the first electrolysis electrode and the second electrolysis electrode,
The apparatus according to any one of claims 1 to 31, wherein the electrolyte chamber is provided between the first electrolysis electrode and the second electrolysis electrode and the top plate.
The apparatus according to claim 32, further comprising a partition wall that partitions an electrolyte chamber between the first electrolysis electrode and the top plate and an electrolyte chamber between the second electrolysis electrode and the top plate.
The apparatus according to claim 33, wherein the partition wall includes an ion exchanger.
The gas production apparatus according to any one of claims 1 to 34 is installed so that a light receiving surface of the photoelectric conversion unit is substantially horizontal,
The gas manufacturing apparatus includes a first gas outlet for discharging the first gas, a second gas outlet for discharging the second gas, and an electrolyte chamber.
An electrolyte is introduced into the electrolyte chamber, and sunlight is incident on the light receiving surface of the photoelectric conversion unit to generate a first gas and a second gas from the first electrolysis electrode and the second electrolysis electrode, respectively. A gas manufacturing method for discharging the first gas and the second gas from the first gas outlet and the second gas outlet, respectively.
A plurality of the gas production apparatuses according to any one of claims 1 to 34, a first gas discharge path, and a second gas discharge path,
Each gas manufacturing apparatus includes a first gas outlet for discharging the first gas and a second gas outlet for discharging the second gas,
The first gas discharge path is electrically connected to the first gas discharge port of each gas production device,
The second gas discharge path is a gas production device array that is electrically connected to the second gas discharge port of each gas production device.