A perovskite solar cell photovoltaic module based on a parallel-series structure and its fabrication method

Abstract

This invention discloses a perovskite solar cell photovoltaic module based on a parallel-series structure and its fabrication method. The invention first fabricates a perovskite solar cell module with a parallel structure. Then, positive and negative electrodes are led out from each individual cell module via external metal electrodes. Multiple cell modules are then connected in series using metal wires. The external metal electrodes can be selected, but are not limited to, physical welding of conductive metal, conductive metal tape, or application of conductive silver paste. This invention proposes a perovskite solar cell module with a parallel-series structure, using extremely thin, flexible, tearable steel plates instead of traditional transparent conductive electrodes. This not only significantly improves the output performance of the perovskite solar module but also simplifies the fabrication process, reduces costs, allows for large-scale production, and has a wide range of applications. Furthermore, this parallel-series structure avoids the problem of large-area failure of the entire device caused by the failure of a single sub-cell.

Description

Technical Field

[0001] This invention belongs to the field of photovoltaic cell technology, specifically relating to a perovskite solar cell photovoltaic module based on a parallel-series structure and its preparation method. Background Technology

[0002] Perovskite solar cells have attracted widespread attention from experts in related fields since their inception due to their numerous advantages. To further promote the commercial application of perovskite solar cells, research on large-area perovskite solar cell modules has become increasingly active. Currently, most large-area perovskite solar cell modules still use a series connection method to link several sub-cells together to obtain higher output power. However, the fabrication process of series-connected cell modules requires laser etching equipment, which undoubtedly increases production costs, causes some environmental pollution, and seriously reduces the yield and batch stability of cell production.

[0003] The commercial application of large-area perovskite solar cell modules mainly involves the fabrication of 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 (ITO) is preferred. 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. Rigid ITO conductive substrates limit 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, the differences in flexibility and interface contact between the substrates and various functional layers during repeated bending result in low mechanical properties; (2) Processing temperature limitation: Since the glass transition temperature of commonly used flexible ITO substrates is low, the processing temperature needs to be controlled within a low temperature range. This limitation greatly narrows the range of material selection and hinders the transfer of mature technology from glass substrates to flexible substrates; (3) Conductivity problem: Although materials such as ITO are commonly used in flexible perovskite solar cells on flexible substrates, they often crack during mechanical deformation, which affects their conductivity and transmittance.

[0004] The tunable optical bandgap of the perovskite active layer in perovskite solar cells is one of the reasons for their enduring popularity. Typically, the energy levels and optical bandgap of adjacent layers in a perovskite solar cell device need to meet appropriate values ​​to ensure efficient carrier transport, thereby achieving higher voltage and current and thus higher photoelectric conversion efficiency. Adjusting the bandgap and energy levels of the perovskite active layer is a common method. In this invention, by adjusting the concentration, content, type, and ratio of substances in the perovskite precursor solution, as well as the amount and type of solvent, perovskite active layers with different energy levels and optical bandgap can be obtained. This allows for effective control of the device's voltage and current to meet different output power requirements. The perovskite precursor solution typically includes organic / inorganic salts or single-crystal / polycrystalline perovskite seeds that constitute the perovskite active layer, as well as solvents. Common organic / inorganic salts include methylamine hydroiodate, imidazolium hydroiodate, stannous iodide, lead iodide, and cesium iodide; common seed crystals include imidazolium perovskite seed crystals and methylamine perovskite seed crystals; common solvents include dimethyl sulfoxide, dimethylformamide, acetonitrile, dimercaptoethanol, and N-methylpyrrolidone. Adjusting the composition of the precursor solution allows for simultaneous adjustment of parameters such as the thickness, band gap, and energy level of the perovskite active layer, meeting different output power requirements. Summary of the Invention

[0005] The purpose of this invention is to provide a method for fabricating perovskite solar cell photovoltaic modules based on a parallel-series structure.

[0006] Another objective of this invention is to provide a perovskite solar cell photovoltaic module based on a parallel-series structure prepared using the above method.

[0007] The first objective of this invention can be achieved through 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) The first conductive electrode is cleaned and hydrophilicized;

[0009] (2) A first carrier transport layer, a perovskite active layer and a second carrier transport layer are sequentially disposed on the first conductive electrode.

[0010] (3) A barrier layer is set on the second carrier transport layer;

[0011] (4) A mask plate is used to set several second conductive electrodes on the barrier layer, and a partition area is provided between two adjacent second conductive electrodes to form several independent sub-cells.

[0012] Each independent sub-cell, from bottom to top, includes 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.

[0013] (5) A number of independent sub-cells are connected in parallel by using metal grid lines to form a battery module. An external metal electrode is provided on the surface of the first conductive electrode to lead out the positive electrode of the battery module, and an external metal electrode is provided on the surface of the metal grid lines to lead out the negative electrode of the battery module.

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

[0015] In the above-mentioned method for fabricating perovskite solar cell photovoltaic modules based on parallel-series structures:

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

[0017] Preferably, the thickness of the ultra-thin tear-resistant steel plate selected in this invention is 0.01 to 0.05 mm, and the sheet resistance is 4.5 to 13.0 mΩ / □.

[0018] Furthermore, the extremely thin, tearable steel plate in this invention needs to be cleaned and treated with a hydrophilic surface before being pasted onto a rigid glass substrate.

[0019] In a preferred embodiment of the present invention, the cleaning process of the first conductive electrode includes: ultrasonically cleaning the first conductive electrode with deionized water and isopropanol for 15 minutes, and then drying it with nitrogen gas; the hydrophilic treatment is performed by cleaning with a plasma cleaner for 50-100 seconds, the plasma cleaner having a power of 180-220W. The ultra-thin steel plate is completely adhered to the rigid glass substrate using double-sided tape, PDMS film, or other methods.

[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 coating, inkjet printing, doctor blade coating, chemical vapor deposition, plasma-enhanced chemical vapor deposition, or atomic layer deposition.

[0022] Preferably, the electron transport layer in step (2) uses titanium dioxide, zinc oxide, cadmium sulfide, zinc sulfide, tin dioxide, indium trioxide, tungsten oxide, cerium oxide, C60, C70, and methyl [6,6]-phenyl-C61-butyrate (PC). 61 The layer is made of any one of the following materials: BM, carbon nanotubes (CNTs), graphene or their derivatives, dopants and composites, with a thickness of 5 to 40 nm.

[0023] Preferably, the hole transport layer in step (2) is made of any one of the following materials: 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'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD), self-assembled monolayers (SAMs), polyethylene glycol (PEG), polycaprolactone (PCL), or their derivatives, dopants, and composite materials, and the thickness of the layer is 5–40 nm.

[0024] Preferably, in step (2), screen printing, slot die coating, inkjet printing, blade coating, and chemical vapor deposition can be used to deposit a perovskite active layer on the first carrier transport layer.

[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 prepared using a perovskite precursor solution containing AX, BX2, a mixture of AX and BX2, or a stacked structure of AX and BX2, wherein A is methylamino CH3NH3. + , Ethylamino group CH3CH2NH3 + , Methamidinyl CH(NH2)2 + and guanidinyl C(NH2)3 + At least one short-chain organic cation containing an amino functional group, or A is Li + Na + K + 、Rb + Ag + Cu + and Cs + At least one monovalent inorganic cation in the composition, where B is Ge 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 in it, where X is F - Cl - CH3COO - ,Br - I - and SCN - At least one monovalent anion in it.

[0027] Preferably, the precursor solution can be configured with different concentrations, different substance 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 10-30 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 prepared by magnetron sputtering, chemical vapor deposition, plasma-enhanced chemical vapor deposition, or atomic layer deposition.

[0031] Preferably, in step (5), a number of independent sub-cells are connected in parallel by means of metal grid lines and two adjacent second conductive electrodes. The metal grid lines are made of gold, silver, copper, aluminum, chromium or bismuth. The metal grid lines are obtained by means of hot evaporation, conductive tape, physical welding or brushing conductive paste.

[0032] That is, the parallel connection method described in step (5) is to directly connect the second conductive electrodes of each sub-cell using metal grid wires. The metal grid wires can be any of the following metal materials with good conductivity: gold, silver, copper, aluminum, chromium, bismuth, etc. The metal grid wires can be processed by any of the following methods: hot evaporation, conductive tape, physical welding, brushing conductive silver paste, etc.

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

[0034] Furthermore, in step (5), the external metal electrode can be selected by physical welding of conductive metal, conductive metal tape, or scraping conductive silver paste, etc. The series connection of multiple battery modules is to use metal wires with good conductivity such as gold, silver, copper, aluminum, and chromium to connect the external metal electrodes in series.

[0035] The mechanism of this invention is as follows: First, a perovskite solar cell module with a parallel structure is prepared. The module is composed of several independent sub-cells connected in parallel. Each sub-cell consists of, 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. The parallel structure means that each sub-cell is connected to the second conductive electrode through metal grid lines to achieve the effect of parallel connection. Then, positive and negative electrodes are led out from the individual cell module through external metal electrodes, and multiple cell modules are connected in series using metal wires. The external metal electrodes can be selected, but are not limited to, physical welding of conductive metal, conductive metal tape, or application of conductive silver paste.

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

[0037] Preferably, the perovskite solar cell photovoltaic module based on a parallel-series structure includes several battery modules connected in series by metal wires. Each battery module includes several sub-cells connected in parallel, a positive electrode, a negative electrode, and a partition region. Each sub-cell consists 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. The partition region is between the second conductive electrodes of two adjacent sub-cells. Several independent sub-cells are connected in parallel by metal grid lines through the second conductive electrodes of two adjacent sub-cells. The first conductive electrode leads out to the positive electrode of the battery module through an external metal electrode. The second conductive electrode leads out to the negative electrode of the battery module through the metal grid lines and the external metal electrode. The external metal electrodes at the positive and negative electrodes of two adjacent battery modules are connected in series by metal wires, which constitutes a perovskite solar cell module with a parallel-series structure.

[0038] Preferably, in this invention, the output voltage and current of the photovoltaic module can be controlled by adjusting the type and thickness of the perovskite active layer, and the output power can be controlled by connecting several individual battery modules in series to meet different power supply requirements.

[0039] Preferably, the present invention can use a transparent conductive electrode as the first conductive electrode or the second 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 adjusted synchronously according to actual requirements.

[0041] In one preferred embodiment of the present invention, 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 and length of the metal grid line can be adjusted according to the actual situation, for example, the width is 0.1cm to 0.5cm.

[0042] The present invention has the following advantages:

[0043] (1) This invention focuses on innovatively selecting an extremely thin, tearable steel plate as the first conductive electrode. This extremely thin metal substrate not only has good electrical conductivity and flexibility, but is also inexpensive and has a simple device fabrication process, thus solving a series of problems caused by the selection of flexible substrates in flexible perovskite solar cell devices.

[0044] (2) This invention proposes a method for preparing a perovskite battery module based on a parallel structure, and achieves the purpose of adjustable output power of the module by connecting multiple battery modules in series. At the same time, it innovatively proposes to use a flexible hand-tearable steel plate, metal film, carbon cloth electrode, etc. to replace the traditional transparent conductive electrode.

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

[0046] (4) The perovskite solar cell module with a parallel-then-series structure proposed in this invention uses extremely thin, flexible, tearable steel plates to replace traditional transparent conductive electrodes, which not only greatly improves the output performance of the perovskite solar cell module, but also has a simple and low-cost manufacturing process, can be mass-produced, and has a wide range of applications. Attached Figure Description

[0047] The present invention will now be further described with reference to the accompanying drawings and embodiments.

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

[0049] Figure 2 This is a plan view of the perovskite solar cell module with a single-block parallel structure in Embodiment 1 of the present invention;

[0050] Figure 3This is a schematic diagram of the battery module structure of a perovskite solar cell module with multiple parallel structures connected in series in Embodiment 1 of the present invention;

[0051] Figure 4 This is a physical image of the perovskite solar cell module with a parallel structure in Embodiment 2 of the present invention;

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

[0053] Figure 6 The JV curves are for the operation of perovskite solar cell modules with parallel-series structures in Examples 2-3 and Comparative Examples 1-2 of this invention. Detailed Implementation

[0054] To make the technical problems, technical solutions, and beneficial effects of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0055] Example 1

[0056] like Figure 1-3 As shown, the perovskite solar cell photovoltaic module based on a parallel-series structure provided by the present invention includes several battery modules connected in series by metal wires 14. Each battery module includes several sub-cells 10 connected in parallel, a positive electrode 11, a negative electrode 12, and a partition region 13. Each sub-cell 10 consists 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. The partition region 13 is between the second conductive electrodes 7 of two adjacent sub-cells. Several independent sub-cells 10 are connected in parallel by metal grid lines 8 through the second conductive electrodes 7 of two adjacent sub-cells. The first conductive electrode 2 leads out the positive electrode 11 of the battery module through an external metal electrode 9. The second conductive electrode 7 leads out the negative electrode 12 of the battery module through the metal grid lines 8 and the external metal electrode 9. The external metal electrodes 9 at the positive and negative electrodes of two adjacent battery modules are connected in series by metal wires 14, which is a perovskite solar cell module with a parallel-series structure.

[0057] The perovskite solar cell module of this invention, with its parallel structure, is composed of several independent sub-cells connected in parallel. Each sub-cell, from bottom to top, 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. Multiple sub-cells are connected in parallel via metal grid lines 8, and adjacent second conductive electrodes 7 are connected in parallel to obtain a single cell module. For ease of fabrication, the entire cell module fabrication process is carried out on a rigid glass substrate 1.

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

[0059] In this embodiment:

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

[0061] In this invention, the extremely thin, tearable steel sheet needs to be cleaned and treated with a hydrophilic surface before it is pasted onto a rigid glass substrate.

[0062] The cleaning process for the first conductive electrode includes: ultrasonically cleaning the first conductive electrode with deionized water and isopropanol for 15 minutes, and then drying it with nitrogen gas; the hydrophilic treatment involves cleaning it with a plasma cleaner for 50-100 seconds, the plasma cleaner having a power of 180-220W. The ultra-thin steel plate is then completely adhered to the rigid glass substrate using double-sided tape, PDMS film, or other methods.

[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 or second carrier transport layer can be prepared by any one of the following methods: magnetron sputtering, thermal evaporation, electron beam deposition, screen printing, slot die coating, inkjet printing, doctor blade coating, chemical vapor deposition, plasma-enhanced chemical vapor deposition, or atomic layer deposition.

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

[0066] The hole transport layer uses any one of the following materials: 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'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD), self-assembled monolayers (SAMs), polyethylene glycol (PEG), polycaprolactone (PCL), or their derivatives, dopants, and composite materials. The thickness of this layer is 5–40 nm.

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

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

[0069] The perovskite active layer is prepared using a perovskite precursor solution containing AX, BX2, a mixture of AX and BX2, or a stacked structure of AX and BX2, wherein A is methylamino CH3NH3. + , Ethylamino group CH3CH2NH3 + , Methamidinyl CH(NH2)2 + and guanidinyl C(NH2)3 + At least one short-chain organic cation containing an amino functional group, or A is Li + Na + K + 、Rb + Ag + Cu + and Cs + At least one monovalent inorganic cation in the composition, where B is Ge 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 in it, where X is F - Cl - CH3COO- ,Br - I - and SCN - At least one monovalent anion in it.

[0070] The precursor solution can be configured with different concentrations, different substance ratios, and different solvent ratios to meet different output power requirements.

[0071] The barrier layer is SnO2, and it 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 10-30 nm.

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

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

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

[0075] Several independent sub-cells are connected in parallel by connecting two adjacent second conductive electrodes using metal grid lines. The metal grid lines are made of gold, silver, copper, aluminum, chromium, or bismuth and are obtained by hot evaporation, conductive tape, physical welding, or brushing conductive paste.

[0076] That is, the parallel connection method is to directly connect the second conductive electrodes of each sub-cell using metal grid wires. The metal grid wires can be any of the metal materials with good conductivity, such as gold, silver, copper, aluminum, chromium, and bismuth. The metal grid wires can be processed by any of the following methods: hot evaporation, conductive tape, physical welding, or brushing conductive silver paste. The design of the metal grid wires 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] External metal electrodes can be connected by conductive metal tape or by applying conductive silver paste. Multiple battery modules are connected in series by using metal wires with good conductivity, such as gold, silver, copper, aluminum, and chromium, through external metal electrodes.

[0079] Example 2

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

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

[0082] (1) Using an ultra-thin, tearable steel plate of 0.01 mm thickness as the first electrode layer, the steel plate is 5 cm × 5 cm in size. The steel plate is cleaned by ultrasonic cleaning with deionized water and isopropanol for 15 minutes and then dried with nitrogen. Hydrophilic treatment: Clean with a plasma cleaner for 100 seconds. The plasma cleaner has a power of 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) Dissolve 1 mg of poly(3-hexylthiophene) (P3HT) in 1 mL of chlorobenzene to prepare a 1 mg / mL P3HT solution. Use a blade coating method to coat a P3HT film on a steel plate. The blade speed is 7 mm / s and the blade height is 1300 μm. The coating is carried out at room temperature and the resulting wet film is annealed at 130 °C for 10 minutes. The hole transport layer thickness is 30 nm.

[0084] (3) A perovskite precursor solution was prepared by dissolving formamide hydroiodide (FAI), lead iodide (PbI2), methyl ammonium chloride (MACI), CsI (cesium iodide), and methyl ammonium bromide (MABr) in a dimethylformamide (DMF):dimethyl sulfoxide (DMSO) ratio of 4:1 (volume ratio). Perovskite films were prepared using a blade coating method with a blade speed of 6 mm / s and a blade height of 2500 μm. The coating was performed at room temperature, and the resulting wet film was annealed at 100 °C for 60 minutes, yielding a perovskite film thickness of 550 nm.

[0085] (4) C60 was deposited on the perovskite active layer using a thermal evaporation method, with a evaporation rate of... Thickness 40nm;

[0086] (5) Transfer the C60 vapor-deposited device to the atomic layer deposition system and deposit 20 nm SnO2 at 90 °C using tetra(dimethylamino)tin (TDMASn) and deionized water precursors.

[0087] (6) Use a photomask (a conventional photomask, the pattern of which complements 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 electrodes. The shaded part is the sputtered second conductive electrode (the same below). A layer of ITO is sputtered on SnO2 to form the second conductive electrode using magnetron sputtering. The magnetron sputtering ITO argon flow rate is 18.22 sccm, the sputtering power is 149W, the sputtering time is 10 minutes, and the film thickness is 60nm.

[0088] The second conductive electrode is composed of multiple independent conductive electrodes, and a partition region 13 is provided between two adjacent conductive electrodes. The width of the partition region is 0.1 cm, thereby forming multiple independent sub-cells.

[0089] Each independent sub-cell consists 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) Copper tape is pasted on the surface of ITO as a metal grid line to connect multiple sub-cells in parallel. The size of the sub-cell is 5cm×0.5cm, and each sub-cell is 0.1cm apart. The metal grid line is 4.7cm long and 0.2cm wide. Then, copper tape is pasted on the surface of the metal grid line as an external metal electrode to lead out the negative electrode. Copper tape is pasted on the surface of the first conductive electrode as an external metal electrode to lead out the positive electrode, forming a battery module with a single parallel structure.

[0091] (8) Connect the external metal electrodes at the positive and negative terminals of two adjacent battery modules in sequence using copper wires. Connect the three battery modules in series to obtain a perovskite solar cell module with a parallel-series structure. A physical image of the perovskite solar cell module with the parallel structure is shown below. Figure 4 As shown in the figure, a physical image of a perovskite solar cell module with a parallel-to-series structure is as follows. Figure 5 As shown;

[0092] (9) Measure the open-circuit voltage (V) of the component output of the two battery modules connected in series. OC The voltage is 1.06V and the current density (J) is 1.06V. sc The value is 19.42 mA.cm -2 The fill factor (FF) is 69.56%, and the photoelectric conversion efficiency (PCE) is 14.32%. Figure 6 As shown.

[0093] Example 3

[0094] This embodiment fabricates a nip-type parallel perovskite solar cell module. The first electrode layer is an extremely thin, tear-away steel plate. The specific fabrication process is shown below:

[0095] (1) Similar to Example 2, an ultra-thin tearable steel plate with a thickness of 0.01 mm was used as the first electrode layer. The size of the steel plate was 5 cm × 5 cm. The steel plate was cleaned by ultrasonic cleaning with deionized water and isopropanol for 15 minutes and then dried with nitrogen. Hydrophilic treatment: the steel plate was cleaned with a plasma cleaner for 100 seconds. The power of the plasma cleaner was 200 W. The ultra-thin steel plate was completely adhered to the rigid glass substrate by double-sided tape or PDMS film and other methods.

[0096] (2) Dilute the purchased 15% water-based tin oxide nanocolloid with deionized water at a ratio of 1:3 (volume ratio) to prepare an aqueous tin oxide solution. Tear the steel plate substrate by hand and heat it to 150°C. Use a high-pressure spray gun to spray a layer of tin oxide film onto the substrate. Anneal the film at 150°C for 60 minutes. The prepared tin oxide film has a thickness of 40nm.

[0097] (3) Similar to Example 2, the perovskite active layer was prepared by a blade coating method. The perovskite precursor solution was prepared by dissolving formamide hydroiodide (FAI), lead iodide (PbI2), methyl ammonium chloride (MACI), and cesium iodide (CsI) in a 23:2 volume ratio of dimercaptoethanol (2ME):N-methylpyrrolidone (NMP). The blade speed was 6 mm / s, the blade height was 2500 μm, and the coating was performed at room temperature. The resulting wet film was then annealed at 100°C for 60 minutes, resulting in a perovskite active layer thickness of 500 nm.

[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. Prepare a hole transport layer on the perovskite active layer using a blade coating method with a blade speed of 6 mm / s and a blade height of 2600 μm. The coating was performed at room temperature, and the resulting wet film was annealed at 130 °C for 10 minutes, resulting in a PTAA layer thickness of 35 nm.

[0099] (5) Transfer the device to an atomic layer deposition system and deposit 20 nm SnO2 at 90 °C using tetra(dimethylamino)tin (TDMASn) and deionized water precursors.

[0100] (6) Using a mask template, 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 149W, the sputtering time was 10 minutes, and the film thickness was 60 nm.

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

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

[0103] (9) Measure the open-circuit voltage (V) of the component output of the two battery modules connected in series. OC The voltage is 1.08V and the current density (Jsc) is 21.81 mA.cm. -2 The fill factor (FF) is 67.18% and the power conversion efficiency (PCE) is 15.92%. Figure 6 As shown.

[0104] Comparative Example 1

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

[0106] (1) Using a common PEN-ITO film as the first electrode layer, with a size of 5cm×5cm, the PEN-ITO film is completely bonded to the rigid glass substrate by using double-sided adhesive or PDMS film or other methods.

[0107] (2) Dissolve 1 mg of poly(3-hexylthiophene) (P3HT) in 1 mL of chlorobenzene to prepare a 1 mg / mL P3HT solution. Spin coat a P3HT film onto an ITO film using a spin coating method. The spin coating speed is 500 rpm for 5 seconds and 3000 rpm for 30 seconds. Spin coating is performed at room temperature and the resulting wet film is annealed at 130°C for 10 minutes. The hole transport layer thickness is 30 nm.

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

[0109] (4) C60 was deposited on the perovskite active layer using a thermal evaporation method, with a evaporation rate of... Thickness 40nm.

[0110] (5) Transfer the device to an atomic layer deposition system and deposit 20 nm SnO2 at 90 °C using tetra(dimethylamino)tin (TDMASn) and deionized water precursors.

[0111] (6) Using a custom mask template, 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 149W, the sputtering time was 10 minutes, and the film thickness was 60 nm.

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

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

[0114] (9) Measure the open-circuit voltage (V) of the component output of the two battery modules connected in series. OC The voltage is 1.06V and the current density (J) is 1.06V. sc The value is 20.15 mA / cm. -2 The fill factor (FF) is 68.24%, and the power conversion efficiency (PCE) is 14.67%. Figure 6 As shown.

[0115] Comparative Example 2

[0116] This embodiment fabricates a nip-type parallel perovskite solar cell module, with the first conductive electrode layer being PEN-ITO. The specific fabrication process is shown below:

[0117] (1) Using a common PEN-ITO film as the first electrode layer, with a size of 5cm×5cm, the PEN-ITO film is completely bonded to the rigid glass substrate by using double-sided adhesive or PDMS film or other methods.

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

[0119] (3) Similar to Example 4, the perovskite active layer was prepared by spin coating. The perovskite precursor solution was prepared by dissolving formamide hydroiodide (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 was 1000 rpm for 10 seconds, 5000 rpm for 30 seconds, and chlorobenzene antisolvent was added dropwise in the last 10 seconds. The spin coating was carried out at room temperature and the resulting wet film was annealed at 100°C for 60 minutes. The thickness of the perovskite active layer was 650 nm.

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

[0121] (5) Transfer the device to the atomic layer deposition system and deposit a 20 nm SnO2 barrier layer at 90 °C using a precursor of tetra(dimethylamino)tin (TDMASn) and deionized water.

[0122] (6) Using a mask template, 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 149W, the sputtering time was 10 minutes, and the film thickness was 60 nm.

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

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

[0125] (9) Measure the open-circuit voltage (V) of the component output of the two battery modules connected in series. OCThe voltage is 1.07V and the current density (Jsc) is 19.84 mA / cm². -2 The fill factor (FF) is 64.16% and the power conversion efficiency (PCE) is 13.59%. Figure 6 As shown.

[0126] By comparing Examples 2-3 with Comparative Examples 1-2, it can be seen that using an ultra-thin, hand-tearable steel plate as the first electrode layer instead of the commonly used PEN-ITO flexible conductive electrode not only does not decrease the photoelectric conversion efficiency of the device but also improves it to a certain extent, demonstrating the feasibility of the idea of ​​using an ultra-thin, hand-tearable steel plate as the first electrode layer proposed in this invention. Furthermore, since the flexible PEN-ITO conductive electrode is easily deformed by heat during the fabrication process, the more widely applicable scraping method cannot be used to fabricate related devices, and the deformation of flexible PEN-ITO can easily lead to local circuit instability. Using this hand-tearable steel plate can better solve this problem. Therefore, this invention adopts a more widely applicable fabrication method, solves the problems existing in traditional fabrication processes, and at the same time, the efficiency of the fabricated device does not decrease significantly, while saving costs.

[0127] It should be noted that the above embodiments are merely further explanations and illustrations of the present invention, and not limitations. For example, the use of extremely thin, tearable steel plates instead of conventional transparent conductive electrodes mentioned in the present invention can also be replaced by other conductive substrates with good conductivity and a certain degree of flexibility; the carrier transport layer is not limited to some of the materials mentioned in the present invention; the regulation of the perovskite active layer can be adjusted according to specific circumstances, and the regulation of different perovskite active layers can meet the regulation of different output voltages and output currents; the selection 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-cells in parallel can also be replaced by other simple parallel connection methods, as long as the purpose of parallel connection is achieved. Therefore, any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention should be considered equivalent substitutions and are included within the protection scope of the present invention.

Claims

1. A method for fabricating a perovskite solar cell photovoltaic module based on a parallel-series structure, characterized in that, Includes the following steps: (1) The first conductive electrode is cleaned and hydrophilicized; (2) A first carrier transport layer, a perovskite active layer, and a second carrier transport layer are sequentially disposed on the first conductive electrode. (3) A barrier layer is set on the second carrier transport layer; (4) A number of second conductive electrodes are set on the barrier layer using a mask plate, and a partition area is provided between two adjacent second conductive electrodes to form several independent sub-cells; Each independent sub-cell, from bottom to top, includes 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. (5) Several independent sub-cells are connected in parallel by using metal grid lines to connect two adjacent second conductive electrodes in parallel. A battery module is formed, and an external metal electrode is provided on the surface of the first conductive electrode to lead out the positive electrode of the battery module, and an external metal electrode is provided on the surface of the metal grid line to lead out the negative electrode of the battery module. (6) Connect the external metal electrodes at the positive and negative terminals of two adjacent battery modules in sequence with metal wires, and connect multiple battery modules in series to obtain a perovskite solar cell module based on a parallel-series structure.

2. The method for fabricating a perovskite solar cell photovoltaic module based on a parallel-series structure according to claim 1, characterized in that, The first conductive electrode mentioned in step (1) is a hand-torn steel plate with a thickness of 0.01~0.05mm and a sheet resistance of 4.5~13.0mΩ / □.

3. The method for fabricating 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, slot coating, inkjet printing, doctor blade coating, chemical vapor deposition, plasma-enhanced chemical vapor deposition, or atomic layer deposition; the electron transport layer in step (2) is prepared using titanium dioxide, zinc oxide, cadmium sulfide, zinc sulfide, tin dioxide, indium trioxide, tungsten oxide, cerium oxide, C60, C70, methyl [6,6]-phenyl-C61-butyrate, and sodium carbon. The electron transport layer is made of any one of the following materials: rice tube, graphene or its derivatives, dopants or composite materials, and the thickness of the electron transport layer is 5~40 nm; the hole transport layer in step (2) is made of any one of the following materials: 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), polyethylenedioxythiophene, 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene, self-assembled monolayer, polyethylene glycol, polycaprolactone or its derivatives, dopants or composite materials, and the thickness of the hole transport layer is 5~40 nm.

4. The method for fabricating 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 prepared using a perovskite precursor solution containing AX, BX2, a mixture of AX and BX2, or a stacked structure of AX and BX2, wherein A is methylamino CH3NH3. + , Ethylamino group CH3CH2NH3 + , Methamidinyl CH(NH2)2 + and guanidinyl C(NH2)3 + At least one short-chain organic cation in it, or A is Li + Na + K + 、Rb + Ag + Cu + and Cs + At least one monovalent inorganic cation in the composition, where B is Ge 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 in it, where X is F - Cl - CH3COO - ,Br - I - and SCN - The perovskite active layer is prepared by screen printing, slot coating, inkjet printing, blade coating or chemical vapor deposition; the precursor solution is prepared by selecting different concentrations, different substance ratios and different solvent ratios to meet different output power requirements.

5. The method for fabricating 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, or plasma-enhanced chemical vapor deposition. The thickness of the barrier layer is 10~30nm. The second conductive electrode in step (4) is 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 fabricating a perovskite solar cell photovoltaic module based on a parallel-series structure according to claim 1, characterized in that, In step (5), a number of independent sub-cells are connected in parallel by using metal grid lines to connect two adjacent second conductive electrodes. The metal grid lines are made of gold, silver, copper, aluminum, chromium or bismuth. The metal grid lines are obtained by hot 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, It is prepared by any one of the methods in claims 2-6.

8. A perovskite solar cell photovoltaic module based on a parallel-series structure, characterized in that, The system comprises several battery modules connected in series using metal wires. Each battery module includes several sub-cells connected in parallel, a positive electrode, a negative electrode, and a separation region. Each sub-cell consists 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. The separation region is located between the second conductive electrodes of two adjacent sub-cells. Several independent sub-cells are connected in parallel using metal grid lines through the second conductive electrodes of two adjacent sub-cells. The first conductive electrode leads out to the positive electrode of the battery module through an external metal electrode. The second conductive electrode leads out to the negative electrode of the battery module through the metal grid lines and the external metal electrode. The external metal electrodes at the positive and negative electrodes of two adjacent battery modules are connected in series using metal wires, thus forming a perovskite solar cell module with a parallel-series structure.

9. The perovskite solar cell photovoltaic module based on a parallel-series structure according to claim 8, characterized in that, The output voltage and current of the module can be controlled by adjusting the type and thickness of the perovskite active layer, and the output power can be controlled by connecting several individual battery modules in series to meet different power supply requirements; the first conductive electrode or the second conductive electrode is a transparent conductive electrode, which is used to prepare semi-transparent or fully transparent perovskite solar cell devices.

10. The perovskite solar cell photovoltaic module based on a parallel-series structure according to claim 8, characterized in that, The standard 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 0.5 cm, and the width of the metal grid line is 0.1 to 0.5 cm.

Images