WO2023123390A1 - 钙钛矿太阳能电池、其制备方法以及用电设备 - Google Patents

钙钛矿太阳能电池、其制备方法以及用电设备 Download PDF

Info

Publication number
WO2023123390A1
WO2023123390A1 PCT/CN2021/143771 CN2021143771W WO2023123390A1 WO 2023123390 A1 WO2023123390 A1 WO 2023123390A1 CN 2021143771 W CN2021143771 W CN 2021143771W WO 2023123390 A1 WO2023123390 A1 WO 2023123390A1
Authority
WO
WIPO (PCT)
Prior art keywords
perovskite
group
solar cell
electron
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2021/143771
Other languages
English (en)
French (fr)
Inventor
梁伟风
孙娟娟
涂保
陈长松
郭永胜
陈国栋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Contemporary Amperex Technology Co Ltd
Original Assignee
Contemporary Amperex Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Contemporary Amperex Technology Co Ltd filed Critical Contemporary Amperex Technology Co Ltd
Priority to CN202180094106.0A priority Critical patent/CN116918480A/zh
Priority to PCT/CN2021/143771 priority patent/WO2023123390A1/zh
Priority to EP21960111.9A priority patent/EP4231803A4/en
Priority to US18/313,394 priority patent/US12402467B2/en
Publication of WO2023123390A1 publication Critical patent/WO2023123390A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • 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
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] 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
    • H10K30/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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 present application relates to the field of batteries, in particular to a perovskite solar battery, a preparation method thereof, and electrical equipment.
  • passivation materials such as thiophene compounds, pyridine compounds, cyclic ether compounds, and fullerenes are used to passivate the surface of perovskite to improve the photoelectricity of perovskite solar cells. Conversion efficiency.
  • passivation materials with monocyclic organic small molecule structures such as thiophene compounds, pyridine compounds, and cyclic ether compounds can only achieve a simple interface passivation effect, and cannot solve the problem in the preparation process of perovskite solar cells. And there will be deep energy level and shallow energy level defects during the operation of the device, and these defects will seriously affect the efficiency and long-term stability of the battery.
  • the organic amine salt of biphenyl compounds and acene compounds can not only passivate the defects on the surface of perovskite well, but also realize energy level adjustment, so it can greatly improve the performance of perovskite solar cells. efficiency and stability.
  • the present application is made in view of the above-mentioned technical problems, and its purpose is to provide a perovskite solar cell, its preparation method, and electrical equipment, which can significantly improve the battery performance and long-term stability of the perovskite solar cell .
  • the first aspect of the present application is to provide a perovskite solar cell, wherein the perovskite solar cell is sequentially equipped with: a back electrode, a hole transport layer, an interface passivation layer, a perovskite layer, an interface Passivation layer, electron transport layer, conductive glass, the HOMO energy level of the interface between the perovskite layer and the interface passivation layer is 0.01-0.4eV, and the energy band gap between the HOMO energy level and the LUMO energy level is 0.01-0.4eV , the interface passivation layer contains: organic amine salts of biphenyl compounds and/or organic amine salts of acene compounds.
  • the HOMO energy level can be increased, while the LUMO energy level changes little.
  • the organic amine salt of the biphenyl compound has: at least one selected from biphenyl, o-terphenyl, m-terphenyl, and p-terphenyl as a core.
  • the polyphenyl structure is used to adjust the perovskite energy level, as the number of benzene rings increases, expanding the ⁇ conjugated system (or ⁇ range) will increase the number of coupled molecular orbitals and enhance the degree of ⁇ delocalization, so the HOMO The energy level increases, while the LUMO energy level changes little.
  • the organic amine salt of the acene-based compound has: at least one selected from naphthalene, anthracene, phenanthrene, tetracene, and pentacene as a core.
  • the polyphenyl structure is used to adjust the perovskite energy level, as the number of benzene rings increases, expanding the ⁇ conjugated system (or ⁇ range) will increase the number of coupled molecular orbitals and enhance the degree of ⁇ delocalization, so the HOMO The energy level increases, while the LUMO energy level changes little.
  • the organic amine salt of the biphenyl compound and/or the organic amine salt of the acene compound also has: an electron-donating group, an electron-withdrawing group and an alkylamine. Different electron-withdrawing and electron-donating functional groups are introduced to play the role of energy level adjustment.
  • the electron-donating group is one or more selected from a super-strong electron-donating group, a strong electron-donating group, a medium electron-donating group, and a weak electron-donating group, wherein,
  • the super electron-donating group is an oxo group
  • the strong electron-donating group is a dialkylamino group, an alkylamino group, an amino group, a hydroxyl group, or an alkoxyl group, wherein the alkyl group has 1 to 10 carbon atoms,
  • the electron-donating group is an amide group or an acyloxy group
  • the weak electron-donating group is an alkyl group, a carboxymethyl group, or a phenyl group;
  • the electron-withdrawing group is one or more selected from a strong electron-withdrawing group, a moderate electron-withdrawing group, and a weak electron-withdrawing group, wherein,
  • the strong electron-withdrawing group is a tertiary amino group, a nitro group, or a trihalomethyl group
  • the electron-withdrawing group is a cyano group or a sulfonic acid group
  • the weak electron-withdrawing group is an acyl group or a carboxyl group.
  • the electron-donating group can increase its HOMO energy level, while the electron-withdrawing group can reduce its LUMO energy level. Through the cooperation of different groups, it can achieve the function of adjusting its energy level position and band gap, and adjust the energy level position of the molecule.
  • the electronic structure of the perovskite surface can be tuned to adjust the energy level of the perovskite to better match the energy level of the hole transport layer.
  • the organic amine salts of biphenyl compounds and/or the organic amine salts of acene compounds also have: selected from sulfonate ion, nitrate ion, acetate ion, phosphate ion, fluoride ion, iodide ion
  • sulfonate ion nitrate ion
  • acetate ion phosphate ion
  • fluoride ion iodide ion
  • anions can improve the electrostatic interaction with cations, and on the other hand, they can improve the binding ability with the A-site and B-site in the perovskite layer, and stabilize the structure of the perovskite layer.
  • the second aspect of the present application is to provide a method for preparing a perovskite solar cell, wherein the method for preparing a perovskite solar cell includes in sequence: (I) a preparation process of an electron transport layer, (II) a perovskite layer and the preparation process of the passivation layer, (III) the preparation process of the hole transport layer and (IV) the preparation process of the back electrode, thus preparing the perovskite solar cell described in the first aspect,
  • the preparation procedure of perovskite layer and passivation layer comprises:
  • the perovskite precursor in the step (1), is dissolved in a solvent to obtain a perovskite precursor solution, wherein the perovskite precursor includes: selected from CsBr, FABr , MABr, CsI, FAI, MAI, CsCl, FACl, MACl more than 1; and selected from PbBr 2 , SnBr 2 , PbI 2 , SnI 2 , PbCl 2 , SnCl 2 or more, the solvent is One or more selected from DMF, DMSO, NMP, and GBL. These solvents can effectively dissolve the perovskite precursor to obtain a perovskite precursor solution.
  • the interface passivation material is dissolved in an anti-solvent to obtain an anti-solvent solution of the interface passivation material, and the anti-solvent is selected from toluene, chlorobenzene, dichloro One of benzene, ethyl acetate and ether.
  • Adding the interface passivation material into the antisolvent to form the antisolvent solution of the interface passivation material can reduce the complicated process of preparing the interface passivation layer and avoid the influence of multiple annealing on each layer. Moreover, the interface passivation material can better bond with the perovskite layer at the interface, stabilize the perovskite layer, and passivate the grain boundary and surface of the perovskite layer at the same time, which can prevent the charge carriers from flowing between the grain boundary and the interface. complex.
  • the anti-solvent solution of the interface passivation material as other solvents, further added selected from benzene, absolute ethanol, isopropanol, butanol, chloroform, methyl butyrate, anisole, One or more of xylene and trimethylbenzene.
  • the concentration of the interface passivation material is 0.1 ⁇ 40 mmol/L. If the concentration of the interface passivation material exceeds 40mmol/L, then because the passivation material is an organic small molecule, the band gap is wider. If it is thicker, it is difficult for carriers to pass through, resulting in a drop in current. If it is lower than 0.1mmol/L, if there are too many defects on the surface of the perovskite, it is difficult for a low-concentration passivation material to completely passivate the defects. Therefore, by making the concentration of the interface passivation material in the range of 0.1 to 40mmol/L In this way, its defects can be completely passivated, and it can also avoid the difficult tunneling of carriers caused by the passivation material being too thick.
  • the spin coating cycle of the perovskite precursor solution is 10-120 seconds. If the spin-coating cycle of the perovskite precursor solution exceeds 120 seconds, the current is too low because the perovskite layer is too thin to absorb sunlight sufficiently; if it is less than 10 seconds, the wet film thickness is too high , perovskite is difficult to achieve better crystallization, so by making the spin coating cycle of the perovskite precursor solution in the range of 10 to 120 seconds, the perovskite can be in a suitable thickness range, and crystallization can be obtained A perovskite film with better quality should not be too thin to absorb sunlight; nor should it be too thick to cause poor perovskite crystallization.
  • the anti-solvent solution of the interface passivation material is added dropwise during the process of spin-coating the perovskite precursor solution.
  • pre-annealing is optionally performed before the annealing in step (3), the pre-annealing temperature is 60-150° C., and the pre-annealing time is 30 minutes or less. If the pre-annealing temperature exceeds 150°C, the perovskite and passivation material will not withstand high temperature and decompose. If it is lower than 60°C, the solvent will be difficult to volatilize and the next layer will be difficult to spread. Therefore, by The pre-annealing temperature is in the range of 60-150° C., so that the solvent can be completely volatilized, and the passivation material can be better spread on the surface of the perovskite without affecting the perovskite phase. And, if the pre-annealing time exceeds 30 minutes, it will cause the perovskite to start to decompose, so make it less than 30 minutes.
  • the annealing temperature is 100-200° C., and the annealing time is 10-120 minutes. If the annealing temperature exceeds 200°C, the perovskite phase will be decomposed due to high temperature, and if it is lower than 100°C, it will be difficult to form a perovskite phase that can realize photoelectric conversion. Therefore, by making the The annealing temperature is in the range of 100-200° C., so that high-quality crystalline perovskite can be obtained.
  • the annealing time exceeds 120 minutes, it will cause the perovskite to start to decompose, if the annealing time is less than 10 minutes, it will cause the solvent to be difficult to volatilize completely, and the perovskite phase with photoelectric conversion is difficult to form, so by making the The annealing time ranges from 10 to 120 minutes, so that a high-quality perovskite layer can be obtained.
  • the preparation process of the electron transport layer after spin-coating the material solution of the electron transport layer on the surface of the conductive glass, annealing is performed to obtain the electron transport layer.
  • the hole transport layer material solution is spin-coated on the surface of the perovskite layer and the passivation layer to obtain the hole transport layer.
  • the electrode position is scraped out, and silver is evaporated to obtain the back electrode.
  • the third aspect of the present application is to provide an electric device, which is provided with the perovskite solar cell according to the first aspect of the present application as a power source or an energy storage unit of the electric device.
  • the defects on the surface of the perovskite can be well passivated, and the energy level can be adjusted, so the efficiency and stability of the perovskite solar cell can be greatly improved.
  • FIG. 1 is a schematic structural view of a perovskite solar cell according to an embodiment of the present application.
  • Fig. 2 is an energy level diagram of a perovskite solar cell according to another embodiment of the present application.
  • Fig. 3 is an energy level diagram of an interface passivation material according to another embodiment of the present application.
  • Fig. 4a is a SEM image of a passivation layer according to another embodiment of the present application
  • Fig. 4b is a partial enlarged view of Fig. 4a.
  • FIG. 5 is a plan view of the perovskite solar cell shown in FIG. 1 .
  • FIG. 6 is a cross-sectional view of the perovskite solar cell shown in FIG. 1 .
  • FIG. 7 is a schematic diagram of passivation of a perovskite solar cell according to an embodiment of the present application.
  • FIG. 8 is a schematic diagram of the preparation process of a perovskite layer and an interface passivation layer in a perovskite solar cell according to an embodiment of the present application.
  • 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 also contemplated. Furthermore, 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 contemplated: 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, wherein 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 “comprising” and “comprising” mentioned in this application mean open or closed.
  • the “comprising” and “comprising” may mean that other components not listed may also 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 perovskite solar cell of the present application can be (metal) back electrode, electron/hole transport layer, passivation layer, perovskite layer, passivation layer, hole/electron transport layer from top to bottom , Conductive glass.
  • the interface passivation layer is formed by passivating the surface of the perovskite layer through the interface passivation material, and the HOMO energy level of the interface between the perovskite layer and the interface passivation layer is 0.01- 0.4eV, the energy band gap between the HOMO energy level and the LUMO energy level is 0.01-0.4eV, and the interface passivation material contains: organic amine salts of biphenyl compounds and/or organic amine salts of acene compounds.
  • the VBMs of the two are -5.5 and -5.2 respectively, and a large energy level difference will lead to a decrease in the opening pressure, while biphenyl
  • the organic amine salt of the compound and/or the organic amine salt of the acene compound will increase the VBM of the perovskite layer, facilitate the extraction of holes, and improve the carrier transport efficiency.
  • biphenyl compounds include biphenyl, o-terphenyl, m-terphenyl and p-terphenyl, and their structural formulas are as follows from left to right:
  • acene compounds include naphthalene, anthracene, phenanthrene, tetracene, and pentacene, and their structural formulas are as follows from left to right:
  • the existing interface passivation materials have a certain effect on improving battery efficiency and stability.
  • organic ammonium salts composed of biphenyl compounds and acene compounds have a more significant effect on battery performance and long-term stability. improvement.
  • biphenyl compounds and acene compounds are polyphenylene ring compounds.
  • the use of polyphenylene rings can increase the energy level position of the valence band on the surface of the organic hybrid perovskite, making it compatible with the hole transport
  • the layer has better energy level matching, which is beneficial to carrier transport to improve battery efficiency.
  • an interface passivation material with a polybenzene structure to adjust the perovskite energy level, as the number of benzene rings increases, expanding the ⁇ conjugated system (or ⁇ range) will increase the number of coupled molecular orbitals, and The degree of ⁇ delocalization is enhanced, so the HOMO energy level increases, while the LUMO energy level changes less.
  • the energy level detection method is carried out by ultraviolet photoelectron spectroscopy (UPS). After the equipment is characterized, its energy level position is calculated through its Fermi edge and cut-off edge. In addition, the ultraviolet-visible spectrophotometer is used to measure its spectral absorption through equipment, and according to the formula conversion, its band gap is measured.
  • UPS ultraviolet photoelectron spectroscopy
  • polyphenyl rings are used as hydrophobic functional groups to cover the surface of the perovskite layer, forming a dense hydrophobic layer, which can improve the water stability of the perovskite layer.
  • the passivation layer covered on the surface of the perovskite layer is a dense hydrophobic layer, thereby improving the water stability of the perovskite layer.
  • the passivation layer included in the perovskite solar cell of the present application is compact, thereby improving the water stability of the perovskite layer.
  • the perovskite solar cell of the present application passivates the surface of the perovskite layer by using an interface passivation material containing an organic amine salt of a biphenyl compound and/or an organic amine salt of an acene compound.
  • An interface passivation layer is formed, and the HOMO energy level of the interface between the perovskite layer and the interface passivation layer is 0.01-0.4eV, and the energy band gap between the HOMO energy level and the LUMO energy level is 0.01-0.4eV, that is, After energy level matching, the opening voltage of the device increases, and after the defect passivation, the carrier recombination decreases, the current increases, the passivation of the defect, and the anchoring of the functional group to the perovskite increase the phase stability of the perovskite. It is not easy to decompose, and the polyphenyl structure will increase the water stability of the perovskite solar cell, which will significantly improve its long-term stability.
  • the organic amine salt of the biphenyl compound and/or the organic amine salt of the acene compound contained in the interface passivation material by introducing different electron-donating groups and electron-withdrawing
  • the group plays the role of energy level adjustment, among which:
  • the electron donating group is one or more selected from super strong electron donating group, strong electron donating group, medium electron donating group and weak electron donating group:
  • Middle electron donating group amide group (-NHCOR), acyloxy group (-OCOR);
  • the above-mentioned alkyl group has 1-10 carbon atoms.
  • the electron-withdrawing group is one or more selected from strong electron-withdrawing groups, medium electron-withdrawing groups, and weak electron-withdrawing groups:
  • Electron-withdrawing groups cyano group (-CN), sulfonic acid group (-SO 3 H);
  • the position of the energy level can be adjusted by adding electron-donating groups and electron-withdrawing groups on the benzene ring.
  • electron-donating groups can increase its HOMO energy level
  • electron-withdrawing groups can reduce its LUMO Energy level
  • adjusting the energy level position of the molecule can adjust the electronic structure of the perovskite layer surface, thereby adjusting the energy level of the perovskite layer , to make it more closely match the energy level of the hole transport layer.
  • the organic amine salt of the biphenyl compound and/or the organic amine salt of the acene compound also have a sulfonate ion ( -SO 3 H), a nitrate ion ( NO 3 - ), acetate ion (CH 3 COO - ), phosphate ion (PO 4 3- ), fluoride ion (F - ), iodide ion (I - ), bromide ion (Br - ), chloride ion (Cl - ) at least one kind of anion.
  • biphenyl and organic amine compounds of acene compounds are used as cations; anion parts are alkyl acids containing O, S, P, N, F, I, Br, and Cl , such as oleic acid, alkyl sulfonic acid, etc., preferably containing O, S, P, N, Cl, Br, I acid radical ions, containing O, S, P, N, Cl, Br, I acid radical ions can be combined with calcium on the one hand
  • the A site in titanium ore forms hydrogen bonds to stabilize organic cations, while some acid radical ions containing O and S can anchor Pb, and the interaction can stabilize the perovskite phase very well, which has a good effect on the long-term stability of solar cells. Effect.
  • the acid radical ion is Cl, Br, I, and an organic acid salt having an alkyl chain is particularly preferable as an anion.
  • the anion part is necessary for energy level adjustment and interface passivation. If halide ions are used as anions, it can make up for the halogen vacancies on the surface of the perovskite layer. If an organic acid salt of an alkyl chain is used as an anion, the alkyl chain has the ability to donate electrons, which will increase the electronegativity of the anion. The binding ability of the A site and the B site in the ore stabilizes the structure of the perovskite.
  • the anion has a certain influence on the passivation effect, and the halogen anion can make up for the defect of the X position, and the F ion can form a hydrogen bond with the A position cation to stabilize the A position cation.
  • Oxygenates such as acetate ions and phosphate ions can better chelate Pb ions, and compared with iodide ions, they can resist oxidation and avoid the formation of harmful substance iodine.
  • the preparation method of the perovskite solar cell of the present application includes in order: (I) preparation process of electron transport layer, (II) preparation process of perovskite layer and passivation layer, (III) preparation of hole transport layer The preparation process and (IV) the preparation process of the back electrode, thereby preparing the perovskite solar cell of the present application.
  • the preparation procedure of perovskite layer and passivation layer comprises:
  • the perovskite precursor is dissolved in a solvent to obtain a perovskite precursor solution, and the perovskite precursor includes: selected from CsBr, FABr, MABr, CsI, FAI, MAI , CsCl, FACl, MACl at least one; and selected from PbBr 2 , SnBr 2 , PbI 2 , SnI 2 , PbCl 2 , SnCl 2 at least one, the solvent is selected from DMF, DMSO, NMP, More than 1 species in GBL.
  • the perovskite precursors include: PbI 2 and FAI combination, PbI 2 and FAI and MAC1 combination, MAI and PbI 2 combination, CsI and PbI 2 combination; from From the viewpoint of crystallization control, the solvent is preferably two or more selected from DMF, DMSO, NMP, and GBL, for example: a combination of DMF and DMSO, a combination of DMF and NMP.
  • the interface passivation material is dissolved in the antisolvent, thereby obtaining the antisolvent solution of the interface passivation material, wherein, from the viewpoint of interface passivation, the interface passivation material is preferably selected from One or more of p-fluorophenethylamine, naphthaleneethylamine, anthraceneethylamine, 2-methoxynaphthylethylamine hydroiodide, and 2-methoxynaphthylethylamine acetate, more preferably selected from naphthalene One or more of ethylamine, anthraceneethylamine, and 2-methoxynaphthylethylamine hydroiodide.
  • the anti-solvent is selected from toluene, chlorobenzene, dichlorobenzene, ethyl acetate One of ester and ether.
  • the preparation process of the perovskite layer is to drop the perovskite precursor solution onto the electron transport layer, spin-coat first, and then add the anti-solvent solution dissolved in the interface passivation material dropwise during the spin-coating process, and spin-coat together .
  • the anti-solvent can extract the solvent in the perovskite precursor solution, and the solute crystallizes out, which is the perovskite layer.
  • the perovskite precursor solution is firstly added dropwise and spin-coated, and after a period of spin-coating, the interface passivation material dissolved in The anti-solvent solution is then spin-coated together, and the perovskite and interface passivation layer are formed simultaneously during the spin-coating process.
  • the interface passivation layer is a layer of interface passivation material spin-coated on the perovskite layer, and an interface passivation layer is formed after annealing, which has the functions of passivation and interface regulation, so as to achieve higher photoelectric conversion efficiency and stability.
  • the concentration of the interface passivation material is 0.1-40 mmol/L, preferably 0.5-2 mmol/L from the viewpoint of passivating the interface of the perovskite layer, more preferably Preferably it is 0.5-1 mmol/L.
  • the spin-coating period of the perovskite precursor solution is 10-120 seconds.
  • the spin coating cycle is preferably 10 to 40 seconds, more preferably 15 to 30 seconds.
  • the anti-solvent solution of the interface passivation material is added dropwise during the process of spin-coating the perovskite precursor solution.
  • the spin-coating cycle of the perovskite precursor solution is 45 seconds, then at the 0th second of the entire cycle, the perovskite precursor solution is dripped at one time, and then at the 0th to 25th second, only the calcium In the 25th second, add the anti-solvent solution of the interface passivation material dropwise to the titanium precursor solution, and spin-coat the perovskite precursor solution and the anti-solvent solution of the interface passivation material at the same time in the 25th to 45th second.
  • the passivation material is added to the anti-solvent, and the thickness of the passivation layer formed on the surface of the perovskite can be controlled by the concentration and the spin-coating cycle. Impact. In this way, passivation can be achieved during the crystallization of perovskite. At this time, the passivation material can better bond with perovskite at the grain boundary and interface, stabilize the perovskite phase, and passivate the grain boundary at the same time. and the surface, which can prevent carriers from recombining at the grain boundary and interface. If the grain boundary is small, it is difficult for conventional interface passivation materials to penetrate deep into the grain boundary. The passivation effect is not good, and it is difficult to passivate defects in all aspects. The application is to add when the perovskite phase is not stable, and it is easier to make up for the defects in each position.
  • the annealing temperature is 100-200° C., and the annealing time is 10-120 minutes.
  • pre-annealing may optionally be performed, the pre-annealing temperature is 60-150° C., and the pre-annealing time is 30 minutes or less. In this application, only one annealing can be performed, or a pre-annealing can be optionally performed before annealing, which avoids multiple annealing of perovskite in the prior art, saves time and cost, and improves the efficiency of battery preparation.
  • the preparation process of the electron transport layer after the electron transport layer material solution is spin-coated on the surface of the conductive glass, annealing is performed to obtain the electron transport layer;
  • the preparation process of the hole transport layer spin-coat the hole transport layer material solution on the surface of the perovskite layer and the passivation layer to obtain the hole transport layer;
  • the preparation process of (IV) the back electrode scrape Silver is deposited on the electrode position to obtain the back electrode, and the perovskite solar cell of the present application is obtained through the above steps (I) to (IV).
  • the present application also provides an electric device, which includes the perovskite solar cell provided by the present application.
  • the perovskite solar cell can be used as a power source of the electric device, and can also be used as an energy storage unit of the electric device.
  • the electrical equipment may include: (1) user solar power supply: small power supply ranging from 10 to 100W, used for military and civilian life in remote areas without electricity, such as plateaus, islands, desert areas, frontier posts, etc., such as lighting, TV, radio recorders etc., 3-5KW home roof grid-connected power generation system, photovoltaic water pump: solve deep water well drinking and irrigation in areas without electricity.
  • Transportation field such as navigation lights, traffic/railway signal lights, traffic warning/sign lights, street lights, high-altitude obstruction lights, highway/railway wireless telephone booths, unattended road shift power supply, etc.
  • Communication/communication field solar energy Unattended microwave relay station, optical cable maintenance station, broadcasting/communication/paging power supply system; rural carrier telephone photovoltaic system, small communication machine, GPS power supply for soldiers, etc.
  • Petroleum, ocean, and meteorological fields cathodes of oil pipelines and reservoir gates Protection of solar power system, oil drilling platform life and emergency power supply, marine detection equipment, meteorological / hydrological observation equipment, etc.;
  • home lighting power supply such as garden lights, street lights, portable lights, camping lights, mountaineering lights, fishing lights, black light
  • Photovoltaic power station 10KW ⁇ 50MW independent photovoltaic power station, wind-solar (firewood) complementary power station, various large-scale parking lot charging stations, etc.
  • Solar building combine solar power generation with building materials Combined, the large buildings in
  • the conductive glass is processed according to the conventional method, and then, proceed in sequence: (I) preparation of the electron transport layer, (II) perovskite layer and passivation layer The preparation of (III) the preparation of the hole transport layer and (IV) the preparation of the back electrode, thereby obtaining the perovskite solar cell involved in Example 1. in particular,
  • the etched FTO conductive glass was ultrasonically cleaned several times with water, acetone, and isopropanol in sequence.
  • the FTO conductive glass was blown to dry the solvent under a nitrogen gun, and put it into a UV ozone machine for further cleaning.
  • the perovskite precursor solution was prepared, stirred magnetically at room temperature for 1 h, and filtered for use. Furthermore, the interface passivation material is dissolved in the anti-solvent to obtain the anti-solvent solution of the interface passivation material, thus, the perovskite precursor solution and the anti-solvent solution of the interface passivation material are respectively configured.
  • pre-annealing may be performed prior to annealing.
  • perovskite solar cells were prepared according to the same method as in Example 1, the difference being that, as shown in Table 1, the following changes were made: the material of the perovskite precursor, the solvent for dissolving the perovskite precursor, Spin coating cycle of perovskite precursor solution, interface passivation material, anti-solvent, concentration of anti-solvent solution of interface passivation material, timing of adding anti-solvent solution of interface passivation material, optional pre-annealing temperature and time, and annealing temperature and time.
  • Comparative Example 1 a perovskite solar cell was prepared according to the same method as in Example 1, with the difference that no interfacial passivation material was added to the antisolvent.
  • a perovskite solar cell was prepared according to the same method as in Example 5, except that the interface passivation material was butylammonium iodide.
  • AM 1.5G spectrum Spectrum: AM 1.5G spectrum; light intensity: 1000W/m 2 ; room temperature 25°C
  • the perovskite precursor solution was first added dropwise, and after a period of spin coating, the solution was added dropwise to dissolve The anti-solvent solution with the interface passivation material is annealed, thereby obtaining the perovskite layer and the passivation layer, and obtaining two layers at one time, avoiding secondary annealing.
  • the perovskite precursor solution in the preparation of perovskite solar cells, was added dropwise first, and after a period of spin coating, the anti-solvent was added dropwise.
  • the anti-solvent was pure chlorobenzene without interface passivation. The material, annealed, yields a perovskite layer without forming a passivation layer.
  • the perovskite precursor solution in the preparation of the perovskite solar cell, the perovskite precursor solution was added dropwise first, and after a period of spin coating, the anti-solvent was added dropwise.
  • the anti-solvent was pure chlorobenzene, and the interface passivation material was Butyl ammonium iodide is annealed to obtain a perovskite layer and form a passivation layer. Compared with Examples 1-20, the battery efficiency is low.
  • 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. .

Landscapes

  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)

Abstract

本申请提供一种钙钛矿太阳能电池、其制备方法、以及用电设备。本申请的钙钛矿太阳能电池依次具备：背电极、空穴传输层、界面钝化层、钙钛矿层、界面钝化层、电子传输层、导电玻璃，钙钛矿层和界面钝化层之间界面的HOMO能级为0.01-0.4eV，HOMO能级与LUMO能级之间的能带隙为0.01-0.4eV，所述界面钝化层含有：联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐。根据本申请的钙钛矿太阳能电池，通过采用联苯类化合物、并苯类化合物的有机胺盐对其中的钙钛矿层进行钝化，会使钙钛矿层VBM的提升，利于空穴的提取，提高载流子的传输效率，从而能够极大提高钙钛矿太阳能电池的效率与稳定性。

Description

钙钛矿太阳能电池、其制备方法以及用电设备 技术领域
本申请涉及电池领域，尤其涉及一种钙钛矿太阳能电池、其制备方法、以及用电设备。
背景技术
在现有的钙钛矿太阳能电池中，利用噻吩类化合物、吡啶类化合物、环状醚化合物、富勒烯等钝化材料对钙钛矿表面进行钝化，从而提高钙钛矿太阳能电池的光电转化效率。
但是，采用噻吩类化合物、吡啶类化合物、环状醚化合物等单环类有机小分子结构的钝化材料，仅能起到单纯的界面钝化效果，并不能解决在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问题，这些缺陷会严重影响电池的效率与长期稳定性。
且采用富勒烯等材料时，其结构会有较大的空间位阻，会导致载流子的复合，严重影响器件的性能。
发明内容
本申请人发现，联苯类化合物与并苯类化合物的有机胺盐不但可以很好地钝化钙钛矿表面的缺陷，而且可以实现能级调节，因此能够极大提高钙钛矿太阳能电池的效率与稳定性。
因此，本申请是鉴于上述技术问题而进行的，其目的在于，提供一种钙钛矿太阳能电池、其制备方法、以及用电设备，能够显著提升钙钛矿太阳能电池的电池性能和长期稳定性。
为了实现上述目的，本申请第一方面在于提供一种钙钛矿太阳能电池，其中，所述钙钛矿太阳能电池依次具备：背电极、空穴传输层、界面钝化层、钙钛矿层、界面钝化层、电子传输层、导电玻璃，钙钛矿层和界面钝化层之间界面的HOMO能级为0.01-0.4eV，HOMO能级与LUMO能级之间的能带隙为0.01-0.4eV，所述界面钝化层含有：联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐。
通过采用多苯结构来调节钙钛矿能级，能够使HOMO能级提高，而LUMO能级变化较小。
在一些实施方式中，所述联苯类化合物的有机胺盐具备：选自联苯、邻三联苯、间三联苯和对三联苯中的1种以上作为母核。在用多苯结构来调节钙钛矿能级时，随着苯环数目的增加，扩展π共轭体系(或π范围)会增加耦合分子轨道的数量，并增强π离域的程度，因此HOMO能级提高，而LUMO能级变化较小。
在一些实施方式中，所述并苯类化合物的有机胺盐具备：选自萘、蒽、菲、并四苯、并五苯中的1种以上作为母核。在用多苯结构来调节钙钛矿能级时，随着苯环数目的增加，扩展π共轭体系(或π范围)会增加耦合分子轨道的数量，并增强π离域的程度，因此HOMO能级提高，而LUMO能级变化较小。
在一些实施方式中，所述联苯类化合物的有机胺盐和/或所述并苯类化合物的有机胺盐还具备：给电子基团、吸电子基团和烷基胺，通过在母核上引入不同的吸电子与给电子官能团，起到能级调节的作用。
所述给电子基团为选自超强给电子基团、强给电子基团、中给电子基团、弱给电子基团中的1种以上，其中，
所述超强给电子基团为氧代基，
所述强给电子基团为二烷基氨基、烷基氨基、氨基、羟基、或烷氧基，其中，所述烷基的碳原子数为1～10，
所述中给电子基团为酰胺基、或酰氧基，
所述弱给电子基团为烷基、羧甲基、或苯基；并且，
所述吸电子基团为选自强吸电子基团、中吸电子基团、和弱吸电子基团中的1种以上，其中，
所述强吸电子基团为叔胺基、硝基、或三卤甲基，
所述中吸电子基团为氰基、或磺酸基，
所述弱吸电子基团为酰基、或羧基。
给电子基团可以提高其HOMO能级，而吸电子基团可以降低其LUMO能级，通过不同基团的配合，可以达到调节其能级位置与带隙的作用，调节该分子的能级位置可以对钙钛矿表面的电子结构进行调整，从而调节钙钛矿的能级，使之与空穴传输层能级更加匹配。
在一些实施方式中，联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐还具备：选自磺酸根离子、硝酸根离子、醋酸根离子、磷酸根离子、氟离子、碘离子、溴离子、氯离子中的1种以上作为阴离子。阴离子可以一方面提高与阳离子的静电作用，另一方面可以提高与钙钛矿层中A位与B位的结合能力，稳定钙钛矿层的结构。
本申请第二方面在于提供一种钙钛矿太阳能电池的制备方法，其中，所述钙钛矿太阳能电池的制备方法依序包括：(I)电子传输层的制备工序、(II)钙钛矿层与钝化层的制备工序、(III)空穴传输层的制备工序以及(IV)背电极的制备工序，由此制备第一方面所述的钙钛矿太阳能 电池，
其中，(II)钙钛矿层与钝化层的制备工序包括：
(1)分别配置钙钛矿前驱体溶液和界面钝化材料的反溶剂溶液；
(2)在旋涂有电子传输层的导电玻璃上，先滴加钙钛矿前驱体溶液进行旋涂，然后滴加界面钝化材料的反溶剂溶液，进而一并进行旋涂；
(3)退火，由此形成钙钛矿层与钝化层。
在一些实施方式中，所述工序(1)中，将钙钛矿前驱体溶解于溶剂中，从而得到钙钛矿前驱体溶液，其中，所述钙钛矿前驱体包括：选自CsBr、FABr、MABr、CsI、FAI、MAI、CsCl、FACl、MACl中的1种以上；和选自PbBr 2、SnBr 2、PbI 2、SnI 2、PbCl 2、SnCl 2中的1种以上，所述溶剂为选自DMF、DMSO、NMP、GBL中的1种以上。所述这些溶剂能够有效溶解所述钙钛矿前驱体而得到钙钛矿前驱体溶液。
在一些实施方式中，所述工序(1)中，将界面钝化材料溶解于反溶剂中，从而得到界面钝化材料的反溶剂溶液，所述反溶剂为选自甲苯、氯苯、二氯苯、乙酸乙酯和乙醚中的1种。
将界面钝化材料加入到反溶剂中而形成界面钝化材料的反溶剂溶液，可以减少制备界面钝化层的繁琐过程，避免了多次退火对各层的影响。并且，界面钝化材料可以在界面处与钙钛矿层更好的键合，稳定钙钛矿层，且可以同时钝化钙钛矿层的晶界和表面，可以防止载流子在晶界和界面处复合。
在一些实施方式中，所述界面钝化材料的反溶剂溶液中，作为其它溶剂，进一步添加选自苯、无水乙醇、异丙醇、丁醇、氯仿、丁酸甲酯、苯甲醚、二甲苯、三甲苯中的1种以上。
在一些实施方式中，所述界面钝化材料的反溶剂溶液中，所述界面钝化材料的浓度为0.1～40mmol/L。如果所述界面钝化材料的浓度超过40mmol/L，则由于钝化材料为有机小分子，带隙较宽，若其较厚，载流子难以穿过，导致电流下降会造成，如果低于0.1mmol/L，则由于钙钛矿表面的缺陷若太多，低浓度的钝化材料难以完全钝化其缺陷，因此，通过使所述界面钝化材料的浓度在0.1～40mmol/L的范围内，从而既可以完全钝化其缺陷，也可以避免因钝化材料太厚导致的载流子难以隧穿。
在一些实施方式中，所述工序(2)中，所述钙钛矿前驱体溶液的旋涂周期为10～120秒。如果所述钙钛矿前驱体溶液的旋涂周期超过120秒，则由于钙钛矿层太薄，导致无法充分吸收太阳光，使电流过低，如果低于10秒，则由于湿膜厚度太高，钙钛矿难以实现较好的结晶，因此通过使所述钙钛矿前驱体溶液的旋涂周期在10～120秒的范围内，从而能够使钙钛矿在合适的厚度范围，可以得到结晶质量较好的钙钛矿薄膜，不至于过薄，无法吸收太阳光；也不至于过厚，钙钛矿结晶太差。
在一些实施方式中，所述工序(2)中，在旋涂钙钛矿前驱体溶液的过程中滴加界面钝化材料的反溶剂溶液。
在一些实施方式中，在所述工序(3)的退火之前，任选地进行预退火，预退火温度为60～150℃，预退火时间为30分钟以下。如果所述预 退火温度超过150℃，则会造成钙钛矿与钝化材料不耐受高温而分解，如果低于60℃，则会造成溶剂难以挥发，使下一层难以铺展，因此，通过使所述预退火温度在60～150℃的范围内，从而能够使得溶剂可以完全挥发，在不影响钙钛矿相的前提下，可以使钝化材料较好的铺展在钙钛矿表面。并且，如果预退火时间超过30分钟，则会造成钙钛矿开始分解，因此使其在30分钟以下。
在一些实施方式中，所述工序(3)中，退火温度为100～200℃，退火时间为10～120分钟。如果所述退火温度超过200℃，则会造成钙钛矿相因不受高温而分解，如果低于100℃，则会造成难以形成可以实现光电转化的钙钛矿相，因此，通过使所述退火温度在100～200℃的范围内，从而能够得到高质量结晶的钙钛矿。并且，如果退火时间超过120分钟，则会造成钙钛矿开始分解，如果退火时间低于10分钟，则会造成溶剂难以挥发完全，具有光电转化的钙钛矿相难以形成，因此通过使所述退火时间在10～120分钟的范围内，从而能够得到得到高质量的钙钛矿层。
在一些实施方式中，在(I)电子传输层的制备工序中，在导电玻璃表面旋涂电子传输层材料溶液后，退火，得到所述电子传输层。
在一些实施方式中，在(III)空穴传输层的制备工序中，在钙钛矿层与钝化层表面旋涂空穴传输层材料溶液，得到所述空穴传输层。
在一些实施方式中，在(IV)背电极的制备工序中，刮出电极位置，蒸镀银，得到所述背电极。
本申请第三方面在于提供一种用电设备，该用电设备具备根据本申请第一方面所述的钙钛矿太阳能电池作为所述用电设备的电源或能 量存储单元。
根据本申请的钙钛矿太阳能电池，既能够很好地钝化钙钛矿表面的缺陷，又能够实现能级调节，因此能够极大提高钙钛矿太阳能电池的效率与稳定性。
附图说明
图1是本申请一个实施方式的钙钛矿太阳能电池的结构示意图。
图2是本申请另一个实施方式的钙钛矿太阳能电池的能级图。
图3是本申请又一个实施方式的界面钝化材料能级图。
图4a是本申请另一个实施方式的钝化层的SEM图，图4b是图4a的局部放大图。
图5是图1所示的钙钛矿太阳能电池的平面图。
图6是图1所示的钙钛矿太阳能电池的截面图。
图7是本申请一个实施方式的钙钛矿太阳能电池的钝化原理图。
图8是本申请一个实施方式的钙钛矿太阳能电池中，钙钛矿层与界面钝化层的制备过程示意图。
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的钙钛矿天阳能电池及其制备方法、电池模块、电池包和电学装置的实施方式。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，除非有其它说明，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它组分，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)。
钙钛矿太阳能电池
参照图1，本申请的钙钛矿太阳能电池从上而下可以依次为(金属)背电极、电子/空穴传输层、钝化层、钙钛矿层、钝化层、空穴/电子传输层、导电玻璃。
在本申请的钙钛矿太阳能电池中，通过界面钝化材料对钙钛矿层的表面进行钝化而形成界面钝化层，钙钛矿层和界面钝化层之间界面的HOMO能级为0.01-0.4eV，HOMO能级与LUMO能级之间的能带隙为0.01-0.4eV，所述界面钝化材料含有：联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐。
参照图2，以FAPbI3(钙钛矿层)与Spiro(空穴传输层)为例，两者的VBM分别为-5.5与-5.2，较大的能级差会导致开压的下降，而采用联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐，会使钙钛矿层VBM的提升，利于空穴的提取，提高载流子的传输效率。
在本申请中，联苯类化合物包括联苯、邻三联苯、间三联苯和对三联苯，它们的结构式从左到右依次如下：
Figure PCTCN2021143771-appb-000001
在本申请中，并苯类化合物包括萘、蒽、菲、并四苯、并五苯，它们的结构式从左到右依次如下：
Figure PCTCN2021143771-appb-000002
现有的界面钝化材料对电池效率与稳定性的提升有一定的效果，与之对比，发现联苯类化合物、并苯类化合物所构成的有机铵盐对电池性能与长期稳定性有着更显著的提升。
具体而言，联苯类化合物、并苯类化合物均为多苯环的化合物，通过多苯环的使用，可提高有机杂化钙钛矿表面的价带能级位置，使其与空穴传输层具有更优异的能级匹配，有利于载流子传输来提升电池效率。参照图3，通过采用具备多苯结构的界面钝化材料来调节钙钛矿能级，随着苯环数目的增加，扩展π共轭体系(或π范围)会增加耦合分子轨道的数量，并增强π离域的程度，因此HOMO能级提高，而LUMO能级变化较小。
能级检测方式是采用紫外光电子能谱(UPS)进行，通过设备表征后，通过其费米边与截至边，计算其能级位置。此外，利用紫外-可见分光光度计通过设备测其光谱吸收，根据公式转化，测其带隙。
进而，联苯类化合物以及并苯类化合物中的多苯环作为给电子官能团的引入一方面可以提升界面钝化材料在缺陷位点的结合能，同时提升界面钝化材料本身结合质子能力进而提升其固有的稳定性。
并且，多苯环作为疏水官能团覆盖在钙钛矿层表面，会形成一层致密的疏水层，可提高钙钛矿层的水稳定性。参照图4a和4b，钙钛矿层表面覆盖的钝化层是致密的疏水层，由此提高钙钛矿层的水稳定性。能级匹配后，利于空穴的提取，空穴传输层对钙钛矿空穴提取能力上升。
参照图5和图6也可以看出，本申请的钙钛矿太阳能电池所包括 的钝化层致密，由此可以提高钙钛矿层的水稳定性。
综上所述，本申请的钙钛矿太阳能电池通过利用含有联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐的界面钝化材料对钙钛矿层的表面进行钝化而形成界面钝化层，并且，钙钛矿层和界面钝化层之间界面的HOMO能级为0.01-0.4eV，HOMO能级与LUMO能级之间的能带隙为0.01-0.4eV，即，进行能级匹配后，器件开压增加，缺陷钝化后，载流子复合减少，电流提升，缺陷的钝化、以及官能团对钙钛矿的锚合，使钙钛矿的相稳定性增加，不易分解，多苯结构会使钙钛矿太阳能电池的水稳定性增加，对其长期稳定性有明显的提升。
在本申请的钙钛矿太阳能电池中，对界面钝化材料所含的联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐，通过引入不同的给电子基团与吸电子基团，起到能级调节的作用，其中：
给电子基团为选自超强给电子基团、强给电子基团、中给电子基团、弱给电子基团中的1种以上：
超强给电子基团：氧负离子(-O-)；
强给电子基团：二烷基氨基(-NR 2)、烷基氨基(-NHR)、氨基(-NH 2)、羟基(-OH)、烷氧基(-OR)；
中给电子基团：酰胺基(-NHCOR)、酰氧基(-OCOR)；
弱给电子基团：烷基(-R)、羧基甲基(-CH 2COOH)、苯基(-Ph)，
上述烷基的碳原子数为1～10。
并且，吸电子基团为选自强吸电子基团、中吸电子基团、和弱吸电子基团中的1种以上：
强吸电子基团：叔胺正离子(-N +R 3)、硝基(-NO 2)、三卤甲基(-CX 3) X＝F、Cl；
中吸电子基团：氰基(-CN)、磺酸基(-SO 3H)；
弱吸电子基团：甲酰基(-CHO)、酰基(-COR)、羧基(-COOH)。
随着联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐的苯环数目的增加，对于合成的难度会越来越高，且较大的结构会导致空间位阻的增加，此时可以通过在苯环上增加给电子基团和吸电子基团来调节能级的位置，总体而言，给电子基团可以提高其HOMO能级，而吸电子基团可以降低其LUMO能级，通过不同基团的配合，可以达到调节其能级位置与带隙的作用，调节该分子的能级位置可以对钙钛矿层表面的电子结构进行调整，从而调节钙钛矿层的能级，使之与空穴传输层能级更加匹配。
进而，在本申请的钙钛矿太阳能电池中，联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐还具备选自磺酸根离子( -SO 3H)、硝酸根离子(NO 3 -)、醋酸根离子(CH 3COO -)、磷酸根离子(PO 4 3-)、氟离子(F -)、碘离子(I -)、溴离子(Br -)、氯离子(Cl -)中的1种以上作为阴离子。
通过将联苯类化合物、并苯类化合物的有机胺化合物做成盐，联苯、并苯作为阳离子；阴离子部分为含O、S、P、N、F、I、Br、Cl的烷基酸，例如油酸、烷基磺酸等，优选含O、S、P、N、Cl、Br、I酸根离子，含有O、S、P、N、Cl、Br、I酸根离子一方面可以与钙钛矿中A位形成氢键，稳定有机阳离子，而一些含O、S的酸根离子可以锚合Pb，相互作用可以很好的稳定钙钛矿相，对太阳能电池的长期稳定性有着较好的效果。更优选酸根离子为Cl、Br、I，特别优选具有 烷基链的有机酸盐作为阴离子。
阴离子部分对于能级调节与界面钝化是一定的，如果选用卤素离子作为阴离子，可以弥补钙钛矿层表面的卤素空位。如果采用烷基链的有机酸盐作为阴离子，该烷基链有给电子的能力，会使阴离子的电负性增大，一方面可以提高与阳离子的静电作用，另一方面可以提高与钙钛矿中A位与B位的结合能力，稳定钙钛矿的结构。
此外，以图7为例，阴离子对钝化效果有着一定的影响，卤素阴离子可以弥补X位的缺陷其中F离子可以与A位阳离子形成氢键，稳定A位阳离子。而含氧酸根如醋酸根离子、磷酸根离子可以更好的螯合Pb离子，且相对于碘离子而言可抗氧化，避免有害物质碘单质的形成。
钙钛矿太阳能电池的制备方法
本申请的钙钛矿太阳能电池的制备方法，其中，依序包括：(I)电子传输层的制备工序、(II)钙钛矿层与钝化层的制备工序、(III)空穴传输层的制备工序以及(IV)背电极的制备工序，由此制备得到本申请的钙钛矿太阳能电池。
其中，(II)钙钛矿层与钝化层的制备工序包括：
(1)分别配置钙钛矿前驱体溶液和界面钝化材料的反溶剂溶液；
(2)在旋涂有电子传输层的导电玻璃上，先滴加钙钛矿前驱体溶液进行旋涂，然后滴加界面钝化材料的反溶剂溶液，进而一并进行旋涂；
(3)退火，由此形成钙钛矿层与钝化层。
所述工序(1)中，将钙钛矿前驱体溶解于溶剂中，从而得到钙钛矿前驱体溶液，所述钙钛矿前驱体包括：选自CsBr、FABr、MABr、CsI、 FAI、MAI、CsCl、FACl、MACl中的1种以上；和选自PbBr 2、SnBr 2、PbI 2、SnI 2、PbCl 2、SnCl 2中的1种以上，所述溶剂为选自DMF、DMSO、NMP、GBL中的1种以上。其中，从控制结晶的观点出发，优选所述钙钛矿前驱体包括：PbI 2与FAI的组合、PbI 2与FAI和MACl的组合、MAI与PbI 2的组合、CsI与PbI 2的组合；从控制结晶的观点出发，优选所述溶剂为选自DMF、DMSO、NMP、GBL中两种或两种以上，例如：DMF与DMSO的组合、DMF与NMP的组合。
所述工序(1)中，将界面钝化材料溶解于反溶剂中，从而得到界面钝化材料的反溶剂溶液，其中，从界面钝化的观点出发，所述界面钝化材料优选为选自对氟苯乙胺、萘乙胺、蒽乙胺、2-甲氧基萘乙胺氢碘酸盐、2-甲氧基萘乙胺醋酸盐中的1种以上，更优选为选自萘乙胺、蒽乙胺、和2-甲氧基萘乙胺氢碘酸盐中的1种以上。进而，从对钙钛矿前驱体溶液中溶剂的相溶难易程度、以及对界面钝化材料的溶解度的观点出发，优选所述反溶剂为选自甲苯、氯苯、二氯苯、乙酸乙酯和乙醚中的1种。
钙钛矿层的制备过程是将钙钛矿前驱体溶液滴加至电子传输层上，先旋涂，然后在旋涂的过程滴加溶解有界面钝化材料的反溶剂溶液，一并进行旋涂。反溶剂能够将钙钛矿前驱体溶液中的溶剂萃取出来，溶质结晶析出，即为钙钛矿层。进一步以图8为例，钙钛矿层与界面钝化层在制备过程中，首先是滴加钙钛矿前驱体溶液，进行旋涂，在旋涂一段时间后，滴加溶解有界面钝化材料的反溶剂溶液，然后一并旋涂，在旋涂过程中同时形成钙钛矿与界面钝化层。
界面钝化层是在钙钛矿层上旋涂一层界面钝化材料，退火后形成 界面钝化层，兼具钝化与界面调控的作用，从而实现较高的光电转化效率与稳定性。
从溶解度、对钙钛矿的溶解情况与溶剂的难易的观点出发，所述界面钝化材料的反溶剂溶液中，作为其它溶剂，进一步添加选自苯、无水乙醇、异丙醇、丁醇、氯仿、丁酸甲酯、苯甲醚、二甲苯、三甲苯中的1种以上。从而可以在不影响钙钛矿层的前提下，可以很好的萃取钙钛矿前驱体溶液的溶剂，使钙钛矿很好的结晶。
此外，所述界面钝化材料的反溶剂溶液中，所述界面钝化材料的浓度为0.1～40mmol/L，从对钙钛矿层界面钝化的观点出发，优选为0.5～2mmol/L，更优选为0.5～1mmol/L。
此外，所述工序(2)中，钙钛矿前驱体溶液的旋涂周期为10～120秒。从得到优异的钙钛矿层的观点出发，旋涂周期优选为10～40秒，更优选为15～30秒。
并且，所述工序(2)中，在旋涂钙钛矿前驱体溶液的过程中滴加界面钝化材料的反溶剂溶液。例如，如果钙钛矿前驱体溶液的旋涂周期为45秒，那么在整个周期的第0秒，一次性滴入钙钛矿前驱体溶液，然后在第0～25秒，先仅旋涂钙钛矿前驱体溶液，在第25秒，一次性滴加界面钝化材料的反溶剂溶液，在第25～45秒，同时旋涂钙钛矿前驱体溶液和界面钝化材料的反溶剂溶液。
将钝化材料加入到反溶剂中，通过浓度与旋涂周期可以控制在钙钛矿表面形成的钝化层的厚度，此做法可以减少制备钝化层的繁琐过程，避免了多次退火对薄膜的影响。由此可以在钙钛矿结晶的过程中实现钝化，此时钝化材料可以在晶界和界面处与钙钛矿更好的键合， 稳定钙钛矿相，且可以同时钝化晶界和表面，可以防止载流子在晶界和界面处复合，若晶界较小，常规的界面钝化材料难以深入至晶界深处，钝化效果不好，难以全方面钝化缺陷，本申请是在钙钛矿相未稳定时加入，较容易弥补各个位置的缺陷。
所述工序(3)中，退火温度为100～200℃，退火时间为10～120分钟。此外，在所述工序(3)的退火之前，可选地进行预退火，预退火温度为60～150℃，预退火时间为30分钟以下。在本申请中可以只进行一次退火，或者可选的在退火之前进行一次预退火，避免了现有技术中钙钛矿的多次退火，节省了时间成本，提高电池制备的效率。
此外，在本申请的钙钛矿太阳能电池的制备方法，在(I)电子传输层的制备工序中，在导电玻璃表面旋涂电子传输层材料溶液后，退火，得到所述电子传输层；在(III)空穴传输层的制备工序中，在钙钛矿层与钝化层表面旋涂空穴传输层材料溶液，得到所述空穴传输层；在(IV)背电极的制备工序中，刮出电极位置，蒸镀银，得到所述背电极，通过上述工序(I)～(IV)，由此得到本申请的钙钛矿太阳能电池。
用电设备
另外，本申请还提供一种用电设备，所述用电设备包括本申请提供的钙钛矿太阳能电池。所述钙钛矿太阳能电池可以用作所述用电设备的电源，也可以用作所述用电设备的能量存储单元。所述用电设备可以包括：(1)用户太阳能电源：小型电源10～100W不等，用于边远无电地区如高原、海岛、牧区、边防哨所等军民生活用电，如照明、电视、收录机等，3～5KW家庭屋顶并网发电系统，光伏水泵：解决无电地区的深水井饮用、灌溉。(2)交通领域：如航标灯、交通/铁路信号灯、 交通警示/标志灯、路灯、高空障碍灯、高速公路/铁路无线电话亭、无人值守道班供电等；(3)通讯/通信领域：太阳能无人值守微波中继站、光缆维护站、广播/通讯/寻呼电源系统；农村载波电话光伏系统、小型通信机、士兵GPS供电等；(4)石油、海洋、气象领域：石油管道和水库闸门阴极保护太阳能电源系统、石油钻井平台生活及应急电源、海洋检测设备、气象/水文观测设备等；(5)家庭灯具电源：如庭院灯、路灯、手提灯、野营灯、登山灯、垂钓灯、黑光灯、割胶灯、节能灯等；(6)光伏电站：10KW～50MW独立光伏电站、风光(柴)互补电站、各种大型停车厂充电站等；(7)太阳能建筑：将太阳能发电与建筑材料相结合，使得未来的大型建筑实现电力自给等，但不限于此。
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1
实施例1所涉及的钙钛矿太阳能电池的制备方法，首先按照常规方法对导电玻璃进行处理，然后，依序进行：(I)电子传输层的制备、(II)钙钛矿层与钝化层的制备、(III)空穴传输层的制备以及(IV)背电极的制备，由此得到实施例1所涉及的钙钛矿太阳能电池。具体而言，
【导电玻璃的处理】
取20片规格为2.0*2.0cm的FTO导电玻璃，两端通过激光刻蚀各去掉0.35cm的FTO，裸露出玻璃基底。
用水、丙酮、异丙醇依次超声清洗刻蚀后的FTO导电玻璃数次。
FTO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。
【(I)电子传输层的制备】
将30％的氧化锡胶体与去离子水按照1：3混合成为10mg/mL的氧化锡胶体水溶液，室温搅拌1h，取70μL作为电子传输层溶液，以4000rpm/s的速率旋涂在紫外臭氧处理后的FTO导电玻璃表面，于150℃加热15min，在150℃热台上退火处理15分钟，得到电子传输层。
此外，氧化锡胶体水溶液的配合比例可以在30％的氧化锡胶体∶水＝1∶1～5的范围内调节。
【(II)钙钛矿层与钝化层的制备】
按照表1所示，配制钙钛矿前驱体溶液，将其在室温下磁力搅拌1h，过滤待用。并且，将界面钝化材料溶于反溶剂中得到界面钝化材料的反溶剂溶液，由此，分别配置得到钙钛矿前驱体溶液和界面钝化材料的反溶剂溶液。在上述旋涂有电子传输层的FTO导电玻璃上，UV照射15min，先在FTO导电玻璃上滴加60μL钙钛矿前驱体溶液进行旋涂，按表1所示，旋涂一段时间后，然后滴加界面钝化材料的反溶剂溶液600μL，一并进行旋涂，接着，150℃退火1h。
可选地，可以在退火之前进行预退火。
【(III)空穴传输层的制备】
在spiro中加入Li-TFSI、tBP、FK209，搅拌1h，过滤作为空穴传 输层材料溶液待用，在上述旋涂完钙钛矿层和钝化层的导电玻璃上滴加60μL spiro，旋涂空穴传输层材料溶液，得到空穴传输层。
【(IV)背电极的制备】
将上述旋涂完空穴传输层的电池刮出电极位置，并用洗液擦去残留的功能层，放入蒸镀Mask中，在真空蒸镀设备中蒸镀80nm的银，得到本申请的钙钛矿太阳能电池。
实施例2～20
在实施例2～20中，按照实施例1相同的方法制备钙钛矿太阳能电池，区别在于如表1所示，分别变更：钙钛矿前驱体的材料、溶解钙钛矿前驱体的溶剂、钙钛矿前驱体溶液的旋涂周期、界面钝化材料、反溶剂、界面钝化材料的反溶剂溶液的浓度、界面钝化材料的反溶剂溶液的滴加时机、可选的预退火温度和时间、以及退火温度和时间。
对比例1
在对比例1中，按照实施例1相同的方法制备钙钛矿太阳能电池，区别在于：反溶剂中未加入界面钝化材料。
对比例2
在对比例2中，按照实施例5相同的方法制备钙钛矿太阳能电池，区别在于：界面钝化材料为丁基碘化胺。
电池性能测试
对实施例1～20以及对比例1～2所得到的钙钛矿太阳能电池进行如下电池效率的测试，结果一并示于表1中。
电池效率测试条件
光谱：AM 1.5G光谱；光强：1000W/m 2；室温25℃
电池效率测试过程
将太阳能电池分别与数字源表的正负极连接，测其光电转化效率。
表1
Figure PCTCN2021143771-appb-000003
Figure PCTCN2021143771-appb-000004
Figure PCTCN2021143771-appb-000005
从表1可以看出：
在实施例1～20中，在钙钛矿太阳能电池的制备中，关于钙钛矿层与钝化层的制备工序，先滴加钙钛矿前驱体溶液，旋涂一段时间后，再滴加溶解有界面钝化材料的反溶剂溶液，退火，由此获得钙钛矿层与钝化层，一次性得到两种层，避免二次退火。
由实施例1～20可知，在本申请的钙钛矿太阳能电池中，通过使用特定的钙钛矿前驱体材料、特定的溶剂、特定的界面钝化材料、特定的反溶剂、控制界面钝化材料在反溶剂中的浓度、特定的钙钛矿前驱体材料溶液的旋涂周期、特定的界面钝化材料的反溶剂溶液的滴加时机、可选的预退火温度和时间、退火温度和时间均在特定范围内、，可以大幅提高电池效率。
在对比例1中，在钙钛矿太阳能电池的制备中，先滴加钙钛矿前驱体溶液，旋涂一段时间后，再滴加反溶剂，反溶剂为纯氯苯，不含界面钝化材料，退火，得到钙钛矿层，没有形成钝化层。在对比例2中，在钙钛矿太阳能电池的制备中，先滴加钙钛矿前驱体溶液，旋涂一段时间后，再滴加反溶剂，反溶剂为纯氯苯，界面钝化材料为丁基碘化胺，退火，得到钙钛矿层，形成钝化层，与实施例1～20相比较，电池效率低下。
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 (11)

  1. 一种钙钛矿太阳能电池，其中，
    所述钙钛矿太阳能电池依次具备：背电极、空穴传输层、界面钝化层、钙钛矿层、界面钝化层、电子传输层、导电玻璃，
    钙钛矿层和界面钝化层之间界面的HOMO能级为0.01-0.4eV，HOMO能级与LUMO能级之间的能带隙为0.01-0.4eV，
    所述界面钝化层含有：联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐。
  2. 根据权利要求1所述的钙钛矿太阳能电池，其中，
    所述联苯类化合物的有机胺盐具备：选自联苯、邻三联苯、间三联苯和对三联苯中的1种以上作为母核。
  3. 根据权利要求2所述的钙钛矿太阳能电池，其中，
    所述并苯类化合物的有机胺盐具备：选自萘、葸、菲、并四苯、并五苯中的1种以上作为母核。
  4. 根据权利要求1～3中任一项所述的钙钛矿太阳能电池，其中，
    所述联苯类化合物的有机胺盐和/或所述并苯类化合物的有机胺盐还具备：给电子基团、吸电子基团和烷基胺，
    所述给电子基团为选自超强给电子基团、强给电子基团、中给电子基团、弱给电子基团中的1种以上，其中，
    所述超强给电子基团为氧代基，
    所述强给电子基团为二烷基氨基、烷基氨基、氨基、羟基、或烷 氧基，其中，所述烷基的碳原子数为1～10，
    所述中给电子基团为酰胺基、或酰氧基，
    所述弱给电子基团为烷基、羧甲基、或苯基；并且，
    所述吸电子基团为选自强吸电子基团、中吸电子基团、和弱吸电子基团中的1种以上，其中，
    所述强吸电子基团为叔胺基、硝基、或三卤甲基，
    所述中吸电子基团为氰基、或磺酸基，
    所述弱吸电子基团为酰基、或羧基。
  5. 根据权利要求1～3中任一项所述的钙钛矿太阳能电池，其中，联苯类化合物的有机胺盐和/或并苯类化合物的有机胺盐还具备：选自磺酸根离子、硝酸根离子、醋酸根离子、磷酸根离子、氟离子、碘离子、溴离子、氯离子中的1种以上作为阴离子。
  6. 一种钙钛矿太阳能电池的制备方法，其中，
    所述钙钛矿太阳能电池的制备方法依序包括：(I)电子传输层的制备工序、(II)钙钛矿层与钝化层的制备工序、(III)空穴传输层的制备工序以及(IV)背电极的制备工序，由此制备权利要求1～5中任一项所述的钙钛矿太阳能电池，
    其中，(II)钙钛矿层与钝化层的制备工序包括：
    (1)分别配置钙钛矿前驱体溶液和界面钝化材料的反溶剂溶液；
    (2)在旋涂有电子传输层的导电玻璃上，先滴加钙钛矿前驱体溶液进行旋涂，然后滴加界面钝化材料的反溶剂溶液，进而一并进行旋涂；
    (3)退火，由此形成钙钛矿层与钝化层。
  7. 根据权利要求6所述的钙钛矿太阳能电池的制备方法，其中，
    所述界面钝化材料的反溶剂溶液中，所述界面钝化材料的浓度为0.1～40mmol/L。
  8. 根据权利要求6所述的钙钛矿太阳能电池的制备方法，其中，
    所述工序(2)中，钙钛矿前驱体溶液的旋涂周期为10～120秒。
  9. 根据权利要求6～8中任一项所述的钙钛矿太阳能电池的制备方法，其中，
    所述工序(3)中，退火温度为100～200℃，退火时间为10～120分钟。
  10. 根据权利要求9所述的钙钛矿太阳能电池的制备方法，其中，
    在所述工序(3)的退火之前，可选地进行预退火，预退火温度为60～150℃，预退火时间为30分钟以下。
  11. 一种用电设备，其中，
    所述用电设备具备权利要1～5中任一项所述的钙钛矿太阳能电池，所述钙钛矿太阳能电池作为所述用电设备的电源或能量存储单元。
PCT/CN2021/143771 2021-12-31 2021-12-31 钙钛矿太阳能电池、其制备方法以及用电设备 Ceased WO2023123390A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202180094106.0A CN116918480A (zh) 2021-12-31 2021-12-31 钙钛矿太阳能电池、其制备方法以及用电设备
PCT/CN2021/143771 WO2023123390A1 (zh) 2021-12-31 2021-12-31 钙钛矿太阳能电池、其制备方法以及用电设备
EP21960111.9A EP4231803A4 (en) 2021-12-31 2021-12-31 PEROVSKITE SOLAR CELL AND PREPARATION METHOD THEREOF, AND ELECTRICAL DEVICE
US18/313,394 US12402467B2 (en) 2021-12-31 2023-05-08 Perovskite solar cell, preparation method therefor and power consuming device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/143771 WO2023123390A1 (zh) 2021-12-31 2021-12-31 钙钛矿太阳能电池、其制备方法以及用电设备

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/313,394 Continuation US12402467B2 (en) 2021-12-31 2023-05-08 Perovskite solar cell, preparation method therefor and power consuming device

Publications (1)

Publication Number Publication Date
WO2023123390A1 true WO2023123390A1 (zh) 2023-07-06

Family

ID=86997247

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/143771 Ceased WO2023123390A1 (zh) 2021-12-31 2021-12-31 钙钛矿太阳能电池、其制备方法以及用电设备

Country Status (4)

Country Link
US (1) US12402467B2 (zh)
EP (1) EP4231803A4 (zh)
CN (1) CN116918480A (zh)
WO (1) WO2023123390A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117202749A (zh) * 2023-09-08 2023-12-08 大连理工大学 一类乙胺硫脲钝化的钙钛矿薄膜及其制备方法和钙钛矿太阳能电池
CN119300615A (zh) * 2024-10-11 2025-01-10 浙江大学宁波“五位一体”校区教育发展中心 一种钙钛矿太阳能电池及其制备方法
CN119384196A (zh) * 2024-10-21 2025-01-28 云南大学 一种利用氟苯胺/二氟苯胺分子提升钙钛矿太阳能电池性能的方法及其应用

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117153897B (zh) * 2023-08-31 2025-04-11 环晟光伏(江苏)有限公司 一种切割边缘包含钝化层的太阳能电池及其制备方法
CN117580383A (zh) * 2023-12-28 2024-02-20 通威太阳能（成都）有限公司 一种钙钛矿太阳电池及其制备方法
CN120614931A (zh) * 2024-03-08 2025-09-09 宁德时代新能源科技股份有限公司 钙钛矿太阳能电池、制备方法、光伏系统、发电装置以及用电装置
CN120730884A (zh) * 2024-03-27 2025-09-30 宁德时代未来能源(上海)研究院有限公司 太阳能电池及其制备方法、光伏组件、发电装置及用电装置
CN118785732B (zh) * 2024-09-11 2024-12-20 正泰新能科技股份有限公司 一种钙钛矿太阳能电池及其制备方法
CN119300618B (zh) * 2024-10-21 2025-06-20 江苏盛开新能科技有限公司 一种钙钛矿太阳能电池、制备方法及制得的叠层钙钛矿电池
CN122121418A (zh) * 2024-11-29 2026-05-29 宁德时代未来能源(上海)研究院有限公司 太阳能电池、光伏器件、用电装置和发电装置
CN119677308B (zh) * 2024-12-05 2025-10-28 电子科技大学 一种柔性锡铅钙钛矿太阳能电池及其制备方法
CN119816167B (zh) * 2025-01-07 2026-01-27 河南省科学院材料研究所 一种提高钙钛矿太阳能电池光照稳定性的方法
CN121057413B (zh) * 2025-10-30 2026-02-06 广东工业大学 一种基于交联界面钝化层的钙钛矿太阳能电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105900255A (zh) * 2013-09-10 2016-08-24 洛桑联邦理工学院 倒置太阳能电池及用于生产倒置太阳能电池的方法
CN111540808A (zh) * 2020-04-03 2020-08-14 华南师范大学 一种苯烷基胺衍生物制备高效率碳电极无机钙钛矿太阳能电池的方法
CN112864325A (zh) * 2019-11-26 2021-05-28 中国石油大学(华东) 一种多功能三苯胺分子表面钝化钙钛矿薄膜的方法
CN113363390A (zh) * 2021-06-25 2021-09-07 南开大学 一种高效率钙钛矿太阳电池及制备方法
CN113809246A (zh) * 2020-06-15 2021-12-17 Tcl科技集团股份有限公司 复合材料及其制备方法和量子点发光二极管

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110061139B (zh) 2013-12-17 2023-04-18 牛津大学科技创新有限公司 包含金属卤化物钙钛矿和钝化剂的光伏装置
CN110635039B (zh) 2019-08-21 2021-01-26 厦门大学 一种钝化钙钛矿的方法及钙钛矿太阳能电池
US20210159022A1 (en) * 2019-11-26 2021-05-27 Hunt Perovskite Technologies, L.L.C. 2d perovskite tandem photovoltaic devices
US12328955B2 (en) * 2020-05-28 2025-06-10 Japan Science And Technology Agency Thin film and method for producing same, circularly polarized light detection element, device and method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105900255A (zh) * 2013-09-10 2016-08-24 洛桑联邦理工学院 倒置太阳能电池及用于生产倒置太阳能电池的方法
CN112864325A (zh) * 2019-11-26 2021-05-28 中国石油大学(华东) 一种多功能三苯胺分子表面钝化钙钛矿薄膜的方法
CN111540808A (zh) * 2020-04-03 2020-08-14 华南师范大学 一种苯烷基胺衍生物制备高效率碳电极无机钙钛矿太阳能电池的方法
CN113809246A (zh) * 2020-06-15 2021-12-17 Tcl科技集团股份有限公司 复合材料及其制备方法和量子点发光二极管
CN113363390A (zh) * 2021-06-25 2021-09-07 南开大学 一种高效率钙钛矿太阳电池及制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of EP4231803A4 *
WANG, FENG ET AL.: "Phenylalkylamine Passivation of Organolead Halide Perovskites Enabling High-Efficiency and Air-Stable Photovoltaic Cells", ADVANCED MATERIALS, vol. 28, 28 September 2016 (2016-09-28), XP055490560, ISSN: 0935-9648, DOI: 10.1002/adma.201603062 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117202749A (zh) * 2023-09-08 2023-12-08 大连理工大学 一类乙胺硫脲钝化的钙钛矿薄膜及其制备方法和钙钛矿太阳能电池
CN119300615A (zh) * 2024-10-11 2025-01-10 浙江大学宁波“五位一体”校区教育发展中心 一种钙钛矿太阳能电池及其制备方法
CN119384196A (zh) * 2024-10-21 2025-01-28 云南大学 一种利用氟苯胺/二氟苯胺分子提升钙钛矿太阳能电池性能的方法及其应用

Also Published As

Publication number Publication date
EP4231803A1 (en) 2023-08-23
EP4231803A4 (en) 2023-12-27
CN116918480A (zh) 2023-10-20
US20230320109A1 (en) 2023-10-05
US12402467B2 (en) 2025-08-26

Similar Documents

Publication Publication Date Title
US12402467B2 (en) Perovskite solar cell, preparation method therefor and power consuming device
Fei et al. Controlled growth of textured perovskite films towards high performance solar cells
Adhikari et al. Crystallization of a perovskite film for higher performance solar cells by controlling water concentration in methyl ammonium iodide precursor solution
Chen et al. Molecular ordering and phase segregation induced by a volatile solid additive for highly efficient all-small-molecule organic solar cells
Wang et al. Monolayer-like hybrid halide perovskite films prepared by additive engineering without antisolvents for solar cells
CN116056531B (zh) 一种基于磷酸基小分子的钙钛矿薄膜及其制备方法与光伏电池应用
Kumar et al. Efficient and stable perovskite solar cells by interface engineering at the interface of electron transport layer/perovskite
CN112864329B (zh) 一种钙钛矿太阳能电池及其制备方法
CN118251022B (zh) 一种反型宽带隙钙钛矿太阳能电池及其制备方法
Wu et al. Integrated planar and bulk dual heterojunctions capable of efficient electron and hole extraction for perovskite solar cells with> 17% efficiency
Venkatesan et al. Moisture-driven phase transition for improved perovskite solar cells with reduced trap-state density
Li et al. Preheating-assisted deposition of solution-processed perovskite layer for an efficiency-improved inverted planar composite heterojunction solar cell
CN119300618B (zh) 一种钙钛矿太阳能电池、制备方法及制得的叠层钙钛矿电池
CN110752298A (zh) 一种基于羟基嘧啶衍生物添加剂的有机太阳能电池活性层及其制备方法
CN117999864A (zh) 钙钛矿太阳能电池和制造方法
WO2011127475A1 (en) Organic photovoltaic devices comprising solution- processed substituted metal-phthalocyanines and exhibiting near-ir photo-sensitivity
Zhang et al. Magnesium acetate additive enables efficient and stable carbon electrode based CsPbI2Br perovskite solar cells
Duan et al. Tuning the crystallization and photothermal aging chemistry of CsPb0. 4Sn0. 6I3 for inorganic perovskite tandem photovoltaics
Diau et al. Perovskite solar cells: Principle, materials and devices
Kayesh et al. Influence of anti-solvents on CH3NH3PbI3 films surface morphology for fabricating efficient and stable inverted planar perovskite solar cells
CN113087636A (zh) 一种碘化物及其制备方法，及基于其的全无机钙钛矿太阳电池及制备方法
JP2025535120A (ja) フラーレン複合材料及びその製造方法、ペロブスカイト太陽電池及びその製造方法、並びに電気装置
Ai et al. Heteroatom substitution and molecular configuration engineering in self-assembled materials for high-efficiency and stable perovskite solar cells
JP2009064616A (ja) 光電変換素子、及び太陽電池
CN114853763B (zh) 一类D-π-A化合物及其在钙钛矿太阳能电池中钝化的应用

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021960111

Country of ref document: EP

Effective date: 20230428

WWE Wipo information: entry into national phase

Ref document number: 202180094106.0

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE