Polymer and perovskite solar cells, photovoltaic modules and power consumers

Abstract

The present application provides a polymer, a perovskite solar cell, a photovoltaic module and a power consumption device. The polymer comprises a repeating unit represented by formula (I), -MRY - formula (I), where M is selected from a substituted or unsubstituted anilino group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenothiazinyl group, or a substituted or unsubstituted phenoxazinyl group, R is selected from a substituted or unsubstituted C1-C10 alkyl group, and Y is selected from a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, or a sulfonic acid group or a salt thereof. When the polymer is applied to a perovskite solar cell, the photoelectric conversion efficiency of the perovskite solar cell can be improved.

Description

[Technical field]

[0001] The present application relates to the field of batteries, in particular polymer and perovskite solar cells, photovoltaic modules and power consuming devices. [Background technology]

[0002] Perovskite solar cells are solar cells that use organometal halide perovskite materials as light-absorbing layers. They have excellent photoelectric properties and simple fabrication methods, bringing new possibilities and hope for solar power generation.

[0003] During the production process of perovskite solar cells, how to further improve their photoelectric conversion efficiency is an issue that needs to be resolved as soon as possible. Summary of the Invention

[0004] The present application has been made in view of the above problems, and has an object to provide polymer, perovskite solar cells, photovoltaic power generation modules and power consuming devices.

[0005] A first aspect of the present application provides a polymer, the polymer comprising a repeat unit shown in formula (I):

[0006] -MRY - formula (I),

[0007] In formula (I),

[0008] M is selected from a substituted or unsubstituted anilino group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenothiazinyl group, or a substituted or unsubstituted phenoxazinyl group;

[0009] R is selected from substituted or unsubstituted C1-C10 alkyl groups;

[0010] Y is selected from a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, or a sulfonic acid group or a salt thereof.

[0011] Thus, in this application, Y, R and M are an organic entity, and when it is introduced to the surface of nickel oxide as a repeating unit of a polymer, Y can provide an effective binding site with trivalent nickel for the polymer, passivate the trivalent nickel on the surface of the nickel oxide, reduce the reaction between high-value nickel such as trivalent nickel and A-site cations, and thereby make the residual lead halide almost absent at the interface, reduce non-radiative recombination at the interface, and improve the device stability and open circuit voltage of the perovskite solar cell. R, as an intermediate connecting N and M, is advantageous in spreading the M group uniformly on the surface of the nickel oxide hole transport layer. The anilino group contained in M ​​can adjust the functional properties of the perovskite solar cell, and has hydrophobicity, which can reduce the impact of oxygen in the external water on the perovskite material, and further improve the device stability and open circuit voltage, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0012] In some embodiments, R is selected from substituted or unsubstituted C1-C8 alkyl groups, and optionally R is selected from substituted or unsubstituted C1-C5 alkyl groups.

[0013] In some embodiments, the repeat unit shown in formula (I) is [ka] [ka] [ka] [ka] The repeating units include one or more repeating units represented by formulas (I-1) to (I-7):

[0014] Here, R1 to R 14 are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxy group, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, a substituted or unsubstituted C1-C5 carboxyalkyl group, or a substituted or unsubstituted C6-C20 aryl group, optionally, when substituted, the substituents are independently selected from at least one of a halogen atom or a nitrogen-containing group;

[0015] The nitrogen-containing group comprises a C2-C10 dialkylamino group, a C1-C5 alkylamino group, an amino group, a trimethylamine group, a triethylamine group, or a tripropylamine group, and optionally R1 to R 14 are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, or a substituted or unsubstituted C1-C5 carboxyalkyl group, and optionally R1 to R 14 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C5 alkoxyl group, or a substituted or unsubstituted C1-C5 alkyl group.

[0016] In some embodiments, Y in the repeat unit of formula (I-2) is selected from a phosphate group, and optionally, the repeat unit of formula (I-2) is [ka] [ka] [ka] [ka] [ka] The repeating units include at least one of the repeating units represented by formulae (I-21) to (I-29).

[0017] In some embodiments, the repeat unit shown in formula (I-3) is [ka] [ka] [ka] [ka] [ka] The repeating units include at least one of the repeating units represented by formulae (I-31) to (I-391).

[0018] In some embodiments, the weight average molecular weight of the polymer is 3000 Da to 20000 Da, optionally 3000 Da to 10000 Da. When the weight average molecular weight of the polymer is in the above range, its distribution on the nickel oxide layer can be uniform, and the thickness of the formed membrane layer is thin.

[0019] According to a second aspect, the present application provides a perovskite solar cell comprising, in order, a hole transport layer, a passivation layer and a perovskite layer, said passivation layer comprising a polymer according to any one of the embodiments of the first aspect of the present application, wherein a LUMO level of said passivation layer is greater than a LUMO level of the perovskite layer and, optionally, the LUMO level of said passivation layer is between the LUMO level of the perovskite layer and the LUMO level of the hole transport layer.

[0020] In some embodiments, the LUMO level of the perovskite layer is within 0.5 eV of the difference between the LUMO level of the passivation layer, and optionally the LUMO level of the perovskite layer is within 0.3 eV of the difference between the LUMO level of the passivation layer.

[0021] In some embodiments, the LUMO level of the passivation layer is within 0.5 eV of the LUMO level of the hole transport layer, and optionally, the LUMO level of the passivation layer is within 0.3 eV of the LUMO level of the hole transport layer.

[0022] In some embodiments, the thickness of the passivation layer is between 0.1 nm and 5 nm, optionally between 1 nm and 3 nm.

[0023] According to a third aspect, the present application provides a perovskite solar cell, the perovskite solar cell comprising a hole transport layer comprising a polymer according to any one of the embodiments of the first aspect of the present application.

[0024] In some embodiments, the thickness of the hole transport layer is from 10 nm to 50 nm, optionally from 15 nm to 30 nm.

[0025] A fourth aspect of the present application further provides a photovoltaic module, the photovoltaic module comprising a perovskite solar cell according to any one of the embodiments of the second or third aspect of the present application.

[0026] A fifth aspect of the present application further provides a power consuming device, the power consuming device comprising a perovskite solar cell according to an embodiment of any one of the second and third aspects of the present application, or a photovoltaic module according to the fourth aspect. [Brief description of the drawings]

[0027] In order to more clearly explain the technical solutions of the embodiments of the present application, the following briefly introduces the drawings that need to be used in the embodiments of the present application. It is obvious that the drawings described below are only some embodiments of the present application, and those skilled in the art can also obtain other drawings based on the drawings without exerting creative efforts.

[0028] [Figure 1] FIG. 1 is a structural schematic diagram of a perovskite solar cell according to some embodiments of the present application. [Diagram 2] FIG. 2 is a structural schematic diagram of a perovskite solar cell according to some further embodiments of the present application. [Diagram 3] 1 is a structural schematic diagram of a power consuming device according to some embodiments of the present application;

[0029] The drawings are not necessarily drawn to scale. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] Hereinafter, embodiments specifically disclosing the polymer and perovskite solar cells and photovoltaic modules of the present application will be described in detail. However, unnecessary detailed description may be omitted. For example, detailed description of well-known matters and duplicated description of structures that are actually the same may be omitted. This is to avoid the following description becoming unnecessarily long and to allow those skilled in the art to easily understand. Note that the drawings and the following description are provided to allow those skilled in the art to fully understand the present application, and are not intended to limit the subject matter described in the claims.

[0031] The "ranges" disclosed in this application are defined in the form of lower and upper limits, and a given range is defined by selecting one lower limit and one upper limit, and the selected lower and upper limits define the boundaries of the particular range. Such defined ranges may be inclusive or exclusive of the end values, and may be arbitrarily combined, i.e., 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 envisaged. It is noted that if 1 and 2 are listed as the minimum range values, and 3, 4, and 5 are listed as the maximum range values, then the ranges 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5 are all envisaged. In this application, unless otherwise specified, a numerical range "a-b" represents a shorthand representation of any combination of real numbers a-b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed herein, and "0-5" is just a shorthand for combinations of these numbers. Also, expressing a parameter as an integer ≧2 is equivalent to disclosing that the parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0032] Unless otherwise stated, all the embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.Unless otherwise stated, all the technical features and optional technical features of the present application can be combined with each other to form a new technical solution.

[0033] Unless otherwise stated, all steps in this application may be performed in sequence or randomly, and preferably in sequence. For example, a method including steps (a) and (b) means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, when it is mentioned that the method may further include step (c), it means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), etc.

[0034] Unless otherwise stated, the terms "comprise" and "comprises" referred to in this application may be open ended or closed ended. For example, "comprise" and "comprises" may further include or include other ingredients not listed, or may include or include only the listed ingredients.

[0035] Unless otherwise stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, "A or B" is satisfied in the following cases: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) but B is true (or exists); and A and B are both true (or exist).

[0036] The term "anilino group" includes a diphenylamine group, a triphenylamine group, or a carbazole group, and the anilino group may be optionally substituted, and the substituents may be halogen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, alkyl groups, or heterocyclic groups.

[0037] The term "alkyl group" includes straight and branched chain alkyl groups. For example, the alkyl group may be a C1-C20 alkyl group, a C1-C12 alkyl group, a C1-C10 alkyl group, a C1-C6 alkyl group, or a C1-C4 alkyl group. In some embodiments, the alkyl group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a heptyl group, a cycloheptyl group, an octyl group, a cyclooctyl group, a nonyl group, and a decyl group. The alkyl group may also be optionally substituted, for example, the alkyl group may be substituted with a halogen to form a halogenated alkyl group. The term "halogenated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been replaced with a halogen atom, and the term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0038] At various places in the present specification, substituents of compounds are disclosed in groups or ranges. Such descriptions are expressly intended to include each individual subcombination of the members of these groups and ranges. For example, the term "C1-C10 alkyl group" refers to any of the following groups and ranges: C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C1-C10, C1-C9, C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, C1-C2, C2-C10, C2-C9, C2-C8, C2-C7, C2-C6, C2-C5, C2-C4, C2-C3, C3-C10, C3-C9, C3 It is expressly anticipated that the disclosure includes -C8, C3-C7, C3-C6, C3-C5, C3-C4, C4-C10, C4-C9, C4-C8, C4-C7, C4-C6, C4-C5, C5-C10, C5-C9, C5-C8, C5-C7, C5-C6, C6-C10, C6-C9, C6-C8, C6-C7, C7-C10, C7-C9, C7-C8, C8-C10 and C8-C9 alkyl groups.

[0039] The term "alkoxyl group" refers to a group in which an alkyl group is connected to an oxygen atom by a single bond. For example, the alkoxyl group may be a C1-C10 alkoxyl group, a C1-C8 alkoxyl group, a C1-C5 alkoxyl group, or a C2-C6 alkoxyl group. In some examples, the alkoxyl group may include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclobutoxy group, a pentoxy group, a isopentoxy group, a neopentoxy group, a tert-pentoxy group, or a cyclopentoxy group.

[0040] The term "amide group" refers to a group formed by replacing a hydroxy group in a carboxyl group with an amino or amine group. For example, the amide group may be a C1-C10 amide group, a C1-C8 amide group, a C1-C5 amide group, a C2-C5 amide group, or a C3-C5 amide group. In some embodiments, the amide group includes a formamide group, an acetamino group, a propionamide group, a butyrylamino group, an isobutyrylamino group, a s-butyrylamino group, a tert-butyrylamino group, a cyclobutyrylamino group, a valeramide group, an isovalerylamino group, a neovalerylamino group, a tert-valerylamino group, or a cyclovalerylamino group.

[0041] The term "ester group" refers to an ester functional group in a carboxylic acid derivative. For example, the ester group may be a C1-C10 ester group, a C1-C8 ester group, a C1-C5 ester group, a C2-C5 ester group, or a C3-C5 ester group. In some examples, the ester group includes a methyl ester group, an ethyl ester group, a propioester group, a butyl ester group, an isobutyl ester group, a s-butyl ester group, a tert-butyl ester group, a cyclobutyl ester group, a pentyl ester group, a isopentyl ester group, a neopentyl ester group, a tert-pentyl ester group, or a cyclopentyl ester group.

[0042] The term "carboxyalkyl group" refers to a group in which an alkyl group and a carboxyl group are linked by a single bond. For example, the carboxyalkyl group can be a C1-C10 carboxyalkyl group, a C1-C8 carboxyalkyl group, a C1-C5 carboxyalkyl group, a C2-C5 carboxyalkyl group, or a C3-C5 carboxyalkyl group. In some examples, the carboxyalkyl group includes a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, a carboxyisobutyl group, a carboxysec-butyl group, a carboxytert-butyl group, a carboxycyclobutyl group, a carboxypentyl group, a carboxyisopentyl group, a carboxyneopentyl group, a carboxytert-pentyl group, and a carboxycyclopentyl group.

[0043] The term "aryl group" refers to a closed aromatic ring or ring system. For example, the aryl group can be a C6-C50 aryl group, a C6-C40 aryl group, a C6-C30 aryl group, a C6-C20 aryl group, or a C6-C10 aryl group, where the C6-C20 aryl group contains 6 to 20 carbon atoms to form the ring. In some embodiments, the aryl group includes a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a biphenyl group, a triphenylene group, a pyrene group, a spirobifluorene group, a perylene group, an indenyl group, and an azulene group.

[0044] The term "dialkylamino group" refers to a group formed by replacing two hydrogen atoms of an amino group with two alkyl groups. For example, the dialkylamino group may be a C2-C20 dialkylamino group, a C2-C10 dialkylamino group, a C4-C10 dialkylamino group, or a C4-C6 dialkylamino group. In some embodiments, the dialkylamino group includes a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diisobutylamino group, a di-s-butylamino group, a di-tert-butylamino group, a dicyclobutylamino group, a dipentylamino group, a diisopentylamino group, a dineopentylamino group, a di-tert-pentylamino group, or a dicyclopentylamino group.

[0045] The term "alkylamino group" refers to a group formed by replacing one hydrogen atom of an amino group with an alkyl group. For example, the alkylamino group may be a C2-C20 alkylamino group, a C2-C10 alkylamino group, a C4-C10 alkylamino group, or a C4-C6 alkylamino group. In some embodiments, the alkylamino group includes a methylamino group, an ethylamino group, a propylamino group, a butylamino group, an isobutylamino group, a sec-butylamino group, a tert-butylamino group, a cyclobutylamino group, a pentylamino group, an isopentylamino group, a neopentylamino group, a tert-pentylamino group, or a cyclopentylamino group.

[0046] The term "halogen atom" refers to fluorine, chlorine, bromine atoms, and the like.

[0047] The term "hydrogen" refers to 1H (protium, H), 2H (deuterium, D) or 3H (tritium, T). In each embodiment, "hydrogen" may be 1H (protium, H).

[0048] In this application, the terms "plurality" and "multiple types" mean two or more than two.

[0049] A perovskite solar cell includes a perovskite layer, a hole transport layer, an electron transport layer, and an electrode. The operation process of a perovskite cell mainly includes the generation and dissociation of excitons, the transport of free carriers, the collection of carriers, and the generation of electric current. The specific process is as follows: In a perovskite solar cell, sunlight is absorbed in the perovskite layer, which absorbs photons to generate excitons, and the excitons are then dissociated into free electrons and holes due to the low Coulomb binding force of the perovskite layer. The dissociated free carriers are transported in the perovskite layer and sent out through the transport layer. The electron transport layer serves to transport electrons and block holes, and the hole transport layer serves to transport holes and block electrons. The electrons and holes sent out through the transport layer are collected by the electrodes to form electric current and voltage, respectively.

[0050] Perovskite solar cells mainly include forward and inverted structures. In the case of a forward structure device, the functional layers through which light is incident and transmitted are, in order, an electron transport layer, a perovskite layer, and a hole transport layer. In the case of an inverted structure device, the functional layers through which light is incident and transmitted are, in order, a hole transport layer, a perovskite layer, and an electron transport layer. Hereinafter, a device with an inverted structure will be described as an example.

[0051] The ideal perovskite structure is ABX3 type or A2CDX6. Taking ABX3 type as an example, BX6 forms a regular octahedron, and BX6 are connected via a shared vertex X to form a three-dimensional framework, and A is fitted into the gap of the octahedron to stabilize the crystal structure. Here, A is a cation with a large radius, B is a cation with a small radius, and X is an anion. Since the range of element types and quantities that can be accommodated in the A, B and X sites is very wide, there are many types of compounds with perovskite type structures.

[0052] Nickel oxide NiO x As a common inorganic hole transport layer material, NiO has a cubic structure similar to NaCl. In the process of producing NiO, it is necessary to add excess oxygen gas, so that NiOOH and Ni2O3 exist simultaneously in nickel oxide. The excess oxygen gas causes a certain number of Ni vacancies to exist in nickel oxide NiOx, which generates holes, making nickel oxide a P-type semiconductor, and nickel oxide has suitable charge carrier mobility and suitable work function. Nickel oxide has a very high light transmittance in the near ultraviolet and visible light wavelength ranges, making it an excellent hole transport layer material. The highest parts of the valence bands of nickel oxide and perovskite materials are relatively compatible, and the light in perovskite can excite holes to move smoothly into the hole transport layer.

[0053] However, the inventors have found that when a nickel oxide hole transport layer is used as the hole transport layer, the surface of the nickel oxide hole transport layer contains oxidizable trivalent nickel ions, which are easily reactive with the A-site cations in the perovskite layer, leaving the A-site vacant and leaving excess lead halide at the interface, which increases the non-radiative recombination at the interface, reducing the open circuit voltage of the perovskite solar cell, and the lead halide causes the decomposition of the perovskite material, resulting in low stability of the entire perovskite solar cell, further reducing the open circuit voltage of the perovskite solar cell, and low photoelectric conversion efficiency of the perovskite solar cell.

[0054] In response to the above problems, the inventors improve the photoelectric conversion efficiency of perovskite solar cells by improving the performance of the hole transport layer, thereby improving the stability and open circuit voltage of the entire perovskite solar cell.

[0055] polymer

[0056] According to a first aspect, the present application provides a polymer.

[0057] The polymer comprises a repeat unit shown in formula (I):

[0058] -MRY - formula (I),

[0059] In formula (I),

[0060] M is selected from a substituted or unsubstituted anilino group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenothiazinyl group, or a substituted or unsubstituted phenoxazinyl group;

[0061] R is selected from substituted or unsubstituted C1-C10 alkyl groups;

[0062] Y is selected from a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, or a sulfonic acid group or a salt thereof.

[0063] The structure shown in formula (I) may be considered to include three parts: M, R, and Y, where Y includes a carboxyl group or its salts, a phosphoric acid group or its salts, or a sulfonic acid group or its salts. When the polymer is applied to a perovskite solar cell, Y may be an active site for binding with trivalent nickel, so that the polymer can be directionally bound with trivalent nickel in the nickel oxide hole transport layer, and the polymer can be uniformly spread on the surface of the nickel oxide hole transport layer. Optionally, the metal cation of the salt may be selected from sodium ions, potassium ions, etc., and for example, Y may include a carboxyl group, sodium carboxylate, potassium carboxylate, etc. By adjusting the Y group, the binding ability of the Y group with trivalent nickel can be controlled, thereby better improving the performance of the perovskite solar cell.

[0064] R is selected from substituted or unsubstituted C1-C10 alkyl groups, and R can reduce steric hindrance when the polymer is applied to perovskite solar cells. Optionally, R is selected from substituted or unsubstituted C1-C8 alkyl groups, and further optionally, R is selected from substituted or unsubstituted C3-C5 alkyl groups. There is no specific limitation on the type of alkyl group, and it can be selected according to actual needs, for example, it can be a chain alkyl group or a cyclic alkyl group, and the chain alkyl group also includes a straight chain alkyl group and a branched chain alkyl group. In addition, the cyclic alkyl group can have a substituent or can have no substituent. The C1-C10 alkyl group may be selected from one of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, nonyl, and decyl groups.

[0065] M is selected from substituted or unsubstituted anilino group, substituted or unsubstituted carbazole group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenothiazinyl group, or substituted or unsubstituted phenoxazinyl group, the introduction of M plays an important role in improving the charge transport property of the hole transport material and improving the performance of the perovskite solar cell, the anilino group has an energy level compatible with the perovskite material, and has the advantages of good solubility, high hole mobility, and effective hole extraction and electron blocking, etc. There is no specific limit to the type of M, and it can be selected according to actual needs, for example, M is selected from diphenylamine group, triphenylamine group, carbazole group, acridinyl group, phenothiazinyl group, or phenoxazinyl group, etc.

[0066] When Y, R and M are introduced into a perovskite solar cell as an organic whole as a repeating unit of a polymer, the polymer can improve the charge transport properties of the hole transport material as a material of the hole transport layer, thereby improving the photoelectric conversion efficiency of the perovskite solar cell. When the polymer is introduced into a perovskite solar cell as a passivation layer of the nickel oxide hole transport layer, Y can provide an effective binding site with trivalent nickel for the polymer, passivate the trivalent nickel on the nickel oxide surface, and reduce the reaction of high-value nickel such as trivalent nickel with A-site cations, thereby making the residual lead halide almost absent at the interface, reducing non-radiative recombination at the interface, and improving the device stability and open circuit voltage of the perovskite solar cell. R, as an intermediate connecting N and M, is advantageous in spreading the M group evenly on the surface of the nickel oxide hole transport layer. The anilino group contained in M ​​can adjust the functional properties of the perovskite solar cell, and has hydrophobic properties, which can reduce the impact of external water oxygen on the perovskite material, further improving the device stability and open circuit voltage, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0067] In some embodiments, R is selected from a substituted or unsubstituted C1-C8 alkyl group, and optionally R is selected from a substituted or unsubstituted C1-C5 alkyl group. Illustratively, R is selected from a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a isopentyl group, a neopentyl group, a tert-pentyl group, or a cyclopentyl group.

[0068] In some embodiments, M may be selected from substituted or unsubstituted diphenylamine groups, and accordingly, the repeat unit shown in formula (I) includes the repeat unit shown in formula (I-1). [ka]

[0069] R1 and R2 are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, a substituted or unsubstituted C1-C5 carboxyalkyl group, or a substituted or unsubstituted aryl group;

[0070] The nitrogen-containing group includes a C2-C10 dialkylamino group, a C1-C5 alkylamino group, an amino group, a trimethylamine group, a triethylamine group, or a tripropylamine group.

[0071] Optionally, when the above groups are substituted, the substituents may be at least one of a halogen atom or a nitrogen-containing group.

[0072] Optionally, R1 and R2 are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amide group, a substituted or unsubstituted C1-C5 ester group, or a substituted or unsubstituted C1-C5 carboxyalkyl group. Atoms such as nitrogen, oxygen, and fluorine are favorable for forming hydrogen bonds with the A-site structure in the perovskite structure, and can improve the stability of the structure.

[0073] Further optionally, R1 and R2 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C5 alkoxyl group, or a substituted or unsubstituted C1-C5 alkyl group, which is highly hydrophobic and advantageous for improving the long-term stability of the perovskite solar cell.

[0074] Exemplarily, R1 and R2 are each independently selected from a hydrogen atom, a fluorine atom, an alkoxyl group, an alkyl group, an ester group, an amide, a primary amine, a secondary amine, or a tertiary amine.

[0075] Optionally, Y is selected from a phosphate group.

[0076] Illustratively, the repeating unit shown in formula (I-1) is [ka] [ka] [ka] [ka] The repeating units include at least one of the repeating units represented by the formulae (I-11) to (I-16).

[0077] In some embodiments, M may be selected from a substituted or unsubstituted triphenylamine group, and accordingly, the repeat unit shown in formula (I) includes the repeat unit shown in formula (I-2). [ka]

[0078] R3 and R4 are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, a substituted or unsubstituted C1-C5 carboxyalkyl group, or a substituted or unsubstituted aryl group;

[0079] the nitrogen-containing group comprises a C2-C10 dialkylamino group, a C1-C5 alkylamino group, an amino group, a trimethylamine group, a triethylamine group, or a tripropylamine group;

[0080] Optionally, when the above groups are substituted, the substituents may be at least one of a halogen atom or a nitrogen-containing group.

[0081] Optionally, R3 and R4 are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amide group, a substituted or unsubstituted C1-C5 ester group, and a substituted or unsubstituted C1-C5 carboxyalkyl group. Atoms such as nitrogen, oxygen, and fluorine are favorable for forming hydrogen bonds with the A-site structure in the perovskite structure, and can improve the stability of the structure.

[0082] Optionally, R3 and R4 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C5 alkoxyl group, or a substituted or unsubstituted C1-C5 alkyl group, the alkoxyl group or the alkyl group being highly hydrophobic and advantageous for improving the long-term stability of the perovskite solar cell.

[0083] Exemplarily, R3 and R4 are each independently selected from a hydrogen atom, a fluorine atom, an alkoxyl group, an alkyl group, an ester group, an amide, a primary amine, a secondary amine, or a tertiary amine.

[0084] Optionally, Y is selected from a phosphate group.

[0085] Illustratively, the repeating unit shown in formula (I-2) is [ka] [ka] [ka] [ka] [ka] The repeating units include at least one of the repeating units represented by formulae (I-21) to (I-29).

[0086] In some embodiments, M may be selected from a substituted or unsubstituted carbazole group, and accordingly, the repeat unit shown in formula (I) includes a repeat unit shown in formula (I-3). [ka]

[0087] R5 and R6 are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, a substituted or unsubstituted C1-C5 carboxyalkyl group, or a substituted or unsubstituted aryl group;

[0088] the nitrogen-containing group comprises a C2-C10 dialkylamino group, a C1-C5 alkylamino group, an amino group, a trimethylamine group, a triethylamine group, or a tripropylamine group;

[0089] Optionally, when the above groups are substituted, the substituents may be halogen atoms or nitrogen-containing groups.

[0090] Optionally, R5 and R6 are each independently selected from a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amide group, a substituted or unsubstituted C1-C5 ester group, and a substituted or unsubstituted C1-C5 carboxyalkyl group. Atoms such as nitrogen, oxygen, and fluorine are favorable for forming hydrogen bonds with the A-site structure in the perovskite structure, and can improve the stability of the structure.

[0091] Optionally, R5 and R6 are each independently selected from a substituted or unsubstituted C1-C5 alkoxy group or a substituted or unsubstituted C1-C5 alkyl group, which is highly hydrophobic and advantageous for improving the long-term stability of the perovskite solar cell.

[0092] Exemplarily, R5 and R6 are each independently selected from a hydrogen atom, a fluorine atom, an alkoxyl group, an alkyl group, an ester group, an amide, a primary amine, a secondary amine, or a tertiary amine.

[0093] Optionally, R is selected from a methyl group or an ethyl group.

[0094] Optionally, Y is selected from a phosphate group or salts thereof, a carboxyl group, or a sulfonic acid group.

[0095] Illustratively, the repeating unit shown in formula (I-3) is [ka] [ka] [ka] [ka] [ka] The repeating units include at least one of the repeating units represented by formulae (I-31) to (I-391).

[0096] In some embodiments, the repeat unit shown in formula (I) may include a repeat unit shown in formula (I-4). [ka]

[0097] R7 and R8 are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, a substituted or unsubstituted C1-C5 carboxyalkyl group, or a substituted or unsubstituted aryl group;

[0098] the nitrogen-containing group comprises a C2-C10 dialkylamino group, a C1-C5 alkylamino group, an amino group, a trimethylamine group, a triethylamine group, or a tripropylamine group;

[0099] Optionally, when the above groups are substituted, the substituents may be halogen atoms or nitrogen-containing groups.

[0100] R7 and R8 are each independently selected from halogen atoms, nitrogen-containing groups, hydroxyl groups, substituted or unsubstituted C1-C5 alkoxyl groups, substituted or unsubstituted C1-C5 amide groups, substituted or unsubstituted C1-C5 ester groups, and substituted or unsubstituted C1-C5 carboxyalkyl groups. Atoms such as nitrogen, oxygen, and fluorine are favorable for forming hydrogen bonds with the A-site structure in the perovskite structure, and can improve the stability of the structure.

[0101] Optionally, R7 and R8 are each independently selected from a substituted or unsubstituted C1-C5 alkoxy group or a substituted or unsubstituted C1-C5 alkyl group, which is highly hydrophobic and advantageous for improving the long-term stability of the perovskite solar cell.

[0102] Optionally, Y is selected from a phosphate group, and the like.

[0103] For example, the repeating unit shown in formula (I-4) is [ka] [ka] [ka] [ka] [ka] The repeating units include one or more of the repeating units represented by formulae (I-41) to (I-49).

[0104] In some embodiments, the repeat unit shown in formula (I) may include a repeat unit shown in formula (I-5). [ka]

[0105] R9 and R 10are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxy group, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, a substituted or unsubstituted C1-C5 carboxyalkyl group, or a substituted or unsubstituted aryl group;

[0106] the nitrogen-containing group comprises a C2-C10 dialkylamino group, a C1-C5 alkylamino group, an amino group, a trimethylamine group, a triethylamine group, or a tripropylamine group;

[0107] Optionally, when the above groups are substituted, the substituents may be halogen atoms or nitrogen-containing groups.

[0108] R9 and R 10 are each independently selected from a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amide group, a substituted or unsubstituted C1-C5 ester group, and a substituted or unsubstituted C1-C5 carboxyalkyl group. Atoms such as nitrogen, oxygen, and fluorine are advantageous in forming hydrogen bonds with the A-site structure in the perovskite structure, and can improve the stability of the structure.

[0109] Optionally, R9 and R 10 are each independently selected from a substituted or unsubstituted C1-C5 alkoxy group or a substituted or unsubstituted C1-C5 alkyl group. The alkoxy group or alkyl group has high hydrophobicity and is advantageous in improving the long-term stability of the perovskite solar cell.

[0110] Optionally, Y is selected from a phosphate group, and the like.

[0111] For example, the repeating unit shown in formula (I-5) is [ka] [ka] [ka] [ka] [ka] The repeating units include one or more of the repeating units represented by formulae (I-51) to (I-59).

[0112] In some embodiments, the repeat unit shown in formula (I) may include a repeat unit shown in formula (I-6). [ka]

[0113] R 11 and R 12 are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxy group, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, a substituted or unsubstituted C1-C5 carboxyalkyl group, or a substituted or unsubstituted aryl group;

[0114] the nitrogen-containing group comprises a C2-C10 dialkylamino group, a C1-C5 alkylamino group, an amino group, a trimethylamine group, a triethylamine group, or a tripropylamine group;

[0115] Optionally, when the above groups are substituted, the substituents may be halogen atoms or nitrogen-containing groups.

[0116] R 11 and R 12 are each independently selected from a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amide group, a substituted or unsubstituted C1-C5 ester group, and a substituted or unsubstituted C1-C5 carboxyalkyl group. Atoms such as nitrogen, oxygen, and fluorine are advantageous in forming hydrogen bonds with the A-site structure in the perovskite structure, and can improve the stability of the structure.

[0117] Optionally, R 11 and R 12 are each independently selected from a substituted or unsubstituted C1-C5 alkoxy group or a substituted or unsubstituted C1-C5 alkyl group. The alkoxy group or alkyl group has high hydrophobicity and is advantageous in improving the long-term stability of the perovskite solar cell.

[0118] Optionally, Y is selected from a phosphate group, etc. For example, the repeat unit shown in formula (I-6) is [ka] [ka] [ka] [ka] [ka] The repeating units include one or more of the repeating units represented by formulae (I-61) to (I-69).

[0119] In some embodiments, the repeat unit shown in formula (I) may include a repeat unit shown in formula (I-7). [ka]

[0120] R 13 and R 14 are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxy group, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, a substituted or unsubstituted C1-C5 carboxyalkyl group, or a substituted or unsubstituted aryl group;

[0121] the nitrogen-containing group comprises a C2-C10 dialkylamino group, a C1-C5 alkylamino group, an amino group, a trimethylamine group, a triethylamine group, or a tripropylamine group;

[0122] Optionally, when the above groups are substituted, the substituents may be halogen atoms or nitrogen-containing groups.

[0123] R 13 and R 14 are each independently selected from a halogen atom, a nitrogen-containing group, a hydroxyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amide group, a substituted or unsubstituted C1-C5 ester group, and a substituted or unsubstituted C1-C5 carboxyalkyl group. Atoms such as nitrogen, oxygen, and fluorine are advantageous in forming hydrogen bonds with the A-site structure in the perovskite structure, and can improve the stability of the structure.

[0124] Optionally, R 13 and R 14are each independently selected from a substituted or unsubstituted C1-C5 alkoxy group or a substituted or unsubstituted C1-C5 alkyl group. The alkoxy group or alkyl group has high hydrophobicity and is advantageous in improving the long-term stability of the perovskite solar cell.

[0125] Optionally, Y is selected from a phosphate group, etc. For example, the repeat unit shown in formula (I-7) is [ka] [ka] [ka] [ka] [ka] The repeating units include one or more of the repeating units represented by formulae (I-71) to (I-79).

[0126] In some embodiments, the weight average molecular weight of the polymer is from 3000 Da to 20000 Da, optionally from 3000 Da to 10000 Da.

[0127] When the weight average molecular weight of the polymer is within the above range, its distribution on the nickel oxide layer can be made uniform, and the thickness of the film layer formed is thin.

[0128] Perovskite Solar Cells

[0129] According to a second aspect, the present application further provides a perovskite solar cell comprising, in order, a hole transport layer, a passivation layer and a perovskite layer, the passivation layer comprising a polymer according to any one of the embodiments of the first aspect of the present application.

[0130] The LUMO level of the passivation layer is higher than the LUMO level of the perovskite layer.

[0131] Optionally, the LUMO level of the passivation layer is between the LUMO level of the perovskite layer and the LUMO level of the hole transport layer.

[0132] In some embodiments, the LUMO level of the perovskite layer is within 0.5 eV of the LUMO level of the passivation layer. Optionally, the LUMO level of the perovskite layer is within 0.3 eV of the LUMO level of the passivation layer.

[0133] In some embodiments, the LUMO level of the passivation layer is within 0.5 eV of the LUMO level of the hole transport layer. Optionally, the LUMO level of the passivation layer is within 0.3 eV of the LUMO level of the hole transport layer.

[0134] The LUMO level refers to the Lowest Unoccupied Molecular Orbital.

[0135] The difference between the LUMO level of the perovskite layer, the LUMO level of the hole transport layer and the LUMO level of the passivation layer meets the above conditions, so that the polymer can be used as a passivation layer between the hole transport layer and the perovskite layer, and the polymer can effectively extract holes and block electron transport, while having high hole mobility.

[0136] Optionally, the hole transport layer includes a nickel oxide hole transport layer. A passivation layer is introduced between the nickel oxide hole transport layer and the perovskite layer, which can passivate trivalent nickel and reduce the risk of reaction between the trivalent nickel in the nickel oxide and the perovskite layer, and improve the stability and open circuit voltage of the entire perovskite solar cell, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0137] In some embodiments, the perovskite solar cell further comprises an electron transport layer, the perovskite layer comprising a first surface and a second surface opposed to each other along a thickness direction of the perovskite layer, an electron transport layer disposed on the first surface, a hole transport layer disposed on the second surface, and a passivation layer disposed between the hole transport layer and the perovskite layer.

[0138] Optionally, the perovskite solar cell may further comprise a hole blocking layer, the hole blocking layer being located on a side of the electron transport layer away from the perovskite layer.

[0139] The perovskite layer is a light absorbing layer that can convert photons into holes and electrons, and its material can be selected from common materials in the art, and is not limited here. The chemical formula of the perovskite layer is ABX3 or A2CDX6, where A is an inorganic or organic or organic-inorganic mixed cation, and can be at least one of CH3NH3(MA), CH(NH2)2(FA) and Cs, B is an inorganic or organic or organic-inorganic mixed cation, and can be at least one of Pb and Sn, and C is an inorganic or organic or organic-inorganic mixed cation, such as Ag. + D is an inorganic or organic or mixed organic-inorganic cation; 3+ , antimony cation Sb 3+ and indium cation In 3+ and X is an inorganic or organic or mixed organic-inorganic anion, and may be at least one of Br or I. Optionally, the band gap of the perovskite layer is 1.20 to 2.30 eV, and optionally, the thickness of the perovskite layer is 200 nm to 1000 nm.

[0140] The electron transport layer, as a kind of transport layer, can effectively transport electrons, reduce the recombination of carriers at the interface between the perovskite layer and the electron transport layer, and improve the photoelectric conversion efficiency of the perovskite solar cell. The electron transport layer is made of [6,6]-phenyl C 61 Methyl butyrate (PC61 BM), [6,6]-phenyl C 71 Methyl butyrate (PC 71 The material may further include at least one of materials such as fullerene C60 (C60), fullerene C70 (C70), tin dioxide (SnO2) or zinc oxide (ZnO) and their derivatives, or materials obtained through doping or passivation.

[0141] The hole transport layer, as a kind of transport layer, can effectively transport holes, reduce the recombination of carriers at the interface between the perovskite layer and the hole transport layer, and improve the photoelectric conversion efficiency of the perovskite solar cell. The material of the hole transport layer includes nickel oxide. Optionally, the manufacturing method of the nickel oxide hole transport layer includes, but is not limited to, the sol method, the sputtering method, the spin coating method of nickel oxide nanoparticles, the blade coating method and the slit coating method.

[0142] For the passivation layer, the polymer may be dissolved in an organic solvent and coated on the surface of the nickel oxide hole transport layer by spin coating, spray coating, blade coating or slit coating, the organic solvent may be methanol, isopropanol, ethanol, chlorobenzene, etc., and the concentration is 0.1-10 mg / mL, and the polymer may form a passivation layer on the surface of the nickel oxide hole transport layer with a thickness of 0.1 nm-5 nm, optionally 1 nm-3 nm, and the organic solvent may be removed from the passivation layer by annealing or vacuum.

[0143] When the thickness of the passivation layer is in the above range, the polymer can be formed on the surface of the nickel oxide hole transport layer essentially in the form of a monolayer, the polymer can be spread evenly, and the thickness of the passivation layer is moderate, which is favorable for the transport of holes and also favorable for the uniform and full coverage of the nickel oxide hole transport layer, thereby completely passivating the trivalent nickel on the nickel oxide surface.

[0144] In some embodiments, the perovskite solar cell further comprises a first electrode and a second electrode. At least one of the first electrode and the second electrode is a transparent conductive glass electrode. For example, the transparent conductive glass electrode is FTO, ITO, AZO, BZO, IZO, etc. The material of the other electrode may be an organic or inorganic or mixed organic-inorganic conductive material, including but not limited to Ag, Cu, C, Au, Al, ITO, AZO, BZO, IZO, etc.

[0145] A structural schematic diagram of a perovskite solar cell according to some embodiments of the present application is shown in Fig. 1. As shown in Fig. 1, a perovskite solar cell 100 includes a transparent electrode 10, a hole transport layer 20, a passivation layer 30, a perovskite layer 40, an electron transport layer 50, and a metal electrode 70, which are disposed in this order along its thickness direction X. The arrow in Fig. 1 indicates the direction of light incidence.

[0146] The manufacturing process for perovskite solar cells is as follows:

[0147] Step S1, provide a transparent conductive glass substrate, etch, clean and dry the transparent conductive glass substrate.

[0148] Step S2: Producing a nickel oxide hole transport layer on the transparent conductive glass electrode after drying.

[0149] Step S3: Coat a polymer on the surface of the nickel oxide hole transport layer that is away from the transparent conductive glass electrode, and remove the solvent by annealing or vacuum to obtain a passivation layer.

[0150] Step S4: Producing a perovskite layer on the surface of the passivation layer facing away from the transparent conductive glass electrode.

[0151] Step S5: fabricating an electron transport layer on the surface of the perovskite layer remote from the transparent conductive glass electrode.

[0152] Step S6: fabricate a metal electrode on the surface of the electron transport layer away from the transparent conductive glass electrode, and package the resulting perovskite solar cell.

[0153] Furthermore, the perovskite solar cell 100 may further include a buffer layer 60, which can transport electrons and block holes, and may be made of 2-(4-tert-butylphenyl)-5-(4-biphenyl)-1,3,4-oxadiazole, Bis(8-hydroxyl)-2-methylquinoline)-(4-phenylphenoxy)aluminum, etc. Of course, the perovskite solar cell 100 does not necessarily need to include the buffer layer 60.

[0154] Perovskite Solar Cells

[0155] According to a third aspect, the present application further provides a perovskite solar cell comprising a hole transport layer, the hole transport layer comprising a polymer according to any one of the embodiments of the first aspect of the present application.

[0156] In some embodiments, the perovskite solar cell further comprises a perovskite layer. The LUMO level of the hole transport layer is greater than the LUMO level of the perovskite layer.

[0157] In some embodiments, the LUMO level of the perovskite layer is within 0.5 eV of the LUMO level of the hole transport layer. Optionally, the LUMO level of the perovskite layer is within 0.3 eV of the LUMO level of the hole transport layer.

[0158] The difference between the LUMO level of the perovskite layer and that of the hole transport layer satisfies the above condition, so that the polymer can be used as a hole transport layer, and the polymer can effectively extract holes and block electron transport while having high hole mobility.

[0159] In some embodiments, the thickness of the hole transport layer is 10 nm to 50 nm, optionally 15 nm to 30 nm. When the thickness of the hole transport layer is in the above range, its hole transport ability can be further improved.

[0160] In some embodiments, the perovskite solar cell further includes an electron transport layer, the specific material of which has been described above and will not be described here.

[0161] In some embodiments, the perovskite solar cell further includes a first electrode and a second electrode, at least one of which is a transparent conductive glass electrode, the specific material of which is as described above and will not be described here.

[0162] 2 shows a schematic structural diagram of a perovskite solar cell according to some embodiments of the present application, and as shown in Fig. 2, the perovskite solar cell 100 includes a transparent electrode 10, a hole transport layer 20, a perovskite layer 40, an electron transport layer 50, and a metal electrode 70, which are disposed in this order along the thickness direction X of the solar cell. The arrow in Fig. 2 indicates the direction of light incidence.

[0163] The manufacturing process for perovskite solar cells is as follows:

[0164] Step S1, provide a transparent conductive glass substrate, etch, clean and dry the transparent conductive glass substrate.

[0165] Step S2: Coat the polymer on the surface of the transparent conductive glass electrode, and remove the solvent by annealing or vacuum to obtain a hole transport layer.

[0166] Step S3: Producing a perovskite layer on the surface of the hole transport layer remote from the transparent conductive glass electrode.

[0167] Step S4: fabricating an electron transport layer on the surface of the perovskite layer facing away from the transparent conductive glass electrode.

[0168] Step S5: fabricate a metal electrode on the surface of the electron transport layer away from the transparent conductive glass electrode, and package the resulting perovskite solar cell.

[0169] Additionally, the perovskite layer 40 may further include a buffer layer 60 .

[0170] Photovoltaic Module

[0171] According to a fourth aspect, the present application further provides a photovoltaic module, the photovoltaic module comprising a perovskite solar cell according to any one of the embodiments of the second or third aspect of the present application. The perovskite solar cell may be used as a power source for the photovoltaic module, or may be used as an energy storage unit for the photovoltaic module. One or more perovskite solar cells may be installed, and when multiple perovskite solar cells are installed, the multiple perovskite solar cells may be connected in series, in parallel, or in series-parallel to form a photovoltaic module, or may be connected in series, in parallel, or in series-parallel to form a battery unit, and then the multiple battery units may be connected in series, in parallel, or in series-parallel to form a whole.

[0172] power consumption equipment

[0173] According to a fifth aspect, the present application further provides a power consuming device, the power consuming device comprising a perovskite solar cell according to any one of embodiments of the second or third aspect of the present application, or a photovoltaic module according to any one of embodiments of the fourth aspect of the present application.

[0174] Perovskite solar cells or photovoltaic modules may be used as a power source for power consuming devices, or as an energy storage unit for power consuming devices, which may be, but are not limited to, mobile devices (e.g., mobile phones, laptops, etc.), electric vehicles (e.g., pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.

[0175] As the power consuming device, a secondary battery, a battery module, or a battery pack can be selected according to the demands of the usage.

[0176] 3 is a schematic diagram of an example power consuming device 200, such as a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, in which a perovskite solar cell 100 can be employed to meet the high power and high energy density demands of the power consuming device.

[0177] Working Example

[0178] The following examples are provided to more specifically describe the contents disclosed in this application, and these examples are used merely for illustrative purposes, and it is obvious to those skilled in the art that various modifications and changes can be made within the scope of the contents disclosed in this application. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are based on weight, all reagents used in the examples are commercially available or can be synthesized by common methods, and can be used directly without further treatment, and all equipment used in the examples can be commercially available.

[0179] Working Example

[0180] Example A

[0181] Polymer Production

[0182] (1) Synthesis of 9-(2-bromoethyl)-9H-carbazole [ka]

[0183] 1.672g of carbazole was dissolved in 25mL of 1,2-dibromoethane, stirred to homogeneous mixing, then 0.5g of tetrabutylammonium bromide and 3mL of 50wt% KOH aqueous solution were added, heated to 50℃, and stirred for 72h to stop the reaction. The product was extracted with dichloromethane, the organic phase was dried with anhydrous MgSO4, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by column chromatography to obtain 9-(2-bromoethyl)-9H-carbazole, where the mobile phase was a mixture of acetone and n-hexane with a volume ratio of 1:10.

[0184] (2) Synthesis of diethyl 2-(9H-carbazol-9-yl)ethyl)phosphonate [ka]

[0185] 1g of 9-(2-bromoethyl)-9H-carbazole was dissolved in 15mL of triethyl phosphite, heated to reflux and reacted for 24h. After the reaction, most of the organic solvent was removed by rotary evaporation, and the product was purified by column chromatography to obtain diethyl 2-(9H-carbazol-9-yl)ethyl)phosphonate, where the mobile phase was a mixture of acetone and n-hexane in a volume ratio of 1:4.

[0186] (3) Synthesis of ethyl diethyl (2-(3,6-dibromo-9H-fluorenyl-9-yl)phosphonate [ka]

[0187] Diethyl 2-(9H-carbazol-9-yl)ethyl)phosphonate (4.88g, 10mmol) was added to a round-bottom flask, N-bromosuccinimide NBS (5.4g, 30mmol) was added, and the mixture was reacted at 0°C for 4h. The reaction product was washed with water and saturated saline, respectively, and the organic phase was extracted with chloroform. The organic phase was combined and the water was removed with anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the product diethyl 2-(3,6-dibromo-9H-fluorenyl-9-yl)phosphonate ethyl.

[0188] (4) Synthesis of diethyl (2-(3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxybenzaldehyde-2-yl)-9H-fluorenyl-9-yl) ethyl phosphonate [ka]

[0189] Take diethyl(2-(3,6-dibromo-9H-fluorenyl-9-yl)ethylphosphonate (2.91 g, 5 mmol) and dissolve it in 20 mL of tetrahydrofuran. In an argon gas atmosphere, inject and release gas and stir at -78°C for 0.5 h. Then take butyllithium (1 mL, dissolved in n-hexane at 2.5 M) and slowly add dropwise to the above system. After the addition is complete, continue to stir for 1 h. Then add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborinane (0.37 g, 20 mmol) dropwise and add -7 After reacting at 8°C for 1 hour, the mixture was warmed to room temperature, and the product was poured into deionized water, extracted three times with chloroform, and the organic phase was taken out. The organic phases were combined and the water was removed with anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The product was recrystallized with isopropanol, and the precipitate was dissolved in chloroform and precipitated by adding methanol to obtain the product diethyl(2-(3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxybenzaldehyde-2-yl)-9H-fluorenyl-9-yl)ethyl phosphonate with higher purity.

[0190] (5) Synthesis of poly[ethyl diethyl(2-(3,6-dimethyl-9H-fluorenyl-9-yl)phosphonate] [ka]

[0191] Take a clean and dry round-bottom flask, add 100 mL of toluene, and add the diethyl(2-(3,6-dibromo-9H-fluorenyl-9-yl)ethyl phosphonate (0.95 g, 1.18 mmol) obtained in step (3) and the diethyl(2-(3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxybenzaldehyde-2-yl)-9H-fluorenyl-9-yl)ethyl phosphonate (0. A mixture of 69 g (1.18 mmol) of 1H-dimethylformamide (Dibenzylidene-BASEacetone)dipalladium Pd2(dba)3 (54 mg, 0.06 mmol), triphenylphosphine PPh3 (54 mg, 0.18 mmol), 2.5 mL of 1 M aqueous potassium carbonate solution, and 0.005 mL of methyltricaprylammonium chloride was mixed in a round-bottom flask, degassed to ensure the argon gas environment, and heated at 90 °C for 5 h. After reaction, add phenylboronic acid pinacol ester (24mg, 1.2mmol) and continue to stir for 20min, then add bromobenzene (0.3g, 1.9mmol) and continue to stir for 20min, cool to room temperature, wash product with water, extract organic phase with chloroform, mix organic phase and remove water with anhydrous magnesium sulfate, remove most of solvent by rotary evaporation, make product saturated in toluene, add product toluene solution dropwise to 500mL methanol, suction filter to take solid matter, wrap with filter paper, use Soxhlet extractor to extract with methanol, acetonitrile, chloroform respectively, take chloroform phase, obtain saturated solution after concentration, add dropwise to 500mL methanol, suction filter to obtain solid matter poly[diethyl(2-(3,6-dimethyl-9H-fluorenyl-9-yl)ethylphosphonate] 0.5g.

[0192] (6) Synthesis of poly[diethyl(2-(3,6-dimethyl-9H-fluorenyl-9-yl)phosphonic acid]

[0193] The repeating unit is represented by formula (I-33). [ka]

[0194] Under argon gas atmosphere, 0.5 g of (6) was dissolved in anhydrous 1,4-dioxane (15 ml) and bromotrimethylsilane (1.73 ml, 13.07 mmol) was added dropwise. The reaction was stirred at 25°C under argon gas atmosphere for 22 hours, then methanol (3 ml) was added and stirred for another 3 hours. Finally, distilled water (10 ml) was added dropwise until the solution became opaque, stirred overnight, the product was filtered and washed with water, dissolved in tetrahydrofuran (1 ml) and precipitated in n-hexane (12 ml), the product was filtered and washed with n-hexane to give 0.360 g of poly[diethyl(2-(3,6-dimethyl-9H-fluorenyl-9-yl)phosphonic acid].

[0195] Example B

[0196] Polymer synthesis

[0197] Synthesis of methyl 3-(9H-carbazol-9-yl)propionate [ka]

[0198] Take a clean and dry round-bottom flask, add 8.3605g (0.05mol) of carbazole, 12.52g (0.075mol) of methyl 3-bromopropionate, 1g of Pd2(dba)3, 5mL of tri-tert-butylphosphine, and 32g of cesium carbonate, then add 100mL of toluene, bleed (nitrogen) gas three times, maintain the nitrogen gas environment in the flask, react at 110℃ for 20h, extract the product with dichloromethane, dry the organic phase with anhydrous MgSO4, and remove the solvent by rotary evaporation to obtain the crude product, which is purified by column chromatography to obtain methyl 3-(9H-carbazol-9-yl)propionate, where the mobile phase is a mixture of ethyl acetate and n-hexane with a volume ratio of 1:10, and the product is 7.52g (59%).

[0199] Synthesis of methyl 3-(3,6-dibromo-9H-carbazol-9-yl)propionate [ka]

[0200] Methyl 3-(9H-carbazol-9-yl)propionate (2.53 g, 10 mmol) was added to a round-bottom flask, and N-bromosuccinimide (NBS) (5.4 g, 30 mmol) was added. The mixture was allowed to react at 0°C for 4 hours. The reaction product was then washed with water and saturated saline, and the organic phase was extracted with chloroform. The organic phases were combined and the water was removed with anhydrous magnesium sulfate. The solvent was removed by rotary evaporation to obtain the product methyl 3-(3,6-dibromo-9H-carbazol-9-yl)propionate.

[0201] Synthesis of methyl 3-(3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-9H-carbazol-9-yl)propionate [ka]

[0202] 3-(3,6-dibromo-9H-carbazol-9-yl)methyl propionate (2.04g, 5mmol) was dissolved in 20mL of tetrahydrofuran, and the mixture was placed under an argon gas atmosphere by gas injection and degassing. Stirred at -78℃ for 0.5h, then butyllithium (1mL, dissolved in n-hexane at 2.5M) was slowly added dropwise to the above system. After the addition was completed, the mixture was stirred for 1h, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborinane (0.37g, 20mmol) was added dropwise. After reacting at 78°C for 1 hour, the mixture was heated to room temperature and the product was poured into deionized water, extracted three times with chloroform, and the organic phase was taken out. The organic phases were combined and the water was removed with anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The product was recrystallized with isopropanol, and the precipitate was dissolved in chloroform and precipitated by adding methanol to obtain the product of higher purity, 3-(3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-9H-carbazol-9-yl)methyl propionate.

[0203] Synthesis of poly[3-(3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-9H-carbazol-9-yl)methyl propionate] [ka] , the repeating unit is represented by the formula (I-36).

[0204] Take a clean and dry round bottom flask, add 100 mL of toluene, and add methyl 3-(3,6-dibromo-9H-carbazol-9-yl)propionate (0.48 g, 1.18 mmol) obtained in step (2) and methyl 3-(3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-9H-carbazol-9-yl)propionate (0.6 g, 1.18 mmol) obtained in step (3). Tris(dibenzylidene-BASEacetone)dipalladium Pd2(dba)3 (54 mg, 0.06 mmol), triphenylphosphine PPh3 (54 mg, 0.18 mmol), 2.5 mL of 1 M potassium carbonate aqueous solution, and 0.005 mL of methyltricaprylammonium chloride were mixed in a round-bottom flask, degassed to ensure the argon gas environment, and reacted at 90 °C for 5 h, followed by the addition of phenylboronic acid pinacoyl boronic acid. Add bromobenzene (0.3g, 1.9mmol) and continue to stir for 20 minutes, then add bromobenzene (0.3g, 1.9mmol) and continue to stir for 20 minutes, cool to room temperature, wash the product with water, extract the organic phase with chloroform, mix the organic phase and remove water with anhydrous magnesium sulfate, remove most of the solvent by rotary evaporation, make the product saturated in toluene, add the toluene solution of the product dropwise to 500mL of methanol, suction filter to take the solid, wrap with filter paper, use Soxhlet extractor to extract with methanol, acetonitrile, chloroform respectively, take the chloroform phase, concentrate to obtain a saturated solution, add dropwise to 500mL of methanol, suction filter to obtain the solid poly[3-(3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-9H-carbazol-9-yl)methyl propionate].

[0205] Synthesis of poly[3-(3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-9H-carbazol-9-yl]propionic acid] [ka] , the repeating unit is (I-35).

[0206] Under argon gas atmosphere, 0.5 g of (4) was dissolved in anhydrous 1,4-dioxane (15 ml) and bromotrimethylsilane (1.73 ml, 13.07 mmol) was added dropwise. The reaction was stirred at 25° C. under argon gas atmosphere for 22 hours, then methanol (3 ml) was added and stirred for 3 hours. Finally, distilled water (10 ml) was added dropwise until the solution became opaque, and stirred overnight. The product was filtered and washed with water, dissolved in tetrahydrofuran (1 ml) and precipitated in n-hexane (12 ml), the product was filtered and washed with n-hexane to give poly[3-(3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-9H-carbazol-9-yl)propionic acid.

[0207] Example D

[0208] Synthesis of poly[2-((2,4-dimethylphenyl)(p-tolyl)amino)ethane-1-sulfonic acid], the repeating unit of which is of formula (I-40). [ka]

[0209] The difference from Example A is that the process of step (1) is as follows. Mix 3.26g (20mmol) of 2-chloroethanesulfonyl chloride, 1.2g (20mmol) of isopropanol and 40ml of 1,2-dichloroethane in round-bottom flask 1, lower the temperature to 0°C, take another flask, weigh 3.34g (20mmol) of carbazole, dissolve in 20ml of 1,2-dichloroethane, stir thoroughly until completely dissolved to obtain carbazole solution, add carbazole solution drop by drop into round-bottom flask 1, after dropwise addition is completed, return the reaction temperature to room temperature, continue reacting for 4h, suction filter, dry and concentrate, and then purify the crude product by column chromatography, the mobile phase is a mixture of dichloromethane and n-hexane with a volume ratio of 1:8, and obtain the product 2-(phenyl(o-tolyl)amino)ethane-1-sulfonate isopropyl. The process of other steps is similar to that of Example A.

[0210] Example E

[0211] The above in Example C was reacted with sodium hydroxide to give the corresponding sodium salt, the repeating unit of which is formula (I-39). [ka]

[0212] Example F

[0213] A method similar to that of Example A was employed to prepare the polymer, with the difference being that 1,2-dibromoethane in step (1) was replaced with 1,2-dibromopropane, and the repeat unit of the polymer was of formula (I-37). [ka]

[0214] Example G

[0215] A method similar to that of Example A was employed to prepare the polymer, with the difference being that 1,2-dibromoethane in step (1) was replaced with 1,2-dibromooctane, and the repeat unit of the polymer was of formula (I-38). [ka]

[0216] Example H

[0217] A method similar to that of Example A was employed to prepare the polymer, with the difference being that carbazole in step (1) was replaced with diphenylamine, and the repeat unit of the polymer was of formula (I-17). [ka]

[0218] Example I

[0219] A method similar to that of Example A was employed to prepare the polymer, except that in step (1) carbazole was replaced with N1,N1-diphenylbenzene-1,3-diamine, and the repeat unit of the polymer was of formula (I-29). [ka]

[0220] Example 1

[0221] Perovskite solar cell manufacturing

[0222] (1) Take 20 pieces of FTO conductive glass with a specification of 2.0*2.0cm, and remove 0.35cm of FTO on both ends by laser etching to expose the glass substrate.

[0223] (2) The FTO conductive glass after etching is ultrasonically cleaned several times using water, acetone, and isopropanol in sequence.

[0224] (3) The FTO conductive glass is dried to remove the solvent using a nitrogen gas spray gun, and then placed in an ultraviolet ozone machine for further cleaning.

[0225] (4) On the UV-ozone treated FTO conductive glass, a 10 mg / mL hole transport layer of nickel oxide nanoparticles (aqueous solution is the solvent) was spin-coated at a speed of 4000 rpm / s, and then annealed on a hot stage at 100 °C for 30 min.

[0226] (5) The polymer prepared in Example A is dissolved in chlorobenzene, and a polymer solution is obtained after dissolving. The polymer solution is spin-coated on the nickel oxide hole transport layer at 3000 rpm / s, and a polymer passivation layer is obtained by vacuum drawing or annealing.

[0227] (6) Lead iodide, formamidine iodide, cesium iodide, methylamine bromide, and lead bromide are weighed and dissolved in a mixed solution of DMF and DMSO, stirred for 3 h, and filtered through a 0.22 μm organic filter membrane to obtain a perovskite precursor solution. The perovskite precursor solution is spin-coated on the obtained polymer passivation layer at 3000 rpm / s, annealed at 100 °C for 30 min, and cooled to room temperature, where the active material of the perovskite layer is the CsFAMA system.

[0228] (7) An electron transport layer, PCBM, was spin-coated on the perovskite layer at 1500 rpm / s, annealed at 100 °C for 10 min, and then the buffer layer, BCP, was immediately spin-coated at 5000 rpm / s.

[0229] (8) The device obtained above was placed in a deposition machine, and a metal electrode (Ag) was deposited to obtain a perovskite solar cell.

[0230] Example 2

[0231] In Example 2, a method similar to that in Example 1 is used to fabricate a perovskite solar cell, with the difference being that in Example 2, the polymer prepared in Example B is used as the passivation layer material.

[0232] Example 3

[0233] In Example 3, a method similar to that in Example 1 is used to fabricate a perovskite solar cell, with the difference being that in Example 3, the polymer prepared in Example C is used as the passivation layer material.

[0234] Example 4

[0235] In Example 4, a method similar to that in Example 1 is used to prepare a perovskite solar cell, with the difference being that in Example 4, the polymer prepared in Example D is used as the passivation layer material.

[0236] Example 5

[0237] In Example 5, a method similar to that in Example 1 is used to prepare a perovskite solar cell, with the difference being that in Example 5, the polymer prepared in Example E is used as the passivation layer material.

[0238] Example 6

[0239] In Example 6, a method similar to that in Example 1 is used to prepare a perovskite solar cell, with the difference being that in Example 6, the polymer prepared in Example F is used as the passivation layer material.

[0240] Example 7

[0241] In Example 7, a method similar to that in Example 1 is used to prepare a perovskite solar cell, with the difference being that in Example 7, the polymer prepared in Example G is used as the passivation layer material.

[0242] Example 8

[0243] In Example 8, a method similar to that in Example 1 is used to fabricate a perovskite solar cell, with the difference being that in Example 8, the polymer prepared in Example H is used as the passivation layer material.

[0244] Example 9

[0245] Example 9 employs a method similar to that of Example 1 to fabricate a perovskite solar cell, with the difference being that Example 9 uses the polymer prepared in Example I as the passivation layer material.

[0246] Comparative Example 1

[0247] In Comparative Example 1, a perovskite solar cell was manufactured using a method similar to that of Example 1, except that in Comparative Example 1, no passivation layer was provided.

[0248] Comparative Example 2

[0249] In Comparative Example 2, a perovskite solar cell was manufactured using a method similar to that of Example 1, with the difference being that in Comparative Example 2, the monomer of diethyl (2-(3,6-dimethyl-9H-fluorenyl-9-yl)phosphonic acid, which is the polymer in Example A, was used as the passivation layer material.

[0250] Comparative Example 3

[0251] In Comparative Example 3, a perovskite solar cell was manufactured using a method similar to that of Example 1, with the difference being that Comparative Example 3 used polystyrene as the passivation layer material.

[0252] The battery performances of Examples 1 to 11 and the Comparative Example are shown in Tables 1 and 2.

[0253] [Table 1]

[0254] [Table 2]

[0255] As can be seen from Tables 1 and 2, compared with Comparative Example 1, Comparative Example 2 has diethyl (2-(3,6-dimethyl-9H-fluorenyl-9-yl)phosphonic acid disposed on the surface of the nickel oxide layer, which can achieve passivation of high-value nickel, but the effect is very low. Comparative Example 3 has a polystyrene layer disposed on the surface of the nickel oxide layer, which not only fails to achieve passivation of high-value nickel, but may even result in a decrease in cell efficiency. The examples of the present application have a specific polymer disposed on the surface of the nickel oxide layer, which can achieve significant passivation of high-value nickel, and can also improve the hole transport performance and electron transport blocking ability, thereby effectively improving the photoelectric conversion efficiency of the perovskite solar cell.

[0256] Examples 10 and 11

[0257] In Examples 10 and 11, perovskite solar cells are fabricated using a method similar to that of Example 1. The difference from Example 1 is that in Examples 10 and 11, the polymer prepared in Example A is used as the passivation layer material, and polymers with different molecular weights can be separated by using a solvent.

[0258] The relevant parameters of Examples 1, 10 and 11 are as shown in Tables 3 and 4.

[0259] [Table 3]

[0260] [Table 4]

[0261] As can be seen from Tables 3 and 4, the photoelectric conversion efficiency of perovskite solar cells can be fine-tuned by controlling the molecular weight of the polymer.

[0262] Example 12

[0263] Perovskite solar cell manufacturing

[0264] (1) Take 20 pieces of FTO conductive glass with a specification of 2.0*2.0cm, and remove 0.35cm of FTO on both ends by laser etching to expose the glass substrate.

[0265] (2) The FTO conductive glass after etching is ultrasonically cleaned several times using water, acetone, and isopropanol in sequence.

[0266] (3) The FTO conductive glass is dried to remove the solvent using a nitrogen gas spray gun, and then placed in an ultraviolet ozone machine for further cleaning.

[0267] (4) The polymer prepared in Example A is dissolved in chlorobenzene, and a polymer solution is obtained after dissolving. The polymer solution is spin-coated on the FTO conductive glass at 3000 rpm / s, and a polymer layer is obtained by vacuum drawing or annealing.

[0268] (5) Lead iodide, formamidine iodide, cesium iodide, methylamine bromide, and lead bromide are weighed and dissolved in a mixed solution of DMF and DMSO, stirred for 3 hours, and filtered using a 0.22 μm organic filter membrane to obtain a perovskite precursor solution. The perovskite precursor solution is spin-coated on the obtained polymer layer at 3000 rpm / s, annealed at 100°C for 30 min, and cooled to room temperature, where the active material of the perovskite layer is the CsFAMA system.

[0269] (6) An electron transport layer, PCBM, was spin-coated on the perovskite layer at 1500 rpm / s, annealed at 100 °C for 10 min, and then the buffer layer, BCP, was immediately spin-coated at 5000 rpm / s.

[0270] (7) The device obtained above was placed in a deposition machine, and a metal electrode (Ag) was deposited to obtain a perovskite solar cell.

[0271] Examples 13 to 15

[0272] In Examples 13 to 15, perovskite solar cells were manufactured using a method similar to that of Example 12. The difference from Example 12 is that in Examples 13 to 15, the polymer manufactured in Example A was used as the hole transport layer material, but the thickness of the polymer layer was adjusted.

[0273]

[0274] [Table 5]

[0275] [Table 6]

[0276] As can be seen from Tables 5 and 6, the photovoltaic conversion efficiency of perovskite solar cells can be fine-tuned by controlling the molecular weight of the polymer.

[0277] Test Part

[0278] 1. Test method for energy band distribution of perovskite solar cells

[0279] Using an ultraviolet photoelectron spectrometer (UPS) and an X-ray photoelectron spectrometer (XPS), the energy band distribution of each sublayer in the obtained electron transport layer, the hole transport layer, and the perovskite absorption layer was examined. The test conditions were room temperature and pressure, and an atmospheric environment, and a He I lamp (21.2 eV) was used as a laser light source. Exemplarily, the model numbers of the UPS and XPS instruments are Escalab 250Xi (Thermo Scientific).

[0280] 2. Test method for power conversion efficiency of perovskite solar cells

[0281] The energy conversion efficiency is obtained by a voltage-current characteristic test, the simulated solar intensity is standard AM1.5G, and the test conditions are normal temperature and pressure, and atmospheric environment. Exemplarily, the model number of the test equipment is photoflame IVS-KA5000.

[0282] Although the present application has been described with reference to the preferred embodiments, various improvements may be made thereto and the elements therein may be replaced with equivalents without departing from the scope of the present application. In particular, the respective technical features mentioned in each embodiment may be combined in any manner, so long as there is no structural contradiction. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions within the scope of the claims. [Explanation of symbols]

[0283] X thickness direction, 100 Perovskite solar cells, 10 transparent electrode, 20 hole transport layer, 30 passivation layer, 40 perovskite layer, 50 electron transport layer, 60 buffer layer, 70 metal electrode. 200 Power consuming equipment.

Claims

1. A polymer comprising a repeat unit as shown in formula (I), -M-R-Y - formula (I), In formula (I), M is selected from a substituted or unsubstituted anilino group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenothiazinyl group, or a substituted or unsubstituted phenoxazinyl group; R is selected from substituted or unsubstituted C1-C10 alkyl groups; A polymer in which Y is selected from a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, or a sulfonic acid group or a salt thereof.

2. R is selected from substituted or unsubstituted C1-C8 alkyl groups; Optionally, R is selected from substituted or unsubstituted C1-C5 alkyl groups.

3. The repeating unit represented by the formula (I) is 【Chemistry 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 The repeating units include one or more repeating units represented by formulas (I-1) to (I-7): Where: R １ ~R １４ are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxy group, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, a substituted or unsubstituted C1-C5 carboxyalkyl group, or a substituted or unsubstituted C6-C20 aryl group, optionally, when substituted, the substituents are independently selected from at least one of a halogen atom or a nitrogen-containing group; the nitrogen-containing group comprises a C2-C10 dialkylamino group, a C1-C5 alkylamino group, an amino group, a trimethylamine group, a triethylamine group, or a tripropylamine group; Optionally, R １ ~R １４ are each independently selected from a hydrogen atom, a halogen atom, a nitrogen-containing group, a hydroxy group, a substituted or unsubstituted C1-C5 alkoxyl group, a substituted or unsubstituted C1-C5 amido group, a substituted or unsubstituted C1-C5 ester group, or a substituted or unsubstituted C1-C5 carboxyalkyl group; Further optionally, R １ ~R １４ are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C5 alkoxyl group, or a substituted or unsubstituted C1-C5 alkyl group.

4. Y in the repeating unit represented by formula (I-2) is selected from a phosphate group, Optionally, the repeating unit shown in formula (I-2) is 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 The polymer according to claim 3, comprising at least one of the repeating units represented by formulas (I-21) to (I-29):

5. The repeating unit represented by the formula (I-3) is 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 The polymer according to claim 3 or 4, comprising at least one of the repeating units represented by formula (I-31) to formula (I-391):

6. 6. The polymer of any one of claims 1 to 5, wherein the weight average molecular weight of the polymer is from 3000 Da to 20000 Da, optionally from 3000 Da to 10000 Da.

7. A perovskite solar cell, comprising, in order: A hole transport layer, a passivation layer and a perovskite layer, said passivation layer comprising a polymer according to any one of claims 1 to 6, Where: the LUMO level of the passivation layer is greater than the LUMO level of the perovskite layer; Optionally, a LUMO level of the passivation layer is between a LUMO level of the perovskite layer and a LUMO level of a hole transport layer.

8. a difference between the LUMO level of the perovskite layer and the LUMO level of the passivation layer is within 0.5 eV; Optionally, the difference between a LUMO level of the perovskite layer and a LUMO level of the passivation layer is within 0.3 eV.

9. a difference between the LUMO level of the passivation layer and the LUMO level of the hole transport layer is within 0.5 eV; 9. The perovskite solar cell of claim 7 or 8, optionally wherein the difference between the LUMO level of the passivation layer and the LUMO level of the hole transport layer is within 0.3 eV.

10. 10. The perovskite solar cell according to any one of claims 7 to 9, wherein the passivation layer has a thickness of from 0.1 nm to 5 nm, optionally from 1 nm to 3 nm.

11. 7. A perovskite solar cell comprising a hole transport layer comprising the polymer of any one of claims 1 to 6.

12. The perovskite solar cell of claim 11, wherein the hole transport layer has a thickness of from 10 nm to 50 nm, optionally from 15 nm to 30 nm.

13. A photovoltaic module comprising the perovskite solar cell according to any one of claims 7 to 12.

14. A power consuming device comprising the perovskite solar cell according to any one of claims 7 to 12 or the photovoltaic module according to claim 13.

Images