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CN112599681A - Perovskite solar cell with improved metal electrode and preparation method thereof - Google Patents

Perovskite solar cell with improved metal electrode and preparation method thereof Download PDF

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CN112599681A
CN112599681A CN202011468912.3A CN202011468912A CN112599681A CN 112599681 A CN112599681 A CN 112599681A CN 202011468912 A CN202011468912 A CN 202011468912A CN 112599681 A CN112599681 A CN 112599681A
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layer
metal electrode
perovskite
solar cell
transport layer
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秦校军
赵志国
赵东明
肖平
董超
熊继光
刘娜
刘家梁
王百月
冯笑丹
梁思超
王森
张�杰
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Huaneng Clean Energy Research Institute
Huaneng Renewables Corp Ltd
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Huaneng Clean Energy Research Institute
Huaneng Renewables Corp Ltd
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    • H—ELECTRICITY
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K30/353—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising blocking layers, e.g. exciton blocking layers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a perovskite solar cell with an improved metal electrode and a preparation method thereof, and belongs to the technical field of solar cell devices. Firstly, preparing a transparent electrode layer on a high-transparency glass layer, preparing and forming an electron transport layer on the transparent electrode layer, preparing a perovskite active layer on the electron transport layer, and preparing a hole transport layer on the perovskite active layer to obtain a perovskite battery main body; carrying out patternable batch preparation on a backboard substrate by adopting physical deposition, cutting according to the shape and the circuit of a main body part of the perovskite battery after deposition to obtain a metal electrode layer, and preparing a barrier layer on the metal electrode layer to obtain an electrode main body; and aligning and superposing the perovskite cell main body and the electrode main body, and slowly cooling to room temperature after heat treatment to obtain the perovskite solar cell with the improved metal electrode. On the premise of obtaining the high-performance solar cell, the production efficiency is improved.

Description

Perovskite solar cell with improved metal electrode and preparation method thereof
Technical Field
The invention belongs to the technical field of solar cell devices, and relates to a perovskite solar cell with an improved metal electrode and a preparation method thereof.
Background
Perovskite solar cells (perovskite solar cells) are solar cells using perovskite type organic metal halide semiconductors as light absorbing materials, and belong to the third generation solar cells, which are also called new concept solar cells. Upon exposure to sunlight, the perovskite layer first absorbs photons to generate electron-hole pairs. These carriers either become free carriers or form excitons due to differences in exciton binding energy of the perovskite material. Furthermore, because these perovskite materials tend to have a lower probability of carrier recombination and higher carrier mobility, the diffusion distance and lifetime of carriers are longer. Then, the non-recombined electrons and holes are respectively collected by an electron transport layer and a hole transport layer, namely the electrons are transported to the equal electron transport layer from the perovskite layer and are finally collected by the ITO; the holes are transported from the perovskite layer to the hole transport layer and finally collected by the metal electrode, and of course, the processes are not always accompanied by some losses of carriers, such as reversible recombination of electrons of the electron transport layer with holes of the perovskite layer, recombination of electrons of the electron transport layer with holes of the hole transport layer (in the case of a non-dense perovskite layer), and recombination of electrons of the perovskite layer with holes of the hole transport layer. These carrier losses should be minimized to improve the overall performance of the cell. Finally, the photocurrent is generated through the electrical circuit connecting the FTO and the metal electrode.
The metal back electrode in the traditional perovskite battery is usually prepared by independently depositing each battery, and the metal back electrode is deposited by using evaporation/sputtering and other methods at the final stage of perovskite battery preparation, so that the production efficiency is low.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a perovskite solar cell having an improved metal electrode and a method for manufacturing the same, which can improve the production efficiency on the premise of obtaining a high-performance solar cell.
The invention is realized by the following technical scheme:
the invention discloses a preparation method of a perovskite solar cell with an improved metal electrode, which comprises the following steps:
preparing a transparent electrode layer on the high-transparency glass layer, preparing and forming an electron transport layer on the transparent electrode layer, preparing a perovskite active layer on the electron transport layer, and preparing a hole transport layer on the perovskite active layer to obtain a perovskite battery main body;
carrying out patternable batch preparation on a backboard substrate by adopting physical deposition, cutting according to the shape and the circuit of a main body part of the perovskite battery after deposition to obtain a metal electrode layer, and preparing a barrier layer on the metal electrode layer to obtain an electrode main body;
and aligning and superposing the perovskite cell main body and the electrode main body, carrying out heat treatment at 100-150 ℃ for 10-30min, and slowly cooling to room temperature to obtain the perovskite solar cell with the improved metal electrode.
Preferably, the transparent electrode layer is FTO, ITO or AZO.
Preferably, before the electron transport layer is formed on the transparent electrode layer, the surface of the flexible transparent electrode substrate is sequentially subjected to ultrasonic treatment for 15min by using deionized water, acetone and isopropanol, then is cleaned for 10min by using ultraviolet light, and is dried by using nitrogen flow.
Preferably, the electron transport layer is prepared by atomic deposition, vapor deposition, magnetron sputtering or spin coating; the electron transport layer comprises tin oxide or titanium oxide nanoparticles, the diameter of the tin oxide or titanium oxide nanoparticles is 2-10nm, and the thickness of the electron transport layer is 10-40 nm.
Preferably, the perovskite active layer is FAPbI3The thickness of the perovskite active layer is 300-600 nm.
Preferably, the material of the hole transport layer is Spiro-OMeTAD, PTAA, nickel oxide, cuprous iodide, PEDOT: PSS, polytereylenes, polythiophenes, polysilanes, triphenylmethanes, triarylamines, hydrazones, pyrazolines, carbazoles, or butadienes; the thickness of the hole transport layer was 100 nm.
Preferably, the backplane substrate of the metal electrode layer is non-conductive glass or polymer plastic, and the metal electrode is gold, silver, copper or aluminum; the thickness of the metal electrode layer is 60-120 nm.
Preferably, the barrier layer is a reduced graphene oxide layer, and the thickness of the barrier layer is 10-20 nm.
Further preferably, the barrier layer is prepared by a solution spin coating method, specifically: adopting chlorobenzene solvent, preparing reduced graphene oxide with the diameter of 0.2-1.0 mu m and the thickness of less than 5nm into slurry with the concentration of 0.5-2mg/mL, and spin-coating the slurry on a substrate for 40-60s at the rotating speed of 1000-4000 rpm.
The perovskite solar cell with the improved metal electrode prepared by the preparation method disclosed by the invention comprises a high-transmittance glass layer, a transparent electrode layer, an electron transport layer, a perovskite active layer, a hole transport layer, a barrier layer and a metal electrode layer which are sequentially connected to form the whole solar cell.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the preparation method of the perovskite solar cell with the improved metal electrode, disclosed by the invention, the metal back electrode can be prepared in a large area at one time and cut as required to obtain the electrode main body suitable for a single solar cell, the electrode main body and the main part of the perovskite cell main body are respectively produced and then combined with the cell main body in a heat treatment mode, so that the production efficiency is improved. On the basis, the perovskite solar cell with the improved metal electrode is constructed, and on the premise of ensuring good performance, the structure of the solar cell can be simplified, the production efficiency can be improved, and the cost can be reduced.
The perovskite solar cell with the improved metal electrode prepared by the preparation method disclosed by the invention is simple in structure, convenient for batch production and good in application prospect.
Drawings
Fig. 1 is a schematic view of the overall structure of the present invention.
In the figure, 102-high transparent glass layer, 104-transparent electrode layer, 106-electron transport layer, 108-perovskite active layer, 110-hole transport layer, 112-barrier layer, 114-barrier layer.
Detailed Description
The invention is described in further detail below with reference to the following figures and examples:
referring to fig. 1, the perovskite solar cell with the improved metal electrode of the present invention comprises a high-permeability glass layer 102, a transparent electrode layer 104, an electron transport layer 106, a perovskite active layer 108, a hole transport layer 110, a barrier layer 112 and a metal electrode layer 114 which are connected in sequence to form an integral solar cell.
High-transmittance glass layer 102 and transparent electrode layer 104: the product can be used in large-scale products, an FTO (or ITO, AZO and the like) transparent electrode deposited on high-transparency glass is used as a substrate of a device, the area is not limited, and the shape, the area, the thickness and the like of the FTO and other transparent electrodes can be controlled by a process means; before use, the surface of the electrode is sequentially treated by deionized water, acetone and isopropanol for 15 minutes, then cleaned by an ultraviolet light cleaning machine for 10 minutes, and dried by nitrogen flow for later use.
Electron transport layer 106 formed on transparent electrode layer 104: tin oxide (SnO) is used in this example2) Titanium oxide (TiO) may also be used2) And the like. The tin oxide layer can be prepared by atomic deposition, vapor deposition, magnetron sputtering, spin coating and other methods. In particular, the layer is prepared by a solution spin coating method, commercial tin oxide nanoparticle (diameter 2-10nm) suspension can be directly used as a spin coating liquid, the preparation of tin oxide layers (10-40nm) with different thicknesses can be carried out on a substrate by using spin coating parameters of 3000-5000rpm and 40-80s, particularly, the tin oxide layer with the thickness of about 20nm can be obtained by using spin coating parameters of 4200rpm and 60s, and in addition, the commercial tin oxide nanoparticle is particularly easy to synthesize in a large scale and low cost manner, and meanwhile, the commercial tin oxide nanoparticle is produced in a large scale by using preparation technologies such as slit coating, scraper coating, silk screen printing, gravure printing, ink-jet coating, ink-jet printing and the like.
A perovskite active layer 108 prepared on the electron transport layer 106 and having the structure ABXnY3-n(A ═ Cs or RNH3Or mixtures thereof in any proportion, R is a suitable hydrocarbyl group; b ═ Pb or Sn or a mixture thereof in any proportion; x, Y ═ Cl, Br, I; n is a real number of 0 to 3), preferably FAPBI is used3The coating layer is generally formed by spin coating, vapor deposition, magnetron sputtering, or the like, and may be formed by a roll-to-roll process suitable for flexible and large-scale production, that is, a slurry of an active material is formed by slit coating, blade coating, screen printing, gravure printing, inkjet coating, inkjet printing, or the like. In particular, in the blade coating method, DMF is used as a solvent, and the perovskite is prepared into slurry with the mass fraction of 15-30%, preferably 25%; the blade coating speed is 10-40mm/s, preferably 20 mm/s; the coating temperature is roomWarming; the distance between the scraper and the substrate is 50 mu m; after coating, annealing at 100-150 ℃ for 20-40 min, preferably 120 ℃ for 30min in nitrogen. The resulting thickness of the perovskite active layer 108 was about 300-600 nm.
The hole transport layer 110 prepared on the perovskite active layer 108 is characterized by organic and inorganic materials matched with the perovskite active material energy level, such as Spiro-OMeTAD, PTAA, nickel oxide, cuprous iodide, PEDOT: PSS, polyparaphenylenes, polythiophenes, polysilanes, triphenylmethanes, triarylamines, hydrazones, pyrazolines, carbazoles, butadienes, and the like. In particular, the layer was prepared using a knife coating method: the slurry used was commercial PEDOT: PSS (AI 4083) in aqueous solution, using isopropanol, according to a 1:3, proportioning and diluting, wherein the coating speed of a scraper is 10-35mm/s, preferably 25 mm/s; the coating temperature is 50-80 ℃, and preferably 60 ℃; the distance between the scraper and the substrate is 50 mu m; after coating, annealing at 85-100 deg.C for 10-30min, preferably 95 deg.C for 20min in nitrogen. The resulting hole transport layer 110 was about 100nm thick.
The metal electrode layer 114 formed on the back sheet substrate, which is a part of the assembly prepared separately from the main body part of the perovskite battery, can be prepared in a large area and cut, and thus can be prepared in large quantities. The backplane substrate may typically use a non-conductive glass/polymer plastic (e.g., PET) or the like. The metal electrode can be a common metal electrode such as gold/silver/copper/aluminum, and the like, and the comprehensive consideration of cost and performance is combined, in the embodiment, the metal electrode can be prepared by using metal silver and performing patternable preparation by using a physical deposition (evaporation) method and the like, and the thickness can be 60-120nm, and is preferably 100 nm; and cutting the perovskite battery according to the shape of the main body part of the perovskite battery and the circuit design after the deposition is finished.
Barrier layer 112 formed on metal electrode layer 114: the layer can be prepared (or not used) for protecting the functional layers of the electrode and the battery, and the penetration and the corrosion of metal, a hole transport layer and the like can be prevented; in this example, the preferred material for the barrier layer 112 is reduced graphene oxide (r-GO), which has good electrical conductivity and physical, chemical, and electrical inertness, and is very stable under normal conditions and suitable for use in such devices. The reduced graphene oxide is a commercial product which can be used directly. The barrier layer can be prepared by a solution spin coating method. Preparing r-GO (with diameter of 0.2-1.0 μm and thickness less than 5nm) into slurry of 0.5-2mg/mL, preferably 1mg/mL, and solvent chlorobenzene; preparing the barrier layer on the substrate with spin coating parameters of 1000-4000rpm for 40-60s, wherein the thickness is 10-20 nm; in particular, a barrier layer having a thickness of about 15nm can be obtained using a spin coating parameter of 3000rpm for 60 s.
And (3) combining the electrode main body with the heat treatment of the perovskite battery main body: and aligning and overlapping the perovskite battery main body and the metal electrode, carrying out heat treatment at the temperature of 100-150 ℃ for 10-30min, such as 120 ℃ and 15min, and then slowly cooling to room temperature to obtain the final battery device.
The preparation process according to the invention is further explained below by means of a specific example:
taking a high-transparency glass substrate with an ITO transparent electrode layer attached on the substrate, wherein the area of the high-transparency glass substrate is 3cm multiplied by 3 cm; directly taking commercial tin oxide nanoparticle (diameter is 2-10nm) suspension as spin coating liquid, preparing a tin oxide layer on a substrate at 4200rpm for 60s, and annealing at 180 ℃ for 10 min; to FAPBI3Preparing a solution with the mass fraction of 25%, wherein DMF is used as a solvent; the coating speed of a scraper is 20 mm/s; the coating temperature is room temperature; the distance between the scraper and the substrate is 50 mu m; annealing at 120 deg.C for 30min in nitrogen after coating; preparing PEDOT: PSS aqueous solution is diluted by isopropanol according to the proportion of 1:3, film coating is carried out by adopting a scraper coating mode under the conditions of 25mm/s, the coating temperature of 60 ℃, the distance between a scraper and a substrate of 50 mu m, and annealing is carried out for 20min at 95 ℃ under nitrogen atmosphere in a glove box; thermally evaporating a gold electrode with the thickness of 100nm on a glass backboard substrate, preparing a barrier layer on the gold electrode by adopting a spin-coating method, preparing r-GO (with the diameter of 0.5-2.0 mu m and the thickness of 2-5nm) into 1mg/mL slurry, and taking chlorobenzene as a solvent; preparing the barrier layer on the substrate by using the spin coating parameters of 3000rpm and 60 s; the two parts are annealed in register at 120 ℃ for 15 min.
The effective area of the obtained battery unit is 1.0cm2And through detection, the maximum photoelectric conversion efficiency of the battery can reach 12.9%.
It should be noted that the above description is only one embodiment of the present invention, and all equivalent changes of the system described in the present invention are included in the protection scope of the present invention. Persons skilled in the art to which this invention pertains may substitute similar alternatives for the specific embodiments described, all without departing from the scope of the invention as defined by the claims.

Claims (10)

1.一种具有改进型金属电极的钙钛矿太阳能电池的制备方法，其特征在于，包括：1. a preparation method of the perovskite solar cell with improved metal electrode, is characterized in that, comprises: 在高透玻璃层(102)上制备透明电极层(104)，在透明电极层(104)上制备形成电子传输层(106)，在电子传输层(106)上制备钙钛矿活性层(108)，在钙钛矿活性层(108)上制备空穴传输层(110)，得到钙钛矿电池主体；A transparent electrode layer (104) is prepared on the high transparent glass layer (102), an electron transport layer (106) is prepared on the transparent electrode layer (104), and a perovskite active layer (108) is prepared on the electron transport layer (106) ), preparing a hole transport layer (110) on the perovskite active layer (108) to obtain the main body of the perovskite battery; 在背板基底上采用物理沉积发进行可图案化的批量制备，沉积完成后按照钙钛矿电池主体部分的形状和电路进行切割得到金属电极层(114)，在金属电极层(114)上制备阻隔层(112)，得到电极主体；The patternable batch preparation is carried out by physical deposition on the backplane substrate. After the deposition is completed, the metal electrode layer (114) is obtained by cutting according to the shape and circuit of the main body of the perovskite battery, and is prepared on the metal electrode layer (114). a barrier layer (112) to obtain an electrode body; 将钙钛矿电池主体与电极主体对准叠合，在100～150℃下热处理10～30min，缓慢冷却至室温，得到具有改进型金属电极的钙钛矿太阳能电池。The main body of the perovskite battery and the main body of the electrode are aligned and stacked, heat treated at 100-150° C. for 10-30 min, and slowly cooled to room temperature to obtain a perovskite solar cell with an improved metal electrode. 2.根据权利要求1所述的具有改进型金属电极的钙钛矿太阳能电池的制备方法，其特征在于，透明电极层(104)为FTO、ITO或AZO。2. The method for preparing a perovskite solar cell with an improved metal electrode according to claim 1, wherein the transparent electrode layer (104) is FTO, ITO or AZO. 3.根据权利要求1所述的具有改进型金属电极的钙钛矿太阳能电池的制备方法，其特征在于，在透明电极层(104)上制备形成电子传输层(106)前，使用去离子水、丙酮和异丙醇对柔性透明电极基底(102)表面依次超声处理15min，然后使用紫外光清洗10min，用氮气流吹干。3. The method for preparing a perovskite solar cell with an improved metal electrode according to claim 1, characterized in that, before the electron transport layer (106) is prepared on the transparent electrode layer (104), deionized water is used The surface of the flexible transparent electrode substrate (102) was ultrasonically treated with , acetone and isopropanol in sequence for 15 min, then cleaned with ultraviolet light for 10 min, and dried with nitrogen flow. 4.根据权利要求1所述的具有改进型金属电极的钙钛矿太阳能电池的制备方法，其特征在于，电子传输层(106)采用原子沉积、气相沉积、磁控溅射或旋涂方法制备；电子传输层(106)包含氧化锡或氧化钛纳米粒子，氧化锡或氧化钛纳米粒子的直径为2～10nm，电子传输层(106)的厚度为10～40nm。4. the preparation method of the perovskite solar cell with improved metal electrode according to claim 1, is characterized in that, electron transport layer (106) adopts atomic deposition, vapor deposition, magnetron sputtering or spin coating method to prepare The electron transport layer (106) comprises tin oxide or titanium oxide nanoparticles, the diameter of the tin oxide or titanium oxide nanoparticles is 2-10 nm, and the thickness of the electron transport layer (106) is 10-40 nm. 5.根据权利要求1所述的具有改进型金属电极的钙钛矿太阳能电池的制备方法，其特征在于，钙钛矿活性层(108)为FAPbI3，钙钛矿活性层(108)的厚度为300～600nm。5. The method for preparing a perovskite solar cell with an improved metal electrode according to claim 1, wherein the perovskite active layer (108) is FAPbI 3 and the thickness of the perovskite active layer (108) is is 300 to 600 nm. 6.根据权利要求1所述的具有改进型金属电极的钙钛矿太阳能电池的制备方法，其特征在于，空穴传输层(110)的材料为Spiro-OMeTAD、PTAA、氧化镍、碘化亚铜、PEDOT：PSS、聚对苯撑乙烯类、聚噻吩类、聚硅烷类、三苯甲烷类、三芳胺类、腙类、吡唑啉类、嚼唑类、咔唑类或丁二烯类；空穴传输层(110)的厚度为100nm。6. the preparation method of the perovskite solar cell with improved metal electrode according to claim 1, is characterized in that, the material of hole transport layer (110) is Spiro-OMeTAD, PTAA, nickel oxide, subiodide Copper, PEDOT: PSS, polyparaphenylenes, polythiophenes, polysilanes, triphenylmethanes, triarylamines, hydrazones, pyrazolines, azoles, carbazoles or butadienes ; The thickness of the hole transport layer (110) is 100 nm. 7.根据权利要求1所述的具有改进型金属电极的钙钛矿太阳能电池的制备方法，其特征在于，金属电极层(114)的背板基底为不导电玻璃或聚合物塑料，金属电极为金、银、铜或铝；金属电极层(114)的厚度为60～120nm。7. the preparation method of the perovskite solar cell with improved metal electrode according to claim 1, is characterized in that, the backplane substrate of metal electrode layer (114) is non-conductive glass or polymer plastic, and the metal electrode is Gold, silver, copper or aluminum; the thickness of the metal electrode layer (114) is 60-120 nm. 8.根据权利要求1所述的具有改进型金属电极的钙钛矿太阳能电池的制备方法，其特征在于，阻隔层(112)为经还原的石墨烯氧化物层，阻隔层(112)的厚度为10～20nm。8. The method for preparing a perovskite solar cell with an improved metal electrode according to claim 1, wherein the barrier layer (112) is a reduced graphene oxide layer, and the thickness of the barrier layer (112) is 10 to 20 nm. 9.根据权利要求8所述的具有改进型金属电极的钙钛矿太阳能电池的制备方法，其特征在于，阻隔层(112)采用溶液旋涂法进行制备，具体为：采用氯苯溶剂，将直径为0.2～1.0μm，厚度小于5nm的经还原的石墨烯氧化物配成浓度为0.5～2mg/mL的浆料，在基底上以1000～4000rpm的转速，旋涂40～60s。9. The method for preparing a perovskite solar cell with an improved metal electrode according to claim 8, wherein the barrier layer (112) is prepared by a solution spin coating method, specifically: using a chlorobenzene solvent, the The reduced graphene oxide with a diameter of 0.2 to 1.0 μm and a thickness of less than 5 nm is prepared into a slurry with a concentration of 0.5 to 2 mg/mL, and spin-coated on the substrate at a speed of 1000 to 4000 rpm for 40 to 60 s. 10.根据权利要求1～9任意一项所述的制备方法制得的具有改进型金属电极的钙钛矿太阳能电池，其特征在于，包括依次连接后形成整体太阳能电池的高透玻璃层(102)、透明电极层(104)、电子传输层(106)、钙钛矿活性层(108)、空穴传输层(110)、阻隔层(112)和金属电极层(114)。10. The perovskite solar cell with an improved metal electrode prepared by the preparation method according to any one of claims 1 to 9, characterized in that it comprises a high-transparency glass layer (102 ), a transparent electrode layer (104), an electron transport layer (106), a perovskite active layer (108), a hole transport layer (110), a blocking layer (112) and a metal electrode layer (114).
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