WO2023141812A1 - 一种钙钛矿太阳能电池、其封装方法及包含其的光伏组件 - Google Patents

一种钙钛矿太阳能电池、其封装方法及包含其的光伏组件 Download PDF

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WO2023141812A1
WO2023141812A1 PCT/CN2022/074001 CN2022074001W WO2023141812A1 WO 2023141812 A1 WO2023141812 A1 WO 2023141812A1 CN 2022074001 W CN2022074001 W CN 2022074001W WO 2023141812 A1 WO2023141812 A1 WO 2023141812A1
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solar cell
perovskite
perovskite solar
transport layer
cell according
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PCT/CN2022/074001
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English (en)
French (fr)
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涂保
孙娟娟
陈长松
郭永胜
陈国栋
欧阳楚英
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宁德时代新能源科技股份有限公司
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Priority to EP22899631.0A priority Critical patent/EP4254514A4/en
Priority to CN202280052612.8A priority patent/CN117751699A/zh
Priority to PCT/CN2022/074001 priority patent/WO2023141812A1/zh
Priority to US18/333,211 priority patent/US11800727B1/en
Publication of WO2023141812A1 publication Critical patent/WO2023141812A1/zh

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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
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • 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
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • 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
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • 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
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
    • 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
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
    • 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
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • 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
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • 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

Definitions

  • the present application relates to the technical field of solar cells, in particular to a perovskite solar cell, a packaging method thereof, and a photovoltaic module containing the same.
  • a solar cell also known as a photovoltaic cell, is a device that directly converts light energy into electrical energy through the photoelectric effect or photochemical effect.
  • Perovskite cells are a new class of solar cells that are widely studied at present. They have rapidly obtained high photoelectric conversion efficiency within a few years after their birth, and their highest photoelectric conversion efficiency has exceeded 25%, which has a good application prospect. Due to the instability of the perovskite material itself, it is easy to decompose under the influence of light, heat, water, oxygen, etc.
  • the stability problem is the biggest obstacle on the road to the industrialization of perovskite batteries.
  • device packaging can block the contact of perovskite materials with water and oxygen, especially water vapor and oxygen to a certain extent, and improve the stability of water and oxygen, but it has little effect on the improvement of thermal stability.
  • the present application was made in view of the above-mentioned problems, and an object thereof is to provide a perovskite solar cell having good thermal stability, a method for encapsulating the same, and a photovoltaic module including the same.
  • the first aspect of the present application provides a perovskite solar cell, which includes the following components arranged in order from bottom to top:
  • the sealed space is formed between the transparent conductive glass substrate and the backplane glass under the action of the encapsulant, and the sealed space contains a mixture of inert gas and methylamine gas, wherein the volume ratio of the inert gas to methylamine gas is 9:1 to 5:5, optional 9:1 to 6:4, more optional 8:2 to 7:3.
  • the structure of the perovskite solar cell described in this application can effectively block the contact between water and oxygen, especially water vapor and oxygen, and the perovskite material, and at the same time prevent the decomposition of the perovskite layer to generate methylamine gas, thereby improving the stability of the perovskite solar cell sex and safety.
  • the absolute pressure in the enclosed space is 2-6 atmospheres.
  • the pressure in the enclosed space within the above range contributes to the formation of a stable package structure.
  • the perovskite layer is consistent with the area of the confined space, and the ratio of the thickness of the perovskite layer to the height of the confined space is 1/5000-1/500, which may be 1/2000-1/750.
  • the inert gas is selected from at least one of nitrogen and argon.
  • the perovskite layer comprises a compound of formula A 1 BX 3 or A 2 CDX 6 , wherein
  • a 1 is selected from at least one of CH 3 NH 3 + (MA + ) or CH(NH 2 ) 2 + (FA + );
  • a 2 is selected from at least one of Li + , Na + , K + , Rb + , and Cs + ;
  • Pb 2+ and Sn 2+ can be selected as at least one;
  • X is selected from at least one of F - , Cl - , Br - , I -, and may be at least one of Cl - , Br - , I - ;
  • C and D are independently selected from organic or inorganic cations, or organic-inorganic mixed cations, optionally transition metal cations, or mixed cations of transition metal cations and CH 3 NH 3 + or CH(NH 2 ) 2 + , more Optionally at least one of Pb(FA 0.83 MA 0.17 ) 3+ , CH 3 NH 3 Pb 3+ , Pb 2+ , Sr 2+ , Bi 3+ , and La 3+ .
  • the perovskite layer includes CH 3 NH 3 PbI 3 , CH(NH 2 ) 2 PbI 3 , Cs 0.05 (FA 0.83 MA 0.17 ) 0.95 Pb(I 0.83 Br 0.17 ) 3 , At least one of CsPbI 3 , CsPbI 2 Br or CsPbIBr 2 .
  • the encapsulant is selected from epoxy encapsulant, silicone encapsulant, polyurethane encapsulant, ethylene-vinyl acetate copolymer, polyvinyl butyral, polyolefin One or more of encapsulation glue.
  • the polyolefin encapsulant is selected from one or more of ethylene octene copolymer and polyisobutylene.
  • the encapsulation glue is selected from ultraviolet light curing encapsulation glue.
  • the transparent conductive glass substrate includes fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide One or more of (BZO), indium-doped zinc oxide (IZO).
  • FTO fluorine-doped tin oxide
  • ITO indium-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • BZO boron-doped zinc oxide
  • IZO indium-doped zinc oxide
  • the first transport layer is an electron transport layer
  • the second transport layer is a hole transport layer
  • the first transport layer is a hole transport layer
  • the The second transport layer is an electron transport layer
  • the electron transport layer includes at least one of the following materials, their derivatives, or materials obtained through doping or passivation: [6,6]-phenyl C 61 butyric acid Methyl ester (PC 61 BM), [6,6]-phenyl C 71 butyric acid methyl ester (PC 71 BM), fullerene C60 (C60), fullerene C70 (C70), tin dioxide (SnO 2 ), zinc oxide (ZnO).
  • the hole transport layer includes at least one of the following materials, their derivatives, or materials obtained through doping or passivation: poly[bis(4-phenyl)(2 ,4,6-trimethylphenyl)amine] (PTAA), poly-3-hexylthiophene (P3HT), triphenylamine (H101) with triptycene as the core, 3,4-ethylenedioxythiophene-methanol Oxytriphenylamine (EDOT-OMeTPA), N-(4-aniline)carbazole-spirobifluorene (CzPAF-SBF), poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) ( PEDOT:PSS), polythiophene, nickel oxide (NiO x ), molybdenum oxide (MoO 3 ), cuprous iodide (CuI), cuprous oxide (Cu 2 O).
  • PEDOT poly(styrenesulfonate)
  • PEDOT
  • the conductive electrode includes at least one of the following materials: Ag, Cu, C, Au, Al, indium-doped tin oxide (ITO), aluminum-doped zinc oxide (AZO) , Boron doped zinc oxide (BZO), indium doped zinc oxide (IZO).
  • ITO indium-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • BZO Boron doped zinc oxide
  • IZO indium doped zinc oxide
  • the thickness of the perovskite layer is 300-1000 nm.
  • a second aspect of the present application provides a packaging method for a perovskite solar cell, which at least includes the following steps:
  • Step 1 providing a perovskite solar cell module, which at least includes a transparent conductive glass substrate, a back glass and a perovskite layer between them; and
  • Step 2 A closed space is formed between the transparent conductive glass substrate and the back glass under the action of the encapsulant, and the volume ratio in the closed space is 9:1 to 5:5, optionally 9:1 to 6: 4. It is more optional to be a mixture of inert gas and methylamine gas in the range of 8:2 to 7:3.
  • a third aspect of the present application provides a photovoltaic module, which includes the perovskite solar cell described in the first aspect of the present application.
  • the photovoltaic module of the present application includes the perovskite solar cell described in the first aspect of the present application, and thus has the same advantages as the perovskite solar cell described in the present application.
  • Figure 1 is a schematic diagram of the structure of a gas-assisted packaging perovskite solar cell.
  • FIG. 2 is a graph showing the photoelectric conversion efficiency (after normalization) of the perovskite solar cells obtained in the comparative examples and examples of the present application as a function of storage time (days).
  • ranges disclosed herein are defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are contemplated. Additionally, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range "a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
  • steps (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c) , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b) and so on.
  • the “comprising” and “comprising” mentioned in this application mean open or closed.
  • the “comprising” and “comprising” may mean that other components not listed may be included or included, or only listed components may be included or included.
  • the term "or” is inclusive unless otherwise stated.
  • the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; or both A and B are true (or exist).
  • the term “consistent area” used in this application means that the projected areas of two objects along a certain direction are roughly equal, and the difference is not more than ⁇ 5%.
  • the area of the perovskite layer is consistent with that of the enclosed space means that the projected areas of the perovskite layer and the enclosed space along the thickness direction of the perovskite layer are approximately equal, and the difference does not exceed ⁇ 5%.
  • the inventors found that encapsulating perovskite solar cells with a mixture of inert gas and methylamine gas can effectively alleviate the phenomenon of yellowing of the device and fogging of the electrodes.
  • the thermal stability of the solar cell can be further improved, and the photoelectric conversion efficiency can be improved.
  • the reason for the above phenomenon may be that the perovskite decomposes during storage, causing methylamine gas to escape from the light-absorbing layer, leaving behind lead iodide, etc.
  • perovskite solar cells described in this application can be applied in various scenarios like conventional perovskite cells, such as power stations, photovoltaic buildings, photovoltaic electronic devices, and the like.
  • the first aspect of the present application provides a perovskite solar cell, which includes the following components arranged in order from bottom to top:
  • the sealed space is formed between the transparent conductive glass substrate and the backplane glass under the action of the encapsulant, and the sealed space contains a mixture of inert gas and methylamine gas, wherein the volume ratio of the inert gas to methylamine gas is 9:1 to 5:5, optional 9:1 to 6:4, more optional 8:2 to 7:3.
  • perovskite solar cells Due to the instability of the perovskite material itself, perovskite solar cells are prone to decomposition under the influence of light, heat, water, oxygen, etc., resulting in a decrease in photoelectric conversion efficiency.
  • the perovskite solar cell described in this application contains an externally added inert gas and methylamine gas, which can effectively block water and oxygen, especially water vapor and oxygen, from contacting with perovskite materials, and at the same time can be used under the condition of concentration difference or positive pressure Effectively inhibit the escape of methylamine gas generated by the decomposition of perovskite, thereby improving the stability of the packaging structure.
  • methylamine gas is flammable, so choosing an appropriate amount can further improve safety performance.
  • Figure 1 shows an example structure of the perovskite solar cell of the present application.
  • the first transmission layer (102) is arranged on the top of the transparent conductive glass substrate (101), the perovskite layer (103) is close to the top of the first transmission layer (102), and the second transmission layer (104) is close to
  • the conductive electrode (105) is located on the upper part of the second transmission layer; the surrounding edges of the transparent conductive glass substrate (101) and the back glass (106) are sealed with encapsulation glue (107), and the perovskite layer (103) is encapsulated in the airtight space (108) formed by the transparent conductive glass substrate (101), the back glass (106) and the encapsulant (107), wherein the airtight space (108) is filled with inert gas and methylamine mixture of gases.
  • the volume ratio of argon and methylamine gas is 10:1
  • the stability of the device is not significantly improved, which is almost equivalent to that of the device without adding methylamine gas.
  • the volume ratio increases from 9:1 to 8:2
  • the volume ratio of argon to methylamine gas continues to increase, for example, when it is greater than 8:2, the normalized efficiency does not change much, indicating that the stability of the battery does not change significantly.
  • the solar cell components can be prepared by methods commonly used in this field, such as sputtering, spin coating and the like.
  • the absolute pressure in the enclosed space is 2-6 atmospheres.
  • the absolute pressure in the confined space at 2-6 atmospheres can effectively prevent the infiltration of external gas and block the contact of the perovskite layer with moisture or oxygen, thereby improving the water and oxygen stability of the perovskite solar cell.
  • keeping the absolute pressure in the enclosed space within the above range can avoid internal rupture due to too much pressure in the enclosed space or insufficient bonding force provided by the encapsulant to form the enclosed space, thereby ensuring the stability of the encapsulation structure.
  • the perovskite layer will still decompose to a certain extent during the use of the perovskite solar cell to generate methylamine gas.
  • the amount of methylamine gas added in the closed space is far more than the amount of methylamine gas produced by the decomposition of the perovskite. Therefore, after a period of use, the volume ratio of the inert gas to the methylamine gas in the closed space or The pressure in the confined space does not change significantly.
  • the perovskite layer is consistent with the area of the confined space, and the ratio of the thickness of the perovskite layer to the height of the confined space is 1/5000-1/500, which may be 1/2000-1/750.
  • the inert gas is selected from at least one of nitrogen and argon.
  • the inert gas keeps the perovskite layer free from oxygen, thereby reducing the possibility of decomposition of the perovskite layer.
  • the perovskite layer includes a compound of formula A 1 BX 3 or A 2 CDX 6 , wherein
  • a 1 is selected from at least one of CH 3 NH 3 + (MA + ) or CH(NH 2 ) 2 + (FA + );
  • a 2 is selected from at least one of Li + , Na + , K + , Rb + , and Cs + ;
  • Pb 2+ and Sn 2+ can be selected as at least one;
  • X is selected from at least one of F - , Cl - , Br - , I -, and may be at least one of Cl - , Br - , I - ;
  • C and D are independently selected from organic or inorganic cations, or organic-inorganic mixed cations, optionally transition metal cations, or mixed cations of transition metal cations and CH 3 NH 3 + or CH(NH 2 ) 2 + , more Optionally at least one of Pb(FA 0.83 MA 0.17 ) 3+ , CH 3 NH 3 Pb 3+ , Pb 2+ , Sr 2+ , Bi 3+ , and La 3+ .
  • the perovskite layer includes CH 3 NH 3 PbI 3 , CH(NH 2 ) 2 PbI 3 , Cs 0.05 (FA 0.83 MA 0.17 ) 0.95 Pb(I 0.83 Br 0.17 ) 3 , At least one of CsPbI 3 , CsPbI 2 Br or CsPbIBr 2 .
  • the material selection of the encapsulant there is no particular limitation on the material selection of the encapsulant, and the encapsulant commonly used in this field can be used.
  • the encapsulant has good adhesiveness, which is sufficient to provide the adhesive force needed to form a closed space.
  • the encapsulant is selected from epoxy encapsulant, silicone encapsulant, polyurethane encapsulant, ethylene-vinyl acetate copolymer, polyvinyl butyral, polyolefin One or more of encapsulation glue.
  • the polyolefin encapsulant is selected from one or more of ethylene octene copolymer and polyisobutylene.
  • the encapsulation glue is selected from ultraviolet light curing encapsulation glue.
  • the present application has no special limitation on the material selection of the transparent conductive glass substrate, and the transparent conductive glass substrate commonly used in this field can be used.
  • the transparent conductive glass substrate includes fluorine-doped tin dioxide (FTO), indium-doped tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide ( One or more of BZO), indium-doped zinc oxide (IZO).
  • FTO fluorine-doped tin dioxide
  • ITO indium-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • BZO boron-doped zinc oxide
  • IZO indium-doped zinc oxide
  • the first transport layer is an electron transport layer
  • the second transport layer is a hole transport layer
  • the first transport layer is a hole transport layer
  • the second transport layer is an electron transport layer
  • the electron transport layer includes at least one of the following materials, their derivatives, or materials obtained by doping or passivation:
  • the hole transport layer includes at least one of the following materials, their derivatives, or materials obtained by doping or passivation:
  • the conductive electrode (105) includes at least one of the following materials: Ag, Cu, C, Au, Al, indium-doped tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron doped zinc oxide (BZO), indium doped zinc oxide (IZO).
  • ITO indium-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • BZO boron doped zinc oxide
  • IZO indium doped zinc oxide
  • the thickness of the perovskite layer is 300-1000 nm.
  • the bandgap of the perovskite layer is 1.20-2.30eV.
  • the measurement of the bandgap of the perovskite layer can be performed by methods commonly used in the art, for example, an ultraviolet absorption curve can be obtained through ultraviolet absorption spectroscopy, and then calculated by Tauc equation.
  • a second aspect of the present application provides a packaging method for a perovskite solar cell, which at least includes the following steps:
  • Step 1 providing a perovskite solar cell module, which at least includes a transparent conductive glass substrate, a back glass and a perovskite layer between them; and
  • Step 2 A closed space is formed between the transparent conductive glass substrate and the back glass under the action of the encapsulant, and the volume ratio in the closed space is 9:1 to 5:5, optionally 9:1 to 6: 4. It is more optional to be a mixture of inert gas and methylamine gas in the range of 8:2 to 7:3.
  • the encapsulation method described in the present application is preferably carried out in a conventional encapsulation container such as a glove box and other airtight pressure equipment under a mixture atmosphere of inert gas and methylamine gas.
  • the pressure in the closed pressure equipment can be adjusted by methods commonly used in the art, such as by adjusting the feed pressure, flow rate, etc. of inert gas and methylamine gas.
  • the perovskite solar cell module in addition to the transparent conductive glass substrate, the back glass and the perovskite layer, the perovskite solar cell module usually also includes components such as an electron transport layer, a hole transport layer and a conductive electrode.
  • Perovskite solar cells have a very wide range of applications in many fields such as power stations, photovoltaic buildings, and photovoltaic electronic devices. It should be understood that the examples provided in the present application are only used to illustrate the application of the perovskite solar cell described in the application, and those skilled in the art understand that the application is not limited to the application provided in the examples.
  • a third aspect of the present application provides a photovoltaic module, which includes the perovskite solar cell described in the first aspect of the present application.
  • the specific composition is: the solvent is N,N-dimethylformamide and dimethyl sulfoxide, and the volume ratio of the two solvents is 4:1, the solid substance is lead iodide (1.0M, namely 1.0mol/L, the same below), lead bromide (0.2M), formamidine hydroiodide (0.95M), methylamine hydrobromide ( 0.19M), cesium iodide (0.06M)), then annealed at 100°C for 30 minutes, and then cooled to room temperature to obtain a perovskite layer with a thickness of about 600nm.
  • the active material of the obtained perovskite layer is Cs 0.05 (FA 0.83 MA 0.17 ) 0.95 Pb(I 0.83 Br 0.17 ) 3 (CsFAMA);
  • step 6) transfer the film layer obtained in step 5) to an evaporation machine, and evaporate Ag metal electrodes;
  • Step 6) gained film layer is transferred in the glove box (the mixture of argon gas and methylamine gas in the glove box, wherein the volume ratio of argon gas and methylamine gas is 6:4, and the absolute pressure in the glove box is 3 atmospheres) for packaging, set 0.5mL of UV-curable adhesive (Norland UV-curable optical adhesive NOA61 ), thus forming a closed space with a volume of about 0.1125cm 3 between the ITO conductive glass and the cover glass.
  • UV-curable adhesive Norland UV-curable optical adhesive NOA61
  • the perovskite solar cell described in Example 1 can be obtained, marked as cell 1 .
  • Example 2 Except that the volume ratio of argon gas to methylamine gas was adjusted to 7:3 in step 7), the other conditions of Example 2 were the same as those of Example 1, and the obtained battery was marked as Battery 2.
  • Example 2 Except that the volume ratio of argon gas to methylamine gas was adjusted to 8:2 in step 7), the other conditions of Example 2 were the same as those of Example 1, and the obtained battery was marked as Battery 3.
  • Example 2 Except that the volume ratio of argon gas to methylamine gas was adjusted to 9:1 in step 7), the other conditions of Example 2 were the same as those of Example 1, and the obtained battery was marked as Battery 4.
  • step 7 the volume ratio of argon gas to methylamine gas is adjusted to 10:1 and 4:6 respectively, the other conditions of Comparative Examples 2 and 3 are the same as in Example 1, and the batteries obtained are marked as battery 6 and battery7.
  • the test method and data processing process after packaging After the device is packaged, it is stored for different days under the conditions of 85°C and 85%RH ( relative humidity).
  • the photoelectric conversion efficiency of the device is calculated according to the short-circuit current, open-circuit voltage and fill factor given by the software.
  • the normalization process takes the efficiency of 0 days as 100%, and divides the subsequent efficiency by the efficiency of 0 days to obtain the remaining proportion after the change.
  • the normalized efficiency change curve can be obtained by plotting the obtained ratio with the number of storage days.
  • the present invention uses the mixture of inert gas and methylamine gas to encapsulate the stability of the obtained perovskite solar cell. Sex is improved.
  • the gas volume ratio is 10:1
  • the stability improvement is not obvious compared with other ratios, and it is not much different from the blank.
  • the gas volume ratio is 4:6, the stability is improved obviously, but the initial efficiency of the device is already obvious. reduce.
  • the volume ratio of argon to methylamine gas increased from 9:1 to 5:5, the stability of the corresponding perovskite solar cells was further improved, and the device efficiency did not change significantly.
  • the volume ratio of amine gas continues to increase, for example, when it is greater than 8:2, the stability of the battery does not change significantly.
  • the present application is not limited to the above-mentioned embodiments.
  • the above-mentioned embodiments are merely examples, and within the scope of the technical solutions of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same effects are included in the technical scope of the present application.
  • various modifications conceivable by those skilled in the art are added to the embodiments, and other forms constructed by combining some components in the embodiments are also included in the scope of the present application. .

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Abstract

本申请提供一种钙钛矿太阳能电池、其封装方法以及包含其的光伏组件。所述钙钛矿太阳能电池包括从下至上依次设置的以下部件：透明导电玻璃基底(101)；第一传输层(102)；钙钛矿层(103)；第二传输层(104)；导电电极(105)；背板玻璃(106)；和封装胶(107)；其中所述透明导电玻璃基底(101)与背板玻璃(106)之间在封装胶(107)的作用下形成密闭空间(108)，所述密闭空间(108)内包含惰性气体和甲胺气体的混合物，其中所述惰性气体与甲胺气体的体积比为9:1至5:5，可选为9:1至6:4，更可选为8:2至7:3。

Description

一种钙钛矿太阳能电池、其封装方法及包含其的光伏组件 技术领域
本申请涉及太阳能电池技术领域，具体涉及一种钙钛矿太阳能电池、其封装方法及包含其的光伏组件。
背景技术
近年来，全球能源短缺和环境污染问题日益突出，太阳能电池作为理想的可再生能源受到越来越多的重视。太阳能电池，又称为光伏电池，是一种通过光电效应或光化学效应将光能直接转化为电能的装置。钙钛矿电池是目前广泛研究的一类新型太阳能电池，其在诞生后的几年内迅速获得了较高的光电转换效率，其最高光电转换效率已超过25％，具有良好的应用前景。由于钙钛矿材料本身的不稳定性，在光、热、水、氧等的影响下极易发生分解，A位阳离子气体的释放会进一步加速钙钛矿结构的瓦解，致使光电转换效率的进一步下降，因此，稳定性问题是钙钛矿电池产业化道路上的最大阻碍。一般通过器件封装可在一定程度上阻绝钙钛矿材料与水氧、特别是水蒸气和氧气的接触，提高水氧稳定性，但对于热稳定性能的改善则作用不大。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种热稳定性良好的钙钛矿太阳能电池、其封装方法以及包含其的光伏组件。
本申请的第一方面提供一种钙钛矿太阳能电池，其包括从下至上依次设置的以下部件：
透明导电玻璃基底；
第一传输层；
钙钛矿层；
第二传输层；
导电电极；
背板玻璃；和
封装胶；
其中所述透明导电玻璃基底与背板玻璃之间在封装胶的作用下形成密闭空间，所述密闭空间内包含惰性气体和甲胺气体的混合物，其中所述惰性气体与甲胺气体的体积比为9:1至5:5，可选为9:1至6:4，更可选为8:2至7:3。
本申请所述钙钛矿太阳能电池的结构可有效阻隔水氧、特别是水蒸气和氧气与钙钛矿材料接触，同时阻碍钙钛矿层分解产生甲胺气体，从而提升钙钛矿太阳能电池的稳定性和安全性。
在任意实施方式中，可选地，所述密闭空间内的绝对压力为2-6个大气压。密闭空间内在上述范围内的压力有助于形成稳定的封装结构。
在任意实施方式中，可选地，所述钙钛矿层与所述密闭空间面积一致，所述钙钛矿层的厚度与所述密闭空间的高度比为1/5000-1/500，可选为1/2000-1/750。
在任意实施方式中，可选地，所述惰性气体选自氮气、氩气中的至少一种。
在任意实施方式中，可选地，所述钙钛矿层包括式A 1BX 3或A 2CDX 6的化合物，其中
A 1选自CH 3NH 3 +(MA +)或CH(NH 2) 2 +(FA +)中的至少一种；
A 2选自Li +、Na +、K +、Rb +、Cs +中的至少一种；
B选自Pb 2+、Sn 2+、Be 2+、Mg 2+、Ca 2+、Sr 2+、Ba 2+、Zn 2+、Ge 2+、Fe 2+、Co 2+、Ni 2+中的至少一种，可选为Pb 2+、Sn 2+中的至少一种；
X选自F -、Cl -、Br -、I -中的至少一种，可选为Cl -、Br -、I -中的至少一种；和
C、D彼此独立地选自有机或无机阳离子、或有机无机混合阳离子，可选地为过渡金属阳离子、或过渡金属阳离子与CH 3NH 3 +或CH(NH 2) 2 +的混合阳离子，更可选地为Pb(FA 0.83MA 0.17) 3+、CH 3NH 3Pb 3+、 Pb 2+、Sr 2+、Bi 3+、La 3+中的至少一种。
在任意实施方式中，可选地，所述钙钛矿层包括CH 3NH 3PbI 3、CH(NH 2) 2PbI 3、Cs 0.05(FA 0.83MA 0.17) 0.95Pb(I 0.83Br 0.17) 3、CsPbI 3、CsPbI 2Br或CsPbIBr 2中的至少一种。
在任意实施方式中，可选地，所述封装胶选自环氧类封装胶、有机硅类封装胶、聚氨酯封装胶、乙烯-醋酸乙烯酯共聚物、聚乙烯醇缩丁醛、聚烯烃类封装胶中的一种或多种。
在任意实施方式中，可选地，所述聚烯烃类封装胶选自乙烯辛烯共聚物、聚异丁烯中的一种或多种。
在任意实施方式中，可选地，所述封装胶选自紫外线光固化封装胶。
在任意实施方式中，可选地，所述透明导电玻璃基底包括氟掺杂二氧化锡(FTO)、铟掺杂氧化锡(ITO)、铝掺杂氧化锌(AZO)、硼掺杂氧化锌(BZO)、铟掺杂氧化锌(IZO)中的一种或多种。
在任意实施方式中，可选地，所述第一传输层为电子传输层，并且所述第二传输层为空穴传输层；或所述第一传输层为空穴传输层，并且所述第二传输层为电子传输层。
在任意实施方式中，可选地，所述电子传输层包括以下材料、其衍生物或其经掺杂或钝化所得材料中的至少一种：[6,6]-苯基C 61丁酸甲酯(PC 61BM)、[6,6]-苯基C 71丁酸甲酯(PC 71BM)、富勒烯C60(C60)、富勒烯C70(C70)、二氧化锡(SnO 2)、氧化锌(ZnO)。
在任意实施方式中，可选地，所述空穴传输层包括以下材料、其衍生物或其经掺杂或钝化所得材料中的至少一种：聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚-3-己基噻吩(P3HT)、以三蝶烯为核的三苯胺(H101)、3,4-乙烯二氧噻吩-甲氧基三苯胺(EDOT-OMeTPA)、N-(4-苯胺)咔唑-螺双芴(CzPAF-SBF)、聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)(PEDOT:PSS)、聚噻吩、氧化镍(NiO x)、氧化钼(MoO 3)、碘化亚铜(CuI)、氧化亚铜(Cu 2O)。
在任意实施方式中，可选地，所述导电电极包括以下材料中的至 少一种：Ag、Cu、C、Au、Al、铟掺杂氧化锡(ITO)、铝掺杂氧化锌(AZO)、硼掺杂氧化锌(BZO)、铟掺杂氧化锌(IZO)。
在任意实施方式中，可选地，所述钙钛矿层的厚度为300-1000nm。
本申请的第二方面提供一种钙钛矿太阳能电池的封装方法，其至少包括以下步骤：
步骤1：提供钙钛矿太阳能电池组件，其至少包括透明导电玻璃基底、背板玻璃和位于二者之间的钙钛矿层；和
步骤2：在透明导电玻璃基底与背板玻璃之间在封装胶的作用下形成密闭空间，所述密闭空间内包含体积比为9:1至5:5，可选为9:1至6:4，更可选为8:2至7:3的惰性气体和甲胺气体的混合物。
本申请的第三方面提供一种光伏组件，其包括本申请第一方面所述的钙钛矿太阳能电池。
本申请的光伏组件包含通过本申请第一方面所述的钙钛矿太阳能电池，因而具有与本申请所述钙钛矿太阳能电池相同的优势。
附图说明
图1为气体辅助封装钙钛矿太阳能电池的结构示意图。
图2为本申请对比例与实施例所得钙钛矿太阳能电池的光电转换效率(归一化后)随存储时间(天)变化的曲线图。
附图标记说明：
101透明导电玻璃基底；102第一传输层；103钙钛矿层；104第二传输层；105导电电极；106背板玻璃；107封装胶；和108密闭空间。
具体实施方式
以下，适当地参照附图详细说明公开了本申请的钙钛矿电池以及封装方法的实施方式，但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解 本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例 来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
需要说明的是，本申请中使用的术语“面积一致”是指两种物体沿某一方向的投影面积大致相等，差异不超过±5％。例如，在本申请中，“钙钛矿层与密闭空间面积一致”是指，钙钛矿层和密闭空间沿钙钛矿层厚度方向上的投影面积大致相等，差异不超过±5％。
发明人在实际工作中发现，通过惰性气体和甲胺气体的混合物对钙钛矿太阳能电池进行封装，可以有效缓解器件发黄、电极呈现雾状等现象。通过调控混合物的压力以及惰性气体与甲胺气体的体积比，可以进一步提升太阳能电池的热稳定性，提高光电转换效率。不希望囿于任何理论，上述现象发生的原因可能是在储存过程中钙钛矿发生了分解，导致甲胺气体从吸光层中逸出，留下碘化铅等。
在进一步研究后发现，本申请所述钙钛矿太阳能电池可以与常规钙钛矿电池一样应用于多种场景中，例如电站、光伏建筑、光伏电子器件等。
[钙钛矿太阳能电池]
本申请的第一方面提供一种钙钛矿太阳能电池，其包括从下至上依次设置的以下部件：
透明导电玻璃基底；
第一传输层；
钙钛矿层；
第二传输层；
导电电极；
背板玻璃；和
封装胶；
其中所述透明导电玻璃基底与背板玻璃之间在封装胶的作用下 形成密闭空间，所述密闭空间内包含惰性气体和甲胺气体的混合物，其中所述惰性气体与甲胺气体的体积比为9:1至5:5，可选为9:1至6:4，更可选为8:2至7:3。
由于钙钛矿材料本身的不稳定性，钙钛矿太阳能电池在光、热、水、氧等的影响下容易发生分解，致使光电转换效率下降。本申请所述钙钛矿太阳能电池包含外部添加的惰性气体和甲胺气体，可有效阻隔水氧、特别是水蒸气和氧气与钙钛矿材料接触，同时可在浓度差或正压的情况下有效抑制钙钛矿分解所产生的甲胺气体的逸出，从而提升封装结构的稳定性。另外，甲胺气体具有易燃性，因此选择适当的用量，能够进一步提高安全性能。
图1给出了本申请钙钛矿太阳能电池的示例结构。参见图1，第一传输层(102)设置在透明导电玻璃基底(101)的上部，钙钛矿层(103)紧贴在第一传输层(102)上部，第二传输层(104)紧贴在钙钛矿层(103)的上部，导电电极(105)位于第二传输层上部；透明导电玻璃基底(101)与背板玻璃(106)四周边缘采用封装胶(107)进行密封，钙钛矿层(103)被封装在透明导电玻璃基底(101)、背板玻璃(106)和封装胶(107)所形成的密闭空间(108)内，其中密闭空间(108)内填充有惰性气体与甲胺气体的混合物。
发明人在进一步研究后发现，通过优化密闭空间内惰性气体与甲胺气体的体积比，能够进一步改善钙钛矿太阳能电池的稳定性。如附图2所示，当氩气与甲胺气体的体积比为10：1时，器件稳定性提升不明显，几乎与不添加甲胺气体的器件相当，随着氩气与甲胺气体的体积比从9:1增加至8:2，钙钛矿太阳能电池的归一化效率随时间变化程度进一步减小，表明电池的稳定性得到改善。但随着氩气与甲胺气体的体积比继续增大，例如大于8:2时，归一化效率则变化不大，表明电池的稳定性变化不明显。这主要是由于钙钛矿太阳能电池中钙钛矿分解产生的甲胺气体的量是一定的，当甲胺气体的体积占比达到20％时即可有效抑制钙钛矿太阳能电池中甲胺气体的逸出，无需进一步增加。最后，对比例3中可以发现，当甲胺气体占比进一步增加， 氩气与甲胺气体的体积比为4：6时，稳定性提升明显，但追踪原始数据可以发现，器件的初始效率已经明显下降。
在本申请中，太阳能电池部件的制备可采用本领域通常使用的方法，例如可通过溅射法、旋涂法等。
在一些实施方式中，可选地，所述密闭空间内的绝对压力为2-6个大气压。
保持密闭空间内的绝对压力为2-6个大气压，可有效防止外部气体渗入，阻隔钙钛矿层与水分或氧气的接触，从而提高钙钛矿太阳能电池的水氧稳定性。同时，保持密闭空间内的绝对压力在上述范围内，可避免密闭空间内压力太大而造成内部破裂或导致封装胶所提供的粘结力不足以形成所述密闭空间，从而确保封装结构稳定。
需要说明的是，尽管存在所添加的惰性气体和甲胺气体的抑制作用，但在钙钛矿太阳能电池的使用过程中，钙钛矿层仍会发生一定程度的分解，产生甲胺气体。然而，密闭空间中所添加的甲胺气体的量远多于钙钛矿分解所产生的甲胺气体的量，因此，在使用一段时间后，密闭空间内惰性气体与甲胺气体的体积比或密闭空间内的压力并无较大变化。
在一些实施方式中，可选地，所述钙钛矿层与所述密闭空间面积一致，所述钙钛矿层的厚度与所述密闭空间的高度比为1/5000-1/500，可选为1/2000-1/750。
在一些实施方式中，可选地，所述惰性气体选自氮气、氩气中的至少一种。惰性气体可保证钙钛矿层不接触氧气，从而降低钙钛矿层分解的可能性。
本申请对钙钛矿层的组成没有特别限制，可采用本领域通常使用的钙钛矿材料。在一些实施方式中，可选地，所述钙钛矿层包括式A 1BX 3或A 2CDX 6的化合物，其中
A 1选自CH 3NH 3 +(MA +)或CH(NH 2) 2 +(FA +)中的至少一种；
A 2选自Li +、Na +、K +、Rb +、Cs +中的至少一种；
B选自Pb 2+、Sn 2+、Be 2+、Mg 2+、Ca 2+、Sr 2+、Ba 2+、Zn 2+、Ge 2+、 Fe 2+、Co 2+、Ni 2+中的至少一种，可选为Pb 2+、Sn 2+中的至少一种；
X选自F -、Cl -、Br -、I -中的至少一种，可选为Cl -、Br -、I -中的至少一种；和
C、D彼此独立地选自有机或无机阳离子、或有机无机混合阳离子，可选地为过渡金属阳离子、或过渡金属阳离子与CH 3NH 3 +或CH(NH 2) 2 +的混合阳离子，更可选地为Pb(FA 0.83MA 0.17) 3+、CH 3NH 3Pb 3+、Pb 2+、Sr 2+、Bi 3+、La 3+中的至少一种。
在一些实施方式中，可选地，所述钙钛矿层包括CH 3NH 3PbI 3、CH(NH 2) 2PbI 3、Cs 0.05(FA 0.83MA 0.17) 0.95Pb(I 0.83Br 0.17) 3、CsPbI 3、CsPbI 2Br或CsPbIBr 2中的至少一种。
在本申请中，对封装胶的选材没有特别限制，可采用本领域中通常使用的封装胶。可选地，所述封装胶具备良好的粘结性，足以提供形成密闭空间所需的粘结力。
在一些实施方式中，可选地，所述封装胶选自环氧类封装胶、有机硅类封装胶、聚氨酯封装胶、乙烯-醋酸乙烯酯共聚物、聚乙烯醇缩丁醛、聚烯烃类封装胶中的一种或多种。
在一些实施方式中，可选地，所述聚烯烃类封装胶选自乙烯辛烯共聚物、聚异丁烯中的一种或多种。
在一些实施方式中，可选地，所述封装胶选自紫外线光固化封装胶。
本申请对透明导电玻璃基底的选材没有特别限制，可采用本领域通常使用的透明导电玻璃基底。在一些实施方式中，可选地，所述透明导电玻璃基底包括氟掺杂二氧化锡(FTO)、铟掺杂氧化锡(ITO)、掺铝氧化锌(AZO)、硼掺杂氧化锌(BZO)、铟掺杂氧化锌(IZO)中的一种或多种。
在一些实施方式中，可选地，所述第一传输层为电子传输层，并且所述第二传输层为空穴传输层；或
所述第一传输层为空穴传输层，并且所述第二传输层为电子传输层。
在一些实施方式中，可选地，所述电子传输层包括以下材料、其衍生物或其经掺杂或钝化所得材料中的至少一种：
[6,6]-苯基C 61丁酸甲酯(PC 61BM)、[6,6]-苯基C 71丁酸甲酯(PC 71BM)、富勒烯C60(C60)、富勒烯C70(C70)、二氧化锡(SnO 2)、氧化锌(ZnO)。
在一些实施方式中，可选地，所述空穴传输层包括以下材料、其衍生物或其经掺杂或钝化所得材料中的至少一种：
聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚-3-己基噻吩(P3HT)、以三蝶烯为核的三苯胺(H101)、3,4-乙烯二氧噻吩-甲氧基三苯胺(EDOT-OMeTPA)、N-(4-苯胺)咔唑-螺双芴(CzPAF-SBF)、聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)(PEDOT:PSS)、聚噻吩、氧化镍(NiO x)、氧化钼(MoO 3)、碘化亚铜(CuI)、氧化亚铜(Cu 2O)。
在一些实施方式中，可选地，所述导电电极(105)包括以下材料中的至少一种：Ag、Cu、C、Au、Al、铟掺杂氧化锡(ITO)、铝掺杂氧化锌(AZO)、硼掺杂氧化锌(BZO)、铟掺杂氧化锌(IZO)。
在一些实施方式中，可选地，所述钙钛矿层的厚度为300-1000nm。
在一些实施方式中，可选地，所述钙钛矿层的带隙为1.20-2.30eV。钙钛矿层带隙的测量可通过本领域通常使用的方法进行，例如可通过紫外吸收光谱测试获得紫外吸收曲线，然后通过Tauc方程计算得到。
[封装方法]
本申请的第二方面提供一种钙钛矿太阳能电池的封装方法，其至少包括以下步骤：
步骤1：提供钙钛矿太阳能电池组件，其至少包括透明导电玻璃基底、背板玻璃和位于二者之间的钙钛矿层；和
步骤2：在透明导电玻璃基底与背板玻璃之间在封装胶的作用下形成密闭空间，所述密闭空间内包含体积比为9:1至5:5，可选为9:1至6:4，更可选为8:2至7:3的惰性气体和甲胺气体的混合物。
本申请所述封装方法优选在惰性气体和甲胺气体的混合物气氛下在常规封装容器例如手套箱等密闭压力设备中进行。可通过本领域 通常使用的方法来调节密闭压力设备内的压力，例如通过调节惰性气体和甲胺气体的进料压力、流量等。
本领域技术人员可以理解的是，钙钛矿太阳能电池组件除透明导电玻璃基底、背板玻璃和钙钛矿层之外，通常还包括电子传输层、空穴传输层和导电电极等组件。
[光伏组件]
钙钛矿太阳能电池在众多领域例如电站、光伏建筑、光伏电子器件等中具有非常广泛的应用。应当理解的是，本申请所提供的实例仅用于说明本申请所述钙钛矿太阳能电池的用途，本领域技术人员理解，所述用途并不局限于示例所提供的用途。
本申请的第三方面提供一种光伏组件，其包括本申请第一方面所述的钙钛矿太阳能电池。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例中使用的原料来源如下表所示：
名称 CAS 厂家
聚[双(4-苯基)(2,4,6-三甲基苯基)胺] 1333317-99-9 西安宝莱特
[6,6]-苯基C 61丁酸甲酯 160848-22-6 西安宝莱特
浴铜灵 4733-39-5 西安宝莱特
碘化铅 10101-63-0 西安宝莱特
甲脒氢碘酸盐 879643-71-7 西安宝莱特
甲胺氢溴酸盐 6876-37-5 西安宝莱特
碘化铯 7789-17-5 西安宝莱特
溴化铅 10031-22-8 西安宝莱特
氯苯 108-90-7 Sigma
N,N-二甲基甲酰胺 68-12-2 Sigma
二甲基亚砜 67-68-5 Sigma
异丙醇 67-63-0 Sigma
实施例1
1)取20片(用于重复实验)规格为2.0×2.0cm(导电玻璃总厚度为1.1mm，其中ITO厚度约100nm)的ITO导电玻璃基底，将2.0×2.0cm面积的两端通过激光刻蚀各去掉宽度为0.35cm、长度为2cm的ITO，裸露出玻璃基底(即底部有效ITO面积变成2×(2-0.35×2)cm 2)；
2)依次用水、丙酮、异丙醇通过超声清洗刻蚀后的ITO导电玻璃数次，直至玻璃表面无异物和污垢，然后将ITO导电玻璃在氮气枪下吹干溶剂，放入紫外臭氧机中进一步清洗；
3)在紫外臭氧处理后的ITO导电玻璃基片上以5000rpm的速率旋涂2mg/mL的聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)的氯苯溶液，然后在100℃下退火10分钟，得到厚度约为20nm的有机空穴传输层；
4)在步骤3)所得膜层上以5000rpm的转速旋涂钙钛矿前驱液(具体组成为：溶剂为N,N-二甲基甲酰胺和二甲基亚砜，两种溶剂体积比为4：1，固体物质为碘化铅(1.0M，即1.0mol/L，下同)、溴化铅(0.2M)、甲脒氢碘酸盐(0.95M)、甲胺氢溴酸盐(0.19M)、碘化铯(0.06M))，然后在100℃下退火30分钟，之后冷却至室温，获得厚度约为600nm的钙钛矿层，所得钙钛矿层的活性物质为Cs 0.05(FA 0.83MA 0.17) 0.95Pb(I 0.83Br 0.17) 3(CsFAMA)；
5)在步骤4)所得膜层上以1500rpm的转速旋涂20mg/mL的[6,6]-苯基C 61丁酸甲酯(PCBM)的氯苯溶液，然后在100℃下退火10分 钟，所得旋涂厚度约为60nm，紧接着以5000rpm的速率旋涂钝化层浴铜灵(BCP)，旋涂厚度约为7nm，获得电子传输层；
6)将步骤5)所得膜层转移到蒸镀机中，蒸镀Ag金属电极；
7)将步骤6)所得膜层转移到手套箱内(手套箱内为氩气和甲胺气体的混合物，其中氩气与甲胺气体的体积比为6:4，手套箱内的绝对压力为3个大气压)进行封装，在尺寸为1.5×1.5×1.1cm的盖板玻璃与ITO导电玻璃包含钙钛矿层的表面相对的表面及四周边缘设置0.5mL的紫外固化胶(Norland紫外固化光学胶NOA61)，从而在ITO导电玻璃和盖板玻璃之间形成体积约0.1125cm 3的密闭空间。
经过上述步骤即可获得实施例1所述钙钛矿太阳能电池，标记为电池1。
实施例2
除在步骤7)中将氩气与甲胺气体的体积比调整为7:3以外，实施例2的其他条件与实施例1相同，获得的电池标记为电池2。
实施例3
除在步骤7)中将氩气与甲胺气体的体积比调整为8:2以外，实施例2的其他条件与实施例1相同，获得的电池标记为电池3。
实施例4
除在步骤7)中将氩气与甲胺气体的体积比调整为9:1以外，实施例2的其他条件与实施例1相同，获得的电池标记为电池4。
比较例1
除在步骤7)中将氩气与甲胺气体的混合物全部替换为氩气，不引入甲胺气体以外，比较例1的其他条件与实施例1相同，获得的电池标记为电池5。
对比例2-3
除在步骤7)中将氩气与甲胺气体的体积比分别调整为10:1和4:6以外，对比例2和3的其他条件与实施例1相同，获得的电池标记为电池6和电池7。
钙钛矿太阳能电池的光电转换效率测试
封装前钙钛矿太阳能电池的光电转换效率测试：借助台湾Entech I-V测试系统进行测试。在AM1.5G光谱，100mW/cm 2光强下进行测试，测试范围为-0.2-1.2V，扫描速率为5mV/s。通过仪器读取短路电流(Jsc)、开路电压(Voc)和填充因子(FF)，然后根据以下公式计算光电转换效率：光电转换效率(PCE)＝Jsc×Voc×FF。
封装后的测试方法及数据处理过程：器件封装后，在85℃、85％RH(相对湿度)条件下存储不同的天数后，在标准模拟太阳光(AM 1.5G,100mW/cm 2，测试范围为-0.2-1.2V，扫描速率为5mV/s)照射下进行测试，根据软件给出的短路电流，开路电压及填充因子等计算器件的光电转换效率。归一化处理即以0天的效率为100％，后续的效率除以0天效率得到变化后的剩余的比例。将所得比值与存储天数作图，即可得到归一化效率变化曲线。
对实施例1-4和比较例1-3所得太阳能电池进行测试获得的短路电流、开路电压、填充因子和光电转换效率随时间变化的情况如下表1至表8中所示。
表1实施例和对比例的结果汇总
Figure PCTCN2022074001-appb-000001
表2氩气与甲胺体积比为6:4时的测试结果
Figure PCTCN2022074001-appb-000002
表3氩气与甲胺体积比为7:3时的测试结果
Figure PCTCN2022074001-appb-000003
表4氩气与甲胺体积比为8:2时的测试结果
Figure PCTCN2022074001-appb-000004
表5氩气与甲胺体积比为9:1时的测试结果
Figure PCTCN2022074001-appb-000005
表6对比例1的测试结果
Figure PCTCN2022074001-appb-000006
表7氩气与甲胺体积比为10:1时的测试结果
Figure PCTCN2022074001-appb-000007
表8氩气与甲胺体积比为4:6时的测试结果
Figure PCTCN2022074001-appb-000008
由表1-表8结合附图2可以看出，相对于仅使用氩气进行封装的钙钛矿太阳能电池，本发明使用惰性气体和甲胺气体的混合物进行封装所得钙钛矿太阳能电池的稳定性均有提升。当气体体积比为10：1时，稳定性提升幅度相对于其他比例不明显，与空白相差不大，当气体体积比为4：6时，稳定性虽然提升明显，但其器件初始效率已经 明显降低。同时，当氩气与甲胺气体的体积比从9:1增加至5：5时，对应钙钛矿太阳能电池的稳定性得到进一步改善，且器件效率变化不明显，同时随着氩气与甲胺气体的体积比继续增大，例如大于8:2时，电池的稳定性变化不明显。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (17)

  1. 一种钙钛矿太阳能电池，其包括从下至上依次设置的以下部件：
    透明导电玻璃基底(101)；
    第一传输层(102)；
    钙钛矿层(103)；
    第二传输层(104)；
    导电电极(105)；
    背板玻璃(106)；和
    封装胶(107)；
    其中所述透明导电玻璃基底(101)与背板玻璃(106)之间在封装胶(107)的作用下形成密闭空间(108)，所述密闭空间(108)内包含惰性气体和甲胺气体的混合物，其中所述惰性气体与甲胺气体的体积比为9:1至5:5，可选为9:1至6:4，更可选为8:2至7:3。
  2. 根据权利要求1所述的钙钛矿太阳能电池，其中所述密闭空间内的绝对压力为2-6个大气压。
  3. 根据权利要求1或2所述的钙钛矿太阳能电池，其中
    所述钙钛矿层与所述密闭空间面积一致，所述钙钛矿层的厚度与所述密闭空间的高度比为1/5000-1/500，可选为1/2000-1/750。
  4. 根据权利要求1至3中任一项所述的钙钛矿太阳能电池，其中所述惰性气体选自氮气、氩气中的至少一种。
  5. 根据权利要求1至4中任一项所述的钙钛矿太阳能电池，其中所述钙钛矿层包括式A 1BX 3或A 2CDX 6的化合物，
    A 1选自CH 3NH 3 +(MA +)或CH(NH 2) 2 +(FA +)中的至少一种；
    A 2选自Li +、Na +、K +、Rb +、Cs +中的至少一种；
    B选自Pb 2+、Sn 2+、Be 2+、Mg 2+、Ca 2+、Sr 2+、Ba 2+、Zn 2+、Ge 2+、Fe 2+、Co 2+、Ni 2+中的至少一种，可选为Pb 2+、Sn 2+中的至少一种；
    X选自F -、Cl -、Br -、I -中的至少一种，可选为Cl -、Br -、I -中的至少一种；和
    C、D彼此独立地选自有机或无机阳离子、或有机无机混合阳离 子，可选地为过渡金属阳离子、或过渡金属阳离子与CH 3NH 3 +或CH(NH 2) 2 +的混合阳离子，更可选地为Pb(FA 0.83MA 0.17) 3+、CH 3NH 3Pb 3+、Pb 2+、Sr 2+、Bi 3+、La 3+中的至少一种。
  6. 根据权利要求1至5中任一项所述的钙钛矿太阳能电池，其中所述钙钛矿层包括CH 3NH 3PbI 3、CH(NH 2) 2PbI 3、Cs 0.05(FA 0.83MA 0.17) 0.95Pb(I 0.83Br 0.17) 3、CsPbI 3、CsPbI 2Br或CsPbIBr 2中的至少一种。
  7. 根据权利要求1至6中任一项所述的钙钛矿太阳能电池，其中
    所述封装胶(107)选自环氧类封装胶、有机硅类封装胶、聚氨酯封装胶、乙烯-醋酸乙烯酯共聚物、聚乙烯醇缩丁醛、聚烯烃类封装胶中的一种或多种。
  8. 根据权利要求7所述的钙钛矿太阳能电池，其中所述聚烯烃类封装胶选自乙烯辛烯共聚物、聚异丁烯中的一种或多种。
  9. 根据权利要求1至6中任一项所述的钙钛矿太阳能电池，其中所述封装胶(107)选自紫外线光固化封装胶。
  10. 根据权利要求1至9中任一项所述的钙钛矿太阳能电池，其中
    所述透明导电玻璃基底(101)包括氟掺杂二氧化锡(FTO)、铟掺杂氧化锡(ITO)、铝掺杂氧化锌(AZO)、硼掺杂氧化锌(BZO)、铟掺杂氧化锌(IZO)中的一种或多种。
  11. 根据权利要求1至10中任一项所述的钙钛矿太阳能电池，其中
    所述第一传输层(102)为电子传输层，并且所述第二传输层(104)为空穴传输层；或
    所述第一传输层(102)为空穴传输层，并且所述第二传输层(104)为电子传输层。
  12. 根据权利要求11所述的钙钛矿太阳能电池，其中
    所述电子传输层包括以下材料、其衍生物或其经掺杂或钝化所得 材料中的至少一种：
    [6,6]-苯基C 61丁酸甲酯(PC 61BM)、[6,6]-苯基C 71丁酸甲酯(PC 71BM)、富勒烯C60(C60)、富勒烯C70(C70)、二氧化锡(SnO 2)、氧化锌(ZnO)。
  13. 根据权利要求11或12所述的钙钛矿太阳能电池，其中
    所述空穴传输层包括以下材料、其衍生物或其经掺杂或钝化所得材料中的至少一种：
    聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚-3-己基噻吩(P3HT)、以三蝶烯为核的三苯胺(H101)、3,4-乙烯二氧噻吩-甲氧基三苯胺(EDOT-OMeTPA)、N-(4-苯胺)咔唑-螺双芴(CzPAF-SBF)、聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)(PEDOT:PSS)、聚噻吩、氧化镍(NiO x)、氧化钼(MoO 3)、碘化亚铜(CuI)、氧化亚铜(Cu 2O)。
  14. 根据权利要求1至13中任一项所述的钙钛矿太阳能电池，其中
    所述导电电极(105)包括以下材料中的至少一种：Ag、Cu、C、Au、Al、铟掺杂氧化锡(ITO)、铝掺杂氧化锌(AZO)、硼掺杂氧化锌(BZO)、铟掺杂氧化锌(IZO)。
  15. 根据权利要求1至14中任一项所述的钙钛矿太阳能电池，其中所述钙钛矿层的厚度为300-1000nm。
  16. 一种钙钛矿太阳能电池的封装方法，其至少包括以下步骤：
    步骤1：提供钙钛矿太阳能电池组件，其至少包括透明导电玻璃基底(101)、背板玻璃(106)和位于二者之间的钙钛矿层(103)；和
    步骤2：在透明导电玻璃基底(101)与背板玻璃(106)之间在封装胶(107)的作用下形成密闭空间(108)，所述密闭空间(108)内包含体积比为9:1至5:5，可选为9:1至6:4，更可选为8:2至7:3的惰性气体和甲胺气体的混合物。
  17. 一种光伏组件，其包括根据权利要求1至15中任一项所述的钙钛矿太阳能电池。
PCT/CN2022/074001 2022-01-26 2022-01-26 一种钙钛矿太阳能电池、其封装方法及包含其的光伏组件 WO2023141812A1 (zh)

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WO2021205336A1 (fr) * 2020-04-06 2021-10-14 Elixens Module photovoltaïque et procédé de fabrication d'un tel module

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