Floatable lead-free monopolar plate perovskite photovoltaic hydrogen production integrated device

Abstract

The invention provides a floatable lead-free single-pole-plate perovskite photovoltaic hydrogen production integrated device. The floatable lead-free single-pole-plate perovskite photovoltaic hydrogen production integrated device comprises a transparent conductive substrate, a packaging part, a photoanode and a photocathode. By arranging the photocathode and the photoanode on the same transparent conductive substrate, series connection is achieved, voltage sufficient to achieve hydrogen production through water splitting is obtained, and assistance of external bias voltage is not needed. And meanwhile, by getting rid of the dependence on connecting parts such as wires in the prior art, the integration level is improved, and the design of a wire-free device is realized. And the packaging part is arranged to realize edge sealing, so that moisture can be prevented from entering the device to cause decomposition of the perovskite material. The transparent conductive substrate is a flexible conductive substrate and is light in weight, so that the device can float on the water surface, the light-transmitting surface is always parallel to the water surface, and the device can receive sunlight more favorably.

Description

Technical Field

[0001] The present invention relates to the field of photoelectric catalysis technology, and in particular to a floating wire-free single-pole plate perovskite photovoltaic hydrogen production integrated device. Background Art

[0002] The development of advanced new energy technologies and devices is a key way to solve the energy crisis, greenhouse effect, environmental pollution and other problems. Efficient use of solar energy and direct conversion of solar energy into renewable fuels (such as hydrogen) using photoelectrochemical methods is an effective strategy to promote the development of a sustainable energy economy. As a photovoltaic material, organic-inorganic hybrid metal halide perovskite has shown excellent photoelectric performance and low cost, and has attracted attention in the field of solar-driven electrocatalysis in recent years. However, most perovskite-based photovoltaic-driven electrocatalytic devices need to be combined in different modules, which rely on additional wires and other components for connection, greatly increasing the cost and space of the device assembly, thus limiting the further commercial development of photoelectrochemical hydrogen production.

[0003] The Chinese patent with the announcement number CN107464881B discloses an integrated device for photolysis of water to produce hydrogen and its manufacturing method, wherein the integrated device includes a photoanode, a perovskite solar cell and a photocathode, characterized in that: the photoanode is insulated and bonded to the transparent conductive substrate of the perovskite solar cell, and is electrically connected to the counter electrode of the perovskite solar cell; the photoanode absorbs ultraviolet light and a part of visible light, and another part of visible light passes through the photoanode to excite the perovskite solar cell to generate a bias; the counter electrode is formed on the perovskite layer or hole transport layer of the perovskite solar cell, and is insulated and bonded to the photocathode, and the photocathode is electrically connected to the transparent conductive substrate of the perovskite solar cell. However, the electrocatalytic devices driven by perovskite solar energy in the above scheme need to be combined in different modules and then connected to the catalytic positive and negative electrodes through wires, which leads to low device integration, and energy loss is inevitable during the transmission of intermediate components such as wires, and multiple solar cells are required to be connected in series to achieve the bias of electrolysis of water. At the same time, in the above scheme, the entire device is buried in water, and the water above inevitably absorbs a certain amount of sunlight, resulting in a loss of light. Therefore, it is very necessary to provide a floating wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device to achieve highly integrated hydrogen production without the need for external bias assistance, and at the same time to reduce the overall density of the device to make the device float so that the light-transmitting surface is parallel to the horizontal plane. Summary of the invention

[0004] In view of this, the present invention provides a floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device. In the floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device, the photoanode and the photocathode use photogenerated electrons to generate chemical energy, and form a series structure inside a conductive substrate. Without the need for external wires and external bias assistance, the holes and electrons generated by the device can drive the oxygen evolution reaction at the anode and the hydrogen evolution reaction at the cathode, respectively. The hydrogen and oxygen finally produced by the device can be separated through the transmission of the cavity channel.

[0005] The present invention provides a floating wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device, comprising a transparent conductive substrate, a packaging part, a photoanode and a photocathode, wherein:

[0006] The encapsulation part comprises at least two first encapsulation sub-parts and a second encapsulation sub-parts, the two first encapsulation sub-parts are arranged opposite to each other and spaced apart, the second encapsulation sub-part is arranged between the two opposite first encapsulation sub-parts, and the first encapsulation sub-part and the second encapsulation sub-part are both arranged on the transparent conductive substrate;

[0007] A first cavity is formed between the first encapsulation sub-portion and the second encapsulation sub-portion located on one side of the transparent conductive substrate, one side of the first cavity is closed and the other side is open, the photoanode is arranged in the first cavity, and a second cavity is formed between the first encapsulation sub-portion and the second encapsulation sub-portion located on the other side of the transparent conductive substrate, one side of the second cavity is closed and the other side is open, the photocathode is arranged in the second cavity, the opening of the first cavity is arranged opposite to the opening of the second cavity, and the photoanode and the photocathode are both arranged on the transparent conductive substrate;

[0008] The photoanode comprises a photoanode electron transport layer, a photoanode perovskite light absorption layer, a photoanode hole transport layer, a photoanode water-isolating electrode layer and a photoanode catalyst layer stacked in sequence from top to bottom;

[0009] The photocathode comprises a photocathode hole transport layer, a photocathode perovskite light absorption layer, a photocathode electron transport layer, a photocathode water-isolating electrode layer and a photocathode catalyst layer which are sequentially stacked from top to bottom.

[0010] On the basis of the above technical scheme, preferably, the materials of the photoanode hole transport layer and / or the photocathode hole transport layer include one or more of inorganic transport materials, organic polymer hole transport materials, organic small molecule materials, and single molecule self-assembly materials, and the thickness of the photoanode hole transport layer and the photocathode hole transport layer are both 1nm to 300nm.

[0011] Based on the above technical solution, preferably, the materials of the photoanode electron transport layer and / or the photocathode electron transport layer include one or more of inorganic electron transport materials and organic electron transport materials, and the thickness of the photoanode electron transport layer and the photocathode electron transport layer are both 1nm to 300nm.

[0012] On the basis of the above technical scheme, preferably, the material chemical formula of the photoanode perovskite light absorbing layer or the photocathode perovskite light absorbing layer is ABX3, wherein the A ions include one or more of inorganic monovalent ions and organic monovalent ions, the B ions include one or more combinations of alkaline earth metal ions and transition metal ions, and the X ions include one or more of halogen ions or pseudo-halogen ions.

[0013] On the basis of the above technical scheme, preferably, the material chemical formula of the photoanode perovskite light absorbing layer or the photocathode perovskite light absorbing layer is ABX3, wherein the A ions include one or more of inorganic monovalent ions and organic monovalent ions, the B ions include one or more combinations of alkaline earth metal ions and transition metal ions, and the X ions include one or more of halogen ions or pseudo-halogen ions.

[0014] More preferably, the photoanode water-isolating electrode layer and / or the photocathode water-isolating electrode layer comprises one or more of noble metals, non-noble metals and carbon-based materials, and the thickness of the photoanode water-isolating electrode layer and the photocathode water-isolating electrode layer are both 10nm to 2000nm.

[0015] More preferably, the photoanode catalyst layer 35 includes one or more of a noble metal catalyst, a non-noble metal catalyst, and a carbon-based catalytic material, and the thickness of the photoanode catalyst is 10 nm to 2000 nm.

[0016] More preferably, the photocathode catalyst layer includes one or more of a noble metal catalyst, a transition metal sulfide, a transition metal phosphide, and a transition metal nitride, and the thickness of the photocathode catalyst is 10 nm to 2000 nm.

[0017] More preferably, the packaging part is composed of an inert water-proof packaging material, and the inert water-proof packaging material includes one or more of ethylene-vinyl acetate copolymer, polyolefin, polymethyl terephthalate, polymethyl methacrylate, polyisobutylene, polyimide, epoxy resin, acrylic resin and the like.

[0018] More preferably, the transparent conductive substrate is a flexible conductive substrate, and the overall density of the floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device is lower than that of water.

[0019] The floating wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device provided by the present invention has the following beneficial effects compared with the prior art:

[0020] (1) By placing the photocathode and the photoanode on the same transparent conductive substrate, a series connection is achieved to obtain a voltage sufficient to split water to produce hydrogen without the need for an external bias. At the same time, by getting rid of the reliance of existing technologies on connecting components such as wires, the integration level is improved to achieve the design of wire-free devices. The encapsulation part is provided to achieve edge sealing, which can prevent moisture from entering the device and causing the perovskite material to decompose.

[0021] (2) A flexible conductive substrate is used as the transparent conductive substrate. Its light weight allows the device to float on the water surface, and the light-transmitting surface always remains parallel to the water surface, which is more conducive to the device receiving sunlight. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present invention 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. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0023] Figure 1 A cross-sectional schematic diagram of a floating wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device provided in an embodiment of the present invention;

[0024] Figure 2 A bottom view of a floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device provided in an embodiment of the present invention.

[0025] Figure 3 A three-dimensional schematic diagram of an integrated device provided in an embodiment of the present invention;

[0026] Figure 4 A schematic diagram of an integrated device provided in an embodiment of the present invention floating on water.

[0027] Explanation of the accompanying drawings: 1. transparent conductive substrate; 2. packaging unit; 21. first packaging sub-unit; 22. second packaging sub-unit; 3. photoanode; 31. photoanode electron transport layer; 32. photoanode perovskite light absorption layer; 33. photoanode hole transport layer; 34. photoanode water-isolating electrode layer; 35. photoanode catalyst layer; 4. photocathode; 41. photocathode hole transport layer; 42. photocathode perovskite light absorption layer; 43. photocathode electron transport layer; 44. photocathode water-isolating electrode layer; 45. photocathode catalyst layer. DETAILED DESCRIPTION

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] Unless otherwise defined, the technical terms or scientific terms used in the present invention shall have the usual meanings understood by persons with ordinary skills in the field to which the present invention belongs. The words "first", "second" and similar words used in the present invention do not indicate any order, quantity or importance, but are only used to distinguish different components. Similarly, words such as "one" or "one" do not indicate quantity restrictions, but indicate the existence of at least one. Words such as "connect" or "connected" are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "Up", "down", "left", "right" and the like are only used to indicate relative positional relationships. When the absolute position of the object being described changes, the relative positional relationship also changes accordingly.

[0030] refer to Figure 1 and Figure 2 The present invention provides a floating wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device, including a transparent conductive substrate 1, a packaging part 2, a photoanode 3 and a photocathode 4.

[0031] The device structure is as follows. A first cavity is formed between the first encapsulation sub-section 21 and the second encapsulation sub-section 22 located on one side of the transparent conductive substrate 1, and the photoanode 3 is arranged in the first cavity, one side of the first cavity is closed, and the other side is open, which is used to form an oxygen transmission channel. A second cavity is formed between the first encapsulation sub-section 21 and the second encapsulation sub-section 22 located on the other side of the transparent conductive substrate 1, and the photocathode 4 is arranged in the second cavity, one side of the second cavity is closed, and the other side is open, which is used to form a hydrogen transmission channel. The opening of the first cavity is arranged opposite to the opening of the second cavity to achieve separation during the preparation of oxygen and hydrogen. The photoanode 3 and the photocathode 4 are both in contact with the transparent conductive substrate 1. Furthermore, the floating wire-free single-pole plate perovskite photovoltaic hydrogen production integrated device can float on the water due to its low density. Collection pipes are arranged in the first cavity and the second cavity to collect the oxygen prepared by the photoanode 3 and the hydrogen prepared by the photocathode 4.

[0032] The transparent conductive substrate 1 is a flexible conductive substrate that can float the wire-free single-pole perovskite photovoltaic hydrogen production integrated device. The overall density is lower than that of pure water. The transparent conductive substrate 1 provides mechanical support for the photoanode 3 and the photocathode 4 at the same time, and can realize the effective transmission and collection of charges. The transparent conductive substrate 1 generally uses materials with good conductivity and light transmittance, such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), etc., to ensure sufficient light intensity and charge transfer efficiency. In this embodiment, a PET film is used, which is light in weight, so that it is used as a flexible conductive substrate, and the overall density of the device is low, which can realize the function of self-floating on water.

[0033] The encapsulation part 2 includes at least two first encapsulation sub-parts 21 and a second encapsulation sub-part 22. The two first encapsulation sub-parts 21 are arranged opposite to each other and at intervals. The second encapsulation sub-part 22 is arranged between the two opposite first encapsulation sub-parts 21. The first encapsulation sub-part 21 and the second encapsulation sub-part 22 are both arranged on the transparent conductive substrate 1.

[0034] The photoanode 3 is arranged in the first cavity, and the photocathode 4 is arranged in the second cavity. The photoanode 3 and the photocathode 4 are connected through a transparent conductive substrate. The two are inverted structures in the sense of semiconductor devices, and the carrier transmission direction is consistent, thereby realizing series connection.

[0035] In this embodiment, the packaging part 2 is composed of an inert water-proof packaging material, and the inert water-proof packaging material is one or more of ethylene-vinyl acetate copolymer, polyolefin, polymethyl terephthalate, polymethyl methacrylate, polyisobutylene, polyimide, epoxy resin, acrylic resin, etc.

[0036] In this embodiment, the passivation layer is mainly used to suppress defect states and dangling bonds on the surface of the photoanode 3 / photocathode 4, reduce surface recombination and charge traps, and improve the utilization rate of carriers. Common passivation layer materials are ammonium ligand salts with alkylammonium chains, cyclic or aromatic ammonium cations, and typical halide anions. The ammonium cations in these salt solutions can be combined with the perovskite surface through A-site vacancies or hydrogen bonds to form a thin molecular layer on the top of the perovskite. By introducing an ultra-thin passivation layer on the surface of the perovskite absorption layer, surface defects can be effectively passivated and the carrier life can be extended. At the same time, the passivation layer can also protect the photoanode perovskite absorption layer 32 / photocathode perovskite absorption layer 42, and improve its chemical stability and durability. The dielectric layer is mainly used to adjust the interface electric field distribution between the photoanode perovskite absorption layer 32 / photocathode perovskite absorption layer 42 and the charge transfer layer, suppress the recombination and scattering of carriers at the interface, and improve the charge transfer efficiency. By introducing a dielectric layer on the surface of the perovskite light absorption layer / charge transfer layer and using insulating materials with high dielectric constants such as Al2O3, SiO2, and ZrO2, the interface energy level arrangement can be effectively regulated, interface recombination can be suppressed, and carrier lifetime can be improved.

[0037] It should be noted that the thickness of each functional layer in the photoanode 3 and the photocathode 4 needs to be strictly controlled within the nanometer scale, generally between 1nm and 300nm. This is because too thick a functional layer will significantly increase the internal resistance of the device and hinder the transmission and collection of carriers, while too thin a functional layer will have difficulty in performing its due function and may even introduce additional interface defects.

[0038] In one example, the photoanode 3 and the photocathode 4 both include a passivation layer and a dielectric layer, and the thickness of the photoanode (3) and the photocathode 4 are both 1 μm to 50 μm.

[0039] In this embodiment, the photoanode 3 includes a photoanode electron transport layer 31, a photoanode perovskite light absorption layer 32, a photoanode hole transport layer 33, a photoanode water-isolating electrode layer 34, and a photoanode catalyst layer 35 stacked in sequence from top to bottom. The photocathode 4 includes a photocathode hole transport layer 41, a photocathode perovskite light absorption layer 42, a photocathode electron transport layer 43, a photocathode water-isolating electrode layer 44, and a photocathode catalyst layer 45 stacked in sequence from top to bottom.

[0040] The materials of the photoanode hole transport layer 33 and / or the photocathode hole transport layer 41 include inorganic transport materials such as nickel oxide (NiO), copper oxide (CuO), cuprous iodide (CuI), copper indium disulfide (CuInS2), zinc tin sulfide (CuZnSnS2), copper thiocyanate (CuSCN), carbon and graphene oxide, polyethylene dioxythiophene-polystyrene sulfonate (PEDOT:PSS), poly [bis (4-phenyl) (4-butylphenyl) amine] (Poly-TPD), poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (P TAA), diarylamine, 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), DFTAB and other organic small molecule materials, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) and (2-(9H-carbazole-9-yl)ethyl)phosphonic acid (2PACz) and other single molecule self-assembly materials, and the thickness of the photoanode hole transport layer 33 and the photocathode hole transport layer 41 is 1nm to 300nm.

[0041] In this embodiment, the main function of the HTL material (Hole Transport Layer, HTL) is to effectively extract the photogenerated holes from the perovskite light absorption layer and transfer them to the external circuit or reaction material. The above-mentioned HTL materials such as Spiro-OMeTAD, PTAA, NiO, etc. have excellent hole transport performance, which can significantly improve the extraction and transport of holes, inhibit the accumulation and recombination of holes inside the device, thereby improving the current density and fill factor.

[0042] The materials of the photoanode electron transport layer 31 and / or the photocathode electron transport layer 43 include inorganic electron transport materials such as TiO2, SnO2, Al2O3, ZnO, and PCBM, C 60 The thickness of the photoanode electron transport layer and the photocathode electron transport layer are both 1nm to 300nm.

[0043] In this embodiment, the above-mentioned ETL materials (Electron Transport Layer, ETL) such as TiO2, SnO2, ZnO, PCBM, etc. have excellent electron transport properties, which can significantly improve the extraction and transmission of electrons, reduce the accumulation and recombination of electrons inside the device, and thus improve the photocurrent density and fill factor. The energy level matching between the ETL material and the perovskite light absorption layer has an important influence on the device performance.

[0044] The material chemical formula of the photoanode perovskite light absorbing layer 32 or the photocathode perovskite light absorbing layer 42 is ABX3, wherein the A ions include Na + , K + , Rb + , Cs + Inorganic monovalent ions such as methylammonium (MA + ), Ami (FA + ), guanidine (GA + ), dimethylammonium (DMA + ), ethylammonium (EA + ), (BA + ), octyl ammonium (OA + ), phenethylammonium (PEA + ) and other organic monovalent ions, B ions include Mg 2+ , Ca 2+ , Ba 2+ Alkaline earth metal ions and Cu 2+ 、Ni 2+ Sn 2+ , Pb 2+ One or more combinations of transition metal ions, X ions include Cl - Br - ,I- Halogen ions or thiocyanate ions (SCN - ), isocyanate ion (OCN - ), fluoroborate ion (BF4 - ), hexafluorophosphate ion (PF6 - ), hexafluorosulfonyl imide anion (TFSI - ) and the like.

[0045] In this embodiment, by adjusting the band gap of ABX3 perovskite, its light absorption range can be broadened to achieve wide-spectrum absorption from ultraviolet to near infrared. + , FA + , Cs + etc.) or B-site cations (such as Pb 2+ Sn 2+ The band gap of perovskite can be continuously adjusted to achieve efficient absorption of visible light to near-infrared light. + or X-position anion Br - The increase in the number of can widen the band gap of perovskite. At the same time, the introduction of smaller B-site ions (such as Sn 2+ etc.) can shorten the perovskite band gap and make the perovskite band gap adjustable.

[0046] Furthermore, the surface defect state density of ABX3 perovskite materials has an important influence on device performance and stability. By introducing appropriate A, B, and X-site ions, the surface defects of perovskite can be passivated, non-radiative recombination can be suppressed, and the carrier lifetime can be improved. For example, the introduction of larger A-site cations (such as GA + , Cs + etc.) can improve the structural stability of perovskite and reduce crystal defects. Introducing smaller B-site ions (such as Mn 2+ 、Cd 2+ etc.) can passivate the surface dangling bonds and inhibit the formation of defect states. - 、NCSe - etc.) can improve the moisture resistance and oxidation resistance of perovskite and extend the life of the device.

[0047] The interfacial electric field distribution between ABX3 perovskite and the electron / hole transport layer has an important influence on the carrier recombination dynamics. By regulating the composition and interface modification of ABX3 perovskite, the interfacial electric field distribution can be adjusted, carrier recombination can be suppressed, and the charge separation efficiency can be improved. For example, the introduction of deeper energy level B-site ions (such as Ni 2+ 、Co 2+The introduction of shallower energy level B-site ions (such as Cu 2+ etc.), a reverse electric field can be formed to prevent electrons from diffusing to the hole transport layer and reduce carrier recombination losses.

[0048] The photoanode water-isolating electrode layer 34 and / or the photocathode water-isolating electrode layer 44 include one or more of precious metals such as gold and platinum, non-precious metals such as aluminum, tin, lead, tungsten, silver, copper, iron, nickel, and carbon-based materials such as carbon nanotubes, graphene, and graphite. The thickness of the photoanode water-isolating electrode layer 34 and the photocathode water-isolating electrode layer 44 are both 10nm to 2000nm.

[0049] In this embodiment, selecting a material with good conductivity (such as carbon, gold, silver, copper, etc.) as the water-blocking electrode can reduce the series resistance of the device, reduce ohmic losses, and promote the rapid transmission and collection of photogenerated carriers. At the same time, by optimizing the thickness of the water-blocking electrode (such as 50nm to 2000nm), it is possible to reduce the reflection loss of the incident light while ensuring good conductivity, thereby improving the light capture efficiency.

[0050] The photoanode catalyst layer 35 includes one or more of noble metal catalysts such as Pt, Ir, Pd, Ru and Rh, non-noble metal catalysts such as manganese oxide, iron oxide and cobalt oxide, carbon materials functionalized with oxygen-containing functional groups, transition metal-heteroatom-carbon and other carbon-based catalytic materials. The photocathode catalyst layer 45 includes one or more of noble metal catalysts such as Pt and Ru, transition metal sulfides such as MoS2, WS2, CoS2, transition metal phosphides such as Ni2P and FeP, and transition metal nitrides such as MoN and VN. The thickness of the photocathode catalyst is 10nm to 2000nm.

[0051] In this embodiment, by selecting an efficient OER catalyst material (such as Ni-TFBDC), it is used to reduce the anode overpotential, accelerate the OER kinetics, and improve the oxygen evolution efficiency. These catalysts usually have a large specific surface area, abundant active sites, and excellent conductivity, which are conducive to charge transfer and surface reactions. By selecting an efficient HER catalyst material (such as platinum, CoP, MoS2, etc.), the cathode overpotential is reduced and the HER kinetics are accelerated.

[0052] Furthermore, in the process of photovoltaic hydrogen production, the catalyst layer must not only withstand the high current density of the electrochemical reaction, but also withstand the high-energy photons of strong light irradiation, which is prone to photocorrosion and dissolution, resulting in decreased catalytic activity and device failure. Catalyst materials with good photocorrosion resistance and chemical stability (such as CoP, Co@BCN, Co-CN, etc.) are selected to delay the degradation and dissolution of the catalyst and improve the long-term stability of the device. These catalysts have strong metal-support interactions, good structural stability and excellent corrosion resistance, aiming to inhibit the erosion of photogenerated carriers and reaction intermediates on the catalyst. By optimizing the composition, morphology and protective layer design of the catalyst, the durability of the device can be further enhanced.

[0053] During the water splitting process, the precipitated hydrogen and oxygen gather on the catalyst surface, which easily hinders the contact between reactants and active sites, resulting in a decrease in reaction efficiency. The use of catalyst materials with porous structures and hydrophobic surfaces (such as CoMoP@C, FeP-CS, etc.) can promote the rapid precipitation and escape of gas products and maintain the activity of the catalyst surface. These catalysts usually have interconnected multi-level pores, hydrophobic microstructures and excellent gas mass transfer capabilities, which are conducive to the nucleation, growth and detachment of bubbles, and can further improve the reaction efficiency.

[0054] Under illumination conditions, the electron / hole transport routes and device working principles in the floating wire-free single-pole perovskite photovoltaic hydrogen production integrated device are as follows:

[0055] On the photoanode 3 side: light passes through the transparent conductive substrate 1 and irradiates the photoanode perovskite light absorption layer 32, and the photogenerated electrons jump from the valence band to the conduction band, leaving holes in the valence band. The photogenerated electrons are extracted by the electron transport layer and transported to the transparent conductive substrate 1, and then transferred to the photocathode 4 side through the transparent conductive substrate 1. The photogenerated holes are extracted by the hole transport layer of the photoanode 33 and transported to the photoanode water-isolating electrode layer 34, and then reach the photoanode catalyst layer 35, and undergo oxygen evolution reaction under the action of the catalyst.

[0056] On the photocathode 4 side: light is irradiated through the transparent conductive substrate 1 to the photocathode perovskite light absorption layer 42, generating electron-hole pairs. The photogenerated holes are extracted by the hole transport layer and transported to the transparent conductive substrate 1 to recombine with the electrons. The photogenerated electrons are extracted and transported by the photocathode electron transport layer 43, pass through the photocathode water-isolating electrode layer 44 to reach the photocathode catalyst layer 45, and undergo a hydrogen evolution reaction under the action of the catalyst.

[0057] Electron transport path: photoanode perovskite light absorption layer 32 → photoanode electron transport layer 31 → transparent conductive substrate 1; photocathode perovskite light absorption layer 42 → photocathode electron transport layer 43 → photocathode water-isolating electrode layer 44 → photocathode catalyst layer 45 (hydrogen evolution).

[0058] Hole transport path: photocathode perovskite light absorption layer 42 → photocathode hole transport layer 41 → transparent conductive substrate 1; photocathode perovskite light absorption layer 32 → photoanode hole transport layer 33 → photoanode water-isolating electrode layer 34 → photoanode catalyst layer 35 (oxygen evolution).

[0059] In this process, the electrons of the hydrogen evolution reaction are at work, and the holes of the oxygen evolution reaction are at work. The holes are transferred from the photoanode 3 side to the photocathode 4 side through the transparent conductive substrate 1, and finally recombine with the electrons generated by the photocathode 4. This design of charge transfer and transmission path is conducive to promoting charge separation and inhibiting carrier recombination, thereby improving the photoelectric conversion efficiency of the device and the performance of solar hydrogen production.

[0060] The working principle of the floating wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device provided by the present invention is as follows:

[0061] (1) The photoanode perovskite light absorbing layer and the photocathode perovskite light absorbing layer capture light energy to form photogenerated carriers, wherein the photogenerated holes generated are extracted by the photoanode hole transport layer or the photocathode hole transport layer, and the photogenerated electrons generated are extracted by the photoanode electron transport layer or the photocathode electron transport layer.

[0062] (2) Holes are extracted from the photoanode and act on the photoanode catalyst to produce an oxygen evolution reaction:

[0063] (3)

[0064] (4) Electrons are extracted from the photocathode and act on the photocathode catalyst to produce a hydrogen evolution reaction:

[0065] (5)2e - +2H + (aq)→H2(g)

[0066] (6) The photogenerated electrons at the photoanode and the photogenerated carriers at the photocathode are finally extracted into the transparent conductive substrate for recombination. Since the photoanode is an inverted structure in the sense of a photocathode semiconductor device, the electrons in the entire circuit move in the same direction, and the photoanode and the photocathode are connected in series.

[0067] (7) It should be noted that the above reaction formula only briefly represents the overall schematic diagram of the working process of the photoanode / photocathode. According to the application scenarios of different photoanode catalysts / photocathode catalysts, the reaction process can be regarded as adjusted. These simple variations are also regarded as the disclosure content of this patent and all fall within the scope of protection of the present invention.

[0068] In an optional embodiment, the preparation process of the floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device is as follows:

[0069] 1. A fluorine-doped tin oxide PET substrate with a length of 10 cm, a width of 10 cm, and a thickness of 680 nm was etched using a femtosecond laser. The etched substrate was then ultrasonically cleaned in a cleaning solution, pure water, and ethanol for 15 min in sequence, and then dried with nitrogen to obtain a transparent conductive substrate.

[0070] 2. Preparation of the photoanode electron transport layer: Use a mask to cover the middle connection and the photocathode end, and use chemical deposition to prepare the photoanode electron transport layer at the photoanode end. Add 5g urea, 5mL hydrochloric acid, 100μL thioglycolic acid, and 1.1g SnCl2·2H2O to 400mL deionized water and disperse evenly; take 20mL of the solution as the mother liquor, dilute the mother liquor with deionized water in a ratio of 1:5 and pour into a glass container. After UV treatment of the transparent conductive substrate for 15min, immerse it in the diluted solution, and place the glassware in a 90℃ oven for 3h for chemical bath deposition. After the reaction is completed, blow dry the transparent conductive substrate with nitrogen, remove the mask at the photocathode end, and heat it at 170℃ for 1h to obtain a SnO2 electron transport layer with a thickness of 40nm.

[0071] 3. Preparation of photocathode hole transport layer: retain the mask covering the middle connection, and use the mask to cover the photoanode end. The photocathode hole transport layer is prepared by spin coating at the photocathode end. Spin the self-assembled molecular solution Me-4PACz at 3000rpm for 30s (acceleration is 1000rpm) to form a thin film, and immediately place it on a 100℃ hot stage for annealing for 10 minutes.

[0072] 4. Preparation of photocathode perovskite light absorbing layer and photoanode perovskite light absorbing layer: retain the mask covering the middle connection, remove the photoanode end mask, and simultaneously prepare the photocathode perovskite light absorbing layer and the photoanode perovskite light absorbing layer by spin coating. 18.2mg CsI, 484mg PbI2, 20.25mg MACl, 160mg FAI are dissolved in a mixed solvent of 500μL DMF and 96μL NMP, and fully mixed to prepare a perovskite precursor solution. The perovskite precursor solution is added dropwise to the photoanode SnO2 electron transport layer or the photocathode hole transport layer, and spin coated at 5000rpm for 60s (acceleration of 1000rpm / s) to form a thin film, which is immediately placed on a 70℃ hot plate for heating for 1min, and then heated at 100℃ for 2h under 30-40% RH conditions to obtain a Cs with a thickness of 750nm. 0.07 FA 0.93 Perovskite light-absorbing layer with PbI3 structure.

[0073] 5. Prepare the photoanode hole transport layer: retain the mask at the middle connection and use the mask to cover the photocathode end. Dissolve 91.4 mg of Spiro-OMeTAD powder in 1 mL of chlorobenzene, then add 21 μL of 520 mg / mL lithium bistrifluoromethanesulfonyl imide (Li-TFSI) / acetonitrile solution, 35.6 μL of 4-tert-butylpyridine and 15 μL of 300 mg / mL cobalt-based (III) bistrifluoromethanesulfonyl imide salt (FK209) / acetonitrile solution, and mix well. Add the solution dropwise to the surface of the passivation layer, and spin coat at 5000 rpm for 30 seconds (acceleration of 2000 rpm / s) to obtain the photoanode hole transport layer.

[0074] 6. Prepare the photocathode electron transport layer: remove the photocathode end mask, keep the mask covering the middle connection, and use the mask to cover the photoanode end. Prepare the photocathode electron transport layer by evaporation, and evaporate 1nm LiF, 25nm C 60 and 2 nm of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) as an electron transport layer.

[0075] 7. Prepare the photoanode water-isolating electrode layer and the photocathode water-isolating electrode layer: evenly coat the commercial carbon slurry on a copper foil of ~20μm, immerse it and the substrate in an ethanol replacement solvent at 35°C, remove the residual organic solvent in the conductive slurry, and form a bottom electrode on the surface. Finally, dry the bottom electrode to obtain a multilayer carbon-based electrode. Attach the prepared multilayer carbon-based electrode to the surface of the photoanode hole transport layer and the photocathode electron transport layer, and hot press for 25s at 35°C and 0.2MPa. After the above operations, a complete photovoltaic hydrogen production device is obtained.

[0076] 8. Package device: Coat an inert water-proof packaging material around the photocathode 4 and the photoanode 3 to achieve an edge-sealing effect, that is, apply one or more combinations of ethylene-vinyl acetate copolymer, polyolefin, polydimethyl terephthalate, polymethyl methacrylate, polyisobutylene, polyimide, epoxy resin, acrylic resin, etc. around the photoanode 3 and the photocathode 4, exposing the electrode part at the upper end, so that the inert packaging material can seal the side edges of the photoanode 3 and the photocathode 4 electrodes to prevent moisture from penetrating from the side of the device.

[0077] 9. Device operation: In this embodiment, the photoanode and photocathode of the floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device are connected in series, the circuit voltage exceeds 2.1V, and the device is immersed in water to start hydrogen production.

[0078] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A floating wire-free single-pole perovskite photovoltaic hydrogen production integrated device, characterized in that: It comprises a transparent conductive substrate (1), a packaging part (2), a photoanode (3) and a photocathode (4), wherein: The encapsulation part (2) comprises at least two first encapsulation sub-parts (21) and a second encapsulation sub-part (22), the two first encapsulation sub-parts (21) are arranged opposite to each other and spaced apart, the second encapsulation sub-part (22) is arranged between the two opposite first encapsulation sub-parts (21), and the first encapsulation sub-part (21) and the second encapsulation sub-part (22) are both arranged on the transparent conductive substrate (1); A first cavity is formed between the first encapsulation sub-portion (21) and the second encapsulation sub-portion (22) located on one side of the transparent conductive substrate (1), one side of the first cavity is closed and the other side is open, the photoanode (3) is arranged in the first cavity, and a second cavity is formed between the first encapsulation sub-portion (21) and the second encapsulation sub-portion (22) located on the other side of the transparent conductive substrate (1), one side of the second cavity is closed and the other side is open, the photocathode (4) is arranged in the second cavity, the opening of the first cavity is arranged opposite to the opening of the second cavity, and the photoanode (3) and the photocathode (4) are both arranged on the transparent conductive substrate (1); The photoanode (3) comprises a photoanode electron transport layer (31), a photoanode perovskite light absorption layer (32), a photoanode hole transport layer (33), a photoanode water-isolating electrode layer (34) and a photoanode catalyst layer (35) which are stacked in sequence from top to bottom; The photocathode (4) comprises a photocathode hole transport layer (41), a photocathode perovskite light absorption layer (42), a photocathode electron transport layer (43), a photocathode water-isolating electrode layer (44), and a photocathode catalyst layer (45) which are stacked in sequence from top to bottom.

2. A floating wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device as claimed in claim 1, characterized in that: The materials of the photoanode hole transport layer (33) and / or the photocathode hole transport layer (41) include one or more of inorganic transport materials, organic polymer hole transport materials, organic small molecule materials, and single molecule self-assembly materials. The thickness of the photoanode hole transport layer (33) and the photocathode hole transport layer (41) are both 1 nm to 300 nm.

3. The floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device according to claim 1, characterized in that: The materials of the photoanode electron transport layer (31) and / or the photocathode electron transport layer (43) both include one or more of an inorganic electron transport material and an organic electron transport material, and the thickness of the photoanode electron transport layer (31) and the photocathode electron transport layer (43) are both 1 nm to 300 nm.

4. The floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device according to claim 1, characterized in that: The photoanode (3) and the photocathode (4) both comprise a passivation layer and a dielectric layer, and the thickness of the photoanode (3) and the photocathode (4) are both 1 μm to 50 μm.

5. The floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device according to claim 1, characterized in that: The material chemical formula of the photoanode perovskite light absorbing layer (32) or the photocathode perovskite light absorbing layer (42) is ABX3, wherein the A ions include one or more of inorganic monovalent ions and organic monovalent ions, the B ions include one or more combinations of alkaline earth metal ions and transition metal ions, and the X ions include one or more of halogen ions or pseudo-halogen ions.

6. The floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device according to claim 1, characterized in that: The photoanode water-isolating electrode layer (34) and / or the photocathode water-isolating electrode layer (44) include one or more of noble metals, non-noble metals and carbon-based materials, and the thickness of the photoanode water-isolating electrode layer (34) and the photocathode water-isolating electrode layer (44) are both 10nm to 2000nm.

7. The floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device according to claim 1, characterized in that: The photoanode catalyst layer (35) comprises one or more of a noble metal catalyst, a non-noble metal catalyst, and a carbon-based catalytic material, and the thickness of the photoanode catalyst is 10 nm to 2000 nm.

8. The floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device according to claim 1, characterized in that: The photocathode catalyst layer (45) comprises one or more of a noble metal catalyst, a transition metal sulfide, a transition metal phosphide, and a transition metal nitride, and the thickness of the photocathode catalyst is 10 nm to 2000 nm.

9. The floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device according to claim 1, characterized in that: The packaging part (2) is made of an inert water-proof packaging material, and the inert water-proof packaging material includes one or more of a resin organic material or an organic copolymer material.

10. The floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device according to claim 1, characterized in that: The transparent conductive substrate (1) is a flexible conductive substrate, and the overall density of the floatable wire-free monopolar plate perovskite photovoltaic hydrogen production integrated device is lower than that of pure water.

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