Photoelectrocatalytic reaction device and laminated perovskite cell preparation method

Abstract

The invention relates to the technical field of chemistry, in particular to a photoelectric catalytic reaction device and a laminated perovskite cell preparation method. The photoelectrocatalysis reaction device comprises a reactor, a diaphragm for dividing the reactor into a photocathode chamber and a photoanode chamber, a light source and a power supply, the photo-anode chamber is filled with a first solution, and the first solution is an aqueous solution; the photocathode chamber is filled with a second solution, the second solution is a methylene succinic acid aqueous solution, and a catalyst for a methylene succinic acid hydrogenation reaction is dissolved in the second solution; the photo-anode is connected with the anode of the power supply and is arranged in the photo-anode chamber; the photocathode is connected with the cathode of the power supply and is arranged 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 for carrying out in-situ reaction with methylene succinic acid in the second solution to generate methyl succinic acid. The embodiment of the invention can improve the utilization rate of hydrogen energy and reduce the production cost.

Description

Technical Field

[0001] The present invention relates to the field of chemical technology, and in particular to a photoelectric catalytic reaction device and a method for preparing a laminated perovskite cell. Background Art

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

[0003] This separation process will result in a waste of hydrogen energy and increase production costs. Summary of the invention

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

[0005] The embodiment of this specification provides a photoelectrocatalytic reaction device, comprising:

[0006] 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, the first solution is an aqueous solution; the photocathode chamber is filled with a second solution, the second solution is an aqueous solution of methylenesuccinic acid, and the second solution contains a catalyst for the hydrogenation reaction of methylenesuccinic acid;

[0007] A photoanode, connected to the anode of the power source and disposed in the photoanode chamber;

[0008] A photocathode, connected to the cathode of the power supply and disposed in the photocathode chamber;

[0009] 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 methylenesuccinic acid in the second solution to generate methylsuccinic acid.

[0010] The present specification also provides a method for preparing a laminated perovskite battery, comprising:

[0011] Cleaning the conductive substrate;

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

[0013] Spin coat 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] Spin-coat PEDOT:PSS on the composite layer as the second hole transport layer;

[0017] Spin coating 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] vapor depositing 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 laminated perovskite battery when executing the computer program.

[0021] The embodiments of this specification also provide a computer-readable storage medium, wherein the computer-readable storage medium stores a computer program, and when the computer program is executed by a processor, the above-mentioned method for preparing a laminated perovskite battery is implemented.

[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, the above-mentioned method for preparing a stacked perovskite battery is implemented.

[0023] The photoelectrocatalytic reaction device of the embodiment of this specification comprises a reactor, a diaphragm for separating the reactor into a photocathode chamber and a photoanode chamber, a light source and a power supply. The anode of the power supply is arranged in the photoanode chamber, and the photoanode chamber is filled with a first solution. The cathode of the power supply is arranged in the photocathode chamber, and the photocathode chamber is filled with a second solution. Thus, photoelectrocatalytic hydrogen production can be achieved to produce hydrogen in the photocathode chamber. In addition, the second solution is an aqueous solution of methylenesuccinic acid, and a catalyst for the hydrogenation reaction of methylenesuccinic acid is dissolved in the second solution. The hydrogen produced in the photocathode chamber can directly react with the methylenesuccinic acid in the second solution in situ to obtain methylsuccinic acid. Thus, the photoelectrocatalytic hydrogen production process is coupled with the hydrogenation reduction process of methylenesuccinic acid, thereby obtaining methylsuccinic acid, a high value-added chemical. This improves the utilization rate of hydrogen energy and reduces the production cost of methylsuccinic acid. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of this specification or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. The drawings described below are only some embodiments recorded in this specification. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0025] Figure 1 This is a functional structure diagram of the photoelectrocatalytic reaction device in the embodiments of this specification;

[0026] Figure 2 This is a schematic diagram of the functional structure of a stacked perovskite battery in an embodiment of this specification;

[0027] Figure 3 It is a schematic diagram of the process of preparing a laminated perovskite battery in an embodiment of this specification;

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

[0029] The technical solutions in the embodiments of this specification will be clearly and completely described below in conjunction with the drawings in the embodiments of this specification. Obviously, the described embodiments are only part of the embodiments of this specification, rather than all of the embodiments. The specific embodiments described herein are only used to explain the present disclosure, rather than to 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 are within the scope of protection of the present disclosure. In addition, relational 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 these entities or operations.

[0030] With the adjustment of the global energy structure, photoelectrocatalytic hydrogen production technology has received widespread attention as a clean and efficient way of energy conversion. Compared with hydrogen production by water electrolysis, photoelectrocatalytic hydrogen production technology saves the use of electrical energy. In the process of synthesizing chemicals using hydrogen produced by photoelectrocatalytic hydrogen production technology, the hydrogen production process and the chemical synthesis process are traditionally two independent processes. This separation process will lead to the waste of hydrogen energy and increase the cost of production.

[0031] If it is possible to couple hydrogen in a single reactor to synthesize high value-added chemicals, the utilization rate of hydrogen energy can be improved, and the synthesis cost of chemicals can also be reduced. To this end, an embodiment of this specification provides a photoelectrocatalytic reaction device. The photoelectrocatalytic reaction device is an integrated reaction device for photoelectrocatalytic hydrogen production coupled with in-situ hydrogenation of methylenesuccinic acid. The photoelectrocatalytic reaction device can be used to couple the photoelectrocatalytic hydrogen production process with the hydrogenation reduction process of methylenesuccinic acid to obtain methylsuccinic acid. The chemical formula of methylsuccinic acid is C5H8O4. Methylsuccinic acid, as an important organic chemical raw material, is widely used in the fields of medicine, pesticides, plastics, etc. This reduces the waste of hydrogen energy, improves the utilization efficiency of hydrogen energy, and thus reduces the synthesis cost of methylsuccinic acid.

[0032] See also Figure 1 The photoelectrocatalytic reaction device may include a reactor 1 , a diaphragm 2 , a power source 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 photocathode chamber 11 and a photoanode chamber 12. The photoanode chamber 12 is filled with a first solution. The photocathode chamber 11 is filled with a second solution. The first solution can be, for example, a pure aqueous solution. The second solution can be, for example, an aqueous solution of methylene succinic acid. Methylene succinic acid is also known as itaconic acid or methylene succinic 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 carbon catalyst or a nickel catalyst, etc. 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 trisulphonic acid sodium salt, Ru-triphenylphosphine trisulphonic acid sodium salt, and Pd-triphenylphosphine trisulphonic acid sodium salt. Under the combined action of the light source and the power supply 3, hydrogen 7 can be generated in the photocathode chamber 11, and oxygen 6 can be generated in the photoanode chamber 12. The diaphragm 2 is used to prevent the hydrogen 7 generated in the photocathode chamber 11 and the oxygen 6 generated in the photoanode chamber 12 from mixing, thereby ensuring safety and efficiency. The diaphragm 2 can also allow specific 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-fluorinated polymer proton exchange membrane.

[0034] In some embodiments, the light source may include a first light source 4. The first light source 4 may be, for example, a xenon light source. The first light source 4 is a light source for providing photoelectrocatalytic hydrogen production. The first light source 4 may irradiate the photocathode chamber 11 to generate hydrogen 7.

[0035] The photocathode chamber 11 of the reactor 1 may be transparent. For example, the photocathode chamber 11 of the reactor 1 may be made of quartz glass, so that the first light source 4 can irradiate the photocathode chamber 11 to generate hydrogen 7 .

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

[0037] The power source 3 may have an anode and a cathode. The anode of the power source 3 may be electrically connected to the photoanode 9. The cathode of the power source 3 may be electrically connected to the photocathode 10.

[0038] In some embodiments, under the photoelectrocatalysis of the first light source 4 and the power source 3, hydrogen 7 can be generated in the photocathode chamber 11, and oxygen 6 can be generated in the photoanode chamber 12. Under the action of the catalyst, the hydrogen 7 generated in the photocathode chamber 11 can directly react with the methylenesuccinic acid in the second solution in situ to produce methylsuccinic acid 8. In situ means that the preparation of hydrogen 7 and the hydrogenation reaction of methylenesuccinic acid are both carried out in the photocathode chamber 11. In the hydrogenation reaction of methylenesuccinic acid, hydrogen 7 is adsorbed on the catalyst surface and activated, and reacts with the carbon-carbon double bond in the methylenesuccinic acid molecule to produce methylsuccinic acid 8. This reduces the waste of hydrogen 7, improves the economic benefits of photoelectrocatalytic hydrogen production, and reduces the production cost of methylsuccinic acid 8.

[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 electrons to jump from the valence band to the conduction band, forming electron-hole pairs. These excited electrons can then participate in the reduction reaction on the cathode surface, converting protons (H + ) is reduced to hydrogen 7 (H2). The remaining holes can react with water at the anode to produce oxygen 6 (O2). The power supply 3 is used to apply an external voltage. The external voltage helps to maintain the effective separation of electrons and holes and promotes their migration to their respective reaction sites.

[0040] In some embodiments, the power source 3 may be a DC power source or a silicon-based solar panel. Figure 2 . The power source 3 can also be a laminated perovskite battery. A laminated perovskite battery refers to a battery formed by connecting two or more perovskite layers with different band gap widths in series. Compared with a DC power supply or a silicon-based battery panel, the use of a laminated perovskite battery as a power source 3 can effectively reduce the cost of hydrogen production. As an example, the laminated perovskite battery may include two perovskite layers with different band gap widths. The two perovskite layers with different band gap widths may include a narrow band gap photoactive layer and a wide band gap photoactive layer. For example, the laminated perovskite battery may include a conductive substrate 31, a first hole transport layer 32, a wide band gap photoactive layer 33, a first interconnect layer 34, a composite layer 35, a second hole transport layer 36, a narrow band gap photoactive layer 37, a second interconnect layer 38 and a back reflection electrode 39 stacked in sequence. Among them, the conductive substrate 31 may include an ITO conductive substrate. The first hole transport layer 32 may include at least one of PTAA and VNPB. The wide band gap photoactive layer 33 may include FA 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 interconnect layer 34 may include C 60 The composite layer 35 may include Ag, MoO x and ITO. The second hole transport layer 36 may include PEDOT:PSS. The narrow bandgap photoactive layer 37 may include 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 I3. The second interconnect layer 38 may include C 60 and BCP. The back reflection electrode 39 may include at least one of Ag, Cu and Au. Due to the use of the above materials and structures, the stacked perovskite cell has a wider spectral response range and higher energy conversion efficiency.

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

[0042] In some embodiments, the light source may further include a second light source 5. The second light source 5 may be, for example, a xenon light source. The second light source 5 is used to irradiate the tandem perovskite cell so that the tandem perovskite cell generates electrical energy.

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

[0044] The sensor includes a first sensor. The first sensor is used to detect the concentration of methylene succinic acid in the second solution. The first sensor may include an optical sensor, an electrochemical sensor, etc. The optical sensor detects the concentration of methylene succinic acid based on the absorption, scattering or fluorescence characteristics of light by methylene succinic acid. The electrochemical sensor converts the concentration of methylene succinic acid into an electrical quantity for detection based on the electrochemical properties of methylene succinic acid. The above-mentioned physicochemical parameters include the concentration of methylene succinic acid. The control device can obtain the concentration detected by the first sensor; the concentration change (e.g., concentration change rate) of methylene succinic acid in the second solution can be determined based on the obtained concentration. The concentration change of methylene succinic acid can reflect the rate of the hydrogenation reaction of methylene succinic acid. The sensor also includes a second sensor. The second sensor is used to detect the concentration of hydrogen 7 in the photocathode chamber 11. The second sensor may include an electrochemical sensor, a thermal conductivity sensor, etc. The control device can obtain the concentration detected by the second sensor.

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

[0046] When the concentration change of methylene succinic acid is greater than or equal to the first threshold value and less than or equal to the second threshold value, the control device may consider that the rate of the methylene succinic acid hydrogenation reaction is normal, and the illumination intensity of the first light source 4 and the second light source 5 may be controlled to remain unchanged. Wherein, if the illumination intensity of the second light source 5 remains unchanged, the voltage of the laminated perovskite battery may remain unchanged. Under the condition that the illumination intensity of the first light source 4 and the voltage of the laminated perovskite battery remain unchanged, the rate of hydrogen 7 generation in the photocathode chamber 11 may remain unchanged, so that the rate of the methylene succinic acid hydrogenation reaction also remains unchanged.

[0047] When the concentration change of methylene succinic acid is greater than the second threshold value, the control device may consider that the rate of the hydrogenation reaction of methylene succinic acid is too fast, and the first light source 4 and the second light source 5 may be controlled to reduce the light intensity to reduce the rate of generation of hydrogen 7, thereby reducing the rate of the hydrogenation reaction of methylene succinic acid. Among them, the light intensity of the second light source 5 is reduced, so that the voltage of the laminated perovskite battery is reduced. Under the condition that the light intensity of the first light source 4 and the voltage of the laminated perovskite battery are both reduced, the rate of generation of hydrogen 7 in the photocathode chamber 11 is reduced, so that the rate of the hydrogenation reaction of methylene succinic acid is also reduced.

[0048] For example, when the concentration change of methylene succinic acid is greater than the second threshold, the control device may calculate the difference between the concentration change of methylene succinic acid and the second threshold, and according to the difference, the illumination intensity of the first light source 4 and the second light source 5 may be reduced. For example, the control device may reduce the current and / or voltage of the first light source 4 and the second light source 5 according to the difference, thereby reducing the illumination intensity of the first light source 4 and the second light source 5.

[0049] When the concentration change of methylene succinic acid is less than the first threshold value, the control device may consider that the rate of the hydrogenation reaction of methylene succinic acid is too slow, and may control the first light source 4 and the second light source 5 to increase the illumination intensity to increase the generation rate of hydrogen 7, thereby increasing the rate of the hydrogenation reaction of methylene succinic acid. Among them, the illumination intensity of the second light source 5 increases, so that the voltage of the laminated perovskite battery increases. Under the condition that the illumination intensity of the first light source 4 and the voltage of the laminated perovskite battery are both increased, the rate of hydrogen 7 generation in the photocathode chamber 11 increases, thereby increasing the rate of the hydrogenation reaction of methylene succinic acid.

[0050] For example, when the concentration change of methylene succinic acid is less than the first threshold, the control device may calculate the difference between the concentration change of methylene succinic acid and the first threshold, and according to the difference, the illumination intensity of the first light source 4 and the second light source 5 may be increased. For example, the control device may increase the current and / or voltage of the first light source 4 and the second light source 5 according to the difference, thereby increasing the illumination 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 value. When the concentration of hydrogen 7 is greater than the third threshold value, the control device may consider that the generation rate of hydrogen 7 is too fast, so that the hydrogenation reaction of methylene succinic acid cannot be consumed in time, and the concentration of hydrogen 7 in the photocathode chamber 11 is too high, which is prone to danger. To this end, the control device can control the first light source 4 and the second light source 5 to reduce the light intensity to reduce the generation rate of hydrogen 7. When the concentration of hydrogen 7 is less than or equal to the third threshold value, the control device can ignore the concentration of hydrogen 7 detected by the second sensor and 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 physicochemical parameters meet the set conditions; if so, control the light source to turn off. Specifically, the control device can determine whether the concentration of methylenesuccinic acid is less than or equal to the fourth threshold; if so, it can be considered that the methylenesuccinic acid in the second solution has been consumed, so that the first light source 4 and the second light source 5 can be controlled to turn off. Among them, turning off the second light source 5 makes the stacked perovskite battery no longer provide electrical energy. In this way, the photoelectrocatalytic hydrogen production and the in-situ hydrogenation reaction of methylenesuccinic acid can be terminated, thereby terminating the synthesis process of methylsuccinic acid 8.

[0053] See also Figure 3 The embodiment of this specification also provides a method for preparing a stacked perovskite battery, comprising the following steps.

[0054] Step 41: Clean the conductive substrate.

[0055] In some embodiments, the conductive substrate may include an ITO (Indium Tin Oxide) conductive substrate.

[0056] In some embodiments, the conductive substrate may be cleaned in sequence with detergent, ultrapure water, acetone and isopropanol under ultrasonic conditions, and placed in an ultraviolet ozone chamber for a set time, which may be, for example, 10 minutes to 30 minutes.

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

[0058] In some embodiments, PTAA, also known as poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], is a polymer material having excellent conductive properties and high transparency. VNPB, also known as N4,N4'-di(naphthalene-1-yl)-N4,N4'-bis(4-vinylphenyl)biphenyl-4,4'-diamine, is a polymer material having excellent conductive properties and high transparency.

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

[0060] Step 43: Spin coating 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.

[0061] In some embodiments, the 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 0.9The solution is spin-coated on a conductive substrate coated with PTAA or VNPB at a set speed, and the spin-coating time can be a set time. For example, the set speed can be 3000-5000 rpm. The spin-coating time can be 30-60 seconds. After spin coating, annealing can be performed at 50-70° C. for 2-5 minutes, and then annealing at 100-120° C. for 5-10 minutes.

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

[0063] In some embodiments, C 60 and dibromocresolsulfonate (BCP) as the first interconnect layer. 60 The deposition thickness of dibromo-o-cresol sulfonate can be 15 to 20 nm. The deposition thickness of dibromo-o-cresol sulfonate can be 3 to 5 nm.

[0064] Step 45: Deposit and sputter a composite layer on the first interconnect layer.

[0065] In some embodiments, metal electrodes and MoO can be deposited on the first interconnect layer. x And sputter ITO as a 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-coat PEDOT:PSS on the composite layer as a second hole transport layer.

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

[0068] In some embodiments, the PEDOT:PSS solution can be spin-coated on the composite layer at a set speed for a set time. For example, the set speed can be 3000-4000 rpm, and the set time can be 30-50 seconds. Then, the composite layer is annealed at 100-110° C. for 5-8 minutes.

[0069] Step 47: Spin coating 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.

[0070] In some embodiments, the narrow bandgap perovskite precursor FA 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 or

[0071] FA 0.6 MA 0.4 Pb 0.4 Sn 0.6 The I3 solution is spin-coated on the second hole transport layer at a set speed, and the spin-coating time can be a set time. For example, the set speed can be 3000-5000 rpm. The spin-coating time can be 30-60 seconds. After spin-coating, annealing can be performed at 100-120° C. for 5-10 minutes.

[0072] Step 48: Evaporate a second interconnect layer on the narrow bandgap photoactive layer.

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

[0074] Step 49: Evaporate a back reflection electrode on the second interconnect layer to obtain a stacked perovskite cell.

[0075] In some embodiments, one of Ag, Cu and Au may be thermally evaporated onto the second interconnect layer to obtain a metal back reflection electrode. The thickness of the metal back reflection electrode may be 70-80 nm.

[0076] The technical solution of the embodiment of this specification can clean the conductive substrate; PTAA or VNPB can be spin-coated on the cleaned conductive substrate as the first hole transport layer; FA can be spin-coated 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; a first interconnect layer can be deposited on the wide bandgap photoactive layer; a composite layer can be deposited and sputtered on the first interconnect layer; PEDOT:PSS can be spin-coated on the composite layer as a second hole transport layer; FA can be spin-coated 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 Sn0.6 I3 is used as a narrow bandgap photoactive layer; a second interconnection layer can be evaporated on the narrow bandgap photoactive layer; a back reflection electrode can be evaporated on the second interconnection layer to obtain a stacked perovskite cell. Thus, a stacked perovskite cell can be obtained through the embodiments of this specification. Using a stacked perovskite cell as an external power source can achieve a higher photoelectric conversion efficiency and reduce the cost of green hydrogen. In addition, due to the use of the above materials and structures, the stacked perovskite cell has a wider spectral response range and higher energy conversion efficiency.

[0077] The following introduces a scenario example of an embodiment of this specification.

[0078] In this scenario example, the conductive substrate can be cleaned; PTAA or VNPB can be spin-coated on the cleaned conductive substrate as the first hole transport layer; FA can be spin-coated 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; a first interconnect layer can be deposited on the wide bandgap photoactive layer; a composite layer can be deposited and sputtered on the first interconnect layer; PEDOT:PSS can be spin-coated on the composite layer as a second hole transport layer; FA can be spin-coated 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 is used as a narrow bandgap photoactive layer; a second interconnect layer can be evaporated on the narrow bandgap photoactive layer; a back reflection electrode can be evaporated on the second interconnect layer to obtain a stacked perovskite cell. Thus, a stacked perovskite cell can be obtained.

[0079] In this scenario example, the reactor can be separated into a photocathode chamber and a photoanode chamber by a diaphragm. A first solution can be injected into the photoanode chamber, and the first solution is a pure aqueous solution. A second solution can be injected into the photocathode chamber, and the second solution is an aqueous solution of methylenesuccinic acid, and a catalyst for the hydrogenation reaction of methylenesuccinic acid is dissolved in the second solution. The anode of the stacked perovskite battery can be arranged in the photoanode chamber, and the cathode of the stacked perovskite battery can be arranged in the photocathode chamber. The reactor can be irradiated with a first light source, and the stacked perovskite battery can be irradiated with a second light source, so that the second solution produces hydrogen under photoelectrocatalysis, and the hydrogen reacts in situ with the methylenesuccinic acid in the second solution in the photocathode chamber to generate methylsuccinic acid.

[0080] See also Figure 4 The embodiment of this specification also provides a stacked perovskite battery preparation device, including the following units.

[0081] A conductive substrate cleaning unit 51 is used to clean the conductive substrate;

[0082] A first hole transport layer spin coating unit 52, used for spin coating 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 used to spin coat the 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;

[0084] A first interconnect layer deposition unit 54, used for depositing a first interconnect layer on the wide bandgap photoactive layer;

[0085] A composite layer sputtering unit 55, used for depositing and sputtering a composite layer on the first interconnect layer;

[0086] A second hole transport layer spin coating unit 56, for spin coating PEDOT:PSS on the composite layer as a second hole transport layer;

[0087] The narrow bandgap photoactive layer spin coating unit 57 is used to spin coat the 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;

[0088] A second interconnect layer evaporation unit 58, used for evaporating a second interconnect layer on the narrow bandgap photoactive layer;

[0089] The back reflection electrode evaporation unit 59 is used to evaporate the back reflection electrode on the second interconnect layer to obtain a laminated perovskite cell.

[0090] The embodiments of the present 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 laminated perovskite battery when executing the computer program.

[0091] The embodiments of this specification also provide a computer-readable storage medium, wherein the computer-readable storage medium stores a computer program, and when the computer program is executed by a processor, the above-mentioned method for preparing a laminated perovskite battery is implemented.

[0092] 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, the above-mentioned method for preparing a stacked perovskite battery is implemented.

[0093] Those skilled in the art will appreciate that this specification may be provided as a method, system, or computer program product. Therefore, this specification may take the form of a complete hardware embodiment, a complete software embodiment, or an embodiment combining software and hardware. Moreover, this specification may 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-ROM, optical storage, etc.) containing computer-usable program code.

[0094] This specification is described with reference to the flowcharts and / or block diagrams of the methods, devices (systems), and computer program products of the embodiments of this specification. It should be understood that each process and / or box in the flowchart and / or block diagram, as well as the combination of the processes and / or boxes in the flowchart and / or block diagram, 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] The various functional units in the embodiments of this specification may be integrated into one processing unit, or each functional unit may exist physically separately, or two or more functional units may be integrated into one processing unit.

[0096] Those skilled in the art will understand that the description of each embodiment in this specification has its own emphasis. For parts not described in detail in a certain embodiment, reference can be made to the relevant description of other embodiments. In addition, it is understood that after reading this specification, those skilled in the art can think of any combination of some or all of the embodiments listed in this specification without creative work, and these combinations are also within the scope of disclosure and protection of this specification.

[0097] Although the present specification is described by way of examples, it is known to those skilled in the art that the above examples are only used to help understand the core idea of ​​the present specification. It is understood by those skilled in the art that there are many variations and changes in 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 source; 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 a catalyst for methylene succinic acid hydrogenation reaction is dissolved in the second solution; A photoanode, connected to the anode of the power source 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 source 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.

2. The device according to claim 1, characterized in that The light source comprises a first light source; The first light source is used to irradiate the photocathode chamber to generate hydrogen.

3. The device according to claim 1, characterized in that The power source includes a perovskite battery; The light source includes a second light source, and the second light source is used to illuminate the perovskite cell to generate electrical energy.

4. The device according to claim 3, characterized in that The perovskite cell is a stacked perovskite cell; The stacked perovskite cell comprises 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.

5. The device according to claim 4, 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 above, the second hole transport layer comprises PEDOT:PSS, 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.

6. The device according to claim 1, characterized in that The apparatus also includes sensors and control equipment; The sensor is disposed in the second solution and is used to detect the physicochemical parameters of the second solution; The control device is used to control the light source according to physicochemical parameters to adjust the rate of the in-situ reaction.

7. The device according to claim 6, characterized in that The control device is also used to determine whether the physicochemical parameters meet the set conditions; if so, control the light source to be turned off.

8. A method for preparing a laminated perovskite battery, characterized in that: include: 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; Spin-coat PEDOT:PSS on the composite layer as the second hole transport layer; Spin coating 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; vapor depositing 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.

9. The method according to claim 8, characterized in that Said The step of depositing a first interconnect layer on the wide bandgap photoactive layer comprises: C is deposited on the wide bandgap photoactive layer. 60 and dibromo-o-cresolsulfonate as a first interconnect layer; The step of depositing and sputtering a composite layer on the first interconnect layer comprises: Ag and MoOx are deposited on the first interconnect layer and ITO is sputtered 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.

10. The method according to claim 8, characterized in that The stacked perovskite cell is applied to a photoelectrocatalytic reaction device; the photoelectrocatalytic reaction device comprises a reactor, a diaphragm for separating the reactor into a photocathode chamber and a photoanode chamber, a light source, a photoanode, and a photocathode; the photoanode is connected to the anode of the stacked perovskite cell and is arranged in the photoanode chamber, and a first solution is filled in the photoanode chamber; the photocathode is connected to the cathode of the stacked perovskite cell and is arranged in the photocathode chamber, and a second solution is filled in the photocathode chamber, and the second solution is an aqueous solution of methylenesuccinic acid, and a catalyst for the hydrogenation reaction of methylenesuccinic acid is dissolved in the second solution; The light source and the stacked perovskite cell 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.

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