Perovskite precursor solution, perovskite thin film, perovskite battery and electric device

Abstract

The invention provides a perovskite precursor solution, a perovskite thin film, a perovskite battery and an electric device. The perovskite precursor solution comprises a perovskite precursor material, a solvent and an additive; the structure of the additive contains a weak reducibility group, and the weak reducibility group has reducibility to 0 valence corresponding to monovalent anions in the perovskite type metal halide in a solution and is inert to divalent cations in the perovskite type metal halide; the additive is halogen acid salt.

Description

Perovskite precursor solution, perovskite film, perovskite battery and electrical device Technical Field

[0001] The present application relates to the technical field of solar cells, and in particular to a perovskite precursor solution, a perovskite film, a perovskite cell and an electrical device. Background Art

[0002] The statements herein merely provide background information related to the present application and do not necessarily constitute prior art.

[0003] Perovskite solar cells (PSCs) are devices that convert solar energy into electrical energy using the photoelectric conversion mechanism of perovskite crystal materials. They are currently the third generation of solar cells and have been extensively researched in recent years due to their high photoelectric conversion efficiency, simple manufacturing process, and low production cost. Despite this, the commercialization and large-scale application of PSCs is still some distance away. Among them, extending the service life of PSCs is a key issue that needs to be addressed.

[0004] Summary of the Invention

[0005] In view of the above problems, the present application provides a perovskite precursor solution, a perovskite film, a perovskite battery and an electrical device. The perovskite precursor solution has good stability, the prepared perovskite film has few defects, and the service life of the perovskite battery can be improved.

[0006] In a first aspect, the present application provides a perovskite precursor solution comprising a perovskite precursor material, a solvent and an additive; wherein the perovskite precursor material comprises a perovskite-type metal halide; the structure of the additive contains a weak reducing group, which has a reducing property to the 0-valent state corresponding to the monovalent anion in the perovskite-type metal halide and is inert to the divalent cation in the perovskite-type metal halide; the additive is a hydrohalide.

[0007] By adding an organic compound hydrohalide salt additive containing a weak reducing group (referred to as the first additive) to the perovskite precursor solution, for the halide metal portion BX2 in the main component ABX3 in the perovskite precursor solution and the perovskite film, on the one hand, the weak reducing group pair can reduce X2 (zero-valent X) to X - , increasing the storage time of the perovskite precursor solution, that is, it has a reducing property on the 0-valence state corresponding to the monovalent anion in the perovskite metal halide; on the other hand, its weak reducing property will not 2+ Restore to B 0, that is, it is inert to the divalent cations in the perovskite metal halide; on the other hand, the additive can participate in the crystallization reaction and be evenly dispersed in the perovskite film, acting as a sacrificial agent to extend the service life of the perovskite device; on the other hand, it can inhibit B 0 The formation of X2 reduces defects at the interface and improves the performance of perovskite devices; by forming hydrohalides, the additives can be promoted to dissolve better in the perovskite precursor solution and be more evenly distributed in the perovskite film. Among them, the perovskite precursor solution is generally a colloidal solution, and the BX2 in the solution is mostly distributed in the system in a state of complexation with the solvent. The weak reducing groups involved in this application are easy to form hydrogen bonds with the perovskite colloidal solution and can be evenly distributed in the colloidal solution; when the crystallization reaction occurs, such additives can have a stronger surface tension on the lower surface (the surface used for coating) when the solvent is quenched, and can form crystal nucleus sites, so that the perovskite is expanded at such sites, promoting crystallization. In addition, for perovskite ABX3, taking FAPbI3 as an example, because it is susceptible to the effects of oxygen, moisture, light and heat, the following equilibrium formula exists: Among them, I2 is easy to sublime and leave the system, causing the entire equilibrium to move to the right, resulting in perovskite degradation; when weak reducing property exists in the system, the 0-valent I2 can be reduced to I - , so that the entire reaction proceeds to the right, which can inhibit the degradation of perovskite, and the weak reducing group itself will not react with Pb 2+ Reacts (shown as Pb 2+ When the weak reducing group is consumed, the corresponding product cannot be regenerated to its original state, so it is a consumable group and a sacrificial agent.

[0008] In some embodiments, the weak reducing group comprises one or more of the following groups: -NHNH-, -SS-, -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group and hydroxynaphthyl group;

[0009] Optionally, the weak reducing group is selected from the group consisting of -NHNH-, -SS-, -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group and hydroxynaphthyl group.

[0010] In some embodiments, in one molecule of the additive, the number of the weak reducing groups is 1 or more;

[0011] Optionally, in one molecule of the additive, the number of the weak reducing groups is an integer selected from 1 to 10; further optionally, the number of the weak reducing groups is 1, 2, 3, 4 or 5; further optionally, the number of the weak reducing groups is 1, 2 or 3; further optionally, the number of the weak reducing groups is 1 or 2;

[0012] Optionally, in one molecule of the additive, the type of the weak reducing group is one or more; further optionally, the type of the weak reducing group is 1, 2, 3 or more.

[0013] In some embodiments, in one molecule of the additive, the number of hydrohalic acid molecules is 1 or more;

[0014] Optionally, in one molecule of the additive, the number of hydrohalic acid molecules is an integer selected from 1 to 10; further optionally, the number of hydrohalic acid molecules is 1, 2, 3, 4 or 5; further optionally, the number of hydrohalic acid molecules is 1 or 2.

[0015] In some embodiments, the halogen in the hydrohalide salt includes one or more of F, Cl, Br and I;

[0016] Optionally, any halogen in the hydrohalide salt is independently F, Cl, Br or I;

[0017] Further optionally, the hydrohalide salt is hydrochloride.

[0018] In some embodiments, the perovskite precursor solution satisfies one or more of the following characteristics:

[0019] The molecular weight of the additive is less than 1000Da; optionally, the molecular weight of the additive is less than or equal to 500Da; further optionally, the molecular weight of the additive is less than or equal to 400Da; further optionally, the molecular weight of the additive is less than or equal to 350Da; further optionally, the molecular weight of the additive is less than or equal to 300Da; further optionally, the molecular weight of the additive is 150 to 300Da;

[0020] The number of carbon atoms in the additive is 2 to 40; further optionally, the number of carbon atoms in the additive is 2 to 25; further optionally, the number of carbon atoms in the additive is 2 to 20; further optionally, the number of carbon atoms in the additive is 2 to 18; further optionally, the number of carbon atoms in the additive is 2 to 15; further optionally, the number of carbon atoms in the additive is 2 to 12; further optionally, the number of carbon atoms in the additive is 2 to 10; further optionally, the number of carbon atoms in the additive is 2 to 8; further optionally, the number of carbon atoms in the additive is 2 to 6;

[0021] The number of non-hydrogen atoms in the additive is 8 to 40; further optionally, the number of non-hydrogen atoms in the additive is 10 to 30; further optionally, the number of non-hydrogen atoms in the additive is 10 to 25; further optionally, the number of non-hydrogen atoms in the additive is 10 to 20; further optionally, the number of non-hydrogen atoms in the additive is 10 to 18.

[0022] The type and quantity of the weak reducing groups in the aforementioned additive (first additive), the type and quantity of the hydrohalic acid molecules, and the molecular weight of the additive (wherein the molecular weight can be indirectly adjusted by adjusting the number of carbon atoms or the number of non-hydrogen atoms) can be finely adjusted to better match with the perovskite precursor material, better reduce the defects of the perovskite film, and better improve the service life of the perovskite battery.

[0023] In some embodiments, the additive has a structure shown in formula (1); L(Z1-R 11 ) p1 ·nHZ (1)

[0024] In formula (1), p1 is 0 or a positive integer; Z is the halogen in the hydrohalide salt, and n is the number of hydrohalic acid molecules in the hydrohalide salt;

[0025] Any R 11 are independently the weak reducing groups and have a valence of 1, optionally, any one of R 11 are independently -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group or hydroxynaphthyl group, further optionally, any one of R 11 are independently -NHNH2, sulfinic acid or phosphinic acid;

[0026] When p1 is 0, the additive is an organic compound hydrohalide salt containing at least one of -NHNH- and -SS-;

[0027] When p1 is a positive integer, L is an alkyl group, heteroalkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, substituted alkyl group, substituted heteroalkyl group, substituted cycloalkyl group, substituted heterocycloalkyl group, substituted aryl group or substituted heteroaryl group with a valence of p1; when L contains a heteroatom, any heteroatom in L is independently a non-carbon, non-hydrogen atom, and is further independently selected from any one of N, S, P, O and B;

[0028] L and all Z1 contain p2 divalent groups selected from the group consisting of -NH-NH- and -SS-, p2 is 0 or a positive integer; (p1+p2)≥1;

[0029] Z1 is a chemical bond, a carbonyl group, -CH2-, -CH(Q1)- or -(Q2)C(Q3)-, wherein Q1, Q2 and Q3 are each independently selected from the group consisting of an alkyl group, a heteroalkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, a substituted alkyl group, a substituted heteroalkyl group, a substituted cycloalkyl group, a substituted heterocycloalkyl group, a substituted aryl group and a substituted heteroaryl group; when Z1 contains a heteroatom, any heteroatom in Z1 is independently a non-carbon, non-hydrogen atom, and is further independently selected from any one of N, S, P, O and B; optionally, Z1 is -CH2-, -CH(Q1)- or -(Q2)C(Q3)-;

[0030] Any R 11 Independently directly bonded to a carbon atom in Z1 or L;

[0031] In formula (1), the alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl group in any one of the substituted alkyl, substituted heteroalkyl, substituted heterocycloalkyl, substituted aryl or substituted heteroaryl contained in L, Z1, Q1, Q2 or Q3 is independently substituted by one or more groups selected from the following group G1: alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, -CN, hydrazine, sulfinic acid, phosphinic acid, -OH, -NH2, -COOH, sulfonic acid, phosphonic acid, boric acid and halogen.

[0032] In some embodiments, the additive satisfies any one or more of the following characteristics:

[0033] L is a chain structure; optionally, L is C 2-20 Chain structure; further optionally, L is C 2-18 Chain structure; further optionally, L is C 2-15 Chain structure; further optionally, L is C 2-12 Chain structure; further optionally, L is C 2-10 Chain structure; further optionally, L is C 2-8 Chain structure;

[0034] L is a ring-containing structure, and the number of ring atoms in L is 3 to 25; alternatively, 3 to 20; further alternatively, 3 to 18; further alternatively, 5 to 18; further alternatively, 5 to 15; further alternatively, 5 to 12; further alternatively, 5, 6, 10, 11 or 12; further alternatively, 6, 10, 11 or 12;

[0035] The number of carbon atoms in L is 2 to 30; alternatively, 2 to 25; further alternatively, 2 to 20; further alternatively, 2 to 18; further alternatively, 2 to 15; further alternatively, 2 to 12; further alternatively, 2 to 10; further alternatively, 2 to 8;

[0036] The number of non-hydrogen atoms in L is 2 to 35; further optionally, the number of non-hydrogen atoms in L is 2 to 30; further optionally, the number of non-hydrogen atoms in the additive is 2 to 25; further optionally, the number of non-hydrogen atoms in the additive is 2 to 20; further optionally, the number of non-hydrogen atoms in the additive is 2 to 18;

[0037] L is a ring-containing structure, and the ring in L is an aromatic ring, an aliphatic ring, or a combination thereof; optionally, the ring in L includes an aromatic ring; further optionally, the number of carbon atoms in L is 3 to 40; further optionally, the number of carbon atoms in L is 3 to 30; further optionally, the number of carbon atoms in L is 3 to 25; further optionally, 3 to 20; further optionally, 3 to 18; further optionally, 5 to 18; further optionally, 5 to 15; further optionally, 5 to 12; further optionally, 5, 6, 10, 11, or 12; further optionally, 6, 10, 11, or 12;

[0038] L is a ring structure containing 2 to 40 carbon atoms; optionally, the number of carbon atoms in L is 3 to 30; further optionally, 3 to 25; further optionally, 3 to 20; further optionally, 3 to 18; further optionally, 4 to 18;

[0039] L is an aliphatic structure; optionally, the number of carbon atoms in L is 2 to 25; further optionally, 2 to 20; further optionally, 2 to 18; further optionally, 2 to 15; further optionally, 2 to 12; further optionally, 2 to 10; further optionally, 2 to 8;

[0040] L is an aromatic structure; optionally, L comprises one or more of aryl, heteroaryl, substituted aryl and substituted heteroaryl; further optionally, L comprises C 6-20 Aryl, C 4-20 Heteroaryl, substituted C 6-20 Aryl and substituted C 4-20 One or more of heteroaryl; further optionally, L comprises C 6-10 Aryl, C 4-10 Heteroaryl, substituted C 6-10 Aryl and substituted C 4-10 one or more of heteroaryl groups;

[0041] p1 is 0, and the additive is a C containing at least one of -NHNH- and -SS- 2-40 Compound hydrohalide;

[0042] p1 is a positive integer selected from 1 to 10; optionally, p1 is 1, 2, 3, 4 or 5; optionally, p1 is 1 or 2;

[0043] p1 is a positive integer, L is the C in p1 valence state 2-18 Alkyl, C 2-18 Heteroalkyl, C 3-20 Cycloalkyl, C 3-20 Heterocycloalkyl, C 6-20 Aryl, C 3-20 Heteroaryl, substituted C 2-18 Alkyl, substituted C 2-18 Heteroalkyl, substituted C 3-20 Cycloalkyl, substituted C 3-20 Heterocycloalkyl, substituted C 6-20 Aryl or substituted C 3-20 Heteroaryl; optionally, L is a C in p1 valence state 2-12 Alkyl, C 2-12 Heteroalkyl, C 3-12 Cycloalkyl, C 3-12 Heterocycloalkyl, C 6-15 Aryl, C 3-15 Heteroaryl, substituted C 2-12 Alkyl, substituted C 2-12 Heteroalkyl, substituted C 3-12 Cycloalkyl, substituted C 3-12 Heterocycloalkyl, substituted C 6-15 Aryl or substituted C 3-15 Heteroaryl; further optionally, L is a C in p1 valence state 2-10 Alkyl, C 2-10 Heteroalkyl, C 5-10 Cycloalkyl, C 4-10 Heterocycloalkyl, C 6-10 Aryl, C 3-10 Heteroaryl, substituted C 2-10 Alkyl, substituted C 2-10 Heteroalkyl, substituted C 5-10 Cycloalkyl, substituted C 4-10 Heterocycloalkyl, substituted C 6-10 Aryl or substituted C 3-10 Heteroaryl; further optionally, L is a linear structure; wherein, when L contains a heteroatom, any heteroatom in L is independently a non-carbon, non-hydrogen atom, and is further independently selected from any one of N, S, P, O and B;

[0044] Q1, Q2 and Q3 are each independently selected from the group consisting of: 1-6 Alkyl, C 1-6 Heteroalkyl, C 3-8 Cycloalkyl, C 3-8 Heterocycloalkyl, C 6-12 Aryl, C 3-11 Heteroaryl, substituted C 1-6 Alkyl, substituted C 1-6 Heteroalkyl, substituted C 3-8 Cycloalkyl, substituted C 3-8 Heterocycloalkyl, substituted C 6-12 Aryl and substituted C 3-11 Heteroaryl; optionally, Q1, Q2 and Q3 are each independently selected from the group consisting of: C 1-3 Alkyl, C 1-3 Heteroalkyl, C 3-6 Cycloalkyl, C 3-6 Heterocycloalkyl, C 6-10 Aryl, C 3-9 Heteroaryl, substituted C 1-3 Alkyl, substituted C 1-3 Heteroalkyl, substituted C 3-6 Cycloalkyl, substituted C 3-6 Heterocycloalkyl, substituted C 6-10 Aryl and substituted C 3-9 Heteroaryl; further optionally, Q1, Q2 and Q3 are each independently selected from the group consisting of: methyl, methoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, piperidinyl (optionally ), piperazinyl (optionally )phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl and N 1～6 Azanaphthyl, and any substituted form of the foregoing groups; wherein, when Q1, Q2 or Q3 is any substituted form of the foregoing, it is independently substituted by one or more (optionally, 1 or 2 to 5, further optionally, 1, 2 or 3) selected from the following group G1 a Substituted by groups in: methyl, cyclopentyl, phenyl, benzyl, methylphenyl, -Ph-Ph, N 1～2 Aza-heterocycloalkyl (optionally a single aza-C 3-8 Cycloalkyl or diazaC 3- 8-cycloalkyl, further optionally mono-azetidinyl, piperidinyl or piperazinyl, further optionally mono-azetidinyl, further optionally mono-azetidinyl ), -CN, hydrazino, sulfinic acid, phosphinic acid, -OH, -NH2, -COOH, sulfonic acid, phosphonic acid, boric acid and halogen (optionally one or more of F, Cl, Br and I);

[0045] The group G1 includes an alkyl group (optionally C 1-8 Alkyl, further optionally C 1-6 Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 Alkyl, further optionally methyl), heteroalkyl (optionally alkoxy or secondary amino, further optionally C 1-8 Alkoxy or C 1-8 Alkylamino, further optionally C 1-6 Alkoxy or C 1-6 Alkylamino, further optionally C 1-4 Alkoxy or C 1-4 Alkylamino, further optionally C 1-3 Alkoxy or C 1-3 Alkylamino, further optionally -NHCH3 or -NHCH2CH3, further optionally -NHCH3), cycloalkyl (optionally C 3-8 Cycloalkyl, further optionally C 3-6 Cycloalkyl, further optionally cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), heterocycloalkyl (optionally 3-8 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-6 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-4 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally piperidinyl, piperazinyl or monoazetidinyl, further optionally ), aryl (optionally C 6-12 Aryl, further optionally C 6-10 aryl, which may be phenyl, naphthyl or biphenyl), heteroaryl (a 6- to 12-membered aryl containing 1 to 6 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 to 4 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 to 3 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 or 2 nitrogen atoms on the ring, which may be further N 1-2 azaphenyl, further optionally monoazaphenyl or diazaphenyl, further optionally pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl), -CN, hydrazine, sulfinic acid, phosphinic acid, -OH, -NH2, -COOH, sulfonic acid, phosphonic acid, boric acid and halogen (optionally one or more of F, Cl, Br and I);

[0046] Z1 is a chemical bond, -CH2-, -CH(Q1)- or -(Q2)C(Q3)-.

[0047] In some embodiments, the additive satisfies any one or more of the following characteristics:

[0048] L is an aliphatic structure and Z1 is a chemical bond or a carbonyl group (Z1 can be optionally a chemical bond);

[0049] L is an aromatic structure and Z1 is not a chemical bond;

[0050] L is phenyl, naphthyl, cyclopentyl, cyclohexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, heptadecyl, n-octadecyl, pyridyl, piperidyl, piperazinyl, N-methylpiperidyl, methylphenyl, dimethylphenyl, biphenyl, naphthyl-substituted phenyl, aminophenyl, C 2-18 alkyl with one or more sulfonic acid group substituents (optionally ethyl with a single sulfonic acid group substituent, further optionally 2-sulfoethyl), C 2-18 alkyl with one or more NH2 substituents (optionally C 2-18 alkyl with one -NH2 substituent, further optionally aminobutyl, still further optionally 4-aminobutyl), C 2-18 alkyl with one or more -(O=)P(OH)2 substituents (optionally C 2-12 alkyl with one -(O=)P(OH)2 substituent, further optionally phosphonopropyl, still further optionally 3-phosphonopropyl), C 02 alkyl with one or more -(O=)PR 2-18 (OH) substituents (optionally C 02 alkyl with one -(O=)PR 2-12 (OH) substituent, optionally C 02 alkyl with one -(O=)PR 2-8 (OH) substituent, still further optionally (CH3)(OH)(R 02 )P(=O)-C 2～8 alkylene-, still further optionally (CH3)(OH)(R 02 )P(=O)-(CH2) 2～8 -, still further optionally (CH3)(OH)(R 02 )P(=O)-(CH2)3-) and R 02 is alkyl (optionally C 1-6 alkyl, further optionally C 1-3 alkyl, still further optionally methyl), C 02 alkyl with one or more -(O=)PR 2-18 (OH) and one or more NH2- substituents (optionally C 02 alkyl with one -(O=)PR 2-18 (OH) and one NH2- substituent, further optionally C 02(OH) and one NH2-substituted C 2-12 Alkyl, further optionally 1 -(O=)PR 02 (OH) and one NH2-substituted C 2-8 Alkyl, further optionally (CH3)(OH)(R 02 )P(=O)-CH2CH2CH(NH2)-), sulfonic acid phenyl, carboxylic acid phenyl, phosphonic acid phenyl and boric acid phenyl;

[0051] Z1 is any of the following divalent groups: methylene, -CH(CH3)-, -CH(benzyl)-, -CH(cyclopentyl)-, -CH(-Ph-Ph)-, -CH(phenyl), -CH(-Ph-CH3)-, and

[0052] The group G1 is a group G2 comprising the following groups: alkyl (optionally C 1-8 Alkyl, further optionally C 1-6 Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 Alkyl, further optionally methyl), heteroalkyl (optionally alkoxy or secondary amino, further optionally C 1-8 Alkoxy or C 1-8 Alkylamino, further optionally C 1-6 Alkoxy or C 1-6 Alkylamino, further optionally C 1-4 Alkoxy or C 1-4 Alkylamino, further optionally C 1-3 Alkoxy or C 1-3 Alkylamino, further optionally -NHCH3 or -NHCH2CH3, further optionally -NHCH3), cycloalkyl (optionally C 3-8 Cycloalkyl, further optionally C 3-6 Cycloalkyl, further optionally cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), heterocycloalkyl (optionally 3-8 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-6 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-4 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally piperidinyl, piperazinyl or monoazetidinyl, further optionally ), aryl (optionally C 6-12 Aryl, further optionally C 6-10Aryl, which may be phenyl, naphthyl or biphenyl) and heteroaryl (a 6- to 12-membered aryl containing 1 to 6 nitrogen atoms on the ring, further a 6- to 12-membered aryl containing 1 to 4 nitrogen atoms on the ring, further a 6- to 12-membered aryl containing 1 to 3 nitrogen atoms on the ring, further a 6- to 12-membered aryl containing 1 or 2 nitrogen atoms on the ring, further N 1-2 Azaphenyl, further optionally monoazaphenyl or diazaphenyl, further optionally pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl); optionally, the group G1 is a group G1 including the following groups b : methyl, cyclopentyl, cyclopentylmethyl, phenyl, benzyl, biphenyl, methylphenyl, piperidinyl (optional ), piperazinyl (optionally ) and monoazetidinyl (optionally ); Optionally, the group G1 includes methyl, cyclopentyl, phenyl, benzyl, biphenyl, methylphenyl, piperidinyl (optionally ) and monoazetidinyl (optionally ).

[0053] This application relates to the weak reducing groups (which can be recorded as R 01 ) can be a monovalent group R 11 , such as -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl or hydroxynaphthyl group, or a divalent group such as -NH-NH-, -SS-, etc., two different valence R 01 It can be any one of the above or a combination of the two. 01 Existing at the end group, it encounters relatively less steric hindrance when interacting with other components in the precursor solution. 01 It also acts as a connecting base, which can flexibly adjust the position in the molecule to regulate steric hindrance, thereby adjusting R 01 The additive contains a weak reducing group R 01 In addition to the hydrohalic acid molecule HZ, it also includes the main part L(Z1-) p1 The main part is an aromatic or aliphatic group, which can generate a certain surface tension on the lower surface during solvent quenching, promoting the formation of crystal nucleation sites and the progress of crystallization reaction. Z1 can be absent; Z1 can also be a spacer group with a length of 1 spacer atom. In this case, the structural characteristics of Z1 can be used to adjust the connected R 11 For example, when L is a benzene ring, R 11When it is a hydrazine group -NHNH2, Z1 is -CH2-, -CH(Q1)- or -(Q2)C(Q3)- (further such as -CH2-), which is beneficial to improving the stability of the perovskite precursor solution and thus extending the shelf life of the precursor.

[0054] In some embodiments, p1 is a positive integer, R 11 is -NHNH2, optionally, at least one Z1 is not a chemical bond.

[0055] In some embodiments, p1 is a positive integer, L is an aromatic group, Z1 is directly connected to the aromatic ring in L, and the corresponding R 11 is -NHNH2, Z1 is not a chemical bond; optionally, R 11 is -CH2-, -CH(Q1)- or -(Q2)C(Q3)-;

[0056] Optionally, Q1, Q2 and Q3 are each independently selected from the following groups: alkyl, aralkyl, heteroaralkyl, substituted alkyl, substituted aralkyl and substituted heteroaralkyl; wherein, when Q1, Q2 or Q3 is any of the substituted forms mentioned above, it is independently substituted by one or more groups selected from the group G1.

[0057] In some embodiments, L is aryl, heteroaryl, substituted aryl, or substituted heteroaryl;

[0058] Optionally, L is C 6-20 Aryl, C 4-20 Heteroaryl, substituted C 6-20 Aryl and substituted C 4-20 Any of heteroaryl; further optionally, L is C 6-10 Aryl, C 4-10 Heteroaryl, substituted C 6-10 Aryl and substituted C 4-10 any of heteroaryl groups;

[0059] Wherein, when L is any of the substituted forms mentioned above, it is independently substituted by one or more groups selected from the group G1.

[0060] Compared to directly attaching a hydrazine group to an aromatic ring (such as a benzene ring), a spacer group (such as an alkylene or substituted alkylene group, further exemplified by -CH2-, -CH(Q1)-, or -(Q2)C(Q3)-, and further exemplified by -CH2-) between the hydrazine group and the benzene ring can improve the stability of the perovskite precursor solution, thereby extending the shelf life of the precursor. Taking benzylhydrazine hydrochloride and phenylhydrazine hydrochloride as examples, the nitrogen of the hydrazine group has a valence of -1 and tends to lose electrons. Therefore, when the nitrogen of the hydrazine group in phenylhydrazine hydrochloride is directly attached to the benzene ring, the strong electron-withdrawing ability of the benzene ring exacerbates the electron loss process of the nitrogen of the hydrazine group, resulting in a relatively short existence of the phenylhydrazine hydrochloride as a sacrificial agent in the perovskite. In contrast, in benzylhydrazine hydrochloride, the hydrazine group and the benzene ring are separated by a methylene structure, and the hydrazine group is directly attached to the carbon atom of the methylene group. The methylene group tends to donate electrons, transferring electrons to the hydrazine group, thereby improving the stability of the benzylhydrazine hydrochloride, which is beneficial for improving the stability of the perovskite precursor solution and extending the shelf life of the precursor.

[0061] Furthermore, the presence of a spacer group between the hydrazine group and the aromatic ring in L facilitates the crystallization reaction and avoids lattice distortion. The spacer group increases steric hindrance, making it difficult for the first additive to enter the perovskite's ABX3 lattice, thus avoiding lattice distortion. Furthermore, because it is similarly soluble in the perovskite precursor solution, it can be evenly dispersed in the perovskite film, guiding crystallization nucleation to a certain extent.

[0062] When there is a spacer group between the hydrazine group and the aromatic ring in L, the life of the perovskite device can be extended. The degradation of perovskite is mainly due to the + and BX2 degradation, hydrochloride can inhibit the degradation of A-site cations. At this time, aromatic hydrazine compounds containing spacer groups can inhibit the degradation of halogen anions, and aromatic hydrazine compounds containing spacer groups are also more stable.

[0063] L can contain aromatic rings or aliphatic chains, which can produce different steric hindrances and electron-donating abilities, leading to different degrees of reactivity. For the same carbon number, aromatic ring structures are preferred over aliphatic chains. On the one hand, aromatic ring structures may not participate in the perovskite lattice. On the other hand, aliphatic chains are more hydrophobic than aromatic ones, which may reduce crystal quality.

[0064] In some embodiments, the additive has any one of the structures of formula (11), formula (12), formula (13), formula (14) and formula (15): Ar(-Z 21 -R 11 ) p1 nHCl (11)

[0065] In formula (11), p1 is a positive integer, Z 21is -CH2-, -CH(Q1)- or -(Q2)C(Q3)-; Ar(-R 11 ) p1 nHCl (12)

[0066] In formula (12), p1 is a positive integer, R 11 is a sulfinic acid group or a phosphinic acid group;

[0067] In formula (13), k1 and k2 are each independently 0 or 1; R 31 and R 32 are each independently an alkylene group; optionally, R 31 and

[0068] R 32 Each independently is C 2-20 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-16 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-12 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-10 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-8 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-6 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-4 alkylene;

[0069] In formula (14) and formula (15), k1 and k2 are each independently 0 or 1; Z 41 and Z 42 are each independently an alkylene group; optionally, Z 41 and Z 42 Each independently is C 2-15 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-12 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-10 Alkylene, further optionally, Z 41 and Z42 Each independently is C 1-8 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-6 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-4 Alkylene, further optionally, Z 41 and Z 42 are each independently methylene, ethylene, propylene or butylene;

[0070] Among them, Ar, Ar 21 and Ar 22 are each independently an aromatic group; optionally, Ar, Ar 21 and Ar 22 The number of ring atoms of each independently is 5 to 15, further optionally 5 to 12, further optionally 5 to 10 or 12, further optionally 5, 6, 10 or 12; alternatively, Ar, Ar 21 and Ar 22 are independently aryl, heteroaryl, substituted aryl or substituted heteroaryl, wherein the aryl or heteroaryl in the substituted aryl or substituted heteroaryl is independently substituted by one or more groups selected from the group G1; when containing heteroatoms, Ar, Ar 21 and Ar 22 Any heteroatom contained in any one of the above-mentioned compounds is independently a non-carbon, non-hydrogen atom, and is further independently selected from any one of N, S, P, O and B.

[0071] When the first additive contains an aromatic ring, it may not participate in the perovskite lattice. On the other hand, it usually has a weaker hydrophobicity than a fatty chain and can improve the crystallization quality.

[0072] In some embodiments, the additive contains a second functional group W 11 , W 11 It can be any group selected from the group consisting of: -COOH, sulfonic acid, phosphonic acid and boric acid;

[0073] In one molecule of the additive, the second functional group W 11 The number j is 1 or more; optionally, j is 1, 2 or 3; further optionally, j is 1 or 2.

[0074] By introducing a weak acidic group (such as but not limited to one or more of -COOH, sulfonic acid, phosphonic acid and boric acid) into the additive, the addition-elimination reaction of A (A is an organic cation) in ABX3 can be inhibited, thereby extending the service life of the perovskite device. In addition, when the acidity is consumed, it can also participate in the replenishment of the perovskite system, thereby enhancing the stability of the perovskite structure. When the weak acidic group coordinates with the B-site cation, it can also enhance electron transport. 11 The trace amount of acid anions can promote the formation of crystal seeds and enhance the quantitative formation of crystal seeds. When the perovskite is annealed, this type of substance is easy to separate from its lattice system, causing the overall perovskite to transform into a stable α phase.

[0075] W 11 Taking -COOH as an example, -COOH can weakly dissociate to produce H + and COO - , H + Can inhibit A + Cationic degradation, COO - It has a strong ability to coordinate with B, enhancing the bulk stability of the perovskite and promoting the long-term stability of the perovskite. It should be noted that the introduction of weak acidic groups cannot replace the salt-forming effect of hydrohalic acid molecules. Hydrohalic acid salt formation (such as hydrochloric acid salt) can significantly improve solubility. When only weak acidic groups are present without the salt-forming effect of hydrohalic acid molecules, it may result in the inability to participate in the perovskite film due to reasons such as the pre-filtration step, or uneven distribution in the perovskite film, and the expected effect of the first additive cannot be exerted or the effect is poor.

[0076] In some embodiments, the additive has any of the following structures: 11 ) j L0(R 02 ) m1 nHCl (2)

[0077] In formula (2), j is a positive integer, m1 is a positive integer; any R 02 are independently the weak reducing groups; L0 is a hydrocarbon group or heteroalkyl group with a valence of m1+j, wherein the heteroalkyl group contains 0, 1 or more substituents selected from the group consisting of: -CN, -OH, halogen (optionally one or more of F, Cl, Br and I), -NH2, -SH, -CF3 and -COOH; optionally, any one of R 02 A group independently selected from the group consisting of: -NHNH-, -NHNH2, sulfinic acid and phosphinic acid groups; (W 11 ) j1 L 01 (Z1-R 11 ) p1 nHCl (21)

[0078] In formula (21), p1 and j1 are each independently a positive integer, and any Z1 and any R 11 Each independently as defined above; L 01 (Z 1- ) p1 Contains p2 divalent weak reducing groups and j2 W 11 , wherein p2 and j2 are each independently 0 or a positive integer; L 01 is a p1+j1 valence hydrocarbon or heterohydrocarbon group, wherein the heterohydrocarbon group contains 0, 1 or more substituents selected from the group consisting of -CN, -OH, halogen (optionally one or more of F, Cl, Br and I), -NH2, -SH, -CF3 and -COOH; (W 11 ) j1 Ar 01 (-Z 31 -R 11 ) p1 nHCl (22)

[0079] In formula (22), p1, j1, any R 11 and any W 11 Each is independently defined as in formula (21); Ar 01 is a divalent aromatic group; wherein the divalent aromatic group contains 0, 1 or more substituents selected from the group consisting of: -CN, -OH, -NH2, -SH, -CF3 and -COOH, halogen; Z 31 is -CH2-, -CH(Q1)- or -(Q2)C(Q3)-; Q1, Q2 and Q3 are each independently selected from the following group G3: hydrocarbon group (optionally C 1-6 Alkyl, further optionally C 1-3 Alkyl, further optionally methyl) and heteroalkyl (optionally alkoxy or alkylamino, further optionally C 1-6 Alkoxy or C 1-6 Alkylamino, further optionally C 1-3 Alkoxy or C 1-3 Alkylamino, further optionally methoxy, ethoxy, -NHCH3 or -NHCH2CH3, further optionally -NHCH3 or -NHCH2CH3, further optionally -NHCH3); wherein the heteroalkyl group contains 0, 1 or more substituents selected from the group consisting of -CN, -OH, halogen (optionally one or more of F, Cl, Br and I), -NH2, -SH, -CF3 and -COOH;

[0080] In formula (23) and formula (24), k1, k2, Z 41 and Z42 Each is independently defined as in formula (14); j31 and j32 are each independently 0 or a positive integer, (j31+j32)≥1; W 31 and W 32 Each is independently any one group selected from the group consisting of -COOH, sulfonic acid, phosphonic acid, boric acid, -NH2 and -SH;

[0081] Among them, Ar 31 and A 32 Each is independently a divalent aromatic group; wherein the divalent aromatic group contains 0, 1 or more substituents selected from the following group: -CN, -OH, amino, thiol and halogen (optionally one or more of F, Cl, Br and I).

[0082] The aforementioned role of the weakly acidic group can be more flexibly exerted by adjusting the type, quantity, location and other characteristics of the weakly acidic group.

[0083] In some embodiments, the additive includes any one or any suitable combination of the following compounds:

[0084] and the case where any of the aforementioned compound salts is substituted by a substituent selected from Group G1;

[0085] wherein n is a positive integer, optionally, n is an integer selected from 1 to 10; further optionally, n is 1, 2, 3, 4 or 5; further optionally, n is 1 or 2;

[0086] Q Ar Any group selected from the group G1; a is 0 or a positive integer (a can be 0, 1 or 2);

[0087] Q 10 is H or Q1; optionally, Q 10 is H; alternatively, Q 10 is Q1;

[0088] a1 and a2 are 0 or positive integers respectively, and a1+a2≥1;

[0089] b1, b2 and b3 are each 0 or a positive integer, and b1+b2+b2≥1, optionally, b2+b3≥1, more optionally, b1=0;

[0090] Q A1 , Q A2 and Q A3 Each independently is Q Ar ;

[0091] q is an integer selected from 2 to 20, optionally an integer from 2 to 18, further optionally an integer from 2 to 16, further optionally an integer from 2 to 12, further optionally an integer from 2 to 10, further optionally an integer from 2 to 8, further optionally 2, 3, 4, 5, 6 or 7;

[0092] c1 and c2 are each independently 0 or 1, optionally, c1+c2≥1;

[0093] Q 51 and Q 52 Each independently is an alkyl group (optionally C 1-6 Alkyl, further optionally C 1-3 alkyl, and further optionally methyl).

[0094] In some embodiments, the additive includes any one or any suitable combination of the following compounds:

[0095] and the case where any of the aforementioned compound salts is substituted by a substituent selected from Group G1;

[0096] Optionally, n is 1 or 2;

[0097] Optionally, n is 1;

[0098] Optionally, n is 2.

[0099] The additives may include any one or any suitable combination of the aforementioned compounds, thereby effectively improving the quality of the perovskite film and reducing defects, thereby effectively increasing the energy conversion efficiency of the perovskite cell. Furthermore, the perovskite cell can maintain good energy conversion efficiency for a long period of time and has good cell stability.

[0100] In some embodiments, the perovskite precursor material comprises a perovskite-type metal halide; the chemical formula of the perovskite-type metal halide is ABX3; wherein A is a monovalent cation, B is a divalent cation, and X is a monovalent anion;

[0101] Optionally, A includes Cs + , K + , Rb + , one or more of monovalent amine cations and monovalent amidino cations;

[0102] Optionally, B includes Pb 2+ 、Sn 2+ 、Fe 2+ 、Mn 2+ 、Ni 2+ 、Ge2+ 、Co 2+ and Sb 2+ One or more of;

[0103] Optionally, X includes I - Br - and Cl - One or more of .

[0104] The first additive provided in this application can improve various types of perovskite precursor material systems, improve the quality of corresponding perovskite films, reduce defects, and extend the life of perovskite batteries.

[0105] In some embodiments, the weight percentage of the additive relative to the B element in the perovskite precursor material is 0.01% to 15%;

[0106] Optionally, the weight percentage of the additive relative to the B element in the perovskite precursor material is 0.01% to 10%;

[0107] Optionally, the weight percentage of the additive relative to the B element in the perovskite precursor material is 0.1% to 8%.

[0108] In some embodiments, the relative molar ratio of the additive to B in the perovskite metal halide is 0.001% to 15%;

[0109] Optionally, the relative molar ratio of the additive to B in the perovskite metal halide is 0.01 to 15%;

[0110] Optionally, the relative molar ratio of the additive to B in the perovskite-type metal halide is 2 to 6.5%.

[0111] In some embodiments, the relative molar ratio of the weak reducing group to the B element in the perovskite-type metal halide is 0.01 to 15%;

[0112] Optionally, the relative molar ratio of the weak reducing group to the B element in the perovskite-type metal halide is 1 to 8%.

[0113] The weak reducing contribution of the first additive to the perovskite precursor solution can be controlled by adjusting one or more of the following methods: the weight ratio percentage of the first additive relative to the B element in the perovskite precursor material, the molar ratio of the first additive relative to the B element in the perovskite precursor material, the relative molar ratio of the weak reducing group to the B element in the perovskite-type metal halide, etc., so as to better play the role of the first additive.

[0114] In some embodiments, the perovskite precursor solution further contains oxidized ions of a multivalent metal element M.

[0115] In some embodiments, the multivalent metal element M includes one or more elements selected from the group consisting of lanthanide elements, Fe, Co, Ni, Ti, Cr, Mn, Y, Rh, and Bi;

[0116] Optionally, the lanthanide elements include one or more elements selected from Ce, Pr, Sm, Eu, Tb and Yb;

[0117] Optionally, the oxidation state ions of the multivalent metal element M include Ce 4+ 、Pr 4+ 、Sm 3+ 、Eu 3+ , Tb 4+ 、Yb 3+ 、Fe 3+ 、Co 3+ 、Ni 3+ 、Ti 4+ Cr 3+ 、Mn 4+ 、Y 3+ and Rh 4+ One or more of;

[0118] Optionally, the oxidized ions of the multivalent metal element M are derived from an organic salt of the metal element M. Further optionally, the organic salt comprises one or more of acetylacetonate, sulfonate and sulfate ester.

[0119] In some embodiments, the perovskite precursor solution contains Ce 3+ -Ce 4+ 、Pr 4+ -Pr 3+ 、Sm 3+ -Sm 2+ 、Eu 3+ -Eu 2+ , Tb 4+ -Tb 3+ 、Yb 3+ -Yb 2+ 、Fe 3+ -Fe 2+ 、Co 3+ -Co 2+ 、Ni 3+ -Ni 2+ 、Ti 4+ -Ti X+ Cr 3+ -Cr 2+ 、Mn 4+ -Mn 2+ 、Y3+ -Y 2+ , Rh 4+ -Rh 2+ and Bi 3+ -Bi 2+ One or more ion pairs in; wherein the ion pair Ti 4+ -Ti X+ Ti X+ The positive charge state is less than 4.

[0120] In some embodiments, the perovskite precursor material comprises the perovskite metal halide;

[0121] The relative molar ratio of the multivalent metal element M to the element B in the perovskite metal halide is 0.001% to 15%;

[0122] Optionally, the relative molar ratio of the multivalent metal element M to the element B in the perovskite metal halide is 0.01% to 15%.

[0123] By introducing the oxidation state of multivalent metal cations into the perovskite precursor solution, it is possible to react with B 0 The reaction forms a reduced cation, and the oxidation state and the reduced state of the multivalent metal cation can form a redox equilibrium pair, which can cyclically inhibit the degradation of BX2 in the perovskite film, thereby extending the life of the perovskite battery and improving the energy conversion efficiency; in addition, it can further inhibit the 0 and X2, reducing defects at the interface and further improving the performance of perovskite devices.

[0124] In a second aspect, the present application provides a perovskite film, which is prepared using the perovskite precursor solution described in the first aspect of the present application.

[0125] In a third aspect, the present application provides a perovskite cell, which includes the perovskite film described in the second aspect of the present application.

[0126] In some embodiments, the perovskite cell is any one of an inverted pin cell and a formal nip cell.

[0127] The perovskite film prepared using the perovskite precursor solution described in the first aspect of the present application has few defects and high quality. The perovskite battery further prepared has high energy conversion efficiency and good battery stability.

[0128] In a fourth aspect, the present application provides an electrical device comprising the perovskite battery described in the third aspect of the present application.

[0129] The details of one or more embodiments of the present application are set forth in the following drawings and description. Other features, objects, and advantages of the present application will become apparent from the description, drawings, and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0130] In order to better describe and illustrate the embodiments or examples of the applications disclosed herein, reference may be made to one or more of the accompanying drawings. The additional details or examples used to describe the accompanying drawings should not be considered to limit the scope of the disclosed applications, the embodiments or examples currently described, and any of the best modes currently understood for these applications. Moreover, the same reference numerals are used throughout the drawings to represent the same components. In the drawings:

[0131] FIG1 is a schematic diagram of a perovskite cell according to an embodiment of the present application, comprising a first electrode, a first transport layer, a perovskite layer, a second transport layer, and a second electrode;

[0132] FIG2 is a schematic diagram of a perovskite cell according to an embodiment of the present application, comprising a substrate layer, a first electrode, a first transport layer, a perovskite layer, a second transport layer, and a second electrode;

[0133] FIG3 is a schematic diagram of a perovskite cell according to an embodiment of the present application;

[0134] Figure 4 is a schematic diagram of an electrical device using a perovskite cell as a power source according to one embodiment of the present application. Reference numerals: 100 is the perovskite cell; 110 is the substrate layer; 120 is the first electrode; 130 is the first transport layer; 140 is the perovskite layer; 150 is the second transport layer; 160 is the second electrode; P1 is the first notched region; P2 is the second notched region; P3 is the third notched region; and 20 is the electrical device. DETAILED DESCRIPTION

[0135] Below, some embodiments of the perovskite precursor solution, perovskite film, perovskite battery and electrical device of the present application are disclosed in detail with appropriate reference to the accompanying drawings. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually the same structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the drawings and the following description are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0136] " range " disclosed in the present application is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and can be arbitrarily combined, that is, any lower limit can form a range with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for specific parameters, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range value 1 and 2 are listed, and if the maximum range value 3,4 and 5 are listed, then the following range can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is merely an abbreviation for a combination of these values. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For example, when a parameter is expressed as an integer selected from "2-10", this is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0137] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0138] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0139] Unless otherwise specified, the terms "include," "contain," and "comprise" used in this application may be open-ended or closed-ended. For example, "include," "contain," and "comprises" may indicate that other components not listed may also be included or comprised, or may indicate that only the listed components are included or comprised.

[0140] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B." Furthermore, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0141] In this application, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0142] In this application, "a plurality of" or "a plurality of" refers to a number greater than or equal to 2 unless otherwise specified. For example, "one or more" means one or more than or equal to two.

[0143] As used herein, "combination thereof", "any combination thereof", "any combination thereof" and the like include all suitable combinations of any two or more of the listed items.

[0144] Herein, the “suitable” mentioned in “suitable combination”, “suitable method”, “any suitable method”, etc. shall be based on the technical solution that can implement the present application.

[0145] Herein, the terms "preferred," "better," "more preferred," and "suitable" are used solely to describe preferred implementations or examples and should not be construed as limiting the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, each "preferred" term is considered independent unless otherwise specified and there are no contradictions or mutual constraints.

[0146] In this application, "further", "further", "particularly" and the like are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of this application.

[0147] In this application, the terms "first," "second," "third," "fourth," "first additive," "second additive," etc., are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor as implicitly indicating the importance or quantity of the indicated technical features. Furthermore, "first," "second," "third," "fourth," etc., serve only for the purpose of non-exhaustive enumeration and description, and should be understood not to constitute a closed-ended limitation on quantity.

[0148] In this application, the term "room temperature" generally refers to 4°C to 35°C, and may refer to 20°C ± 5°C. In some embodiments of this application, room temperature refers to 20°C to 30°C.

[0149] In this application, when referring to a data range, if the unit is only after the right endpoint, it means that the units of the left and right endpoints are the same. For example, 3~5h or 3-5h both mean that the units of the left endpoint "3" and the right endpoint "5" are both hours.

[0150] The weights of the relevant components mentioned in the examples of this application may not only refer to the content of each component, but also represent the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the examples of this application, it is within the scope disclosed in the examples of this application. Furthermore, the weights mentioned in the examples of this application may be mass units known in the chemical industry, such as μg, mg, g, and kg.

[0151] As used herein, unless otherwise specified, "alkyl" refers to a monovalent residue derived from a saturated hydrocarbon containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof, by the loss of one hydrogen atom. Phrases containing this term, such as "C1-9 alkyl," refer to an alkyl group containing 1 to 9 carbon atoms, and each occurrence may independently be a C1 alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl, a C6 alkyl, a C7 alkyl, a C8 alkyl, or a C9 alkyl group. Suitable examples include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(C H3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (- CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH( )2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3 and octyl (-(CH2)7CH3).

[0152] Herein, unless otherwise specified, "heteroalkyl" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an alkyl group, and the non-carbon atom can be an N atom, an O atom, an S atom, a P atom, etc. The following is explained using O, N, and S as examples. For example, if the carbon atom connected to the adjacent group in the alkyl group is replaced by a non-carbon atom O, N, or S, the resulting heteroalkyl group is an alkoxy group (e.g., -OCH3, etc.), an amino group (e.g., -NHCH3, -N(CH3)2, etc.) or a thioalkyl group (e.g., -SCH3). If the carbon atom not directly connected to the adjacent group in the alkyl group is replaced by a non-carbon atom O, N, or S, the resulting heteroalkyl group is an alkoxyalkyl group (e.g., -CH2CH2-O-CH3, etc.), an alkylaminoalkyl group (e.g., -CH2NHCH3, -CH2N(CH3)2, etc.) or an alkylthioalkyl group

[0153] (e.g., -CH2-S-CH3). If a terminal carbon atom of an alkyl group is replaced with a non-carbon atom, the resulting heteroalkyl group can be a hydroxyalkyl group (e.g., -CH2CH2-OH), an aminoalkyl group (e.g., -CH2NH2), or a mercaptoamino group (e.g., -CH2CH2-SH). Phrases containing the term "heteroalkyl," for example, "C1-C9 heteroalkyl" or "C1-9 heteroalkyl," refer to heteroalkyl groups containing from 1 to 9 carbon atoms, each occurrence of which can be, independently of one another, a C1 heteroalkyl, a C2 heteroalkyl, a C3 heteroalkyl, a C4 heteroalkyl, a C5 heteroalkyl, a C6 heteroalkyl, a C7 heteroalkyl, a C8 heteroalkyl, or a C9 heteroalkyl.

[0154] In this article, unless otherwise specified, "cycloalkyl" has the same meaning as "non-aromatic cycloalkyl", which refers to a monovalent residue formed by a non-aromatic hydrocarbon (saturated hydrocarbon or unsaturated hydrocarbon) containing a ring carbon atom losing a hydrogen atom on the ring, that is, a monovalent connection site is formed directly on the ring. Cycloalkyl derived from non-aromatic saturated hydrocarbons can be recorded as saturated cycloalkyl, and cycloalkyl derived from non-aromatic unsaturated hydrocarbons can be recorded as unsaturated cycloalkyl. Cycloalkyl can be a monocyclic alkyl, a spirocyclic alkyl, or a bridged cycloalkyl. Phrases containing this term, for example, "C3-C9 cycloalkyl" or C 3-9 "Cycloalkyl" refers to a cycloalkyl group containing 3 to 9 carbon atoms, each occurrence of which can be independently C3 cycloalkyl, C4 cycloalkyl, C5 cycloalkyl, C6 cycloalkyl, C7 cycloalkyl, C8 cycloalkyl or C9 cycloalkyl. Suitable examples include, but are not limited to, cyclopropyl Cyclobutyl Cyclopentyl Cyclohexyl In addition, "cycloalkyl" may also contain one or more double bonds, and representative examples of cycloalkyl containing double bonds include, but are not limited to, cyclopentenyl (including, but not limited to, ), cyclohexenyl (including but not limited to ), cyclohexadiene (including but not limited to ) group, cyclopentadienyl (including but not limited to ) and cyclobutadienyl (including but not limited to )wait.

[0155] As used herein, unless otherwise specified, "heterocycloalkyl" refers to a cycloalkyl group in which at least one carbon atom is replaced by a non-carbon atom, which may be a N atom, an O atom, an S atom, or the like, and may be a saturated ring or a partially unsaturated ring. Phrases containing this term, for example, "C4-C9 heterocyclyl" refers to a heterocyclyl group containing 4 to 9 carbon atoms, which, when present, may be independently C4 heteroalkyl, C5 heteroalkyl, C6 heteroalkyl, C7 heteroalkyl, C8 heteroalkyl, or C9 heteroalkyl. Suitable examples include, but are not limited to, dihydropyridyl, tetrahydropyridyl (piperidyl), tetrahydrothienyl, sulfur-oxidized tetrahydrothienyl, tetrahydrofuranyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, dihydroindole, and the like.

[0156] In this article, unless otherwise specified, "aryl" refers to an aromatic hydrocarbon group derived from an aromatic hydrocarbon compound by losing a hydrogen atom, that is, a monovalent linking site formed directly on the ring. It can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic aromatic groups, at least one is an aromatic ring system. For example, "C6-C 10 "Aryl" refers to an aromatic group containing 6 to 10 carbon atoms, each occurrence of which can be independently C6 aryl, C8 aryl, C9 aryl or C 10 Aryl. For example, "C6~C 20 "Aryl" refers to an aromatic group containing 6 to 20 carbon atoms, each occurrence of which can be independently but not limited to C6 arylaryl (such as phenyl), C6 arylaryl (such as benzocyclobutenyl), C8 aryl (such as phenylcyclobutenyl), C9 aryl (such as indenyl), C 10 Aryl (such as naphthyl), C 12 Aryl (such as acenaphthenyl, biphenyl), C 13 Aryl (such as fluorenyl), C 14 Aryl (such as anthracenyl, phenanthrenyl), C 18 Aryl (such as triphenylene) or C 20 Aryl (eg, perylene). Examples of suitable aromatic cyclic hydrocarbon compounds include, but are not limited to, benzene, stycyclobutene, biphenyl, indene, naphthalene, acenaphthene, fluorene, anthracene, phenanthrene, triphenylene, perylene, and derivatives thereof.

[0157] In this article, unless otherwise specified, "heteroaryl" refers to a heterocyclic group with aromaticity, which can be a monovalent group formed by replacing at least one carbon atom of an aryl group with a non-carbon atom, or a monovalent group formed by replacing at least one carbon atom of a cyclopentadienyl group with a non-carbon atom, wherein the non-carbon atom can be, but is not limited to, a nitrogen atom, an oxygen atom, or a sulfur atom. For example, "C1-C 10 The term "heteroaryl" refers to a heteroaryl group containing 1 to 10 carbon atoms, which can be independently C1 heteroaryl (such as tetrazolyl, etc.), C2 heteroaryl (such as triazolyl, oxadiazolyl, etc.), C3 heteroaryl (such as imidazolyl, etc.), C4 heteroaryl (such as furyl, etc.), C5 heteroaryl (such as pyridyl, etc.), C6 heteroaryl, C7 heteroaryl (such as benzimidazole, etc.), C8 heteroaryl (such as indolyl, etc.), C9 heteroaryl (such as quinolyl, etc.) or C 10 Heteroaryl (such as pyrrolobipyridinyl). Also for example, "C3~C 20 "Heteroaryl" refers to a heteroaryl group containing 3 to 20 carbon atoms, each occurrence of which can be independently but not limited to C2 heteroaryl, C3 heteroaryl, C4 heteroaryl, C5 heteroaryl, C6 heteroaryl, C8 heteroaryl, C9 heteroaryl, C 10 Heteroaryl, C 12 Heteroaryl, C 13 Heteroaryl, C 14 Heteroaryl, C 18 Heteroaryl or C 20 Heteroaryl. Suitable examples include, but are not limited to, heteroaryl groups derived from the following heteroaromatic rings (number of carbon atoms is indicated in brackets): furan (C4), benzofuran (C8), thiophene (C4), benzothiophene (C8), pyrrole (C4), pyrazole (C3), triazole (C2), imidazole (C3), oxazole (C3), oxadiazole (C2), thiazole (C3), tetrazole (C1), indole (C8), carbazole (C 12 ), pyrroloimidazole (C5), pyrrolopyrrole (C6), thienopyrrole (C6), thienothiophene (C6), furopyrrole (C6), furofuran (C6), thienofuran (C6), thienopyridine (C7), furopyridine (C7), benzoxazole (C7), benzisoxazole (C7), benzothiazole (C7), benzisothiazole (C7), benzimidazole (C7), pyridine (C5), pyrazine (C4), pyridazine (C4), pyrimidine (C4), triazine (C3), quinoline (C9), isoquinoline (C9), naphthyridine (C8, such as o-naphthyridine), quinoxaline (C8), phenanthridine (C 13 ), primary pyridine (C 11 ), quinazoline (C8) and quinazolinone (C8).

[0158] As used herein, unless otherwise specified, "alkylene" refers to a hydrocarbon group having two monovalent radical centers derived from an alkane by removing two hydrogen atoms (or derived from an alkyl group by losing another hydrogen atom), which may be a saturated branched alkyl group or a saturated straight-chain alkyl group. For example, "C1-C9 alkylene" means that the alkyl portion contains 1 to 9 carbon atoms, and each occurrence may be independently C1 alkylene, C2 alkylene, C3 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene or C9 alkylene. Suitable examples include, but are not limited to, methylene (-CH2-), 1,1-ethyl (-CH(CH3)-), 1,2-ethyl (-CH2CH2-), 1,1-propyl (-CH(CH2CH3)-), 1,2-propyl (-CH2CH(CH3)-), 1,3-propyl (-CH2CH2CH2-) and 1,4-butyl (-CH2CH2CH2CH2-)

[0159] As used herein, "halogen" or "halo" refers to F, Cl, Br or I, unless otherwise specified.

[0160] Herein, unless otherwise specified, "amino" may be a primary amino group (-NH2), a secondary amino group (>NH), a tertiary amino group (>N-) or a quaternary amino group (>N + <).

[0161] Herein, unless otherwise specified, a hydroxyl group is -OH, a carboxyl group is -COOH, a cyano group is -CN, a hydrazine group is -NHNH2, a divalent hydrazine group is -NHNH-, a sulfinic acid group is -S(=O)OH, a phosphinic acid group is (*-)2P(=O)OH, a sulfonic acid group is -S(=O)2OH, a phosphonic acid group is (*-)P(=O)(OH)2, and a boric acid group is (*-)B(OH)2. The * in the phosphinic acid group indicates that the group is connected to a carbon atom or H and at least one of the groups is connected to a carbon atom, the * in the phosphonic acid group indicates that the group is connected to a carbon atom, and the * in the boric acid group indicates that the group is connected to a carbon atom.

[0162] In this application, for atoms, groups, or compound residues that participate in forming a covalent bond, its valence refers to the number of attachment sites of the atom, group, or compound residue that participates in forming the covalent bond. For example, the valence of an alkyl group (-CH3) is monovalent, and the valence of an alkylene group (-CH2-) is divalent. For another example, the valence of groups such as -OH, -COOH, -CN, -NHNH2, and -S(=O)OH is monovalent, and the valence of -NHNH- and -SS- is divalent. For those skilled in the art, it is understood that this "valence" is different from the charge state of an ion.

[0163] In the application, "charge state of an ion" refers to the charge of the ion, which can carry either a positive or negative charge. For example, a ferric ion (Fe 3+ ) has a positive charge of 3, and the iodine anion (I - ) has a negative charge state of 1.

[0164] In perovskite cells, the main components of the perovskite precursor solution and the perovskite film, ABX3, are unstable, and the metal halide part BX2 of AX·BX2 is easily degraded, such as I in lead-iodine-based perovskite. - Easily oxidized to I2, Pb 2+ Easily reduced to Pb 0 This results in an increase in defect density, resulting in a shorter lifespan and lower efficiency of perovskite cells.

[0165] When A is an organic cation, an addition-elimination reaction may also occur, accelerating the decomposition reaction of BX2:

[0166] Based on this, in the first aspect, the present application provides a perovskite precursor solution, which includes a weak reducing group (which can be recorded as R 01 ) and in the form of a hydrohalide salt, which may be referred to herein as the "first additive." The "first" in "first additive" is used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor as implicitly designating the importance or quantity of the indicated technical features.

[0167] In this application, unless otherwise specified, the “weak reducing group” used herein may be denoted as R 01 , refers to a group with the following reducing properties: this weak reducing group has reducing properties for the zero-valent state corresponding to the monovalent anion in the perovskite metal halide, and is inert to the divalent cation in the perovskite metal halide. In the perovskite precursor solution, this weak reducing property can reduce the zero-valent state X2 back to the negative ion X - , but will not convert divalent cations B 2+ B reduced to zero valence 0 , that is, it has reducing properties to the 0-valent state X, and at the same time has reducing properties to the divalent cation B 2+is inert. The weak reducing group may be a monovalent group or a polyvalent group, wherein the polyvalent weak reducing group may be divalent. Examples of divalent weak reducing groups include, but are not limited to, -NHNH- and -SS-. Examples of monovalent weak reducing groups include, but are not limited to, -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group, and hydroxynaphthyl group. The weak reducing group may include one or more of the following groups: -NHNH-, -SS-, -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group, and hydroxynaphthyl group, and may further include one or more of the following groups: -NHNH-, -SS-, -NHNH2, sulfinic acid group, and phosphinic acid group, and may further include one or more of the following groups: -NHNH2, sulfinic acid group, and phosphinic acid group.

[0168] The X in the perovskite precursor solution can be detected before and after adding an additive to the base solution of the perovskite precursor solution. - and B 2+ The concentration of the two ions is determined based on the concentration changes of the two ions to determine whether the reducing property of the additive is within the scope of "weak reducing property" in this application. - The concentration increases and B 2+ If the concentration remains basically unchanged, it is considered whether the reducing property of the additive is within the scope of "weak reducing property" in this application. - and B 2+ The concentration of can be determined by appropriately selecting a method in the field of organic chemistry that can characterize the concentration of two ions. The selected method should be compatible with the perovskite precursor solution system in this application. - For I - For example, starch potassium iodide reagent can be used to detect I - Changes in ion concentration.

[0169] In some embodiments, the weak reducing group has reducing properties on the zero-valence state of the following monovalent anions in the perovskite-type metal halide: Br - , I - or a combination thereof, that is, the weak reducing group has reducing properties to Br, I, or a combination thereof in the perovskite precursor solution. In some embodiments, the weak reducing group has reducing properties to I in the perovskite precursor solution.

[0170] In some embodiments, the present application provides a perovskite precursor solution comprising a perovskite precursor material, a solvent, and an additive; wherein the perovskite precursor material comprises a perovskite-type metal halide; the structure of the additive (i.e., the first additive) contains a weak reducing group, which is reducing to the 0-valent state corresponding to the monovalent anion in the perovskite-type metal halide, and is inert to the divalent cations in the perovskite-type metal halide; the additive is a hydrohalide.

[0171] In the present application, "the additive" and "the first additive", unless otherwise specified, refer to the aforementioned hydrohalide additive with weak reducing properties.

[0172] By adding an organic compound hydrohalide salt additive containing a weak reducing group (referred to as the first additive) to the perovskite precursor solution, for the halide metal portion BX2 in the main component ABX3 in the perovskite precursor solution and the perovskite film, on the one hand, the weak reducing group pair can reduce X2 (zero-valent X) to X - , increasing the storage time of the perovskite precursor solution, that is, it has a reducing property on the 0-valence state corresponding to the monovalent anion in the perovskite metal halide; on the other hand, its weak reducing property will not 2+ Restore to B 0 , that is, it is inert to the divalent cations in the perovskite metal halide; on the other hand, the additive can participate in the crystallization reaction and be evenly dispersed in the perovskite film, acting as a sacrificial agent to extend the service life of the perovskite device; on the other hand, it can inhibit B 0 The formation of X2 reduces defects at the interface and improves the performance of perovskite devices; by forming hydrohalides, the additives can be promoted to dissolve better in the perovskite precursor solution and be more evenly distributed in the perovskite film. Among them, the perovskite precursor solution is generally a colloidal solution, and the BX2 in the solution is mostly distributed in the system in a state of complexation with the solvent. The weak reducing groups involved in this application are easy to form hydrogen bonds with the perovskite colloidal solution and can be evenly distributed in the colloidal solution; when the crystallization reaction occurs, such additives can have a stronger surface tension on the lower surface (the surface used for coating) when the solvent is quenched, and can form crystal nucleus sites, so that the perovskite is expanded at such sites, promoting crystallization. In addition, for perovskite ABX3, taking FAPbI3 as an example, because it is susceptible to the effects of oxygen, moisture, light and heat, the following equilibrium formula exists: Among them, I2 is easy to sublime and leave the system, causing the entire equilibrium to move to the right, resulting in perovskite degradation; when weak reducing property exists in the system, the 0-valent I2 can be reduced to I - , so that the entire reaction proceeds to the right, which can inhibit the degradation of perovskite, and the weak reducing group itself will not react with Pb2+ Reacts (shown as Pb 2+ When the weak reducing group is consumed, the corresponding product cannot be regenerated to its original state, so it is a consumable group and a sacrificial agent.

[0173] In some embodiments, the weak reducing group comprises one or more of the following groups: -NHNH-, -SS-, -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group and hydroxynaphthyl group;

[0174] Optionally, the weak reducing group is selected from the group consisting of -NHNH-, -SS-, -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group and hydroxynaphthyl group.

[0175] In some embodiments, the weak reducing group is selected from the group consisting of: -NHNH-, -SS-, -NHNH2, sulfinic acid group, and phosphinic acid group.

[0176] In some embodiments, the weak reducing group includes at least one of -NHNH- and -SS-.

[0177] In some embodiments, the weak reducing group includes at least one of -NHNH2, a sulfinic acid group, and a phosphinic acid group.

[0178] In some embodiments, the weak reducing group includes at least one of -NHNH- and -NHNH2.

[0179] In some embodiments, the weakly reducing group comprises a sulfinic acid group.

[0180] In some embodiments, the weakly reducing group comprises a sulfinic acid group.

[0181] In some embodiments, the number of weak reducing groups (referred to as m) in one molecule of the first additive is one or more. In one molecule of the first additive, the number of weak reducing groups can be an integer selected from 1 to 10; further, the number of weak reducing groups can be 1, 2, 3, 4, or 5; further, the number of weak reducing groups can be 1, 2, or 3; further, the number of weak reducing groups can be 1 or 2. In some embodiments, m is 1. In some embodiments, m is 2.

[0182] When the number of weak reducing groups in the first additive molecule is greater than 1, the types of weak reducing groups may be the same or different. In some embodiments, in one molecule of the first additive, the types of weak reducing groups are one or more, for example, 1, 2, 3 or more, or 1, 2, 3, 4 or more. In some embodiments, the types of weak reducing groups in the first additive molecule are 1 to 5, and further may be 1 to 3. In some embodiments, the type of weak reducing groups in the first additive molecule is 1. In some embodiments, the type of weak reducing groups in the first additive molecule is 2. In some embodiments, the type of weak reducing groups in the first additive molecule is 3.

[0183] In some embodiments, the number of hydrohalic acid molecules (denoted as n) in one molecule of the first additive is 1 or more. The number of hydrohalic acid molecules in one molecule of the first additive can be an integer selected from 1 to 10; further, the number of hydrohalic acid molecules can be 1, 2, 3, 4, or 5; further, the number of hydrohalic acid molecules can be 1 or 2. In some embodiments, n is 1. In some embodiments, n is 2.

[0184] In some embodiments, the halogen in the hydrohalide salt includes one or more of F, Cl, Br and I;

[0185] Optionally, any halogen in the hydrohalide salt is independently F, Cl, Br or I;

[0186] Further optionally, the hydrohalide salt is hydrochloride.

[0187] In some embodiments, the first additive is a small molecule compound, further monodisperse. For a monodisperse small molecule compound, all of its molecules have a single numerical molecular weight. Further, in some embodiments, the molecular weight of the first additive is less than 1000Da, optionally, the molecular weight of the first additive is less than or equal to 500Da, further optionally, the molecular weight of the first additive is less than or equal to 300Da, further optionally, the molecular weight of the first additive is 100 to 300Da, and can also be any of the following molecular weights or an interval selected from any two of the following molecular weights: 100Da, 150Da, 200Da, 250Da, 300Da, etc., for example, it can also be selected from 150 to 300Da.

[0188] In some embodiments, the number of carbon atoms in the first additive is 2 to 40; further optionally, the number of carbon atoms in the first additive is 2 to 25; further optionally, the number of carbon atoms in the first additive is 2 to 20; further optionally, the number of carbon atoms in the first additive is 2 to 18; further optionally, the number of carbon atoms in the first additive is 2 to 15; further optionally, the number of carbon atoms in the first additive is 2 to 12; further optionally, the number of carbon atoms in the first additive is 2 to 10; further optionally, the number of carbon atoms in the first additive is 2 to 8; further optionally, the number of carbon atoms in the first additive is 2 to 6. Non-limiting examples of the number of carbon atoms in the first additive can be any of the following: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, etc., and can also be an interval consisting of any two of the above carbon atom numbers, for example, 2-30, 3-30, 4-30, 6-30, 2-25, 3-25, 4-25, 6-25, 2-20, 3-20, 4-20, 6-20, 2-18, 3-18, 4-18, 6-18, etc.

[0189] In this application, unless otherwise specified, “the number of carbon atoms in the first additive” refers to the number of carbon atoms contained in one molecule of the first additive.

[0190] In some embodiments, the number of non-hydrogen atoms in the first additive is 8 to 40; further optionally, the number of non-hydrogen atoms in the first additive is 10 to 30; further optionally, the number of non-hydrogen atoms in the first additive is 10 to 25; further optionally, the number of non-hydrogen atoms in the first additive is 10 to 20; further optionally, the number of non-hydrogen atoms in the first additive is 10 to 18. Non-limiting examples of the number of non-hydrogen atoms in the first additive can be any of the following: 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 28, 30, 35, etc., and can also be an interval consisting of any two of the above carbon atom numbers, such as 8 to 30, 8 to 25, 8 to 20, 10 to 30, 10 to 25, 10 to 20, etc.

[0191] In some embodiments, the first additive is a hydrohalide salt of an organic compound containing at least one of -NHNH- and -SS-. The number of carbon atoms in the first additive may be as defined in any suitable embodiment herein. The number of non-hydrogen atoms in the first additive may be as defined in any suitable embodiment herein. For example, the first additive may be a C-containing salt of at least one of -NHNH- and -SS-. 2-40 Compound hydrohalide.

[0192] The type and quantity of the weakly reducing groups in the aforementioned additive (first additive), the type and quantity of the hydrohalic acid molecules, and the molecular weight of the additive can be finely adjusted to better match the perovskite precursor material, better reduce defects in the perovskite film, and better improve the service life of the perovskite cell. The molecular weight of the first additive can be indirectly adjusted by adjusting the number of carbon atoms or non-hydrogen atoms.

[0193] In some embodiments, the first additive is a hydrohalide salt, and n HZ are complexed in one molecule, and any Z is independently a halogen atom. n is the number of hydrohalic acid molecules in one molecule of the first additive, and can refer to the definition above. n can be an integer selected from 1 to 10, and can also be 1, 2, 3, 4 or 5, and can further be 1 or 2. In some embodiments, n=1. In some embodiments, n=2. In some embodiments, the first additive is a combination of n being a plurality of different integers, corresponding to a combination of first additive molecules with different numbers of HZ. For example, n can be a combination of 1 and 2. In this case, among the additives in the perovskite precursor solution, n is 1 in some molecules and 2 in other molecules.

[0194] In some embodiments, in a first aspect, a perovskite precursor solution comprises a perovskite precursor material, a solvent, and an additive; one molecule of the first additive contains m R 01 , any R 01 are independently weak reducing groups; the first additive is a hydrohalide salt, and n HZ are complexed in one molecule, and any Z is independently a halogen atom; wherein m and n are each independently a positive integer.

[0195] In some embodiments, in a first aspect, a perovskite precursor solution comprises a perovskite precursor material, a solvent, and an additive; one molecule of the first additive contains m R 01 , any R 01 Any group independently selected from the following group: -NHNH-, -SS-, -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group and hydroxynaphthyl group; the first additive is a hydrohalide salt, and n HZ are complexed in one molecule, and any Z is independently a halogen atom; wherein m and n are each independently a positive integer.

[0196] In some embodiments, any Z is independently F, Cl, Br or I; alternatively, Z is Cl.

[0197] By adding a compound hydrohalide additive containing a weak reducing group (such as but not limited to one or more of -NHNH-, -SS-, -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group and hydroxynaphthyl group) to the perovskite precursor solution, the halide metal portion BX2 in the main component ABX3 in the perovskite precursor solution and the perovskite film can be reduced to X2 by reducing the zero-valent state of X2 to X - Increase the storage time of the perovskite precursor solution. On the other hand, its weak reducing property will not 2+ B reduced to zero valence 0 On the other hand, the additive can participate in the crystallization reaction and be evenly dispersed in the perovskite film, acting as a sacrificial agent to extend the service life of the perovskite device. On the other hand, it can inhibit B 0 The formation of X2 reduces defects at the interface and improves the performance of perovskite devices. By forming hydrohalides (such as hydrochlorides), the additives can be better dissolved in the perovskite precursor solution and more evenly distributed in the perovskite film. Taking chloride ions as an example, it can also enhance electron transport, thereby improving the performance of perovskite devices.

[0198] In some embodiments, Z is chlorine. In this case, the first additive is a hydrochloride containing a weak reducing group. On the one hand, a trace amount of Cl - Hydrochloric acid itself promotes perovskite crystallization, has minimal side reactions, and does not participate in the crystal lattice. Furthermore, hydrochloric acid is more soluble than other hydrohalides. Furthermore, hydrochloric acid is readily soluble in perovskite precursor solutions in solvent systems such as DMF (dimethylformamide), NMP (N-methylpyrrolidone), and DMSO (dimethyl sulfoxide). Compared to weak acid salts, hydrochloric acid salts more readily incorporate into perovskite systems, whereas weak acid salts are less likely to do so.

[0199] In some embodiments, the first additive has a structure shown in formula (1); L(Z1-R 11 ) p1 ·nHZ (1);

[0200] In formula (1), p1 is 0 or a positive integer; n is a positive integer; Z is the halogen in the hydrohalide salt, and n is the number of hydrohalic acid molecules in the hydrohalide salt;

[0201] Any R 11 is independently the weak reducing group and has a valence of 1 (optionally, any one R 11 are independently -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group or hydroxynaphthyl group; further optionally, any one of R 11 are independently -NHNH2, sulfinic acid or phosphinic acid; further, any one of R 11are independently -NHNH2 or sulfinyl);

[0202] When p1 is 0, the first additive is a hydrohalide salt of an organic compound containing at least one of -NHNH- and -SS- (the molecular weight of the first additive may be directly or indirectly as defined above; further, the first additive may be a C 2-40 Compound hydrohalide, the number of carbon atoms in the first additive may be further defined);

[0203] When p1 is a positive integer, L is an alkyl group, heteroalkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, substituted alkyl group, substituted heteroalkyl group, substituted cycloalkyl group, substituted heterocycloalkyl group, substituted aryl group or substituted heteroaryl group with a valence of p1; when L contains a heteroatom, any heteroatom in L is independently a non-carbon, non-hydrogen atom (further independently selected from any one of N, S, P, O and B);

[0204] L and all Z1 contain p2 divalent groups selected from the group consisting of -NH-NH- and -SS-, p2 is 0 or a positive integer; (p1+p2)≥1;

[0205] Z1 is a chemical bond, a carbonyl group, -CH2-, -CH(Q1)- or -(Q2)C(Q3)-, wherein Q1, Q2 and Q3 are each independently selected from the group consisting of an alkyl group, a heteroalkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, a substituted alkyl group, a substituted heteroalkyl group, a substituted cycloalkyl group, a substituted heterocycloalkyl group, a substituted aryl group and a substituted heteroaryl group; when Z1 contains a heteroatom, any heteroatom in Z1 is independently a non-carbon, non-hydrogen atom (further independently selected from any one of N, S, P, O and B); optionally, Z1 is -CH2-, -CH(Q1)- or -(Q2)C(Q3)-;

[0206] Any R 11 Independently directly bonded to a carbon atom in Z1 or L;

[0207] In formula (1), the alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl group in any one of the substituted alkyl, substituted heteroalkyl, substituted heterocycloalkyl, substituted aryl or substituted heteroaryl contained in L, Z1, Q1, Q2 or Q3 is independently substituted by one or more groups selected from the following group G1: alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, -CN, hydrazine, sulfinic acid, phosphinic acid, -OH, -NH2, -COOH, sulfonic acid, phosphonic acid, boric acid and halogen.

[0208] This application relates to the weak reducing groups (which can be recorded as R01 ) can be a monovalent group R 11 , such as -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl or hydroxynaphthyl group, or a divalent group such as -NH-NH-, -SS-, etc., two different valence R 01 It can be any one of the above or a combination of the two. 01 Existing at the end group, it encounters relatively less steric hindrance when interacting with other components in the precursor solution. 01 It also acts as a connecting base, which can flexibly adjust the position in the molecule to regulate steric hindrance, thereby adjusting R 01 The additive contains a weak reducing group R 01 In addition to the hydrohalic acid molecule HZ, it also includes the main part L(Z1-) p1 The main part is an aromatic or aliphatic group, which can generate a certain surface tension on the lower surface (the lower surface refers to the surface used for coating) when the solvent is quenched, promoting the formation of crystal nucleation sites and the progress of the crystallization reaction. Z1 can be absent; Z1 can also be a spacer group with a length of 1 spacer atom. In this case, the structural characteristics of Z1 can be used to adjust the connected R 11 For example, when L is a benzene ring, R 11 When it is a hydrazine group -NHNH2, Z1 is -CH2-, -CH(Q1)- or -(Q2)C(Q3)- (further such as -CH2-), which is beneficial to improving the stability of the perovskite precursor solution and thus extending the shelf life of the precursor.

[0209] In this application, unless otherwise stated, R 11 Is a monovalent weak reducing group. 11 It can be independently any one of -NHNH2, sulfinic acid group, phosphinic acid group, hydroxyphenyl group and hydroxynaphthyl group, further any one of -NHNH2, sulfinic acid group and phosphinic acid group; further any one of -NHNH2, sulfinic acid group. In some embodiments, R 11 In some embodiments, R 11 It is a sulfinic acid group.

[0210] In some embodiments, Q1, Q2 and Q3 are each independently selected from the group consisting of: alkyl (optionally C 1-8 Alkyl, further optionally C 1-6 Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 Alkyl, further optionally methyl), heteroalkyl (optionally alkoxy or secondary amino, further optionally C 1-8 Alkoxy or C 1-8Alkylamino, further optionally C 1-6 Alkoxy or C 1-6 Alkylamino, further optionally C 1-4 Alkoxy or C 1-4 Alkylamino, further optionally C 1-3 Alkoxy or C 1-3 Alkylamino, further optionally -NHCH3 or -NHCH2CH3, further optionally -NHCH3), cycloalkyl (optionally C 3-8 Cycloalkyl, further optionally C 3-6 Cycloalkyl, further optionally cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), heterocycloalkyl (optionally 3-8 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-6 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-4 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally piperidinyl, piperazinyl or monoazetidinyl, further optionally ), aryl (optionally C 6-12 Aryl, further optionally C 6-10 aryl, which may be phenyl, naphthyl or biphenyl), heteroaryl (a 6- to 12-membered aryl containing 1 to 6 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 to 4 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 to 3 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 or 2 nitrogen atoms on the ring, which may be further N 1-2 Azaphenyl, further optionally monoazaphenyl or diazaphenyl, further optionally pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl), substituted alkyl (such as benzyl, When Z1 contains a heteroatom, any heteroatom in Z1 is independently a non-carbon, non-hydrogen atom (which can further be independently selected from any one of N, S, P, O and B).

[0211] In the present application, unless otherwise specified, the group G1 group is a group consisting of one or more substituents, which may include but are not limited to alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, -CN, hydrazine, sulfinic acid, phosphinic acid, -OH, -NH2, -COOH, sulfonic acid, phosphonic acid, boric acid and halogen.

[0212] In the present application, a "halogen" substituent, which may also be referred to as a halo group, is considered to fall within the scope of a "group" in the present application.

[0213] In some embodiments, the group G1 includes an alkyl group (optionally C 1-8Alkyl, further optionally C 1-6 Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 Alkyl, further optionally methyl), heteroalkyl (optionally alkoxy or secondary amino, further optionally C 1-8 Alkoxy or C 1-8 Alkylamino, further optionally C 1-6 Alkoxy or C 1-6 Alkylamino, further optionally C 1-4 Alkoxy or C 1-4 Alkylamino, further optionally C 1-3 Alkoxy or C 1-3 Alkylamino, further optionally -NHCH3 or -NHCH2CH3, further optionally -NHCH3), cycloalkyl (optionally C 3-8 Cycloalkyl, further optionally C 3-6 Cycloalkyl, further optionally cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), heterocycloalkyl (optionally 3-8 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-6 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-4 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally piperidinyl, piperazinyl or monoazetidinyl, further optionally ), aryl (optionally C 6-12 Aryl, further optionally C 6-10 aryl, which may be phenyl, naphthyl or biphenyl), heteroaryl (a 6- to 12-membered aryl containing 1 to 6 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 to 4 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 to 3 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 or 2 nitrogen atoms on the ring, which may be further N 1-2 azaphenyl, further optionally monoazaphenyl or diazaphenyl, further optionally pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl), -CN, hydrazine, sulfinic acid, phosphinic acid, -OH, -NH2, -COOH, sulfonic acid, phosphonic acid, boric acid and halogen (optionally one or more of F, Cl, Br and I).

[0214] In some embodiments, the group G1 is a group G2 comprising the following groups: alkyl (optionally C 1-8 Alkyl, further optionally C 1-6 Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 Alkyl, further optionally methyl), heteroalkyl (optionally alkoxy or secondary amino, further optionally C1-8 Alkoxy or C 1-8 Alkylamino, further optionally C 1- 6 alkoxy or C 1-6 Alkylamino, further optionally C 1-4 Alkoxy or C 1-4 Alkylamino, further optionally C 1-3 Alkoxy or C 1-3 Alkylamino, further optionally -NHCH3 or -NHCH2CH3, further optionally -NHCH3), cycloalkyl (optionally C 3-8 Cycloalkyl, further optionally C 3-6 Cycloalkyl, further optionally cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), heterocycloalkyl (optionally 3-8 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-6 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-4 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally piperidinyl, piperazinyl or monoazetidinyl, further optionally ), aryl (optionally C 6-12 Aryl, further optionally C 6-10 Aryl, which may be phenyl, naphthyl or biphenyl) and heteroaryl (a 6- to 12-membered aryl containing 1 to 6 nitrogen atoms on the ring, further a 6- to 12-membered aryl containing 1 to 4 nitrogen atoms on the ring, further a 6- to 12-membered aryl containing 1 to 3 nitrogen atoms on the ring, further a 6- to 12-membered aryl containing 1 or 2 nitrogen atoms on the ring, further N 1-2 Azaphenyl, further optionally monoazaphenyl or diazaphenyl, further optionally pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl); optionally, the group G1 is a group G1 including the following groups b : methyl, cyclopentyl, cyclopentylmethyl, phenyl, benzyl, biphenyl, methylphenyl, piperidinyl (optional ), piperazinyl (optionally ) and monoazetidinyl (optionally ); Optionally, the group G1 includes methyl, cyclopentyl, phenyl, benzyl, biphenyl, methylphenyl, piperidinyl (optionally ) and monoazetidinyl (optionally ).

[0215] In some embodiments, Q1, Q2 and Q3 are each independently selected from the group consisting of: 1-6 Alkyl, C 1-6 Heteroalkyl, C 3- 8 cycloalkyl, C 3-8 Heterocycloalkyl, C6-12 Aryl, C 3-11 Heteroaryl, substituted C 1-6 Alkyl, substituted C 1-6 Heteroalkyl, substituted C 3-8 Cycloalkyl, substituted C 3-8 Heterocycloalkyl, substituted C 6-12 Aryl and substituted C 3-11 Heteroaryl; optionally, Q1, Q2 and Q3 are each independently selected from the group consisting of: C 1-3 Alkyl, C 1-3 Heteroalkyl, C 3-6 Cycloalkyl, C 3-6 Heterocycloalkyl, C 6-10 Aryl, C 3-9 Heteroaryl, substituted C 1-3 Alkyl, substituted C 1-3 Heteroalkyl, substituted C 3-6 Cycloalkyl, substituted C 3-6 Heterocycloalkyl, substituted C 6-10 Aryl and substituted C 3-9 Heteroaryl; further optionally, Q1, Q2 and Q3 are each independently selected from the group consisting of: methyl, methoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, piperidinyl (optionally ), piperazinyl (optionally )phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl and N 1～6 Azanaphthyl, and any substituted form of the foregoing groups; wherein, when Q1, Q2 or Q3 is any substituted form of the foregoing, it can be independently substituted by one or more (optionally, 1 or 2 to 5, further optionally, 1, 2 or 3) selected from the following group G1 a Substituted by groups in: methyl, cyclopentyl, phenyl, benzyl, methylphenyl, -Ph-Ph, N 1～2 Aza-heterocycloalkyl (optionally a single aza-C 3- 8-cycloalkyl or diaza C 3-8 Cycloalkyl, further optionally monoazetidinyl, piperidinyl or piperazinyl, further optionally monoazetidinyl, further optionally monoazetidinyl ), -CN, hydrazino, sulfinic acid, phosphinic acid, -OH, -NH2, -COOH, sulfonic acid, phosphonic acid, boric acid and halogen (optionally one or more of F, Cl, Br and I).

[0216] In some embodiments, Z1 is a chemical bond, a carbonyl group, or a methylene group (ie, -CH2-) or -CH(Q1)-.

[0217] In some embodiments, Z1 is a chemical bond, a carbonyl group, or a methylene group (ie, -CH2-).

[0218] In some embodiments, Z1 is -CH2-, -CH(Q1)-, or -(Q2)C(Q3)-.

[0219] In some embodiments, Z1 is methylene.

[0220] In some embodiments, Z1 is -CH(Q1)- or -(Q2)C(Q3)-. Preferably, Q1, Q2 and Q3 are substituents with small steric hindrance to avoid affecting the crystallization of perovskite. The substituents with small steric hindrance, for example, the number of rings in the ring structure is ≤3 (can be 1, 2 or 3), and the number of carbon atoms in the chain structure is ≤12 (optionally, ≤10, further optionally, ≤8, further optionally, ≤6; for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and can also be an interval consisting of any two of the aforementioned integers, for example, 1 to 10, 1 to 8, 1 to 6, etc.).

[0221] In some embodiments, Z1 is -CH(Q1)-.

[0222] In some embodiments, Z1R 11 -C(=O)NHNH2. According to the intermediate bridging theory, this may be beneficial for prolonging the stable existence of the functional group -NHNH2. Furthermore, under special circumstances (such as light exposure and heating), it may coordinate with the B-site cations of the perovskite layer, enhancing stability.

[0223] In some embodiments, Z1 is connected to an aromatic ring in L, and Z1 may or may not be a carbonyl group. In some embodiments, Z1 is not a carbonyl group. In other embodiments, Z1 is a carbonyl group. In some embodiments, R 11 It is -NHNH2.

[0224] In some embodiments, Z1 is a chemical bond, -CH2-, -CH(Q1)-, or -(Q2)C(Q3)-.

[0225] In some embodiments, Z1 is a chemical bond.

[0226] In some embodiments, Z1 is -CH2-.

[0227] In some embodiments, Z1 is -CH(Q1); further, Q1 can be methyl, phenyl, cyclopentyl, benzyl, -Ph-CH3, Any one of the above.

[0228] In the present application, when referring to -Ph-, the two connection sites can be ortho, meta or para. In some embodiments, -Ph- is 1,4-phenylene.

[0229] In some embodiments, Z1 is any of the following divalent groups: methylene, -CH(CH3)-, -CH(benzyl)-, -CH(cyclopentyl)-, -CH(-Ph-Ph)-, -CH(phenyl), -CH(-Ph-CH3)-, and .

[0230] In the present application, L can correspond to a compound molecule or a part of a compound structure. When L is a compound molecule, p1 is 0, and the overall valence of L is 0, and L contains a multivalent weak reducing group (such as a divalent weak reducing group). When L is a part of a compound structure, it can be a group composed of multiple atoms and has p1 groups that can be connected to -Z1-R 11 Location.

[0231] Unless otherwise stated, L in this application contains carbon atoms.

[0232] In some embodiments, L can be a chain structure or a ring structure.

[0233] In this application, unless otherwise specified, a "chain structure" does not contain a ring structure and can be a straight chain or a branched chain. A straight chain structure such as (-CH2-) n , a branched structure such as -CH2CH2-CH(CH3)-. The branched structure includes a main chain and branches grafted to the main chain, and the branched portion contains non-hydrogen atoms and can contain one or more of carbon atoms and heteroatoms.

[0234] In this application, the ring in the "ring-containing structure" can be an aromatic ring, an aliphatic ring, or a combination thereof. Examples of aromatic rings include benzene rings, naphthalene rings, pyridine rings, and biphenyl rings. Examples of aliphatic rings include hexyl rings, pentyl rings, and monoazetidinyl rings.

[0235] In some embodiments, L may be an aliphatic structure or an aromatic structure.

[0236] In this application, those skilled in the art will understand the meaning of "aliphatic structure" and "aromatic structure." An "aromatic structure" may contain one or more of an aryl group and a heteroaryl group. An "aliphatic structure" does not contain any aromatic structure, and does not contain either an aryl group or a heteroaryl group.

[0237] In some embodiments, L is a chain structure; further, the number of carbon atoms in L can be as defined above. For example, L can be C 2-20 Chain structure; further optionally, L is C 2-18 Chain structure; further optionally, L is C 2-15 Chain structure; further optionally, L is C 2-12 Chain structure; further optionally, L is C2-10 Chain structure; further optionally, L is C 2-8 Chain structure.

[0238] In some embodiments, L is a ring-containing structure, and further, the number of ring atoms in L can be 3 to 25; alternatively, 3 to 20; further alternatively, 3 to 18; further alternatively, 5 to 18; further alternatively, 5 to 15; further alternatively, 5 to 12; further alternatively, 5, 6, 10, 11 or 12; further alternatively, 6, 10, 11 or 12. The number of ring atoms in L can also be any of the following: 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, etc., and can also be an interval selected from any two of the foregoing numbers of ring atoms, for example, 6 to 25, 6 to 20, 6 to 18, 6 to 15, 6 to 12, 6 to 10, etc.

[0239] In this application, unless otherwise specified, "ring-membering atoms" refer to the non-hydrogen atoms that make up the ring backbone. For example, benzene has 6 non-hydrogen atoms, naphthalene has 10, toluene has 6, biphenyl has 12, pyridine has 6, hexyl ring has 6, pentyl ring has 5, piperidine has 6, piperazine has 6, and benzyl has 6.

[0240] In this application, a "non-hydrogen atom" may be a carbon atom or a heteroatom. A "heteroatom" is a type of atom other than a carbon atom and a hydrogen atom, also referred to as a "non-carbon, non-hydrogen atom." Non-limiting examples of heteroatoms include N, S, P, O, and B.

[0241] In some embodiments, the number of carbon atoms in L is 2 to 40, and can also be any of the following numbers: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, etc., and can also be an interval selected from any two of the foregoing numbers, for example, 2 to 40, 2 to 35, 3 to 40, 3 to 35, 4 to 40, 4 to 35, 6 to 40, 6 to 35, 8 to 40, 8 to 35, etc.

[0242] In some embodiments, the number of carbon atoms in L is 2 to 30, and can also be any of the following numbers: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, etc., and can also be an interval selected from any two of the above numbers, for example, 2 to 2 5. 2~20, 2~18, 2~15, 2~12, 2~10, 2~8, 3~30, 3~25, 3~20, 3~18, 3~15, 3~12, 3~10, 4~30, 4~25, 4~20, 4~18, 4~15, 4~12, 4~10, 6~30, 6~25, 6~20, 6~18, 6~15, 6~12, 6~10, etc.

[0243] In some embodiments, L is a ring-containing structure, and further, the number of carbon atoms in L can be defined as in any of the previous embodiments. For example, L can be a ring-containing structure containing 2 to 40 carbon atoms; alternatively, the number of carbon atoms in L is 3 to 30; further alternatively, 3 to 25; further alternatively, 3 to 20; further alternatively, 3 to 18; further alternatively, 4 to 18.

[0244] In some embodiments, the number of non-hydrogen atoms in L is 2 to 35, and can also be any of the following numbers: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, etc., and can also be selected from An interval consisting of any two of the above quantities, for example, 2-30, 2-25, 2-20, 2-18, 2-15, 2-12, 2-10, 2-8, 4-35, 4-30, 4-25, 4-20, 4-18, 4-15, 4-12, 4-10, 6-35, 6-30, 6-25, 6-20, 6-18, 6-15, 6-12, 6-10, etc.

[0245] In some embodiments, L is a ring-containing structure, and further, the ring in L can be an aromatic ring, an aliphatic ring, or a combination thereof.

[0246] In some embodiments, the ring in L includes an aromatic ring, and further, the number of carbon atoms in L can be as defined above. For example, it can be 3 to 40; further alternatively, the number of carbon atoms in L is 3 to 30; further alternatively, the number of carbon atoms in L is 3 to 25; further alternatively, it is 3 to 20; further alternatively, it is 3 to 18; further alternatively, it is 5 to 18; further alternatively, it is 5 to 15; further alternatively, it is 5 to 12; further alternatively, it is 5, 6, 10, 11 or 12; further alternatively, it is 6, 10, 11 or 12.

[0247] In some embodiments, the ring in L includes an aliphatic ring. Further, the number of carbon atoms in L can be as defined above, for example, it can be 2 to 40; alternatively, the number of carbon atoms in L is 3 to 40; further alternatively, the number of carbon atoms in L is 3 to 30; further alternatively, the number of carbon atoms in L is 3 to 25; further alternatively, it is 3 to 20; further alternatively, it is 3 to 18; further alternatively, it is 5 to 18; further alternatively, it is 5 to 15; further alternatively, it is 5 to 12; further alternatively, it is 5, 6, 10, 11 or 12; further alternatively, it is 6, 10, 11 or 12.

[0248] In some embodiments, L is an aliphatic structure, and further, the number of carbon atoms in L can be as defined above. For example, the number of carbon atoms in L can be 2 to 25; further optionally 2 to 20; further optionally 2 to 18; further optionally 2 to 15; further optionally 2 to 12; further optionally 2 to 10; further optionally 2 to 8.

[0249] In some embodiments, L is an aromatic structure. Further, the number of carbon atoms in L can be as defined above. For example, L can include one or more of aryl, heteroaryl, substituted aryl, and substituted heteroaryl; 6-20 Aryl, C 4-20 Heteroaryl, substituted C 6-20 Aryl and substituted C 4-20 One or more of heteroaryl; further optionally, L comprises C 6-10 Aryl, C 4-10 Heteroaryl, substituted C 6-10 Aryl and substituted C 4-10 One or more heteroaryl groups.

[0250] When p1=0, the structure of the first additive is L·nHZ. At this time, the monovalent weak reducing group R 11The number of is 0, and L contains a multivalent weakly reducing group, such as a divalent weakly reducing group. Furthermore, for example, when p1 = 0, L may contain one or more divalent groups selected from the group consisting of -NH-NH- and -SS-. It is understood that when L does not contain -NH-NH- and contains only one weakly reducing group, -SS-, L contains an atom or group capable of donating a lone pair of electrons, thereby enabling complexation with the hydrohalide molecule.

[0251] In some embodiments, p1 is a positive integer, which can be further selected from a positive integer of 1 to 10; optionally, p1 is 1, 2, 3, 4 or 5; optionally, p1 is 1 or 2.

[0252] In some embodiments, p1 is 0, 1, or 2.

[0253] When p1 is a positive integer (ie, ≥1), the first additive includes at least one monovalent weak reducing group.

[0254] In some embodiments, p1 is a positive integer, L is a C 2-18 Alkyl, C 2-18 Heteroalkyl, C 3-20 Cycloalkyl, C 3- 20 Heterocycloalkyl, C 6-20 Aryl, C 3-20 Heteroaryl, substituted C 2-18 Alkyl, substituted C 2-18 Heteroalkyl, substituted C 3-20 Cycloalkyl, substituted C 3-20 Heterocycloalkyl, substituted C 6-20 Aryl or substituted C 3-20 Heteroaryl; optionally, L is a C in p1 valence state 2- 12 Alkyl, C 2-12 Heteroalkyl, C 3-12 Cycloalkyl, C 3-12 Heterocycloalkyl, C 6-15 Aryl, C 3-15 Heteroaryl, substituted C 2-12 Alkyl, substituted C 2-12 Heteroalkyl, substituted C 3-12 Cycloalkyl, substituted C 3-12 Heterocycloalkyl, substituted C 6-15 Aryl or substituted C 3- 15 Heteroaryl; further optionally, L is a C in p1 valence state 2-10 Alkyl, C 2-10 Heteroalkyl, C 5-10 Cycloalkyl, C 4-10 Heterocycloalkyl, C 6-10Aryl, C 3-10 Heteroaryl, substituted C 2-10 Alkyl, substituted C 2-10 Heteroalkyl, substituted C 5-10 Cycloalkyl, substituted C 4- 10 Heterocycloalkyl, substituted C 6-10 Aryl or substituted C 3-10 Heteroaryl; further optionally, L is a linear structure; wherein, when L contains heteroatoms, any one of the heteroatoms in L is independently a non-carbon, non-hydrogen atom, and further independently selected from any one of N, S, P, O, and B.

[0255] In some embodiments, L is phenyl, naphthyl, cyclopentyl, cyclohexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, heptadecyl, n-octadecyl, pyridyl, piperidyl, piperazinyl, N-methylpiperidyl, methylphenyl, dimethylphenyl, biphenyl, naphthyl-substituted phenyl, aminophenyl, C 2-18 alkyl substituted with one or more sulfonic acid groups (optionally ethyl substituted with a single sulfonic acid group, further optionally 2-sulfoethyl), C 2-18 alkyl substituted with one or more NH2 groups (optionally C 2-18 alkyl substituted with one -NH2 group, further optionally C 2-18 alkyl, further optionally aminobutyl, and still further optionally 4-aminobutyl), C 2-12 alkyl substituted with one or more -(O=)P(OH)2 groups (optionally C 02 alkyl substituted with one -(O=)P(OH)2 group, further optionally C 2-18 alkyl, further optionally phosphonopropyl, and still further optionally 3-phosphonopropyl), C 02 alkyl substituted with one or more -(O=)PR 2-12 (OH) groups (optionally C 02 alkyl substituted with one -(O=)PR 2-8 (OH) group, further optionally C 02 (CH3)(OH)(R 2～8 )P(=O)-C 02 alkylene-, still further optionally (CH3)(OH)(R 2～8 )P(=O)-(CH2) 02 -, still further optionally (CH3)(OH)(R 02 )P(=O)-(CH2)3-), and R 1-6 is alkyl (optionally C 1-3alkyl, further optionally methyl), one or more -(O=)PR 02 (OH) and one or more NH2-substituted C 2-18 Alkyl (optionally 1 -(O=)PR 02 (OH) and one NH2-substituted C 2-18 Alkyl, further optionally 1 -(O=)PR 02 (OH) and one NH2-substituted C 2-12 Alkyl, further optionally 1 -(O=)PR 02 (OH) and one NH2-substituted C 2-8 Alkyl, further optionally (CH3)(OH)(R 02 )P(=O)-CH2CH2CH(NH2)-), sulfonic acid phenyl, carboxylic acid phenyl, phosphonic acid phenyl and boric acid phenyl

[0256] In some embodiments, L is an aliphatic structure and Z1 is a chemical bond or a carbonyl group (Z1 can optionally be a chemical bond).

[0257] In some embodiments, L is an aromatic structure and Z1 is not a chemical bond.

[0258] In some embodiments, p1 is a positive integer, and R 11 When all are -NHNH2, at least one R 11 Connected to -CH2-, -CH(Q1)- or -(Q2)C(Q3)-; the definitions of Q1, Q2 and Q3 can refer to the structure of any embodiment herein, for example, Q1, Q2 and Q3 can be each independently selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and substituted heteroaryl;

[0259] Optionally, Q1, Q2 and Q3 are each independently selected from the following groups: alkyl, aralkyl, heteroaralkyl, substituted alkyl, substituted aralkyl and substituted heteroaralkyl; wherein, when Q1, Q2 or Q3 is any of the above substituted forms, it can be independently substituted by one or more groups selected from the group G1.

[0260] Compared to directly attaching a hydrazine group to an aromatic ring (such as a benzene ring), a spacer group (such as an alkylene or substituted alkylene group, further exemplified by -CH2-, -CH(Q1)-, or -(Q2)C(Q3)-, and further exemplified by -CH2-) between the hydrazine group and the benzene ring can improve the stability of the perovskite precursor solution, thereby extending the shelf life of the precursor. Taking benzylhydrazine hydrochloride and phenylhydrazine hydrochloride as examples, the nitrogen of the hydrazine group has a valence of -1 and tends to lose electrons. Therefore, when the nitrogen of the hydrazine group in phenylhydrazine hydrochloride is directly attached to the benzene ring, the strong electron-withdrawing ability of the benzene ring exacerbates the electron loss process of the nitrogen of the hydrazine group, resulting in a relatively short existence of the phenylhydrazine hydrochloride as a sacrificial agent in the perovskite. In contrast, in benzylhydrazine hydrochloride, the hydrazine group and the benzene ring are separated by a methylene structure, and the hydrazine group is directly attached to the carbon atom of the methylene group. The methylene group tends to donate electrons, transferring electrons to the hydrazine group, thereby improving the stability of the benzylhydrazine hydrochloride, which is beneficial for improving the stability of the perovskite precursor solution and extending the shelf life of the precursor.

[0261] Furthermore, the presence of a spacer group between the hydrazine group and the aromatic ring in L facilitates the crystallization reaction and avoids lattice distortion. The spacer group increases steric hindrance, making it difficult for the first additive to enter the perovskite's ABX3 lattice, thus avoiding lattice distortion. Furthermore, because it is similarly soluble in the perovskite precursor solution, it can be evenly dispersed in the perovskite film, guiding crystallization nucleation to a certain extent.

[0262] When there is a spacer group between the hydrazine group and the aromatic ring in L, the life of the perovskite device can be extended. The degradation of perovskite is mainly due to the + and BX2 degradation, hydrochloride can inhibit the degradation of A-site cations. At this time, aromatic hydrazine compounds containing spacer groups can inhibit the degradation of halogen anions, and aromatic hydrazine compounds containing spacer groups are also more stable.

[0263] L can contain aromatic rings or aliphatic chains, which can produce different steric hindrances and electron-donating abilities, leading to different degrees of reactivity. For the same carbon number, aromatic ring structures are preferred over aliphatic chains. On the one hand, aromatic ring structures may not participate in the perovskite lattice. On the other hand, aliphatic chains are more hydrophobic than aromatic ones, which may reduce the crystal quality.

[0264] In some embodiments, when p1 is a positive integer, Z1 is directly connected to the aromatic ring in L, and the corresponding R 11 When it is a hydrazine group, Z1 is not a chemical bond. Further, R 11is -CH2-, -CH(Q1)- or -(Q2)C(Q3)-. The definitions of Q1, Q2 and Q3 can refer to the structure of any embodiment herein. For example, Q1, Q2 and Q3 can be independently selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and substituted heteroaryl; alternatively, Q1, Q2 and Q3 can be independently selected from the group consisting of alkyl, aralkyl, heteroaralkyl, substituted alkyl, substituted aralkyl and substituted heteroaralkyl; wherein, when Q1, Q2 or Q3 is any of the substituted forms above, it can be independently substituted by one or more groups selected from Group G1.

[0265] In some embodiments, p1 in the first additive is 1, R 11 is a hydrazine group, R 11 Not directly connected to the phenyl group. 11 An example of a group directly linked to a phenyl group is phenylhydrazine hydrochloride.

[0266] In some embodiments, L includes a sulfur-containing group, for example -SH. In this case, the number of -SH groups may be ≤5, for example 1, 2, 3, 4 or 5. This can promote the complexing ability of the perovskite precursor solution and may promote the crystallization of perovskite. 2+ stability and inhibit its dissociation during long-term use.

[0267] In some embodiments, p1 is a positive integer, R 11 is -NHNH2, optionally, at least one Z1 is not a chemical bond.

[0268] In some embodiments, p1 is a positive integer, and at least one R 11 is -NHNH2, any Z1 connected to -NHNH2 is independently -CH2-, -CH(Q1)- or -(Q2)C(Q3)-; L is an aromatic group, at least one -Z1-R 11 connected to the aromatic ring in L;

[0269] The definitions of Q1, Q2 and Q3 can refer to the structure in any embodiment of the present invention. For example, Q1, Q2 and Q3 can be independently selected from the following groups: alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and substituted heteroaryl; optionally, Q1, Q2 and Q3 are independently selected from the following groups: alkyl, aralkyl, heteroaralkyl, substituted alkyl, substituted aralkyl and substituted heteroaralkyl; wherein, when Q1, Q2 or Q3 is any of the substituted forms mentioned above, it can be independently substituted by one or more groups selected from the group G1.

[0270] In some embodiments, L is aryl, heteroaryl, substituted aryl, or substituted heteroaryl;

[0271] Optionally, L is C 6-20 Aryl, C 4-20 Heteroaryl, substituted C 6-20 Aryl and substituted C 4-20 Any of heteroaryl; further optionally, L is C 6-10 Aryl, C 4-10 Heteroaryl, substituted C 6-10 Aryl and substituted C 4-10 any of heteroaryl groups;

[0272] Wherein, when L is any of the substituted forms mentioned above, it can be independently substituted by one or more groups selected from the group G1.

[0273] When the first additive contains an aromatic ring, it may not participate in the perovskite lattice. On the other hand, it usually has a weaker hydrophobicity than a fatty chain and can improve the crystallization quality.

[0274] In some embodiments, the first additive has a structure shown in formula (11): Ar(-Z 21 -R 11 ) p1 nHCl (11)

[0275] In formula (11), p1 is a positive integer, Z 21 is -CH2-, -CH(Q1)- or -(Q2)C(Q3)-.

[0276] In some embodiments, the first additive has a structure shown in formula (12): Ar(-R 11 ) p1 nHCl (12)

[0277] In formula (12), p1 is a positive integer, R 11 It is a sulfinic acid group or a phosphinic acid group.

[0278] In some embodiments, the first additive has a structure represented by formula (13):

[0279] In formula (13), k1 and k2 are each independently 0 or 1; R 31 and R 32 are each independently an alkylene group; optionally, R 31 and R 32 Each independently is C 2-20 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-16 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-12 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-10 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-8 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-6 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-4 Alkylene.

[0280] In some embodiments, the first additive has a structure represented by formula (14):

[0281] In some embodiments, the first additive has a structure shown in formula (15):

[0282] In formula (14) and formula (15), k1 and k2 are each independently 0 or 1; Z 41 and Z 42 are each independently an alkylene group. 41 and Z 42 Each independently is C 2-15 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-12 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-10 Alkylene, further optionally, Z 41 and Z42 Each independently is C 1- 8 alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-6 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-4 Alkylene, further optionally, Z 41 and Z 42 Each is independently a methylene group, an ethylene group, a propylene group or a butylene group.

[0283] In some embodiments, Ar, Ar 21 and Ar 22 Each independently is an aromatic group. In some embodiments, Ar, Ar 21 and Ar 22 The number of ring atoms of each of the following is independently 5 to 15, further optionally 5 to 12, further optionally 5 to 10 or 12, further optionally 5, 6, 10 or 12. In other embodiments, Ar, Ar 21 and Ar 22 Each is independently an aryl, a heteroaryl, a substituted aryl or a substituted heteroaryl; wherein the aryl or heteroaryl in the substituted aryl or the substituted heteroaryl is independently substituted by one or more groups selected from the group G1. When containing heteroatoms, Ar, Ar 21 and Ar 22 Any heteroatom contained in any one of the above-mentioned compounds is independently a non-carbon, non-hydrogen atom, and is further independently selected from any one of N, S, P, O and B.

[0284] In some embodiments, Ar, Ar 21 and Ar 22 Each independently contains no more than 3 (eg, 1, 2, or 3) rings.

[0285] In some embodiments, any "cycloalkyl", "heterocycloalkyl", "aryl" or "heteroaryl" mentioned herein independently contains no more than 3 (eg, 1, 2 or 3) rings.

[0286] In some embodiments, any “substituted cycloalkyl”, “substituted heterocycloalkyl”, “substituted aryl”, or “substituted heteroaryl” referred to herein independently contains no more than 3 (eg, 1, 2, or 3) rings.

[0287] In some embodiments, L contains a weak acidic group, such as -COOH, sulfonic acid, phosphonic acid, and boric acid. Taking -COOH as an example, -COOH can weakly dissociate to form H +and COO - , H + Can inhibit A + Cationic degradation, COO - It has a strong ability to coordinate with B, enhancing the bulk stability of the perovskite and promoting the long-term stability of the perovskite. It should be noted that the introduction of weak acidic groups cannot replace the salt-forming effect of hydrohalic acid molecules. Hydrohalic acid salt formation (such as hydrochloric acid salt) can significantly improve solubility. When only weak acidic groups are present without the salt-forming effect of hydrohalic acid molecules, it may result in the inability to participate in the perovskite film due to reasons such as the pre-filtration step, or uneven distribution in the perovskite film, and the expected effect of the first additive cannot be exerted or the effect is poor.

[0288] In some embodiments, the first additive contains j second functional groups W 11 , W 11 is any group selected from the group consisting of: -COOH, sulfonic acid, phosphonic acid, and boric acid. 11 The number j can be 1 or more; optionally, j is 1, 2 or 3; further optionally, j is 1 or 2.

[0289] By introducing a weak acidic group (such as but not limited to one or more of -COOH, sulfonic acid, phosphonic acid and boric acid) into the first additive, the addition-elimination reaction of A (A is an organic cation) in ABX3 can be inhibited, thereby extending the service life of the perovskite device. In addition, when the acidity is consumed, it can also participate in the replenishment of the perovskite system to enhance the stability of the perovskite structure. When the weak acidic group coordinates with the B-site cation, it can also enhance electron transport. 11 The trace amount of acid anions can promote the formation of crystal seeds and enhance the quantitative formation of crystal seeds. When the perovskite is annealed, this type of substance is easy to separate from its lattice system, causing the overall perovskite to transform into a stable α phase.

[0290] In some embodiments, the first additive has a structure shown in formula (2): 11 ) j L0(R 02 ) m1 nHCl (2)

[0291] In formula (2), j is a positive integer, m1 is a positive integer; any R 02 are independently the weak reducing groups (optionally, any one of R 02A group independently selected from the group consisting of -NHNH-, -NHNH2, sulfinic acid and phosphinic acid groups); L0 is an m1+j valence hydrocarbon group or heterohydrocarbon group, wherein the heterohydrocarbon group contains 0, 1 or more substituents selected from the group consisting of -CN, -OH, halogen (optionally one or more of F, Cl, Br and I), -NH2, -SH, -CF3 and -COOH.

[0292] In some embodiments, the first additive has a structure shown in formula (21): 11 ) j1 L 01 (Z1-R 11 ) p1 nHCl (21)

[0293] In formula (21), p1 and j1 are each independently a positive integer, and any Z1 and any R 11 Each independently as defined above; L 01 (Z 1- ) p1 The weak reducing group (R 01 ) and j2 W 11 , wherein p2 and j2 are each independently 0 or a positive integer; L 01 It is a p1+j1 valence hydrocarbon group or heterohydrocarbon group, wherein the heterohydrocarbon group contains 0, 1 or more substituents selected from the following group: -CN, -OH, halogen (optionally one or more of F, Cl, Br and I), -NH2, -SH, -CF3 and -COOH.

[0294] In some embodiments, the first additive has a structure shown in formula (22): 11 ) j1 Ar 01 (-Z 31 -R 11 ) p1 nHCl (22)

[0295] In formula (22), p1, j1, any R 11 and any W 11 Each is independently defined as in formula (21); Ar 01 is a divalent aromatic group; wherein the divalent aromatic group contains 0, 1 or more substituents selected from the group consisting of: -CN, -OH, -NH2, -SH, -CF3 and -COOH, halogen; Z 31 is -CH2-, -CH(Q1)- or -(Q2)C(Q3)-; Q1, Q2 and Q3 are each independently selected from the following group G3: hydrocarbon group (optionally C 1-6Alkyl, further optionally C 1-3 Alkyl, further optionally methyl) and heteroalkyl (optionally alkoxy or alkylamino, further optionally C 1-6 Alkoxy or C 1-6 Alkylamino, further optionally C 1-3 Alkoxy or C 1-3 Alkylamino, further optionally methoxy, ethoxy, -NHCH3 or -NHCH2CH3, further optionally -NHCH3 or -NHCH2CH3, further optionally -NHCH3); wherein the heteroalkyl group contains 0, 1 or more substituents selected from the group consisting of -CN, -OH, halogen (optionally one or more of F, Cl, Br and I), -NH2, -SH, -CF3 and -COOH.

[0296] In some embodiments, the first additive has a structure represented by formula (23):

[0297] In some embodiments, the first additive has a structure represented by formula (24):

[0298] In formula (23) and formula (24), k1, k2, Z 41 and Z 42 Each is independently defined as in formula (14); j31 and j32 are each independently 0 or a positive integer, (j31+j32)≥1; W 31 and W 32 Each is independently any one group selected from the group consisting of -COOH, sulfonic acid, phosphonic acid, boric acid, -NH2 and -SH;

[0299] Ar 31 and A 32 Each of them can be independently a divalent aromatic group; wherein the divalent aromatic group contains 0, 1 or more substituents selected from the following group: -CN, -OH, amino, thiol and halogen (optionally one or more of F, Cl, Br and I).

[0300] The aforementioned role of the weak acid group can be more flexibly exerted by adjusting the type, quantity, location and other characteristics of the weak acid group.

[0301] In some embodiments, the number of rings in the first additive is ≤3, and can be 1, 2, or 3.

[0302] In some embodiments, the first additive includes any one or any suitable combination of the following compounds:

[0303] and the case where any of the aforementioned compound salts is substituted by a substituent selected from Group G1;

[0304] Wherein, n is as defined above, n can be a positive integer, further, n can be an integer selected from 1 to 10; further optionally, n is 1, 2, 3, 4 or 5; further optionally, n can be 1 or 2;

[0305] Q Ar Any group selected from the group G1; a is 0 or a positive integer (a can be 0, 1 or 2);

[0306] Q 10 is H or Q1; optionally, Q 10 is H; alternatively, Q 10 is Q1;

[0307] a1 and a2 are 0 or positive integers respectively, and a1+a2≥1;

[0308] b1, b2 and b3 are each 0 or a positive integer, and b1+b2+b2≥1, optionally, b2+b3≥1, more optionally, b1=0;

[0309] Q A1 , Q A2 and Q A3 Each independently is Q Ar ;

[0310] q is an integer selected from 2 to 20, optionally an integer from 2 to 18, further optionally an integer from 2 to 16, further optionally an integer from 2 to 12, further optionally an integer from 2 to 10, further optionally an integer from 2 to 8, further optionally 2, 3, 4, 5, 6 or 7;

[0311] c1 and c2 are each independently 0 or 1, optionally, c1+c2≥1;

[0312] Q 51 and Q 52 Each independently is an alkyl group (optionally C 1-6 Alkyl, further optionally C 1-3 alkyl, and further optionally methyl).

[0313] In some embodiments, the first additive includes any one or any suitable combination of the following compounds:

[0314] And any of the above compound salts is substituted by a substituent selected from the group G1. The definition of n in the above structure can be as described above. In some embodiments, n can be 1 or 2; in some embodiments, n is 1, and in other embodiments, n is 2. For example, Can be

[0315] The first additive may include any one or any suitable combination of the aforementioned compounds, thereby effectively improving the quality of the perovskite film and reducing defects, thereby effectively increasing the energy conversion efficiency of the perovskite cell. Furthermore, the perovskite cell can maintain good energy conversion efficiency for a long period of time and has good cell stability.

[0316] In some embodiments, the perovskite precursor material comprises a perovskite-type metal halide; the chemical formula of the perovskite-type metal halide is ABX3; wherein A is a monovalent cation, B is a divalent cation, and X is a monovalent anion.

[0317] In some embodiments, A includes Cs + , K + , Rb + , one or more of monovalent amine cations and monovalent amidino cations. Non-limiting examples of monovalent amine cations include CH3NH3 + (Methylamine, MA + ), ammonium (NH4 + ). Non-limiting examples of monovalent amidinium cations include NH2CH=NH2 + (Formamidine, can be written as FA + ).

[0318] In some embodiments, B includes Pb 2+ 、Sn 2+ 、Fe 2+ 、Mn 2+ 、Ni 2+ 、Ge 2+ 、Co 2+ and Sb 2+ One or more of .

[0319] In some embodiments, X comprises I - Br - and Cl - One or more of .

[0320] In some embodiments, X comprises I - Br - One or two of X can be 1 - Br -Or a combination thereof. In some embodiments, X is 1 - .

[0321] The first additive provided in this application can improve various types of perovskite precursor material systems, improve the quality of corresponding perovskite films, reduce defects, and extend the life of perovskite batteries.

[0322] In some embodiments, the weight percentage of the first additive relative to the B element in the perovskite precursor material is 0.01% to 15%; alternatively, the weight percentage of the first additive relative to the B element in the perovskite precursor material is 0.01% to 10%; alternatively, the weight percentage of the first additive relative to the B element in the perovskite precursor material is 0.1% to 8%. The weight percentage of the first additive relative to the B element in the perovskite precursor material can also be selected from any one of the following percentages or a range consisting of any two of the following percentages: 0.01%, 0.05%, 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.

[0323] In some embodiments, the relative molar ratio of the first additive to the B element in the perovskite metal halide is 0.001% to 15%; optionally, the relative molar ratio of the first additive to the B element in the perovskite metal halide is 0.01 to 15%; optionally, the relative molar ratio of the first additive to the B element in the perovskite metal halide is 2.0 to 6.5%. The relative molar ratio of the first additive to the B element in the perovskite metal halide can also be selected from any one of the following percentages or an interval consisting of any two of the following percentages: 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.

[0324] In some embodiments, the R 01 The relative molar ratio of the R to the B element in the perovskite metal halide is 0.01 to 15%. 01 The relative molar ratio of the R to the B element in the perovskite metal halide is 1.0 to 8.0%. 01The relative molar ratio of the B element to the perovskite metal halide can also be selected from any of the following percentages or an interval consisting of any two of the following percentages: 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.

[0325] The weak reducing contribution of the first additive to the perovskite precursor solution can be controlled by adjusting one or more of the following methods: the weight ratio percentage of the first additive relative to the B element in the perovskite precursor material, the molar ratio of the first additive relative to the B element in the perovskite precursor material, the relative molar ratio of the weak reducing group to the B element in the perovskite-type metal halide, etc., so as to better play the role of the first additive.

[0326] In some embodiments, the perovskite precursor solution further contains oxidized ions of a multivalent metal element M.

[0327] In this application, unless otherwise specified, a "multivalent metal element" refers to a metal element having multiple valence states that can exist stably.

[0328] In some embodiments, the multivalent metal element M includes one or more elements selected from the group consisting of lanthanide elements, Fe, Co, Ni, Ti, Cr, Mn, Y, Rh, and Bi;

[0329] Optionally, the lanthanide elements include one or more elements selected from Ce, Pr, Sm, Eu, Tb and Yb;

[0330] Optionally, the oxidation state ions of the multivalent metal element M include Ce 4+ 、Pr 4+ 、Sm 3+ 、Eu 3+ , Tb 4+ 、Yb 3+ 、Fe 3+ 、Co 3+ 、Ni 3+ 、Ti 4+ Cr 3+ 、Mn 4+ 、Y 3+ and Rh 4+ One or more of;

[0331] Optionally, the oxidized ions of the multivalent metal element M are derived from an organic salt of the metal element M. Further optionally, the organic salt comprises one or more of acetylacetonate, sulfonate and sulfate ester.

[0332] In some embodiments, the perovskite precursor solution contains Ce 3+ -Ce 4+ 、Pr 4+ -Pr 3+ 、Sm 3+ -Sm 2+ 、Eu 3+ -Eu 2+ , Tb 4+ -Tb 3+ 、Yb 3+ -Yb 2+ 、Fe 3+ -Fe 2+ 、Co 3+ -Co 2+ 、Ni 3+ -Ni 2+ 、Ti 4+ -Ti X+ Cr 3+ -Cr 2+ 、Mn 4+ -Mn 2+ 、Y 3+ -Y 2+ 、 Rh 4+ -Rh 2+ and Bi 3+ -Bi 2+ One or more ion pairs in the ion pair Ti 4+ -Ti X+ Ti X+ The positive charge state is less than 4.

[0333] By introducing the oxidation state of multivalent metal cations into the perovskite precursor solution, it is possible to react with B 0 The reaction forms a reduced cation, and the oxidation state and the reduced state of the multivalent metal cation can form a redox equilibrium pair, which can cyclically inhibit the degradation of BX2 in the perovskite film, thereby extending the life of the perovskite battery and improving the energy conversion efficiency; in addition, it can further inhibit the 0 and X2, reducing defects at the interface and further improving the performance of perovskite devices.

[0334] In some embodiments, the multivalent metal element M can be added by adding a second additive. Eu can be introduced by adding Eu(acau)3 (wherein acau is the abbreviation of acetylacetone). 3+ , and can form Eu in the perovskite precursor solution 3+ -Eu 2+ Ion pairs. For example, Fe can be introduced by adding Fe(acau)3 3+, and can form Fe in the perovskite precursor solution 3+ -Fe 2+ ion pair.

[0335] In this application, unless otherwise specified, the “second additive” refers to a raw material that can form the aforementioned multivalent metal element M or its ion pair after being added to the perovskite precursor solution.

[0336] In some embodiments, the perovskite precursor material comprises the aforementioned perovskite metal halide; the relative molar ratio of the multivalent metal element M to B in the perovskite metal halide is 0.001% to 15%; optionally, the relative molar ratio of the multivalent metal element M to B in the perovskite metal halide is 0.01% to 15%. The relative molar ratio of the multivalent metal element M to B in the perovskite metal halide can also be selected from any one of the following percentages or an interval consisting of any two of the following percentages: 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.

[0337] The same method as above can be used for detection B 2+ A concentration-similar method is used to detect the content of multivalent metal elements M and the content of corresponding ions with different valences.

[0338] In a second aspect, the present application provides a perovskite film, which is prepared using the perovskite precursor solution described in the first aspect of the present application.

[0339] The perovskite film prepared using the perovskite precursor solution described in the first aspect of the present application has few defects and high quality. The perovskite battery further prepared has high energy conversion efficiency and good battery stability.

[0340] In some embodiments, the perovskite film is prepared by a method comprising the following steps: applying the perovskite precursor solution described in the first aspect of the present application to a preset position, and performing annealing treatment to prepare the perovskite film.

[0341] The coating can be performed by a slot coating method.

[0342] The annealing temperature can be 100-180°C, for example, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 180°C, etc., and can also be selected from a temperature range consisting of any two of the above temperatures, such as 100-150°C, etc.

[0343] In a third aspect, the present application provides a perovskite cell, which includes the perovskite film described in the second aspect of the present application.

[0344] In some embodiments, the present application provides a perovskite cell comprising an electron transport layer, a hole transport layer, and the perovskite film described in the second aspect of the present application, wherein the perovskite film is disposed between the electron transport layer and the hole transport layer.

[0345] In some embodiments, the present application provides a perovskite battery comprising a positive electrode, a negative electrode, and the perovskite film described in the second aspect of the present application, wherein the perovskite film is disposed between the positive electrode and the negative electrode.

[0346] In some embodiments, the present application provides a perovskite battery comprising a positive electrode, an electron transport layer, the perovskite film described in the second aspect of the present application, a hole transport layer, and a negative electrode, arranged in sequence. Furthermore, the battery can be either an inverted PIN battery or a formal NIP battery.

[0347] The perovskite film described in the second aspect of the present application, which may also be referred to as a perovskite layer, is also the light-absorbing layer in the perovskite cell.

[0348] When a perovskite cell is operating, after the light-absorbing layer is exposed to light, the internal electrons gain energy and break free from the constraints of the light-absorbing layer to form negatively charged electron carriers. At the same time, positively charged hole carriers are formed, thereby forming electron-hole pairs. The free electrons and free holes are transmitted in opposite directions through the corresponding transport layers, causing the electrons and holes to flow, forming an external current and realizing the conversion of light energy into electrical energy. Furthermore, after the perovskite layer absorbs photons, it is stimulated to produce electron-hole pairs. The electron-hole pairs further dissociate to form free carriers with opposite charges. The free electrons are transmitted to the positive electrode through the electron transport layer, and the free holes are transmitted to the negative electrode through the hole transport layer. The two free carriers are collected by the corresponding electrodes, further forming a photocurrent in the perovskite cell circuit.

[0349] The electron transport layer can extract and transport electron carriers and block the passage of free holes.

[0350] The hole transport layer can extract and transport hole carriers and block the passage of free electrons.

[0351] It is understood that the perovskite battery further comprises two electrodes, one of which serves as a positive electrode to collect electron carriers transported via the electron transport layer, and the other serves as a negative electrode to collect hole carriers transported via the hole transport layer.

[0352] In some embodiments, the electron transport layer material can be one or more of the following materials and their derivatives: imide compounds, quinone compounds, fullerenes and their derivatives, methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), calcium titanate (CaTiO3), lithium fluoride (LiF), calcium fluoride (CaF2), poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT:PSS), poly 3-hexylthiophene (P3HT), triphenylamine with triptycene as the core (H101), 3,4-ethylenedioxythiophene ... Dioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamino)carbazole-spirobifluorene (CzPAF-SBF), polythiophene, metal oxides, silicon oxide (SiO2), strontium titanate (SrTiO3), cuprous thiocyanate (CuSCN), etc.; among which the metal elements can include one of Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga and Cr to obtain multiple elements.

[0353] In some embodiments, the hole transport layer can be at least one of the following materials and their derivatives: 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), polytriarylamine (PTAA), nickel oxide (NiO x ), poly 3,4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT:PSS), WO3, etc., one or more materials that can transport holes and block electrons.

[0354] In some embodiments, the perovskite cell 100 includes the structure shown in Figure 1, including a first electrode 120, a first transport layer 130, a perovskite layer 140, a second transport layer 150, and a second electrode 160 arranged in sequence. Furthermore, the structural layers are stacked in sequence as shown.

[0355] In some embodiments, the perovskite solar cell 100 includes the structure shown in Figure 2, including a substrate layer 110, a first electrode 120, a first transmission layer 130, a perovskite layer 140, a second transmission layer 150, and a second electrode 160 arranged in sequence. Furthermore, the structural layers are stacked in sequence as shown.

[0356] In some embodiments, the perovskite cell includes the structure shown in Figure 3 (a vertical cross-sectional structure diagram of the device), including a base layer 110, a first electrode 120, a first transmission layer 130, a perovskite layer 140, a second transmission layer 150, and a second electrode 160 stacked in sequence. Among them, P1, P2, and P3 are cross-layer etching areas, which are used to divide the film layer prepared over a large area into different components, so that it presents a series battery structure; wherein P1, P2, and P3 are respectively used to connect the structural layers arranged apart, so that the structural layer between the first electrode and the second electrode forms a loop, and the perovskite cell is formed into a perovskite cell component. P1, P2, and P3 can each independently be a linear etching area, also called an etching line. P1, P2, and P3 can each independently be a laser etching area. The number of P1, P2, and P3 can each independently be one or more. In Figure 3, P1 penetrates the first transmission layer and the bottom of the first electrode from the surface of the first transmission layer and is connected to the base layer, so that the left and right sides of the divided P1 are not connected to each other (to achieve insulation), and the material in the P1 etching area is consistent with that in the perovskite layer; P2 penetrates the second transmission layer, the perovskite layer, and the first transmission layer from the surface of the second transmission layer and is connected to the surface of the first electrode, and the material in the P2 etching area is consistent with that of the second electrode; P3 penetrates the second electrode, the second transmission layer, the perovskite layer, the first transmission layer from the surface of the second electrode to the surface of the first electrode, and no material is filled in the P3 etching area.

[0357] In some embodiments, the width of P1 is 10-50 μm, for example, 30 μm.

[0358] In some embodiments, the width of P2 is 10-200 μm, for example, 150 μm. Furthermore, the distance between P2 and P1 can be 20-80 μm, for example, 20 μm.

[0359] In some embodiments, the width of P3 is 10-50 μm, for example, 15 μm. Furthermore, the distance between P3 and P2 can be 20-40 μm, for example, 20 μm.

[0360] In some embodiments, P1 in the perovskite cell can extend from the surface of the first transport layer to the bottom of the first electrode, and the filling material of P1 is consistent with the perovskite layer (as shown in FIG3 ). In other embodiments, P1 in the perovskite cell can also extend from the surface of the first electrode to the bottom, and the filling material in P1 is consistent with the first transport layer.

[0361] In some embodiments, one of the "first transport layer" and the "second transport layer" is an electron transport layer and the other is a hole transport layer. In some embodiments, the first transport layer is an electron transport layer. In some embodiments, the first transport layer is a hole transport layer.

[0362] In some embodiments, one of the "first electrode" and the "second electrode" is a transparent electrode for light incidence. In some embodiments, the first electrode is a transparent electrode.

[0363] In some embodiments, the material of the transparent electrode may be exemplified by, but not limited to, one or more of the following materials: FTO (fluorine-doped tin oxide), ITO (tin-doped indium oxide), AZO (aluminum-doped zinc oxide transparent conductive glass), BZO (boron-doped zinc oxide), IZO (indium zinc oxide), IWO (tungsten-doped indium oxide), etc.

[0364] In some embodiments, the second electrode comprises a conductive material, which may be an organic conductive material, an inorganic conductive material, or a combination thereof. Non-limiting examples of inorganic conductive materials include metallic conductive materials: any one of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt), magnesium (Mg), or any suitable mixture thereof. The conductive material may be a conductive oxide. Further, non-limiting examples of conductive oxides may include FTO, ITO, IWO, aluminum-doped zinc oxide (AZO), and the like.

[0365] In some embodiments, the perovskite cell is any one of an inverted pin cell and a formal nip cell.

[0366] The perovskite cells provided in this application may include formal and trans types.

[0367] Officially, the perovskite cell includes a transparent electrode and an electron transport layer, a perovskite layer, a hole transport layer and a second electrode layer stacked in sequence on the transparent electrode.

[0368] For the trans type, the perovskite cell includes a transparent electrode and a hole transport layer, a perovskite layer, an electron transport layer and a second electrode layer sequentially stacked on the transparent electrode, wherein the transparent electrode is used for light incidence.

[0369] In some embodiments, the perovskite cell includes the following structures arranged in sequence: a substrate layer (which may be a glass substrate or a flexible substrate, a first electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode. The flexible substrate may include one or more materials selected from polyethylene terephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyethylene naphthalate, etc. Optionally, the first electrode is a transparent electrode for light incidence.

[0370] In some embodiments, the perovskite cell comprises the following structure, arranged in sequence: a substrate layer (glass or flexible), a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode. Optionally, the first electrode is a transparent electrode for light incidence. The definition of flexible substrate is described above.

[0371] The substrate layer involved in the implementation manner or examples of the present application may be, but is not limited to, a glass substrate or a flexible substrate.

[0372] In some embodiments, the substrate layer is a flexible substrate layer. Furthermore, the substrate layer may be made of, for example (but not limited to), an organic polymer material, and may be made of one or more of the following materials mixed in different proportions: including but not limited to polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), and the like.

[0373] In some embodiments, the base layer 110 in the structure shown in FIG3 is a light-incident glass base.

[0374] The specifications of the perovskite cell are not particularly limited and may be, but not limited to, 300 mm×300 mm.

[0375] It is understood that the structure of the perovskite cell involved in this application is not limited to the structural layers listed above. Other functional layers, such as buffer layers, may also be introduced as needed. In some embodiments, the perovskite cell may be provided with a buffer layer of appropriate energy level, which can play one or more roles in reducing energy barriers, promoting energy level matching, improving carrier extraction efficiency, passivating interface defects, protecting the light absorption layer, inhibiting the oxidative decomposition of water molecules and oxygen in the cell, improving photoelectric conversion efficiency, and improving the stability of the perovskite cell. Depending on the location of the buffer layer, the types of buffer layers may include a buffer layer between the hole transport layer and the anode, a buffer layer between the electron transport layer and the cathode, a buffer layer between the hole transport layer and the absorption layer, and a buffer layer between the electron transport layer and the absorption layer. Materials that can be used for the buffer layer in the perovskite cell may include, but are not limited to, Cu2O, NiO, AZO, TiO2, etc. In a fourth aspect, the present application provides an electrical device comprising the perovskite cell described in the third aspect of this application.

[0376] In some embodiments, the perovskite cell can be used as a power generation device for an electrical device. The type of power generation device can include, but is not limited to, an integrated power generation device. The location of the power generation device can include, but is not limited to, the roof or back panel of a vehicle.

[0377] Furthermore, the above-mentioned electrical devices may include mobile devices, such as mobile phones, laptop computers, etc., electric vehicles, electric trains, ships and satellites, power generation systems, etc., but are not limited thereto.

[0378] Figure 4 shows an example of an electric device 20. The electric device 20 is a car, and can further be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.

[0379] As another example, the electric device may be a mobile phone, a tablet computer, a laptop computer, a calculator, etc.

[0380] As another example, the power-consuming device may be a wearable device, such as a watch.

[0381] Below, some embodiments of the present application are described. The embodiment described below is exemplary, is only used to explain the present application, and cannot be construed as limiting the present application. In the embodiment, if no technology or conditions are indicated, it is carried out according to the description above, or according to the technology or conditions described in the document in this area or according to the product specification. Reagents used or instruments that are not indicated by the manufacturer are conventional products that can be obtained commercially, or can be synthesized in a conventional manner by commercially available products.

[0382] In the following embodiments, "room temperature" refers to 20°C to 30°C, and further, may be 25°C.

[0383] The types of first additives involved in the following embodiments can be found in Table 1. These first additives can be purchased commercially, or can be obtained by reacting the pure compound of the uncomplexed hydrohalide salt with a hydrohalic acid to form a salt, or can be prepared by a conventional method reported in the literature, and then reacted with a hydrohalic acid to form a salt to obtain the first additive. Among them, commercially available reagents can also be prepared according to existing methods. Among them, the salt-forming reaction with a hydrohalic acid and the preparation of some self-made pure compounds can be achieved according to conventional synthetic methods in the field of organic chemistry. The pure compound of the first additive and its hydrohalide salt can be structurally identified by one or more of the following detection methods, including but not limited to: Fourier transform infrared (FT-IR) spectroscopy, ultraviolet spectroscopy, hydrogen nuclear magnetic resonance (H-NMR) spectroscopy. 1 H NMR (H NMR) method, X-ray diffraction (XRD), gel permeation chromatography (GPC), high performance liquid chromatography (HPLC), mass spectrometry, single crystal X-ray diffraction (SCXRD), inductively coupled plasma spectroscopy (ICP), etc. The sample preparation methods and testing methods of these testing methods are known to those skilled in the art, and the testing parameters can be appropriately adjusted according to the specific structure and material properties of the compound.

[0384] It should be noted that in the following embodiments, hydrochloride is used as a non-limiting example of a hydrohalide salt. It is understood that in the present application, the hydrochloric acid molecules in the first additive structure can also be replaced with other types of hydrohalic acid molecules, that is, the hydrochloride can be replaced with other types of hydrohalide salts. For those skilled in the art, it is easy to refer to the following non-limiting design examples to verify the improvement effect of the corresponding first additive structure on the perovskite precursor solution and perovskite film provided in the present application.

[0385] The first four digits of the first additive compound number in Table 1 correspond to the type of pure compound. Identical first four digits indicate that the same pure compound can be used for preparation. The last digit represents the number of hydrohalic acid molecules contained in a molecule, with A, B, C, ..., Z representing 1, 2, 3, ..., 26, respectively. When the first four digits are used to refer to the first additive, there is no particular limit on the number of hydrohalic acid salt molecules contained in a molecule. In Table 1, where the number of HCl is marked as n, unless otherwise specified, it indicates that the corresponding first additive corresponds to a combination of two salt forms, n = 1 and n = 2.

[0386] Table 1. Weakly reducing compound hydrohalide salt additive (first additive)

[0387] In Table 1, the molecular weight of each first additive is less than 500 Da.

[0388] Example 1. Preparation of perovskite precursor solution, perovskite film and perovskite cell.

[0389] The perovskite cell prepared in Example 1 adopts an inverted pin structure.

[0390] 1.1. Preparation of the first electrode of the component

[0391] A set of 300mm×300mm FTO conductive glass was etched with infrared laser. P1 was about 30μm wide. The entire glass was divided into 44 sub-cells along the long side. The series resistance of different sub-cells was greater than 10MΩ. 10mm above and below were used as the component welding area.

[0392] The etched conductive glass surface was cleaned twice with acetone and isopropyl alcohol in sequence, immersed in deionized water for ultrasonic treatment for 10 minutes, dried in a forced air drying oven, and placed in a drying room (with humidity below 2% RH, relative humidity) to serve as the first electrode.

[0393] 1.2. Preparation of the component hole transport layer: nickel oxide layer

[0394] The cleaned conductive glass was placed in magnetron sputtering to deposit a hole transport layer of nickel oxide (denoted as NiO x , where Ni can be Ni 2+ or Ni 3+ ), the nickel oxide layer is about 15nm thick.

[0395] 1.3. Preparation of the Module Perovskite Main Layer

[0396] 0.001% (relative to the molar concentration of Pb) of the first additive C001A was added to a 1.25M FAPbI3 perovskite precursor solution using dimethylformamide (DMF) as the solvent to form a perovskite precursor solution containing the first additive, which was then sealed for later use.

[0397] The perovskite precursor solution containing the first additive is coated on the nickel oxide prepared above by a slit coating method to a thickness of about 500 nm, and then annealed at 100° C. for 20 minutes.

[0398] 1.4. Preparation of component electron transport layer

[0399] The substrate with the perovskite absorption layer prepared was placed in a vacuum thermal evaporation device and vacuumed to 4×10 -4 Pa, deposited 30nm C 60 , 8nm BCP (bathocuproine) as the component electron transport layer;

[0400] 1.5. Preparation of the Second Electrode of the Component

[0401] After the electron transport layer was deposited in the vacuum thermal evaporation equipment, 10 nm Ag was deposited on the surface and then the vacuum was broken and taken out. P2 was laser etched. The width of P2 was 150 μm and the depth was etched to the FTO layer. The interval between P2 and P1 was 20 μm. Then the substrate was placed in the evaporation equipment again and vacuumed to 4×10 -4 After Pa, a layer of Ag is continuously deposited with a thickness of about 80 nm;

[0402] After cooling, the vacuum is broken and the P second green laser is used to etch P3. The width of P3 is 15 μm and the depth is etched to the FTO layer. The interval between P3 and P2 is 20 μm (the positions of the etched lines are P1 / P2 / P3 in sequence).

[0403] Then use infrared edge cleaning on the component, that is, etching 10mm on both sides of the component.

[0404] Examples 2 to 26, 31-34. A technical solution basically the same as that of Example 1 is adopted, except that the materials of each structure of the perovskite battery (first electrode, first transport layer, perovskite layer, second transport layer and second electrode), the types of the first additive and the second additive, and the amounts of the additives can be found in Tables 1, 2 and 3.

[0405] Example 27 uses a component with a formal NIP structure and is prepared using the following method:

[0406] 1.1. Preparation of the first electrode of the component

[0407] A set of 300mm×300mm FTO conductive glass was etched with infrared laser. P1 was about 30μm wide. The entire glass was divided into 44 sub-cells along the long side. The series resistance of different sub-cells was greater than 10MΩ. 10mm above and below were used as the component welding area.

[0408] The etched conductive glass surface was cleaned twice with acetone and isopropyl alcohol in sequence, immersed in deionized water for ultrasonic treatment for 10 minutes, dried in a forced air drying oven, and placed in a drying room (humidity below 2%) to serve as the first electrode.

[0409] 1.2. Preparation of Component Electron Transport Layer: Tin Oxide Layer

[0410] The cleaned conductive glass is placed in a chemical solution deposition device for chemical deposition (CBD deposition) to deposit an electron transport layer of SnO2 with a thickness of about 50 nm.

[0411] 1.3. Preparation of the Module Perovskite Main Layer

[0412] 0.01% (relative to the molar concentration of Pb) of the first additive C001A was added to a 1.25M FAPbI3 perovskite precursor solution using DMF as the solvent to form a perovskite precursor solution containing the first additive, which was then sealed for later use.

[0413] The perovskite precursor solution containing the first additive was coated on the nickel oxide prepared above by slit coating method to a thickness of about 500 nm and annealed at 100 ° C for 20 min.

[0414] 1.4. Preparation of component hole transport layer

[0415] On the substrate with the perovskite absorber layer prepared, 20nm Spiro-OMeTAD was deposited as the component hole transport layer using the slot coating method;

[0416] 1.5. Preparation of the Second Electrode of the Component

[0417] After the hole transport layer is deposited, the component is placed in a vacuum thermal evaporation device and vacuumed to 4×10 -4Pa, 10nm Ag was deposited on its surface and then the vacuum was broken and taken out, and P2 was laser etched. The width of P2 was 150μm and the depth was etched to the FTO layer. The interval between P2 and P1 was 20μm. Then the substrate was placed in the evaporation equipment again and vacuumed to 4×10 -4 After Pa, a layer of Ag is continuously deposited with a thickness of about 80 nm;

[0418] After cooling, the vacuum is broken and P seconds of green laser is used to etch P3. The width of P3 is 15 μm and the depth is etched to the FTO layer. The interval between P3 and P2 is 20 μm (the positions of the etched lines are P1 / P2 / P3 in sequence).

[0419] The formal NIP components of Examples 28-30 can be prepared using methods substantially the same as those of Example 27, with the differences being shown in Tables 1-3.

[0420] Comparative Examples 1 to 18 respectively adopt the same technical solutions as Examples 1, 16-18, 4, 20-24, 15, 25-27, 29-30, 6, and 5, except that the first additive in this application is not added. See Tables 2 and 3 for details.

[0421] Comparative Examples 19 to 24. A technical solution basically the same as Example 1 was adopted, except that the types of additives were different, wherein no hydrohalide was complexed in Comparative Example 19, no weak reducing group was present in Comparative Example 20, the reducing property of the reducing group in Comparative Example 21 was too strong, the reducing property of the reducing group in Comparative Example 22 was too weak, and the additives in Comparative Examples 23-24 had no reducing property.

[0422] Comparative Example 25: The same technical solution as Example 27 was used, with the amount of the first additive being substantially the same, except for the type of additive. See Tables 1-3.

[0423] Table 2.

[0424] In Table 2, the additives in Examples 1-35 are the first additives provided herein. The weight ratio of the first additive to B and the molar ratio of the weakly reducing group to B can be calculated based on the molar ratio of the first additive to B. Wherein, B is the element corresponding to the divalent cation of the perovskite-type metal halide in the perovskite layer.

[0425] Table 3.

[0426] Example 35. Ion pairs containing multivalent metal elements M

[0427] 35.1. Preparation of the first electrode of the assembly

[0428] A set of 300mm×300mm FTO conductive glass was etched with infrared laser. P1 was about 30μm wide. The entire glass was divided into 44 sub-cells along the long side. The series resistance of different sub-cells was greater than 10MΩ. 10mm above and below were used as the component welding area.

[0429] The etched conductive glass surface was cleaned twice with acetone and isopropyl alcohol in sequence, immersed in deionized water for ultrasonic treatment for 10 minutes, dried in a forced air drying oven, and placed in a drying room (humidity below 2% RH) to serve as the first electrode.

[0430] 35.2. Preparation of Component Hole Transport Layer: Nickel Oxide Layer

[0431] The cleaned conductive glass was placed in a magnetron sputtering process to deposit a hole transport layer of nickel oxide (NiO x ), the nickel oxide layer is about 15nm thick.

[0432] 35.3. Preparation of Module Perovskite Main Layer

[0433] 0.001% (relative to the molar concentration of Pb) of the first additive C001A was added to a 1.25M FAPbI3 perovskite precursor solution using DMF (dimethylformamide) as the solvent. A second additive Eu(acau)3 (where acau is the abbreviation for acetylacetone) was also added to form a perovskite precursor solution, which was then sealed for later use.

[0434] The perovskite precursor solution containing additives was coated on the nickel oxide prepared above by slit coating method with a thickness of about 500 nm and annealed at 100 ° C for 20 min.

[0435] 35.4. Preparation of Component Electron Transport Layer

[0436] The substrate with the perovskite absorption layer prepared was placed in a vacuum thermal evaporation device and vacuumed to 4×10 -4 Pa, deposited 30nm C 60 , 8nm BCP as the component electron transport layer;

[0437] 35.5. Preparation of the Second Electrode of the Component

[0438] After the electron transport layer was deposited in the vacuum thermal evaporation equipment, 10 nm Ag was deposited on the surface and then the vacuum was broken and taken out. P2 was laser etched. The width of P2 was 150 μm and the depth was etched to the FTO layer. The interval between P2 and P1 was 20 μm. Then the substrate was placed in the evaporation equipment again and vacuumed to 4×10 -4 After Pa, a layer of Ag is continuously deposited with a thickness of about 80 nm;

[0439] After cooling, the vacuum is broken and the P second green laser is used to etch P3. The width of P3 is 15 μm and the depth is etched to the FTO layer. The interval between P3 and P2 is 20 μm (the positions of the etched lines are P1 / P2 / P3 in sequence).

[0440] Then use infrared edge cleaning on the component, that is, etching 10mm on both sides of the component.

[0441] Examples 36 to 41 are basically the same technical solutions as Example 35, except for the basic system (containing weakly reducing compound salts), ion pair types, and their raw materials and additives. Please refer to Table 4.

[0442] Table 4.

[0443] In Table 4, the molar amount of the second additive is numerically equal to the molar amount of the ion to metal element, and therefore, the molar ratio of the ion to metal element relative to B is numerically equal to the molar ratio of the second additive to B.

[0444] Test Method

[0445] 1. Energy conversion efficiency test

[0446] At 1000W / m 2 The energy conversion efficiency of the components was tested under a solar simulator.

[0447] At room temperature and pressure, a standard AM1.5G sunlight light source was used to simulate sunlight. A four-channel digital source meter (Keithley 2440) was used to measure the volt-ampere characteristic curve of the component under the light source. The open-circuit voltage (Voc), short-circuit current density (Jsc), and fill factor (FF) of the component were obtained, thereby obtaining the energy conversion efficiency (Eff) of the component.

[0448] “Normal temperature and pressure” refers to normal pressure: the pressure is one atmosphere when the temperature is 25°C; normal temperature refers to 20°C to 30°C, and further, can be 25°C.

[0449] The test values ​​of initial energy conversion efficiency can be found in Table 5.

[0450] 2.Battery stability performance

[0451] After the test, the battery was placed in an ambient environment (relative humidity of 65%-85% RH, ambient temperature of approximately 15-40°C, specifically 25°C) and left out of the light for at least 500 hours. The energy conversion efficiency was then retested. The ratio of the module efficiency after 500 and 1000 hours of exposure to the ambient air to the initial efficiency was calculated. This relative efficiency was used as a performance parameter for module stability. The test results can be found in Table 5.

[0452] Test results and analysis

[0453] Compared to Comparative Examples 1-18 in which the first additive in the present application is not added, Examples 1-34 all add the first additive provided by the present application. According to the test results of the perovskite cells prepared according to the corresponding embodiments, the initial energy conversion efficiency and the relative efficiency after 500h and 1000h are significantly improved, and it can be seen that the battery stability is significantly enhanced. The first additives in Examples 1-34 all contain one or more weak reducing groups. In addition, Examples 1-4, 9, 11-23, 29-34 have aromatic end groups or linking groups, Examples 5-6 and 10 have aliphatic cyclic end groups or linking groups, and Examples 7-8 and 24-27 all have aliphatic chain end groups or linking groups. In Examples 1-6, 9, 12-20, 32 and other embodiments, a spacer group is provided between the aromatic end group or linking group and the weak reducing group -NHNH2.

[0454] Compared with Comparative Examples 1-18 in which the first additive in the present application is not added, Examples 35-37 and 39-41 all add the second additive provided in the present application, introducing the oxidized ions of the multivalent metal element M and the corresponding ion pairs into the perovskite precursor solution. According to the test results of the perovskite batteries prepared according to the corresponding embodiments, the initial energy conversion efficiency and the relative efficiency after 500 hours and 1000 hours of storage are improved.

[0455] Compared with comparative examples 1-18 in which the first additive in the present application is not added, Example 38 adds both the first additive and the second additive, and the initial energy conversion efficiency is significantly improved, and the relative efficiency after 500h and 1000h is also significantly improved.

[0456] The additive used in Comparative Example 19 did not form a salt but was a pure compound. The results showed that compared with the technical solutions provided in this application such as Example 1, the initial energy conversion efficiency and the relative efficiency after 500h and 1000h of placement were significantly reduced, and the battery stability was significantly deteriorated.

[0457] The additive of comparative example 20 has no weak reducing group and has a different salt formation method. The results show that compared with the technical solutions provided in this application such as Example 1, the initial energy conversion efficiency and the relative efficiency after 500h and 1000h of placement are significantly reduced, and the battery stability is significantly deteriorated.

[0458] Compared with the first additive provided in this application such as Example 1, the reducing property of the reducing group in Example 21 is too strong, the reducing property of the reducing group in Example 22 is too weak, and the additives in Examples 23-24 have no reducing property. The results show that the initial energy conversion efficiency and the relative efficiency after 500h and 1000h of placement have different degrees of decrease.

[0459] Compared with the first additive provided in Example 27, the additive in Comparative Example 25 has no reducing property. It was found that the initial energy conversion efficiency and the relative efficiency after 500 hours and 1000 hours of storage were significantly reduced.

[0460] Table 5.

[0461] According to the exploratory research data of the inventors of this application, when the hydrohalic acid molecules in the first additive of this application are replaced with other organic acid molecules, the solubility of some of them decreases significantly, and the improvement effect on the energy conversion efficiency of perovskite batteries and battery stabilizers of some of them becomes significantly worse.

[0462] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0463] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and within the scope of the technical solution of the present application, embodiments that have substantially the same structure as the technical idea and exert the same effect are all included in the technical scope of the present application. The above-mentioned embodiments only express several embodiments of the present application, and their descriptions are relatively detailed, but they cannot be understood as limiting the scope of the patent. In addition, without departing from the scope of the subject matter of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of constructing by combining some of the constituent elements in the embodiments are also included in the scope of the present application. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all fall within the scope of protection of the present application. Therefore, the scope of protection of the present application shall be based on the attached claims, and the description and drawings may be used to explain the content of the claims.

Claims

1. A perovskite precursor solution comprising a perovskite precursor material, a solvent and an additive; in, The perovskite precursor material comprises a perovskite-type metal halide; the structure of the additive comprises a weak reducing group, which has reducing properties to the 0-valent state corresponding to the monovalent anion in the perovskite-type metal halide and is inert to the divalent cation in the perovskite-type metal halide; the additive is a hydrohalide.

2. The perovskite precursor solution according to claim 1, in, The weak reducing group includes one or more of the following groups: -NHNH-, -SS-, -NHNH 2 , sulfinic acid group, phosphinic acid group, hydroxyphenyl group and hydroxynaphthyl group; Optionally, the weak reducing group is selected from the group consisting of: -NHNH-, -SS-, -NHNH 2 , sulfinic acid group, phosphinic acid group, hydroxyphenyl group and hydroxynaphthyl group.

3. The perovskite precursor solution according to claim 1 or 2, in, In one molecule of the additive, the number of the weak reducing groups is 1 or more; Optionally, in one molecule of the additive, the number of the weak reducing groups is an integer selected from 1 to 10; further optionally, the number of the weak reducing groups is 1, 2, 3, 4 or 5; further optionally, the number of the weak reducing groups is 1, 2 or 3; further optionally, the number of the weak reducing groups is 1 or 2; Optionally, in one molecule of the additive, the type of the weak reducing group is one or more; further optionally, the type of the weak reducing group is 1, 2, 3 or more.

4. The perovskite precursor solution according to any one of claims 1 to 3, in, In one molecule of the additive, the number of the hydrohalic acid molecules is 1 or more; Optionally, in one molecule of the additive, the number of hydrohalic acid molecules is an integer selected from 1 to 10; further optionally, the number of hydrohalic acid molecules is 1, 2, 3, 4 or 5; further optionally, the number of hydrohalic acid molecules is 1 or 2.

5. The perovskite precursor solution according to any one of claims 1 to 4, in, The halogen in the hydrohalide salt includes one or more of F, Cl, Br and I; Optionally, any halogen in the hydrohalide salt is independently F, Cl, Br or I; Further optionally, the hydrohalide salt is a hydrochloride salt.

6. The perovskite precursor solution according to any one of claims 1 to 5, in, Satisfy one or more of the following characteristics: The molecular weight of the additive is less than 1000Da; optionally, the molecular weight of the additive is less than or equal to 500Da; further optionally, the molecular weight of the additive is less than or equal to 400Da; further optionally, the molecular weight of the additive is less than or equal to 350Da; further optionally, the molecular weight of the additive is less than or equal to 300Da; further optionally, the molecular weight of the additive is 150 to 300Da; The number of carbon atoms in the additive is 2 to 40; further optionally, the number of carbon atoms in the additive is 2 to 25; further optionally, the number of carbon atoms in the additive is 2 to 20; further optionally, the number of carbon atoms in the additive is 2 to 18; further optionally, the number of carbon atoms in the additive is 2 to 15; further optionally, the number of carbon atoms in the additive is 2 to 12; further optionally, the number of carbon atoms in the additive is 2 to 10; further optionally, the number of carbon atoms in the additive is 2 to 8; further optionally, the number of carbon atoms in the additive is 2 to 6; The number of non-hydrogen atoms in the additive is 8 to 40; further optionally, the number of non-hydrogen atoms in the additive is 10 to 30; further optionally, the number of non-hydrogen atoms in the additive is 10 to 25; further optionally, the number of non-hydrogen atoms in the additive is 10 to 20; further optionally, the number of non-hydrogen atoms in the additive is 10 to 18.

7. The perovskite precursor solution according to any one of claims 1 to 6, in, The additive has a structure shown in formula (1); L(Z 1 -R 11 ) p1 ·nHZ (1) In formula (1), p1 is 0 or a positive integer; Z is the halogen in the hydrohalide salt, and n is the number of hydrohalic acid molecules in the hydrohalide salt; Any R 11 are independently the weak reducing groups and have a valence of 1. Optionally, any one of R 11 Independently -NHNH 2 , sulfinic acid group, phosphinic acid group, hydroxyphenyl group or hydroxynaphthyl group, further optionally, any one of R 11 Independently -NHNH 2 , sulfinic acid group or phosphinic acid group; When p1 is 0, the additive is an organic compound hydrohalide salt containing at least one of -NHNH- and -SS-; When p1 is a positive integer, L is an alkyl group, heteroalkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, substituted alkyl group, substituted heteroalkyl group, substituted cycloalkyl group, substituted heterocycloalkyl group, substituted aryl group or substituted heteroaryl group with a valence of p1; when L contains heteroatoms, any heteroatom in L is independently a non-carbon, non-hydrogen atom, and is further independently selected from any one of N, S, P, O and B; L and all Z 1 contains p2 divalent groups selected from the group consisting of: -NH-NH- and -SS-, p2 is 0 or a positive integer; (p1+p2)≥1; Z 1 For chemical bonds, carbonyl groups, -CH 2 -、-CH(Q 1 )-or-(Q 2 )C(Q 3 )-, where Q 1 , Q 2 and Q 3 Each of the following groups is independently selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and substituted heteroaryl; Z 1 When there are heteroatoms in Z 1 Any heteroatom in is independently a non-carbon, non-hydrogen atom, and is further independently selected from any one of N, S, P, O and B; Optionally, Z 1 -CH 2 -、-CH(Q 1 )-or-(Q 2 )C(Q 3 )-; Any R 11 Independently with Z 1 or the carbon atoms in L are directly connected; In formula (1), L, Z 1 , Q 1 , Q 2 or Q 3 The alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl in any of the substituted alkyl, substituted heteroalkyl, substituted heterocycloalkyl, substituted aryl or substituted heteroaryl is independently substituted by one or more groups selected from the following group G1: alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, -CN, hydrazine, sulfinic acid, phosphinic acid, -OH, -NH 2 , -COOH, sulfonic acid, phosphonic acid, boric acid and halogen.

8. The perovskite precursor solution according to claim 7, in, The additive meets any one or more of the following characteristics: L is a chain structure; optionally, L is C 2-20 Chain structure; optionally, L is C 2-18 Chain structure; further optionally, L is C 2-15 Chain structure; further optionally, L is C 2-12 Chain structure; further optionally, L is C 2-10 Chain structure; further optionally, L is C 2-8 Chain structure; L is a ring-containing structure, and the number of ring atoms in L is 3 to 25; alternatively, 3 to 20; further alternatively, 3 to 18; further alternatively, 5 to 18; further alternatively, 5 to 15; further alternatively, 5 to 12; further alternatively, 5, 6, 10, 11 or 12; further alternatively, 6, 10, 11 or 12; The number of carbon atoms in L is 2 to 30; alternatively, 2 to 25; further alternatively, 2 to 20; further alternatively, 2 to 18; further alternatively, 2 to 15; further alternatively, 2 to 12; further alternatively, 2 to 10; further alternatively, 2 to 8; The number of non-hydrogen atoms in L is 2 to 35; further optionally, the number of non-hydrogen atoms in L is 2 to 30; further optionally, the number of non-hydrogen atoms in the additive is 2 to 25; further optionally, the number of non-hydrogen atoms in the additive is 2 to 20; further optionally, the number of non-hydrogen atoms in the additive is 2 to 18; L is a ring-containing structure, and the ring in L is an aromatic ring, an aliphatic ring or a combination thereof; further optionally, the ring in L includes an aromatic ring; further optionally, the number of carbon atoms in L is 3 to 40; further optionally, the number of carbon atoms in L is 3 to 30; further optionally, the number of carbon atoms in L is 3 to 25; further optionally, 3 to 20; further optionally, 3 to 18; further optionally, 5 to 18; further optionally, 5 to 15; further optionally, 5 to 12; further optionally, 5, 6, 10, 11 or 12; further optionally, 6, 10, 11 or 12; L is a ring structure containing 2 to 40 carbon atoms; optionally, the number of carbon atoms in L is 3 to 30; further optionally, 3 to 25; further optionally, 3 to 20; further optionally, 3 to 18; further optionally, 4 to 18; L is an aliphatic structure; optionally, the number of carbon atoms in L is 2 to 25; further optionally, 2 to 20; further optionally, 2 to 18; further optionally, 2 to 15; further optionally, 2 to 12; further optionally, 2 to 10; further optionally, 2 to 8; L is an aromatic structure; optionally, L comprises one or more of aryl, heteroaryl, substituted aryl and substituted heteroaryl; further optionally, L comprises C 6-20 Aryl, C 4-20 Heteroaryl, substituted C 6-20 Aryl and substituted C 4-20 One or more of heteroaryl; further optionally, L comprises C 6-10 Aryl, C 4-10 Heteroaryl, substituted C 6-10 Aryl and substituted C 4-10 one or more of heteroaryl groups; p1 is 0, and the additive is a C 2-40 Compounds Hydrohalides; p1 is a positive integer selected from 1 to 10; optionally, p1 is 1, 2, 3, 4 or 5; optionally, p1 is 1 or 2; p1 is a positive integer, L is C in p1 valence state 2-18 Alkyl, C 2-18 Heteroalkyl, C 3-20 Cycloalkyl, C 3-20 Heterocycloalkyl, C 6-20 Aryl, C 3-20 Heteroaryl, substituted C 2-18 Alkyl, substituted C 2-18 Heteroalkyl, substituted C 3-20 Cycloalkyl, substituted C 3-20 Heterocycloalkyl, substituted C 6-20 Aryl or substituted C 3-20 Heteroaryl; optionally, L is C in p1 valence state 2-12 Alkyl, C 2-12 Heteroalkyl, C 3-12 Cycloalkyl, C 3-12 Heterocycloalkyl, C 6-15 Aryl, C 3-15 Heteroaryl, substituted C 2-12 Alkyl, substituted C 2-12 Heteroalkyl, substituted C 3-12 Cycloalkyl, substituted C 3-12 Heterocycloalkyl, substituted C 6-15 Aryl or substituted C 3-15 Heteroaryl; further optionally, L is C in p1 valence state 2-10 Alkyl, C 2-10 Heteroalkyl, C 5-10 Cycloalkyl, C 4-10 Heterocycloalkyl, C 6-10 Aryl, C 3-10 Heteroaryl, substituted C 2-10 Alkyl, substituted C 2-10 Heteroalkyl, substituted C 5-10 Cycloalkyl, substituted C 4-10 Heterocycloalkyl, substituted C 6-10 Aryl or substituted C 3-10 Heteroaryl; further optionally, L is a linear structure; wherein, when L contains heteroatoms, any heteroatom in L is independently a non-carbon, non-hydrogen atom, and is further independently selected from any one of N, S, P, O and B; Q 1 , Q 2 and Q 3 Each independently selected from the following groups: 1-6 Alkyl, C 1-6 Heteroalkyl, C 3-8 Cycloalkyl, C 3-8 Heterocycloalkyl, C 6-12 Aryl, C 3-11 Heteroaryl, substituted C 1-6 Alkyl, substituted C 1-6 Heteroalkyl, substituted C 3-8 Cycloalkyl, substituted C 3-8 Heterocycloalkyl, substituted C 6-12 Aryl and substituted C 3-11 heteroaryl; optionally, Q 1 , Q 2 and Q 3 Each independently selected from the following groups: 1-3 Alkyl, C 1-3 Heteroalkyl, C 3-6 Cycloalkyl, C 3-6 Heterocycloalkyl, C 6-10 Aryl, C 3-9 Heteroaryl, substituted C 1-3 Alkyl, substituted C 1-3 Heteroalkyl, substituted C 3-6 Cycloalkyl, substituted C 3-6 Heterocycloalkyl, substituted C 6-10 Aryl and substituted C 3-9 heteroaryl; further optionally, Q 1 , Q 2 and Q 3 Each independently selected from the group consisting of: methyl, methoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, piperidinyl (optionally ), piperazinyl (optionally )phenyl, naphthyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl and N 1～6 aza-naphthyl, and substituted forms of any of the foregoing groups; wherein Q 1 , Q 2 or Q 3 When it is any of the above substituted forms, it is independently substituted by 1 or more (optionally, 1 or 2 to 5, further optionally, 1, 2 or 3) selected from the following group G1 a Substituted by groups in: methyl, cyclopentyl, phenyl, benzyl, methylphenyl, -Ph-Ph, N 1～2 Aza-heterocycloalkyl (optionally monoaza-C 3-8 Cycloalkyl or diazaC 3- 8 Cycloalkyl, further optionally monoazetidinyl, piperidinyl or piperazinyl, further optionally monoazetidinyl, further optionally monoazetidinyl ), -CN, hydrazine, sulfinic acid, phosphinic acid, -OH, -NH 2 , -COOH, sulfonic acid, phosphonic acid, boric acid and halogen (can be one or more of F, Cl, Br and I); The group G1 includes an alkyl group (optionally C 1-8 Alkyl, further optionally C 1-6 Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 alkyl, further optionally methyl), heteroalkyl (optionally alkoxy or secondary amino, further optionally C 1-8 Alkoxy or C 1-8 Alkylamino, further optionally C 1-6 Alkoxy or C 1-6 Alkylamino, further optionally C 1-4 Alkoxy or C 1-4 Alkylamino, further optionally C 1-3 Alkoxy or C 1-3 Alkylamino, further optionally -NHCH 3 or -NHCH 2 CH 3 , further optional -NHCH 3 ), cycloalkyl (optionally C 3-8 Cycloalkyl, further optionally C 3-6 Cycloalkyl, further optionally cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), heterocycloalkyl (optionally 3-8 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-6 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-4 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally piperidinyl, piperazinyl or monoazetidinyl, further optionally ), aryl (optionally C 6-12 Aryl, further optionally C 6-10 aryl, which may be phenyl, naphthyl or biphenyl), heteroaryl (a 6- to 12-membered aryl containing 1 to 6 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 to 4 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 to 3 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 or 2 nitrogen atoms on the ring, which may be further N 1-2 azaphenyl, further optionally monoazaphenyl or diazaphenyl, further optionally pyridyl, pyrimidyl, pyrazinyl or pyridazinyl), -CN, hydrazine, sulfinic acid, phosphinic acid, -OH, -NH 2 , -COOH, sulfonic acid, phosphonic acid, boric acid and halogen (can be one or more of F, Cl, Br and I); Z 1 For chemical bonds, -CH 2 -、-CH(Q 1 )-or-(Q 2 )C(Q 3 )-.

9. The perovskite precursor solution according to claim 8, in, The additive meets any one or more of the following characteristics: L is an aliphatic structure and Z 1 is a chemical bond or a carbonyl group (Z 1 (optionally a chemical bond); L is an aromatic structure and Z 1 Not a chemical bond; L is phenyl, naphthyl, cyclopentyl, cyclohexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, heptadecyl, n-octadecyl, pyridyl, piperidyl, piperazinyl, N-methylpiperidyl, methylphenyl, dimethylphenyl, biphenyl, naphthyl-substituted phenyl, aminophenyl, or C substituted with one or more sulfonic acid groups. 2-18 Alkyl (optionally ethyl with a monosulfonic acid substituent, further optionally 2-sulfonic acid ethyl), 1 or more NH 2 Substituted C 2-18 Alkyl (optionally one -NH 2 Substituted C 2-18 alkyl, further optionally aminobutyl, further optionally 4-aminobutyl), one or more -(O=)P(OH) 2 Substituted C 2-18 Alkyl (optionally 1 -(O=)P(OH) 2 Substituted C 2-12 alkyl, further optionally phosphonopropyl, further optionally 3-phosphonopropyl), 1 or more - (O=)PR 02 (OH)-substituted C 2-18 Alkyl (optionally 1 -(O=)PR 02 (OH)-substituted C 2-12 Alkyl, optionally 1 -(O=)PR 02 (OH)-substituted C 2-8 Alkyl, further optionally (CH 3 )(OH)(R 02 )P(=O)-C 2～8 Alkylene-, further optionally (CH 3 )(OH)(R 02 )P(=O)-(CH 2 ) 2～8 -, further optional (CH 3 )(OH)(R 02 )P(=O)-(CH 2 ) 3 -) and R 02 is an alkyl group (optionally C 1-6 Alkyl, further optionally C 1-3 alkyl, further optionally methyl), one or more -(O=)PR 02 (OH) and 1 or more NH 2 -Substituent C 2-18 Alkyl (optionally 1 -(O=)PR 02 (OH) and 1 NH 2 -Substituent C 2-18 Alkyl, further optionally one -(O=)PR 02 (OH) and 1 NH 2 -Substituent C 2-12 Alkyl, further optionally 1 -(O=)PR 02 (OH) and 1 NH 2 -Substituent C 2-8 Alkyl, further optionally (CH 3 )(OH)(R 02 )P(=O)-CH 2 CH 2 CH(NH 2 )-), sulfonate phenyl, carboxylate phenyl, phosphonate phenyl and borate phenyl; Z 1 Any of the following divalent groups: methylene, -CH(CH 3 )-, -CH(benzyl)-, -CH(cyclopentyl)-, -CH(-Ph-Ph)-, -CH(phenyl), -CH(-Ph-CH 3 )-and The group G1 is a group G2 comprising the following groups: alkyl (optionally C 1-8 Alkyl, further optionally C 1-6 Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 alkyl, further optionally methyl), heteroalkyl (optionally alkoxy or secondary amino, further optionally C 1-8 Alkoxy or C 1-8 Alkylamino, further optionally C 1-6 Alkoxy or C 1-6 Alkylamino, further optionally C 1-4 Alkoxy or C 1-4 Alkylamino, further optionally C 1-3 Alkoxy or C 1-3 Alkylamino, further optionally -NHCH 3 or -NHCH 2 CH 3 , further optional -NHCH 3 ), cycloalkyl (optionally C 3-8 Cycloalkyl, further optionally C 3-6 Cycloalkyl, further optionally cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), heterocycloalkyl (optionally 3-8 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-6 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally 3-4 membered heterocycloalkyl containing 1 or 2 N atoms in the ring, further optionally piperidinyl, piperazinyl or monoazetidinyl, further optionally ), aryl (optionally C 6-12 Aryl, further optionally C 6-10 aryl, which may be phenyl, naphthyl or biphenyl) and heteroaryl (a 6- to 12-membered aryl containing 1 to 6 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 to 4 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 to 3 nitrogen atoms on the ring, which may be further 6- to 12-membered aryl containing 1 or 2 nitrogen atoms on the ring, which may be further N 1-2 azaphenyl, further optionally monoazaphenyl or diazaphenyl, further optionally pyridyl, pyrimidyl, pyrazinyl or pyridazinyl); optionally, the group G1 is a group G1 including the following groups b : methyl, cyclopentyl, cyclopentylmethyl, phenyl, benzyl, biphenyl, methylphenyl, piperidinyl (optional ), piperazinyl (optionally ) and monoazetidinyl (optionally ); Optionally, the group G1 includes methyl, cyclopentyl, phenyl, benzyl, biphenyl, methylphenyl, piperidinyl (optionally ) and monoazetidinyl (optionally )。 10. The perovskite precursor solution according to any one of claims 7 to 9, in, p1 is a positive integer, R 11 -NHNH 2 , optionally, at least one Z 1 Not a chemical bond.

11. The perovskite precursor solution according to any one of claims 7 to 10, in, p1 is a positive integer, L is an aromatic group, Z 1 directly connected to the aromatic ring in L, and the corresponding R 11 -NHNH 2 , Z 1 is not a chemical bond; optionally, R 11 -CH 2 -、-CH(Q 1 )-or-(Q 2 )C(Q 3 )-; Optionally, Q 1 , Q 2 and Q 3 are each independently selected from the group consisting of an alkyl group, an aralkyl group, a heteroaralkyl group, a substituted alkyl group, a substituted aralkyl group, and a substituted heteroaralkyl group; wherein Q 1 , Q 2 or Q 3 When it is any of the substituted forms described above, it is independently substituted by one or more groups selected from the group G1.

12. The perovskite precursor solution according to claim 11, in, L is aryl, heteroaryl, substituted aryl or substituted heteroaryl; Optionally, L is C 6-20 Aryl, C 4-20 Heteroaryl, substituted C 6-20 Aryl and substituted C 4-20 Any of the heteroaryl groups; further optionally, L is C 6-10 Aryl, C 4-10 Heteroaryl, substituted C 6-10 Aryl and substituted C 4-10 any of the heteroaryl groups; Wherein, when L is any of the substituted forms mentioned above, it is independently substituted by one or more groups selected from the group G1.

13. The perovskite precursor solution according to any one of claims 7 to 12, in, The additive has a structure of any one of formula (11), formula (12), formula (13), formula (14) and formula (15): Ar(-Z 21 -R 11 ) p1 ·nHCl (11) In formula (11), p1 is a positive integer, Z 21 -CH 2 -、-CH(Q 1 )-or-(Q 2 )C(Q 3 )-; On (-R 11 ) p1 nHCl (12) In formula (12), p1 is a positive integer, R 11 is a sulfinic acid group or a phosphinic acid group; In formula (13), k1 and k2 are each independently 0 or 1; R 31 and R 32 are each independently an alkylene group; optionally, R 31 and R 32 Each independently is C 2-20 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-16 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-12 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-10 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-8 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-6 Alkylene, further optionally, R 31 and R 32 Each independently is C 2-4 Alkylene; In formula (14) and formula (15), k1 and k2 are each independently 0 or 1; Z 41 and Z 42 are each independently an alkylene group; optionally, Z 41 and Z 42 Each independently is C 2-15 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-12 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-10 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-8 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-6 Alkylene, further optionally, Z 41 and Z 42 Each independently is C 1-4 Alkylene, further optionally, Z 41 and Z 42 Each is independently methylene, ethylene, propylene or butylene; Among them, Ar, Ar 21 and Ar 22 are each independently an aromatic group; optionally, Ar, Ar 21 and Ar 22 The number of ring atoms of each of the following is independently 5 to 15, further optionally 5 to 12, further optionally 5 to 10 or 12, further optionally 5, 6, 10 or 12; alternatively, Ar, Ar 21 and Ar 22 are independently aryl, heteroaryl, substituted aryl or substituted heteroaryl, wherein the aryl or heteroaryl in the substituted aryl or substituted heteroaryl is independently substituted by one or more groups selected from the group G1; when containing heteroatoms, Ar, Ar 21 and Ar 22 Any heteroatom contained in any one of them is independently a non-carbon, non-hydrogen atom, and is further independently selected from any one of N, S, P, O and B.

14. The perovskite precursor solution according to any one of claims 1 to 13, in, The additive contains a second functional group W 11 , W 11 is any group selected from the group consisting of: -COOH, sulfonic acid, phosphonic acid and boric acid; In one molecule of the additive, the second functional group W 11 The number j is 1 or more; optionally, j is 1, 2 or 3; further optionally, j is 1 or 2.

15. The perovskite precursor solution according to claim 14, in, The additive has any of the following structures: (W 11 ) j L 0 (R 02 ) m1 ·nHCl (2) In formula (2), j is a positive integer, m1 is a positive integer; any R 02 are independently the weak reducing groups; L 0 is a hydrocarbon group or heterohydrocarbon group with a valence of m1+j, wherein the heterohydrocarbon group contains 0, 1 or more substituents selected from the group consisting of: -CN, -OH, halogen (optionally one or more of F, Cl, Br and I), -NH 2 、-SH、-CF 3 and -COOH; optionally, any one of R 02 A group independently selected from the group consisting of: -NHNH- containing groups, -NHNH 2 , sulfinic acid group and phosphinic acid group; (W 11 ) j1 L 01 (Z 1 -R 11 ) p1 ·nHCl (21) In formula (21), p1 and j1 are each independently positive integers, and any Z 1 and any R 11 Each independently as defined in any one of claims 7 to 14; L 01 (Z 1- ) p1 Contains p2 divalent weak reducing groups and j2 W 11 , where p2 and j2 are each independently 0 or a positive integer; L 01 is a p1+j1-valent hydrocarbon group or heterohydrocarbon group, wherein the heterohydrocarbon group contains 0, 1 or more substituents selected from the following group: -CN, -OH, halogen (optionally one or more of F, Cl, Br and I), -NH 2 、-SH、-CF 3 and -COOH; (W 11 ) j1 Ar 01 (-Z 31 -R 11 ) p1 ·nHCl (22) In formula (22), p1, j1, any R 11 and any W 11 Each is independently defined as in formula (21); Ar 01 is a divalent aromatic group; wherein the divalent aromatic group contains 0, 1 or more substituents selected from the following group: -CN, -OH, -NH 2 、-SH、-CF 3 and -COOH, halogen; Z 31 -CH 2 -、-CH(Q 1 )-or-(Q 2 )C(Q 3 )-;Q 1 , Q 2 and Q 3 Each independently selected from the following groups in Group G3: hydrocarbon group (optionally C 1-6 Alkyl, further optionally C 1-3 alkyl, further optionally methyl) and heteroalkyl (optionally alkoxy or alkylamino, further optionally C 1-6 Alkoxy or C 1-6 Alkylamino, further optionally C 1-3 Alkoxy or C 1-3 Alkylamino, further optionally methoxy, ethoxy, -NHCH 3 or -NHCH 2 CH 3 , further optional -NHCH 3 or -NHCH 2 CH 3 , further optional -NHCH 3 ); wherein the heteroalkyl group contains 0, 1 or more substituents selected from the group consisting of: -CN, -OH, halogen (optionally one or more of F, Cl, Br and I), -NH 2 、-SH、-CF 3 and -COOH; In formula (23) and formula (24), k1, k2, Z 41 and Z 42 Each is independently defined as in formula (14); j31 and j32 are each independently 0 or a positive integer, (j31+j32)≥1; W 31 and W 32 Each is independently any group selected from the following group: -COOH, sulfonic acid, phosphonic acid, boric acid, -NH 2 and -SH; Among them, Ar 31 and A 32 Each is independently a divalent aromatic group; wherein the divalent aromatic group contains 0, 1 or more substituents selected from the following group: -CN, -OH, amino, thiol and halogen (optionally one or more of F, Cl, Br and I).

16. The perovskite precursor solution according to any one of claims 1 to 15, in, The additives include any one or any suitable combination of the following compounds: And the case where any of the aforementioned compound salts is substituted by a substituent selected from the group G1 described in any one of claims 7 to 9; Wherein, n is a positive integer, optionally, n is an integer selected from 1 to 10; further optionally, n is 1, 2, 3, 4 or 5; further optionally, n is 1 or 2; Q Ar Any group selected from the group G1; a is 0 or a positive integer (a can be 0, 1 or 2); Q 10 H or Q 1 ; Optionally, Q 10 is H; alternatively, Q 10 Q 1 ; a1 and a2 are 0 or positive integers respectively, and a1+a2≥1; b1, b2 and b3 are 0 or positive integers respectively, and b1+b2+b2≥1, optionally, b2+b3≥1, more optionally, b1=0; Q A1 , Q A2 and Q A3 Each independently is Q Ar ; q is an integer selected from 2 to 20, and may be an integer from 2 to 18, and may be an integer from 2 to 16, and may be an integer from 2 to 12, and may be an integer from 2 to 10, and may be an integer from 2 to 8, and may be an integer from 2, 3, 4, 5, 6 or 7; c1 and c2 are each independently 0 or 1, optionally, c1+c2≥1; Q 51 and Q 52 Each independently is an alkyl group (optionally C 1-6 Alkyl, further optionally C 1-3 Alkyl, further optionally methyl).

17. The perovskite precursor solution according to claim 16, in, The additives include any one or any suitable combination of the following compounds: and the case where any of the aforementioned compound salts is substituted by a substituent selected from the group G1; Optionally, n is 1 or 2; Optionally, n is 1; Optionally, n is 2.

18. The perovskite precursor solution according to any one of claims 1 to 17, in, The perovskite precursor material comprises a perovskite-type metal halide; the chemical formula of the perovskite-type metal halide is ABX 3 ; Wherein, A is a monovalent cation, B is a divalent cation, and X is a monovalent anion; Optionally, A includes Cs + , K + , Rb + , one or more of monovalent amine cations and monovalent amidino cations; Optionally, B includes Pb 2+ Sn 2+ , Fe 2+ , Mn 2+ 、Ni 2+ ,Ge 2+ 、Co 2+ and Sb 2+ One or more of; Optionally, X includes I - Br - and Cl - One or more of .

19. The perovskite precursor solution according to claim 18, in, The weight percentage of the additive relative to the B element in the perovskite precursor material is 0.01% to 15%; Optionally, the weight percentage of the additive relative to the B element in the perovskite precursor material is 0.01% to 10%; Optionally, the weight percentage of the additive relative to the B element in the perovskite precursor material is 0.1% to 8%.

20. The perovskite precursor solution according to claim 18 or 19, in, The relative molar ratio of the additive to B in the perovskite metal halide is 0.001% to 15%; Optionally, the relative molar ratio of the additive to B in the perovskite metal halide is 0.01 to 15%; Optionally, the relative molar ratio of the additive to B in the perovskite-type metal halide is 2 to 6.5%.

21. The perovskite precursor solution according to any one of claims 18 to 20, in, The relative molar ratio of the weak reducing group to the B element in the perovskite-type metal halide is 0.01 to 15%; Optionally, the relative molar ratio of the weak reducing group to the B element in the perovskite-type metal halide is 1 to 8%.

22. The perovskite precursor solution according to any one of claims 1 to 21, in, The perovskite precursor solution also contains oxidized ions of multivalent metal elements M.

23. The perovskite precursor solution according to claim 22, in, The multivalent metal element M includes one or more elements selected from the group consisting of lanthanide elements, Fe, Co, Ni, Ti, Cr, Mn, Y, Rh and Bi; Optionally, the lanthanide elements include one or more elements of Ce, Pr, Sm, Eu, Tb and Yb; Optionally, the oxidation state ions of the multivalent metal element M include Ce 4+ , Pr 4+ 、Sm 3+ 、Eu 3+ , Tb 4+ , Yb 3+ , Fe 3+ 、Co 3+ 、Ni 3+ 、Ti 4+ Cr 3+ , Mn 4+ , Y 3+ and Rh 4+ One or more of; Optionally, the oxidized ions of the multivalent metal element M are derived from an organic salt of the metal element M. Further optionally, the organic salt comprises one or more of acetylacetonate, sulfonate and sulfate ester salt.

24. The perovskite precursor solution according to claim 22 or 23, in, The perovskite precursor solution contains Ce 3+ -Ce 4+ , Pr 4+ -Pr 3+ 、Sm 3+ -Sm 2+ 、Eu 3+ -Eu 2+ , Tb 4+ -Tb 3+ , Yb 3+ -Yb 2+ , Fe 3+ -Fe 2+ 、Co 3+ -Co 2+ 、Ni 3+ -Ni 2+ 、Ti 4+ -Ti X+ Cr 3+ -Cr 2+ , Mn 4+ -Mn 2+ , Y 3+ -Y 2+ , Rh 4+ -Rh 2+ and Bi 3+ -Bi 2+ One or more ion pairs; wherein the ion pair Ti 4+ -Ti X+ Ti X+ The positive charge state is less than 4.

25. The perovskite precursor solution according to any one of claims 1 to 24, in, The perovskite precursor material comprises the perovskite metal halide as claimed in claim 15; The relative molar ratio of the multivalent metal element M to the element B in the perovskite metal halide is 0.001% to 15%; Optionally, the relative molar ratio of the multivalent metal element M to the element B in the perovskite metal halide is 0.01% to 15%.

26. A perovskite film, prepared using the perovskite precursor solution according to any one of claims 1 to 25.

27. A perovskite battery comprising the perovskite film according to claim 26.

28. The perovskite cell according to claim 27, in, The perovskite cell is any one of a trans-pin cell and a formal nip cell.

29. An electrical device comprising the perovskite cell according to claim 27 or 28.

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