Polymer, preparation method therefor, perovskite cell, photovoltaic module, electrical apparatus and power generation apparatus

Abstract

A polymer, a preparation method therefor, a perovskite cell, a photovoltaic module, an electrical apparatus, and a power generation apparatus. The perovskite cell comprises a hole transport layer and a perovskite layer which are successively arranged in the thickness direction of the perovskite cell, the hole transport layer comprising a polymer. The polymer comprises a first repetitive unit and a second repetitive unit, at least one of the first repetitive unit and the second repetitive unit comprising a hole transport material. The technical solution of the present application can improve the stability of perovskite cells.

Description

Polymer and preparation method thereof, perovskite cell, photovoltaic module, power utilization device, power generation device Cross-reference to Related Applications

[0001] This application claims priority to Chinese Patent Application No. 202411388927.7, filed on September 30, 2024, entitled “Polymer and preparation method thereof, perovskite cell, photovoltaic module, power utilization device, power generation device”, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0002] The present application relates to the technical field of solar cells, and more particularly, to a polymer and a preparation method thereof, a perovskite cell, a photovoltaic module, a power utilization device, and a power generation device. BACKGROUND

[0003] A perovskite cell is a solar cell that uses a perovskite material as a light-absorbing layer, has excellent photoelectric performance, and has a simple preparation method, bringing new space and hope for photovoltaic power generation.

[0004] The structural composition of a perovskite cell is crucial to the performance of the perovskite cell. Therefore, how to provide a perovskite cell to further improve the stability of the perovskite cell is a problem to be solved. SUMMARY

[0005] The present application is made in view of the above problem, and aims to provide a polymer and a preparation method thereof, a perovskite cell, a photovoltaic module, a power utilization device, and a power generation device to improve the stability of the perovskite cell.

[0006] In a first aspect, a perovskite cell is provided, comprising: a hole transport layer and a perovskite layer arranged in sequence along a thickness direction of the perovskite cell, the hole transport layer comprising a polymer, the polymer comprising a first repeating unit and a second repeating unit, at least one of the first repeating unit and the second repeating unit comprising a hole transport material.

[0007] In the present application, the hole transport layer comprises a polymer, which is relatively stable and is not prone to migration and diffusion, which is conducive to improving the stability of the hole transport layer and the perovskite layer. In addition, the hole transport layer comprising the polymer is also conducive to reducing the risk of water and oxygen entering between the hole transport layer and the perovskite layer, which is conducive to improving the stability of the perovskite layer. Therefore, the technical solution of the present application can improve the stability of the perovskite cell.

[0008] In some embodiments, the first repeating unit is different from the second repeating unit. The first and second repeating units are different, and at least one of the first and second repeating units comprises a hole transport material, such that the hole transport layer has a hole transport capability while also having other properties such as better wettability, which is conducive to further improving the stability of the perovskite cell or improving the photoelectric conversion efficiency of the perovskite cell.

[0009] In some embodiments, in the first repeating unit, the hole transport material comprises a substituted or unsubstituted anilino group. The anilino group can adjust the functional properties of the perovskite cell and has certain hydrophobic properties, which can reduce the influence of external water and oxygen on the perovskite layer, thereby improving the stability of the perovskite cell.

[0010] In some embodiments, the first repeating unit comprises a substituted or unsubstituted triphenylamine group. The triphenylamine group has high stability, and the polymer comprising the triphenylamine group has high stability when applied to the perovskite cell.

[0011] In some embodiments, the structural formula of the first repeating unit satisfies:

[0012] In formula (I),

[0013] R5 comprises at least one of H, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted benzene ring, a substituted or unsubstituted heterocycle, or a substituted or unsubstituted benzo-heterocycle;

[0014] R6 comprises H, a benzene ring, a C1-C10 alkyl group, or an acid group, the acid group comprising at least one of:

[0015] In the above technical solution, R5 can serve as a linking group connecting the anilino group and R6, and R6 can serve as an anchoring group to anchor the surface of the hole transport layer, thereby further improving the stability of the perovskite cell.

[0016] In some embodiments, the structural formula of the first repeating unit further comprises R1, R2, R3, and R4, wherein R1 and R2 are located at any position of a first benzene ring and a second benzene ring of the first repeating unit, respectively, R3 and R4 are located at any position of a third benzene ring of the first repeating unit, the first benzene ring and the second benzene ring are benzene rings of the first repeating unit that are not provided with R5, and the third benzene ring is a benzene ring of the first repeating unit that is provided with R5; R1-R4 each independently comprises at least one of H, a substituted or unsubstituted C1-C8 alkyl group, a methoxy group, a halogen, or a methylthio group.

[0017] In the above embodiments, by setting the substituents, the performance of the polymer is regulated, so that the perovskite battery has higher stability.

[0018] In some embodiments, R5 includes a substituted or unsubstituted C1-C10 alkyl group. In this way, the R5 group can play a role in reducing steric hindrance, and the polymer can have higher stability, thereby facilitating the improvement of the stability of the perovskite battery.

[0019] In some embodiments, R6 includes at least one of

[0020] In the above technical solutions, the polymer has higher stability, and the perovskite battery has higher stability.

[0021] In some embodiments, the second repeating unit includes at least one of a substituted or unsubstituted aniline group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted thiazine group, a substituted or unsubstituted acridine group, or a substituted or unsubstituted phenoxazine group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted thiophene group, or a substituted or unsubstituted benzothiophene group. The above-mentioned second repeating unit is matched with the first repeating unit, which is conducive to obtaining a polymer with a suitable energy level, and the energy level between the hole transport layer and the perovskite layer is more matched, which is conducive to reducing the accumulation of charge carriers between the hole transport layer and the perovskite layer, facilitating the rapid transport of charge carriers, thereby facilitating the improvement of the stability of the perovskite battery.

[0022] In some embodiments, the structural formula of the second repeating unit satisfies: -M-Y- formula (II-1);

[0023] In formula (II-1),

[0024] M includes at least one of a substituted or unsubstituted aniline group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted thiazine group, a substituted or unsubstituted acridine group, or a substituted or unsubstituted phenoxazine group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted thiophene group, or a substituted or unsubstituted benzothiophene group;

[0025] Y includes at least one of the following groups:

[0026] In the above technical solutions, the M group is conducive to realizing the better hole transport capacity or stability, hydrophobicity, etc. of the polymer, and the Y group can be used as an anchoring group to anchor the surface in contact with the hole transport layer, so that the polymer can exist more stably, thereby facilitating the further improvement of the stability of the perovskite battery.

[0027] In some embodiments, the structural formula of the second repeating unit satisfies: -M-L-Y- formula (II-2);​

[0028] In formula (II-2),

[0029] L includes at least one of H, a substituted or unsubstituted C1-C8 alkyl, a substituted or unsubstituted benzene ring, a substituted or unsubstituted heterocycle, or a substituted or unsubstituted benzo-heterocycle.

[0030] In the technical solution, the M group is conducive to realizing good hole transport capacity or stability, hydrophobicity, and other properties of the polymer, the L group can be used as a connecting group connecting the M group and the Y group, and the Y group can be used as an anchoring group to anchor the surface in contact with the hole transport layer, so that the polymer can exist more stably, and the stability of the perovskite battery can be further improved.

[0031] In some embodiments, the second repeating unit includes at least one of the following structures:

[0032] X includes at least one of H, a substituted or unsubstituted C1-C8 alkyl, a methoxy group, a halogen, or a methylthio group, and * indicates a connection site of M and L or Y.

[0033] In the technical solution, by selecting the second repeating unit, the perovskite battery has higher stability.

[0034] In some embodiments, the structural formula of the polymer satisfies at least one of the following:

[0035] wherein n is 2-50.

[0036] In the technical solution, the polymer is relatively stable and is not prone to migration and diffusion, and the energy level between the polymer and the perovskite is matched, which is conducive to the rapid transport of carriers. Therefore, when the polymer satisfying the structural formula is applied to a perovskite battery, the perovskite battery has higher stability.

[0037] In some embodiments, n is 5-30. In this way, the polymer has a large degree of polymerization, the polymer is relatively stable and is not prone to decomposition and migration, which is conducive to improving the stability of the perovskite battery.

[0038] In some embodiments, the weight average molecular weight of the polymer is 1000 Da-25000 Da.

[0039] In some embodiments, the weight average molecular weight of the polymer is 1000 Da-10000 Da.

[0040] In the technical solution, the weight average molecular weight of the polymer meets the range, the polymer is relatively stable and is not prone to migration, and the stability of the perovskite battery is improved.

[0041] In some embodiments, the perovskite battery further comprises a first electrode layer, and the hole transport layer is located between the first electrode layer and the perovskite layer in the thickness direction of the perovskite battery. In this way, the transport of carriers is facilitated.

[0042] In some embodiments, the hole transport layer comprises a passivation layer, and the passivation layer comprises the polymer, and the passivation layer is located between the first electrode layer and the perovskite layer in the thickness direction of the perovskite battery.

[0043] In the technical solution, the passivation layer is beneficial to reducing the recombination of carriers, promoting the rapid transport of carriers, and thus improving the stability of the perovskite battery.

[0044] In some embodiments, the hole transport layer comprises a hole transport base layer and the passivation layer, and the passivation layer is located between the hole transport base layer and the perovskite layer in the thickness direction of the perovskite battery. In this way, the hole transport base layer is used for transporting holes, the passivation layer is used for transporting holes and reducing the risk of substances in the hole transport base layer or substances in the external environment entering the perovskite layer, and the perovskite battery has high stability.

[0045] In some embodiments, the difference between the HOMO energy level of the passivation layer and the HOMO energy level of the perovskite layer is -1.0 eV to 1.0 eV.

[0046] In some embodiments, the difference between the HOMO energy level of the passivation layer and the HOMO energy level of the perovskite layer is -0.5 eV to 0.5 eV.

[0047] In the technical solution, the HOMO energy level of the passivation layer is matched with the HOMO energy level of the perovskite layer, the transport of carriers is facilitated, the accumulation of carriers at the interface between the perovskite layer and the passivation layer is reduced, the adverse effects on the interface are reduced, the long-term stability of the perovskite battery is improved, and the photoelectric conversion efficiency of the perovskite battery is improved.

[0048] In some embodiments, the HOMO energy level of the passivation layer is greater than or equal to the HOMO energy level of the perovskite layer. In this way, the transport of holes is facilitated, and the photoelectric conversion efficiency and the stability of the perovskite battery are improved.

[0049] In some embodiments, the HOMO energy level of the passivation layer is -5.8 eV to -4.8 eV. In this way, the transport of holes is facilitated, and the photoelectric conversion efficiency of the perovskite battery is improved.

[0050] In some embodiments, the thickness d of the passivation layer is 1-20 nm. In this way, the passivation layer has a suitable thickness, and the perovskite cell has high stability.

[0051] In some embodiments, the perovskite cell comprises, in sequence along the incident direction of the light source, a first electrode layer, the hole transport layer, the perovskite layer, an electron transport layer, and a second electrode layer, the incident direction of the light source being parallel to the thickness direction of the perovskite cell. The perovskite cell described above can be a perovskite cell of an inverted structure. After being irradiated, the perovskite layer can convert photons into holes and electrons, the electron transport layer can effectively transport electrons, the hole transport layer can effectively transport holes, and the first electrode layer and the second electrode layer can collect electrons and form an electric current and a voltage, so that electric energy can be generated by the perovskite cell.

[0052] In some embodiments, the perovskite cell comprises, in sequence along the incident direction of the light source, a first electrode layer, an electron transport layer, the perovskite layer, the hole transport layer, and a second electrode layer, the incident direction of the light source being parallel to the thickness direction of the perovskite cell. The perovskite cell described above can be a perovskite cell of a normal structure.

[0053] In some embodiments, the first electrode layer comprises at least one of an organic conductive material, an inorganic conductive material, and an organic-inorganic hybrid conductive material, the second electrode layer comprises at least one of an organic conductive material, an inorganic conductive material, and an organic-inorganic hybrid conductive material, the inorganic conductive material comprises one or more of a carbon material, a metal material and an alloy thereof, and a transparent conductive metal oxide, the organic conductive material comprises one or more of polyacrylic acid, polyimide, polyaniline, polythiophene and derivatives thereof, and polypyrrole, and at least one of the first electrode layer and the second electrode layer is a light-transmitting electrode layer.

[0054] In some embodiments, the first electrode layer comprises a transparent conductive metal oxide, and the second electrode layer comprises a metal. In this way, sunlight can pass through the first electrode layer.

[0055] In some embodiments, the first electrode layer comprises at least one of ITO, FTO, BZO, AZO, IZO, GZO, or IWO, and the second electrode layer comprises at least one of Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, or Mg. The first electrode layer described above has the characteristics of being transparent or translucent, which is conducive to the transmission of sunlight through the first electrode layer; the second electrode layer has good conductivity, and through the above combination, the perovskite cell has high photoelectric conversion efficiency.

[0056] In a second aspect, a photovoltaic assembly is provided, comprising: the perovskite cell of the first aspect and any possible implementation thereof.

[0057] In some embodiments, the photovoltaic assembly further comprises: a substrate layer and an encapsulation layer, the perovskite cell is disposed on the substrate layer, and the encapsulation layer is configured to encapsulate the perovskite cell.

[0058] In a third aspect, a power consumption device is provided, comprising: the photovoltaic assembly of the second aspect and any possible implementation thereof.

[0059] In a fourth aspect, a power generation device is provided, comprising: the photovoltaic assembly of the second aspect and any possible implementation thereof.

[0060] In a fifth aspect, a polymer is provided, comprising a first repeating unit and a second repeating unit, at least one of the first repeating unit and the second repeating unit comprising a hole transport material.

[0061] In some embodiments, a structural formula of the polymer satisfies at least one of the following:

[0062] wherein n is 2-50.

[0063] In a sixth aspect, a preparation method of a polymer is provided, comprising: providing a first repeating unit and a second repeating unit, at least one of the first repeating unit and the second repeating unit comprising a hole transport material; and performing a polymerization reaction on the first repeating unit and the second repeating unit to obtain the polymer. BRIEF DESCRIPTION OF DRAWINGS

[0064] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly introduced as follows. Obviously, the drawings described below are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of the drawings.

[0065] FIG. 1 is a schematic diagram of a perovskite cell according to an embodiment of the present application;

[0066] FIG. 2 is a schematic diagram of a perovskite cell according to an embodiment of the present application;

[0067] FIG. 3 is a schematic diagram of a photovoltaic assembly according to an embodiment of the present application;

[0068] FIG. 4 is a schematic diagram of a preparation method of a polymer according to an embodiment of the present application;

[0069] FIG. 5 is a schematic diagram of a power consumption device according to an embodiment of the present application;

[0070] The accompanying drawings are not necessarily drawn to scale.

[0071] Reference Signs:

[0072] 1: perovskite cell; 11: first electrode layer; 12: hole transport layer; 13: perovskite layer; 14: electron transport layer; 15: second electrode layer; 121: hole transport base layer; 122: passivation layer; 2: photovoltaic module; 21: base layer; 22: encapsulation layer; 100: vehicle; 30: controller; 40: motor. DETAILED DESCRIPTION

[0073] Embodiments of the polymer of the present application and the method for producing the same, the perovskite cell, the photovoltaic module, the electric device, and the power generation device are explained in detail with appropriate reference to the accompanying drawings, but there are cases where unnecessary detailed explanations are omitted. For example, there are cases where detailed explanations of matters that are well known, repeated explanations of actually identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following explanations are provided so that those skilled in the art can fully understand the present application, and are not intended to limit the subject matter recited in the claims.

[0074] The ranges disclosed herein are defined by the lower and upper limits of the range in the form of a range, and the given range is defined by selecting one lower limit and one upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The ranges defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, i.e., any lower limit can be combined with any upper limit to form a range. For example, if the ranges 60-120 and 80-110 are listed for a particular parameter, it is understood that the ranges 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, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, unless otherwise stated, a numerical range "a-b" represents a shorthand manner of describing each and every numerical value that is contained within the range, wherein a and b are both real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed herein, and "0-5" is merely a shorthand manner of describing those numerical combinations. In addition, when it is stated that a parameter is an integer ≥ 2, it is equivalent to disclose that the parameter is, for example, an integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and the like.

[0075] All embodiments of the present application and optional embodiments can be combined with each other to form new technical solutions, if not otherwise specified.

[0076] If not particularly specified, all the technical features of the present application and optional technical features can be combined with each other to form new technical solutions.

[0077] If not particularly specified, all the steps of the present application can be performed in sequence or randomly, preferably in sequence. For example, the method comprises steps (a) and (b), which means that the method can comprise steps (a) and (b) performed in sequence, or steps (b) and (a) performed in sequence. For example, the method can further comprise step (c), which means that step (c) can be added to the method in any order, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0078] The term "anilino" includes diphenylamino and triphenylamino. In addition, the anilino group can be optionally substituted, and the substituent group can be a halogen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, an alkyl group or a heterocyclic group, etc.

[0079] The term "alkyl" encompasses straight and branched chain alkyl groups. For example, the alkyl group can be a C1-C20 alkyl group, a C1-C12 alkyl group, a C1-C10 alkyl group, a C1-C6 alkyl group, a C1-C4 alkyl group. In some embodiments, the alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, cyclobutyl, pentyl, isopentyl, neopentyl, t-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, nonyl, and decyl, etc. In addition, the alkyl group can be optionally substituted, for example, the alkyl group is substituted with a halogen to form a haloalkyl group. The term "haloalkyl" refers to an alkyl group in which some or all of the hydrogen atoms are replaced with halogen atoms, and the term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0080] Throughout the specification, substituents of compounds are disclosed in groups. It is specifically intended that the description include each and every individual subcombination of the members of these groups. For example, the term "Ci-Cio alkyl" specifically intends 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-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.

[0081] The term "alkoxy" refers to a group in which an alkyl group is attached to an oxygen atom by a single bond. For example, an alkoxy group can be a C1-C10 alkoxy group, a C1-C8 alkoxy group, a C1-C5 alkoxy group, a C2-C6 alkoxy group. In some embodiments, an alkoxy group can include methoxy, ethoxy, propoxy, butoxy, isobutoxy, sec-butoxy, t-butoxy, cyclobutoxy, pentoxy, isopentoxy, neopentoxy, t-pentoxy, cyclopentoxy.

[0082] The term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, and the like.

[0083] The term "hydrogen" refers to1H (protium, H),2H (deuterium, D), or3H (tritium, T). In various embodiments, "hydrogen" can be1H (protium, H).

[0084] In the present application, the terms "a plurality" and "a plurality of" refer to two or more.

[0085] The perovskite cell includes a perovskite layer, a hole transport layer and an electron transport layer, and an electrode. The working process of the perovskite cell mainly includes generation and separation of excitons, transport of free carriers, collection of carriers and generation of current. The specific process is as follows: in the perovskite cell, sunlight is absorbed by the perovskite layer, the perovskite layer absorbs photons to generate excitons, and due to the low Coulomb force binding of the perovskite layer, the excitons are then separated into free electrons and holes. The separated free carriers are transported in the perovskite layer and transported out through the transport layer. The electron transport layer plays a role of transporting electrons and blocking holes, and the hole transport layer plays a role of transporting holes and blocking electrons. The electrons and holes transported out through the transport layer are collected by the electrode to form current and voltage.

[0086] The perovskite cell mainly includes a normal structure and an inverted structure. The functional layers through which light is incident in the normal structure device are in the order of an electron transport layer, a perovskite layer and a hole transport layer. The functional layers through which light is incident in the inverted structure device are in the order of a hole transport layer, a perovskite layer and an electron transport layer. Next, the inverted structure device is taken as an example for illustration.

[0087] The perovskite layer includes a perovskite. The ideal structure of the perovskite is ABX3 type or A2CDX6 type. Taking the ABX3 type as an example, the B ion is located at the center of the cubic cell and surrounded by six X ions to form a coordination cubic octahedron, and the coordination number is 6; the A ion is located at the corner of the cubic cell and surrounded by 12 X ions to form a coordination octahedron, and the coordination number is 12. Among them, A is a large radius cation, B is a small radius cation, and X is an anion. Since the A, B and X sites are very wide in the range of accommodated element types and quantities, there are many types of compounds with perovskite structure.

[0088] The perovskite has poor stability. When the functional layer adjacent to the perovskite layer includes some oxidized materials (for example, the hole transport layer adjacent to the perovskite layer includes nickel oxide), the perovskite of the perovskite layer is easy to degrade, which is not conducive to the improvement of the stability of the perovskite cell.

[0089] In some processing modes, a passivation layer is arranged between the hole transport layer and the perovskite layer to isolate the hole transport layer and the perovskite layer, the passivation layer includes self-assembled small molecules, the self-assembled small molecules include anchor groups that can be combined with a substrate (for example, an FTO electrode layer or a nickel oxide layer) and top functional groups for regulating surface properties, the self-assembled small molecules can act as intermediaries to achieve the combination between the hole transport layer and the perovskite layer, and at the same time, the self-assembled small molecules can also isolate the contact between the perovskite and the hole transport layer, thereby improving the stability of the perovskite battery. However, the stability of the self-assembled small molecules is poor, and the combination of the interface between the passivation layer including the self-assembled small molecules and the perovskite layer and the hole transport layer is weak. After being irradiated by high-energy photons, the bonds inside the self-assembled small molecules are broken, the interface combination between the passivation layer and the perovskite layer and the hole transport layer is destroyed, and the self-assembled small molecules are prone to move at the interface and even migrate into the perovskite layer. Therefore, the passivation layer including the self-assembled small molecules has a weak effect on improving the stability of the perovskite battery.

[0090] Therefore, the passivation layer including the self-assembled small molecules has a weak effect on improving the stability of the perovskite battery.

[0091] [Perovskite battery]

[0092] FIG. 1 is a schematic diagram of a perovskite battery according to an embodiment of the present application. In some embodiments of the present application, for example, referring to FIG. 1, the perovskite battery 1 includes a hole transport layer 12 and a perovskite layer 13 arranged in sequence along the thickness direction of the perovskite battery 1, the hole transport layer 12 includes a polymer, and the polymer includes first repeating units and second repeating units, at least one of the first repeating units and the second repeating units includes a hole transport material.

[0093] The polymer includes the first repeating units and the second repeating units, that is, the polymer can be a copolymer formed by the first repeating units and the second repeating units. In the case where the first repeating units and the second repeating units are the same, the polymer can be a homopolymer of the first repeating units.

[0094] Compared with the self-assembled small molecules, the polymer has a larger molecular weight and is more stable, and after being affected by the external environment (for example, after being irradiated by high-energy photons), the polymer is not easily destroyed, so that the hole transport layer 12 and the perovskite layer 13 can still maintain good combination, and water and oxygen are not easy to enter between the hole transport layer 12 and the perovskite layer 13, thereby the perovskite layer 13 is less affected by the external water and oxygen, and the perovskite battery 1 has higher stability, which is beneficial to improve the service life of the perovskite battery 1; in addition, compared with the self-assembled small molecules, the polymer is not easy to migrate, and the risk of the polymer moving to the perovskite layer 13 is lower, and the influence on the perovskite layer 13 and the hole transport layer 12 is smaller, and the perovskite battery 1 has higher stability, which is beneficial to improve the service life of the perovskite battery 1.

[0095] In the embodiments of the present application, the hole transport layer 12 includes a polymer, which is relatively stable and not easy to migrate and diffuse, which is beneficial to improve the stability of the hole transport layer 12; in addition, the hole transport layer 12 including the polymer is also beneficial to reduce the risk of water and oxygen entering between the hole transport layer 12 and the perovskite layer 13, thereby reducing the risk of water and oxygen entering the perovskite layer 13, which is beneficial to improve the stability of the perovskite layer 13. Therefore, the technical scheme of the embodiments of the present application can improve the stability of the perovskite battery 1.

[0096] In some embodiments, the first repeating unit is different from the second repeating unit.

[0097] The first repeating unit and the second repeating unit are different, and at least one of the first repeating unit and the second repeating unit includes a hole transport material, so that the hole transport layer 12 not only has hole transport capability, but also has other properties such as better wettability, which is beneficial to further improve the stability of the perovskite battery 1 or improve the photoelectric conversion efficiency of the perovskite battery 1.

[0098] In some embodiments, in the first repeating unit, the hole transport material includes a substituted or unsubstituted anilino group.

[0099] The anilino group can adjust the functional characteristics of the perovskite battery 1 and has certain hydrophobic properties, which can reduce the influence of external water and oxygen on the perovskite layer 13, thereby improving the stability of the perovskite battery 1.

[0100] In some embodiments, the first repeating unit includes a substituted or unsubstituted triphenylamine group.

[0101] The triphenylamine group has higher stability, and the polymer including the triphenylamine group has higher stability when applied to the perovskite battery.

[0102] In some embodiments, the structural formula of the first repeating unit satisfies:

[0103] In formula (I),

[0104] R5 includes at least one of H, a substituted or unsubstituted C1-C10 alkyl, a substituted or unsubstituted benzene ring, a substituted or unsubstituted heterocycle, or a substituted or unsubstituted benzo-heterocycle;

[0105] R6 includes H, a benzene ring, a C1-C10 alkyl, or an acid group, the acid group including at least one of:

[0106] R5 is a linking group connecting the anilino group and R6. R5 can be H, so that R6 is directly connected to the anilino group; R5 can also be a group other than H, such as a methylene group, and R6 is connected to the anilino group through the methylene group.

[0107] The acid group in R6 can be anchored to the surface of the hole transport layer 12 as an anchoring group. For example, in the case where the hole transport layer 12 includes nickel oxide, the R6 group has good binding ability with trivalent nickel, the hole transport layer 12 is more stable, and the perovskite battery 1 has better stability.

[0108] In the above technical solution, R5 can be a linking group connecting the anilino group and R6, and R6 can be an anchoring group anchored to the surface in contact with the hole transport layer 12, so that the polymer can exist more stably, which is conducive to further improving the stability of the perovskite battery 1.

[0109] In some embodiments, the structural formula of the first repeating unit further includes R1, R2, R3, and R4, wherein R1 and R2 are located at any position of a first benzene ring and a second benzene ring of the first repeating unit, respectively, R3 and R4 are located at any position of a third benzene ring of the first repeating unit, the first benzene ring and the second benzene ring are benzene rings of the first repeating unit which are not provided with R5, and the third benzene ring is a benzene ring of the first repeating unit which is provided with R5; R1-R4 each independently includes at least one of H, a substituted or unsubstituted C1-C8 alkyl, a methoxy group, a halogen, or a methylthio group.

[0110] The R1, R2, R3, and R4 groups can be the same group or different groups. For example, R1 is a methoxy group, R2 is one of halogen elements, R3 is a methylthio group, and R4 is a methyl group. For another example, R1, R2, R3, and R4 are all methyl groups. For another example, R1 is a methoxy group, R2 is one of halogen elements, and R3 and R4 are methyl groups.

[0111] There are five substitutable positions on the first benzene ring connected to N, and R1may be located at any one of the five substitutable positions; there are five substitutable positions on the second benzene ring connected to N, and R2may be located at any one of the five substitutable positions; there are four substitutable positions on the third benzene ring connected to N, and R3and R4may be located at any two of the four substitutable positions, respectively.

[0112] As an example, the structural formula of the first repeating unit can be As another example, the structural formula of the first repeating unit can be

[0113] In the above embodiments, by the arrangement of the substituents, the performance of the polymer can be regulated to make the perovskite battery have higher stability.

[0114] In some embodiments, R5includes a substituted or unsubstituted C1-C10alkyl group. In this way, the R5group can play a role in reducing steric hindrance, and the polymer can have higher stability, thereby facilitating the improvement of the stability of the perovskite battery 1.

[0115] In some embodiments, R6includes at least one of

[0116] In the above technical solutions, the polymer has higher stability, and the perovskite battery 1 has higher stability.

[0117] In some embodiments, the second repeating unit includes at least one of a substituted or unsubstituted aniline group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted thiazine group, a substituted or unsubstituted acridine group, or a substituted or unsubstituted phenoxazine group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted thiophene group, or a substituted or unsubstituted benzothiophene group.

[0118] By the combination of the first repeating unit and the above-mentioned second repeating unit, the polymer has a more suitable energy level, and the energy levels between the hole transport layer and the perovskite layer are more matched, which can reduce the accumulation of charge carriers between the hole transport layer and the perovskite layer, facilitate the rapid transport of charge carriers, and facilitate the improvement of the stability of the perovskite battery 1.

[0119] In some embodiments, the structural formula of the second repeating unit satisfies: -M-Y- formula (II-1);

[0120] In formula (II-1),

[0121] ​M includes at least one of a substituted or unsubstituted anilino group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted thienazinyl group, a substituted or unsubstituted acridinyl group, or a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted thiophene group, or a substituted or unsubstituted benzothiophene group;

[0122] Y includes at least one of the following groups:

[0123] In the technical solution, the M group is conducive to realizing good hole transport capability or stability, hydrophobicity, and other properties of the polymer, the Y group can be used as an anchoring group to anchor the surface in contact with the hole transport layer 12, so that the polymer can exist more stably, and the stability of the perovskite battery 1 is further improved.

[0124] In some embodiments, the structure of the second repeating unit satisfies: -M-L-Y- formula (II-2);

[0125] In formula (II-2),

[0126] L includes at least one of H, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted benzene ring, a substituted or unsubstituted heterocycle, or a substituted or unsubstituted benzo-heterocycle.

[0127] In formula (II-2), M and Y can be the same structure as M and Y in formula (II-1). M includes at least one of a substituted or unsubstituted anilino group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted thienazinyl group, a substituted or unsubstituted acridinyl group, or a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted thiophene group, or a substituted or unsubstituted benzothiophene group; Y includes at least one of the following groups:

[0128] In the technical solution, the M group is conducive to realizing good hole transport capability or stability, hydrophobicity, and other properties of the polymer, the L group can be used as a linking group connecting the M group and the Y group, and the Y group can be used as an anchoring group to anchor the surface in contact with the hole transport layer 12, so that the polymer can exist more stably, and the stability of the perovskite battery 1 is further improved.

[0129] In some embodiments, the second repeating unit includes at least one of the following structures:

[0130] X includes at least one of H, a substituted or unsubstituted C1-C8 alkyl group, a methoxy group, a halogen, or a methylthio group, and * indicates a connection site of M and L or Y.

[0131] In the technical solution, the perovskite battery 1 has higher stability by selecting the second repeating unit.

[0132] In some embodiments, the structural formula of the polymer satisfies at least one of the following:

[0133] wherein n is 2-50.

[0134] In the above embodiments, n can be 2, 3, 5, 10, 20, 25, 30, 40, 50, or any value within the above range.

[0135] In the above embodiments, the polymer has a relatively appropriate molecular weight, the polymer is relatively stable and is not prone to decomposition and migration, and the energy level between the polymer and the perovskite is relatively matched, which is conducive to the rapid transport of carriers. When the polymer satisfying the above structural formula is applied to the perovskite battery 1, the perovskite battery 1 has higher stability.

[0136] In some embodiments, n is 5-30. In this way, the polymer has a relatively large degree of polymerization, the polymer is relatively stable and is not prone to decomposition and migration, which is conducive to improving the stability of the perovskite battery 1.

[0137] In some embodiments, the weight average molecular weight of the polymer is 1000 Da-25000 Da.

[0138] The weight average molecular weight of the polymer can be 1000 Da, 2000 Da, 3000 Da, 5000 Da, 8000 Da, 10000 Da, 15000 Da, 20000 Da, 25000 Da, or any value within the above range.

[0139] In some embodiments, the weight average molecular weight of the polymer is 1000 Da-10000 Da.

[0140] In the above embodiments, the weight average molecular weight of the polymer satisfies the above range, the polymer is relatively stable and is not prone to decomposition and migration, which is conducive to improving the stability of the perovskite battery 1.

[0141] In some embodiments, the perovskite battery 1 further comprises a first electrode layer 11, and the hole transport layer 12 is located between the first electrode layer 11 and the perovskite layer 13 in the thickness direction of the perovskite battery 1.

[0142] As an example, in the thickness direction of the perovskite battery 1, along the incident direction of sunlight, the sunlight sequentially passes through the first electrode layer 11, the hole transport layer 12, and the perovskite layer 13.

[0143] As an example, in the thickness direction of the perovskite cell 1, along the incident direction of sunlight, the sunlight sequentially passes through the perovskite layer 13, the hole transport layer 12, and the first electrode layer 11. It should be noted that before passing through the perovskite layer 13, the sunlight can also pass through the electron transport layer.

[0144] In the above embodiment, after being irradiated by sunlight, the hole transport layer 12 generates holes, and the holes can be transported via the first electrode layer 11 or the perovskite layer 13, thereby facilitating the transport of holes in the carriers.

[0145] In some embodiments, the hole transport layer 12 includes a passivation layer 122, the passivation layer 122 includes a polymer, and the passivation layer 122 is located between the first electrode layer 11 and the perovskite layer 13 in the thickness direction of the perovskite cell 1.

[0146] As an example, the hole transport layer 12 only includes the passivation layer 122, the passivation layer 122 includes a polymer, and the passivation layer 122 is located between the first electrode layer 11 and the perovskite layer 13.

[0147] In the above technical solution, the passivation layer 122 is located between the first electrode layer 11 and the perovskite layer 13, and the arrangement of the passivation layer 122 is beneficial to reducing the recombination of carriers and promoting the rapid transport of carriers, thereby facilitating the improvement of the stability of the perovskite cell 1.

[0148] FIG. 2 is a schematic diagram of a perovskite cell according to an embodiment of the present application. In some embodiments, referring to FIG. 2, the hole transport layer 12 includes a hole transport base layer 121 and a passivation layer 122, and the passivation layer 122 is located between the hole transport base layer 121 and the perovskite layer 13 in the thickness direction of the perovskite cell 1.

[0149] The hole transport base layer 121 includes a hole transport material, and the material of the hole transport base layer 121 is different from the material of the passivation layer 122. As an example, the hole transport base layer 121 includes nickel oxide, and the passivation layer 122 includes a copolymer of aniline and thiophene.

[0150] In the above embodiment, the hole transport base layer 121 is used to transport holes, the passivation layer 122 is used to transport holes and reduce the risk of substances in the hole transport base layer 121 or substances in the external environment entering the perovskite layer 13, and the perovskite cell 1 has high stability.

[0151] In some embodiments, the difference between the HOMO energy level of the passivation layer 122 and the HOMO energy level of the perovskite layer 13 is -1.0 eV to 1.0 eV.

[0152] The difference between the HOMO level of the passivation layer 122 and the HOMO level of the perovskite layer 13 is the value of the HOMO level of the passivation layer 122 minus the HOMO level of the perovskite layer 13.

[0153] The difference between the HOMO level of the passivation layer 122 and the HOMO level of the perovskite layer 13 can be -1.0 eV, -0.8 eV, -0.6 eV, -0.5 eV, -0.3 eV, -0.1 eV, 0 eV, 0.1 eV, 0.3 eV, 0.5 eV, 0.8 eV, 1.0 eV, or any value within the above range.

[0154] In the above embodiments, the difference between the HOMO level of the passivation layer 122 and the HOMO level of the perovskite layer 13 is small, and the HOMO level of the passivation layer 122 and the HOMO level of the perovskite layer 13 are well matched, which facilitates the transport of carriers, reduces the accumulation of carriers at the interface between the perovskite layer 13 and the passivation layer 122, and further reduces the adverse effects on the interface, thereby improving the long-term stability of the perovskite battery 1. In addition, it is also beneficial to improve the photoelectric conversion efficiency of the perovskite battery 1.

[0155] In some embodiments, the difference between the HOMO level of the passivation layer 122 and the HOMO level of the perovskite layer 13 is -0.5 eV to 0.5 eV. In this way, the energy levels between the perovskite layer 13 and the passivation layer 122 are more matched, which facilitates further improvement of the stability and photoelectric conversion efficiency of the perovskite battery 1.

[0156] In some embodiments, the HOMO level of the passivation layer 122 is greater than or equal to the HOMO level of the perovskite layer 13. In this way, the transport of holes is more facilitated, which is beneficial to improve the photoelectric conversion efficiency of the perovskite battery 1.

[0157] In some embodiments, the HOMO level of the passivation layer 122 is -5.8 eV to -4.8 eV.

[0158] The HOMO level of the passivation layer 122 can be -5.8 eV, -5.4 eV, -5.2 eV, -5.1 eV, -4.9 eV, -4.8 eV, or any value within the above range.

[0159] In the above embodiments, the HOMO level of the passivation layer 122 is within a suitable range, and the energy levels between the passivation layer 122 and the perovskite layer 13 are well matched, and the perovskite battery 1 has high photoelectric conversion efficiency and stability.

[0160] In some embodiments, the thickness d of the passivation layer 122 is 1 nm to 20 nm.

[0161] The thickness d of the passivation layer 122 can be 1 nm, 3 nm, 5 nm, 8 nm, 10 nm, 12 nm, 15 nm, 18 nm, 20 nm, or any value within the above range.

[0162] In the above embodiment, the passivation layer 122 has a suitable thickness, and the perovskite cell 1 has high stability.

[0163] In some embodiments, the perovskite cell 1 includes, in order along the thickness direction of the perovskite cell 1, a first electrode layer 11, a hole transport layer 12, a perovskite layer 13, an electron transport layer 14, and a second electrode layer 15.

[0164] After being irradiated with light, the perovskite layer 13 can convert photons into holes and electrons, the electron transport layer 14 can effectively transport electrons, the hole transport layer 12 can effectively transport holes, and the first electrode layer 11 and the second electrode layer 15 can collect electrons and form a current and a voltage, so that electrical energy can be generated by the perovskite cell 1.

[0165] In some embodiments, the perovskite cell 1 includes, in order along the incident direction of the light source, a first electrode layer 11, a hole transport layer 12, a perovskite layer 13, an electron transport layer 14, and a second electrode layer 15, and the incident direction of the light source is parallel to the thickness direction of the perovskite cell 1. The perovskite cell can be a perovskite cell 1 of an inverted structure.

[0166] In some embodiments, the perovskite cell 1 includes, in order along the incident direction of the light source, a first electrode layer 11, an electron transport layer 14, a perovskite layer 13, a hole transport layer 12, and a second electrode layer 15, and the incident direction of the light source is parallel to the thickness direction of the perovskite cell 1. The perovskite cell can be a perovskite cell 1 of a normal structure.

[0167] In some embodiments, the first electrode layer 11 includes at least one of an organic conductive material, an inorganic conductive material, and an organic-inorganic hybrid conductive material, the second electrode layer 15 includes at least one of an organic conductive material, an inorganic conductive material, and an organic-inorganic hybrid conductive material, the inorganic conductive material includes one or more of a carbon material, a metal material and an alloy thereof, and a transparent conductive metal oxide; the organic conductive material includes one or more of polyacrylic acid, polyimide, polyaniline, polythiophene and derivatives thereof, and polypyrrole; and at least one of the first electrode layer 11 and the second electrode layer 15 is a light-transmitting electrode layer.

[0168] The transparent conductive metal oxide can include at least one of indium tin oxide (ITO), lanthanide metal doped indium oxide, fluorine doped tin oxide (FTO), antimony doped tin oxide, boron doped zinc oxide (BZO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), indium tungsten oxide (IWO), and the metal can include at least one of Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W. The organic conductive material includes at least one of graphite, graphene, carbon nanotube.

[0169] The first electrode layer 11 and the second electrode layer 15 can be the same material or different materials.

[0170] As an example, the first electrode layer 11 includes a transparent conductive metal oxide, the second electrode layer 15 includes a metal, and the perovskite battery 1 has an inverted structure.

[0171] As an example, the first electrode layer 11 includes a transparent conductive metal oxide, the second electrode layer 15 includes a transparent conductive metal oxide, and the perovskite battery 1 has a normal structure.

[0172] As an example, the first electrode layer 11 includes fluorine doped tin oxide FTO, and the second electrode layer 15 includes Cu.

[0173] At least one of the first electrode layer 11 and the second electrode layer 15 is a light-transmitting electrode layer. In this way, sunlight is facilitated to pass through the perovskite battery 1, and in turn, to facilitate the generation of electrical energy.

[0174] In some embodiments, the first electrode layer 11 includes a transparent conductive metal oxide, and the second electrode layer 15 includes a metal.

[0175] In the above embodiments, in the direction of incidence of sunlight, the first electrode layer 11, the hole transport layer 12, the perovskite layer 13, the electron transport layer 14, and the second electrode layer 15 are sequentially arranged, the first electrode layer 11 includes a transparent conductive metal oxide, the second electrode layer 15 includes a metal, and the perovskite battery 1 can be a perovskite battery having an inverted structure.

[0176] In some embodiments, the first electrode layer 11 includes at least one of ITO, FTO, BZO, AZO, IZO, GZO, or IWO, and the second electrode layer 15 includes at least one of Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, or Mg. The above first electrode layer 11 has the characteristics of being transparent or semi-transparent, which is conducive to the transmission of sunlight through the first electrode layer 11; the second electrode layer 15 has good conductivity, and through the above combination, the perovskite battery 1 has a higher photoelectric conversion efficiency.

[0177] In some embodiments, the perovskite layer 13 includes a perovskite material, which can include a perovskite-type metal halide, a chemical formula of which includes ABX3or A2CDX6. A represents a monovalent inorganic cation, an organic cation, or an organic-inorganic hybrid cation, B represents a divalent inorganic cation, an organic cation, or an organic-inorganic hybrid cation, C represents a monovalent inorganic cation, an organic cation, or an organic-inorganic hybrid cation, D represents a trivalent inorganic cation, an organic cation, or an organic-inorganic hybrid cation, and X represents a monovalent inorganic anion, an organic anion, or an organic-inorganic hybrid anion. A represents a monovalent inorganic cation, which optionally includes one or more of Li + , Na + , K + , Rb + , and Cs + ; A represents an organic cation, which optionally includes at least one of methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, formamidinium, and imidazolium, more optionally, one or more of an organic amine ion and Cs+. B includes a divalent cation, which optionally includes a divalent cation of one or more of lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, and europium, etc. C represents a monovalent inorganic cation, which optionally includes one or more of Cs + , Ag + , K + , and Ru + . D represents a trivalent metal cation, which optionally includes one or more of Bi 3+ , Ni 3+ , Fe 3+ , Sb 3+ , In 3+ , and Cu 3+ , more optionally, one or more of In 3+ , Bi 3+ , and Sb 3+ . X represents a halogen ion, which optionally includes one or more of F - , Cl - , Br - , and I - , more optionally, one or more of Cl - , Br - , and I - .

[0178] In some embodiments, the hole transport base layer 121 comprises a hole transport material, and the hole transport material can include, but is not limited to, one or more of 2,2',7,7'-tetrakis(N,N-p-methoxyphenylamine)-9,9'-spirobifluorene, methoxytriphenylamine-fluoromethylformamide, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid, poly 3-hexylthiophene, triptycene-core triphenylamine, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-aniline)carbazole-spirobifluorene, polythiophene, phosphonic monomer, carbazyl monomer, sulfonic monomer, triphenylamine monomer, aromatic monomer, metal oxide, cuprous iodide, and cuprous thiocyanate, wherein the metal element in the metal oxide can include one or more of Ni, Mo, and Cu.

[0179] In some embodiments, the electron transport layer 14 comprises an electron transport material, and the electron transport material can include, but is not limited to, one or more of the following materials and derivatives thereof: imide compounds, quinone compounds, fullerene and derivatives thereof, methoxytriphenylamine-fluoromethylformamide (OMeTPA-FA), calcium titanate (CaTiO3), lithium fluoride (LiF), calcium fluoride (CaF2), poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid (PEDOT:PSS), poly 3-hexylthiophene (P3HT), triptycene-core triphenylamine (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-aniline)carbazole-spirobifluorene (CzPAF-SBF), polythiophene, metal oxide, silicon oxide (SiO2), strontium titanate (SrTiO3), calcium titanate, lithium fluoride, calcium fluoride, cuprous thiocyanate (CuSCN), etc.; wherein the metal element in the metal oxide can include one or more of Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, and Cr.

[0180] [Photovoltaic module]

[0181] FIG. 3 is a schematic diagram of a photovoltaic module according to an embodiment of the present application. The embodiment of the present application provides a photovoltaic module 2, for example, referring to FIG. 3, the perovskite cell 1 in any possible embodiment described above is provided on the photovoltaic module 2.

[0182] In some embodiments, the photovoltaic module 2 further comprises a substrate layer 21 and an encapsulation layer 22, the perovskite cell 1 is disposed on at least one side surface of the substrate layer 21, and the encapsulation layer 22 is configured to encapsulate the perovskite cell 1.

[0183] The perovskite cell 1 can be arranged on one side surface of the substrate layer 21 in the thickness direction, or arranged on both side surfaces of the substrate layer 21 in the thickness direction. As an example, as shown in FIG. 3, the perovskite cell 1 is arranged on one side surface of the substrate layer 21.

[0184] By arranging the encapsulation layer 22, the perovskite cell 1 can be isolated from the external environment, reducing the adverse effects of water and oxygen in the external environment on the perovskite cell 1, and improving the stability and service life of the perovskite cell 1.

[0185] The substrate layer 21 can be a rigid substrate layer or a flexible substrate layer. The rigid substrate layer can be transparent glass, and the material of the flexible substrate layer includes an organic polymer material. Further, the material of the flexible substrate layer can be mixed in different proportions by one or more of the following materials: polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), poly naphthalene dimethyl glycol ester (PEN), polydimethylsiloxane (PDMS), and the like.

[0186] The material of the encapsulation layer 22 includes encapsulation glue, which includes one or more of epoxy encapsulation glue, silicone encapsulation glue, polyurethane encapsulation glue, ultraviolet light curing encapsulation glue, ethylene-vinyl acetate copolymer, polyvinyl butyral, ethylene octene copolymer, polyisobutylene, and polyolefin encapsulation glue.

[0187] As an example, the photovoltaic module can be prepared by the following method.

[0188] The first electrode layer 11 is arranged on the substrate layer 21, and the hole transport base layer 121, the passivation layer 122, the perovskite layer 13, the electron transport layer 14, and the second electrode layer 15 are sequentially arranged on the first electrode layer 11 to obtain the perovskite cell 1. The encapsulation glue is coated on the periphery of the perovskite cell 1 to cover the back plate layer and is press-fit to obtain the photovoltaic module 2. The encapsulation glue can cover the entire perovskite cell 1.

[0189] [Polymer]

[0190] The embodiment of the present application provides a polymer, which includes a first repeating unit and a second repeating unit, and at least one of the first repeating unit and the second repeating unit includes a hole transport material.

[0191] In some embodiments, the structural formula of the polymer satisfies at least one of the following:

[0192] Wherein, n is 2-50.

[0193] [Preparation method of polymer]

[0194] Figure 4 is a schematic diagram of a polymer preparation method according to an embodiment of this application. Some embodiments of this application provide polymer preparation methods. For example, referring to Figure 4, preparation method 300 includes the following steps.

[0195] Step 310, providing a first repeating unit and a second repeating unit, at least one of the first repeating unit and the second repeating unit comprising a hole transport material.

[0196] Step 320: The first repeating unit and the second repeating unit are subjected to a polymerization reaction to obtain a polymer.

[0197] [Electrical appliances]

[0198] This application provides an electrical device, including a photovoltaic module 2 from any of the above embodiments.

[0199] Electrical devices can include vehicles, mobile phones, portable devices, laptops, ships, spacecraft, electric toys, and power tools, etc. Vehicles can be gasoline-powered cars, natural gas-powered cars, or new energy vehicles; new energy vehicles can be pure electric vehicles, hybrid electric vehicles, or range-extended electric vehicles, etc. Spacecraft include airplanes, rockets, space shuttles, and spacecraft, etc. Electric toys include stationary or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc. Power tools include metal cutting power tools, grinding power tools, assembly power tools, and railway power tools, such as electric drills, electric grinders, electric wrenches, electric screwdrivers, electric hammers, impact drills, concrete vibrators, and electric planers, etc. This application does not impose any special limitations on the above-mentioned electrical devices.

[0200] Electronic devices can also be used to store electrical energy, for example, in applications such as energy storage power stations.

[0201] Figure 5 is a schematic diagram of an electrical device according to an embodiment of this application. For example, referring to Figure 5, the electrical device is a vehicle. The vehicle 100 can be a gasoline vehicle, a natural gas vehicle, or a new energy vehicle. The new energy vehicle can be a pure electric vehicle, a hybrid electric vehicle, or a range-extended electric vehicle, etc. A motor 40, a controller 30, and a photovoltaic module 2 can be installed inside the vehicle 100. The controller 30 is used to control the photovoltaic module 2 to supply power to the motor 40. For example, the photovoltaic module 2 can be installed at the bottom, front, or rear of the vehicle 100. The photovoltaic module 2 can be used to supply power to the vehicle 100. For example, the photovoltaic module 2 can serve as the operating power source for the vehicle 100, for example, for the electrical needs of the vehicle 100's starting, navigation, and operation. In another embodiment of this application, the photovoltaic module 2 can not only serve as the operating power source for the vehicle 100, but also as the driving power source for the vehicle 100, replacing or partially replacing gasoline or natural gas to provide driving power to the vehicle 100.

[0202] [Power generation device]

[0203] The power generation device according to any one of the above embodiments.

[0204] The power generation device can be used in the field of solar cells and the like. For example, the photovoltaic module 2 is arranged outdoors, and after the photovoltaic module 2 absorbs sunlight, electric energy can be generated, and thus the power generation device including the photovoltaic module 2 can be used for power generation.

[0205] Hereinafter, the embodiments of the present application will be described. The embodiments described below are exemplary and are intended to explain the present application only, and should not be understood as limiting the present application. In the embodiments, unless a specific technique or condition is specified, the technique or condition described in the literature in the art or according to the product manual is used. The reagents or instruments not specified by the manufacturer are all conventional products that can be obtained commercially.

[0206] [Embodiments]

[0207] Embodiment 1

[0208] In embodiment 1, the photovoltaic module 2 includes a substrate layer 21, a perovskite cell 1, and an encapsulation layer 22 which are sequentially stacked; the perovskite cell 1 includes a first electrode layer 11, a hole transport layer 12, a perovskite layer 13, an electron transport layer 14, and a second electrode layer 15, the hole transport layer 12 includes a hole transport base layer 121 and a passivation layer 122, the passivation layer 122 includes a polymer, and the thickness of the passivation layer 122 is 10 nm.

[0209] In embodiment 1, the structural formula of the polymer is Formula (III-1).

[0210] The synthesis process of the polymer in embodiment 1 is as follows:

[0211] (1) Step 1

[0212] In step 1, a first intermediate product is prepared through a C-N coupling reaction. The specific process is as follows: a clean and dry reaction bottle is taken, a magnetic stirrer is added, then raw material A (1 eq), raw material B (1 eq), catalyst tris(dibenzylideneacetone)dipalladium (0.02 eq), ligand tri-tert-butylphosphine (0.08 eq), cesium carbonate (2 eq) are mixed, an appropriate amount of toluene is added, and the bottle is degassed three times to make the bottle an inert atmosphere. The temperature in the reaction bottle is raised to 110°C, and the reaction is carried out overnight (about 16 h). The obtained product is extracted with saturated brine and water, and the oil phase is dried with anhydrous magnesium sulfate, then filtered and concentrated. The final product is separated by column chromatography, and different materials can be separated by different polarities.

[0213] In step 1, the raw material A is The raw material B is The first intermediate product is

[0214] (2) Step 2

[0215] In step 2, the first intermediate product is treated to obtain the second intermediate product, which is 2-(4-(bis(4-bromophenylamino)phenyl)ethyl acetate, and the structural formula of the second intermediate product is

[0216] The specific process in step 2 is as follows:

[0217] Take a clean and dry round-bottom flask, add a magnetic stirrer, the first intermediate product (1 eq), N-bromosuccinimide NBS (2 eq), and then add an appropriate amount of chloroform, react at 0°C for 4 hours, and the process point plate is detected. After the reaction is complete, add an appropriate amount of water, extract the product with chloroform, dry the oil phase with anhydrous magnesium sulfate, and then perform filtration, concentration, and drying.

[0218] (3) Step 3

[0219] In step 3, the third intermediate product N,N-bis(4-(4,4,5,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-4-amine is prepared using raw material C.

[0220] The raw material C is 4,4'-dibromo-4"-phenyltriphenylamine, and the structural formula of the raw material C is The structural formula of the third intermediate product is

[0221] The specific preparation process is as follows: dissolve the raw material C (1 eq) in anhydrous tetrahydrofuran, add a 2.5M hexane solution of n-butyl lithium n-BuLi (4 eq) dropwise at -78°C, and stir. After stirring at -78°C for 1 hour, add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxazolidine (40 eq) dropwise, and stir at -78°C for 1 hour, then heat to room temperature. Pour the reaction mixture into distilled water, extract the resulting product with saturated brine and water, dry the oil phase with anhydrous magnesium sulfate, and then perform filtration, concentration, and separation of the final product by column chromatography. Different materials are separated using different polarities.

[0222] (4) Step 4

[0223] In step 4, the third intermediate product and the second intermediate product are subjected to a C-C coupling polymerization reaction to obtain a fourth intermediate product.

[0224] The fourth intermediate product has a structural formula of

[0225] The specific process is as follows: a clean and dry reaction bottle is taken, a magnetic sub is added, and then the two intermediate products (1 eq), the third intermediate product (1 eq), tetrakis triphenylphosphine palladium (0.02 eq), triphenylphosphine (0.08 eq), 50% K2CO3 aqueous solution (2 eq), tetrabutylammonium bromide (0.01 eq), and an appropriate amount of toluene are added, and the bottle is subjected to three times of air exhaust to make the bottle an inert atmosphere. The reaction bottle is warmed to 110°C, and the reaction is carried out overnight (about 16 h). The obtained product is extracted with saturated brine and water, and the oil phase is dried with anhydrous magnesium sulfate and then subjected to suction filtration and concentration. The final product is separated by column chromatography, and different materials are separated by using different polarities.

[0226] It should be noted that after the polymerization reaction, bromobenzene or phenylboronic acid pinacol can be added for end-capping.

[0227] (5) Step 5

[0228] The fourth intermediate product is subjected to hydrolysis to obtain the polymer in Example 1.

[0229] In step 5, the specific process is as follows: a clean and dry round-bottom flask is taken, the fourth intermediate product (1 eq) is dispersed in an appropriate amount of ethanol, and NaOH aqueous solution (2 eq) is added, and the reaction is carried out at 70°C for a period of time. The reaction stop time is determined according to the plate condition to ensure complete reaction, and then the temperature is lowered to room temperature, hydrochloric acid is added to adjust the pH, and when the solution pH reaches 2-3, the addition is stopped, the product is extracted with dichloromethane, and then dried with anhydrous magnesium sulfate, and then subjected to suction filtration and concentration. The final product is separated by column chromatography, and different materials are separated by using different polarities.

[0230] It should be noted that after obtaining the polymer, it can be separated and purified by Soxhlet extraction. For example, methanol, acetone, dichloromethane, and chloroform are used in sequence for Soxhlet extraction to obtain polymers of different molecular weights.

[0231] In Example 1, the above-mentioned polymer is used to prepare a photovoltaic module including a perovskite battery, and the specific process is as follows.

[0232] Preparation of the photovoltaic module:

[0233] (1) Take a group of FTO conductive glass with a size of 1.5 cm x 1.5 cm, protect 2 / 3 of the FTO conductive glass by M3 waterproof tape, and etch off 1 / 3 of the FTO by using Zn powder and 1 mol / L hydrochloric acid; clean the etched FTO conductive glass several times with acetone and isopropyl alcohol, and finally immerse in deionized water for 10 min of ultrasonic;

[0234] (2) After drying the FTO conductive glass in the air drying oven, spin-coat the precursor solution of NiOx nanoparticles (10 mg / mL, solvent is water) at a speed of 4000 rpm-6500 rpm in the glove box (N2 atmosphere), heat on the hot table at 100°C for 15 min, to obtain the nickel oxide hole transport layer;

[0235] (3) After spinning the NiOx, spin-coat the polymer ethanol solution (1 mg / mL) at a speed of 3000 rpm-4500 rpm, heat on the hot table at 100°C for 10 min, to obtain the passivation layer;

[0236] (4) After spinning the passivation layer, spin-coat the perovskite layer, and then immediately heat at 110°C for 30 min on the hot table in the glove box, and anneal to room temperature, wherein the active substance in the perovskite layer is MAPbI3;

[0237] (5) After spinning the perovskite layer, place the fixed clamp into the vacuum thermal evaporation equipment to evaporate C60 (thickness of 30 nm) and bathocuproin BCP (thickness of 7 nm) in sequence, to obtain the electron transport layer; then evaporate Cu (thickness of 60 nm) at an evaporation rate of to obtain the perovskite solar cell;

[0238] (6) Apply a layer of encapsulating glue around and on the surface of the perovskite solar cell, the encapsulating glue is colorless and transparent epoxy resin glue, cover the glass back plate layer on the encapsulating glue and press fit, and stand still for 2 h, to solidify the encapsulating glue, to obtain the photovoltaic module.

[0239] Example 2

[0240] The difference between Example 2 and Example 1 is that the polymer used is different.

[0241] In Example 2, the preparation process of the polymer can refer to the preparation process of the polymer in Example 1, except that step 3 is omitted in Example 2, the raw material C is changed from 4,4'-dibromo-4"-phenyltriphenylamine to 1,4-bis(pinacolato)diboron, and in step 4, 1,4-bis(pinacolato)diboron is used to react with the second intermediate product.

[0242] In Example 2, the structural formula of the polymer is

[0243] Example 3

[0244] Example 3 differs from Example 1 in that the polymer used is different.

[0245] In Example 3, the preparation process of the polymer can refer to the preparation process of the polymer in Example 1, except that the second intermediate product is obtained by self-polymerization and hydrolysis.

[0246] In Example 3, the structural formula of the polymer is

[0247] Example 4

[0248] Example 4 differs from Example 1 in that the polymer used is different.

[0249] In Example 4, the preparation process of the polymer can refer to the preparation process of the polymer in Example 1, except that 4,4'-dibromo-4"-phenyltriphenylamine is replaced by 4,4"-dibromo-5'-phenyl-1,1':3',1'-terphenyl.

[0250] The preparation method of 4,4"-dibromo-5'-phenyl-1,1':3',1'-terphenyl is as follows: take a clean and dry round-bottom flask, add a magnetic sub, 1,3,5-triphenylbenzene (1 eq), NBS (2 eq), then add an appropriate amount of chloroform, react at 0°C for 4h, and the process point plate is detected, after the reaction is completed, add an appropriate amount of water, the product is extracted with chloroform, the oil phase is dried with anhydrous magnesium sulfate, and then filtered, concentrated. The final product is separated by column chromatography, and the mobile phase is EA / Hex=1:20, to obtain a white solid.

[0251] In Example 4, the structural formula of the polymer is

[0252] Examples 5-7

[0253] Examples 5-7 differ from Example 1 in that the polymer used is different.

[0254] In Examples 5-7, the structural formula of the polymer used is formula (III-5), formula (III-6), and formula (III-7), respectively, as shown below:

[0255] The synthesis method of the polymer of Example 5 is as follows.

[0256] (1) Step 1

[0257] Dissolve 3,8-dibromo-11,12-dihydroindolo[2,3-A]carbazole (CAS: 845619-86-5) (1 eq) in 1,2-dibromoethane (30 eq), then add tetrabutylammonium bromide (0.2 eq) and 50% aqueous KOH (5 eq); stir the reaction at 60 °C overnight (a balloon must be inserted on the stopper to balance the pressure created by the heating, so as not to unplug the stopper); take a sample of the mixture to spot on TLC, using acetone: n-hexane 1:24 v / v as the developing solvent, and cool to room temperature after determining that the reaction is complete; extract, dry the organic layer with anhydrous Na2SO4, and rotary evaporate to the minimum volume after suction filtration; purify the crude product by column chromatography (acetone and hexane 1:124 v / v), and dry in a vacuum oven at 70 °C overnight to obtain the first intermediate product.

[0258] (2) Step 2

[0259] Dissolve the first intermediate product (0.8 g, 2.42 mmol) in triethyl phosphite (30 eq), and heat the reaction mixture to reflux overnight; continue to spot on TLC, using acetone: n-hexane 6:19 v / v as the developing solvent; evaporate the excess triethyl phosphite using reduced pressure distillation to obtain the crude product; purify the crude product by column chromatography (acetone / n-hex 1:4 v / v), and dry in a vacuum oven at 70 °C overnight to obtain the second intermediate product.

[0260] (3) Step 3

[0261] Dissolve N,N-bis(4-bromophenyl)-2,4,6-trimethylbenzenamine (CAS: 663943-27-9) (5 mmol) in tetrahydrofuran, and stir at -78 °C for 0.5 h under an argon atmosphere after purging with argon, then slowly drop butyllithium (1 mL, 2.5 M in n-hexane) dropwise into the above system, continue to stir for 1 h after the dropwise addition, then add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 mmol) dropwise, and react at -78 °C for 1 h, then raise to room temperature; pour the product after the reaction into deionized water, then extract with chloroform three times, combine the organic phases, dry with anhydrous magnesium sulfate, and rotary evaporate to remove the solvent; recrystallize the product with isopropyl alcohol, dissolve the precipitate in chloroform, and precipitate with methanol to obtain the third intermediate product.

[0262] (4) Step 4

[0263] The second intermediate and the third intermediate are subjected to a polymerization reaction. Specifically, a clean and dry round bottom flask is taken and toluene, the second intermediate (1 eq), the third intermediate (1 eq), tris(dibenzylidene-base acetone) dipalladium Pd2(dba)3 (0.02 eq), triphenylphosphine PPh3 (0.08 eq), and a 1 M aqueous solution of potassium carbonate (2 eq) and methyltrioctylammonium chloride (2 eq) are mixed in the round bottom flask, which is subjected to a nitrogen purge to ensure an argon atmosphere. The mixture is heated at 90 °C for 5 h, while stirring continuously. After the starting materials are consumed, pinacolbenzoborane (0.1 eq) is added and stirring is continued for 20 min. Bromobenzene (0.1 eq) is then added and stirring is continued for another 20 min. The mixture is allowed to cool to room temperature, and the product is washed with water. The organic phase is extracted with chloroform, and the organic phases are combined. The mixture is dried over anhydrous magnesium sulfate, and most of the solvent is removed by rotary evaporation. The product is saturated in toluene, and the toluene solution of the product is added dropwise to methanol. The solid fraction is collected by suction filtration, wrapped in filter paper, and extracted with methanol, acetonitrile, and chloroform, respectively, using a Soxhlet extractor. The chloroform phase is concentrated and dried to obtain the fourth intermediate.

[0264] (5) Step 5

[0265] The fourth intermediate (1 eq) is dissolved in anhydrous 1,4-dioxane under an argon atmosphere, and trimethylsilyl bromide (10 eq) is added dropwise. The mixture is stirred at 25 °C for 22 h under an argon atmosphere. Then, methanol is added and stirring is continued for 3 h. Finally, distilled water is added dropwise until the solution becomes opaque, and stirring is continued overnight. If no solid precipitates, the mixture is distilled under reduced pressure until the liquid becomes turbid, and distilled water is added until a solid precipitates. The filtered product is dissolved in tetrahydrofuran (1 mL) and precipitated in n-hexane (15 mL). The precipitate is washed with n-hexane, suction filtered, and dried to obtain the polymer.

[0266] The polymer of Example 6 is synthesized as follows.

[0267] (1) Step 1

[0268] In Step 1, the first intermediate is prepared by a C-N coupling reaction. Specifically, a clean and dry reaction flask is taken, and a magnetic stir bar is added. Then, raw material A (1 eq), raw material B (1 eq), catalyst tris(dibenzylideneacetone)dipalladium (0.02 eq), ligand tri-tert-butylphosphine (0.08 eq), and cesium carbonate (2 eq) are mixed. An appropriate amount of toluene is added, and the flask is subjected to a nitrogen purge three times to ensure an inert atmosphere. The temperature of the reaction flask is increased to 110 °C, and the reaction is continued overnight (about 16 h). The product is extracted with saturated brine and water, and the oil phase is dried over anhydrous magnesium sulfate. The mixture is suction filtered and concentrated. The final product is separated by column chromatography, in which different materials can be separated using different polarities.

[0269] In step 1, the raw material A is The raw material B is The first intermediate product is

[0270] (2) Step 2

[0271] In step 2, the first intermediate product is treated to obtain the second intermediate product, which is 2-(4-(bis(4-bromophenylamino)phenyl)ethyl acetate, and the structural formula of the second intermediate product is

[0272] The specific process in step 2 is as follows:

[0273] Take a clean and dry round-bottom flask, add a magnetic stirrer, the first intermediate product (1 eq), N-bromosuccinimide NBS (2 eq), and then add an appropriate amount of chloroform, react at 0°C for 4h, and the process point plate is detected. After the reaction is complete, add an appropriate amount of water, extract the product with chloroform, dry the oil phase with anhydrous magnesium sulfate, and then perform filtration, concentration, and drying. No further purification is needed.

[0274] (3) Step 3

[0275] Dissolve the second intermediate product (5 mmol) in tetrahydrofuran, and charge and discharge to make it under argon atmosphere, stir at -78°C for 0.5h, then slowly drop butyllithium (1 mL, 2.5M in n-hexane) into the above system dropwise, continue to stir for 1h after dropping, then add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 mmol) dropwise, react at -78°C for 1h, then warm to room temperature, pour the product after reaction into deionized water, then extract with chloroform three times, take the organic phase, combine the organic phases, dry with anhydrous magnesium sulfate, remove the solvent by rotary evaporation, recrystallize the product with isopropyl alcohol, dissolve the precipitate in chloroform, add methanol to precipitate, and the third intermediate product can be obtained.

[0276] (4) Step 4

[0277] Dissolve 3,6-bromo-9H-carbazole (0.6 g, 3.07 mmol) in 1,4-dibromobutane (25 eq), then add tetrabutylammonium bromide (0.2 eq) and 50% aqueous KOH (5 eq); react and stir at 60 °C overnight (a balloon is inserted on the stopper to balance the pressure generated by heating, so as not to pop the stopper); take a sample mixture to perform TLC spotting, using acetone: n-hexane (1:24 by volume) as the developing agent; after determining that the reaction is complete, cool to room temperature. Extract, dry the organic layer with anhydrous Na2SO4, and rotary evaporate to the minimum volume after suction filtration to obtain the crude product; purify the crude product by column chromatography (acetone: hexane = 1:124 by volume), and dry in a vacuum oven at 70 °C overnight to obtain the fourth intermediate product.

[0278] (5) Step 5

[0279] Dissolve the fourth intermediate product (0.8 g, 2.42 mmol) in triethyl phosphite (30 eq), and heat the reaction mixture to reflux overnight; continue to perform TLC spotting, using acetone: n-hexane (6:19 by volume) as the developing agent; evaporate the excess triethyl phosphite using reduced pressure distillation, and obtain the crude product; purify the crude product by column chromatography (acetone / n-hexane = 1:4 by volume), and dry in a vacuum oven at 70 °C overnight to obtain the fifth intermediate product.

[0280] (6) Step 6

[0281] The third intermediate product and the fifth intermediate product are subjected to a polymerization reaction to obtain the sixth intermediate product. Specifically, take a clean and dry reaction bottle, add a magnetic stirrer, then add the third intermediate product (1 eq), the fifth intermediate product (1 eq), tetrakis(triphenylphosphine)palladium (0.02 eq), triphenylphosphine (0.08 eq), 50% aqueous K2CO3 solution (2 eq), tetrabutylammonium bromide (0.01 eq), and an appropriate amount of toluene, and perform three times of air suction to make the bottle an inert atmosphere. Heat the reaction bottle to 110 °C, and react overnight (about 16 h). Extract the obtained product with saturated brine and water, dry the oil phase with anhydrous magnesium sulfate, and perform suction filtration and concentration to obtain the sixth intermediate product. The sixth intermediate product is separated by column chromatography, in which different materials are separated using different polarities.

[0282] (7) Step 7

[0283] The sixth intermediate product is hydrolyzed to obtain a seventh intermediate product. Specifically, a clean and dry round-bottom flask is taken, the sixth intermediate product (1 eq) is dispersed into an appropriate amount of ethanol, an aqueous NaOH solution (2 eq) is added, and the reaction is carried out at 70°C for a period of time. The reaction stopping time is determined according to the point plate condition to ensure complete reaction. After cooling to room temperature, hydrochloric acid is added to adjust the pH. When the pH of the solution reaches 2-3, the dropping is stopped. The product is extracted with dichloromethane, dried with anhydrous magnesium sulfate, and then filtered and concentrated to obtain the seventh intermediate product. The seventh intermediate product is separated by column chromatography, in which different materials are separated by different polarity.

[0284] (8) Step 8

[0285] The seventh intermediate product is hydrolyzed to obtain a polymer. Specifically, a clean and dry round-bottom flask is taken, the seventh intermediate product (1 eq) is dispersed into an appropriate amount of ethanol, an aqueous NaOH solution (2 eq) is added, and the reaction is carried out at 70°C for a period of time. The reaction stopping time is determined according to the point plate condition to ensure complete reaction. After cooling to room temperature, hydrochloric acid is added to adjust the pH. When the pH of the solution reaches 2-3, the dropping is stopped. The product is extracted with dichloromethane, dried with anhydrous magnesium sulfate, and then filtered and concentrated to obtain the polymer. The polymer is separated by column chromatography, in which different materials are separated by different polarity.

[0286] The polymer in Example 7 can be obtained by polymerizing monomer 1 and monomer 2. The structural formula and synthesis method of monomer 1 and monomer 2 are as follows.

[0287] The structural formula of monomer 1 is

[0288] The structural formula of monomer 2 is

[0289] The synthesis method of monomer 1 is as follows.

[0290] (1) Step 1

[0291] In a 100 mL round-bottom flask, 1-bromo-4-(2-bromoethyl)benzene (1 eq) and triethyl phosphite (50 eq) are added; the mixture is heated at 135°C overnight and stirred; after cooling to room temperature, the excess solvent is distilled off; purified by silica gel column chromatography, eluted with pure petroleum ether to obtain [2-(4-bromophenyl)ethyl] diethyl phosphonate, which is vacuum dried at 70°C for 12 h to obtain the first intermediate product.

[0292] (2) Step 2

[0293] N,N'-Bis(4-bromophenyl)benzidine (CAS: 585570-08-7) was mixed with iodobenzene in a 1:1 ratio and reacted to obtain the second intermediate product. Specifically, N,N'-Bis(4-bromophenyl)benzidine (1 eq), iodobenzene (1 eq), catalyst tris(dibenzylideneacetone)dipalladium (0.02 eq), ligand tri-tert-butylphosphine (0.08 eq), cesium carbonate (2 eq) were mixed, and an appropriate amount of toluene was added. The bottle was degassed three times to make the bottle an inert atmosphere. The temperature in the reaction bottle was raised to 110°C, and the reaction was carried out overnight (about 16 h). The product obtained was extracted with saturated brine and water, and the oil phase was dried with anhydrous magnesium sulfate, then filtered and concentrated to obtain the second intermediate product. The second intermediate product was separated by column chromatography, and different materials can be separated by different polarity.

[0294] (3) Step 3

[0295] The second intermediate product and the first intermediate product were reacted to obtain monomer 1. Specifically, the second intermediate product (1 eq), the first intermediate product (1 eq), catalyst tris(dibenzylideneacetone)dipalladium (0.02 eq), ligand tri-tert-butylphosphine (0.08 eq), cesium carbonate (2 eq) were mixed, and an appropriate amount of toluene was added. The bottle was degassed three times to make the bottle an inert atmosphere. The temperature in the reaction bottle was raised to 110°C, and the reaction was carried out overnight (about 16 h). The product obtained was extracted with saturated brine and water, and the oil phase was dried with anhydrous magnesium sulfate, then filtered and concentrated to obtain monomer 1. Monomer 1 was separated by column chromatography, and different materials can be separated by different polarity.

[0296] The synthesis method of monomer 2 is as follows.

[0297] (1) Step 1

[0298] In a 100 mL round-bottom flask, p-bromobromobenzyl (CAS: 589-15-1) (1 eq) and triethyl phosphite (50 eq) were added; the mixture was heated at 135°C overnight and stirred; after cooling to room temperature, the excess solvent was distilled off; purified by silica gel column chromatography, eluted with pure petroleum ether, and dried at 70°C under vacuum for 12 h to obtain the first intermediate product.

[0299] (2) Step 2

[0300] In step 2, monomer 2 was prepared from the first intermediate product according to steps 1 to 3 of the polymer in Example 6.

[0301] (3) Step 3

[0302] In step 3, a polymerization reaction was carried out by using monomer 1 and monomer 2 with reference to step 4 in Example 5; and then, a hydrolysis reaction was carried out with reference to step 5 in Example 5, to obtain the polymer of Example 7.

[0303] Comparative Example 1

[0304] Comparative Example 1 differs from Example 1 in that no passivation layer is provided.

[0305] Comparative Example 2

[0306] Comparative Example 2 differs from Example 1 in that no polymer is used to prepare the passivation layer, but a self-assembled small molecule is used to prepare the passivation layer. The self-assembled small molecule is (4-(3,6-dimethyl-9H-carbazol-9-yl)butyl)phosphonic acid, CAS: 2747959-96-0.

[0307] The test results of the photovoltaic modules of the examples and comparative examples are shown in Table 1. In Table 1, the energy level is the HOMO energy level, and the passivation layer energy level-perovskite layer energy level is the value of the HOMO energy level of the passivation layer minus the HOMO energy level of the perovskite layer. Table 1 Test results of examples and comparative examples

[0308] The stability of the perovskite battery in the examples of the present application can be embodied by the normalized efficiency. The higher the normalized efficiency and the less the normalized efficiency decays as the use time increases, the higher the stability of the perovskite battery.

[0309] As shown in Examples 1-7 and Comparative Example 1, by providing a passivation layer between the hole transport layer and the perovskite layer, the stability of the perovskite battery can be improved, and the service life of the perovskite battery can be improved. As shown in Examples 1-7 and Comparative Example 2, by selecting the polymer in the examples of the present application as the material of the passivation layer, the stability of the perovskite battery can be further improved, and the service life of the perovskite battery can be further improved.

[0310] As shown in Examples 1-7, a variety of different polymers can be selected as the material of the passivation layer, which is beneficial to improve the stability of the perovskite battery.

[0311] As shown in Examples 1-7, the energy level difference between the passivation layer and the perovskite layer is small, the energy levels between the passivation layer and the perovskite layer are matched, and the stability of the perovskite battery is also high. As shown in Examples 3, 5, 6, and 7, the polymer includes anchor groups such as carboxyl groups and phosphoric acid groups, which is beneficial to improve the stability of the perovskite battery.

[0312] The following briefly introduces the test methods of the physicochemical parameters and performance parameters involved in the examples of the present application. It should be understood that the following test methods are only examples, and other test methods known in the art can also be used for testing.

[0313] 1. Test of photoelectric conversion efficiency

[0314] At room temperature and atmospheric pressure, the test is performed in accordance with the national standard IEC61215 using a standard light source of AM1.5G simulated sunlight source. The intensity of the light is corrected using a crystalline silicon solar cell to reach a solar intensity. The volt-ampere characteristic curve of the solar cell under the irradiation of the light source is measured using a four-channel digital source meter (Keithley 2440) to obtain the open-circuit voltage Voc, short-circuit current density Jsc, fill factor FF, and energy conversion efficiency Eff.

[0315] 2. Test of stability

[0316] After the test, the perovskite cell is placed in an atmospheric environment (relative humidity of 65-85%, ambient temperature of about 15-40°C) and placed in the light for a period of time. The energy conversion efficiency is tested again (each test is stopped until there is no hysteresis phenomenon in the positive and negative scans, and the energy conversion efficiency is recorded). The ratio of the solar cell efficiency after the corresponding time of placement to the initial efficiency is calculated as the normalized efficiency of the solar cell after the corresponding time of placement.

[0317] The normalized efficiency = retested efficiency / initial efficiency x 100%, wherein the retested efficiency is the efficiency measured after the corresponding time of placement (e.g. 10 days or 30 days), and the initial efficiency is the efficiency measured after 0 days of placement.

[0318] 3. Test of energy band distribution of perovskite cell

[0319] The energy band distribution of the electron transport layer, hole transport layer and perovskite absorption layer obtained is tested using an ultraviolet photoelectron spectrometer (UPS) and an X-ray photoelectron spectrometer (XPS). The test conditions are room temperature, atmospheric pressure and atmospheric environment, and a He I lamp (21.2 eV) is used as the laser source. Exemplarily, the UPS and XPS equipment model is Escalab 250Xi (Thermo Scientific).

[0320] 4. Test of polymer

[0321] As an example, nuclear magnetic resonance spectroscopy (NMR) and liquid chromatography-mass spectrometry (HPLC-MS) are used to determine the molecular structure of the monomer or polymer.

[0322] As another example, time-of-flight secondary ion mass spectrometry (ToF-SIMS) can be used to test the polymer in the passivation layer, and X-ray photoelectron spectroscopy (XPS) testing, nuclear magnetic resonance spectroscopy testing and Fourier infrared spectrometer testing can be used to determine the groups included in the polymer.

[0323] The polymerization degree and the molecular weight of the polymer were measured by gel permeation chromatography (GPC).

[0324] 5. Test of thickness of passivation layer

[0325] The thickness of the passivation layer was measured by time-of-flight secondary ion mass spectrometer (ToF-SIMS).

[0326] Note that the present application is not limited to the above-described embodiments. The above-described embodiments are merely examples, and embodiments having substantially the same configuration and exerting the same effects as the technical idea of the present application are included in the technical scope of the present application. Furthermore, other modes constructed by applying various modifications to the embodiments or combining part of the configurations of the embodiments that a person skilled in the art can conceive without departing from the gist of the present application are also included in the scope of the present application.

Claims

1. A perovskite cell, characterized in that, Comprise: a hole transport layer and a perovskite layer disposed in sequence along a thickness direction of the perovskite cell, the hole transport layer comprising a polymer, the polymer comprising a first repeating unit and a second repeating unit, at least one of the first repeating unit and the second repeating unit comprising a hole transport material.

2. The perovskite cell according to claim 1, characterized in that, The first repeating unit is different from the second repeating unit.

3. The perovskite cell according to claim 1 or 2, characterized in that, In the first repeating unit, the hole transport material comprises a substituted or unsubstituted anilino group.

4. The perovskite cell according to claim 3, characterized in that, The first repeating unit comprises a substituted or unsubstituted triphenylamine group.

5. The perovskite cell according to claim 4, characterized in that, the structural formula of the first repeating unit satisfies: In formula (I), R5 comprises at least one of H, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted benzene ring, a substituted or unsubstituted heterocyclic ring, or a substituted or unsubstituted benzo-heterocyclic ring; R6includes H, a benzene ring, a C1-C10 alkyl group, or an acid group, the acid group including at least one of the following groups:

6. The perovskite cell according to claim 5, characterized in that, The structural formula of the first repeating unit further comprises R1, R2, R3, and R4, wherein R1 and R2 are located at any position of a first benzene ring and a second benzene ring of the first repeating unit, respectively, R3 and R4 are located at any position of a third benzene ring of the first repeating unit, the first benzene ring and the second benzene ring are benzene rings of the first repeating unit which are not provided with R5, and the third benzene ring is a benzene ring of the first repeating unit which is provided with R5; R1-R4 each independently comprise at least one of H, a substituted or unsubstituted C1-C8 alkyl group, a methoxy group, a halogen, or a methylthio group.

7. The perovskite cell according to claim 5 or 6, characterized in that, R5 comprises a substituted or unsubstituted C1-C10 alkyl group.

8. The perovskite cell according to any one of claims 5-7, characterized in that, R6includes at least one of 9. The perovskite cell according to any one of claims 1-8, wherein, The second repeating unit comprises at least one of a substituted or unsubstituted anilino group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted thienazinyl group, a substituted or unsubstituted acridinyl group, or a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted thiophene group, or a substituted or unsubstituted benzothiophene group.

10. The perovskite cell according to claim 9, characterized in that, The structural formula of the second repeating unit satisfies formula (II-1): -M-Y-; In formula (II-1), M comprises at least one of a substituted or unsubstituted anilino group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted thienazinyl group, a substituted or unsubstituted acridinyl group, or a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted thiophene group, or a substituted or unsubstituted benzothiophene group; Y comprises at least one of the following groups:

11. The perovskite cell according to claim 10, characterized in that, The structural formula of the second repeating unit satisfies formula (II-2): -M-L-Y-; In formula (II-2), L comprises at least one of H, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted benzene ring, a substituted or unsubstituted heterocyclic ring, or a substituted or unsubstituted benzo-heterocyclic ring.

12. The perovskite cell according to claim 10 or 11, characterized in that, The second repeating unit comprises at least one of the following structures: X comprises at least one of H, a substituted or unsubstituted C1-C8 alkyl group, a methoxy group, a halogen, or a methylthio group, and * indicates a connection site of M and L or Y.

13. The perovskite cell according to any one of claims 1-12, wherein, The structural formula of the polymer satisfies at least one of the following: Wherein, n is 2-50.

14. The perovskite cell of claim 13, wherein, The polymer has a polymerization degree of 5-30.

15. The perovskite cell according to any one of claims 1-14, wherein, The polymer has a weight average molecular weight of 1000 Da-25000 Da.

16. The perovskite cell of claim 15, wherein, The polymer has a weight average molecular weight of 1000 Da-10000 Da.

17. The perovskite cell according to any one of claims 1-16, wherein, The perovskite cell further comprises a first electrode layer, and the hole transport layer is located between the first electrode layer and the perovskite layer along a thickness direction of the perovskite cell.

18. The perovskite cell of claim 17, wherein, The hole transport layer comprises a passivation layer comprising the polymer, the passivation layer being located between the first electrode layer and the perovskite layer along a thickness direction of the perovskite cell.

19. The perovskite cell of claim 18, wherein, The hole transport layer comprises a hole transport base layer and the passivation layer, the passivation layer being located between the hole transport base layer and the perovskite layer along a thickness direction of the perovskite cell, the passivation layer comprising the polymer.

20. The perovskite cell according to claim 18 or 19, characterized in that, The difference between the HOMO energy level of the passivation layer and the HOMO energy level of the perovskite layer is -1.0 eV to 1.0 eV.

21. The perovskite cell of claim 20, wherein, The difference between the HOMO energy level of the passivation layer and the HOMO energy level of the perovskite layer is -0.5 eV to 0.5 eV.

22. The perovskite cell according to any one of claims 18-21, wherein, The HOMO energy level of the passivation layer is greater than or equal to the HOMO energy level of the perovskite layer.

23. The perovskite cell according to any one of claims 18-22, wherein, The HOMO energy level of the passivation layer is -5.8 eV to -4.8 eV.

24. The perovskite cell of any one of claims 18-23, wherein, The thickness d of the passivation layer is 1 nm to 20 nm.

25. The perovskite cell of any one of claims 1-24, wherein, The perovskite cell comprises a first electrode layer, the hole transport layer, the perovskite layer, an electron transport layer, and a second electrode layer arranged in sequence along an incident direction of a light source, the incident direction of the light source being parallel to a thickness direction of the perovskite cell.

26. The perovskite cell of any one of claims 1-24, wherein, The perovskite cell comprises a first electrode layer, an electron transport layer, the perovskite layer, the hole transport layer, and a second electrode layer arranged in sequence along an incident direction of a light source, the incident direction of the light source being parallel to a thickness direction of the perovskite cell.

27. The perovskite cell according to claim 25 or 26, wherein The first electrode layer comprises at least one of an organic conductive material, an inorganic conductive material, and an organic-inorganic hybrid conductive material, the second electrode layer comprises at least one of an organic conductive material, an inorganic conductive material, and an organic-inorganic hybrid conductive material, the inorganic conductive material comprises one or more of a carbon material, a metal material and an alloy thereof, and a transparent conductive metal oxide, the organic conductive material comprises one or more of polyacrylic acid, polyimide, polyaniline, polythiophene and derivatives thereof, and polypyrrole, and at least one of the first electrode layer and the second electrode layer is a light-transmitting electrode layer.

28. The perovskite cell of claim 27, wherein, The first electrode layer comprises a transparent conductive metal oxide, and the second electrode layer comprises a metal.

29. The perovskite cell of claim 28, wherein, The first electrode layer comprises at least one of ITO, FTO, BZO, AZO, IZO, GZO, or IWO, and the second electrode layer comprises at least one of Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, or Mg.

30. A photovoltaic module, characterized in that, The perovskite cell comprises: The perovskite cell according to any one of claims 1-29.

31. The photovoltaic module of claim 30, wherein, The photovoltaic module further comprises: A substrate layer and an encapsulation layer, the perovskite cell being arranged on at least one side surface of the substrate layer, and the encapsulation layer being used for encapsulating the perovskite cell.

32. An electrical device, comprising: The photovoltaic module comprises: The photovoltaic module according to claim 30 or 31.

33. A power generation device, comprising: The photovoltaic module comprises: The polymer comprises a first repeating unit and a second repeating unit, at least one of the first repeating unit and the second repeating unit comprising a hole transport material.

34. A polymer, characterized in that, Wherein, n is 2-50.

35. The polymer of claim 34, wherein, The structural formula of the polymer satisfies at least one of the following: The photovoltaic module comprises:

36. A method of making a polymer, characterized by, ​ A first repeating unit and a second repeating unit are provided, at least one of the first repeating unit and the second repeating unit comprising a hole transport material; The first repeating unit and the second repeating unit are subjected to a polymerization reaction to obtain the polymer.

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