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CN110504370A - A method for preparing cesium-doped hybrid perovskite solar cells in an air environment - Google Patents

A method for preparing cesium-doped hybrid perovskite solar cells in an air environment Download PDF

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CN110504370A
CN110504370A CN201910610653.4A CN201910610653A CN110504370A CN 110504370 A CN110504370 A CN 110504370A CN 201910610653 A CN201910610653 A CN 201910610653A CN 110504370 A CN110504370 A CN 110504370A
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layer
cesium
liquid
solution
doped
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寿春晖
范海东
杨松旺
龚水平
洪凌
彭浩
陈文华
邱鹤
蒋新伟
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Shanghai Institute of Ceramics of CAS
Zhejiang Energy Group Research Institute Co Ltd
Zhejiang Tiandi Environmental Protection Technology Co Ltd
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Shanghai Institute of Ceramics of CAS
Zhejiang Energy Group Research Institute Co Ltd
Zhejiang Tiandi Environmental Protection Technology Co Ltd
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Priority to CN201910610653.4A priority Critical patent/CN110504370A/en
Publication of CN110504370A publication Critical patent/CN110504370A/en
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    • 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
    • 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
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

The present invention relates to the methods that caesium doping mixing perovskite solar battery is prepared in air environment, and steps are as follows: TiO is prepared on transparent conducting glass2Compacted zone is immersed in TiCl4In aqueous solution, rinsed after then taking out with deionized water and ethyl alcohol；One layer of TiO of spin coating on gained sample2Nanocrystalline slurry, obtains TiO2Mesoporous layer；Caesium doping mixing perovskite solution is prepared in the air environment of relatively dry, in TiO2Spin coating caesium doping mixing perovskite solution on mesoporous layer, sample is placed on hot plate after spin coating and is heated, caesium doping mixing perovskite light-absorption layer is obtained after being cooled to room temperature, in one layer of hole transmission layer of its surface spin coating, one layer of gold, silver or aluminium electrode are deposited on hole transmission layer, caesium doping mixing perovskite solar battery is finally made.The beneficial effects of the present invention are: the composition, structure and performance of perovskite light-absorption layer can be adjusted by the relative amount of each component of adjusting the present invention provides a kind of compositing formula of perovskite light-absorption layer.

Description

A method of preparing caesium doping mixing perovskite solar battery in air environment
Technical field
The invention belongs to technical field of solar batteries, are related to a kind of preparation method of perovskite solar battery, specifically It is related to one kind and prepares caesium doping organic-inorganic mixing perovskite solar battery (abbreviation perovskite solar-electricity in air environment Pond) method.
Background technique
Peter out in fossil fuel, under the status that environmental pollution is got worse, develop the clean energy resourcies such as solar energy at For the inevitable choice of human society.Perovskite material has light absorpting ability strong, and carrier mobility is big, carrier diffusion distance Long, preparation method is simple, the advantage that ingredient is adjustable.In recent years, the photoelectricity that perovskite solar battery is promoted rapidly due to it Transfer efficiency and receive significant attention, the peak efficiency authenticated at present has reached 24.2%, shows perovskite solar battery Excellent properties and the bright outlook.
The preparation method of organic inorganic hybridization perovskite thin film forms it, structure, pattern, carrier mobility, current-carrying Carrier diffusion length, photoelectric conversion efficiency and stability have great influence.Stabilization of the perovskite light absorbent in air environment Property it is poor, generally require the inert gas environment for relying on low humidity low oxygen content, but the price of inert atmosphere glove box is high, and Operating space is too small, is unfavorable for the industrial application of perovskite battery.Therefore, if perovskite can be prepared in air environment too Positive energy battery, can not only reduce battery cost, moreover it is possible to improve preparation efficiency.
Caesium (Cs) element belongs to I A race of period 6, is the alkali metal of the maximum on-radiation of atomic radius, can be independent As the position the A atom in perovskite, full-inorganic perovskite solar battery is prepared.Cs+It can also be with CH3NH3 +、NH2- CH=NH2 + And C4H9NH3 +The mixing of at least one of equal cations prepares polynary cation mixing perovskite solar battery.Research shows that (FAPbI3)1-x(MAPbBr3)xMixed-cation perovskite battery have be more than 20% transfer efficiency (M.Saliba, S.Orlandi,T.Matsui,S.Aghazada,M.Cavazzini,J.-P.Correa-Baena,P.Gao, R.Scopelliti,E.Mosconi,K.-H.Dahmen,F.De Angelis,A.Abate,A.Hagfeldt,G.Pozzi, M.Graetzel, M.K.Nazeeruddin, Nat.Energy 2016,1,15017), and Cs+The FAPbI of doping3Perovskite Solar battery has than pure FAPbI3Stronger light durability and moisture-proof (J.-W.Lee, D.-H.Kim, H.-S.Kim, S.-W.Seo,S.M.Cho,N.-G.Park,Adv.Energy Mater.2015,5,1501310)。
Preparation method used in the document of published mixing perovskite solar battery all must be strictly controlled at present Humidity and oxygen content usually carry out in the glove box of control atmosphere, but glove box is expensive, and operating space is small, no Conducive to the large-scale production of perovskite solar battery.
Summary of the invention
The purpose of the present invention is overcoming deficiency in the prior art, one kind preparation high efficiency caesium in air environment is provided and is mixed The method of miscellaneous triple cationic mixing perovskite solar battery is regulated and controled by the ingredient of perovskite light-absorption layer, i.e. adjusting Cs+、CH3NH3 +、NH2- CH=NH2 +Relative amount the performance of perovskite is adjusted and optimized.
This method that caesium doping mixing perovskite solar battery is prepared in air environment, comprising the following steps:
1) it after transparent conducting glass (such as fluorine-doped tin oxide electro-conductive glass, FTO) is by ultraviolet and ozone clean, uses Sol evenning machine coats one layer of tetraisopropyl titanate solution on its surface, keeps the temperature 10~60 minutes at 400~600 DEG C, prepares TiO2It causes Close layer；
2) TiO will be covered2The electro-conductive glass of compacted zone is immersed in certain density TiCl4In aqueous solution, 50~80 DEG C of heat preservations 30~60min is rinsed after taking-up with deionized water and ethyl alcohol, and keeps the temperature 10~60 minutes at 400~600 DEG C；
3) one layer of TiO of spin coating on the sample obtained by step 2)2Nanocrystalline slurry keeps the temperature 10~60 points at 400~600 DEG C Clock obtains TiO2Mesoporous layer；
4) caesium doping calcium mixture is prepared in the air environment of relatively dry (18~23 DEG C of temperature, relative humidity≤30%) Titanium ore solution does not need the humidity and oxygen content of strictly controlled environment, that is, needs not rely on low humidity in glove box, low oxygen content (H2O < 0.5ppm, O2< 10ppm) condition；Spin coating caesium (Cs) doping mixing perovskite solution, drop on the sample obtained by step 3) Start to rotate within the 3rd~8 second after liquid feeding drop, 800~1500 revs/min of revolving speed (rpm), continues 8~12 seconds, revolving speed mentions later Up to 4000~7000rpm continues 15~25 seconds, and rapid the 25th~30 second that caesium doping mixing perovskite solution is added dropwise Anti-solvent is added dropwise, anti-solvent processing is so that surface is uniform, smooth；After spin coating, sample is placed on 90~120 DEG C of hot plates Heating 0.5~2 hour；
5) after sample obtained by step 4) is cooled to room temperature, caesium doping mixing perovskite light-absorption layer is obtained, in its surface spin coating One layer of hole transmission layer；
6) one layer of gold, silver or aluminium electrode are deposited on the hole transmission layer that step 5) obtains using the method for hot evaporation, Caesium doping mixing perovskite solar battery is finally made.
As preferred: tetraisopropyl titanate solution used in step 1) is configured by A liquid and B liquid, and A liquid includes appropriate Acetylacetone,2,4-pentanedione, tetraisopropyl titanate, second alcohol and water；B liquid includes suitable ethyl alcohol, hydrochloric acid and water；B liquid is poured into A when configuration In liquid, 24~72 hours are stood after stirring a period of time.
As preferred: TiO used in step 3)2Nanocrystalline slurry includes ethyl alcohol, nano-TiO2, ethyl cellulose and pine The saturating alcohol of fuel-economizing, the slurry have excellent mobility and certain viscosity, can be obtained by way of spin coating and sintering uniformly Mesoporous layer.
As preferred: in step 4) caesium doping mixing perovskite solution the preparation method is as follows:
4.1) the caesium doping mixing perovskite solution is the precursor solution of caesium doping mixing perovskite light-absorption layer, is changed Formula is ABX3, wherein A is Cs+、CH3NH3 +(MA)、NH2- CH=NH2 +(FA) or C4H9NH3 +In equal monovalent cations at least One kind, B Pb2+、Sn2+、Ge2+、Co2+、Fe2+、Mn2+、Cu2+Or Ni2+At least one of, X Cl-、Br-Or I-Equal anion At least one of；Divide A liquid and B liquid using preceding solution: A liquid group is divided into 0.8~1.2M FAI, 0.9~1.3M PbI2, 0.1~ 0.3M MABr and 0.1~0.3M PbBr2, solvent is that the volume ratio of DMF and DMSO, DMF and DMSO are 1:5~6:1；B liquid Including 1.0~2.0M CsI, solvent is dimethyl sulfoxide (DMSO)；
4.2) when configuring A liquid, directly by a certain amount of FAI, PbI2, MABr and PbBr2Solid powder mixing, and DMF is added With the mixed solvent of DMSO；
4.3) A liquid and B liquid are uniformly mixed into several pieces solution according to a certain percentage, and mixed solution adds at 50~80 DEG C Heat simultaneously stirs 40~80 minutes；According to Cs in the several pieces solution+The difference of concentration, calculates and the composition formula for writing out solution is CsX(FA0.83MA0.17)(1-X)Pb(I0.83Br0.17)3, the wherein value of X are as follows: 0.02 < X < 0.15, i.e. cesium ion account for whole A sun The 2%~15% of ion total mole number.
As preferred: anti-solvent includes at least one of chlorobenzene, ether, ethyl acetate or toluene in step 4).
As preferred: the metal electrode of hot evaporation is vaporized on 1*10 with a thickness of 80~120nm in step 6)-5~1*10- 7It is carried out under the air pressure of torr.
As preferred: the doping mixing perovskite solar battery of caesium made from step 6) successively includes transparent leads from the bottom up Electric substrate, electron transfer layer, caesium doping mixing perovskite light-absorption layer, hole transmission layer and metal are to electrode.
The beneficial effects of the present invention are:
1, the preparation process of caesium of the invention doping organic-inorganic mixing perovskite solution needs not rely on expensive gloves Case, it is only necessary to which the operation in the air environment (18~23 DEG C of temperature, relative humidity≤30%) of relatively dry is not required to strictly control Humidity and oxygen content processed, preparation condition is milder, is conducive to large-scale production and application.
2, the present invention provides a kind of compositing formulas of perovskite light-absorption layer, can be contained by adjusting the opposite of each component Amount, is adjusted the composition, structure and performance of perovskite light-absorption layer.
3, the present invention also provides a kind of high efficiency solar cell according to made from above-mentioned preparation method, the solar-electricities Pond has excellent photoelectric conversion efficiency, preferable repeatability and stability, and preparation process is easy to operate, easily controllable.
4, the caesium doping organic-inorganic mixing perovskite film surface prepared by the present invention is smooth, uniform.
Detailed description of the invention
Fig. 1 is the J-V curve graph of embodiment 1 (doping of 5% caesium) and comparative example 1 (no caesium adulterates) battery；
Fig. 2 is the J-V curve graph of embodiment 2 (air environment of relatively dry) and comparative example 2 (glove box) battery；
Fig. 3 is the J-V curve graph of embodiment 3 (quickly vapor deposition) and comparative example 3 (slowly vapor deposition) battery.
Specific embodiment
The present invention is described further below with reference to embodiment.The explanation of following embodiments is merely used to help understand this Invention.It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, also Can be with several improvements and modifications are made to the present invention, these improvement and modification also fall into the protection scope of the claims in the present invention It is interior.
Embodiment 1: the mixed-cation perovskite solar battery of caesium doping 5%
1) it is cleaned by ultrasonic FTO glass 30min with alkalis, deionized water, acetone, dehydrated alcohol and isopropanol respectively, It finally dries up, and carries out UV-ozone processing.
2) TiO is prepared on FTO glass substrate2Compacted zone, precursor solution include following component: tetraisopropyl titanate (0.3mol/L), acetylacetone,2,4-pentanedione (0.45mol/L), hydrochloric acid (0.09mol/L), water (1.8mol/L), solvent is ethyl alcohol.
3) precursor solution is drawn, is added dropwise on the FTO glass substrate cleaned up, solution is made to be paved with the entire surface FTO, It is formed a film using spin-coating method, spin speed 3000rpm, time 20s.Then 510 DEG C of sintering 30min in Muffle furnace or hot plate.
4) TiO will be covered2The FTO glass immersion of compacted zone is in certain density TiCl4In aqueous solution, 70 DEG C of heat preservations 40min is rinsed after taking-up with deionized water and ethyl alcohol, and keeps the temperature 30 minutes at 510 DEG C.
5) one layer of nano-TiO of spin coating on sample2Colloid contains the bonding such as ethyl cellulose, the saturating alcohol of turpentine oil in colloid Agent and pore creating material obtain TiO in 510 DEG C of heat preservation 30min2Mesoporous layer.
6) the mixed-cation perovskite solution of caesium doping 5% is configured in the air environment of relatively dry.
7) 30 microlitres of Cs are measured0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3Perovskite precursor solution is dripped in TiO2It is situated between In aperture layer, start to rotate within the 5th second after dropwise addition drop, 1200 revs/min of revolving speed (rpm), for 12 seconds, revolving speed improves later It is for 20 seconds to 6000rpm, and a certain amount of chlorobenzene is added dropwise rapidly within the 29th second in dropwise addition perovskite solution.
8) after spin coating, sample is placed on 100 DEG C of hot plates and is heated 1 hour.
9) after sample is cooled to room temperature, in one layer 2,2' of its surface spin coating, 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) Amino] -9,9'- spiral shell, two fluorenes (Spiro-OMeTAD), revolving speed 4000rpm is for 20 seconds, obtains hole transmission layer.
10) method for using hot evaporation, is deposited the silver electrode of one layer of 100nm thickness on the hole transport layer.
Comparative example 1: the mixed-cation perovskite solar battery of no caesium doping
Comparative example 1 measures 30 microlitres of (FA when preparing perovskite light-absorption layer0.83MA0.17)Pb(I0.83Br0.17)3Perovskite Precursor solution is added dropwise in TiO2On mesoporous layer.Remaining step and material all keep strict conformance with embodiment 1.
Fig. 1 shows the J-V curve of embodiment 1 (doping of 5% caesium) and comparative example 1 (no caesium adulterates) battery, in identical voltage Under, embodiment 1 has than the higher current density of comparative example 1, therefore the 1 photoelectric conversion performance of embodiment of caesium doping is more preferable.
Embodiment 2: the mixed-cation perovskite solar battery of caesium doping 5% is prepared in the environment of relatively dry.
Configuration caesium doping 5% is mixed in the air environment (18~23 DEG C of temperature, relative humidity≤30%) of relatively dry Cations perovskite solution, and carry out the preparation of perovskite thin film.Specific steps and embodiment 1 are consistent.
Comparative example 2: the mixed-cation perovskite battery of caesium doping 5% is prepared in glove box.
Comparative example 2 is in strict control oxygen content and water content (H2O < 0.5ppm, O2< 10ppm) argon gas or nitrogen atmosphere In prepare perovskite thin film, hole transmission layer.Concrete operation step and embodiment 2 are consistent.
Fig. 2 is shown under identical material and preparation parameter, and 2 current density of embodiment is slightly below comparative example 1, but has and compare The higher open-circuit voltage of ratio 2, therefore embodiment 2 has higher photoelectric conversion efficiency.Illustrate the air ring in relatively dry The battery prepared in border can be higher than the battery efficiency prepared in glove box.
Embodiment 3: caesium doping 5% mixed-cation perovskite solar battery, silver electrode evaporation rate be 1000 angstroms/ Second, 1200 angstroms of evaporation thickness, i.e., 1200 angstrom Ag metals are deposited in two seconds.Remaining operation and preparation process are the same as embodiment 1.
Comparative example 3: caesium doping 5% mixed-cation perovskite solar battery, silver electrode be deposited when, first 0.5 angstrom/ 100 angstroms are deposited under second rate, after 1100 angstroms are deposited under 1.5 angstroms per seconds.Remaining operation and preparation process are the same as embodiment 1.
Fig. 3 is shown under identical material and preparation parameter, and embodiment 3 uses the evaporation rate of 1000 angstroms per seconds, is obtained Battery short circuit current density is much higher than the battery being slowly deposited.Illustrate to prepare silver electrode using higher evaporation rate, can obtain To the battery of higher efficiency.
The efficiency test of battery is carried out using solar simulator.

Claims (7)

1.一种在空气环境中制备铯掺杂混合钙钛矿太阳能电池的方法，其特征在于：包括以下步骤：1. A method for preparing cesium-doped hybrid perovskite solar cells in an air environment, characterized in that: comprise the following steps: 1)透明导电玻璃通过紫外和臭氧清洁之后，使用匀胶机在其表面涂覆一层钛酸四异丙酯溶液，在400～600℃保温10～60分钟，制备TiO2致密层；1) After the transparent conductive glass is cleaned by ultraviolet light and ozone, a layer of tetraisopropyl titanate solution is coated on the surface of the transparent conductive glass with a homogenizer, and kept at 400-600°C for 10-60 minutes to prepare a dense layer of TiO 2 ; 2)将覆盖TiO2致密层的导电玻璃浸泡在一定浓度的TiCl4水溶液中，50～80℃保温30～60min，取出后用去离子水和乙醇冲洗，并在400～600℃保温10～60分钟；2) Soak the conductive glass covered with dense layer of TiO 2 in a certain concentration of TiCl 4 aqueous solution, keep it warm at 50-80°C for 30-60min, take it out, rinse it with deionized water and ethanol, and keep it warm at 400-600°C for 10-60 minutes. minute; 3)在步骤2)所得样品上旋涂一层TiO2纳米晶浆料，在400～600℃保温10～60分钟，得到TiO2介孔层；3) Spin-coat a layer of TiO2 nanocrystalline slurry on the sample obtained in step 2), and heat it at 400-600° C. for 10-60 minutes to obtain a TiO2 mesoporous layer; 4)在温度18～23℃、相对湿度≤30％的空气环境中制备铯掺杂混合钙钛矿溶液；在步骤3)所得样品上旋涂铯掺杂混合钙钛矿溶液，滴加液滴之后的第3～8秒开始旋转，转速800～1500rpm，持续8～12秒，之后转速提高至4000～7000rpm，持续15～25秒，并且在滴加铯掺杂混合钙钛矿溶液的第25～30秒滴加反溶剂；旋涂结束后，将样品放置于90～120℃热板上加热0.5～2小时；4) Prepare a cesium-doped mixed perovskite solution in an air environment with a temperature of 18-23°C and a relative humidity of ≤30%; spin-coat the cesium-doped mixed perovskite solution on the sample obtained in step 3), and add droplets After that, the rotation starts in the 3rd to 8th second, and the rotation speed is 800~1500rpm, which lasts for 8~12 seconds, and then the rotation speed is increased to 4000~7000rpm, which lasts for 15~25 seconds. Add anti-solvent dropwise for ~30 seconds; after spin coating, place the sample on a hot plate at 90-120°C and heat for 0.5-2 hours; 5)步骤4)所得样品冷却至室温后，得到铯掺杂混合钙钛矿吸光层，在其表面旋涂一层空穴传输层；5) After the sample obtained in step 4) is cooled to room temperature, a cesium-doped mixed perovskite light-absorbing layer is obtained, and a hole transport layer is spin-coated on its surface; 6)使用热蒸镀的方法在步骤5)得到的空穴传输层上蒸镀一层金、银或者铝电极，最后制得铯掺杂混合钙钛矿太阳能电池。6) Evaporating a layer of gold, silver or aluminum electrodes on the hole transport layer obtained in step 5) by thermal evaporation, and finally preparing a cesium-doped hybrid perovskite solar cell. 2.根据权利要求1所述的在空气环境中制备铯掺杂混合钙钛矿太阳能电池的方法，其特征在于：步骤1)中使用的钛酸四异丙酯溶液由A液和B液配置而成，A液包括乙酰丙酮、钛酸四异丙酯、乙醇和水；B液包括乙醇、盐酸和水；配置时将B液倒入A液中，搅拌一段时间后静置24～72小时。2. the method for preparing cesium-doped hybrid perovskite solar cell in air environment according to claim 1, is characterized in that: the tetraisopropyl titanate solution used in step 1) is configured by A liquid and B liquid Liquid A includes acetylacetone, tetraisopropyl titanate, ethanol and water; Liquid B includes ethanol, hydrochloric acid and water; when preparing, pour liquid B into liquid A, stir for a period of time and let it stand for 24 to 72 hours . 3.根据权利要求1所述的在空气环境中制备铯掺杂混合钙钛矿太阳能电池的方法，其特征在于：步骤3)中使用的TiO2纳米晶浆料包括乙醇、纳米TiO2、乙基纤维素和松节油透醇。3. the method for preparing cesium-doped hybrid perovskite solar cells in an air environment according to claim 1, characterized in that: the TiO2 nanocrystal slurry used in step 3) comprises ethanol, nano- TiO2 , ethyl alcohol Base cellulose and turpentine through alcohol. 4.根据权利要求1所述的在空气环境中制备铯掺杂混合钙钛矿太阳能电池的方法，其特征在于：步骤4)中铯掺杂混合钙钛矿溶液的制备方法如下：4. the method for preparing cesium-doped mixed perovskite solar cell in air environment according to claim 1, is characterized in that: the preparation method of cesium-doped mixed perovskite solution in step 4) is as follows: 4.1)所述铯掺杂混合钙钛矿溶液为铯掺杂混合钙钛矿吸光层的前驱体溶液，其化学式为ABX3，其中A为Cs+、CH3NH3 +(MA)、NH2-CH＝NH2 +(FA)或C4H9NH3 +中的至少一种，B为Pb2+、Sn2+、Ge2+、Co2+、Fe2+、Mn2+、Cu2+或Ni2+中的至少一种，X为Cl-、Br-或I-中的至少一种；使用前溶液分A液和B液：A液组分为0.8～1.2M FAI、0.9～1.3M PbI2、0.1～0.3M MABr和0.1～0.3MPbBr2，其溶剂为DMF和DMSO，DMF与DMSO的体积比为1:5～6:1；B液包括1.0～2.0M CsI，其溶剂为DMSO；4.1) The cesium-doped mixed perovskite solution is the precursor solution of the cesium-doped mixed perovskite light-absorbing layer, and its chemical formula is ABX 3 , wherein A is Cs + , CH 3 NH 3 + (MA), NH 2 -CH = NH 2+ (FA) or at least one of C 4 H 9 NH 3 + , B is Pb 2+ , Sn 2+ , Ge 2+ , Co 2+ , Fe 2+ , Mn 2+ , Cu At least one of 2+ or Ni 2+ , X is at least one of Cl - , Br - or I - ; before use, the solution is divided into liquid A and liquid B: the components of liquid A are 0.8~1.2M FAI, 0.9 ～1.3M PbI 2 , 0.1～0.3M MABr and 0.1～0.3MPbBr 2 , the solvents are DMF and DMSO, the volume ratio of DMF to DMSO is 1:5～6:1; B liquid contains 1.0～2.0M CsI, its The solvent is DMSO; 4.2)配置A液时，直接将一定量的FAI、PbI2、MABr和PbBr2固体粉末混合，并加入DMF和DMSO的混合溶剂；4.2) When preparing liquid A, directly mix a certain amount of FAI, PbI 2 , MABr and PbBr 2 solid powders, and add a mixed solvent of DMF and DMSO; 4.3)A液和B液按照一定比例均匀混合成若干份溶液，混合后的溶液在50～80℃加热并搅拌40～80分钟；根据所述若干份溶液中Cs+浓度的不同，计算并写出溶液的组成式为CsX(FA0.83MA0.17)(1-X)Pb(I0.83Br0.17)3，其中X的取值为：0.02<X<0.15，即铯离子占全部A位阳离子总摩尔数的2％～15％。4.3) Liquid A and liquid B are uniformly mixed into several solutions according to a certain ratio, and the mixed solution is heated and stirred at 50-80°C for 40-80 minutes; according to the difference in the concentration of Cs + in the several solutions, calculate and write The composition formula of the solution is Cs X (FA 0.83 MA 0.17 ) (1-X) Pb(I 0.83 Br 0.17 ) 3 , where the value of X is: 0.02<X<0.15, that is, cesium ions account for the total A-site cations 2% to 15% of the number of moles. 5.根据权利要求1所述的在空气环境中制备铯掺杂混合钙钛矿太阳能电池的方法，其特征在于：步骤4)中反溶剂包括氯苯、乙醚、乙酸乙酯或者甲苯中的至少一种。5. the method for preparing cesium-doped hybrid perovskite solar cell in air environment according to claim 1, is characterized in that: in step 4), anti-solvent comprises at least in chlorobenzene, ether, ethyl acetate or toluene A sort of. 6.根据权利要求1所述的在空气环境中制备铯掺杂混合钙钛矿太阳能电池的方法，其特征在于：步骤6)中热蒸镀的金属电极厚度为80～120nm，蒸镀在1*10-5～1*10-7torr的气压下进行。6. The method for preparing a cesium-doped hybrid perovskite solar cell in an air environment according to claim 1, characterized in that: in step 6), the thickness of the thermally evaporated metal electrode is 80-120nm, and the thickness of the evaporated metal electrode is 80-120nm. *10 -5 to 1*10 -7 torr air pressure. 7.根据权利要求1所述的在空气环境中制备铯掺杂混合钙钛矿太阳能电池的方法，其特征在于：步骤6)制得的铯掺杂混合钙钛矿太阳能电池从下往上依次包括透明导电衬底、电子传输层、铯掺杂混合钙钛矿吸光层、空穴传输层和金属对电极。7. the method for preparing cesium-doped hybrid perovskite solar cell in air environment according to claim 1, is characterized in that: the cesium-doped hybrid perovskite solar cell that step 6) makes is successively from bottom to top It includes a transparent conductive substrate, an electron transport layer, a cesium-doped mixed perovskite light-absorbing layer, a hole transport layer and a metal counter electrode.
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