Photoelectrocatalytic reactor and method for preparing a stacked perovskite cell

Abstract

The present specification relates to the technical field of chemistry, and particularly relates to a photoelectrocatalytic reaction device and a preparation method of a stacked perovskite battery. The photoelectrocatalytic reaction device comprises a reactor, a diaphragm for separating the reactor into a photo-cathode chamber and a photo-anode chamber, a light source and a power source; the photo-anode chamber is filled with a first solution, and the first solution is an aqueous solution; the photo-cathode chamber is filled with a second solution, and the second solution is an aqueous methylene succinic acid solution, and the second solution is dissolved with a catalyst for hydrogenation reaction of methylene succinic acid; the photo-anode is connected with an anode of the power source, and is arranged in the photo-anode chamber; the photo-cathode is connected with a cathode of the power source, and is arranged in the photo-cathode chamber; the light source and the power source are used for photoelectrocatalysis, so as to generate hydrogen in the photo-cathode chamber; and the hydrogen is used for in-situ reaction with the methylene succinic acid in the second solution to generate methyl succinic acid. The present specification can improve the utilization rate of hydrogen energy and reduce the production cost.

Description

TECHNICAL FIELD

[0001] The present specification relates to the technical field of chemistry, and particularly relates to a photoelectrocatalytic reaction device and a preparation method of a stacked perovskite battery. BACKGROUND

[0002] Hydrogen production technology is an important energy supply technology in new energy technology, and has important significance for promoting energy transformation and sustainable development. Hydrogen produced by hydrogen production technology can be used to synthesize chemicals. In the process of synthesizing chemicals by using hydrogen produced by hydrogen production technology, the hydrogen production process and the chemical synthesis process are traditionally two independent processes.

[0003] Such a separate process can cause waste of hydrogen energy and increase production costs. SUMMARY

[0004] The embodiments of the present specification provide a photoelectrocatalytic reaction device and a preparation method of a stacked perovskite battery, which are used to improve the utilization rate of hydrogen energy and reduce production costs.

[0005] The embodiments of the present specification provide a photoelectrocatalytic reaction device, which comprises:

[0006] a reactor, a diaphragm for separating the reactor into a light cathode chamber and a light anode chamber, a light source, and a power source; the light anode chamber is filled with a first solution, and the first solution is an aqueous solution; the light cathode chamber is filled with a second solution, and the second solution is a methylene succinic acid aqueous solution, and the second solution contains a catalyst for methylene succinic acid hydrogenation reaction;

[0007] a light anode connected to the anode of the power source and arranged in the light anode chamber;

[0008] a light cathode connected to the cathode of the power source and arranged in the light cathode chamber;

[0009] The light source and the power source are used for photoelectrocatalysis to generate hydrogen in the light cathode chamber; and the hydrogen is used for in-situ reaction with methylene succinic acid in the second solution to generate methyl succinic acid.

[0010] The embodiments of the present specification also provide a preparation method of a stacked perovskite battery, which comprises:

[0011] cleaning a conductive substrate;

[0012] spinning PTAA or VNPB as a first hole transport layer on the cleaned conductive substrate;

[0013] spinning FA on the first hole transport layer 0.8 Cs 0.3 PbI 1.8Br 1.2 or FA 0.8 Cs 0.2 PbI 2.1 Br 0.9 as a wide-bandgap photoactive layer;

[0014] depositing a first interconnect layer on the wide bandgap photoactive layer;

[0015] depositing and sputtering a composite layer on the first interconnect layer;

[0016] PEDOT:PSS was spin-coated on the composite layer as a second hole transport layer;

[0017] Spin-coat FA on the second hole transport layer 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 or FA 0.6 MA 0.4 Pb 0.4 Sn 0.6 I3 serves as a narrow-bandgap photoactive layer;

[0018] evaporating a second interconnect layer on the narrow bandgap photoactive layer;

[0019] A back reflection electrode is evaporated on the second interconnect layer to obtain a stacked perovskite cell.

[0020] The embodiments of this specification also provide a computer device, including a memory, a processor, and a computer program stored in the memory and executable on the processor, wherein the processor implements the above-mentioned method for preparing a stacked perovskite battery when executing the computer program.

[0021] The embodiments of this specification also provide a computer-readable storage medium, which stores a computer program. When the computer program is executed by a processor, it implements the above-mentioned method for preparing a stacked perovskite battery.

[0022] The embodiments of this specification also provide a computer program product, which includes a computer program, and when the computer program is executed by a processor, it implements the above-mentioned method for preparing a stacked perovskite battery.

[0023] The photoelectrocatalytic reaction device of the embodiment of the present specification comprises a reactor, a diaphragm for separating the reactor into a photo-cathode chamber and a photo-anode chamber, a light source and a power source. The anode of the power source is arranged in the photo-anode chamber, and the photo-anode chamber is filled with a first solution. The cathode of the power source is arranged in the photo-cathode chamber, and the photo-cathode chamber is filled with a second solution. Thus, photoelectrocatalytic hydrogen production can be realized to produce hydrogen in the photo-cathode chamber. In addition, the second solution is a methylene succinic acid aqueous solution, and the second solution contains a catalyst for the hydrogenation reaction of methylene succinic acid. The hydrogen produced in the photo-cathode chamber can directly react with methylene succinic acid in the second solution in situ to obtain methyl succinic acid. Thus, the photoelectrocatalytic hydrogen production process is coupled with the hydrogenation reduction process of methylene succinic acid, so as to obtain the high-value-added chemical methyl succinic acid. In this way, the utilization rate of hydrogen energy is improved, and the production cost of methyl succinic acid is reduced. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present specification or the prior art, the drawings needed to be used in the embodiment or prior art description will be briefly introduced as follows. The drawings in the following description are only some embodiments described in the present specification, and other drawings can also be obtained according to these drawings without creative labor for those skilled in the art.

[0025] Figure 1 It is a functional structure schematic diagram of the photoelectrocatalytic reaction device in the embodiment of the present specification.

[0026] Figure 2 It is a functional structure schematic diagram of the stacked perovskite battery in the embodiment of the present specification.

[0027] Figure 3 It is a flowchart schematic diagram of the preparation method of the stacked perovskite battery in the embodiment of the present specification.

[0028] Figure 4 It is a functional structure schematic diagram of the preparation device of the stacked perovskite battery in the embodiment of the present specification. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present specification will be described clearly and completely in the embodiments of the present specification in combination with the drawings in the embodiments of the present specification. Obviously, the described embodiments are only part of the embodiments of the present specification, rather than all the embodiments. The specific embodiments described herein are only used to explain the present disclosure, rather than limit the present disclosure. Based on the described embodiments of the present disclosure, all other embodiments obtained by those of ordinary skill in the art belong to the scope of protection of the present disclosure. In addition, the relationship terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between the entities or operations.

[0030] With the adjustment of global energy structure, photoelectrocatalytic hydrogen production technology as a clean and efficient energy conversion method has been widely concerned. Compared with water electrolysis hydrogen production, photoelectrocatalytic hydrogen production technology saves the use of electricity. In the process of synthesizing chemicals by using hydrogen produced by photoelectrocatalytic hydrogen production technology, the traditional hydrogen production process and the chemical synthesis process are two independent processes. This separated process will cause the waste of hydrogen energy and increase the production cost.

[0031] If hydrogen can be coupled to synthesize high value-added chemicals in a single reactor, the utilization rate of hydrogen energy can be improved, and the synthesis cost of chemicals can also be reduced. For this purpose, the present specification provides a photoelectrocatalytic reaction device. The photoelectrocatalytic reaction device is an integrated reaction device for coupling photoelectrocatalytic hydrogen production and in-situ hydrogenation of methylenesuccinic acid. Through the photoelectrocatalytic reaction device, the photoelectrocatalytic hydrogen production process can be coupled with the hydrogenation reduction process of methylenesuccinic acid, so as to obtain methylsuccinic acid. The chemical formula of methylsuccinic acid is C5H8O4. Methylsuccinic acid is an important organic chemical raw material, which has a wide application in the fields of medicine, pesticide and plastic. In this way, the waste of hydrogen energy is reduced, the utilization efficiency of hydrogen energy is improved, and the synthesis cost of methylsuccinic acid is reduced.

[0032] Please refer to Figure 1 . The photoelectrocatalytic reaction device can include a reactor 1, a diaphragm 2, a power supply 3, a light source, a photoanode 9 and a photocathode 10.

[0033] In some embodiments, the diaphragm 2 is used to separate the reactor 1 into a photo-cathode chamber 11 and a photo-anode chamber 12. The photo-anode chamber 12 is filled with a first solution. The photo-cathode chamber 11 is filled with a second solution. The first solution can be, for example, a pure water solution. The second solution can be, for example, a methylene succinic acid water solution. Methylene succinic acid is also known as itaconic acid or methylene butane dioic acid, and has a chemical formula of C5H6O4. Methylene succinic acid can be obtained from renewable resources. A catalyst for the hydrogenation reaction of methylene succinic acid is dissolved in the second solution. The catalyst can be, for example, a palladium on carbon catalyst or a nickel catalyst, among others. The catalyst can improve the reaction rate and efficiency of the hydrogenation reaction of methylene succinic acid. The catalyst can be, for example, one of Rh-triphenylphosphine trisodium 3,4,5-trisulfonate, Ru-triphenylphosphine trisodium 3,4,5-trisulfonate, Pd-triphenylphosphine trisodium 3,4,5-trisulfonate. Under the joint action of the light source and the power source 3, hydrogen gas 7 can be generated in the photo-cathode chamber 11 and oxygen gas 6 can be generated in the photo-anode chamber 12. The diaphragm 2 is used to prevent the hydrogen gas 7 generated in the photo-cathode chamber 11 from mixing with the oxygen gas 6 generated in the photo-anode chamber 12, thereby ensuring safety and efficiency. The diaphragm 2 can also allow certain ions to pass, such as hydrogen ions. Thus, the diaphragm 2 can achieve selective permeation. The diaphragm 2 can be, for example, one of a perfluorosulfonic acid membrane, a nafion recast membrane, and a non-fluoropolymer proton exchange membrane.

[0034] In some embodiments, the light source can include a first light source 4. The first light source 4 can be, for example, a xenon lamp light source. The first light source 4 is a light source for providing photo-electro-catalytic hydrogen production. The first light source 4 can irradiate the photo-cathode chamber 11 to generate hydrogen gas 7.

[0035] The photo-cathode chamber 11 of the reactor 1 can be transparent. For example, the photo-cathode chamber 11 of the reactor 1 can be quartz glass. This allows the first light source 4 to irradiate the photo-cathode chamber 11 to generate hydrogen gas 7.

[0036] In some embodiments, a photo-anode 9 can be provided in the photo-anode chamber 12, for example, in the first solution of the photo-anode chamber 12. The photo-anode 9 can be a titanium mesh coated with Pt (platinum) or Ir (iridium). A photo-cathode 10 can be provided in the photo-cathode chamber 11, for example, in the second solution of the photo-cathode chamber 11. The photo-cathode 10 can be one of NiO, Cu2O, CuO, or CuNb2O6. The photo-cathode 10 can be, for example, a noble cathode Pt (platinum) or Ir (iridium) one of the catalysts deposited.

[0037] The power source 3 can have an anode and a cathode. The anode of the power source 3 can be electrically connected to the photo-anode 9. The cathode of the power source 3 can be electrically connected to the photo-cathode 10.

[0038] In some embodiments, under the photoelectrocatalysis of the first light source 4 and the power source 3, hydrogen gas 7 can be generated in the photo-cathode chamber 11, and oxygen gas 6 can be generated in the photo-anode chamber 12. Under the action of the catalyst, the hydrogen gas 7 generated in the photo-cathode chamber 11 can directly react with the methylene succinic acid in the second solution in situ to obtain methyl succinic acid 8. In situ means that the preparation of hydrogen gas 7 and the hydrogenation reaction of methylene succinic acid are both carried out in the photo-cathode chamber 11. In the hydrogenation reaction of methylene succinic acid, hydrogen gas 7 is adsorbed on the surface of the catalyst and activated, and reacts with the carbon-carbon double bond in the methylene succinic acid molecule to generate methyl succinic acid 8. Thus, the waste of hydrogen gas 7 is reduced, the economic benefit of photoelectrocatalytic hydrogen production is improved, and the production cost of methyl succinic acid 8 is reduced.

[0039] The first light source 4 can provide the necessary photon energy for the cathode material. When the energy of the photon is greater than or equal to the band gap of the cathode material, it can excite the electrons to jump from the valence band to the conduction band, forming an electron-hole pair. These excited electrons can then participate in the reduction reaction on the surface of the cathode, reducing the protons (H + ) in the water molecule into hydrogen gas 7 (H2). The remaining holes can then oxidize the water at the anode to produce oxygen gas 6 (O2). The power source 3 is used to apply an external voltage. The external voltage helps to keep the electrons and holes effectively separated and promotes their migration to the respective reaction sites.

[0040] In some embodiments, the power source 3 can be a direct current power source or a silicon-based solar panel. Alternatively, please refer to Figure 2 . The power source 3 can also be a stacked perovskite battery. The stacked perovskite battery refers to a battery formed by connecting two or more perovskite layers with different band gap widths in series. Compared with a direct current power source or a silicon-based solar panel, using a stacked perovskite battery as a power source 3 can effectively reduce the cost of hydrogen production. As an example, the stacked perovskite battery can include two perovskite layers with different band gap widths. The two perovskite layers with different band gap widths can include a narrow-band-gap photoactive layer and a wide-band-gap photoactive layer. For example, the stacked perovskite battery can include a conductive substrate 31, a first hole transport layer 32, a wide-band-gap photoactive layer 33, a first interconnection layer 34, a composite layer 35, a second hole transport layer 36, a narrow-band-gap photoactive layer 37, a second interconnection layer 38, and a back reflector 39 stacked in sequence. The conductive substrate 31 can include an ITO conductive substrate. The first hole transport layer 32 can include at least one of PTAA and VNPB. The wide-band-gap photoactive layer 33 can include FAPbI 0.8 Cs 0.3 PbI 1.8 Br 1.2 and FA 0.8 Cs 0.2 PbI 2.1 Br0.9 The first interconnection layer 34 can include at least one of C 60 , dibromo-o-cresol sulfone. The composite layer 35 can include Ag, MoO x , and ITO. The second hole transport layer 36 can include PEDOT:PSS. The narrow-bandgap photoactive layer 37 can include at least one of F 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3and FA 0.6 MA 0.4 Pb 0.4 Sn 0.6 I3. The second interconnection layer 38 can include at least one of C 60 , and BCP. The back reflective electrode 39 can include at least one of Ag, Cu, and Au. Due to the adoption of the above-mentioned materials and structures, the stacked perovskite cell has a wider spectral response range and higher energy conversion efficiency.

[0041] The bandgap width of the above-mentioned wide-bandgap photoactive layer 33 can be greater than or equal to a first threshold value. The bandgap width of the above-mentioned narrow-bandgap photoactive layer 37 can be less than or equal to a second threshold value.

[0042] In some embodiments, the light source can further include a second light source 5. The second light source 5 can be, for example, a xenon lamp light source. The second light source 5 is used to irradiate the stacked perovskite cell to generate electrical energy.

[0043] In some embodiments, the photoelectrocatalytic reaction device can further include a sensor and a control device. The sensor can be disposed in the second solution of the photocathode chamber 11, and is used to detect the physicochemical parameters of the second solution. The control device can control the light source according to the physicochemical parameters to adjust the rate of the hydrogenation reaction of methylene succinic acid. The control device can include a host computer or the like.

[0044] The sensor includes a first sensor. The first sensor is configured to detect the concentration of methanedisulfonic acid in the second solution. The first sensor can include an optical sensor, an electrochemical sensor, or the like. The optical sensor detects the concentration of methanedisulfonic acid based on the absorption, scattering, or fluorescence of methanedisulfonic acid to light. The electrochemical sensor detects the concentration of methanedisulfonic acid by converting the concentration of methanedisulfonic acid into an electrical quantity based on the electrochemical property of methanedisulfonic acid. The above-mentioned physical and chemical parameters include the concentration of methanedisulfonic acid. The control device can obtain the concentration detected by the first sensor; and can determine the change amount (e.g., the change rate) of the concentration of methanedisulfonic acid in the second solution according to the obtained concentration. The change amount of the concentration of methanedisulfonic acid can reflect the rate of the hydrogenation reaction of methanedisulfonic acid. The sensor further includes a second sensor. The second sensor is configured to detect the concentration of hydrogen 7 in the photoelectrode chamber 11. The second sensor can include an electrochemical sensor, a thermal conductivity sensor, or the like. The control device can obtain the concentration detected by the second sensor.

[0045] The control device can compare the change amount of the concentration of methanedisulfonic acid with the second threshold value and the first threshold value to determine the rate of the hydrogenation reaction of methanedisulfonic acid. The second threshold value can be greater than or equal to the first threshold value.

[0046] When the change amount of the concentration of methanedisulfonic acid is greater than or equal to the first threshold value and less than or equal to the second threshold value, the control device can consider that the rate of the hydrogenation reaction of methanedisulfonic acid is normal, and can control the illumination intensity of the first light source 4 and the second light source 5 to remain unchanged. In this case, the illumination intensity of the second light source 5 remains unchanged, and thus the voltage of the stacked perovskite battery remains unchanged. Under the condition that the illumination intensity of the first light source 4 and the voltage of the stacked perovskite battery remain unchanged, the rate of the generation of hydrogen 7 in the photoelectrode chamber 11 remains unchanged, and thus the rate of the hydrogenation reaction of methanedisulfonic acid also remains unchanged.

[0047] When the change amount of the concentration of methanedisulfonic acid is greater than the second threshold value, the control device can consider that the rate of the hydrogenation reaction of methanedisulfonic acid is too fast, and can control the first light source 4 and the second light source 5 to reduce the illumination intensity to reduce the rate of the generation of hydrogen 7, thereby reducing the rate of the hydrogenation reaction of methanedisulfonic acid. In this case, the illumination intensity of the second light source 5 is reduced, and thus the voltage of the stacked perovskite battery is reduced. Under the condition that the illumination intensity of the first light source 4 and the voltage of the stacked perovskite battery are reduced, the rate of the generation of hydrogen 7 in the photoelectrode chamber 11 is reduced, and thus the rate of the hydrogenation reaction of methanedisulfonic acid is also reduced.

[0048] For example, when the concentration variation of methylenesuccinic acid is greater than the second threshold, the control device can calculate the difference between the concentration variation of methylenesuccinic acid and the second threshold; and can reduce the light intensity of the first light source 4 and the second light source 5 according to the difference. For example, the control device can reduce the current and / or voltage of the first light source 4 and the second light source 5 according to the difference, so as to reduce the light intensity of the first light source 4 and the second light source 5.

[0049] When the concentration variation of methylenesuccinic acid is less than the first threshold, the control device can consider that the rate of the hydrogenation reaction of methylenesuccinic acid is too slow, and can control the first light source 4 and the second light source 5 to increase the light intensity, so as to increase the generation rate of hydrogen 7, thereby increasing the rate of the hydrogenation reaction of methylenesuccinic acid. Wherein, the light intensity of the second light source 5 is increased, so that the voltage of the stacked perovskite battery is increased. Under the condition that the light intensity of the first light source 4 and the voltage of the stacked perovskite battery are both increased, the generation rate of hydrogen 7 in the photo-cathode chamber 11 is increased, thereby increasing the rate of the hydrogenation reaction of methylenesuccinic acid.

[0050] For example, when the concentration variation of methylenesuccinic acid is less than the first threshold, the control device can calculate the difference between the concentration variation of methylenesuccinic acid and the first threshold; and can increase the light intensity of the first light source 4 and the second light source 5 according to the difference. For example, the control device can increase the current and / or voltage of the first light source 4 and the second light source 5 according to the difference, so as to increase the light intensity of the first light source 4 and the second light source 5.

[0051] The control device can also determine whether the concentration of hydrogen 7 is greater than or equal to a third threshold. When the concentration of hydrogen 7 is greater than the third threshold, the control device can consider that the generation rate of hydrogen 7 is too fast, so that the hydrogenation reaction of methylenesuccinic acid cannot be consumed in time, and the concentration of hydrogen 7 in the photo-cathode chamber 11 is too high, which is easy to cause danger. Therefore, the control device can control the first light source 4 and the second light source 5 to reduce the light intensity, so as to reduce the generation rate of hydrogen 7. When the concentration of hydrogen 7 is less than or equal to the third threshold, the control device can ignore the concentration of hydrogen 7 detected by the second sensor, and does not control the first light source 4 and the second light source 5.

[0052] In some embodiments, the control device can also determine whether the physical parameter satisfies a set condition; if yes, the light source is controlled to be turned off. Specifically, the control device can determine whether the concentration of methylenesuccinic acid is less than or equal to a fourth threshold; if yes, it can be considered that the methylenesuccinic acid in the second solution is consumed, so that the first light source 4 and the second light source 5 can be controlled to be turned off. Wherein, the second light source 5 is turned off, so that the stacked perovskite battery no longer provides electric energy. In this way, the photoelectrocatalytic hydrogen production and the in-situ hydrogenation reaction of methylenesuccinic acid can be ended, thereby ending the synthesis process of methylsuccinic acid 8.

[0053] Please refer toFigure 3 The embodiments of the present specification also provide a preparation method of a stacked perovskite battery, comprising the following steps.

[0054] Step 41: performing cleaning treatment on the conductive substrate.

[0055] In some embodiments, the conductive substrate can include an ITO (indium tin oxide) conductive substrate.

[0056] In some embodiments, the conductive substrate can be sequentially cleaned with a detergent, ultrapure water, acetone and isopropyl alcohol under ultrasonic conditions, and placed in an ultraviolet ozone chamber for a set period of time. The set period of time can be, for example, 10-30 minutes.

[0057] Step 42: spin-coating PTAA or VNPB as a first hole transport layer on the cleaned conductive substrate.

[0058] In some embodiments, PTAA, which can also be referred to as poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], is a high polymer material with excellent electrical conductivity and high transparency. VNPB, which can also be referred to as N4,N4'-di(naphthalen-1-yl)-N4,N4'-bis(4-vinylphenyl)biphenyl-4,4'-diamine, is a high polymer material with excellent electrical conductivity and high transparency.

[0059] In some embodiments, a chlorobenzene solution of PTAA or a chlorobenzene solution of VNPB can be spin-coated on the cleaned conductive substrate at a set rotation speed, and the spin-coating time can be a set time. For example, the set rotation speed can be 2000-5000 r.p.m. The spin-coating time can be 20-40 s. The spin-coated conductive substrate can then be annealed at 120-150 °C for 5-10 min.

[0060] Step 43: spin-coating FA 0.8 Cs 0.3 PbI 1.8 Br 1.2 or FA 0.8 Cs 0.2 PbI 2.1 Br 0.9 as a wide-bandgap photoactive layer.

[0061] In some embodiments, a wide-bandgap perovskite precursor FA 0.8 Cs 0.3 PbI 1.8 Br 1.2 or FA 0.8 Cs 0.2 PbI 2.1 Br 0.9A solution of PEDOT:PSS is spin-coated on the conductive substrate coated with PTAA or VNPB at a set rotation speed, and the spin-coating time can be set. For example, the set rotation speed can be 3000-5000 r.p.m. The spin-coating time can be 30-60 s. After spin-coating, annealing can be performed at 50-70 °C for 2-5 min, and then at 100-120 °C for 5-10 min.

[0062] Step 44: Depositing a first interlayer on the wide-bandgap photoactive layer.

[0063] In some embodiments, C 60 and dibromo-o-cresol sulfone (BCP) can be sequentially deposited on the wide-bandgap photoactive layer as the first interlayer. The deposition thickness of C 60 may be 15-20 nm. The deposition thickness of dibromo-o-cresol sulfone can be 3-5 nm.

[0064] Step 45: Depositing and sputtering a composite layer on the first interlayer.

[0065] In some embodiments, a metal electrode and MoO x can be deposited on the first interlayer, and ITO is sputtered as the composite layer. The deposition thickness of the metal electrode can be 1-2 nm. The metal electrode can be one of Ag (silver), Cu (copper), and Au (gold). The deposition thickness of MoOx can be 3-5 nm. The sputtering thickness of ITO is 100-120 nm.

[0066] Step 46: Spin-coating PEDOT:PSS as a second hole transport layer on the composite layer.

[0067] In some embodiments, PEDOT:PSS, also known as poly[3,4-ethylenedioxythiophene]:polystyrene sulfonic acid or PEDOT / PSS, is a high-performance conductive polymer material.

[0068] In some embodiments, a PEDOT:PSS solution can be spin-coated on the composite layer at a set rotation speed for a set time. For example, the set rotation speed can be 3000-4000 r.p.m., and the set time can be 30-50 s. Then, annealing is performed at 100-110 °C for 5-8 min.

[0069] Step 47: Spin-coating F 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 or FA 0.6 MA 0.4 Pb 0.4 Sn 0.6 I3 as a narrow-bandgap photoactive layer.

[0070] In some embodiments, a narrow-bandgap perovskite precursor FA 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3or

[0071] FA 0.6 MA 0.4 Pb 0.4 Sn 0.6 I3is spin-coated on the second hole transport layer at a set rotation speed, and the spin-coating time can be a set time. For example, the set rotation speed can be 3000-5000 r.p.m. The spin-coating time can be 30-60 s. After spin-coating, annealing can be performed at 100-120 °C for 5-10 min.

[0072] Step 48: evaporating a second interlayer on the narrow-bandgap photoactive layer.

[0073] In some embodiments, C 60 and BCP can be thermally evaporated on the narrow-bandgap photoactive layer as the second interlayer. The thickness of C 60 may be 15-25 nm. The thickness of BCP can be 3-5 nm.

[0074] Step 49: evaporating a back reflective electrode on the second interlayer to obtain a stacked perovskite cell.

[0075] In some embodiments, one of Ag, Cu and Au can be thermally evaporated on the second interlayer to obtain a metal back reflective electrode. The thickness of the metal back reflective electrode can be 70-80 nm.

[0076] The technical solutions of the embodiments of the present specification can clean the conductive substrate; spin-coat PTAA or VNPB on the cleaned conductive substrate as the first hole transport layer; spin-coat FA 0.8 Cs 0.3 PbI 1.8 Br 1.2 or FA 0.8 Cs 0.2 PbI 2.1 Br 0.9 as the wide-bandgap photoactive layer; deposit a first interlayer on the wide-bandgap photoactive layer; deposit and sputter a composite layer on the first interlayer; spin-coat PEDOT:PSS on the composite layer as the second hole transport layer; spin-coat FA 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3or FA 0.6 MA 0.4 Pb 0.4 Sn0.6 I3 as a narrow-bandgap photoactive layer; a second interconnection layer can be evaporated on the narrow-bandgap photoactive layer; a back reflective electrode can be evaporated on the second interconnection layer to obtain a tandem perovskite cell. Thus, a tandem perovskite cell can be obtained by the embodiments of the present specification. By using the tandem perovskite cell as an external power source, higher photoelectric conversion efficiency can be obtained, and the cost of green hydrogen can be reduced. In addition, due to the use of the above-mentioned materials and structures, the tandem perovskite cell has a wider spectral response range and higher energy conversion efficiency.

[0077] A scenario example of the embodiments of the present specification is introduced below.

[0078] In the scenario example, the conductive substrate can be subjected to cleaning treatment; PTAA or VNPB can be spin-coated on the cleaned conductive substrate as a first hole transport layer; FA 0.8 Cs 0.3 PbI 1.8 Br 1.2 or FA 0.8 Cs 0.2 PbI 2.1 Br 0.9 as a wide-bandgap photoactive layer; a first interconnection layer can be deposited on the wide-bandgap photoactive layer; a composite layer can be deposited and sputtered on the first interconnection layer; PEDOT:PSS can be spin-coated on the composite layer as a second hole transport layer; FA 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 or FA 0.6 MA 0.4 Pb 0.4 Sn 0.6 I3 as a narrow-bandgap photoactive layer; a second interconnection layer can be evaporated on the narrow-bandgap photoactive layer; a back reflective electrode can be evaporated on the second interconnection layer to obtain a tandem perovskite cell. Thus, a tandem perovskite cell can be obtained.

[0079] In the scenario example, the reactor can be divided into a light cathode chamber and a light anode chamber by a diaphragm. A first solution can be injected into the light anode chamber, and the first solution is a pure water solution. A second solution can be injected into the light cathode chamber, and the second solution is a methylene succinic acid aqueous solution, and the second solution contains a catalyst for the hydrogenation reaction of methylene succinic acid. The anode of the tandem perovskite cell can be arranged in the light anode chamber, and the cathode of the tandem perovskite cell can be arranged in the light cathode chamber. A first light source can be used to irradiate the reactor, and a second light source can be used to irradiate the tandem perovskite cell, so that the second solution produces hydrogen gas under photoelectrocatalysis, and the hydrogen gas reacts in situ with the methylene succinic acid in the second solution to generate methyl succinic acid.

[0080] Referring to Figure 4 The embodiment of the present specification also provides a preparation device of a laminated perovskite battery, comprising the following units.

[0081] The conductive substrate cleaning unit 51 is configured to clean the conductive substrate;

[0082] The first hole transport layer spin coating unit 52 is configured to spin coat PTAA or VNPB as a first hole transport layer on the cleaned conductive substrate;

[0083] The wide-bandgap photoactive layer spin coating unit 53 is configured to spin coat FAPbI3 as a wide-bandgap photoactive layer on the first hole transport layer; 0.8 Cs 0.3 PbI 1.8 Br 1.2 or FAPbI3 0.8 Cs 0.2 PbI 2.1 Br 0.9 as a wide-bandgap photoactive layer;

[0084] The first interlayer deposition unit 54 is configured to deposit a first interlayer on the wide-bandgap photoactive layer;

[0085] The composite layer sputtering unit 55 is configured to deposit and sputter a composite layer on the first interlayer;

[0086] The second hole transport layer spin coating unit 56 is configured to spin coat PEDOT:PSS as a second hole transport layer on the composite layer;

[0087] The narrow-bandgap photoactive layer spin coating unit 57 is configured to spin coat FAPbI3 as a narrow-bandgap photoactive layer on the second hole transport layer; 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 or FAPbI3 0.6 MA 0.4 Pb 0.4 Sn 0.6 I3 as a narrow-bandgap photoactive layer;

[0088] The second interlayer evaporation unit 58 is configured to evaporate a second interlayer on the narrow-bandgap photoactive layer;

[0089] The back reflector evaporation unit 59 is configured to evaporate a back reflector on the second interlayer to obtain a laminated perovskite battery.

[0090] The embodiment of the present specification also provides a computer device, comprising a memory, a processor, and a computer program stored in the memory and capable of running on the processor, and the processor implements the above preparation method of a laminated perovskite battery when executing the computer program.

[0091] The embodiment of the present specification also provides a computer readable storage medium, which stores a computer program, and the computer program is executed by a processor to implement the above-mentioned preparation method of a stacked perovskite battery.

[0092] The embodiment of the present specification also provides a computer program product, which comprises a computer program, and the computer program is executed by a processor to implement the above-mentioned preparation method of a stacked perovskite battery.

[0093] Those skilled in the art can understand that the present specification can be provided as a method, a system, or a computer program product. Therefore, the present specification can take the form of an entirely hardware embodiment, an entirely software embodiment, or an embodiment combining software and hardware. Moreover, the present specification can take the form of a computer program product implemented on one or more computer-usable storage media (including, but not limited to, disk storage, CD-ROMs, optical storage, etc.) containing computer-usable program code.

[0094] The present specification is described with reference to flowcharts and / or block diagrams of the methods, devices (systems), and computer program products of the embodiments of the present specification. It should be understood that each flow and / or block in the flowcharts and / or block diagrams, and the combination of the flows and / or blocks in the flowcharts and / or block diagrams can be implemented by computer program instructions. The computer can be a personal computer, a laptop computer, a cellular phone, a camera phone, a smart phone, a personal digital assistant, a media player, a navigation device, an email device, a game console, a tablet computer, a wearable device, or a combination of any of these devices.

[0095] Each functional unit in the embodiments of the present specification can be integrated in one processing unit, or each functional unit can exist physically, or two or more functional units can be integrated in one processing unit.

[0096] Those skilled in the art can understand that the description of each embodiment of the present specification is focused on, and the part not described in detail in an embodiment can refer to the related description of other embodiments. In addition, it can be understood that, after reading the present specification document, those skilled in the art can think of combining some or all of the embodiments listed in the present specification without creative labor, and these combinations are also within the scope of the present specification.

[0097] Although the present specification is described through embodiments, those skilled in the art know that the above embodiments are only used to help understand the core idea of the present specification. Those skilled in the art can understand that there are many variations and changes of the present specification. It is hoped that the appended claims include these variations and changes without departing from the spirit of the present specification.

Claims

1. A photoelectrocatalytic reaction device, characterized in that: include: a reactor, a diaphragm for separating the reactor into a photocathode chamber and a photoanode chamber, a light source, and a power supply; The photoanode chamber is filled with a first solution, which is an aqueous solution; the photocathode chamber is filled with a second solution, which is an aqueous solution of methylene succinic acid, and the second solution contains a catalyst for the hydrogenation reaction of methylene succinic acid; a photoanode, connected to the anode of the power supply and disposed in the photoanode chamber; a photocathode connected to the cathode of the power supply and disposed in the photocathode chamber; The light source and the power supply are used for photoelectrocatalysis to generate hydrogen in the photocathode chamber; The hydrogen is used to react in situ with the methylenesuccinic acid in the second solution to generate methylsuccinic acid; The power source includes a perovskite battery; the light source includes a first light source and a second light source, the first light source is used to irradiate the photocathode chamber to generate hydrogen; the second light source is used to irradiate the perovskite battery to generate electrical energy; The apparatus further comprises a first sensor and a control device; The first sensor is provided in the second solution and is used to detect the concentration of methylenesuccinic acid in the second solution; The control device is used to control the light intensity of the first light source and the second light source to remain unchanged when the concentration change of methylene succinic acid is greater than or equal to the first threshold and less than or equal to the second threshold; when the concentration change of methylene succinic acid is greater than the second threshold, control the first light source and the second light source to reduce the light intensity; when the concentration change of methylene succinic acid is less than the first threshold, control the first light source and the second light source to increase the light intensity.

2. The device according to claim 1, characterized in that The perovskite cell is a stacked perovskite cell; The stacked perovskite cell includes a conductive substrate, a first hole transport layer, a wide bandgap photoactive layer, a first interconnect layer, a composite layer, a second hole transport layer, a narrow bandgap photoactive layer, a second interconnect layer and a back reflection electrode stacked in sequence.

3. The device according to claim 2, characterized in that The first hole transport layer includes at least one of PTAA and VNPB, and the wide bandgap photoactive layer includes FA 0.8 Cs 0.3 PbI 1.8 Br 1.2 and FA 0.8 Cs 0.2 PbI 2.1 Br 0.9 At least one of the second hole transport layer comprises PEDOT:PSS, and the narrow bandgap photoactive layer comprises FA 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 and FA 0.6 MA 0.4 Pb 0.4 Sn 0.6 At least one of I3.

4. A method for preparing a stacked perovskite battery, characterized in that: The stacked perovskite cell is applied to the photoelectrocatalytic reaction device according to any one of claims 1 to 3, and the method comprises: Cleaning the conductive substrate; Spin-coating PTAA or VNPB on the cleaned conductive substrate as a first hole transport layer; Spin-coat FA on the first hole transport layer 0.8 Cs 0.3 PbI 1.8 Br 1.2 or FA 0.8 Cs 0.2 PbI 2.1 Br 0.9 as a wide-bandgap photoactive layer; depositing a first interconnect layer on the wide bandgap photoactive layer; depositing and sputtering a composite layer on the first interconnect layer; PEDOT:PSS was spin-coated on the composite layer as a second hole transport layer; Spin-coat FA on the second hole transport layer 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 or FA 0.6 MA 0.4 Pb 0.4 Sn 0.6 I3 serves as a narrow-bandgap photoactive layer; evaporating a second interconnect layer on the narrow bandgap photoactive layer; A back reflection electrode is evaporated on the second interconnect layer to obtain a stacked perovskite cell.

5. The method according to claim 4, characterized in that described Depositing a first interconnect layer on the wide bandgap photoactive layer comprises: C is deposited sequentially on the wide bandgap photoactive layer. 60 and dibromo-o-cresolsulfonate as the first interconnecting layer; The step of depositing and sputtering a composite layer on the first interconnect layer includes: Depositing Ag and MoOx on the first interconnect layer and sputtering ITO as a composite layer; The step of evaporating a second interconnect layer on the narrow bandgap photoactive layer comprises: Thermal evaporation of C on the narrow bandgap photoactive layer 60 and BCP as the second interconnection layer.

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