Perovskite solar cell photovoltaic module based on parallel-series structure and preparation method thereof

Abstract

The invention discloses a perovskite solar cell photovoltaic module based on a parallel-series structure and a preparation method thereof, and the method comprises the steps: firstly preparing a perovskite solar cell module with a parallel structure, then leading out a positive electrode and a negative electrode on a single cell module through an external metal electrode, and enabling a plurality of cell modules to be connected in series through a metal wire, the external metal electrode can be selected from but not limited to physical welding of conductive metal, conductive metal adhesive tape or blade coating of conductive silver paste and the like. According to the perovskite solar cell module with the parallel-to-series structure, a traditional transparent conductive electrode is replaced by an extremely thin hand-torn steel plate with certain flexibility, so that the output performance of the perovskite solar cell module is greatly improved, the preparation process is simple, the cost is low, large-scale production can be carried out, the application market is wide, and the application prospect is wide. And meanwhile, the problem of large-area failure of the whole device caused by failure of a single sub-battery is avoided by the parallel-first and then series-second battery structure.

Description

Technical Field

[0001] The present invention belongs to the technical field of photovoltaic cells, and in particular relates to a perovskite solar cell photovoltaic component based on a parallel-series structure and a preparation method thereof. Background Art

[0002] Perovskite solar cells have attracted extensive attention from experts in related fields since their birth due to their many advantages. In order to further promote the commercial application of perovskite solar cells, research on large-area perovskite solar cell modules has become increasingly popular. At present, most large-area perovskite solar cell modules still use a series connection to connect several sub-cells in series to obtain higher output power. At the same time, laser etching equipment is required in the preparation process of battery modules with series structures, which undoubtedly increases production costs, causes certain environmental pollution, and seriously reduces the yield rate and batch stability of battery production.

[0003] The commercial application of large-area perovskite solar cell modules is mainly to prepare solar panels for centralized power generation. Conventional perovskite solar panels still use commonly used transparent conductive electrodes (ITO, FTO, etc.), among which indium tin oxide (Indium Tin Oxide) is the most Indium oxide (ITO) is widely used due to its superior performance, but ITO still has the following disadvantages: 1. Its stability is easily affected by ambient temperature and humidity, and indium and tin are rare earth elements, which makes ITO expensive. 2. The rigid ITO conductive substrate limits its application in flexible devices. Flexible ITO conductive substrates still have the following problems: (1) Low mechanical properties: Although flexible ITO substrates have advantages such as light weight and compatibility with curved surfaces, they have outstanding advantages in wearable and self-powered portable electronic products. However, they have problems such as flexibility differences and interface contact with various functional layers during repeated bending, resulting in low mechanical properties. (2) Processing temperature limitation: Since the glass transition temperature of commonly used flexible ITO substrates is low, their processing temperature needs to be controlled at a relatively low temperature. This limitation greatly narrows the range of material selection and hinders the transfer of mature technology from glass substrates to flexible substrates. (3) Conductive performance issues: On flexible substrates, although materials such as ITO are commonly used in flexible perovskite solar cells, they often crack during mechanical deformation, thereby affecting their conductivity and transmittance.

[0004] The advantage of adjustable optical band gap of the perovskite active layer in perovskite solar cells is also one of the reasons why it has always attracted much attention. Generally, the energy levels and optical band gaps of adjacent layers in perovskite solar cell devices need to meet appropriate values ​​in order to effectively transmit the generated carriers, so as to obtain higher voltage and current and thus obtain higher photoelectric conversion efficiency, among which adjusting the band gap and energy level of the perovskite active layer is a common method. In the present invention, by adjusting the concentration, content, type, ratio of the substance in the perovskite precursor solution, the amount and type of the solvent, a perovskite active layer with different energy levels and optical band gaps can be obtained, which can effectively regulate the voltage and current of the device to meet different output power requirements. The perovskite precursor solution usually includes organic / inorganic salts or single crystal, polycrystalline perovskite seeds and other substances and solvents that constitute the perovskite active layer. Common organic / inorganic salts include methylamine hydroiodide, methylamido hydroiodide, stannous iodide, lead iodide, cesium iodide, etc.; common seeds include methylamido perovskite seeds and methylamine perovskite seeds, etc.; common solvents include dimethyl sulfoxide, dimethylformamide, acetonitrile, dimercaptoethanol, N-methylpyrrolidone, etc. By adjusting the components of the precursor solution, the thickness, band gap, energy level and other parameters of the perovskite active layer can be adjusted synchronously to meet different output power requirements. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing a perovskite solar cell photovoltaic module based on a parallel-series structure.

[0006] The present invention also aims to provide a perovskite solar cell photovoltaic module based on a parallel-series structure prepared by the above method.

[0007] The first object of the present invention can be achieved by the following technical solution: A method for preparing a perovskite solar cell photovoltaic module based on a parallel-series structure, comprising the following steps:

[0008] (1) cleaning and hydrophilizing the first conductive electrode;

[0009] (2) sequentially disposing a first carrier transport layer, a perovskite active layer, and a second carrier transport layer on the first conductive electrode;

[0010] (3) providing a blocking layer on the second carrier transport layer;

[0011] (4) using a mask plate to set a plurality of second conductive electrodes on the barrier layer, with a partition area provided between two adjacent second conductive electrodes, to form a plurality of independent sub-cells;

[0012] Each independent sub-cell includes, from bottom to top, a first conductive electrode, a first carrier transport layer, a perovskite active layer, a second carrier transport layer, a blocking layer and a second conductive electrode;

[0013] (5) using metal grid lines to connect a number of independent sub-batteries in parallel by connecting two adjacent second conductive electrodes in parallel to form a battery module, arranging an external metal electrode on the surface of the first conductive electrode to lead out the positive electrode of the battery module, and arranging an external metal electrode on the surface of the metal grid lines to lead out the negative electrode of the battery module;

[0014] (6) Using metal wires to sequentially connect the external metal electrodes at the positive and negative poles of two adjacent battery modules, multiple battery modules are connected in series to obtain a perovskite solar cell module based on a parallel-series structure.

[0015] In the above-mentioned method for preparing a perovskite solar cell photovoltaic module based on a parallel-series structure:

[0016] Preferably, the first conductive electrode described in step (1) is a hand-torn steel plate, a metal film or a carbon cloth electrode.

[0017] Preferably, the ultra-thin hand-tearable steel plate used in the present invention has a thickness of 0.01 to 0.05 mm and a square resistance of 4.5 to 13.0 mΩ / □.

[0018] Furthermore, the extremely thin hand-tearable steel plate in the present invention needs to be cleaned and surface-hydrophilic treated before being pasted on the rigid glass substrate.

[0019] As a preferred embodiment of the present invention, the cleaning treatment of the first conductive electrode includes: using deionized water and isopropyl alcohol to ultrasonically clean the first conductive electrode for 15 minutes, and then blowing it dry with nitrogen; the hydrophilic treatment is to use a plasma cleaning machine to clean for 50 to 100 seconds, and the power of the plasma cleaning machine is 180 to 220 W. Double-sided tape or PDMS film or other methods are used to completely adhere the ultra-thin steel plate to the rigid glass substrate.

[0020] Preferably, in step (2), the first carrier transport layer is an electron transport layer, and the second carrier transport layer is a hole transport layer, or in step (2), the first carrier transport layer is a hole transport layer, and the second carrier transport layer is an electron transport layer.

[0021] Preferably, in step (2), the first carrier transport layer or the second carrier transport layer is prepared by any one of magnetron sputtering, thermal evaporation, electron beam deposition, screen printing, slot die, inkjet printing, doctor blade coating, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition.

[0022] Preferably, the electron transport layer in step (2) is made of titanium dioxide, zinc oxide, cadmium sulfide, zinc sulfide, tin dioxide, indium trioxide, tungsten oxide, cerium oxide, carbon 60 (C60), carbon 70 (C70), [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 Any one of BM), carbon nanotubes (CNTs), graphene or their derivatives, dopants and composite materials, and the layer thickness is 5 to 40 nm.

[0023] Preferably, the hole transport layer in step (2) uses any one of nickel oxide, vanadium oxide, molybdenum oxide, copper sulfide, cuprous thiocyanate, copper oxide, cuprous oxide, cobalt oxide, scandium oxide, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3-hexylthiophene-2,5-diyl) (P3HT), polyethylenedioxythiophene (PEDOT), 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), self-assembled monolayers (SAMs), polyethylene glycol (PEG), polycaprolactone (PCL) or their derivatives, dopants and composites, and the layer thickness is 5 to 40 nm.

[0024] Preferably, in step (2), the perovskite active layer can be deposited on the first carrier transport layer by, but not limited to, screen printing, slot die, inkjet printing, doctor blade coating, or chemical vapor deposition.

[0025] Preferably, the perovskite deposition method in step (2) can be a one-step method or a two-step method.

[0026] Preferably, the perovskite active layer in step (2) is made of a perovskite precursor solution containing AX, BX2, a mixture of AX and BX2, or a laminated structure of AX and BX2, wherein A is a methylamino group CH3NH3 + , ethylamino CH3CH2NH3 + 、CarboxamidinoylCH(NH2)2 + and guanidine C(NH2)3 + At least one short-chain organic cation containing an amine functional group, or A is Li + 、Na + , K + , Rb + 、Ag + , Cu + and Cs + At least one monovalent inorganic cation in 2+ Sn 2+ , Pb 2+ 、Be 2+Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cu 2+ , Fe 2+ , Mn 2+ 、Zn 2+ 、Co 2+ and Ni 2+ At least one divalent metal ion, X is F - , Cl - 、CH3COO - Br - ,I - and SCN - At least one monovalent anion.

[0027] Preferably, the precursor solution can be selected to have different concentrations, different material ratios, and different solvent ratios to meet different output power requirements.

[0028] Preferably, the barrier layer in step (3) is SnO2, and the barrier layer is prepared by atomic layer deposition, chemical vapor deposition, plasma enhanced chemical vapor deposition, etc., and the thickness of the barrier layer is 10 to 30 nm.

[0029] Preferably, in step (4), the second conductive electrode is an indium tin oxide ITO, a fluorine-doped tin oxide FTO or an aluminum-doped zinc oxide AZO transparent conductive electrode.

[0030] Preferably, the second conductive electrode is made by magnetron sputtering, chemical vapor deposition, plasma enhanced chemical vapor deposition or atomic layer deposition.

[0031] Preferably, in step (5), a plurality of independent sub-batteries are connected in parallel by connecting two adjacent second conductive electrodes in parallel using a metal grid line, the material of the metal grid line is gold, silver, copper, aluminum, chromium or bismuth, and the metal grid line is obtained by thermal evaporation, conductive tape, physical welding or brushing conductive slurry.

[0032] That is, the parallel connection method described in step (5) is to directly connect the second conductive electrodes of each sub-battery using a metal grid line. The material of the metal grid line can be any one of metal materials with good conductive properties such as gold, silver, copper, aluminum, chromium, bismuth, etc. The metal grid line processing method can be any one of thermal evaporation, conductive tape, physical welding, brushing conductive silver paste, etc.

[0033] Preferably, the external metal electrode in step (5) is a conductive metal, a conductive tape or a conductive silver paste.

[0034] Furthermore, in step (5), the external metal electrode can be selected by physical welding of conductive metal, conductive metal tape or coating of conductive silver paste, and the series connection of multiple battery modules is carried out by connecting the external metal electrodes in series in sequence using metal wires with good conductive properties such as gold, silver, copper, aluminum, chromium, etc.

[0035] The mechanism implemented by the present invention is: first, a perovskite solar cell module with a parallel structure is prepared, and the cell module is composed of a number of independent sub-cells connected in parallel, wherein a single sub-cell is, from bottom to top, a first conductive electrode, a first carrier transport layer, a perovskite active layer, a second carrier transport layer, a barrier layer and a second conductive electrode, and the parallel structure means that each sub-cell is connected to the second conductive electrode through a metal grid line to achieve a parallel effect; then, the positive and negative poles are led out on the single cell module through an external metal electrode, and a plurality of cell modules are connected in series using a metal wire, and the external metal electrode can be selected from but not limited to physical welding of conductive metal, conductive metal tape or scraping of conductive silver paste.

[0036] The above second object of the present invention can be achieved by the following technical solution: a perovskite solar cell photovoltaic module based on a parallel-series structure is prepared by any of the above methods.

[0037] Preferably, the perovskite solar cell photovoltaic module based on the parallel-series structure comprises a plurality of battery modules connected in series by metal wires, each battery module comprises a plurality of sub-batteries, a positive electrode, a negative electrode and a partition area connected in parallel, each sub-battery comprises a first conductive electrode, a first carrier transport layer, a perovskite active layer, a second carrier transport layer, a barrier layer and a second conductive electrode, the second conductive electrodes of two adjacent sub-batteries are between the second conductive electrodes of the adjacent sub-batteries as a partition area, a metal grid line is used to connect a plurality of independent sub-batteries in parallel by connecting the second conductive electrodes of the two adjacent sub-batteries in parallel, the first conductive electrode leads out the positive electrode of the battery module through an external metal electrode, the second conductive electrode leads out the negative electrode of the battery module through a metal grid line and an external metal electrode, a metal wire is used to sequentially connect the external metal electrodes at the positive and negative electrodes of the two adjacent battery modules, and a plurality of battery modules are connected in series, that is, a perovskite solar cell module with a parallel-series structure.

[0038] Preferably, in the present invention, the output voltage and current of the photovoltaic module can be regulated by adjusting the type and thickness of the perovskite active layer, and the output power can be regulated by connecting a number of single battery modules in series to meet different power supply requirements.

[0039] Preferably, in the present invention, the first conductive electrode or the second conductive electrode may be a transparent conductive electrode to prepare a semi-transparent or fully transparent perovskite solar cell device.

[0040] Preferably, the size of the battery module of the present invention can be synchronously adjusted according to actual requirements.

[0041] As one of the preferred embodiments of the present invention, the conventional size of each battery module of the present invention is 5cm×5cm~50cm×50cm, each battery module includes 6~20 sub-batteries, the width of the partition area is 0.1~0.5cm, and the width and length of the metal grid line can be adjusted according to actual conditions, for example, the width is 0.1cm~0.5cm.

[0042] The present invention has the following advantages:

[0043] (1) The present invention focuses on innovatively selecting an ultra-thin hand-torn steel plate as the first conductive electrode. This ultra-thin metal substrate not only has good electrical conductivity and flexibility, but is also cheap and has a simple device preparation process, thus solving a series of problems caused by the selection of a flexible substrate in the above-mentioned flexible perovskite solar cell device;

[0044] (2) The present invention proposes a method for preparing a perovskite battery module based on a parallel structure, and realizes the purpose of adjusting the output power of the module by connecting multiple battery modules in series. At the same time, it innovatively proposes the use of hand-torn steel plates, metal films, carbon cloth electrodes, etc. with certain flexibility to replace traditional transparent conductive electrodes;

[0045] (3) The present invention not only solves the problem of complex preparation process of perovskite solar cell modules with traditional series structure, greatly saving production costs, but also avoids the problem of large-scale failure of the entire device caused by failure of a single sub-cell.

[0046] (4) The perovskite solar cell module of the present invention has a parallel-first-then-series structure, and uses an extremely thin hand-torn steel plate with a certain degree of flexibility to replace the traditional transparent conductive electrode. This not only greatly improves the output performance of the perovskite solar cell module, but also has a simple preparation process and low cost, can be mass-produced, and has a wide range of application markets. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] The present invention will be further described below in conjunction with embodiments with reference to the accompanying drawings.

[0048] Figure 1 This is a cross-sectional schematic diagram of a single-block parallel-structured perovskite solar cell module in Example 1 of the present invention;

[0049] Figure 2 It is a schematic plan view of a single perovskite solar cell module with a parallel structure in Example 1 of the present invention;

[0050] Figure 3This is a schematic diagram of the battery assembly structure of a plurality of perovskite solar cell modules connected in series in parallel in Example 1 of the present invention;

[0051] Figure 4 This is a physical picture of the parallel structured perovskite solar cell module in Example 2 of the present invention;

[0052] Figure 5 This is a physical picture of a perovskite solar cell module with a parallel-series structure in Example 2 of the present invention;

[0053] Figure 6 The working JV curves of the parallel-series structured perovskite solar cell modules in Examples 2-3 of the present invention and Comparative Examples 1-2 are shown. DETAILED DESCRIPTION

[0054] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments.

[0055] Example 1

[0056] like Figure 1-3 As shown, the perovskite solar cell photovoltaic module based on the parallel-series structure provided by the present invention includes a plurality of battery modules connected in series by metal wires 14, each battery module includes a plurality of sub-batteries 10, a positive electrode 11, a negative electrode 12 and a partition area 13 connected in parallel, each sub-battery 10 is composed of a first conductive electrode 2, a first carrier transport layer 3, a perovskite active layer 4, a second carrier transport layer 5, a barrier layer 6 and a second conductive electrode 7, and the partition area 13 is between the second conductive electrodes 7 of two adjacent sub-batteries, and a plurality of independent sub-batteries 10 are connected in parallel by using a metal grid line 8 to connect the second conductive electrodes 7 of two adjacent sub-batteries in parallel, the first conductive electrode 2 leads to the positive electrode 11 of the battery module through an external metal electrode 9, and the second conductive electrode 7 leads to the negative electrode 12 of the battery module through the metal grid line 8 and the external metal electrode 9, and the external metal electrodes 9 at the positive and negative electrodes of the two adjacent battery modules are sequentially connected by using a metal wire 14, and a plurality of battery modules are connected in series, that is, a perovskite solar cell module with a parallel-series structure.

[0057] That is, the parallel structure perovskite solar cell module of the present invention is composed of a number of mutually independent sub-cells connected in parallel. The structure of each sub-cell includes a first electrode layer 2, a first carrier transport layer 3, a perovskite active layer 4, a second carrier transport layer 5, a barrier layer 6 and a second electrode layer 7 from bottom to top. Multiple sub-cells are connected in parallel to two adjacent second conductive electrodes 7 through metal grid lines 8 to obtain a single cell module. For ease of preparation, the entire cell module preparation process is carried out on a rigid glass substrate 1.

[0058] Therefore, in this embodiment, a single parallel-structured perovskite solar cell module is composed of a plurality of sub-cells 10, a positive electrode 11, a negative electrode 12 and a partition region 13; a series-structured perovskite solar cell assembly is composed of a plurality of battery modules with a parallel structure connected to external metal electrodes at the positive and negative electrodes using metal wires 14.

[0059] In this embodiment:

[0060] The first conductive electrode may be a hand-torn steel plate, a metal film or a carbon cloth electrode, wherein the hand-torn steel plate has a thickness of 0.01 to 0.05 mm and a square resistance of 4.5 to 13.0 mΩ / □.

[0061] The extremely thin hand-tearable steel plate in the present invention needs to be cleaned and surface-hydrophilic treated before being pasted on a rigid glass substrate.

[0062] The cleaning treatment of the first conductive electrode includes: using deionized water and isopropyl alcohol to ultrasonically clean the first conductive electrode for 15 minutes, and then blowing it dry with nitrogen; the hydrophilic treatment is to use a plasma cleaning machine to clean it for 50 to 100 seconds, and the power of the plasma cleaning machine is 180 to 220 W. Double-sided tape or PDMS film or other methods are used to completely adhere the ultra-thin steel plate to the rigid glass substrate.

[0063] The first carrier transport layer is an electron transport layer, and the second carrier transport layer is a hole transport layer, or in step (2), the first carrier transport layer is a hole transport layer, and the second carrier transport layer is an electron transport layer.

[0064] The first carrier transport layer or the second carrier transport layer is prepared by any one of magnetron sputtering, thermal evaporation, electron beam deposition, screen printing, slot die, inkjet printing, doctor blade coating, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition.

[0065] The electron transport layer is made of titanium dioxide, zinc oxide, cadmium sulfide, zinc sulfide, tin dioxide, indium trioxide, tungsten oxide, cerium oxide, C60, C70, [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 Any one of BM), carbon nanotubes (CNTs), graphene or their derivatives, dopants and composite materials, and the layer thickness is 5 to 40 nm.

[0066] The hole transport layer uses any one of nickel oxide, vanadium oxide, molybdenum oxide, copper sulfide, cuprous thiocyanate, copper oxide, cuprous oxide, cobalt oxide, scandium oxide, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3-hexylthiophene-2,5-diyl) (P3HT), polyethylenedioxythiophene (PEDOT), 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), self-assembled monolayers (SAMs), polyethylene glycol (PEG), polycaprolactone (PCL) or their derivatives, dopants and composite materials, and the layer thickness is 5 to 40 nm.

[0067] The perovskite active layer may be deposited on the first carrier transport layer by, but is not limited to, screen printing, slot die, inkjet printing, doctor blade coating, or chemical vapor deposition.

[0068] The perovskite deposition method can be a one-step method or a two-step method.

[0069] The perovskite active layer is made of a perovskite precursor solution containing AX, BX2, a mixture of AX and BX2, or a laminated structure of AX and BX2, wherein A is a methylamine group CH3NH3 + , ethylamino CH3CH2NH3 + 、CarboxamidinoylCH(NH2)2 + and guanidine C(NH2)3 + At least one short-chain organic cation containing an amine functional group, or A is Li + 、Na + , K + , Rb + 、Ag + , Cu + and Cs + At least one monovalent inorganic cation in 2+ Sn 2+ , Pb 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cu 2+ , Fe 2+ , Mn 2 + 、Zn 2+ 、Co 2+ and Ni 2+ At least one divalent metal ion, X is F - , Cl - 、CH3COO- Br - ,I - and SCN - At least one monovalent anion.

[0070] The precursor solution can be selected to have different concentrations, different material ratios, and different solvent ratios to meet different output power requirements.

[0071] The barrier layer is SnO2, and the barrier layer is prepared by atomic layer deposition, chemical vapor deposition, plasma enhanced chemical vapor deposition, etc. to avoid damaging the underlying structure during the deposition of the second conductive electrode. The thickness of the barrier layer is 10 to 30 nm.

[0072] The second conductive electrode is an indium tin oxide ITO, a fluorine-doped tin oxide FTO or an aluminum-doped zinc oxide AZO transparent conductive electrode.

[0073] The second conductive electrode is made by magnetron sputtering, chemical vapor deposition, plasma enhanced chemical vapor deposition or atomic layer deposition.

[0074] The mask is a conventional mask, and its pattern is complementary to the pattern of the second conductive electrode, for example Figure 1 As shown, the structure of the mask is similar to the blank part of the second conductive electrode. A metal baffle can be used as a mask to block the sputtering of the second conductive electrode. The shaded part is the sputtered second conductive electrode.

[0075] A plurality of independent sub-batteries are connected in parallel by connecting two adjacent second conductive electrodes in parallel using a metal grid line, wherein the material of the metal grid line is gold, silver, copper, aluminum, chromium or bismuth, and the metal grid line is obtained by thermal evaporation, conductive tape, physical welding or brushing conductive slurry.

[0076] That is, the parallel connection method is to use metal grid lines to directly connect the second conductive electrodes of each sub-battery. The material of the metal grid lines can be any one of metal materials with good conductive properties such as gold, silver, copper, aluminum, chromium, bismuth, etc. The metal grid line processing method can be any one of thermal evaporation, conductive tape, physical welding, brushing conductive silver paste, etc. The design of the metal grid lines needs to take into account the subsequent external metal electrodes.

[0077] The external metal electrode is a conductive metal tape or a conductive silver paste.

[0078] The external metal electrode can be made by using conductive metal tape or coating conductive silver paste. The series connection of multiple battery modules is to use metal wires with good conductivity such as gold, silver, copper, aluminum, chromium, etc. to connect in series in sequence through external metal electrodes.

[0079] Example 2

[0080] The method for preparing a perovskite solar cell photovoltaic module based on a parallel-series structure provided in this embodiment comprises the following steps:

[0081] like Figure 1 As shown, this embodiment is based on Figure 1 The structure shown is used to prepare a pin-type parallel structure perovskite solar cell module, where the first electrode layer is an extremely thin hand-torn steel plate. The specific preparation process is as follows:

[0082] (1) A 0.01 mm thick ultra-thin hand-torn steel plate is used as the first electrode layer. The size of the steel plate is 5 cm × 5 cm. The steel plate is cleaned by ultrasonic cleaning with deionized water and isopropyl alcohol for 15 minutes and then blown dry with nitrogen. Hydrophilic treatment: Use a plasma cleaner to clean for 100 seconds. The power of the plasma cleaner is 200 W. Use double-sided tape or PDMS film or other methods to completely adhere the ultra-thin steel plate to the rigid glass substrate.

[0083] (2) 1 mg of poly (3-hexylthiophene) (P3HT) was dissolved in 1 mL of chlorobenzene to prepare a 1 mg / mL P3HT solution, and a P3HT film was coated on a steel plate by a doctor blade method. The speed of the doctor blade was 7 mm / s, and the height of the doctor blade was 1300 μm. The doctor blade was coated at room temperature and the obtained wet film was annealed at 130° C. for 10 minutes. The obtained hole transport layer had a thickness of 30 nm.

[0084] (3) Dissolve methylamino hydroiodide (FAI), lead iodide (PbI2), methylammonium chloride (MACI), CsI (cesium iodide), and methylammonium bromide (MABr) in dimethylformamide (DMF): dimethyl sulfoxide (DMSO) = 4:1 (volume ratio) in a certain proportion to prepare a perovskite precursor solution. The perovskite film was prepared by a doctor blade coating method with a doctor blade speed of 6 mm / s. The doctor blade height was 2500 μm, and the coating was performed at room temperature. The obtained wet film was annealed at 100 °C for 60 minutes. The thickness of the obtained perovskite film was 550 nm.

[0085] (4) C60 is evaporated on the perovskite active layer by thermal evaporation. The evaporation rate is Thickness: 40nm;

[0086] (5) The C60-deposited device was transferred to an atomic layer deposition system, and 20 nm SnO2 was deposited at 90 °C using a precursor of tetrakis(dimethylamino)tin (TDMASn) and deionized water;

[0087] (6) Use a mask plate (the mask plate is a conventional mask plate, and its pattern is complementary to the pattern of the second conductive electrode, such as Figure 1As shown, the structure of the mask is similar to the blank part between the second conductive electrodes. A metal baffle can be used as a mask to block the sputtering of the second conductive electrode. The shaded part is the sputtered second conductive electrode, the same below). A layer of ITO is sputtered on SnO2 by magnetron sputtering to form the second conductive electrode. The magnetron sputtering ITO has an argon gas flow rate of 18.22 sccm, a sputtering power supply power of 149 W, a sputtering time of 10 minutes, and a film thickness of 60 nm.

[0088] The second conductive electrode is composed of a plurality of independent conductive electrodes, and a partition area 13 is provided between two adjacent conductive electrodes, and the width of the partition area is 0.1 cm, thereby forming a plurality of independent sub-batteries;

[0089] Each independent subcell is composed of a first conductive electrode, a first carrier transport layer, a perovskite active layer, a second carrier transport layer, a barrier layer and a second conductive electrode;

[0090] (7) Pasting copper tape on the ITO surface as a metal grid line to connect multiple sub-cells in parallel, the size of the sub-cell is 5 cm × 0.5 cm, each sub-cell is 0.1 cm apart, the metal grid line is 4.7 cm long and 0.2 cm wide, then pasting copper tape on the surface of the metal grid line as an external metal electrode to lead out the negative electrode, and pasting copper tape on the surface of the first conductive electrode as an external metal electrode to lead out the positive electrode, forming a single parallel structure battery module;

[0091] (8) Use copper wires to sequentially connect the external metal electrodes at the positive and negative poles of two adjacent battery modules, and connect the three battery modules in series to obtain a parallel-series structure perovskite solar cell module. The actual picture of the parallel structure perovskite solar cell module is as follows: Figure 4 As shown, the actual picture of the parallel-series structure of the perovskite solar cell module is as follows Figure 5 As shown;

[0092] (9) Measure the output open circuit voltage (V OC ) is 1.06V, current density (J sc ) is 19.42mA.cm -2 , fill factor (FF) is 69.56%, and photoelectric conversion efficiency (PCE) is 14.32%. Figure 6 shown.

[0093] Example 3

[0094] In this embodiment, a perovskite solar cell module with a nip-type parallel structure is prepared. The first electrode layer is an extremely thin hand-torn steel plate. The specific preparation process is as follows:

[0095] (1) Similar to Example 2, a 0.01 mm thick ultra-thin hand-torn steel plate was used as the first electrode layer. The size of the steel plate was 5 cm×5 cm. The steel plate was cleaned: the hand-torn steel plate was ultrasonically cleaned with deionized water and isopropyl alcohol for 15 minutes, and then dried with nitrogen gas; hydrophilic treatment: a plasma cleaning machine was used for cleaning for 100 s. The power of the plasma cleaning machine was 200 W. Double-sided tape or PDMS film or other methods were used to completely adhere the ultra-thin steel plate to the rigid glass substrate;

[0096] (2) diluting the purchased aqueous tin oxide nanocolloid with a mass fraction of 15% with deionized water at a ratio of 1:3 (volume ratio) to prepare a tin oxide aqueous solution, heating the hand-torn steel plate substrate at 150° C., spraying a layer of tin oxide film on the substrate using a high-pressure spray gun, and annealing the film at 150° C. for 60 minutes. The prepared tin oxide film has a thickness of 40 nm;

[0097] (3) Similar to Example 2, the treatment method for the perovskite active layer is still prepared by the scraping method. The precursor solution of the perovskite is methyl iodide (FAI), lead iodide (PbI2), methyl ammonium chloride (MACI), cesium iodide (CsI), dissolved in dimercaptoethanol (2ME): N-methylpyrrolidone (NMP) = 23:2 (volume ratio) according to a certain ratio, and the scraper speed is 6mm / s. The scraper height is 2500μm, and the scraping is carried out at room temperature and the obtained wet film is annealed at 100℃ for 60 minutes. The thickness of the obtained perovskite active layer is 500nm;

[0098] (4) Dissolve 10 mg of poly (4-phenyl) (2,4,6-trimethylphenyl) amine) (PTAA) in 1 mL of chlorobenzene to prepare a 10 mg / mL PTAA solution, and use a doctor blade method to prepare a hole transport layer on the perovskite active layer. The doctor blade speed is 6 mm / s. The doctor blade height is 2600 μm. The doctor blade is applied at room temperature and the obtained wet film is annealed at 130°C for 10 minutes. The thickness of the obtained PTAA layer is 35 nm.

[0099] (5) The device was transferred to an atomic layer deposition system and 20 nm of SnO2 was deposited at 90 °C using a precursor of tetrakis(dimethylamino)tin (TDMASn) and deionized water.

[0100] (6) Using a mask, a layer of ITO was sputtered on SnO2 by magnetron sputtering. The magnetron sputtering ITO argon gas flow rate was 18.22 sccm, the sputtering power was 149 W, the sputtering time was 10 minutes, and the film thickness was 60 nm;

[0101] (7) Pasting copper tape on the ITO surface as a metal grid line to connect multiple sub-cells in parallel. The size of the sub-cell is 5 cm × 0.5 cm. Each sub-cell is 0.1 cm apart. The metal grid line is 4.7 cm long and 0.2 cm wide. Then, paste copper tape on the metal grid line and the surface of the positive electrode area as an external metal electrode to form a single parallel structure battery module;

[0102] (8) Using copper wires to sequentially connect external metal electrodes at the positive and negative electrodes of adjacent battery modules, and connecting multiple modules in series to obtain a perovskite solar cell module with a parallel-series structure;

[0103] (9) Measure the output open circuit voltage (V OC ) is 1.08V, and the current density (Jsc) is 21.81mA.cm -2 , fill factor (FF) is 67.18%, and photoelectric conversion efficiency (PCE) is 15.92%. Figure 6 shown.

[0104] Comparative Example 1

[0105] like Figure 1 As shown, this example is based on Figure 1 The structure shown is used to prepare a pin-type parallel structure perovskite solar cell module, where the first electrode layer is PEN-ITO. The specific preparation process is as follows:

[0106] (1) Using a commonly used PEN-ITO film as the first electrode layer, the size is 5 cm × 5 cm, and the PEN-ITO film is completely bonded to a rigid glass substrate using double-sided tape or PDMS film or other methods;

[0107] (2) 1 mg of poly (3-hexylthiophene) (P3HT) was dissolved in 1 mL of chlorobenzene to prepare a 1 mg / mL P3HT solution, and a layer of P3HT film was spin-coated on the ITO film by spin coating. The spin coating speed was 500 rpm for 5 seconds and 3000 rpm for 30 seconds. The spin coating was performed at room temperature and the obtained wet film was annealed at 130°C for 10 minutes. The obtained hole transport layer had a thickness of 30 nm.

[0108] (3) Dissolve methylamino hydroiodide (FAI), lead iodide (PbI2), methylammonium chloride (MACI), cesium iodide (CsI), and methylammonium bromide (MABr) in dimethylformamide (DMF): dimethyl sulfoxide (DMSO) = 4:1 in a certain ratio to prepare a perovskite precursor solution. The perovskite film was prepared by spin coating at a speed of 1000 rpm for 10 seconds, 5000 rpm for 30 seconds, and chlorobenzene antisolvent was added in the last 10 seconds. Spin coating was performed at room temperature and the obtained wet film was annealed at 100°C for 60 minutes. The thickness of the obtained perovskite film was 650 nm.

[0109] (4) C60 is evaporated on the perovskite active layer by thermal evaporation. The evaporation rate is Thickness: 40nm.

[0110] (5) The device was transferred to an atomic layer deposition system and 20 nm of SnO2 was deposited at 90 °C using a precursor of tetrakis(dimethylamino)tin (TDMASn) and deionized water.

[0111] (6) Using a customized mask, a layer of ITO was sputtered on SnO2 by magnetron sputtering. The argon flow rate of magnetron sputtering ITO was 18.22 sccm, the sputtering power was 149 W, the sputtering time was 10 minutes, and the film thickness was 60 nm.

[0112] (7) Pasting copper tape on the ITO surface as a metal grid line to connect multiple sub-cells in parallel. The size of the sub-cell is 5 cm × 0.5 cm. Each sub-cell is 0.1 cm apart. The metal grid line is 4.7 cm long and 0.2 cm wide. Then, paste copper tape on the metal grid line and the surface of the positive electrode area as an external metal electrode to form a single parallel structure battery module;

[0113] (8) Using copper wires to sequentially connect external metal electrodes at the positive and negative electrodes of adjacent battery modules, and connecting multiple modules in series to obtain a perovskite solar cell module with a parallel-series structure;

[0114] (9) Measure the output open circuit voltage (V OC ) is 1.06V, current density (J sc ) is 20.15mA.cm -2 , fill factor (FF) is 68.24%, and photoelectric conversion efficiency (PCE) is 14.67%. Figure 6 shown.

[0115] Comparative Example 2

[0116] In this embodiment, a nip-type parallel structure perovskite solar cell module is prepared, and the first conductive electrode layer is PEN-ITO. The specific preparation process is as follows:

[0117] (1) Using a commonly used PEN-ITO film as the first electrode layer, the size is 5 cm × 5 cm, and the PEN-ITO film is completely bonded to a rigid glass substrate using double-sided tape or PDMS film or other methods;

[0118] (2) diluting the purchased 15% mass fraction aqueous tin oxide nanocolloid with deionized water in a ratio of 1:3 to prepare a tin oxide aqueous solution, and preparing a tin oxide film on the PEN-ITO film by spin coating, with a spin coating rate of 500 rpm for 5 seconds and 4000 rpm for 30 seconds. The film was annealed at 150° C. for 60 minutes. The prepared tin oxide film had a thickness of 40 nm;

[0119] (3) Similar to Example 4, the spin coating method is still used for the treatment of the perovskite active layer. The precursor solution of the perovskite is prepared by dissolving methyl iodide (FAI), lead iodide (PbI2), methyl ammonium chloride (MACI), and cesium iodide (CsI) in a certain ratio of dimercaptoethanol (2ME): N-methylpyrrolidone (NMP) = 23:2. The spin coating speed is 1000 rpm for 10 seconds, 5000 rpm for 30 seconds, and chlorobenzene anti-solvent is added dropwise for the last 10 seconds. The spin coating is carried out at room temperature and the obtained wet film is annealed at 100°C for 60 minutes. The thickness of the obtained perovskite active layer is 650 nm.

[0120] (4) 10 mg of poly (3-hexylthiophene) (P3HT) was dissolved in 1 mL of chlorobenzene to prepare a 10 mg / mL P3HT solution. The hole transport layer was prepared on the perovskite active layer by spin coating. The spin coating speed was 500 rpm for 5 seconds and 3000 rpm for 30 seconds. The wet film was annealed at 130°C for 10 minutes. The thickness of the obtained P3HT film was 35 nm.

[0121] (5) The device was transferred to an atomic layer deposition system and a 20 nm SnO2 barrier layer was deposited at 90 °C using a precursor of tetrakis(dimethylamino)tin (TDMASn) and deionized water;

[0122] (6) Using a mask, a layer of ITO was sputtered on SnO2 by magnetron sputtering. The magnetron sputtering ITO argon gas flow rate was 18.22 sccm, the sputtering power was 149 W, the sputtering time was 10 minutes, and the film thickness was 60 nm;

[0123] (7) Pasting copper tape on the ITO surface as a metal grid line to connect multiple sub-cells in parallel, the size of the sub-cell is 5 cm × 0.5 cm, each sub-cell is 0.1 cm apart, and the metal grid line is 4.7 cm long and 0.2 cm wide; then pasting copper tape on the metal grid line and the surface of the positive electrode area as an external metal electrode to form a single parallel structure battery module;

[0124] (8) Using copper wires to sequentially connect external metal electrodes at the positive and negative electrodes of adjacent battery modules, and connecting multiple modules in series to obtain a perovskite solar cell module with a parallel-series structure;

[0125] (9) Measure the output open circuit voltage (V OC) is 1.07V, and the current density (Jsc) is 19.84mA.cm -2 , fill factor (FF) is 64.16%, and photoelectric conversion efficiency (PCE) is 13.59%. Figure 6 shown.

[0126] By comparing Examples 2-3 with Comparative Examples 1-2, it can be seen that the use of an ultra-thin hand-torn steel plate as the first electrode layer instead of the commonly used PEN-ITO flexible conductive electrode not only does not reduce the photoelectric conversion efficiency of the device, but is improved to a certain extent, indicating the feasibility of the idea of ​​using an ultra-thin hand-torn steel plate as the first electrode layer proposed by the present invention. At the same time, since the flexible PEN-ITO conductive electrode is easily deformed by heat during the preparation process, it is impossible to use the scraping method with a wider range of applications to prepare related devices, and the deformation of the flexible PEN-ITO can easily lead to local circuit instability. The use of this hand-torn steel plate can better solve this problem. Therefore, the present invention adopts a preparation method with a wider range of applications to solve the problems existing in the traditional preparation process. At the same time, the efficiency of the prepared device is not significantly reduced, and costs are saved.

[0127] It should be pointed out that the above embodiments are only further explanations and illustrations of the present invention, rather than limitations. For example, the use of extremely thin hand-torn steel plates to replace conventional transparent conductive electrodes mentioned in the present invention can also be replaced by other conductive substrates with good conductivity and certain flexibility; the carrier transport layer is not limited to some substances mentioned in the present invention; the regulation of the perovskite active layer can be regulated according to specific circumstances, and the regulation of different perovskite active layers can meet the regulation of different output voltages and output currents; the choice of metal grid lines in the present invention can be replaced by different conductive materials; the method of using metal grid lines to connect multiple sub-batteries in parallel can also be replaced by other simple parallel methods, as long as the purpose of parallel connection is achieved. Therefore, any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A method for preparing a perovskite solar cell photovoltaic module based on a parallel-series structure, characterized in that: The following steps are involved: (1) cleaning and hydrophilizing the first conductive electrode; (2) sequentially disposing a first carrier transport layer, a perovskite active layer, and a second carrier transport layer on the first conductive electrode; (3) providing a blocking layer on the second carrier transport layer; (4) using a mask plate to set a plurality of second conductive electrodes on the barrier layer, with a partition area provided between two adjacent second conductive electrodes, to form a plurality of independent sub-cells; Each independent sub-cell includes, from bottom to top, a first conductive electrode, a first carrier transport layer, a perovskite active layer, a second carrier transport layer, a blocking layer and a second conductive electrode; (5) using metal grid lines to connect a number of independent sub-batteries in parallel by connecting two adjacent second conductive electrodes in parallel to form a battery module, arranging an external metal electrode on the surface of the first conductive electrode to lead out the positive electrode of the battery module, and arranging an external metal electrode on the surface of the metal grid lines to lead out the negative electrode of the battery module; (6) Using metal wires to sequentially connect the external metal electrodes at the positive and negative poles of two adjacent battery modules, multiple battery modules are connected in series to obtain a perovskite solar cell module based on a parallel-series structure.

2. The method for preparing a perovskite solar cell photovoltaic module based on a parallel-series structure according to claim 1, characterized in that: The first conductive electrode described in step (1) is a hand-tearable steel plate, the thickness of the hand-tearable steel plate is 0.01-0.05 mm, and the square resistance is 4.5-13.0 mΩ / □.

3. The method for preparing a perovskite solar cell photovoltaic module based on a parallel-series structure according to claim 1, characterized in that: In step (2), the first carrier transport layer is an electron transport layer, and the second carrier transport layer is a hole transport layer, or in step (2), the first carrier transport layer is a hole transport layer, and the second carrier transport layer is an electron transport layer; the first carrier transport layer or the second carrier transport layer is prepared by magnetron sputtering, thermal evaporation, electron beam deposition, screen printing, slit coating, inkjet printing, blade coating, chemical vapor deposition, plasma enhanced chemical vapor deposition or atomic layer deposition; the electron transport layer in step (2) is prepared by titanium dioxide, zinc oxide, cadmium sulfide, zinc sulfide, tin dioxide, indium trioxide, tungsten oxide, cerium oxide, carbon 60, carbon 70, [6,6]-phenyl-C61-butyric acid methyl ester, carbon nanotubes tube, graphene or any one of their derivatives, dopants or composite materials, the thickness of the electron transport layer is 5 to 40 nm; the hole transport layer in step (2) uses any one of nickel oxide, vanadium oxide, molybdenum oxide, copper sulfide, cuprous thiocyanate, copper oxide, cuprous oxide, cobalt oxide, scandium oxide, poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] PTAA, poly (3-hexylthiophene-2,5-diyl), polyethylene dioxythiophene, 2,2',7,7'-tetrakis [N,N-di (4-methoxyphenyl) amino] -9,9'-spirobifluorene, self-assembled monolayer, polyethylene glycol, polycaprolactone or any one of their derivatives, dopants or composite materials, the thickness of the hole transport layer is 5 to 40 nm.

4. The method for preparing a perovskite solar cell photovoltaic module based on a parallel-series structure according to claim 1, characterized in that: The perovskite active layer in step (2) is made of a perovskite precursor solution containing AX, BX2, a mixture of AX and BX2, or a laminated structure of AX and BX2, wherein A is a methylamine group CH3NH3 + , ethylamino CH3CH2NH3 + 、Carboxamidinoyl CH(NH2)2 + and guanidine C(NH2)3 + At least one short-chain organic cation containing an amine functional group, or A is Li + 、Na + , K + , Rb + 、Ag + , Cu + and Cs + At least one monovalent inorganic cation in 2+ Sn 2+ , Pb 2+ 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cu 2+ , Fe 2+ , Mn 2+ 、Zn 2+ 、Co 2+ and Ni 2+ At least one divalent metal ion, X is F - , Cl - 、CH3COO - Br - ,I - and SCN - At least one monovalent anion in the perovskite active layer; the perovskite active layer is prepared by screen printing, slit coating, inkjet printing, doctor blade coating or chemical vapor deposition; the precursor solution is prepared by selecting different concentrations, different material ratios, and different solvent ratios to meet different output power requirements.

5. The method for preparing a perovskite solar cell photovoltaic module based on a parallel-series structure according to claim 1, characterized in that: The barrier layer in step (3) is SnO2, and the barrier layer is prepared by atomic layer deposition, chemical vapor deposition, plasma enhanced chemical vapor deposition, etc., and the thickness of the barrier layer is 10 to 30 nm; the second conductive electrode in step (4) is an indium tin oxide ITO, fluorine-doped tin oxide FTO or aluminum-doped zinc oxide AZO transparent conductive electrode; the second conductive electrode is prepared by magnetron sputtering, chemical vapor deposition, plasma enhanced chemical vapor deposition or atomic layer deposition.

6. The method for preparing a perovskite solar cell photovoltaic module based on a parallel-series structure according to claim 1, characterized in that: In step (5), a plurality of independent sub-batteries are connected in parallel by connecting two adjacent second conductive electrodes in parallel using a metal grid line, wherein the material of the metal grid line is gold, silver, copper, aluminum, chromium or bismuth, and the metal grid line is obtained by thermal evaporation, conductive tape, physical welding or brushing conductive paste; in step (6), the external metal electrode is a conductive metal, conductive tape or conductive silver paste.

7. A perovskite solar cell photovoltaic module based on a parallel-series structure, characterized in that: The method is prepared by any one of claims 1 to 6.

8. A perovskite solar cell photovoltaic module based on a parallel-series structure, characterized in that: The invention comprises a plurality of battery modules connected in series by metal wires, each battery module comprises a plurality of sub-batteries, a positive electrode, a negative electrode and a partition area connected in parallel, each sub-battery comprises a first conductive electrode, a first carrier transport layer, a perovskite active layer, a second carrier transport layer, a barrier layer and a second conductive electrode, the second conductive electrodes of two adjacent sub-batteries are provided as a partition area, a plurality of independent sub-batteries are connected in parallel by connecting the second conductive electrodes of two adjacent sub-batteries in parallel by metal grid lines, the first conductive electrode leads out the positive electrode of the battery module through an external metal electrode, the second conductive electrode leads out the negative electrode of the battery module through a metal grid line and an external metal electrode, the external metal electrodes at the positive and negative electrodes of two adjacent battery modules are connected in sequence by metal wires, and a plurality of battery modules are connected in series, thus forming a perovskite solar cell module with a parallel-series structure.

9. The perovskite solar cell photovoltaic module based on the parallel-series structure according to claim 8, characterized in that: The output voltage and current of the component are regulated by adjusting the type and thickness of the perovskite active layer, and the output power is regulated by connecting a number of single battery modules in series to meet different power supply requirements; the first conductive electrode or the second conductive electrode is a transparent conductive electrode to prepare a semi-transparent or fully transparent perovskite solar cell device.

10. The perovskite solar cell photovoltaic module based on a parallel-series structure according to claim 8, characterized in that: The conventional size of each battery module is 5cm×5cm to 50cm×50cm, each battery module includes 6 to 20 sub-batteries, the width of the partition area is 0.1 to 0.5cm, and the width of the metal grid line is 0.1 to 0.5cm.

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