WO2023123394A1 - 钙钛矿太阳能电池和制造方法 - Google Patents

钙钛矿太阳能电池和制造方法 Download PDF

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WO2023123394A1
WO2023123394A1 PCT/CN2021/143789 CN2021143789W WO2023123394A1 WO 2023123394 A1 WO2023123394 A1 WO 2023123394A1 CN 2021143789 W CN2021143789 W CN 2021143789W WO 2023123394 A1 WO2023123394 A1 WO 2023123394A1
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acid
perovskite
layer
ring
solar cell
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French (fr)
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梁伟风
孙娟娟
陈长松
涂保
郭文明
郭永胜
陈国栋
栾博
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Contemporary Amperex Technology Co Ltd
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Priority to JP2024536255A priority Critical patent/JP2024546528A/ja
Priority to PCT/CN2021/143789 priority patent/WO2023123394A1/zh
Priority to CN202180102688.2A priority patent/CN117999864A/zh
Priority to KR1020247022572A priority patent/KR20240116815A/ko
Priority to EP21963472.2A priority patent/EP4231329B1/en
Priority to US18/197,731 priority patent/US12376486B2/en
Publication of WO2023123394A1 publication Critical patent/WO2023123394A1/zh
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    • H—ELECTRICITY
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    • 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
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    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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    • 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
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • 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
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    • 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
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K30/88—Passivation; Containers; Encapsulations
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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
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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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
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • 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 invention relates to a perovskite solar cell with improved stability and a manufacturing method of the perovskite solar cell.
  • perovskite crystal structure is relatively fragile, it is difficult to maintain the crystal lattice shape unchanged for a long time under the use environment, which has become a factor that significantly affects the life of perovskite solar cells.
  • CN 106062983 A proposes that when manufacturing perovskite solar cells, a passivation layer containing passivators such as thiophene and pyridine is further formed on the precipitated perovskite layer.
  • passivation layer containing passivators such as thiophene and pyridine
  • the method of forming a passivation layer is usually to coat a solution containing a perovskite precursor on the layer carrying the perovskite layer, and then apply an anti-solvent to extract the perovskite solvent to make the perovskite
  • the structure is precipitated, the excess solvent is removed by heating, and the perovskite becomes an effective perovskite phase, the passivation agent is coated on the surface of the perovskite, and finally the solvent is annealed to form a passivation layer on the perovskite layer.
  • there is room for further simplification in such a method of forming a passivation layer there is room for further simplification in such a method of forming a passivation layer.
  • the problem to be solved by the present invention is to provide a perovskite solar cell, which includes a passivation layer with a better effect in improving cell efficiency and stability, and the manufacture of a perovskite solar cell containing the passivation layer method.
  • One aspect of the present invention is a perovskite solar cell comprising at least an electrode, an electron transport layer, a hole transport layer, a perovskite layer and a passivation layer,
  • the above-mentioned passivation layer contains a passivating agent, and the passivating agent includes an aza-fused bicyclic compound and/or an organic salt formed by an aza-fused bicyclic compound and an acid, and each condensed ring of the aza-fused bicyclic compound is independently It is a five-membered or six-membered saturated ring, unsaturated ring or aromatic ring, and the condensed ring of the aza-fused bicyclic compound contains 1 to 5 nitrogen atoms, and the above-mentioned condensed ring is a ring without substituents or is substituted with 1 or A ring having two substituents having 1 to 3 carbon atoms.
  • the above-mentioned aza-condensed bicyclic compound is selected from pteridine, 1,5,7-triazidebicyclo(4.4.0)dec-5-ene, quinazoline, quinoline, 1 ,5-diazabicyclo[4.3.0]-5-nonene, imidazo[1,2-a]pyrimidine, 5,6,7,8-tetrahydroindolizine, 1-methyl-2,3 - one of dihydro-1H-pyrrolizine and 2,4-dimethylquinoline.
  • the acid ion in the organic salt is selected from one of the acid ion containing O, S, P, N, F, I, Br, Cl, C and H.
  • the acid radical ion is preferably selected from the acid radical ion of one of acetic acid, phosphoric acid, nitric acid, chloric acid, sulfonic acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid .
  • the passivation layer is preferably a layer formed by applying an antisolvent in which a passivating agent is dissolved on the perovskite layer.
  • the anti-solvent is selected from toluene, chlorobenzene, dichlorobenzene, ethyl acetate, ether, benzene, absolute ethanol, isopropanol, butanol, chloroform, methyl butyrate, anisole, xylene and mesitylene at least one.
  • the molar ratio of the perovskite in the perovskite layer to the passivating agent in the passivation layer is 100-800, may be 200-600 or 250-400.
  • Another aspect of the present invention is to provide a power generation device using the above-mentioned perovskite solar cell. Accordingly, it is possible to provide a power generating device with improved efficiency and stability.
  • Another aspect of the present invention is to provide an electrical device using the above-mentioned perovskite solar cell.
  • a power consumption device with improved efficiency and stability.
  • Another aspect of the present invention is to provide a method of forming the passivation layer in the above-mentioned perovskite solar cell, the method is characterized in that it includes the following steps:
  • the passivating agent includes an aza-fused bicyclic compound and/or an organic salt formed by an aza-fused bicyclic compound and an acid
  • each condensed ring of the aza-fused bicyclic compound is independently a five-membered or six-membered saturated Ring, unsaturated ring or aromatic ring
  • the condensed ring of the aza-fused bicyclic compound contains 1 to 5 nitrogen atoms
  • the above-mentioned condensed ring is a ring without substituents or is substituted with 1 or 2 carbon atoms and the number of carbon atoms is 1 to 5 3 substituent ring.
  • the aza-fused bicyclic compound is selected from pteridine, 1,5,7-triazidebicyclo(4.4.0)dec-5-ene, quinazoline, quinoline, 1,5-diazepine Heterobicyclo[4.3.0]-5-nonene, imidazo[1,2-a]pyrimidine, 5,6,7,8-tetrahydroinsonine, 1-methyl-2,3-dihydro-1H - one of pyrrolizine and 2,4-dimethylquinoline.
  • the acid ion in the organic salt is selected from one of the acid ion containing O, S, P, N, F, I, Br, Cl, C and H.
  • the acid ion is selected from one of the acid ion from acetic acid, phosphoric acid, nitric acid, chloric acid, sulfonic acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid.
  • the preferred anti-solvent is selected from toluene, chlorobenzene, dichlorobenzene, ethyl acetate, ether, benzene, absolute ethanol, isopropanol, butanol, chloroform, methyl butyrate, anisole, xylene and at least one of trimethylbenzene.
  • the concentration of the passivating agent in the anti-solvent is preferably 0.1-10 mmol/mL.
  • the molar ratio of the perovskite precursor in the perovskite precursor solution to the passivating agent in the anti-solvent is 200-8000, may be 800-1600 or 1000-1200.
  • a passivation layer can be formed by a simpler method, and the surface and grain boundaries of the perovskite structure can be comprehensively passivated, thereby providing a perovskite solar cell with better cell efficiency and stability.
  • the efficiency and stability of the cell can be improved, and according to the manufacturing method of the present invention, the perovskite solar cell having the above-mentioned advantages can be provided in a more convenient manner.
  • Figure 1 is a schematic diagram of the structure of a perovskite solar cell.
  • Figure 2 is a schematic diagram of the perovskite structure.
  • 1 substrate; 2: first electrode; 3: electron/hole conducting layer; 4: perovskite layer; 5: passivation layer; 6: hole/electron conducting layer; 7: second electrode
  • the perovskite solar cell of the present invention includes a first electrode layer 2 , an electron transport layer 3 , a perovskite layer 4 , a passivation layer 5 , a hole transport layer 6 and a second electrode layer 7 in sequence.
  • the perovskite structure When light is irradiated on the perovskite layer, the perovskite structure absorbs the energy of the photons to generate free electrons and holes (hereinafter sometimes electrons and holes are collectively referred to as "carriers"), and the generated free electrons and holes They are respectively conducted to the first electrode and the second electrode through the electron transport layer and the hole transport layer, and a voltage is generated between the first electrode and the second electrode, thereby realizing energy conversion between photoelectricity.
  • carriers free electrons and holes
  • a passivation layer 5 is formed on one side of the perovskite layer 4, but the present invention is not limited to this structure, for example, it can also be formed on any side of the perovskite layer 4
  • a passivation layer 5 is formed on one side or both sides.
  • the perovskite layer contains crystals of a perovskite structure, and has a crystal structure as shown in FIG. 2 .
  • the perovskite structure commonly used in solar cells can be expressed as an ABX 3 structure, where A is a positively charged ion with a certain size, such as ions of alkali metals such as cesium, methylamine (CH 3 NH 2 ), formamidine (HNCHNH 2 ) and other small molecule nitrogen-containing organic compound ions, etc.; the B position is an ion of a transition metal element, such as an ion of Pb or Sn; the X position is a halogen ion, such as a Br or I ion.
  • A is filled in the BX octahedron composed of B and X, thereby forming a lattice structure, so there is a certain size requirement for the A-site cation, usually the size The requirement is called “tolerance factor”, and the tolerance factor needs to be between 0.8-1.2. If the tolerance factor is too large or too small, the stability of the lattice structure will be significantly affected, or the expected structure cannot be formed.
  • the instability of the perovskite structure specifically, it is related to the deep and shallow energy level defects in the preparation process of perovskite solar cells and the operation of the device. These defects seriously affect the efficiency and long-term stability of the cell.
  • the instability of the calcium structure also comes from the fact that it is prone to hydrolysis when encountering water.
  • the passivation layer is a layer arranged between the perovskite layer and the electron transport layer and/or hole transport layer in order to improve the stability of the perovskite structure and the life of the solar cell device, and contains a passivator.
  • the inventors of the present invention found that, compared with the existing passivating agents, the following passivating agents are more effective in improving battery efficiency and prolonging battery life.
  • the passivating agent in the present invention includes aza-fused bicyclic compounds and/or organic salts formed by aza-fused bicyclic compounds and acids, and each condensed ring of the aza-fused bicyclic compounds is independently five-membered or six-membered Saturated ring, unsaturated ring or aromatic ring, and the condensed ring of the aza-fused bicyclic compound contains 1 to 5 nitrogen atoms, and the above-mentioned condensed ring is a ring without substituents or is substituted with 1 or 2 carbon atoms A ring with 1 to 3 substituents.
  • the substituent on the above-mentioned condensed ring it can be a hydrocarbon group, an alcohol group, an ether group, an ester group, an aldehyde group, a ketone group, a carboxyl group, a carbonyl group, an amide group, an imide group, or a combination thereof.
  • formamidine is used in the A site
  • formamidine is used as an organic component.
  • the high temperature of direct sunlight and the non-radiative recombination caused by defects will cause the device to heat up, which will cause the volatilization of formamidine, resulting in defects in the A site.
  • Most of the existing interface passivators form a two-dimensional structure to prevent the volatilization of A-site cations, but the A-site may be displaced to form multiple defects.
  • the increase of defects will increase the internal resistance of the device due to the capture of carriers such as free electrons or holes, increase the difficulty of carrier extraction, and reduce the short-circuit current.
  • the decomposition of perovskite will lead to the decrease of device stability. Therefore, passivation using existing passivators is not effective in improving the long-term stability of devices.
  • the above-mentioned passivating agent containing aza-fused bicyclic compound and/or its organic salt formed with acid is used to passivate the defects on the grain boundary and surface of the perovskite.
  • the nitrogen atom on the ring in the above-mentioned aza-fused bicyclic compound in the passivator of the present invention and/or its organic salt formed with an acid has a stronger ability to combine protons, and forms a strong chemical bond with the A position, which can It prevents the decomposition or volatilization of A-site cations due to various reasons, and it is not easy to generate harmful hydrogen vacancies during use, which improves the stability of passivation and the efficiency of devices.
  • aza-fused bicyclic compound examples include those used in Examples, but the present invention is not limited to these compounds.
  • the principle is not certain, but it can be speculated that compared with the prior art, the number of rings in the compound used in the present invention increases, which improves the hydrophobic performance of the material, and can be introduced as a hydrophobic functional group, which can significantly improve the performance of perovskite. water stability.
  • the nitrogen on the nitrogen heterocycle has a strong proton binding energy with the A site of the perovskite, it can inhibit the loss of the A site ions, thereby enhancing the passivation effect.
  • the acid radical ion in the organic salt formed with the above compound is selected from one of the acid radical ions containing O, S, P, N, F, I, Br, Cl, C and H.
  • one kind of acid ion selected from acetic acid, phosphoric acid, nitric acid, chloric acid, sulfonic acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid can be mentioned.
  • the acid ion is preferably from one selected from hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, because when halogen is selected as the acid ion, the halogen vacancies on the surface of the perovskite can be compensated.
  • the acid ion is more preferably from hydrofluoric acid.
  • the acid ion is preferably from one of acids containing oxygen, sulfur, phosphorus, etc., for example, from one of carboxylic acid, sulfonic acid, sulfuric acid and phosphoric acid.
  • the acid radical ions from these acids can form hydrogen bonds with the ions at the A site, and at the same time anchor the ions at the B site, thereby stabilizing the ions at the A site and the B site, further stabilizing the perovskite structure, and improving the performance of the battery device. effect on long-term stability.
  • the ratio of the molar weight of the perovskite in the perovskite layer to the passivating agent in the passivation layer is 100 to 800 , can be 200-600 or 300-400.
  • the amount of the passivating agent is too small relative to the perovskite, defects in the perovskite structure cannot be sufficiently passivated, and ideal hydrophobicity cannot be imparted.
  • the amount of passivating agent is too much, the effect of passivation will be saturated and the cost-effectiveness ratio will be reduced. In addition, it may cause adverse effects such as hindering carrier transport, increasing internal resistance, and even battery failure.
  • the electron transport layer and the hole transport layer are layers formed on both sides of the perovskite layer and the passivation layer, which are respectively used to transport free electrons and holes generated on the perovskite layer. By separating the electrons from the holes and further transporting them to the first electrode and the second electrode, the recombination of holes and electrons is avoided to reduce the lossy conversion efficiency. It should be noted that FIG. 1 only shows one possible situation of the present invention, and the positions of the electron transport layer and the hole transport layer of the present invention can also be interchanged.
  • At least one of the electron transport layer and the hole transport layer has a light transmittance in the visible light band of 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more.
  • this layer is composed of conventional electron transport materials, which can be appropriately selected by those skilled in the art within the range favorable to the conversion efficiency.
  • tin oxide, titanium oxide, PCBM, C60 preferably tin oxide can be used.
  • the preparation method of this layer can be prepared by appropriately combining conventional methods such as coating, vapor deposition, and annealing.
  • this layer is composed of conventional hole-transport materials, which can be appropriately selected by those skilled in the art within the range favorable to the conversion efficiency.
  • PTAA, spiro, PEDOT:PSS, preferably spiro can be used.
  • the preparation method of this layer can be prepared by appropriately combining conventional methods such as coating, vapor deposition, and annealing.
  • the first electrode is laminated on the direction opposite to the direction of the perovskite layer of the electron transport layer, and is an electrode for guiding the electrons conducted by the electron transport layer to the outside for utilization.
  • the second electrode is stacked on the hole transport layer in a direction opposite to the direction of the perovskite layer, and is an electrode for guiding the holes conducted by the hole transport layer to the outside for utilization. It should be noted that FIG. 1 only shows a situation that the present invention can adopt, and the positions of the first electrode and the second electrode in the present invention can also be interchanged.
  • the first electrode and the second electrode when they are non-transparent electrodes, they can be made of conventional materials used for electrodes, and those skilled in the art can select them appropriately within the range that is beneficial to the conversion efficiency. For example, gold, silver, copper, aluminum, etc. can be used, and gold is preferable.
  • the preparation method of this layer can be prepared by appropriately combining conventional methods such as coating, vapor deposition, and annealing.
  • At least one of the first electrode and the second electrode is a transparent electrode, and the transmittance of the transparent electrode in the visible light band is above 50%, above 60%, above 70%, above 80%, above 90%, or above 95%.
  • a transparent electrode it can be made of conventional materials used for transparent electrodes, and those skilled in the art can select appropriately within the range that is conducive to conversion efficiency.
  • conductive oxides, metal grids, ultra-thin metal layers, nano-metal wires, carbon-based transparent materials, polymers, etc. can be used. Conductive oxides are preferable from the viewpoint of high light transmittance.
  • the preparation method of the electrode it can be prepared by appropriately combining conventional methods such as coating, vapor deposition, and annealing.
  • the substrate is used to support the whole perovskite solar cell, which is convenient for operation and assembly.
  • the substrate can be organic or inorganic flexible materials such as polyimide (PI), polybutylene terephthalate (PET), polyamide (PA), polycarbonate (PC), ultra-thin glass, or Rigid materials such as glass plates and metal plates can also be used.
  • PI polyimide
  • PET polybutylene terephthalate
  • PA polyamide
  • PC polycarbonate
  • ultra-thin glass or Rigid materials such as glass plates and metal plates can also be used.
  • At least one substrate has a light transmittance of 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% in the visible light band above.
  • the light-transmitting substrate is arranged on the side of the transparent electrode.
  • the substrate can also be omitted.
  • the manufacture method of perovskite solar cell of the present invention comprises:
  • conventional methods such as spin coating, blade coating, roller coating, and spray coating can be used for the coating of step 1 and step 2, but from the viewpoint of better thickness control, spin coating is preferred.
  • Such a manufacturing method can simplify the steps of preparing the passivation layer and avoid the influence of multiple annealing on the perovskite structure. And passivation can be achieved in the process of forming the perovskite structure.
  • the method of the present invention reduces the number of annealing treatments, avoids multiple annealing of perovskite, saves time and cost, and improves preparation efficiency.
  • the passivating agent is added when the perovskite phase is not stable, and the passivating agent can better bond with the perovskite at the grain boundary and surface, making the perovskite phase more stable.
  • the passivating agent not only exists on the surface of the perovskite layer, but also can penetrate deep into the grain boundary, it can simultaneously passivate the grain boundary and the surface to achieve all-round passivation. This can more effectively prevent electrons and holes from recombining at grain boundaries and surfaces. Moreover, even in the case of small grain boundaries, using the method of the present invention, the passivating agent with larger molecular volume can enter deep into the grain boundaries. Meanwhile, since the passivating agent exists only in the antisolvent, the passivating agent does not affect the formation of the perovskite structure. This is difficult to achieve with existing technologies.
  • the perovskite precursor solution includes a perovskite precursor and a solvent.
  • a perovskite precursor is a substance containing A ions, B ions, and X ions.
  • the perovskite precursor solution includes, for example, a mixture of BX 2 and AX in a solvent.
  • A as mentioned above, can be selected from alkali metals such as cesium or small molecule nitrogen-containing organic compounds such as methylamine and formamidine, B is Sn or Pb, and X is a halogen.
  • the solvent in the perovskite precursor solution as long as it can dissolve BX 2 and AX, can be miscible with the anti-solvent, and can be removed by heating, it can be appropriately selected from conventionally used solvents. Those skilled in the art can select any appropriate combination from the prior art to prepare the perovskite precursor solution.
  • the molar ratio of BX 2 to AX is 1 or more, 1.01 or more, 1.02 or more, 1.03 or more, 1.04 or more, 1.05 or more from the viewpoint that the perovskite layer structure can be sufficiently formed , From the perspective of cost saving, consider below 1.5, below 1.4, below 1.3, below 1.2, below 1.1.
  • the concentration of the perovskite precursor is used to adjust the thickness of the formed perovskite layer.
  • the ideal concentration is 0.2 ⁇ 5mmol/mL, 0.3 ⁇ 4mmol/mL based on the BX 2 concentration. mL, 0.4 ⁇ 3mmol/mL, 0.5 ⁇ 2mmol/mL. At this concentration, a satisfactory perovskite structure is favored.
  • the tolerance factor of A ions needs to be 0.8 to 1.2. If the tolerance factor exceeds 1.2 due to too large ion volume, it will cause lattice deformation, or it will be difficult to fill the B-X octahedral structure, resulting in the inability to form a perovskite structure. concerns. Even if the structure can be formed, the crystallization process of perovskite is blocked, resulting in the reduction of perovskite crystal quality, the formation of excessive grain boundaries, the generation of deep energy level defects, the capture of carriers, and the reduction of photoelectric conversion efficiency. and stability concerns.
  • the tolerance factors are preferably 0.8 to 1.2. This is because if there is a larger molecule, the crystal structure will be destroyed as described above, and even if it is used as an additive, the crystal quality will be poor due to the larger structure, making it difficult to achieve good stability.
  • the passivating agent-containing solution in this method includes an anti-solvent and a passivating agent.
  • the anti-solvent is the solvent used to transform the perovskite precursor into the perovskite structure.
  • the anti-solvent in the present invention is the little solvent of the solubility of perovskite precursor, is selected from toluene, chlorobenzene, dichlorobenzene, ethyl acetate, ether, benzene, dehydrated alcohol, isopropanol, butanol, chloroform, At least one of methyl butyrate, anisole, xylene and mesitylene.
  • the anti-solvent is preferably added to at least one first anti-solvent selected from toluene, chlorobenzene, dichlorobenzene and ethyl acetate and selected from diethyl ether, benzene, absolute ethanol, isopropanol, butanol, chloroform, butanol
  • the solubility of the precursor to the anti-solvent can be adjusted, so that when the anti-solvent contacts the precursor in the precursor solution, the perovskite structure can be controlled precipitation rate and crystal size.
  • the ratio (volume) of the first anti-solvent to the second anti-solvent is 100:0-100:50, preferably 100:0-100:10.
  • the anti-solvent is mixed in such a ratio, the precipitation rate and crystal size of the perovskite structure can be advantageously controlled.
  • the anti-solvent of the present invention contains the passivating agent of the present invention, which will not be repeated here. It should be noted that even the passivating agent in the prior art can also be used in the forming method of the passivation layer of the present invention. As a passivating agent in the prior art.
  • the concentration of the passivating agent is 0.1-10 mmol/mL, may be 0.5-8 mmol/mL, 1-5 mmol/mL, 2-3 mmol/mL.
  • the content of the passivating agent in the passivation layer can be easily controlled without affecting the precipitation of the perovskite structure.
  • the molar ratio (R) of the perovskite precursor in the perovskite precursor solution to the passivating agent in the antisolvent is 200-8000, and can be 800-1600 or 1000-1200.
  • R The molar ratio (R) of the perovskite precursor in the perovskite precursor solution to the passivating agent in the antisolvent.
  • annealing treatment is performed after coating the perovskite precursor solution and anti-solvent.
  • the solvent and anti-solvent in the precursor solution are volatilized, and the precursor precipitates to form a perovskite structure to form a perovskite layer and a passivation layer.
  • the passivator passivates the grain boundaries and surfaces of the perovskite structure.
  • the conditions of the annealing treatment can be appropriately set according to the type of solvent used and the parameters of the annealing equipment, and are not particularly limited. However, from the viewpoint of obtaining a well-ordered perovskite structure, annealing at 80° C. to 200° C. for 10 minutes to 2 hours may be used. For example, the annealing conditions in Examples described later can be adopted.
  • the power generation device of the present invention is a power generation device comprising the above-mentioned perovskite solar cells, and there may be one or more perovskite solar cells.
  • the power plant also has a control system and a transmission system.
  • the power generating device of the present invention adjusts the electric energy generated from the solar cell to the electric energy that can match the electric equipment through the control system and the transmission system. It should be noted that the term “comprising" here refers to the situation that the power generating device is electrically connected to the solar cell.
  • the electrical device of the present invention is an electrical device comprising the above-mentioned perovskite solar cell, and there may be one or more perovskite solar cells.
  • the power consumption device also has a system for utilizing electric energy generated from the above-mentioned perovskite solar cell. Examples of such systems using electric energy include systems that convert electric energy into kinetic energy, internal energy, light energy, or chemical energy. It should be noted that the term “comprising" here refers to the situation that the electrical device is electrically connected to the solar cell.
  • the orientation or positional relationship indicated by the technical terms “inside” and “outside” are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the embodiment of the present application and simplifying the description. It does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation, and thus should not be construed as limiting the embodiments of the present application.
  • the conductive glass with spin-coated electron transport layer was irradiated with UV for 15 minutes, 60 ⁇ L of perovskite solution was added dropwise on the glass, 600 ⁇ L of anti-solvent for dissolving passivation material was added, and annealed at 150 °C for 1 h, thereby simultaneously forming perovskite layer and passivation layer. layer, finally forming a perovskite layer with a thickness of 500nm and a passivation layer with a thickness of 2nm.
  • the ratio (molar ratio) of the amount of perovskite to the passivator was 300.
  • a perovskite solar cell was fabricated in the same manner as in Example 1, except that the formation conditions of the perovskite layer and the passivation layer were replaced with those shown in Table 1 and Table 2.
  • perovskite solar cells were fabricated in the same manner as in Example 1.
  • a perovskite solar cell was fabricated in the same manner as in Example 1 except that no passivator was added.
  • each embodiment, comparative example and reference example are the average value of the IV test result of the undamaged battery after the stability test, efficiency retention rate, the number of damaged batteries and the damage rate. in Table 4 below.
  • the perovskite solar cell using the passivator of the present invention has a more obvious effect on improving device efficiency and stability than that without using the passivator of the present invention.
  • the efficiency of the battery decays significantly; in the case of the same cation, it is better to use an organic acid containing O, S, P, N and other elements as the acid ion passivation effect.
  • the battery damage rate of the perovskite solar cell using the passivator of the present invention is significantly suppressed after being left for a period of time.
  • the perovskite solar cell obtained by using the passivation layer and the perovskite layer manufacturing method of the present invention is compared with that not using the method of the present invention, and the perovskite avoids secondary heating and annealing, and the device stability is improved. Better; and in the case of wet film, adding passivation material and controlling crystallization can make passivation material better filled in the grain boundary and surface, the perovskite is better protected, and the stability of perovskite is increased.
  • the present invention can provide a perovskite solar cell with high energy conversion efficiency and excellent stability, and a method for manufacturing the solar cell. This is of great significance for coping with climate change and building an ecological civilization.

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Abstract

本发明提供一种至少包括电极、电子传输层、空穴传输层、钙钛矿层和钝化层的钙钛矿太阳能电池。其中，钝化层中含有钝化剂，钝化剂包括氮杂稠合双环化合物和/或由氮杂稠合双环化合物与酸形成的有机盐，氮杂稠合双环化合物的每个稠环独立地为五元或六元的饱和环、不饱和环或芳香环，且氮杂稠合双环化合物的稠环包含1～5个氮原子，上述稠环为无取代基的环或者为取代有1或2个碳原子数为1～3的取代基。

Description

钙钛矿太阳能电池和制造方法 技术领域
本发明涉及一种提高了稳定性的钙钛矿太阳能电池，以及钙钛矿太阳能电池的制造方法。
背景技术
随着减缓地球变暖的趋势和生态文明建设成为受到越来越多的关注，能源的多元化和绿色能源的开发也受到越来越多的瞩目。其中，将太阳能转换成电能的太阳能发电在能量转换时没有碳排放，并且设备的设置自由度高，因而得到广泛的应用。但是，目前主流的太阳能发电装置为使用了基于单晶硅或多晶硅的硅基太阳能电池板，这样的硅基太阳能电池板存在电池板重量大、生产工艺复杂、生产过程中能耗和成本较大等的问题。
为了解决上述问题，提出了能够利用溶液工艺制作的太阳能电池。这些之中，包含钙钛矿型结晶结构作为光转换层的太阳能电池由于其接近硅基太阳能电池的转换效率而备受关注。
但是，由于钙钛矿型结晶结构较为脆弱，在使用环境下不易长时间维持晶格形态的不变，成为显著影响钙钛矿太阳能电池寿命的因素。
为了提高钙钛矿型结晶的稳定性，CN 106062983 A中提出，在制造钙钛矿太阳能电池时，在析出的钙钛矿层上进一步形成含有噻吩、吡啶等钝化剂的钝化层。但是本发明人发现，现有技术中的钝化剂选择方面还存在改进余地。
另外，现有技术中，作为形成钝化层的方法通常是在承载钙钛矿层的层上涂布含有钙钛矿前驱体的溶液，之后涂布反溶剂萃取钙钛矿溶剂，使钙钛矿结构析出，加热除去过量溶剂，并使钙钛矿变成有效钙钛矿相，在钙钛矿表面涂布钝化剂，最后退火除去溶剂，在钙钛矿层上形成钝化层。但是，这样的生成钝化层的方法也存在进一步简易化的余地。
发明内容
发明所要解决的课题
钙钛矿太阳能电池制备过程以及器件运行过程会存在深能级与浅能级缺陷，这些缺陷严重影响电池的效率与长期稳定性，实验发现，有机小分子铵盐可以钝化钙钛矿表面的缺陷，提高器件效率与稳定性。然而，目前存在的钝化剂，多为单环类有机小分子胺，其在提高电池器件效率和稳定性方面效果效果仍不够令人满意。
本发明所要解决的课题在于，提供一种的钙钛矿太阳能电池，其包含在提高电池效率与稳定性方面效果更佳的钝化层，以及含有该钝化层的钙钛矿太阳能电池的制造方法。
用于解决课题的技术方案
本发明的一个方面为一种钙钛矿太阳能电池，其至少包括电极、电子传输层、空穴传输层、钙钛矿层和钝化层，
上述钝化层中含有钝化剂，钝化剂包括氮杂稠合双环化合物和/或由氮杂稠合双环化合物与酸形成的有机盐，氮杂稠合双环化合物的每个稠环独立地为五元或六元的饱和环、不饱和环或芳香环，且氮杂稠合双环化合物的稠环包含1～5个氮原子，上述稠环为无取代基的环或者为取代有1或2个碳原子数为1～3的取代基的环。
上述钙钛矿太阳能电池中，优选上述氮杂稠合双环化合物选自蝶啶、1,5,7-三叠氮双环(4.4.0)癸-5-烯、喹唑啉、喹啉、1,5-二氮杂双环[4.3.0]-5-壬烯、咪唑并[1,2-a]嘧啶、5,6,7,8-四氢吲嗪、1-甲基-2,3-二氢-1H-吡咯里嗪和2,4-二甲基喹啉中的一种。
上述钙钛矿太阳能电池中，优选有机盐中的酸根离子选自含O、S、P、N、F、I、Br、Cl、C和H的酸根离子中的一种。
上述钙钛矿太阳能电池中，优选酸根离子选自来自醋酸、磷酸、硝酸、氯酸、磺酸、硫酸、氢氟酸、氢氯酸、氢溴酸和氢碘酸中的一种的酸根离子。
上述钙钛矿太阳能电池中，优选钝化层是通过将溶解有钝化剂的反溶剂涂布于钙钛矿层上而形成的层。反溶剂选自甲苯、氯苯、二氯苯、乙酸乙酯、乙醚、苯、无水乙醇、异丙醇、丁醇、氯仿、丁酸甲酯、苯 甲醚、二甲苯和三甲苯中的至少一种。
上述钙钛矿太阳能电池中，优选钙钛矿层中的钙钛矿与钝化层中的钝化剂的摩尔量之比为100～800，可以为200～600或250～400。
由此，通过使用上述钝化剂，能够得到提高了电池效率与稳定性的钙钛矿太阳能电池。
本发明的另一个方面在于提供一种使用了上述钙钛矿太阳能电池的一种发电装置。由此，能够提供提高了效率与稳定性的发电装置。
本发明的另一个方面在于提供一种使用了上述钙钛矿太阳能电池的一种用电装置。由此，能够提供提高了效率与稳定性的用电装置。
本发明的另一个方面在于提供一种形成上述钙钛矿太阳能电池中的钝化层的方法，该方法的特征在于包括以下步骤：
在承载钙钛矿层的层上涂布钙钛矿前驱体溶液后，直接涂布含有钝化剂的反溶剂，之后进行退火的步骤；
其中，钝化剂包括氮杂稠合双环化合物和/或由氮杂稠合双环化合物与酸形成的有机盐，氮杂稠合双环化合物的每个稠环独立地为五元或六元的饱和环、不饱和环或芳香环，且氮杂稠合双环化合物的稠环包含1～5个氮原子，上述稠环为无取代基的环或者为取代有1或2个碳原子数为1～3的取代基的环。
上述方法中，优选氮杂稠合双环化合物选自蝶啶、1,5,7-三叠氮双环(4.4.0)癸-5-烯、喹唑啉、喹啉、1,5-二氮杂双环[4.3.0]-5-壬烯、咪唑并[1,2-a]嘧啶、5,6,7,8-四氢吲嗪、1-甲基-2,3-二氢-1H-吡咯里嗪和2,4-二甲基喹啉中的一种。
上述方法中，优选有机盐中的酸根离子选自含O、S、P、N、F、I、Br、Cl、C和H的酸根离子中的一种。
上述方法中，优选酸根离子选自来自醋酸、磷酸、硝酸、氯酸、磺酸、硫酸、氢氟酸、氢氯酸、氢溴酸和氢碘酸的酸根离子中的一种。
上述方法中，优选反溶剂选自甲苯、氯苯、二氯苯、乙酸乙酯、乙醚、苯、无水乙醇、异丙醇、丁醇、氯仿、丁酸甲酯、苯甲醚、二甲苯和三甲苯中的至少一种。
上述方法中，优选反溶剂中，钝化剂的浓度为0.1～10mmol/mL。
上述方法中，优选钙钛矿前驱体溶液中的钙钛矿前驱体与反溶剂中的钝化剂的摩尔量之比为200～8000，可以为800～1600或1000～1200。
由此，能够利用更简便的方法形成钝化层，对钙钛矿结构的表面和晶界全方位地钝化，提供电池效率与稳定性更好的钙钛矿太阳能电池。发明效果
根据本发明的钙钛矿太阳能电池，能够提高电池效率与稳定性，并且根据本发明的制造方法，能够以更加简便的方式提供具有上述优点的钙钛矿太阳能电池。
附图说明
图1是钙钛矿太阳能电池的结构示意图。
图2是钙钛矿结构结构示意图。
符号说明
1：基底；2：第一电极；3：电子/空穴传导层；4：钙钛矿层；5：钝化层；6：空穴/电子传导层；7：第二电极
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
1 钙钛矿太阳能电池
首先对于本发明的钙钛矿太阳能电池进行简述。如图1所示，本发明的钙钛矿太阳能电池中依次包括第一电极层2、电子传输层3、钙钛矿层4、钝化层5、空穴传输层6和第二电极层7。在当光照射到钙钛矿层上时，钙钛矿结构吸收光子的能量，产生自由电子和空穴(以下有时将电子和空穴统称为“载流子”)，产生的自由电子与空穴分别通 过电子传输层和空穴传输层被传导至第一电极和第二电极，在第一电极和第二电极之间产生电压，由此实现光电之间的能量转化。需要说明的是，图1仅为示意性地表示在钙钛矿层4的一侧形成钝化层5的一种实施方式，但本发明不限于此结构，例如也可以在钙钛矿层4的任一侧或两侧形成有钝化层5。
1.1 钙钛矿层4
钙钛矿层中含有钙钛矿结构的晶体，具有图2所示结晶的结构。常规用于太阳能电池的钙钛矿结构可以表述为ABX 3结构，其中A为具有一定大小且带正电的离子，例如有铯等碱金属的离子，甲胺(CH 3NH 2)、甲脒(HNCHNH 2)等小分子含氮有机物的离子等；B位为过渡金属元素的离子，例如Pb或Sn的离子；X位为卤素离子，例如Br或I的离子。
需要说明的是，在常见的ABX 3结构中，在由B和X构成的B-X八面体中填充A，由此形成晶格结构，因此对A位阳离子有一定的尺寸的要求，通常将该尺寸要求称为“容忍因子”，该容忍因子需要在0.8－1.2之间。该容忍因子过大或过小时，都会显著影响晶格结构的稳定性，或者无法形成所期待的结构。
关于钙钛矿结构的不稳定性，具体而言，与钙钛矿太阳能电池制备过程以及器件运行过程存在的深能级与浅能级缺陷有关，这些缺陷严重影响电池的效率与长期稳定性。另外，钙结构的不稳定性还来源于在遇到水时容易发生水解。
1.2 钝化层5
钝化层是为了提高钙钛矿结构的稳定性和太阳能电池设备的寿命，而在钙钛矿层与电子传输层和/或空穴传输层之间设置的层，其中含有钝化剂。
本发明人发现，与现有的钝化剂相比，使用下述钝化剂时，对于提升电池效率、延长电池寿命的效果更好。本发明中的钝化剂包括氮杂稠合双环化合物和/或由氮杂稠合双环化合物与酸形成的有机盐，氮杂稠合双环化合物的每个稠环独立地为五元或六元的饱和环、不饱和环或芳香环，且氮杂稠合双环化合物的稠环包含1～5个氮原子，上述稠环 为无取代基的环或者为取代有1或2个碳原子数为1～3的取代基的环。
作为上述稠环上的取代基，可以为烃基、醇基、醚基、酯基、醛基、酮基、羧基、羰基、酰胺基、酰亚胺基、或它们的组合，具体来说可以举出甲基、乙基、正丙基、异丙基；甲醇基、乙醇基、正丙醇基、异丙醇基；甲醚基、乙醚基、丙醚基；甲酯基、乙酯基、丙酯基；甲醛基、乙醛基、丙醛基；甲酮基、乙酮基、丙酮基；甲酸基、乙酸基、丙酸基；甲酰胺基、乙酰胺基、丙酰胺基。
在A位使用了例如甲脒的情况下，甲脒作为有机成分，因太阳直射的高温和缺陷导致的非辐射复合都会导致器件升温，会导致甲脒的挥发，导致A位的缺陷。现有的界面钝化剂大多是形成二维结构，阻止A位阳离子的挥发，但A位可能发生移位，形成多处缺陷。而缺陷的增多，会因捕获自由电子或者空穴等载流子，导致器件的内阻增加，载流子提取难度增加，短路电流减小。而钙钛矿的分解会导致器件稳定性的降低。因此利用现有钝化剂进行的钝化对于提升器件的长期稳定性效果不佳。
而在本发明中，采用上述含有氮杂稠合双环化合物和/或其与酸形成的有机盐的钝化剂来钝化钙钛矿晶界和表面的缺陷。
本发明的钝化剂中的上述氮杂稠合双环化合物和/或其与酸形成的有机盐中的环上的氮原子具有较强的结合质子能力，与A位形成一个强的化学键，可以防止A位阳离子因各种原因导致的分解或者挥发，在使用过程中不易产生有害的氢空位，提升了钝化的稳定性以及器件的效率。
该氮杂稠合双环化合物的具体例可以举出实施例中所使用的物质，但本发明并不限于这些化合物。
其原理并不确定，但可以推测是与现有技术相比，本发明所使用的化合物中的环的个数增多，提高了材料的疏水性能，能够引入作为疏水官能团，可显著提升钙钛矿的水稳定性。另外由于氮杂环上的氮与钙钛矿A位有着较强的质子结合能，可以抑制A位离子的流失，由此增强了钝化效果。
与上述化合物形成的有机盐中的酸根离子选自含O、S、P、N、F、 I、Br、Cl、C和H的酸根离子中的一种。
具体而言可以列举选自来自醋酸、磷酸、硝酸、氯酸、磺酸、硫酸、氢氟酸、氢氯酸、氢溴酸和氢碘酸中的一种酸根离子。
酸根离子优选来自选自氢氟酸、氢氯酸、氢溴酸和氢碘酸中的一种，这是由于在选用卤素作为酸根离子时，可以弥补钙钛矿表面的卤素空位。从能够弥补X位的缺陷、能够与A位阳离子形成氢键从而稳定A位阳离子的方面出发，酸根离子较优选来自氢氟酸。
另外酸根离子优选来自含氧、硫、磷等酸中的一种，例如来自羧酸、磺酸、硫酸和磷酸中的一种。这是由于来自这些酸的酸根离子能够与A位的离子形成氢键，同时可以锚合B位的离子，从而稳定A位和B位的离子，进一步达到稳定钙钛矿结构，提升电池器件的长期稳定性的效果。
上述钙钛矿太阳能电池中，优选钙钛矿层中的钙钛矿与钝化层中的钝化剂的摩尔量之比(钙钛矿的摩尔量/钝化剂的摩尔量)为100～800，可以为200～600或300～400。相对于钙钛矿，钝化剂的量过少时无法充分对钙钛矿结构的缺陷进行钝化，也无法赋予理想的疏水性。而钝化剂的量过多时，钝化的效果达到饱和而费效比降低，另外有可能造成妨碍载流子传输、内阻增大甚至电池失效等不良影响。
1.3电子传输层3和空穴传输层6
电子传输层和空穴传输层是成于钙钛矿层和钝化层两侧的层，其分别用于传输在钙钛矿层上通过生成的自由电子和空穴。通过将电子与空穴分离并进一步传输至第一电极和第二电极，避免空穴和电子复合而使损转换效率降低。需要说明的是，图1中仅示出了本发明可以采取的一种情况，本发明的电子传输层和空穴传输层的位置也可以互换。
电子传输层和空穴传输层中的至少一方在可见光波段的透光率在50％以上、60％以上、70％以上、80％以上、90％以上、95％以上。
作为电子传输层，该层由常规的电子传输材料构成，本领域技术人员能够在有利于转换效率的范围内适当选取。例如可以使用氧化锡、氧化钛、PCBM、C60，优选氧化锡。另外关于该层的制备方法，能够通 过适当组合涂布、蒸镀、退火等常规方法制备。
作为空穴传输层，该层由常规的空穴传输材料构成，本领域技术人员能够在有利于转换效率的范围内适当选取。例如可以使用PTAA、spiro、PEDOT：PSS，优选spiro。另外关于该层的制备方法，能够通过适当组合涂布、蒸镀、退火等常规方法制备。
1.4第一电极2和第二电极7
第一电极叠层于电子传输层的与钙钛矿层方向相反的方向，是将电子传输层所传导出来的电子引导至外部以供利用的电极。第二电极叠层于空穴传输层的与钙钛矿层方向相反的方向，是将空穴传输层所传导出来的空穴引导至外部以供利用的电极。需要说明的是，图1中仅示出了本发明可以采取的一种情况，本发明的第一电极和第二电极的位置也可以互换。
作为第一电极和第二电极，在其为非透明电极时，可以由常规的用于电极的材料构成，本领域技术人员能够在有利于转换效率的范围内适当选取。例如可以使用金、银、铜、铝等，优选金。另外关于该层的制备方法，能够通过适当组合涂布、蒸镀、退火等常规方法制备。
第一电极和第二电极中的至少一方为透明电极，该透明电极在可见光波段的透光率在50％以上、60％以上、70％以上、80％以上、90％以上、95％以上。作为透明电极时，可以由常规的用于透明电极的材料构成，本领域技术人员能够在有利于转换效率的范围内适当选取。例如可以使用导电氧化物、金属网格、超薄金属层、纳米金属线、碳基透明材料、聚合物等。从透光性高的方面出发优选导电氧化物。另外关于该电极的制备方法，能够通过适当组合涂布、蒸镀、退火等常规方法制备。
1.5基底1
在需要的情况下，在第一电极和/或第二电极的外侧还可以具有基底。基底用于支撑钙钛矿太阳能电池整体，方便操作和组装等。
该基底可以为聚酰亚胺(PI)、聚对苯二甲酸丁二醇酯(PET)、聚酰胺(PA)、聚碳酸酯(PC)、超薄玻璃等有机或无机的柔性材质，或者也可以为玻璃板、金属板等刚性材质。
在第一电极和第二电极的外侧均具有基底的情况下，至少一个基底在可见光波段的透光率在50％以上、60％以上、70％以上、80％以上、90％以上、95％以上。并且该透光的基底配置在透明的电极一侧。
另外，在第一电极和/或第二电极具有足以支撑钙钛矿太阳能电池的能力时，基底也可以省略。
2 钙钛矿太阳能电池的制造方法
本发明的钙钛矿太阳能电池的制造方法包括：
在承载钙钛矿层的层上涂布钙钛矿前驱体溶液(步骤1)，在钙钛矿前驱体溶液层之上直接涂布含有上述钝化剂的反溶剂(步骤2)，进行退火(步骤3)。其中，步骤1和步骤2的涂布可以采用旋涂、刮涂、辊涂、喷涂等常规方法，但从能够较好地控制厚度的观点出发，优选旋涂。
这样的制造方法能够简化制备钝化层的步骤，避免多次退火对钙钛矿结构的影响。并且能够在形成钙钛矿结构的过程中实现钝化。
具体而言，本发明的方法与现有技术相比，减少了退火处理的次数，避免了钙钛矿的多次退火，能够节省时间成本、提高制备效率。
并且，本发明的方法中，在钙钛矿相未稳定时加入钝化剂，钝化剂可以在晶界和表面处与钙钛矿更好地键合，使钙钛矿相更加稳定。
由于钝化剂不仅存在于钙钛矿层表面，还能够深入至晶界深处，因此能够同时钝化晶界和表面，实现全方位的钝化。这样能够更有效地防止电子与空穴在晶界和表面处复合。而且，即使在晶界较小的情况下，利用本发明的方法，也能够使分子体积较大的钝化剂进入晶界深处。同时，由于钝化剂仅存在于反溶剂中，该钝化剂并不会影响钙钛矿结构的形成。这是利用现有技术难以实现的。
2.1 钙钛矿前驱体溶液
钙钛矿前驱体溶液中包含钙钛矿前驱体和溶剂。具体来说，钙钛矿前驱体是包含A离子、B离子和X离子的物质。钙钛矿前驱体溶液可以列举例如BX 2与AX在溶剂中的混合物。其中，A如前面所述，可以为选自铯等碱金属或甲胺、甲脒等小分子含氮有机物化合物，B为 Sn或Pb，X为卤素。
关于钙钛矿前驱体溶液中的溶剂，只要能够溶解BX 2与AX、与反溶剂互溶，并且能够通过加热除去即可，可以从目前常规使用的溶剂中适当选择。本领域技术人员可以从现有技术中选择任意适当的组合来制备钙钛矿前驱体溶液。
关于以摩尔计的BX 2与AX之比(BX 2/AX)，从能够充分形成钙钛矿层结构的角度考虑，该比为1以上、1.01以上、1.02以上、1.03以上、1.04以上、1.05以上，从节约成本的角度考虑1.5以下、1.4以下、1.3以下、1.2以下、1.1以下。
钙钛矿前驱体溶液中，钙钛矿前驱体的浓度用于调节所形成的钙钛矿层的厚度，关于其理想的浓度，以BX 2浓度计算，为0.2～5mmol/mL、0.3～4mmol/mL、0.4～3mmol/mL、0.5～2mmol/mL。在该浓度时，有利于形成令人满意的钙钛矿结构。
需要说明的是，A离子的容许因子需要为0.8～1.2，如果因离子体积过大导致容许因子超出1.2，会导致晶格变形，或者难以填充至B-X八面体结构进而导致无法形成钙钛矿结构的担忧。即使能够形成该结构，也会因钙钛矿在结晶的过程被阻断，导致钙钛矿结晶质量降低，形成过多的晶界，产生深能级缺陷，捕获载流子，导致光电转化效率和稳定性的降低担忧。
在含有两种以上A离子时，优选其容许因子均为0.8～1.2。这是由于若存在较大分子，会与上述一样破坏结晶结构，即使作为添加剂使用，也会因较大的结构，导致结晶质量差，难以达到良好的稳定性。
2.2 含有钝化剂的溶液
本方法中的含有钝化剂的溶液包括反溶剂和钝化剂。
反溶剂是用于使钙钛矿前驱体转变为钙钛矿结构的溶剂。本发明中的反溶剂是钙钛矿前驱体的溶解度小的溶剂，选自甲苯、氯苯、二氯苯、乙酸乙酯、乙醚、苯、无水乙醇、异丙醇、丁醇、氯仿、丁酸甲酯、苯甲醚、二甲苯和三甲苯中的至少一种。反溶剂优选为向选自甲苯、氯苯、二氯苯和乙酸乙酯中的至少一种第一反溶剂中添加选自乙醚、苯、无水乙醇、异丙醇、丁醇、氯仿、丁酸甲酯、苯甲醚、二甲苯和三甲苯 中的至少一种的第二反溶剂而成的混合溶剂。
通过调节反溶剂中第一反溶剂与第二反溶剂的比例，能够调节前驱体对于反溶剂的溶解性，由此在反溶剂与前驱体溶液中的前驱体接触时，能够控制钙钛矿结构的析出速度和结晶尺寸。
反溶剂中，第一反溶剂与第二反溶剂之比(体积)为100：0～100：50，优选100：0～100：10。以这样的比例混合制造反溶剂时，能够有利地控制钙钛矿结构的析出速度和结晶尺寸。
本发明的反溶剂中含有本发明的钝化剂，在此不再进行重复说明。需要说明的是，即使是现有技术中的钝化剂，也可以用于本发明的钝化层的形方法。作为现有技术中的钝化剂。
在反溶剂中，钝化剂的浓度为0.1～10mmol/mL，可以为0.5～8mmol/mL、1～5mmol/mL、2～3mmol/mL。在上述范围内时，能够在不影响钙钛矿结构析出的同时，便于控制钝化层中钝化剂的含量。
钙钛矿前驱体溶液中的钙钛矿前驱体与反溶剂中的钝化剂的摩尔量之比(R)为200～8000，可以为800～1600或1000～1200。相对于钙钛矿前驱体，钝化剂的量过少时无法充分对钙钛矿结构的缺陷进行钝化，也无法赋予理想的疏水性。而钝化剂的量过多时，钝化的效果达到饱和而费效比降低，另外有可能造成妨碍载流子传输、内阻增大甚至电池失效等不良影响。
2.3 退火
本发明中，在涂布完钙钛矿前驱体溶液和反溶剂后，进行退火处理。退火处理过程中，前驱体溶液中的溶剂和反溶剂挥发，前驱体析出形成钙钛矿结构形成钙钛矿层和钝化层，同时钝化剂将钙钛矿结构的晶界和表面钝化。
退火处理的条件可以依照所使用的溶剂种类和退火设备参数适当设定，没有特别限定。但从能够获取良好秩序的钙钛矿结构的角度出发，可以为在80℃～200℃退火10分钟～2小时。例如可以采后述实施例中的退火条件。
3 发电装置
本发明的发电装置是包含上述钙钛矿太阳能电池的发电装置，该钙钛矿太阳能电池可以是一个或多个。该发电装置还具有控制系统和传输系统。本发明的发电装置通过控制系统和传输系统，将从上述太阳能电池产生的电能调整为能够匹配用电设备的电能。需要说明的是，这里所说“包含”是指发电装置与太阳能电池存在电连接的情况。
4 用电装置
本发明的用电装置是包含上述钙钛矿太阳能电池的用电装置，该钙钛矿太阳能电池可以是一个或多个。该用电装置还具有利用从上述钙钛矿太阳能电池产生的电能的系统。该利用电能的系统可以列举例如将电能转换成动能、内能、光能或化学能等的系统。需要说明的是，这里所说“包含”是指用电装置与太阳能电池存在电连接的情况。
实施例
下面将对本申请技术方案的实施例进行详细的描述。以下实施例仅用于更加清楚地说明本申请的技术方案，因此只作为示例，而不能以此来限制本申请的保护范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同；本文中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请；本申请的说明书和权利要求书及上述附图说明中的术语“包括”和“具有”以及它们的任何变形，意图在于覆盖不排他的含有。
在本申请实施例的描述中，技术术语“第一”“第二”等仅用于区别不同对象，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量、特定顺序或主次关系。在本申请实施例的描述中，“多个”的含义是两个以上，除非另有明确具体的限定。
在本文中提及“实施例”意味着，结合实施例描述的特定特征、结构或特性可以包含在本申请的至少一个实施例中。在说明书中的各个位置出现该短语并不一定均是指相同的实施例，也不是与其它实施例互斥的独立的或备选的实施例。本领域技术人员显式地和隐式地理解的是，本文所描述的实施例可以与其它实施例相结合。
在本申请实施例的描述中，术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。
在本申请实施例的描述中，技术术语“内”“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请实施例和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请实施例的限制。
本申请实施例中仅示出常规结构的钙钛矿太阳能电池，但本发明也能够适用于倒置结构的钙钛矿太阳能电池。
钙钛矿太阳能电池的制作
实施例1
【电子传输层的制备】
将15％氧化锡溶液与去离子水按照1:3混合，室温搅拌1h，取70μL，旋涂在导电玻璃表面，于150℃加热15分钟。
【钙钛矿层与钝化层的制备】
将作为AX的碘甲脒和氯甲胺与作为BX 2的碘化铅以(BX 2/AX＝1.05)添加至DMF与DMSO的混合溶液(DMF:DMSO＝4:1)中，配制钙钛矿溶液，室温下磁力搅拌1h，过滤待用。溶液中钙钛矿前驱体的最终浓度以碘化铅计为1.5mmol/mL。将后述表1和表2中的钝化材料溶于反溶剂中。向旋涂完电子传输层的导电玻璃UV照射15分钟，在玻璃上滴加60μL钙钛矿溶液，加入溶解钝化材料的反溶剂600μL，150℃退火1h，由此同时形成钙钛矿层与钝化层，最终形成厚度为500nm的钙钛矿层和厚度为2nm的钝化层。钙钛矿相对于钝化剂的量之比(摩尔比)为300。
【空穴传输层的制备】
在spiro中加入Li-TFSI、tBP、FK209，搅拌1h，过滤待用。在形成有钙钛矿层和钝化层的导电玻璃上滴加60μL spiro，旋涂，形成空穴传输层。
【背电极的制备】
在上述旋涂形成的空穴传输层之上，通过常规方法形成在真空蒸镀设备中蒸镀厚度为80nm的银，得到完整的钙钛矿太阳能电池。
实施例2～16
除了将钙钛矿层与钝化层的形成条件替换为表1、表2所示以外，均以与实施例1相同方式制作了钙钛矿太阳能电池。
比较例1～3
除了将表1、表2所示钝化剂添加至钙钛矿前驱体溶液中，并且在反溶剂中未添加钝化剂以外，均以与实施例1相同方式制作了钙钛矿太阳能电池。
比较例4
除了未添加钝化剂以外，均以与实施例1相同方式制作了钙钛矿太阳能电池。
【表1】
Figure PCTCN2021143789-appb-000001
【表2】
Figure PCTCN2021143789-appb-000002
电池特性测试(I－V测试)
对于通过上述方式得到的各实施例和比较例的太阳能电池各20个，利用光焱公司太阳光模拟器，在25℃一个太阳光强度下进行了I－V测试，将各个实施例和比较例的太阳能电池的测试结果的平均值示于下表3。
【表3】
Figure PCTCN2021143789-appb-000003
稳定性试验
将通过上述方式得到的各实施例和比较例的太阳能电池各20个，储存在可控制湿度的手套箱中，以恒温25摄氏度，恒湿60％RH的条件下进行了30天的老化处理，由此进行了稳定性测试，将各实施例、比较例和参考例在稳定性试验后未损坏的电池的I－V测试结果的平均值、效率保持率、损坏电池的个数以及损坏率示于下表4。
【表4】
Figure PCTCN2021143789-appb-000004
从上述表3和4的结果可知，使用了本发明的钝化剂的钙钛矿太阳能电池与未使用本发明钝化剂的相比，在提高器件效率与稳定性方面有着更明显的效果，不进行钝化的电池在放置一段时间后，电池效率衰减明显；在阳离子相同的情况下，采用含O、S、P、N等元素的有机酸作为酸根离子钝化效果更佳。并且，使用了本发明钝化剂的钙钛矿太阳能电池在放置一段时间后的电池损坏率得到了显著抑制。
另外还发现，使用了本发明的钝化层与钙钛矿层的制造方法得到的钙钛矿太阳能电池与未使用本发明的方法的相比，钙钛矿避免了二次加热退火，器件稳定性较好；而且在湿膜的情况下加钝化材料，控制结晶，可以使钝化材料更好的填充在晶界与表面，钙钛矿得到更好的保护，钙钛矿的稳定性增加。
产业上的可利用性
本发明能够提供一种能量转化效率高并且稳定性优异的钙钛矿太阳能电池，以及制造该太阳能电池的方法。这对于应对气候变化、建设生态文明具有极为重要的意义。

Claims (15)

  1. 一种钙钛矿太阳能电池，其特征在于，
    至少包括电极、电子传输层、空穴传输层、钙钛矿层和钝化层，以及任选的基底层，所述钝化层中含有钝化剂，所述钝化剂包括氮杂稠合双环化合物和/或由所述氮杂稠合双环化合物与酸形成的有机盐，所述氮杂稠合双环化合物的每个稠环独立地为五元或六元的饱和环、不饱和环或芳香环，且所述氮杂稠合双环化合物的稠环包含1～5个氮原子，
    所述稠环为无取代基的环或者为取代有1或2个碳原子数为1～3的取代基的环。
  2. 如权利要求1所述的钙钛矿太阳能电池，其特征在于，
    所述氮杂稠合双环化合物选自蝶啶、1,5,7-三叠氮双环(4.4.0)癸-5-烯、喹唑啉、喹啉、1,5-二氮杂双环[4.3.0]-5-壬烯、咪唑并[1,2-a]嘧啶、5,6,7,8-四氢吲嗪、1-甲基-2,3-二氢-1H-吡咯里嗪和2,4-二甲基喹啉中的一种。
  3. 如权利要求1或2所述的钙钛矿太阳能电池，其特征在于，
    所述有机盐中的酸根离子选自含O、S、P、N、F、I、Br、Cl、C和H的酸根离子中的一种。
  4. 如权利要求3所述的钙钛矿太阳能电池，其特征在于，
    所述酸根离子选自来自醋酸、磷酸、硝酸、氯酸、磺酸、硫酸、氢氟酸、氢氯酸、氢溴酸和氢碘酸中的一种的酸根离子。
  5. 如权利要求1～4中任一项所述的钙钛矿太阳能电池，其特征在于，
    所述钝化层是通过将溶解有所述钝化剂的反溶剂涂布于所述钙钛矿层上而形成的层，
    所述反溶剂选自甲苯、氯苯、二氯苯、乙酸乙酯、乙醚、苯、无水乙醇、异丙醇、丁醇、氯仿、丁酸甲酯、苯甲醚、二甲苯和三甲苯中的 至少一种。
  6. 如权利要求1～5中任一项所述的钙钛矿太阳能电池，其特征在于，
    所述钙钛矿层中的钙钛矿与所述钝化层中的所述钝化剂的摩尔量之比为100～800，可以为200～600或250～400。
  7. 一种发电装置，其特征在于，
    包含权利要求1～6中任一项所述的钙钛矿太阳能电池。
  8. 一种用电装置，其特征在于，
    包含权利要求1～6中任一项所述的钙钛矿太阳能电池。
  9. 一种钙钛矿太阳能电池的制造方法，其特征在于，包括
    在承载钙钛矿层的层上涂布钙钛矿前驱体溶液后，直接涂布含有钝化剂的反溶剂，之后进行退火的步骤；
    所述钝化剂包括氮杂稠合双环化合物或由所述氮杂稠合双环化合物与酸形成的有机盐，
    所述氮杂稠合双环化合物的每个稠环独立地为五元或六元的饱和环、不饱和环或芳香环，且所述氮杂稠合双环化合物的稠环包含1～5个氮原子，
    所述稠环为无取代基的环或者为取代有1或2个碳原子数为1～3的取代基的环。
  10. 如权利要求9所述的制造方法，其特征在于，
    所述氮杂稠合双环化合物选自蝶啶、1,5,7-三叠氮双环(4.4.0)癸-5-烯、喹唑啉、喹啉、1,5-二氮杂双环[4.3.0]-5-壬烯、咪唑并[1,2-a]嘧啶、5,6,7,8-四氢吲嗪、1-甲基-2,3-二氢-1H-吡咯里嗪和2,4-二甲基喹啉中的一种。
  11. 如权利要求9或10所述的制造方法，其特征在于，
    所述有机盐中的酸根离子选自含O、S、P、N、F、I、Br、Cl、C 和H的酸根离子中的一种。
  12. 如权利要求11中所述的制造方法，其特征在于，
    所述酸根离子选自来自醋酸、磷酸、硝酸、氯酸、磺酸、硫酸、氢氟酸、氢氯酸、氢溴酸和氢碘酸中的一种的酸根离子。
  13. 如权利要求9～12中任一项所述的制造方法，其特征在于，
    所述反溶剂选自甲苯、氯苯、二氯苯、乙酸乙酯、乙醚、苯、无水乙醇、异丙醇、丁醇、氯仿、丁酸甲酯、苯甲醚、二甲苯和三甲苯中的至少一种。
  14. 如权利要求9～13中任一项所述的制造方法，其特征在于，
    在所述反溶剂中，所述钝化剂的浓度为0.1～10mmol/mL。
  15. 如权利要求9～14中任一项所述的制造方法，其特征在于，
    所述钙钛矿前驱体溶液中的钙钛矿前驱体与所述反溶剂中的所述钝化剂的摩尔量之比为200～8000，可以为800～1600或1000～1200。
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