Photovoltaic hydrogen production method and device

Abstract

The invention relates to the technical field of batteries, in particular to a photovoltaic hydrogen production method and device.The method comprises the following steps that sunlight penetrates through at least part of electrolyte to reach an organic photovoltaic device for power generation, and hydrogen production is completed; and the electrolyte comprises water. According to the method provided by the invention, each spectral region of sunlight can be effectively utilized, and the energy utilization rate is improved; moreover, photons in an infrared light region are used for heating the electrolyte, so that the use of an additional heating device is reduced, the production cost is reduced, and the energy utilization rate is further improved; the method provided by the invention can also optimize the structure of the used device.

Description

Technical Field

[0001] The present application relates to the field of photovoltaic hydrogen production, and specifically to a method and device for photovoltaic hydrogen production. Background Art

[0002] As the global energy supply and demand system transforms towards low-carbon and carbon-free, renewable energy such as solar energy and hydrogen energy are increasingly valued. Among them, the main way to utilize solar energy is to prepare photovoltaic cells or solar thermal power generation, and currently several large-scale photovoltaic or solar thermal power stations of hundreds of megawatts have been built in China. However, in the process of utilizing solar energy, due to changes in day and night or weather, the conversion of solar energy to electrical energy is volatile and random. A feasible solution is to convert excess electrical energy into hydrogen that is easy to store in order to smooth out the fluctuations of solar energy and improve the level of absorption. In addition, as a clean energy technology, hydrogen production by electrolysis of water does not produce greenhouse gas emissions during the production process, which helps to improve environmental quality.

[0003] However, there are also some problems with using solar power generation and then electrolyzing water to produce hydrogen. On the one hand, solar power generation equipment and water electrolysis hydrogen production equipment are usually located in different locations, so it is necessary to generate solar power first, then transport it through the power grid, and finally electrolyze water to produce hydrogen at the electrolysis plant. This process will introduce additional external circuit equipment, such as junction boxes, inverters, and power grid conductors, which will increase the cost of hydrogen production and energy loss in the transportation process. On the other hand, the widely used operating temperature for industrial water electrolysis hydrogen production is an alkaline aqueous solution of 70-80°C, so additional heating resistors need to be added to heat the electrolyte, which will also cause new energy losses.

[0004] Therefore, it is crucial to develop a method that does not require additional heating of the electrolyte during the electrolysis of water to produce hydrogen and can make full use of solar energy. Summary of the invention

[0005] In view of the above problems, the present application provides a method and device for photovoltaic hydrogen production, which can effectively utilize all spectral regions of sunlight and improve energy utilization. Moreover, the electrolyte is heated by photons in the infrared light region, which reduces the use of additional heating devices, reduces production costs, and further improves energy utilization. The method described in the present application can also optimize the structure of the device used.

[0006] In a first aspect, the present application provides a method for producing hydrogen from photovoltaic power plants, the method comprising the following steps:

[0007] Passing sunlight through at least a portion of the electrolyte to reach the organic photovoltaic device to generate electricity and produce hydrogen;

[0008] The electrolyte includes water.

[0009] Compared with inorganic photovoltaic cells, organic photovoltaic devices are a type of solar power generation technology with the advantages of spectrally adjustable and easy solution processing. Organic photovoltaic devices are expected to occupy special application scenarios in the future energy field with their unique advantages. The entire solar light source is divided into ultraviolet light, visible light and infrared light. Generally speaking, organic photovoltaic devices can only absorb photons in the ultraviolet and visible light regions (the absorption spectrum is generally before 1000nm) and convert them into electrons; therefore, photons in the infrared region of solar radiation (the absorption spectrum is generally after 1000nm) cannot be effectively utilized by organic photovoltaic devices, so solar energy is partially wasted.

[0010] In the technical solution of the implementation mode of the present application, sunlight passes through the electrolyte, and the water in the electrolyte first absorbs the photons in the infrared region of the sunlight radiation, which can heat the electrolyte and reduce the resistance of the electrolyte; then the photons in the ultraviolet and visible regions of the sunlight radiation pass through the electrolyte to reach the organic photovoltaic device for power generation, thereby realizing hydrogen production. In the above method, each spectral region of sunlight can be effectively utilized, which improves the energy utilization rate; moreover, the electrolyte is heated by photons in the infrared region, which reduces the use of additional heating devices, reduces production costs, and further improves energy utilization rate; the method described in the present application can also optimize the structure of the device used.

[0011] Preferably, the organic photovoltaic device is at least partially disposed in an electrolyte, or the organic photovoltaic device is disposed below the electrolyte.

[0012] In the technical solution of the implementation mode of the present application, the organic photovoltaic device is directly arranged in the electrolyte, or below the electrolyte, and can directly use sunlight for underwater photovoltaic water electrolysis to produce hydrogen. There is no need to convert solar energy into electrical energy and then transport it through the power grid before entering the electrolyte for hydrogen production. This simplifies the process and saves equipment and transportation costs as well as energy utilization.

[0013] Preferably, the organic photovoltaic device is at least partially disposed in the electrolyte, and the distance between the organic photovoltaic device and the electrolyte surface is 0 to 10 cm, and is not equal to 0 cm, for example, 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, etc.

[0014] Preferably, the organic photovoltaic device comprises a water- and oxygen-blocking packaging component.

[0015] In the technical solution of the implementation mode of the present application, a water-proof and oxygen-proof packaging component is provided in the organic photovoltaic device, which can reduce the corrosion of the electrolyte to the organic photovoltaic device and extend the service life of the organic photovoltaic device.

[0016] Preferably, the material of the water- and oxygen-blocking packaging component includes any one of glass, quartz, polymethyl methacrylate, polyisobutylene, polyethylene, thermoplastic polyurethane, ethylene vinyl acetate or cyclized perfluoropolymer, or a combination of at least two thereof.

[0017] Preferably, the adhesive used in the water- and oxygen-blocking packaging component includes any one of silicone, polyurethane, polyolefin resin, urea-formaldehyde resin, phenol-formaldehyde resin or melamine resin, or a combination of at least two of them.

[0018] Preferably, the organic photovoltaic device comprises an organic photovoltaic cell.

[0019] Preferably, the organic photovoltaic cell comprises any one of a flexible cell, a rigid cell, a tandem cell or a stacked cell, or a combination of at least two of them.

[0020] Preferably, the organic photovoltaic cell comprises an organic photovoltaic material.

[0021] Preferably, the organic photovoltaic material comprises a donor organic photovoltaic material and an acceptor organic photovoltaic material.

[0022] Preferably, the mass ratio of the donor organic photovoltaic material to the acceptor organic photovoltaic material is 1:(0.1-5), wherein 0.1-5 can be 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, etc.

[0023] Preferably, the donor organic photovoltaic material includes any one of P3HT, PBDB-TF, PBDB-T, PBDB-TCl, D18, D18-Cl, PBQx-TF, PBQx-TCl, PB-2F, PB-2 or PTO2, or a combination of at least two thereof.

[0024] Preferably, the acceptor organic photovoltaic material includes any one of BTP-eC9, BTP-eC9-2Cl, Y6, BO-4I, ITIC, IT-4F, L8-BO, FPCC-Br, FPCC-Cl, ITCC-Cl, ITCC, FTCC-Br, FCC-Cl, GS-ISO, BTA3, F-BTA3, Cl-BTA3 or ITO-4F, or a combination of at least two thereof.

[0025] As an example, the molecular formula of the donor organic photovoltaic material is as follows:

[0026]

[0027]

[0028] As an example, the molecular formula of the acceptor organic photovoltaic material is as follows:

[0029]

[0030]

[0031]

[0032] In the present application, the weight average molecular weight of the organic photovoltaic material is in the range of 10000-500000, for example, 20000, 40000, 60000, 100000, 200000, 300000, 400000, 500000, etc., preferably 100000; in the molecular formula, n is the degree of polymerization, which ranges from 10-500, for example, 50, 100, 200, 300, 400, etc., preferably 100.

[0033] Preferably, the electrolyte in the electrolyte solution includes any one of a strong base, a weak base, a weak acid or water, or a combination of at least two of them.

[0034] As an example, the strong base includes sodium hydroxide and / or potassium hydroxide.

[0035] As an example, the weak base includes any one of ammonia monohydrate (NH3·H2O), aluminum hydroxide (Al(OH)3), methylamine, alanine (C3H5O2NH2), sodium phosphate, sodium hydrogen phosphate, sodium bicarbonate or sodium carbonate, or a combination of at least two thereof.

[0036] As an example, the weak acid includes any one or a combination of at least two of sodium dihydrogen phosphate, ammonium chloride, acetic acid, sodium bisulfate, hypochlorous acid, oxalic acid, carbonic acid, hydrocyanic acid, citric acid or ferrocyanide.

[0037] Preferably, the electrolyte also includes an exchange membrane and / or a catalytic electrode.

[0038] In the present application, there is no limitation on the type of exchange membrane, and materials known in the art can be used. As an example, the exchange membrane can be an ion exchange membrane and / or a proton exchange membrane.

[0039] As an example, the exchange membrane is selected from ion exchange membranes such as anion exchange membranes, and the electrolyte includes water and / or weak base.

[0040] As an example, the exchange membrane is selected from a proton exchange membrane, and the electrolyte includes water and / or a weak acid.

[0041] As an example, the electrolyte includes a potassium hydroxide (KOH) or sodium hydroxide (NaOH) solution with a mass concentration of 20%-40%.

[0042] Preferably, the material of the catalytic electrode includes any one of platinum, platinum (Pt), iridium (Ir), nickel (Ni), iron (Fe), cobalt (Co), carbon (C), indium tin oxide (ITO) or fluorine-doped tin oxide (FTO) or a combination of at least two thereof.

[0043] Preferably, the electrolyte also includes a catalyst.

[0044] Preferably, the catalyst comprises iridium oxide (IrO2) and / or ruthenium oxide (RuO2).

[0045] In a second aspect, the present application provides a device for photovoltaic hydrogen production, the device comprising an electrolyzer;

[0046] The electrolytic cell includes an organic photovoltaic device, and / or at least a portion of the bottom of the electrolytic cell is provided with an organic photovoltaic device.

[0047] In the photovoltaic water electrolysis device in the prior art, generally speaking, the solar power generation equipment and the water electrolysis hydrogen production equipment are usually located in different locations, that is, after the solar power generation equipment generates electricity, it is transported through the power grid to the water electrolysis hydrogen production equipment for hydrogen production. This process requires the introduction of additional external circuit equipment, such as junction boxes, inverters, and power grid conductors, etc., which increases the cost of hydrogen production and energy loss in the transportation process.

[0048] In the technical solution of the implementation mode of the present application, the organic photovoltaic device is arranged in the electrolytic cell, and / or the organic is used as a part of the bottom of the electrolytic cell; the above-mentioned arrangement belongs to the preparation of an integrated photovoltaic cell water electrolysis device, omitting additional external circuit equipment, such as a junction box, an inverter and grid conductors, etc., thereby reducing the cost investment of hydrogen production and the energy loss in the transportation process.

[0049] In actual use, sunlight passes through the electrolyte in the electrolyzer, and the water in the electrolyte absorbs photons in the infrared light region, heating the electrolyte and reducing the resistance of the electrolyte; photons in the ultraviolet and visible light regions pass through the electrolyte to reach the organic photovoltaic device for power generation, thereby achieving hydrogen production.

[0050] Based on the above process, the device described in the present application can make effective use of all spectral regions of sunlight, thereby improving energy utilization; moreover, by using photons in the infrared light region to heat the electrolyte, the use of additional heating devices can be reduced, production costs are reduced, and the structure of the device is optimized.

[0051] In the present application, the material of the side wall or bottom of the electrolytic cell can be a material known in the art. For example, it has the characteristics of acid resistance, alkali resistance or organic solvent resistance. Specifically, it can include polymer materials such as polytetrafluoroethylene, polycarbonate, polyetheretherketone phenolic resin; ceramic materials; stainless steel, titanium alloy, platinum, nickel, gold, silver and other metal materials; or at least two combinations, such as metal plating on the inner surface of ceramics. As an example, the material of the side wall of the electrolytic cell can be a light-transmitting material to meet the use requirements of sunlight passing through the side wall into the electrolyte. The light-transmitting material can be a material known in the art, and the light-transmitting material includes any one of quartz, glass or polymethyl methacrylate or a combination of at least two.

[0052] Preferably, the electrolytic cell comprises an upper cover, and the material of the upper cover comprises a light-transmitting material.

[0053] In the technical solution of the implementation mode of the present application, a light-transmitting material is used as the upper cover of the electrolytic cell, and sunlight can more easily pass through the upper cover to reach the electrolyte, thereby improving the utilization rate of sunlight.

[0054] Preferably, the material of the upper cover includes any one of quartz, glass or polymethyl methacrylate, or a combination of at least two of them.

[0055] Preferably, the organic photovoltaic device comprises a forward device and / or a reverse device.

[0056] Preferably, the organic photovoltaic device comprises a water- and oxygen-blocking packaging component.

[0057] In the technical solution of the implementation mode of the present application, a water-proof and oxygen-proof packaging component is provided for the organic photovoltaic device, which can reduce the corrosion of the electrolyte on the internal components of the organic photovoltaic device, such as the organic photovoltaic cell, and extend the service life of the organic photovoltaic device working under the electrolyte.

[0058] Preferably, the organic photovoltaic device comprises an organic photovoltaic cell.

[0059] As an example, multiple organic photovoltaic cells can be connected in series to form a battery module. The battery modules can be used individually or in combination, such as using multiple battery modules in series.

[0060] Preferably, the number of cells of the organic photovoltaic cell is ≥ 2, such as 3, 4, 6, 8, etc.

[0061] Preferably, the electrolytic cell comprises an exchange membrane and / or a catalytic electrode.

[0062] Preferably, the catalytic electrodes include at least two. As an example, the electrodes are placed at the bottom of the electrolyzer. Different electrodes are used for producing hydrogen and oxygen respectively.

[0063] Preferably, the exchange membrane is arranged between catalytic electrodes.

[0064] In the technical solution of the embodiment of the present application, the exchange membrane is arranged between the catalytic electrodes, that is, the exchange membrane is used to separate the electrodes for hydrogen production and oxygen production, so as to collect hydrogen and oxygen respectively. Therefore, the device of the present application can also produce oxygen on the basis of hydrogen production.

[0065] As an example, the organic photovoltaic device further includes a negative electrode and a positive electrode, and the negative electrode and the positive electrode are each independently connected to the catalytic electrode.

[0066] Preferably, the device further comprises a hydrogen collecting component.

[0067] As an example, the device further comprises an oxygen collection component.

[0068] Compared with the prior art, this application has at least the following beneficial effects:

[0069] The method described in the present application can effectively utilize all spectral regions of sunlight, thereby improving energy utilization; moreover, by utilizing photons in the infrared light region to heat the electrolyte, the use of additional heating devices is reduced, production costs are reduced, and energy utilization is further improved; the method described in the present application can also optimize the structure of the device used.

[0070] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the detailed description of the preferred embodiments below. The accompanying drawings are only for the purpose of illustrating the preferred embodiments and are not to be considered as limiting the present application. Moreover, the same reference numerals are used throughout the accompanying drawings to represent the same components. In the accompanying drawings:

[0072] Figure 1 This is a schematic diagram of an organic photovoltaic device provided in Example 1 of the present application immersed in an electrolyte to electrolyze water to produce hydrogen.

[0073] Figure 2 This is a schematic diagram of using the organic photovoltaic device provided in Example 2 of the present application as the bottom cover of an electrolyzer to electrolyze water to produce hydrogen.

[0074] Figure 3 The absorption coefficient of water at different wavelengths provided in this application.

[0075] Figure 4 Schematic diagram of a cell module of an organic photovoltaic device in some embodiments of the present application.

[0076] Figure 5 Current density-voltage curve of the cell module of the organic photovoltaic device provided in this application at AM 1.5G and 5 cm underwater.

[0077] Figure 6 The sunlight source provided for this application is continuously irradiated Figure 1 Graph showing changes in electrolyte temperature when using the device shown.

[0078] Figure 7 The sunlight source provided for this application is continuously irradiated Figure 2 Graph showing electrolyte temperature variation when using the device shown.

[0079] Figure 8 This is a schematic diagram of the organic photovoltaic device of Example 1 in Comparative Example 1, which is placed outside the electrolyte for electrolysis.

[0080] Among them, 1-sunlight source; 2-ultraviolet light; 3-visible light; 4-infrared light; 5-upper cover; 6-electrolyzer; 7-organic photovoltaic device; 8-first platinum electrode; 9-second platinum electrode; 10-ion exchange membrane; 11-hydrogen collecting component; 12-oxygen collecting component; 13-first battery; 14-second battery; 15-negative electrode; 16-positive electrode; 17-photovoltaic cell; 18-combiner box; 19-inverter; 20-electricity grid connection; 21-electrolysis device; 22-heating device. DETAILED DESCRIPTION

[0081] The following embodiments of the technical solution of the present application are described in detail in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0082] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the specification and claims of this application and the above-mentioned figure descriptions and any variations thereof are intended to cover non-exclusive inclusions.

[0083] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0084] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B can represent: A exists, A and B exist at the same time, and B exists. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0085] Example 1

[0086] This embodiment provides a method for producing hydrogen from photovoltaics, which specifically includes: transmitting sunlight through at least a portion of an electrolyte to reach an organic photovoltaic device to generate electricity and produce hydrogen.

[0087] The method uses a device such as Figure 1 As shown, the device includes a square electrolytic cell 6, which is 5 cm long, 5 cm wide, 12 cm high, and 1 mm thick. The upper cover 5 is made of highly transparent quartz. An organic photovoltaic device 7 is placed in the electrolytic cell. A first platinum electrode 8 is led out from the negative electrode of the organic photovoltaic cell in the organic photovoltaic device, and a second platinum electrode 9 is led out from the positive electrode of the organic photovoltaic cell. Both platinum electrodes are 1 cm long, 1 cm wide, and 0.1 mm thick. The first platinum electrode is used as a catalytic electrode to produce hydrogen, and the second platinum electrode is used as a catalytic electrode to produce oxygen. The two sides are separated by an ion exchange membrane 10 (brand Fumasep, grade FAA-3-PK-130); the device also includes a hydrogen collection component 11 and an oxygen collection component 12.

[0088] The light source received by the whole device is the sunlight source 1, which is divided into ultraviolet light region (UV), visible light region (Vis) and infrared light region (IR). Since the electrolyte (mainly composed of water) has a large absorption coefficient for near-infrared light, and weak absorption for ultraviolet and visible light regions, only ultraviolet light 2 and visible light 3 can reach the surface of the solar cell, and infrared light 4 will be absorbed by the electrolyte for heating. Figure 3 The absorption coefficients of water at different wavelengths provided can support the above description.

[0089] The organic photovoltaic device is specifically prepared by the following method:

[0090] The organic photovoltaic materials PBQx-TF and FPCC-Br were dissolved and blended in a toluene solution at a mass ratio of 1:1.2 at 90°C, and a cell module of an organic photovoltaic device was prepared by a doctor blade method, such as Figure 4 As shown, the battery module is composed of a first battery 13 and a second battery 14 connected in series. The effective area of ​​each battery is 5 cm long and 0.8 cm wide. The effective area of ​​a single battery is 4 square centimeters, and the effective area of ​​the entire battery module is 8 square centimeters.

[0091] Outside the effective area, there are two silver electrodes as the negative electrode 15 and the positive electrode 16, and the single silver electrode is 5 cm long and 0.8 cm wide. The silver electrode is prepared by vacuum evaporation of metallic silver; the prepared battery module is encapsulated by a square glass with a length of 5.2 cm and a width of 3.2 cm, and the adhesive used for encapsulation is epoxy resin. During encapsulation, pins are reserved on the silver electrode to connect the first platinum electrode and the second platinum electrode.

[0092] Performance Testing

[0093] The two battery modules in Example 1 are connected in series to form an organic photovoltaic device. The current density-voltage curve at AM 1.5G (the standard spectrum on the earth's surface) and 5 cm underwater is as follows: Figure 5 The specific parameters are shown in Table 1. Test method The specific method is to use a 1.5G AM spectrum (100mW cm -2 ) solar simulator (SS-F5-3A, Guangyan Technology Co., Ltd.) and Keithley2400 source meter were used to measure the current density-voltage curve. The scanning mode of the measurement was forward scanning from -0.5-2.5V with a step length of 0.02V. The energy conversion efficiency of the same organic photovoltaic device at AM 1.5G and 5 cm underwater was 11.9% and 11.6% respectively. The energy conversion efficiency at 5 cm underwater was not significantly reduced, which means that most of the photons in the ultraviolet and visible regions passed through the electrolyte smoothly, reached the surface of the organic photovoltaic device, and were absorbed and converted into electrons.

[0094] Table 1. Photovoltaic performance of organic photovoltaic devices with two-cell modules under different light sources

[0095]

[0096] The photovoltaic parameters of the organic photovoltaic device in Example 1 at different underwater depths are tested, and the results are shown in Table 2. The results show that the organic photovoltaic device described in the present application still has a very high energy conversion efficiency at different underwater depths.

[0097] Table 2. Photovoltaic parameters of the organic photovoltaic device (single cell module) in Example 1 at different underwater depths

[0098]

[0099]

[0100] Reference Figure 1 The packaged organic photovoltaic device was placed in the device described in Example 1, and an electrolyte (1 mol / L KOH aqueous solution) was added to the electrolytic cell for electrolysis, wherein the distance between the organic photovoltaic device and the electrolyte surface was 5 cm.

[0101] After 30 minutes of electrolysis, a total of 66.4 ml of hydrogen was collected, equivalent to 2.963 mmol of hydrogen. The calculated conversion efficiency of solar energy to hydrogen is 9.8%. In addition, the temperature of the electrolyte will gradually increase with the extension of electrolysis time, such as Figure 6 As shown, when the sunlight source shines continuously Figure 1 When the device shown is used, the temperature rises to 41.5°C after 180 minutes, and the temperature remains stable after subsequent continuous illumination.

[0102] Comparative Example 1

[0103] The organic photovoltaic device of Example 1 is placed outside the electrolyte for electrolysis (eg Figure 8 ), that is, the initial temperature of the electrolyte is room temperature 25°C, the solar light source first enters the organic photovoltaic device to be converted into electrical energy, and then electrolysis is performed. The device includes a photovoltaic cell 17, a solar light source 1, a junction box 18, an inverter 19, an electric energy grid 20, and an electrolysis device 21, wherein a heating device 22 is particularly required to heat the electrolyte from the initial temperature to a suitable electrolysis temperature of 80°C.

[0104] After 30 minutes of electrolysis, a total of 55.5 ml of hydrogen was collected, equivalent to about 2.479 mmol of hydrogen. The calculated solar energy to hydrogen conversion efficiency was 8.2%.

[0105] By comparing Example 1 with Comparative Example 1, it can be seen that the method and device described in the present application can improve the efficiency of hydrogen production by photovoltaic water electrolysis.

[0106] Example 2

[0107] The difference from Example 1 is that the devices used are different, such as Figure 2 As shown, the advantage of using an organic photovoltaic device as the bottom of the electrolytic cell is that the volume of the electrolyte is smaller, which helps to achieve a higher electrolyte temperature, as follows:

[0108] The device includes a square electrolytic cell 6, which is 5 cm long, 5 cm wide, 7 cm high and 1 mm thick. The upper cover 5 is highly transparent quartz to allow the sunlight source 1 to enter. The organic photovoltaic device 7 used in Example 1 is used as the bottom cover of the electrolytic cell. In the organic photovoltaic device, the negative electrode of the organic photovoltaic cell leads to a first platinum sheet electrode 8, and the positive electrode of the organic photovoltaic cell leads to a second platinum sheet electrode 9. Both platinum sheet electrodes are 1 cm long, 1 cm wide and 0.1 mm thick. The first platinum sheet electrode is used as a catalytic electrode to produce hydrogen, and the second platinum sheet electrode is used as a catalytic electrode to produce oxygen. The two sides are separated by an ion exchange membrane 10; the device also includes a hydrogen collection component 11 and an oxygen collection component 12.

[0109] An electrolyte (1 mol / L KOH aqueous solution) was placed in the electrolytic cell for electrolysis, and the distance between the organic photovoltaic device and the electrolyte surface was 5 cm.

[0110] Performance Testing

[0111] After 30 minutes of electrolysis, a total of 71.8 ml of hydrogen was collected, equivalent to 3.204 mmol of hydrogen. The calculated conversion efficiency of solar energy to hydrogen is 10.6%. In addition, the temperature of the electrolyte will gradually increase with the extension of electrolysis time, such as Figure 7 As shown, when the sun shines continuously Figure 2 When the device is used as shown, the temperature rises to 49.8°C after 180 minutes and remains stable after subsequent continuous illumination.

[0112] In summary, the method and device described in this application can electrolyze water to produce hydrogen in situ with organic photovoltaic cells, thus eliminating external circuit equipment such as junction boxes, inverters, and grid conductors. At the same time, the organic photovoltaic cells are immersed in the electrolyte, and the photons in the infrared region of sunlight will be absorbed by the electrolyte to heat the electrolyte and reduce the resistance of the electrolyte, but the photons in the ultraviolet and visible regions will pass through the electrolyte to reach the surface of the organic photovoltaic cells for power generation, thereby reducing the energy loss of solar water electrolysis to produce hydrogen from two aspects.

[0113] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be included in the scope of the claims and specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in the various embodiments can be combined in any way. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims.

Claims

1. A method for producing hydrogen from photovoltaics, characterized in that: The method comprises the following steps: Passing sunlight through at least a portion of the electrolyte to reach the organic photovoltaic device to generate electricity and produce hydrogen; The electrolyte includes water.

2. The method according to claim 1, characterized in that The organic photovoltaic device is at least partially disposed in an electrolyte, or the organic photovoltaic device is disposed below the electrolyte; Preferably, the organic photovoltaic device is at least partially disposed in an electrolyte, and the distance between the organic photovoltaic device and the surface of the electrolyte is 0 to 10 cm, and is not equal to 0 cm; Preferably, the organic photovoltaic device comprises a water-blocking and oxygen-blocking packaging component; Preferably, the material of the water- and oxygen-blocking packaging component includes any one or a combination of at least two of glass, quartz, polymethyl methacrylate, polyisobutylene, polyethylene, thermoplastic polyurethane, ethylene vinyl acetate or cyclized perfluoropolymer; Preferably, the adhesive used in the water- and oxygen-blocking packaging component includes any one of silicone, polyurethane, polyolefin resin, urea-formaldehyde resin, phenol-formaldehyde resin or melamine resin, or a combination of at least two of them.

3. The method according to claim 1 or 2, characterized in that: The organic photovoltaic device comprises an organic photovoltaic cell; Preferably, the organic photovoltaic cell comprises any one or a combination of at least two of a flexible cell, a rigid cell, a series or parallel cell, or a stacked cell; Preferably, the organic photovoltaic cell comprises an organic photovoltaic material; Preferably, the organic photovoltaic material comprises a donor organic photovoltaic material and an acceptor organic photovoltaic material; Preferably, the mass ratio of the donor organic photovoltaic material to the acceptor organic photovoltaic material is 1:(0.1-5); Preferably, the donor organic photovoltaic material includes any one or a combination of at least two of P3HT, PBDB-TF, PBDB-T, PBDB-TCl, D18, D18-Cl, PBQx-TF, PBQx-TCl, PB-2F, PB-2 or PTO2; Preferably, the acceptor organic photovoltaic material includes any one of BTP-eC9, BTP-eC9-2Cl, Y6, BO-4I, ITIC, IT-4F, L8-BO, FPCC-Br, FPCC-Cl, ITCC-Cl, ITCC, FTCC-Br, FCC-Cl, GS-ISO, BTA3, F-BTA3, Cl-BTA3 or ITO-4F, or a combination of at least two thereof.

4. The method according to any one of claims 1 to 3, characterized in that: The electrolyte in the electrolyte solution includes any one of a strong base, a weak base, a weak acid or water, or a combination of at least two of them.

5. The method according to any one of claims 1 to 4, characterized in that: The electrolyte also includes an exchange membrane and / or a catalytic electrode; Preferably, the material of the catalytic electrode includes any one of platinum, iridium, nickel, iron, cobalt, carbon, indium tin oxide or fluorine-doped tin oxide, or a combination of at least two thereof; Preferably, the electrolyte further includes a catalyst; Preferably, the catalyst comprises iridium oxide and / or ruthenium oxide.

6. A device for photovoltaic hydrogen production, characterized in that: The device includes an electrolytic cell; The electrolytic cell includes an organic photovoltaic device, and / or at least a portion of the bottom of the electrolytic cell is provided with an organic photovoltaic device.

7. The device according to claim 6, characterized in that The electrolytic cell comprises an upper cover, and the material of the upper cover comprises a light-transmitting material; Preferably, the material of the upper cover includes any one of quartz, glass or polymethyl methacrylate, or a combination of at least two of them.

8. The device according to claim 6 or 7, characterized in that The organic photovoltaic device comprises a forward device and / or a reverse device; Preferably, the organic photovoltaic device comprises a water- and oxygen-blocking packaging component; Preferably, the organic photovoltaic device comprises an organic photovoltaic cell; Preferably, the number of cells of the organic photovoltaic cell is ≥2.

9. The device according to any one of claims 6 to 8, characterized in that: The electrolytic cell comprises an exchange membrane and / or a catalytic electrode; Preferably, the catalytic electrodes include at least two; Preferably, the exchange membrane is arranged between catalytic electrodes.

10. The device according to any one of claims 6 to 9, characterized in that: The device also includes a hydrogen collection component.

Images