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

Abstract

The invention discloses a perovskite precursor solution, a perovskite thin film, a perovskite battery and an electric device. The perovskite precursor solution comprises a surfactant, the structure of the surfactant comprises a hydrophilic group, a hydrophobic group and a first functional group which are different from one another, the first functional group is a Lewis basic group containing lone pair electrons, and the lone pair electrons exist in at least one of N atoms and S atoms.

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. In particular, the energy conversion efficiency of PSCs is a key factor restricting the industrialization of PSCs.

[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 can significantly improve the energy conversion efficiency of the battery.

[0006] In a first aspect, the present application provides a perovskite precursor solution comprising a perovskite precursor material, a solvent, and a surfactant; the surfactant comprises a hydrophilic group, a hydrophobic group, and a first functional group, wherein the first functional group is a Lewis basic group containing a lone pair of electrons, and the lone pair of electrons is present in at least one of a nitrogen atom and a sulfur atom;

[0007] The first functional group, the hydrophilic group and the hydrophobic group are different from each other.

[0008] In the structure of the surfactant having a hydrophilic group and a hydrophobic group, a lone pair of electrons can be provided by a specific type of atom (including a specific atom of at least one of N and S), so that the surfactant has suitable Lewis base properties. On the one hand, it can improve the wettability of the perovskite precursor solution on the substrate surface, and on the other hand, it can more stably complex with the divalent metal ions in the perovskite precursor material and better passivate multiple defects such as lead vacancies and iodine vacancies in the perovskite. By introducing the surfactant with this special structure into the perovskite precursor solution, the uniformity of the perovskite film can be improved and the energy conversion efficiency of the battery can be improved. In addition, the perovskite precursor solution is conducive to the preparation of large-area (such as ≥1cm 2 )Perovskite thin films.

[0009] In some embodiments, the first functional group comprises -NR 11 -NR 12 R 13 and -SH; wherein R 11 and R 12 Each independently represents H or a hydrocarbon group; R 13 is H, a hydrocarbon group or a hydrocarbon group substituted with a monovalent hydrophilic group;

[0010] Optionally, R 11 and R 12 are each independently H or alkyl, further optionally, R 11 and R 12 Each independently is H or C 1-6 Alkyl, further optionally, R 11 and R 12 Each independently is H or C 1-3 Alkyl; further optionally, R 11 and R 12 are each independently H or methyl; further optionally, R 11 and R 12 All are H;

[0011] Optionally, R 13 is H, an alkyl group or an alkyl group substituted with a monovalent hydrophilic group, and further optionally, the alkyl groups in the alkyl group or the alkyl group substituted with a monovalent hydrophilic group are each independently C 1-20 Alkyl, further optionally C 1-18 Alkyl, further optionally C 1-15 Alkyl, further optionally C 1-12 Alkyl, further optionally C 1-10 Alkyl, further 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;

[0012] Optionally, R 13 is H or a hydrocarbon group, further optionally H or an alkyl group, further optionally H or C 1-20 Alkyl, further optionally H or C 1-18 Alkyl, further optionally H or C 1-15 Alkyl, further optionally H or C 1-12 Alkyl, further optionally H or C 1-10 Alkyl, further optionally H or C 1-8 Alkyl, further optionally H or C1-6 Alkyl, further optionally H or C 1-4 Alkyl, further optionally H or C 1-3 Alkyl, further optionally H or methyl;

[0013] Alternatively, examples of the monovalent hydrophilic group may include, but are not limited to, one or more of: a carboxyl group, a sulfonic acid group, a sulfonic acid salt, a sulfate group, a sulfate salt, a phosphate group, a phosphate salt, a monohydrogen phosphate group, a monohydrogen phosphate salt, a primary amino group, a primary amino salt, a secondary amino group, a secondary amino salt, a quaternary ammonium salt, -CONH2, and a hydroxyl group;

[0014] Optionally, R 11 、R 12 and R 13 are all H; further optionally, the first functional group is selected from one or both of -NH-NH2 and -SH.

[0015] A group having at least one of an NN structure and a -SH structure can be used as the first functional group. In this case, it can provide more suitable Lewis base properties, thereby playing a better role in improving the wettability of the perovskite precursor solution and reducing vacancy defects in the perovskite, thereby better improving the uniformity of the perovskite film, and is also more beneficial to improving the energy conversion efficiency of the battery.

[0016] In some embodiments, the hydrophilic group includes one or more of a carboxyl group, a sulfonic acid group, a sulfonic acid salt, a sulfate group, a sulfate salt, a phosphate group, a phosphate salt, a monohydrogen phosphate group, a monohydrogen phosphate salt, a primary amino group, a primary amino salt, a secondary amino group, a secondary amino salt, a divalent tertiary amino group, a quaternary ammonium salt, -CONH2, a hydroxyl group, an ether group, an ester group, -CONH-, and a divalent phosphate group;

[0017] Optionally, the sulfonic acid salt, sulfate salt, phosphate salt and monohydrogen phosphate salt are alkali metal salts of the corresponding acids;

[0018] Optionally, the primary amino salt and the secondary amino salt are salts formed by corresponding amines and acids, respectively; optionally, the acid is an organic acid or an inorganic acid; the organic acid includes one or more of carboxylic acid, phosphonic acid and sulfonic acid; the inorganic acid includes one or more of hydrohalic acid, phosphoric acid and sulfuric acid, and optionally, the inorganic acid includes one or more of hydrochloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid and sulfuric acid;

[0019] Optionally, the hydrophilic group includes at least one of a quaternary ammonium ion and an alkali metal ion.

[0020] In some embodiments, the hydrophilic groups include *-COOH, *-S(=O)2OH, *-S(=O)2OM, *-OS(=O)2OH, *-OS(=O)2OM, *-O-(O=)P(OH)2, *-NH2、*-NH2·n2A cd 、*-NHR0、*-NHR0·n1A cd 、 One or more of *-CONH2, *-OH and a hydrophilic linking group L0; wherein the hydrophilic linking group L0 includes *-CONH-*, *-NHCO-*, *-C(=O)O-*, *-OC(=O)-*, *-O-(O=)P(OM 01 )-O-*, *-NH-*, and *-O-*;

[0021] Wherein, any "*" represents a linking site to a carbon atom;

[0022] Any M is independently an alkali metal ion;

[0023] Any M1 and any M2 are each independently an alkali metal ion;

[0024] Any R 10 are independently hydrocarbyl;

[0025] Any A cd is independently an acid molecule; n2 is 1 or 2; n1 is 1;

[0026] Any R0 is independently a hydrocarbon group or a substituted hydrocarbon group; the substituted hydrocarbon group is substituted by one or more hydrophilic groups;

[0027] R 01 is an alkyl group; R 02 is a hydrocarbon group; R 03 is an alkyl group;

[0028] M 01 It is absent or is H or an alkali metal ion.

[0029] In some embodiments, the surfactant satisfies any one or more of the following characteristics:

[0030] Any M is independently lithium, sodium or potassium;

[0031] Any one M1 and any one M2 are each independently lithium, sodium or potassium;

[0032] Any R 10 Independently C 1-10 Alkyl, optionally C1-8 Alkyl, further optionally C 1-6 Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 alkyl;

[0033] Any A cd is independently an organic acid or inorganic acid molecule; the organic acid includes one or more of carboxylic acid, phosphonic acid and sulfonic acid; the inorganic acid includes one or more of hydrohalic acid, phosphoric acid and sulfuric acid, and optionally, the inorganic acid includes one or more of hydrochloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid and sulfuric acid;

[0034] Any R0 is independently alkyl; alternatively, any R0 is independently C 1-3 Alkyl; further optionally, R0 is methyl;

[0035] R 01 C 1-3 alkyl; optionally, R 01 is methyl;

[0036] R 02 C 1-8 Alkyl or benzene ring substituted C 1-3 Alkylene, the benzene ring is phenyl or surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl;

[0037] R 03 C 1-3 alkyl; optionally, R 03 is methyl;

[0038] M 01 Absent or H, lithium, sodium or potassium;

[0039] At least one side of the hydrophilic linking group L0 is connected to a monovalent hydrophilic group.

[0040] The surfactant provided herein can contain various types of hydrophilic groups, thereby being able to more flexibly adjust the surface tension of the surfactant, and more flexibly play the wettability of the perovskite precursor solution and the passivation effect on the vacancy defects in the perovskite. When the structure of the surfactant includes an alkali metal salt hydrophilic group, it is conducive to further passivating the perovskite layer interface defects. When the structure of the surfactant includes at least one of a primary amino group, a secondary amino group or a tertiary amino group, it is conducive to passivating the bulk phase defects. When the structure of the surfactant includes a quaternary ammonium salt, it is conducive to controlling the nucleation rate and promoting grain growth. When the structure of the surfactant is complexed with an acid molecule, it is conducive to the uniformity of the large-area film formation of the perovskite layer. The hydrophilic group can be not only a monovalent hydrophilic group located at the end group, but also a multivalent group as a connecting group, and can also be a combination of monovalent or multivalent hydrophilic groups, so that by adjusting the position, number and other parameters of the hydrophilic group, a coordinated combination with the hydrophobic group and the first functional group can be formed, thereby giving the perovskite precursor solution better wettability, reducing vacancy defects in the perovskite, improving the uniformity of the perovskite film, and thus improving the energy conversion efficiency of the battery.

[0041] In some embodiments, the hydrophobic group includes C 8-20 carbon chain;

[0042] Optionally, the C 8-20 The carbon chain is a straight chain or branched structure;

[0043] Optionally, the C 8-20 The main chain atom length of the carbon chain is 6 to 20; further optionally, the C 8-20 The main chain atoms of the carbon chain are 8 to 20 in length; further optionally, the C 8-20 The main chain atoms of the carbon chain are 8 to 18 in length; further optionally, the C 8-20 The carbon chain has a main chain atom length of 10 to 18 C 10-20 carbon chain;

[0044] Optionally, the C 8-20 The carbon chain is a saturated or unsaturated structure;

[0045] Optionally, the C 8-20 The carbon chain is either aromatic or aliphatic;

[0046] Optionally, the molecular structure of the surfactant includes one or more of the C 8-20 Carbon chain.

[0047] By introducing a hydrophobic group of a certain size into the structure of the surfactant, it can be combined with the hydrophilic group and the first functional group to form a hydrophilic-hydrophobic balance that is more suitable for the perovskite precursor solution of the present application. While playing the role of the lone pair electrons in the first functional group, the perovskite precursor solution system can be made more stable and better dispersed, with better wettability to the substrate, thereby better improving the uniformity of the perovskite film.

[0048] In some embodiments, the hydrophobic group further comprises one or more of an arylene group Ar0 and an aralkyl group ArA;

[0049] Optionally, the arylene group Ar0 is C 6-18 Arylene, further optionally, the arylene Ar0 is phenylene or one or more C 1-3 Alkyl-substituted phenylene;

[0050] Optionally, the aralkyl group ArA is a C 1-18 Alkyl, wherein any one of the aryl groups Ar1 is independently phenyl or is replaced by one or more C 1-4 Alkyl-substituted phenyl; further optionally, any one of the aryl groups Ar1 is independently phenyl or substituted by one or more C 1-3 Alkyl-substituted phenyl; further optionally, any one of the aryl groups Ar1 is independently phenyl or benzyl; further optionally, the aralkyl group ArA is benzyl.

[0051] Aromatic rings can be introduced into the hydrophobic structure of the surfactant, which is more conducive to the interaction between the surfactant molecules and the perovskite components and is conducive to better dissolution in the perovskite precursor solution.

[0052] In some embodiments, in one molecule of the surfactant, the number of the hydrophilic group, the hydrophobic group, and the first functional group is independently one or more;

[0053] Optionally, in one molecule of the surfactant, the number of the first functional groups is 1 or 2 to 5;

[0054] Optionally, in one molecule of the surfactant, the number of the hydrophilic groups is 1 or 2 to 5.

[0055] The number of hydrophilic groups, hydrophobic groups and first functional groups in the surfactant can be adjusted separately, so that the surfactant can simultaneously obtain a suitable hydrophilic-hydrophobic balance and lone-pair electron Lewis basicity in a wider range.

[0056] In some embodiments, the molar percentage of the first functional group relative to the divalent metal ions in the perovskite precursor material is 0.001 mol% to 5 mol%;

[0057] Optionally, the molar percentage of the first functional group relative to the divalent metal ions in the perovskite precursor material is 0.1 mol% to 2.5 mol%.

[0058] The amount of the first functional group can be adjusted according to the amount of divalent metal ions in the perovskite precursor material, thereby better realizing the synergistic effect of the surfactant and the perovskite precursor material while taking into account improving the wettability of the perovskite precursor solution and reducing the vacancy defects in the perovskite, thereby better improving the uniformity of the perovskite film, which is also more beneficial to improving the energy conversion efficiency of the battery.

[0059] In some embodiments, the first functional group and the hydrophilic group are each independently attached to a carbon atom of the hydrophobic group.

[0060] In some embodiments, the surfactant comprises one or more of the following compounds:

[0061] In formula (I-1), q1 and q2 are each independently 0 or a positive integer, and q1+q2≥1, L 21 and L 22 Each independently represents a polyvalent hydrocarbon group having a main chain length of 8 to 20 atoms; 01 and Z 02 Each is independently a covalent bond, a carbonyl group or -NHC(=O)-*, where * points to U 03 ;U 03 is a trivalent hydrocarbon group; M 01 Not present or H or alkali metal ion; L 10 C 1-6 Alkylene; R 01 is an alkyl group; R 02 is a hydrocarbon group; in one molecule, F 01 and F 02 At least one of them is the first functional group, and the other one is independently H or the first functional group;

[0062] In formula (I-2), M 02 is an alkali metal ion;

[0063] In formula (I-3), Z1 is a covalent bond or a linker group Z 10 , where Z 10Any one selected from the group consisting of -CO-NH, -NH-CO-, -C(=O)-O-, -OC(=O)-, -NH-C(=O)-O-, -OC(=O)-NH-, and -O-; U N is a j+1 valence group; j is a positive integer; any Q 01 are independently -OH or -COOM 03 , M 03 is H or alkali metal ion;

[0064] In formula (I-4), R 01 is an alkyl group; R 02 is a hydrocarbon group;

[0065] In formula (I-2), formula (I-3), formula (I-4) and formula (I-5), F 03 are independently the first functional group;

[0066] In formula (I-2), formula (I-3), formula (I-4) and formula (I-5), q3 is independently an integer ≥ 1, L 23 Each independently represents a polyvalent hydrocarbon group having a main chain atomic length of 8 to 20.

[0067] In some embodiments, the surfactant satisfies one or more of the following characteristics:

[0068] In formula (I-1), L 21 and L 22 Each independently is a linear or branched type; optionally, L 21 and L 22 Each independently is a linear C 8-20 Alkylidene or branched C 8-20 Multivalent hydrocarbon group; further optionally, L 21 and L 22 Each independently is a linear C 8-20 Alkylene; further optionally, L 21 and L 22 Each independently is a linear C 8-20 Alkylene or linear C 8-20 Alkenylene; further optionally, L 21 and L 22 Each independently is a linear C 10-18 Alkylene or linear C 10-18 Alkenylene; further optionally, L 21 and L 22 Each independently is a linear C 12-18 Alkylene or linear C 12-18 alkenylene;

[0069] In formula (I-1), U 03 A trivalent alkyl group or R 21 、R 22 and R 23 are each independently an alkylene group; alternatively, U 03 Trivalent C 2-10 Alkyl or trivalent C 3-10 A tertiary amino group, further optionally, U 03 -CH 2- CR 04 (-)-CH2-、>CH-L 04 -, or N(-CH2CH2-)3, R 04 H or C 1-4 Alkyl (R 04 further optionally H, methyl or ethyl, further optionally H), L 04 C 1-6 Alkylene (L 04 Further optional C 1-4 Alkylene, further optionally C 1-4 alkylene, further optionally methylene, 1,2-ethylene, 1,3-propylene or 1,4-butylene); optionally, R 21 、R 22 and R 23 Each independently is C 1-4 Alkylene, further optionally, R 21 、R 22 and R 23 Each independently is C 1-3 Alkylene, further optionally, R 21 、R 22 and R 23 are each independently methylene or ethylene, further optionally, R 21 、R 22 and R 23 All are ethylene;

[0070] In formula (I-1), M 01 Absent or H, lithium, sodium or potassium ions;

[0071] In formula (I-1), L 10 C 1-4 Alkylene, which may be ethylene or propylene, may further be ethylene;

[0072] In formula (I-1), R 01 C 1-3 alkyl; optionally, R 01 is methyl;

[0073] In formula (I-1), R 02 C 1-8 Alkyl or benzene ring substituted C 1-3 Alkylene, the benzene ring is phenyl or surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl;

[0074] In formula (I-2), M 02 is H, lithium ion, sodium ion or potassium ion;

[0075] In formula (I-3), U N Contains 0, 1 or more hydrophilic linking groups L 01 A polyvalent hydrocarbon group, optionally, U N Contains 0, 1 or more hydrophilic linking groups L 01 A polyvalent saturated hydrocarbon group, any one of the hydrophilic linking groups L 01 are independently *-CONH-*, *-NHCO-*, *-C(=O)O-*, *-OC(=O)-*, *-O-(O=)P(OM 01 )-O-* or *-O-*, wherein * represents the connection site to the carbon atom, M 01 Absent or H, lithium, sodium or potassium ions; or, U N is a trivalent alkyl group or a tetravalent alkyl group, optionally, U N The number of carbon atoms is 3 to 10, further optionally 3 to 6, further optionally 3, 4 or 5, and further optionally, U N -CH 2- CR 05 (-)-CH2-,R 05 is H, methyl or ethyl, further optionally, R 05 H; or, U N It is a trivalent tertiary amino group, which can be a trivalent C 3-10 A tertiary amino group may further be N(-CH2CH2-)3;

[0076] In formula (I-3), U N The number of non-hydrogen atoms is 2 to 40, optionally 2 to 30, further optionally 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, further optionally 2 to 6, further optionally 2, 3, 4 or 5;

[0077] In formula (I-3), j is an integer selected from 1 to 5, may be an integer selected from 1 to 4, and may be 1, 2 or 3;

[0078] In formula (I-4), R 01 C 1-3 alkyl; optionally, R 01 is methyl;

[0079] In formula (I-4), R 02 C 1-8 Alkyl or benzene ring substituted C 1-3 Alkylene, the benzene ring is phenyl or surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl;

[0080] In formula (I-2), formula (I-3) and formula (I-4), L 23 are independently linear or branched; optionally, L 23 Each independently is a straight chain C 8-20 Alkylidene or branched C 8-20 Multivalent hydrocarbon group; further optionally, L 23 Each independently is a straight chain C 8-20 Alkylene or linear C 8-20 Alkenylene; further optionally, L 23 Each independently is a straight chain C 10-18 Alkylene or linear C 10-18 Alkenylene; further optionally, L 23 Each independently is a straight chain C 12-18 Alkylene or linear C 12-18 Alkenylene.

[0081] In some embodiments, the surfactant comprises one or more of the following compounds:

[0082] Among them, M 01 It is absent or is H or an alkali metal ion.

[0083] For surfactants containing quaternary ammonium salt groups, while regulating film formation, they can interact with the perovskite intermediate phase, regulate the crystallization nucleation rate and crystallization rate, and promote grain growth.

[0084] For surfactants containing monohydrogen phosphate groups, the interface between the perovskite layer and the hole transport layer can be passivated.

[0085] For branched surfactants containing at least two hydrophobic carbon chains, the damage of water to the perovskite layer can be avoided.

[0086] For linear surfactants containing sulfonates, bulk defects are reduced and the short-circuit current density (Jsc) is increased.

[0087] For surfactants whose hydrophilic groups include one or more hydroxyl groups, the solubility of the surfactant in the precursor solution can be increased, thereby improving the uniformity of large-area coating.

[0088] For surfactants whose hydrophilic groups include one or more carboxyl groups, bulk defects can be reduced and device stability can be improved.

[0089] In some embodiments, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.001 mol% to 5 mol%;

[0090] Optionally, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.001% to 2.5%;

[0091] Further optionally, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.01% to 1%;

[0092] Further optionally, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.01% to 0.5%.

[0093] The amount of the first functional group can be adjusted by adjusting the content of the surfactant, thereby better realizing the synergistic effect of the surfactant and the perovskite precursor material while taking into account improving the wettability of the perovskite precursor solution and reducing the vacancy defects in the perovskite, thereby better improving the uniformity of the perovskite film, which is also more beneficial to improving the energy conversion efficiency of the battery.

[0094] In some embodiments, the solvent includes a first solvent and a second solvent, and the boiling point of the first solvent is lower than the boiling point of the second solvent.

[0095] In some embodiments, the first solvent comprises one or more of N,N-dimethylformamide, 2-methoxyethanol, and acetonitrile;

[0096] The second solvent includes one or more of N-methylpyrrolidone, diphenyl sulfoxide, and dimethylpropylene urea.

[0097] In some embodiments, the volume ratio of the first solvent to the second solvent is 3 to 10;

[0098] Optionally, the volume ratio of the first solvent to the second solvent is 3-5.

[0099] Solvents with different boiling points can be used in combination to adjust the solvent evaporation rate and thus the morphology of the perovskite film when preparing the perovskite film, thereby improving the uniformity of the film and being more conducive to improving the energy conversion efficiency of the perovskite battery.

[0100] In a second aspect, the present application provides a perovskite film, which is prepared by coating and annealing the perovskite precursor solution described in the first aspect of the present application, or at least contains the non-solvent component in the perovskite precursor solution described in the first aspect of the present application.

[0101] The perovskite film prepared using the perovskite precursor solution described in the first aspect of the present application has good contact with the substrate, the film is uniform and has few defects, and the corresponding perovskite battery has high energy conversion efficiency.

[0102] In some embodiments, the area of ​​the perovskite film is ≥1 cm 2 .

[0103] For large-area perovskite films (e.g. ≥1cm 2 ) It is relatively difficult to obtain a relatively uniform perovskite film. Compared with perovskite precursor solutions using traditional surfactants, the perovskite precursor solution provided by this application containing the surfactant of the aforementioned first functional group has significant advantages in improving the uniformity of large-area perovskite films.

[0104] 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.

[0105] In some embodiments, the area of ​​the perovskite film is ≥1 cm 2 ;

[0106] Optionally, the area of ​​the perovskite film is ≥4 cm 2 .

[0107] In a fourth aspect, the present application provides an electrical device comprising the perovskite battery described in the third aspect of the present application.

[0108] 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

[0109] 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:

[0110] 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;

[0111] 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;

[0112] FIG3 is a schematic diagram of a perovskite cell according to an embodiment of the present application;

[0113] FIG4 is a schematic diagram of an electrical device in which a perovskite cell according to an embodiment of the present application is used as a power generation device.

[0114] Explanation of the accompanying figures: 100 is a perovskite cell; 110 is a substrate layer; 120 is a first electrode; 130 is a first transmission layer; 140 is a perovskite layer; 150 is a second transmission layer; 160 is a second electrode; P1 is a first notch area; P2 is a second notch area; P3 is a third notch area; 20 is an electrical device. DETAILED DESCRIPTION

[0115] 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.

[0116] " 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, the numerical range "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is merely an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to listing the parameter as, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and so on. 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.

[0117] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0118] 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.

[0119] Unless otherwise specified, the terms "include," "contain," and "comprise" used in this application are open-ended or closed-ended. For example, "include," "contain," and "comprise" may indicate that the present invention may also include or contain other members, elements, or method steps not listed, or may indicate that the present invention may include or contain only the listed members, elements, or method steps.

[0120] 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).

[0121] 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.

[0122] 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.

[0123] The terms "combination thereof", "any combination thereof", "any combination thereof" and the like used in this application include all suitable combinations of any two or more of the listed items.

[0124] In this application, the “suitable” mentioned in “suitable combination”, “suitable method”, “any suitable method”, etc. shall be based on the technical solution that can implement this application.

[0125] In this application, the terms "preferred," "better," "more preferred," and "suitable" are used solely to describe preferred implementations or examples and should not limit the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, each "preferred" term is independent unless otherwise specified and there are no contradictions or mutual constraints.

[0126] In this application, the terms "optionally," "optional," and "optional" are optional, meaning they may be present or absent, i.e., they may be either of two parallel options: "present" or "absent." If a technical solution contains multiple "optional" clauses, each "optional" clause is considered independent unless otherwise specified and there are no conflicts or constraints.

[0127] In this application, "further", "further", "particularly" and the like are used for descriptive purposes to indicate the differences in content between different technical solutions, but should not be understood as limiting the scope of protection of this application.

[0128] In this application, the terms "first," "second," "third," "fourth," etc. in "the first aspect," "the second aspect," "the third aspect," "the fourth aspect," etc. are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor should they be understood as implicitly indicating the importance or quantity of the indicated technical features. Furthermore, "first," "second," "third," "fourth," etc. serve only as non-exhaustive enumeration and description, and should be understood not to constitute a closed-ended limitation on quantity.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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 that the atom, group, or compound residue participates in forming a 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, and -NHNH2 is monovalent, and the valence of -NHNH- is divalent. For those skilled in the art, it is understood that this "valence" is different from the charge state of an ion.

[0133] 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.

[0134] In this application, unless otherwise specified, "hydrocarbyl" refers to a monovalent or polyvalent group composed of carbon atoms and hydrogen atoms, and refers to a group formed when the corresponding hydrocarbon loses one or more hydrogen atoms, forming a corresponding covalent bonding site at the position of the lost hydrogen atom. If the valence state of "hydrocarbyl" is not directly or indirectly specified, it generally refers to a monovalent hydrocarbon group. For example, references to "alkyl," "cycloalkyl," "aryl," "heteroalkyl," "heterocycloalkyl," and "heteroaryl" generally refer to monovalent alkyl, monovalent cycloalkyl, monovalent aryl, monovalent heteroalkyl, monovalent heterocycloalkyl, and monovalent heteroaryl, respectively, unless the valence state is directly or indirectly specified.

[0135] In the present application, "multivalent hydrocarbon group" refers to a multivalent group formed by the corresponding hydrocarbon losing multiple hydrogen atoms (such as ≥2, further such as 2, 3, 4, etc.).

[0136] In this application, Arabic numerals may be used to subscript the number of atoms, for example, C 8-20 The hydrocarbyl group means a hydrocarbyl group having 8 to 20 carbon atoms.

[0137] In the present application, unless otherwise specified, "hydroxyl" refers to -OH.

[0138] In this application, the term "hydrocarbon" or "hydrocarbon compound" refers to a compound composed of carbon atoms and hydrogen atoms.

[0139] In the present application, unless otherwise specified, "hydrocarbon group" refers to a monovalent residue formed by a hydrocarbon compound losing a hydrogen atom.

[0140] In this application, unless otherwise specified, "alkyl" refers to a monovalent residue formed by the loss of one hydrogen atom 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. Phrases containing this term, for example, "C1-9 alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, and each occurrence can independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, or C9 alkyl. 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).

[0141] In this application, unless otherwise specified, "alkylene" refers to a hydrocarbon group derived from an alkane by removing two hydrogen atoms (or derived from an alkyl group by losing another hydrogen atom), having two monovalent radical centers, which can be a saturated branched alkyl group or a saturated straight-chain alkyl group. For example, "C1-C9 alkylene" or "C1-9 alkylene" means that the alkyl portion contains 1 to 9 carbon atoms, and each occurrence can 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-).

[0142] In this application, unless otherwise specified, "aromatic hydrocarbon compound" refers to a hydrocarbon compound containing an aromatic ring. The aromatic ring may or may not have a substituent. When a substituent is present on the aromatic ring, the number of such substituents may be one or more, and the substituents may be aromatic or non-aromatic. For example, the substituents may be phenyl, alkyl, or alkenyl (e.g., vinyl).

[0143] In this application, unless otherwise specified, "aryl" refers to an aromatic hydrocarbon group derived from an aromatic hydrocarbon compound by losing a hydrogen atom on the aromatic ring, that is, a monovalent linking site formed directly on the aromatic ring. It can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. For example, "C6-C 10 Aryl" or "C 6-10 "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" or "C 6-20 "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 20Aryl (eg, perylene). Examples of suitable aromatic cyclic hydrocarbon compounds include, but are not limited to, benzene, toluene, stycyclobutene, biphenyl, indene, naphthalene, acenaphthene, fluorene, anthracene, phenanthrene, triphenylene, perylene, and derivatives thereof.

[0144] In this application, unless otherwise specified, "heteroatom" refers to non-hydrogen, non-carbon atoms, such as O, N, S, P, B, etc.

[0145] In this application, unless otherwise specified, "heteroalkyl" means that at least one carbon atom in the hydrocarbon group is replaced by a heteroatom, and the heteroatom may be, but is not limited to, an N atom, an O atom, an S atom, a P atom, a B atom, etc.

[0146] The commercialization of perovskite cells on a large scale is still some distance away. The energy conversion efficiency of perovskite films is a key factor hindering their industrialization. Furthermore, the uniformity of perovskite films is a crucial factor in improving energy conversion efficiency. To improve the uniformity of perovskite films, surfactants can be added. However, improper addition of surfactants can lead to defects in the perovskite crystals, resulting in poor performance of perovskite solar cells.

[0147] In response to the above-mentioned common technical problems, in the first aspect, the present application provides a perovskite precursor solution, which includes a surfactant, the structure of which includes a hydrophilic group, a hydrophobic group and a first functional group, wherein the first functional group is a Lewis basic group containing a lone pair of electrons, and the lone pair of electrons exists in at least one of the N atom and the S atom; the first functional group, the hydrophilic group and the hydrophobic group are different from each other.

[0148] In this application, unless otherwise specified, "hydrophilic group" and "hydrophobic group" have well-known meanings in the art. Generally, "hydrophilic group" refers to a group that can dissolve in water or is easily affinity with water, and "hydrophobic group" refers to a group that has no affinity for water, is insoluble in water, or has very low water solubility. It is understood that "hydrophilic group" and "hydrophobic group" are relative. Non-limiting examples of hydrophobic groups suitable for use in this application may include medium- and long-chain hydrocarbon groups (such as C 8-20 Hydrocarbon), C 7-25 Aromatic hydrocarbon groups, etc. In the present application, some groups with better hydrophilicity than long-chain alkyl groups can be used as "hydrophilic groups" in this article. Non-limiting examples of hydrophilic groups suitable for the present application may include one or more of proton acid, proton base, ether group (-O-), ester group (-COO-), amide group (-CONH-), etc.; combined with acid-base proton theory ( acid-base theory, Brønsted-Lowry acid-base theory), examples of proton acids include carboxyl groups, sulfonic acid groups, sulfonic acid salts, sulfate groups, phosphoric acid groups, etc., as well as groups of organic or inorganic acid molecules such as complex carboxylic acid, phosphonic acid, sulfonic acid, hydrohalic acid, sulfuric acid, and phosphoric acid; examples of proton bases include hydroxyl groups, primary amino groups, secondary amino groups, quaternary ammonium salts, etc.

[0149] As used herein, the term "lone pair" has a well-known meaning in the art, referring to the presence of non-bonding electrons not used to form a covalent bond. "Lone" refers to the absence of a bond, and "bonded" refers to the pairing of two electrons with opposite spins. For example, the two nitrogen atoms in -NH-NH- and -NH-NH2, as well as the sulfur atom in -SH, all have lone pairs.

[0150] In this application, unless otherwise specified, "Lewis base" has the commonly known meaning in the art, generally referring to a base defined according to Gilbert Newton Lewis' acid-base electronic theory. More specifically, it refers to a substance that can donate electron pairs, which may include ions, atomic groups or molecules.

[0151] In the present application, unless otherwise specified, a "Lewis basic group" refers to a group that can donate an electron pair.

[0152] In the present application, unless otherwise specified, a "Lewis basic group containing a lone pair of electrons" means that the group contains an atom with a lone pair of electrons and the group can donate an electron pair.

[0153] In some embodiments, the present application provides a perovskite precursor solution comprising a perovskite precursor material, a solvent, and a surfactant; the structure of the surfactant includes a hydrophilic group, a hydrophobic group, and a first functional group, wherein the first functional group is a Lewis basic group containing a lone pair of electrons, and the lone pair of electrons exists in at least one of an N atom and an S atom; the first functional group, the hydrophilic group, and the hydrophobic group are different from each other.

[0154] In the structure of surfactants with hydrophilic and hydrophobic groups, lone pairs of electrons can be provided by specific types of atoms (including specific atoms of at least one of N and S), giving the surfactant suitable Lewis base properties. On the one hand, this can improve the wettability of the perovskite precursor solution on the substrate surface, and on the other hand, it can more stably complex with the divalent metal ions in the perovskite precursor material, better passivating multiple defects in the perovskite, such as lead vacancies and iodine vacancies. By introducing this special structure of surfactant into the perovskite precursor solution, the uniformity of the perovskite film can be improved, and the energy conversion efficiency of the battery can be improved.

[0155] In addition, the perovskite precursor solution provided in this application is conducive to the preparation of large-area (such as ≥1cm 2 )Perovskite thin films.

[0156] In some embodiments, the first functional group comprises -NR 11 -NR 12 R 13 and -SH; wherein R 11 and R 12 Each independently is H or a hydrocarbon group, R 13 The hydrophilic group is H, a hydrocarbyl group or a hydrocarbyl group substituted with a monovalent hydrophilic group, wherein the monovalent hydrophilic group can be selected from any suitable monovalent hydrophilic group herein. Examples of the monovalent hydrophilic group can include, but are not limited to, one or more of a carboxyl group, a sulfonic acid group, a sulfonic acid salt, a sulfate group, a sulfate salt, a phosphate group, a phosphate salt, a monohydrogen phosphate group, a monohydrogen phosphate salt, a primary amino group, a primary amino salt, a secondary amino group, a secondary amino salt, a quaternary ammonium salt, -CONH2 and a hydroxyl group.

[0157] In some embodiments, R 11 and R 12 Each independently is H or C 1-20 Hydrocarbon, further optionally H or C 1-18 Hydrocarbon, further optionally H or C 1-15 Hydrocarbon, further optionally H or C 1-12 Hydrocarbon, further optionally H or C 1-10 Hydrocarbon, further optionally H or C 1-8 Hydrocarbon, further optionally H or C 1-6 Hydrocarbon, further optionally H or C 1-4 Hydrocarbon, further optionally H or C 1-3 The hydrocarbon group may further be H or methyl.

[0158] In some embodiments, R 13 is H, a hydrocarbon group or a hydrocarbon group substituted by a monovalent hydrophilic group; the hydrocarbon groups in the hydrocarbon group or the hydrocarbon group substituted by a monovalent hydrophilic group are each independently C 1-20 Hydrocarbyl, optionally C 1-18 Hydrocarbon, further optionally C 1-15 Hydrocarbon, further optionally C 1-12 Hydrocarbon, further optionally C 1-10 Hydrocarbon, further optional C 1-8 Hydrocarbon, further optionally C 1-6 Hydrocarbon, further optionally C 1-4 Hydrocarbon, further optionally C 1-3 The hydrocarbon group may further be a methyl group. The definition of the monovalent hydrophilic group may be as described above.

[0159] In some embodiments, R 11 and R 12 are each independently H or alkyl, optionally, R 11 and R 12 Each independently is H or C 1-6 Alkyl, further optionally, R 11 and R 12 Each independently is H or C 1-3 Alkyl; further optionally, R 11 and R 12 are each independently H or methyl; further optionally, R 11 and R 12 are H; further optionally, R 11 and R 12 are all H; further optionally, the first functional group is selected from one or both of -NH-NH2 and -SH.

[0160] In some embodiments, R 13 It can be H, alkyl or alkyl substituted by a hydrophilic group; the alkyl in the alkyl or alkyl substituted by a monovalent hydrophilic group can each independently be C 1-20 Alkyl, optionally C 1-18 Alkyl, further optionally C 1-15 Alkyl, further optionally C 1-12 Alkyl, further optionally C 1-10 Alkyl, further optionally C 1-8 Alkyl, further optionally C 1-6 Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 The alkyl group may further be a methyl group. The definition of the monovalent hydrophilic group may be as described above.

[0161] In some embodiments, R 13 is H or a hydrocarbon group, further optionally H or an alkyl group, further optionally H or C 1-20 Alkyl, further optionally H or C 1-18 Alkyl, further optionally H or C 1-15 Alkyl, further optionally H or C 1- 12 Alkyl, further optionally H or C 1-10 Alkyl, further optionally H or C 1-8 Alkyl, further optionally H or C 1- 6 alkyl, further optionally H or C 1-4 Alkyl, further optionally H or C 1-3Alkyl, further optionally H or methyl. In some embodiments, R 13 is H. In some embodiments, R 13 is a hydrocarbon group, and may also be as defined above.

[0162] In some embodiments, the first functional group comprises -NR 11 -NHR 13 and -SH, one or more, R 11 and R 13 are each independently H or a hydrocarbon group, optionally, R 11 and R 13 are each independently H or alkyl, further optionally, R 11 and R 13 Each independently is H or C 1-6 Alkyl, further optionally, R 11 and R 13 Each independently is H or C 1-3 Alkyl; further optionally, R 11 and R 13 are each independently H or methyl.

[0163] In some embodiments, the first functional group comprises -NH-NHR 13 and -SH, one or more, R 13 It can be H or hydrocarbon group, R 13 See also the preceding definitions.

[0164] A group having at least one of an NN structure and a -SH structure can be used as the first functional group. In this case, it can provide more suitable Lewis base properties, thereby playing a better role in improving the wettability of the perovskite precursor solution and reducing vacancy defects in the perovskite, thereby better improving the uniformity of the perovskite film, and is also more beneficial to improving the energy conversion efficiency of the battery.

[0165] When the surfactant contains a -NN- structure, it can be a monovalent hydrazine group or a divalent hydrazine group. The two nitrogen atoms in the -NN- structure can provide a pair of lone electrons. For example, the perovskite-type metal halide ABX3 in the perovskite precursor material, B is Pb 2+ , X is I - For example, surfactants containing -NN- structure can provide a certain reducing property while acting as Lewis bases, which can reduce iodine and inhibit the oxidation of iodide ions, thus reducing or avoiding the imbalance of stoichiometric ratio and the defects caused by it. Among them, the monovalent hydrazine group is located at the end of the chain, and the divalent hydrazine group is located in the middle of the chain. Among them, the monovalent hydrazine group at the end of the chain is more likely to react with Pb 2+ Generate interaction and better passivation effect.

[0166] When the surfactant contains -SH, the sulfur atom can provide two pairs of lone pairs of electrons. This type of surfactant has stronger reducing properties and interacts better with the perovskite components. It can promote the uniform film formation of the perovskite solution while improving the crystallization growth rate, promoting grain growth, and optimizing the bulk crystallization quality.

[0167] In the surfactant, when the types of the first functional groups in one molecule are greater than or equal to two, the number of any one first functional group can independently be 1 or more (for the case of "more than one", such as ≥2, further such as 2 to 8, further such as 2 to 5, further such as 2, 3 or 4).

[0168] In some embodiments, the hydrophilic group includes one or more of a carboxyl group, a sulfonic acid group, a sulfonic acid salt, a sulfate group, a sulfate salt, a phosphate group, a phosphate salt, a monohydrogen phosphate ester group, a monohydrogen phosphate ester salt, a primary amino group, a primary amino salt, a secondary amino group, a secondary amino salt, a divalent tertiary amino group, a quaternary ammonium salt, -CONH2, a hydroxyl group, an ether group, an ester group, -CONH-, and a divalent phosphate ester group.

[0169] In the present application, unless otherwise specified, for the hydrophilic groups listed above, the carboxyl group is -COOH; the sulfonic acid group is -SO3H, -S(=O)2OH; the sulfonic acid group can be a salt of -SO3M, where M is an alkali metal ion, such as lithium, sodium, potassium, and further such as sodium and potassium; the sulfate group is -OS(=O)2OH; the sulfate group can be a salt of -OS(=O)2OM, where M is an alkali metal ion, such as lithium, sodium, potassium, and further such as sodium and potassium; the phosphate group is -OP(=O)(OH)2; the phosphate salt can be a salt formed by replacing at least one hydrogen in -OP(=O)(OH)2 with an alkali metal ion; the monohydrogen phosphate group can be a salt formed by replacing one H in -OP(=O)(OH)2 with a hydrocarbon ion. The group formed by replacing a hydrocarbon group or a substituted hydrocarbon group may further be a group formed by replacing one H by an alkyl group or a substituted alkyl group, the substituted hydrocarbon group or the substituted alkyl group may each independently contain a heteroatom, and further may each independently contain any suitable hydrophilic group in the present application; the monohydrogen phosphate salt may be a salt formed by replacing one H by a hydrocarbon group or a substituted hydrocarbon group in -OP(=O)(OH)2 and replacing the other H by an alkali metal ion; the primary amino group is -NH2; the primary amino salt is a group formed by complexing -NH2 with an acid molecule; the secondary amino group has a>NH (or is recorded as -NH-) structure, which may be -NHR0, R0 is a hydrocarbon group, optionally an alkyl group, and further optionally C 1-3 Alkyl, further optionally methyl; secondary amino salt is a group formed by the complexation of secondary amino group and acid molecule; divalent tertiary amino group is -NR0-, and the definition of R0 can be the same as that of secondary amino group; quaternary ammonium salt has>N +<structure and connects four carbon atoms, can be *-N + R 01 R 02 R 03 , where R 01 is an alkyl group; R 02 is a hydrocarbon group, R 03 is an alkyl group; -CONH2 is a monovalent amide group; a hydroxyl group is -OH; an ether group is -O-; an ester group is -CO-O- or -O-CO-; -CONH- is a divalent amide group; a divalent phosphate group can be -O-(O=)P(OM 01 )-O-,M 01 is absent or is H or an alkali metal ion. Unless otherwise stated, one or two covalent attachment sites of the hydrophilic groups listed herein are attached to a carbon atom.

[0170] In some embodiments, the hydrophilic group includes one or more of a carboxyl group, a sulfonic acid group, a sulfonic acid salt, a sulfate group, a sulfate salt, a phosphate group, a phosphate salt, a monohydrogen phosphate group, a monohydrogen phosphate salt, a primary amino group, a primary amino salt, a secondary amino group, a secondary amino salt, a quaternary ammonium salt, -CONH2, and a hydroxyl group.

[0171] In some embodiments, the hydrophilic group includes one or more of a carboxyl group, a sulfonic acid group, a sulfonic acid salt, a sulfate group, a sulfate salt, a phosphate group, a phosphate salt, a primary amino group, a primary amino salt, a secondary amino group, a secondary amino salt, a quaternary ammonium salt, -CONH2, and a hydroxyl group.

[0172] In some embodiments, the sulfonic acid salt, sulfate salt, phosphate salt, and monohydrogen phosphate salt are alkali metal salts of the corresponding acids.

[0173] In some embodiments, the primary amino salt and the secondary amino salt are salts formed by corresponding amines and acids; optionally, the acid is an organic acid or an inorganic acid; the organic acid includes one or more of carboxylic acid, phosphonic acid and sulfonic acid; the inorganic acid includes one or more of hydrohalic acid, phosphoric acid and sulfuric acid, optionally, the inorganic acid includes one or more of hydrochloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid and sulfuric acid.

[0174] In some embodiments, the hydrophilic group includes at least one of a quaternary ammonium ion and an alkali metal ion.

[0175] The surfactant provided herein can contain various types of hydrophilic groups, thereby being able to more flexibly adjust the surface tension of the surfactant, and more flexibly play the wettability of the perovskite precursor solution and the passivation effect on the vacancy defects in the perovskite. When the structure of the surfactant includes an alkali metal salt hydrophilic group, it is conducive to further passivating the perovskite layer interface defects. When the structure of the surfactant includes at least one of a primary amino group, a secondary amino group or a tertiary amino group, it is conducive to passivating the bulk phase defects. When the structure of the surfactant includes a quaternary ammonium salt, it is conducive to controlling the nucleation rate and promoting grain growth. When the structure of the surfactant is complexed with an acid molecule, it is conducive to the uniformity of the large-area film formation of the perovskite layer.

[0176] The hydrophilic group can be not only a monovalent hydrophilic group located at the end group, but also a multivalent group as a connecting group, and can also be a combination of monovalent or multivalent hydrophilic groups, so that by adjusting the position, number and other parameters of the hydrophilic group, a coordinated combination with the hydrophobic group and the first functional group can be formed, thereby giving the perovskite precursor solution better wettability, reducing vacancy defects in the perovskite, improving the uniformity of the perovskite film, and thus improving the energy conversion efficiency of the battery.

[0177] In some embodiments, the hydrophilic groups include *-COOH, *-S(=O)2OH, *-S(=O)2OM, *-OS(=O)2OH, *-OS(=O)2OM, *-O-(O=)P(OH)2, *-NH2、*-NH2·n2A cd 、*-NHR0、*-NHR0·n1A cd 、 (like ), *-CONH2, *-OH and one or more of the hydrophilic linking groups L0; wherein the hydrophilic linking group L0 includes *-CONH-*, *-NHCO-*, *-C(=O)O-*, *-OC(=O)-*, *-O-(O=)P(OM 01 )-O-*, *-NH-*, and *-O-*;

[0178] Wherein, any "*" represents a linking site to a carbon atom;

[0179] Any one of M is independently an alkali metal ion (may be independently lithium, sodium or potassium, and further may be independently sodium or potassium);

[0180] Any one of M1 and any one of M2 are each independently an alkali metal ion (which may each independently be lithium, sodium or potassium, and further may each independently be sodium or potassium);

[0181] Any R 10 are independently hydrocarbon groups (which may be independently C 1-10 Alkyl, further independently C 1-8 Alkyl, further independently C 1-6 Alkyl, further independently C 1-4 Alkyl, further independently C 1-3 alkyl, further such as methyl, ethyl or propyl);

[0182] Any A cd is independently an acid molecule (any A cd It can be independently an organic acid or an inorganic acid molecule; the organic acid can include one or more of carboxylic acid, phosphonic acid and sulfonic acid; the inorganic acid includes one or more of hydrohalic acid, phosphoric acid and sulfuric acid, and optionally, the inorganic acid includes one or more of hydrochloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid and sulfuric acid); n2 is 1 or 2; n1 is 1;

[0183] Any R0 is independently a hydrocarbon group or a substituted hydrocarbon group; the substituted hydrocarbon group is substituted by one or more hydrophilic groups; optionally, any R0 is independently an alkyl group; further optionally, any R0 is independently C 1-3 Alkyl; further optionally, R0 is methyl;

[0184] R 01 is an alkyl group (optionally, R 01 C 1-3 Alkyl; further optionally, R 01 is methyl);

[0185] R 02 is a hydrocarbon group (optionally, R 02 C 1-8 Alkyl or benzene ring substituted C 1-3 Alkylene, the benzene ring is phenyl or surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; further optionally, R 02 is methyl or benzyl);

[0186] R 03 is an alkyl group (optionally, R 03 or C 1-3 Alkyl; further optionally, R 03 is methyl);

[0187] M 01 Absent or H or alkali metal ion (optionally, M 01 is absent or is H, lithium, sodium or potassium, further optionally, M 01 In some embodiments, M01 does not exist. At this time, the O there exists in the form of negative ions (*-O-(O=)P(O - )-O-*). In some embodiments, M 01 It is H or an alkali metal ion, further may be H, lithium, sodium or potassium, and further may be H, sodium or potassium.

[0188] When the hydrophilic group includes multiple groups listed above, different hydrophilic groups can be connected to different carbon atoms, or two hydrophilic groups can be connected and combined to form a new hydrophilic group. Among them, M 20 The definition of M can refer to but is not limited to 01 ;M 20 It may not exist or be H or an alkali metal ion (the alkali metal ion may be lithium, sodium or potassium, and may further be sodium or potassium); R 20 It can be an alkyl group substituted with a hydrophilic group; optionally, R 20 is an alkyl group substituted with a quaternary ammonium salt group; further optionally, R 20 is a choline-substituted alkyl group; further optionally, R 20 is an alkyl group substituted with acetylcholine; in addition, the alkyl group in the alkyl group substituted with the hydrophilic group may be C 1-10 Alkyl, further optionally C 1-8 Alkyl, further optionally C 1- 6 alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 Alkyl. For example, *-NHR 30 , where R 30 It can be an alkyl group substituted by one or more hydrophilic groups; optionally, R 30 C substituted by one or more hydrophilic groups 1-3 alkyl.

[0189] In some embodiments, at least one side of the hydrophilic linker L0 is connected to a monovalent hydrophilic group.

[0190] In some embodiments, the surfactant satisfies any one or more of the following characteristics:

[0191] Any M is independently lithium, sodium or potassium;

[0192] Any one M1 and any one M2 are each independently lithium, sodium or potassium;

[0193] Any R 10 Independently C 1-10 Alkyl, optionally C 1-8 Alkyl, further optionally C 1-6Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 alkyl;

[0194] Any A cd is independently an organic acid or inorganic acid molecule; the organic acid includes one or more of carboxylic acid, phosphonic acid and sulfonic acid; the inorganic acid includes one or more of hydrohalic acid, phosphoric acid and sulfuric acid, and optionally, the inorganic acid includes one or more of hydrochloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid and sulfuric acid;

[0195] Any R0 is independently alkyl; alternatively, any R0 is independently C 1-3 Alkyl; further optionally, R0 is methyl;

[0196] R 01 C 1-3 alkyl; optionally, R 01 is methyl;

[0197] R 02 C 1-8 Alkyl or benzene ring substituted C 1-3 Alkylene, the benzene ring is phenyl or surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl;

[0198] R 03 C 1-3 alkyl; optionally, R 03 is methyl;

[0199] M 01 Absent or H, lithium, sodium or potassium;

[0200] At least one side of the hydrophilic linking group L0 is connected to a monovalent hydrophilic group.

[0201] In some embodiments, the hydrophobic group comprises a carbon chain, further comprising C 8-20 Carbon chain.

[0202] In this application, unless otherwise specified, "carbon chain" refers to a monovalent group having a plurality of carbon atoms linearly connected in sequence from the attachment site to the farthest end group, or a polyvalent group connected to a plurality of attachment sites through a plurality of carbon atoms linearly connected in sequence (for example, a divalent group connected to two attachment sites). The carbon atoms sequentially connected along the longest interval constitute the main chain carbon atoms of the carbon chain. For example, the main chain carbon atoms of the trivalent group -CH2CH2CH(CH2-)-CH2CH2CH2CH2- are 7, and the main chain carbon atoms of the trivalent group -CH2CH(CH2CH2CH2-)-CH2CH2CH2CH2- are 8. It should be noted that the hydrogen atoms on these main chain carbon atoms can be substituted by hydrocarbon groups or heteroalkyl groups. When substituted by heteroalkyl groups, the heteroatoms can be present in the form of, but not limited to, the aforementioned hydrophilic groups.

[0203] In this application, unless otherwise specified, the connection site of the carbon chain in the surfactant is connected to the heteroatom in the surfactant, or forms a heteroatom-containing linking group with an adjacent atom or atomic group, such as an ester group (-CO-O- or -O-CO-), an amide group (-CO-NH- or -NH-CO-), an ether bond (-O-), a secondary amino group (-NH-), a divalent tertiary amino group (-N(CH3)-), etc.

[0204] In this application, C 8-20 A carbon chain refers to a carbon chain having 8 to 20 carbon atoms. 8-20 The number of carbon atoms in the carbon chain may also be 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, or an interval formed by any two of the aforementioned values, such as 8-18, 10-18, 12-18, etc. Non-limiting examples of the carbon chain include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, octylene, nonylene, decylene, divalent undecyl, divalent dodecyl, divalent tridecyl, divalent tetradecyl, divalent pentadecyl, divalent hexadecyl, divalent heptadecyl, divalent octadecyl, divalent nonadecyl, divalent eicosyl, or an unsaturated form of any of the foregoing groups, or a form in which at least one hydrogen in any of the foregoing containing or unsaturated structures is replaced by a hydrocarbon group or a heterohydrocarbon group.

[0205] By introducing a hydrophobic group of a certain size into the structure of the surfactant, it can be combined with the hydrophilic group and the first functional group to form a hydrophilic-hydrophobic balance that is more suitable for the perovskite precursor solution of the present application. While playing the role of the lone pair electrons in the first functional group, the perovskite precursor solution system can be made more stable and better dispersed, with better wettability to the substrate, thereby better improving the uniformity of the perovskite film.

[0206] In some embodiments, the carbon chain in the hydrophobic group is a straight chain or branched structure. 8-20 The carbon chain is a straight chain or branched structure. 8-20 The carbon chain does not contain a ring structure and has good molecular flexibility, which can adjust the flexibility of the perovskite film.

[0207] In some embodiments, the C 8-20 The main chain atom length of the carbon chain is 6 to 20; further optionally, the C 8-20 The main chain atoms of the carbon chain are 8 to 20 in length; further optionally, the C 8-20 The main chain atoms of the carbon chain are 8 to 18 in length; further optionally, the C 8-20 The carbon chain has a main chain atom length of 10 to 18 C 10-20 Carbon chain. 8-20 The carbon chain backbone atoms may be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 in length, or may be an interval consisting of any two of the aforementioned lengths. 8-20 The number of carbon atoms in a carbon chain is greater than or equal to the length of the main chain atoms.

[0208] In this application, unless otherwise specified, the "main chain atomic length of a carbon chain" refers to the length of the spacer atom connecting two designated sites (one of which is a connection site and the other is a connection site or endpoint), and the spacer atom length refers to the number of carbon atoms sequentially connected between the two connection sites; for a polyvalent carbon chain containing three or more connection sites, the main chain atomic length is the number of carbon atoms sequentially connected between the two connection sites with the farthest spacing. For example, the spacer atom length of 1,3-propylene is 3, the spacer atom length of 1,2-propylene is 2, the spacer atom length of the divalent group -CH(CH2CH3)- is 1, and the spacer atom length of the trivalent group -CH2CH2CH(CH2-)-CH2CH2CH2CH2- is 7 (corresponding to ), the spacer atom length of the trivalent group -CH2CH(CH2CH2CH2-)-CH2CH2CH2CH2- is 8.

[0209] In some embodiments, the C 8-20The carbon chain is a saturated structure or an unsaturated structure. Non-limiting examples of saturated structures include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, octylene, nonylene, decylene, divalent undecyl, divalent dodecyl, divalent tridecyl, divalent tetradecyl, divalent pentadecyl, divalent hexadecyl, divalent heptadecyl, divalent octadecyl, divalent nonadecyl, and divalent eicosyl. It can further be a linear form of any of the aforementioned groups, such as monovalent -(CH2)9CH3, divalent -(CH2) 10 -, monovalent -(CH2) 11 CH3, divalent -(CH2) 12 -, monovalent -(CH2) 13 CH3, divalent -(CH2) 14 -, monovalent -(CH2) 15 CH3, divalent -(CH2) 16 -, monovalent -(CH2) 17 CH3, divalent -(CH2) 18 -, etc. Non-limiting examples of unsaturated structures are unsaturated forms of the aforementioned saturated structures, which may include one or more (e.g., 2 or 3, further such as 2) carbon-carbon unsaturated bonds. Furthermore, the carbon-carbon unsaturated bonds may be, but are not limited to, alkenyl or alkynyl. Non-limiting examples of unsaturated structures are further such as CH3-(CH2)4-CH=CHCH2CH=CH-(CH2)7C(=O)-, in which the right-side connection site is replaced by oxygen, the main chain atom length of the carbon chain is 18, and it is an unsaturated form containing two unsaturated carbon-carbon double bonds.

[0210] For another example, At least include the following carbon chains: monovalent carbon chain CH3-(CH2)4-CH=CHCH2CH=CH-(CH2)7C(=O)- and divalent carbon chain -(CH2) 14 C(=O)-; It can also be considered that the surfactant includes at least the following carbon chains: a monovalent carbon chain CH3-(CH2)4-CH=CHCH2CH=CH-(CH2)7- and a divalent carbon chain -(CH2) 14 -, in this case, the two longer carbon chains are respectively connected to the carbon atoms in the divalent linking group ester group -C(=O)-O-.

[0211] In some embodiments, the C 8-20 The carbon chain is either an aromatic chain or an aliphatic chain.

[0212] In this application, unless otherwise specified, an "aromatic chain" includes at least one aromatic ring. An aliphatic chain does not contain any aromatic ring. Those skilled in the art are aware of the meaning of "aromatic ring", which refers to a ring with aromatic properties, which can be an aromatic ring or a heteroaromatic ring. The ring atoms of an "aromatic ring" are all carbon atoms. The reducing substituent of a heteroaromatic ring includes at least one heteroatom. The valence state of the aromatic ring is not particularly limited and can be monovalent or polyvalent, for example, monovalent or divalent. For an aromatic chain, the aromatic ring can be used to provide main chain atoms (such as -CH2-Ph-CH2-), or it can be a substituent without participating in the main chain composition (such as -CH2-CH(Ph)-CH2-, -CH2-CH(pyridyl)-CH2-). Ph represents a benzene ring.

[0213] In some embodiments, the molecular structure of the surfactant includes one or more of the C 8-20 In the molecular structure of the surfactant, the C 8-20 The number of carbon chains can be 1 or more, such as 1 or 2.

[0214] In some embodiments, the hydrophobic group includes one or more of an arylene group Ar0 and an aralkyl group ArA.

[0215] In some embodiments, the hydrophobic group includes an arylene group Ar0.

[0216] In some embodiments, the hydrophobic group comprises an aralkyl group ArA.

[0217] In this application, unless otherwise specified, "arylene" refers to a divalent aromatic hydrocarbon group derived from an aromatic hydrocarbon compound by losing two hydrogen atoms on the aromatic ring, that is, directly forming two monovalent connection sites on the ring, or "arylene" refers to a divalent aromatic hydrocarbon group formed by losing another hydrogen atom on the aromatic ring based on an aryl group. Substituents may or may not be present on the aromatic ring of the arylene group. When substituents are present, the substituents may be aromatic or non-aromatic. It is understood that the substituents on the aromatic ring should also be considered hydrocarbon groups. For example, "C 6-12 "Arylene" means that the group has 6 to 12 carbon atoms, and each occurrence can be independently C6 arylene, C7 arylene, C8 arylene, C9 arylene, C 10 Arylene, C1 arylene, C 12 Suitable examples include, but are not limited to, phenylene, In this application, unless otherwise specified, the terminal Indicates the site of covalent bond attachment.

[0218] In this application, unless otherwise specified, "aralkane" refers to a hydrocarbon compound formed by replacing one or more hydrogen atoms on an aromatic ring with an alkyl group; further, unless otherwise specified, it generally refers to a hydrocarbon formed by replacing one hydrogen atom on an aromatic ring with an alkyl group. Unless otherwise specified, "aralkyl" refers to a hydrocarbon group derived from the loss of a hydrogen atom from the alkyl carbon of the corresponding aralkane; that is, the aralkyl group is connected through the "alkyl" carbon.

[0219] In some embodiments, the arylene group Ar0 is C 6-18 Arylene, further can be phenylene or one or more C 1- The phenylene group may be substituted with an alkyl group, or may be substituted with one or more methyl groups.

[0220] In some embodiments, the arylene group Ar0 is a phenylene group.

[0221] In some embodiments, the aralkyl group ArA is a C 1-18 Alkyl, wherein any one of the aryl groups Ar1 is independently phenyl or is replaced by one or more C 1-4 Alkyl-substituted phenyl; further optionally, any one of the aryl groups Ar1 is independently phenyl or substituted by one or more C 1-3 Alkyl-substituted phenyl; further optionally, any one of the aryl groups Ar1 is independently phenyl or benzyl.

[0222] In some embodiments, the aralkyl group ArA is benzyl.

[0223] For example, The carbon chain includes the following: -(CH2) 11 - and benzyl. For example, The carbon chain includes the following: -(CH2) 11 - and phenylene.

[0224] Aromatic rings can be introduced into the hydrophobic structure of the surfactant, which is more conducive to the interaction between the surfactant molecules and the perovskite components and can promote better dissolution of the surfactant in the perovskite precursor solution.

[0225] In some embodiments, in one molecule of the surfactant, the number of the hydrophilic group, the hydrophobic group, and the first functional group is independently one or more.

[0226] In some embodiments, in one molecule of the surfactant, the number of the first functional groups is 1 or 2 to 5 (such as 1 or 2, 3, 4 or 5, further such as 1 or 2 or 3, further such as 1 or 2).

[0227] In some embodiments, in one molecule of the surfactant, the number of the first functional groups may be 1 to 5, and further may be 1 to 3.

[0228] In some embodiments, in one molecule of the surfactant, the number of the hydrophilic groups is 1 or 2 to 5 (such as 1 or 2, 3, 4 or 5, further such as 1 or 2 or 3, further such as 1 or 2).

[0229] In some embodiments, in one molecule of the surfactant, the number of the hydrophilic groups is 1 to 5, and further can be 1 to 3.

[0230] The number of hydrophilic groups, hydrophobic groups and first functional groups in the surfactant can be adjusted separately, so that the surfactant can simultaneously obtain a suitable hydrophilic-hydrophobic balance and lone-pair electron Lewis basicity in a wider range.

[0231] In some embodiments, in one molecule of the surfactant, the number of the hydrophilic groups is 1 to 5, and further can be 1 to 3.

[0232] In some embodiments, the molar percentage of the first functional group relative to the divalent metal ions in the perovskite precursor material is 0.001 mol% to 5 mol%. The molar percentage of the first functional group relative to the divalent metal ions in the perovskite precursor material can also be selected from any one of the following molar percentages: 0.001 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, 0.04 mol%, 0.05 mol%, 0.06 mol%, 0.08 mol%, 0.1 mol%, 0.12 mol%, 0.14 mol%, 0.15 mol%, 0.16 mol%, 0.18 mol%, 0.2 mol%, 0.22 mol%, 0.24 mol%, 0.25 mol%, 0.26 mol%, 0.28 mol%, 0.3 mol%. %, 0.35mol%, 0.4mol%, 0.45mol%, 0.5mol%, 0.55mol%, 0.6mol%, 0.65v0.7mol%, 0.75mol%, 0.8mol%, 0.9mol%, 1mol%, 1.2mol%, 1.4mol%, 1.5mol%, 1.6mol%, 1.8mol%, 2mol%, 2.5mol%, 3mol%, 3.5mol%, 4mol%, 4.5mol%, 5mol%, etc., and can also be selected from the interval consisting of any two of the above molar percentages, for example, 0.01mol% to 2.5mol%, 0.1mol% to 1mol%.

[0233] The amount of the first functional group can be adjusted according to the amount of divalent metal ions in the perovskite precursor material, thereby better realizing the synergistic effect of the surfactant and the perovskite precursor material while taking into account improving the wettability of the perovskite precursor solution and reducing the vacancy defects in the perovskite, thereby better improving the uniformity of the perovskite film, which is also more beneficial to improving the energy conversion efficiency of the battery.

[0234] In some embodiments, the first functional group and the hydrophilic group are each independently connected to a carbon atom of the hydrophobic group, either directly or indirectly via a linker.

[0235] In some embodiments, the surfactant comprises one or more of the following compounds:

[0236] In formula (I-1), q1 and q2 are each independently 0 or a positive integer, and q1+q2≥1, L 21 and L 22 Each independently represents a polyvalent hydrocarbon group having a main chain length of 8 to 20 atoms; 01 and Z 02 Each is independently a covalent bond, a carbonyl group or -NHC(=O)-*, where * points to U 03 ;U 03 is a trivalent hydrocarbon group; M 01 It does not exist or is H or alkali metal ion (also refer to the above M 01 Definition of L 10 C 1-6 Alkylene; R 01 is an alkyl group; R 02 is a hydrocarbon group; in one molecule, F 01 and F 02 At least one of them is the first functional group, and the other one is independently H or the first functional group;

[0237] In formula (I-2), M 02 is an alkali metal ion;

[0238] In formula (I-3), Z1 is a covalent bond or a linker group Z 10 , where Z 10 Any one selected from the group consisting of -CO-NH, -NH-CO-, -C(=O)-O-, -OC(=O)-, -NH-C(=O)-O-, -OC(=O)-NH-, and -O-; U N is a j+1 valence group; j is a positive integer; any Q 01 are independently -OH or -COOM03 , M 03 is H or alkali metal ion;

[0239] In formula (I-4), R 01 is an alkyl group; R 02 is a hydrocarbon group;

[0240] In formula (I-2), formula (I-3), formula (I-4) and formula (I-5), F 03 are independently the first functional group;

[0241] In formula (I-2), formula (I-3), formula (I-4) and formula (I-5), q3 is independently an integer ≥ 1, L 23 Each independently represents a polyvalent hydrocarbon group having a main chain atomic length of 8 to 20.

[0242] In some embodiments, q1 and q2 are each independently 0 or a positive integer, and q1+q2≥1. Alternatively, q1+q2 is an integer from 1 to 5 (e.g., 1, 2, 3, 4, or 5), and further optionally 1 or 2. In some embodiments, q1 is 1 or 2, and q2 is 0. In some embodiments, q1 is 1 and q2 is 0. In other embodiments, q1 is 2 and q2 is 0.

[0243] In some embodiments, q3 is 1 or an integer greater than or equal to 2, and can further be 1 or 2. In some embodiments, q3 is 1. In other embodiments, q3 is 2.

[0244] In some embodiments, the surfactant includes a compound represented by formula (I-1), and may further be a compound represented by formula (I-1). The compound represented by formula (I-1) is readily soluble in the perovskite precursor solution, has little or no effect on the viscosity of the original solution, and is conducive to large-area film formation.

[0245] In some embodiments, the surfactant includes a compound represented by formula (I-2), and may further be a compound represented by formula (I-2). The compound represented by formula (I-2) can reduce elemental iodine (using iodine as an example in which X in ABX3 is iodine) while improving film formation, thereby filling vacancies and effectively suppressing the generation of perovskite phase defects.

[0246] In some embodiments, the surfactant includes a compound represented by formula (I-3), and may further be a compound represented by formula (I-3). The compound represented by formula (I-3) improves solubility while filling A-site defects, stabilizing the perovskite structure, and improving the stability of the film after crystallization.

[0247] In some embodiments, the surfactant includes a compound represented by formula (I-4), and may further be a compound represented by formula (I-4). The compound represented by formula (I-4) can promote film formation while reducing the number of defects at the interface and optimizing carrier transport at the interface.

[0248] For surfactants containing quaternary ammonium salt groups, while regulating film formation, they can interact with the perovskite intermediate phase, adjust the crystallization nucleation rate and crystallization rate, and promote grain growth.

[0249] For surfactants containing phosphate groups, the interface between the perovskite layer and the hole transport layer can be passivated.

[0250] For branched surfactants containing at least two hydrophobic carbon chains, the damage of water to the perovskite layer can be avoided.

[0251] For linear surfactants containing sulfonates, bulk defects can be reduced and short-circuit current density can be increased.

[0252] For surfactants whose hydrophilic groups include one or more hydroxyl groups, the solubility of the surfactant in the precursor solution can be increased, thereby improving the uniformity of large-area coating.

[0253] For surfactants whose hydrophilic groups include one or more carboxyl groups, bulk defects can be reduced and device stability can be improved.

[0254] In some embodiments, in Formula (I-1), L 21 and L 22 Each independently is a straight chain or branched type, and each independently can be a saturated structure or an unsaturated structure; optionally, L 21 and L 22 Each independently is a linear C 8-20 Alkylidene or branched C 8-20 Multivalent hydrocarbon group; further optionally, L 21 and L 22 Each independently is a linear C 8-20 Alkylene; further optionally, L 21 and L 22 Each independently is a linear C 8-20 Alkylene or linear C 8-20 Alkenylene; further optionally, L 21 and L 22 Each independently is a linear C 10-18 Alkylene or linear C 10-18 Alkenylene; further optionally, L 21 and L 22 Each independently is a linear C 12-18 Alkylene or linear C12-18 Alkenylene. L 21 and L 22 Examples of saturated structures include *-(CH2)9-*; examples of unsaturated structures include *-(CH2)4-CH=CHCH2CH=CH-(CH2)7-*, * indicating a linking site.

[0255] Straight chain L 21 or L 22 Non-limiting examples of * are nonylene*-(CH2)9-*, * indicating the site of attachment.

[0256] Branched L 21 or L 22 Non-limiting examples of trivalent hydrocarbon groups include *-(CH2)2-CH(-*)CH2-CH=CHCH2CH=CH-(CH2)7-, *, and *-(CH2)2-CH2CH2-CH=C(-*)CH2CH=CH-(CH2)7-, respectively.

[0257] In some embodiments, in Formula (I-1), U 03 A trivalent alkyl group or R 21 、R 22 and R 23 are each independently an alkylene group; alternatively, U 03 Trivalent C 2-10 Alkyl or trivalent C 3-10 A tertiary amino group, further optionally, U 03 -CH 2- CR 04 (-)-CH2-、>CH-L 04 -, or N(-CH2CH2-)3, R 04 H or C 1-4 Alkyl (R 04 further optionally H, methyl or ethyl, further optionally H), L 04 C 1-6 Alkylene (L 04 Further optional C 1-4 Alkylene, further optionally C 1- 4-alkylene, further optionally methylene, 1,2-ethylene, 1,3-propylene or 1,4-butylene); optionally, R 21 、R 22 and R 23 Each independently is C 1-4 Alkylene, further optionally, R 21 、R 22 and R 23 Each independently is C1-3 Alkylene, further optionally, R 21 、R 22 and R 23 are each independently methylene or ethylene, further optionally, R 21 、R 22 and R 23 All are ethylene.

[0258] In some embodiments, in Formula (I-1), M 01 It is absent or is H, lithium ion, sodium ion or potassium ion.

[0259] In some embodiments, in Formula (I-1), L 10 C 1-4 The alkylene group may be ethylene or propylene, and may be further ethylene.

[0260] In some embodiments, in Formula (I-1), R 01 C 1-3 alkyl; optionally, R 01 It is a methyl group.

[0261] In some embodiments, in Formula (I-1), R 02 C 1-8 Alkyl or benzene ring substituted C 1-3 Alkylene, the benzene ring is phenyl or surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl.

[0262] In some embodiments, in Formula (I-2), M 02 It is H, lithium ion, sodium ion or potassium ion.

[0263] In some embodiments, in formula (I-3), j is an integer selected from 1 to 5, and may be an integer selected from 1 to 4, and may be 1, 2, or 3.

[0264] In some embodiments, R 01 C 1-3 alkyl; optionally, R 01 It is a methyl group.

[0265] In some embodiments, R 02 C 1-8 Alkyl or benzene ring substituted C 1-3 Alkylene, the benzene ring is phenyl or surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl.

[0266] In some embodiments, in Formula (I-3), U N Contains 0, 1 or more hydrophilic linking groups L 01 A polyvalent hydrocarbon group, optionally, U N Contains 0, 1 or more hydrophilic linking groups L 01 A polyvalent saturated hydrocarbon group, any one of the hydrophilic linking groups L 01 are independently *-CONH-*, *-NHCO-*, *-C(=O)O-*, *-OC(=O)-*, *-O-(O=)P(OM 01 )-O-* or *-O-*, wherein * represents the connection site to the carbon atom, M 01 It is absent or is H, lithium ion, sodium ion or potassium ion.

[0267] In some embodiments, in formula (I-3), U N is a trivalent alkyl group or a tetravalent alkyl group, optionally, U N The number of carbon atoms is 3 to 10, further optionally 3 to 6, further optionally 3, 4 or 5, and further optionally, U N -CH 2- CR 05 (-)-CH2-,R 05 is H, methyl or ethyl, further optionally, R 05 For H.

[0268] In some embodiments, in formula (I-3), U N It is a trivalent tertiary amino group, which can be a trivalent C 3-10 The tertiary amino group may further be N(-CH2CH2-)3.

[0269] In some embodiments, in formula (I-3), U N The number of non-hydrogen atoms is 2 to 40, optionally 2 to 30, further optionally 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, further optionally 2 to 6, further optionally 2, 3, 4 or 5.

[0270] In some embodiments, in formula (I-3), j is an integer selected from 1 to 5, and may be an integer selected from 1 to 4, and may be 1, 2, or 3.

[0271] In some embodiments, in formula (I-4), R 01 C 1-3 alkyl; optionally, R 01 It is a methyl group.

[0272] In some embodiments, in formula (I-4), R 02 C 1-8 Alkyl or benzene ring substituted C 1-3 Alkylene, the benzene ring is phenyl or surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl.

[0273] In some embodiments, in Formula (I-2), Formula (I-3) and Formula (I-4), L 23 are independently linear or branched, and may be saturated or unsaturated; optionally, L 23 Each independently is a straight chain C 8-20 Alkylidene or branched C 8-20 Multivalent hydrocarbon group; further optionally, L 23 Each independently is a straight chain C 8-20 Alkylene or linear C 8-20 Alkenylene; further optionally, L 23 Each independently is a straight chain C 10-18 Alkylene or linear C 10-18 Alkenylene; further optionally, L 23 Each independently is a straight chain C 12-18 Alkylene or linear C 12-18 Alkenylene. L 23 Examples of saturated structures include *-(CH2)9-*; examples of unsaturated structures include *-(CH2)4-CH=CHCH2CH=CH-(CH2)7-*, *, which are attachment sites.

[0274] In this application, unless otherwise specified, "alkenylene" refers to a hydrocarbon group having two monovalent radical centers derived from an alkenyl group by removing a hydrogen atom, which may be an unsaturated branched hydrocarbon group or an unsaturated straight hydrocarbon group. For example, "C 2-9 "Alkenylene" means an alkenyl moiety containing 2 to 9 carbon atoms, each occurrence of which is independently C2 alkenylene, C4 alkenylene, C5 alkenylene, C6 alkenylene, C7 alkenylene, C8 alkenylene or C9 alkenylene. Suitable examples include, but are not limited to, 1,2-vinyl (-CH=CH-).

[0275] In this application, the term "alkenyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a chain-like olefin compound. The hydrogen atom may be located on a carbon-carbon double bond or on an alkyl substituent of the carbon-carbon double bond. Phrases containing this term, for example, "C2- 10"Alkenyl" refers to an alkenyl group containing 2 to 10 carbon atoms, each occurrence of which can be independently C2 alkenyl, C3 alkenyl, C4 alkenyl, C5 alkenyl, C6 alkenyl, C7 alkenyl, C8 alkenyl, C9 alkenyl or C 10 Suitable examples include, but are not limited to, vinyl (CH2=CH-), allyl (CH2=CH-CH2-), CH3-CH=CH-, and the like.

[0276] In some embodiments, the surfactant satisfies one or more of the following characteristics:

[0277] In formula (I-1), L 21 and L 22 Each independently is a linear or branched type; optionally, L 21 and L 22 Each independently is a linear C 8-20 Alkylene; further optionally, L 21 and L 22 Each independently is a linear C 8-20 Alkylene or linear C 8-20 Alkenylene; further optionally, L 21 and L 22 Each independently is a linear C 10-18 Alkylene or linear C 10-18 Alkenylene; further optionally, L 21 and L 22 Each independently is a linear C 12-18 Alkylene or linear C 12-18 alkenylene;

[0278] In formula (I-1), U 03 A trivalent alkyl group or R 21 、R 22 and R 23 are each independently an alkylene group; alternatively, U 03 Trivalent C 2-10 Alkyl or trivalent C 3-10 A tertiary amino group, further optionally, U 03 -CH 2- CR 04 (-)-CH2-、>CH-L 04 -, or N(-CH2CH2-)3, R 04 H or C 1-4 Alkyl (R 04 further optionally H, methyl or ethyl, further optionally H), L 04 C 1-6 Alkylene (L 04 Further optional C1-4 Alkylene, further optionally C 1-4 alkylene, further optionally methylene, 1,2-ethylene, 1,3-propylene or 1,4-butylene); optionally, R 21 、R 22 and R 23 Each independently is C 1-4 Alkylene, further optionally, R 21 、R 22 and R 23 Each independently is C 1-3 Alkylene, further optionally, R 21 、R 22 and R 23 are each independently methylene or ethylene, further optionally, R 21 、R 22 and R 23 All are ethylene;

[0279] In formula (I-1), M 01 Absent or H, lithium, sodium or potassium ions;

[0280] In formula (I-1), L 10 C 1-4 Alkylene, which may be ethylene or propylene, may further be ethylene;

[0281] In formula (I-1), R 01 C 1-3 alkyl; optionally, R 01 is methyl;

[0282] In formula (I-1), R 02 C 1-8 Alkyl or benzene ring substituted C 1-3 Alkylene, the benzene ring is phenyl or surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl;

[0283] In formula (I-2), M 02 is H, lithium ion, sodium ion or potassium ion;

[0284] In formula (I-3), U N Contains 0, 1 or more hydrophilic linking groups L 01 A polyvalent hydrocarbon group, optionally, U N Contains 0, 1 or more hydrophilic linking groups L 01 A polyvalent saturated hydrocarbon group, any one of the hydrophilic linking groups L 01are independently *-CONH-*, *-NHCO-*, *-C(=O)O-*, *-OC(=O)-*, *-O-(O=)P(OM 01 )-O-* or *-O-*, wherein * represents the connection site to the carbon atom, M 01 Absent or H, lithium, sodium or potassium ions; or, U N is a trivalent alkyl group or a tetravalent alkyl group, optionally, U N The number of carbon atoms is 3 to 10, further optionally 3 to 6, further optionally 3, 4 or 5, and further optionally, U N -CH 2- CR 05 (-)-CH2-,R 05 is H, methyl or ethyl, further optionally, R 05 H; or, U N It is a trivalent tertiary amino group, which can be a trivalent C 3-10 A tertiary amino group may further be N(-CH2CH2-)3;

[0285] In formula (I-3), U N The number of non-hydrogen atoms is 2 to 40, optionally 2 to 30, further optionally 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, further optionally 2 to 6, further optionally 2, 3, 4 or 5;

[0286] In formula (I-3), j is an integer selected from 1 to 5, may be an integer selected from 1 to 4, and may be 1, 2 or 3;

[0287] In formula (I-4), R 01 C 1-3 alkyl; optionally, R 01 is methyl;

[0288] In formula (I-4), R 02 C 1-8 Alkyl or benzene ring substituted C 1-3 Alkylene, the benzene ring is phenyl or surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl;

[0289] In formula (I-2), formula (I-3) and formula (I-4), L 23 are independently linear or branched; optionally, L 23 Each independently is a straight chain C8-20 Alkylene; further optionally, L 23 Each independently is a straight chain C 8-20 Alkylene or linear C 8-20 Alkenylene; further optionally, L 23 Each independently is a straight chain C 10-18 Alkylene or linear C 10-18 Alkenylene; further optionally, L 23 Each independently is a straight chain C 12-18 Alkylene or linear C 12-18 Alkenylene.

[0290] In some embodiments, the surfactant includes one or more of the following compounds, and can be any one or any suitable combination of the following compounds:

[0291] In the above compounds, M 01 The definition of is consistent with the above. In some embodiments, M 01 Does not exist, taking compound C1 as an example, this corresponds to

[0292] In some embodiments, the surfactant includes one or more of the following compounds, which can be any one or any suitable multiple of the following compounds: Compound C1, Compound C2, Compound C3, Compound C4, Compound C5, Compound C6, Compound C8 and Compound C9.

[0293] When any of the above compounds contains a chiral atom, it can be in any suitable stereoisomer form. For example,

[0294] Can be

[0295] Also for example the following stereoisomer structures:

[0296] In some embodiments, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.001 mol% to 5 mol%; optionally, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.001% to 2.5%; further optionally, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.01% to 1%; further optionally, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.01% to 0.5%. The molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material can also be selected from any one of the following molar percentages: 0.001 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, 0.04 mol%, 0.05 mol%, 0.06 mol%, 0.08 mol%, 0.1 mol%, 0.12 mol%, 0.14 mol%, 0.15 mol%, 0.16 mol%, 0.18 mol%, 0.2 mol%, 0.22 mol%, 0.24 mol%, 0.25 mol%, 0.26 mol%, 0.28 mol%, 0.3 mol%, 0.35 mol%, 0.4mol%, 0.45mol%, 0.5mol%, 0.55mol%, 0.6mol%, 0.65v0.7mol%, 0.75mol%, 0.8mol%, 0.9mol%, 1mol%, 1.2mol%, 1.4mol%, 1.5mol%, 1.6mol%, 1.8mol%, 2mol%, 2.5mol%, 3mol%, 3.5mol%, 4mol%, 4.5mol%, 5mol%, etc., and can also be selected from the interval consisting of any two of the above molar percentages, for example, 0.01mol% to 2.5mol%, 0.01mol% to 2mol%, 0.01mol% to 1mol%.

[0297] The amount of the first functional group can be adjusted by adjusting the content of the surfactant, thereby better realizing the synergistic effect of the surfactant and the perovskite precursor material while taking into account improving the wettability of the perovskite precursor solution and reducing the vacancy defects in the perovskite, thereby better improving the uniformity of the perovskite film, which is also more beneficial to improving the energy conversion efficiency of the battery.

[0298] In some embodiments, the solvent includes a first solvent and a second solvent, wherein the boiling point of the first solvent is lower than the boiling point of the second solvent. As non-limiting examples, the first solvent may include, but is not limited to, one or more of N,N-dimethylformamide, 2-methoxyethanol, and acetonitrile; and the second solvent may include, but is not limited to, one or more of N-methylpyrrolidone, diphenyl sulfoxide, and dimethylpropylene urea.

[0299] In this application, the boiling point of the solvent can be tested using known methods and instruments. Unless otherwise specified, the boiling points of the first and second solvents refer to the boiling points tested at room temperature and normal pressure. Unless otherwise specified, "room temperature" herein refers to, for example, 20-35°C, further, 20-30°C, and further, 25°C. Unless otherwise specified, "normal pressure" herein refers to standard atmospheric pressure.

[0300] In some embodiments, the volume ratio of the first solvent to the second solvent is 3 to 10; alternatively, the volume ratio of the first solvent to the second solvent is 3 to 5. The volume ratio of the first solvent to the second solvent may also be any of the following ratios: 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, etc., or may be selected from an interval consisting of any two of the foregoing ratios.

[0301] Solvents with different boiling points can be used in combination to adjust the solvent evaporation rate and thus the morphology of the perovskite film when preparing the perovskite film, thereby improving the uniformity of the film and being more conducive to improving the energy conversion efficiency of the perovskite battery.

[0302] 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.

[0303] In some embodiments, A includes Cs + , K + , Rb + 、Li + , organic amine cations, etc. The organic amine cations may include one or more of monovalent amine cations and monovalent amidinium cations.

[0304] Non-limiting examples of monovalent amine cations include (NR 21 R 22 R 23 R 24 ) + 、(R 21 R 22 N=CR 23 R24 ) + 、(R 21R22 NC(R 25 )=NR 23 R 24 ) + or (R 21 R 22 NC(NR 25 R 26 )=R 23 R 24 ) + , where R 21 、R 22 、R 23 、R 24 、R 25 and R 26 Each independently selected from H, C 1-20 Alkyl, aryl, substituted C 1-20 Alkyl or substituted aryl; wherein, C 1-20 Alkyl and substituted C 1-20 The "C" in the alkyl group 1-20 "alkyl" are each independently C 1-15 Alkyl, further optionally C 1-10 Alkyl, further 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. The "aryl" in aryl and substituted aryl is independently selected from C 6-20 Aryl, further optionally C 6-12 Aryl, further optionally C 6-10 Aryl, further optionally phenyl or naphthyl, further optionally phenyl. Substituted C1 -20 The substituents in the alkyl and substituted aryl groups are each independently C 1-10 Hydrocarbon, further optionally C 1-6 Alkyl or C 6-10 The aryl group may further be methyl or phenyl.

[0305] 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 + ).

[0306] In the present application, unless otherwise specified, B is a divalent metal ion.

[0307] 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 .

[0308] In some embodiments, B may include, but is not limited to, divalent metal ions of one or more of the following elements: lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, and europium.

[0309] In some embodiments, X comprises I - Br - 、Cl - and F - One or more of .

[0310] In some embodiments, X comprises I - Br - and Cl - One or more of .

[0311] 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 - .

[0312] In a second aspect, the present application provides a perovskite film, which is prepared by coating and annealing the perovskite precursor solution described in the first aspect of the present application, or at least contains the non-solvent component in the perovskite precursor solution described in the first aspect of the present application.

[0313] The perovskite film prepared using the perovskite precursor solution described in the first aspect of the present application has good contact with the substrate, the film is uniform and has few defects, and the corresponding perovskite battery has high energy conversion efficiency.

[0314] 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.

[0315] The coating can be performed by a slot coating method.

[0316] 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.

[0317] The uniformity of perovskite films, especially those produced over large areas, is a key factor hindering the industrialization of perovskite solar cells. Currently, the mainstream method for preparing large-area perovskite films is coating, which requires the perovskite precursor solution to have low surface tension and good wettability. To achieve this, surfactants are typically added to the perovskite precursor solution. However, improperly added surfactants can cause defects in the perovskite crystals, leading to poor performance of perovskite solar cells.

[0318] In some embodiments, the area of ​​the perovskite film is ≥1 cm 2 , further, for example 1cm 2 , 1.5cm 2 , 2cm 2 , 3cm 2 , 4cm 2 Etc., such as being greater than or equal to any of the aforementioned areas, and such as being selected from the interval consisting of any two of the aforementioned areas.

[0319] In some embodiments, the area of ​​the perovskite film is ≥4 cm 2 .

[0320] For large-area perovskite films (e.g. ≥1cm 2 ) It is relatively difficult to obtain a relatively uniform perovskite film. Compared with perovskite precursor solutions using traditional surfactants, the perovskite precursor solution provided by this application containing the surfactant of the aforementioned first functional group has significant advantages in improving the uniformity of large-area perovskite films.

[0321] 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.

[0322] 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.

[0323] 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.

[0324] 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.

[0325] 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.

[0326] 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.

[0327] The electron transport layer can extract and transport electron carriers and block the passage of free holes.

[0328] The hole transport layer can extract and transport hole carriers and block the passage of free electrons.

[0329] 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.

[0330] In some embodiments, the electron transport layer material may include but is not limited to 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 (H101) with triptycene as the core, 3,4 -ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamino)carbazole-spirobifluorene (CzPAF-SBF), polythiophene, metal oxides, silicon oxide (SiO2), strontium titanate (SrTiO3), cuprous thiocyanate (CuSCN), etc.; wherein the metal elements may include one or more of Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga and Cr.

[0331] In some embodiments, the hole transport layer may include, but is not limited to, one or more 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 and other materials can transport holes and block electrons.

[0332] 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.

[0333] 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.

[0334] 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.

[0335] In some embodiments, the width of P1 is 10-50 μm, for example, 30 μm.

[0336] 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.

[0337] 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.

[0338] 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.

[0339] 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.

[0340] 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.

[0341] 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), BZO (boron-doped zinc oxide), IZO (indium zinc oxide), IWO (tungsten-doped indium oxide), etc.

[0342] In some embodiments, the second electrode comprises a conductive material, and further, the conductive material can be an organic conductive material, an inorganic conductive material, or a combination thereof. Non-limiting examples of inorganic conductive materials include metal conductive materials, and further, the metal conductive material can include any one of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt), magnesium (Mg), etc., or any suitable mixture of the foregoing elements. The conductive material can include a conductive oxide, and further, the conductive material can be a conductive oxide; non-limiting examples of conductive oxides can include one or more of FTO, ITO, IWO, AZO, etc.

[0343] In some embodiments, the perovskite cell is any one of an inverted pin cell and a formal nip cell.

[0344] The perovskite cells provided in this application may include formal and trans types.

[0345] 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.

[0346] 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.

[0347] In some embodiments, the perovskite cell comprises the following structure 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 comprise one or more materials selected from polyethylene terephthalate, polyimide, polyethylene, polypropylene, polystyrene, and polyethylene naphthalate. Optionally, the first electrode is a transparent electrode for light incidence.

[0348] 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.

[0349] 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.

[0350] 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.

[0351] In some embodiments, the base layer 110 in the structure shown in FIG3 is a light-incident glass base.

[0352] The specifications of the perovskite cell are not particularly limited and may be, but not limited to, 300 mm×300 mm.

[0353] It is understood that the structure of the perovskite cell involved in this application may not be 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 with a suitable energy level, which may play one or more roles in reducing the energy level barrier, promoting energy level matching, improving carrier extraction efficiency, passivating interface defect states, protecting the light absorption layer, inhibiting water molecules and oxygen from oxidative decomposition of 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 four types: 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.

[0354] In a fourth aspect, the present application provides an electrical device comprising the perovskite battery described in the third aspect of the present application.

[0355] The structure of the perovskite cell may be, but is not limited to, a single junction, a stacked structure, or other structures.

[0356] In some embodiments, the perovskite cell can be used as a power generation device in 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.

[0357] 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.

[0358] 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.

[0359] As another example, the electric device may be a mobile phone, a tablet computer, a laptop computer, a calculator, etc.

[0360] As another example, the electrical device may be a wearable device, such as a watch. Below, some embodiments of the present application are described. The embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If the technology or conditions are not specified in the embodiments, they shall be carried out according to the description above, or according to the technology or conditions described in the literature in this field or according to the product instructions. The reagents or instruments used that do not indicate the manufacturer are conventional products that can be obtained commercially, or can be synthesized in a conventional manner through commercially available products.

[0361] In the following embodiments, room temperature refers to 20°C to 30°C, and further, may be 25°C.

[0362] In the following examples, unless otherwise specified, the following raw materials can be purchased commercially or can be prepared by simple chemical modification of commercially available raw materials. The intermediates and final products synthesized in each example, including the surfactants of the present application, 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 ( 1 H NMR) method, gel permeation chromatography (GPC) method, high performance liquid chromatography (HPLC) method, mass spectrometry, etc. The sample preparation methods and test methods of these test methods are known to those skilled in the art, and the test parameters can be appropriately adjusted according to the specific structure and material properties of the compound. For those skilled in the art, given the structural formula of the target compound, it is possible to combine the test results of the above test methods to determine whether the compound of the target structure has been synthesized. 1 Taking H NMR as an example, the structure can be identified based on parameters such as peak position, peak shape, and integrated area ratio in the H NMR spectrum to confirm whether a specific group disappears or appears.

[0363] In the following examples, unless otherwise specified, NBS is N-bromosuccinimide, DMF is N,N-dimethylformamide, and DMSO is dimethyl sulfoxide.

[0364] Preparation Example: Preparation of surfactant

[0365] 1 H NMR measurements were performed using a Bruker AVANCE NEO nuclear magnetic resonance (NMR) spectrometer with tetramethylsilane (TMS) as the internal standard, a scanning power of 400 MHz, and deuterated dimethylformamide (dDMF) as the solvent.

[0366] High performance liquid chromatography (HPLC) test: Thermo Fisher Ultimate 3000 standard; solvent acetonitrile.

[0367] Mass spectrometry test: Shimadzu gas chromatograph / mass spectrometer GCMS-QP2010; solvent: acetone.

[0368] Lecithin uses CAS: 8002-43-5. In the following Preparation Examples 1-8, the lecithin raw materials involved are from the same source.

[0369] Preparation Example 1. Preparation of hydrazine-modified lecithin (Su1)

[0370] Step 1: Synthesis of brominated lecithin

[0371] Take a clean and dry round-bottom flask, add 5.4g of NBS, 0.03mol of AuCl3, 60mL of dichloroethane, 0.06mol of lecithin (CAS: 8002-43-5) and a magnet, react at 80℃ for 11 hours, and monitor the reaction process by high performance liquid chromatography (HPLC). If there is still raw material remaining after 11 hours, extend the reaction time appropriately. When the reaction is complete, filter out the insoluble matter, concentrate the mother liquor by vacuum distillation, and obtain brominated lecithin by column chromatography (mobile phase is petroleum ether / ethyl acetate volume ratio 20:1).

[0372] Step 2: Synthesis of hydrazine-modified lecithin

[0373] In a clean, dry round-bottom flask, 0.07 mol of K₂CO₃, 0.07 mol of NaI, and 0.07 mol of hydrazine hydrate were added sequentially to 0.007 mol of bromophosphatidylcholine. 100 mL of DMF and a magnetic stirrer were then added and a suspension was obtained. The mixture was heated to 80°C for 24 hours, filtered, and concentrated to remove the solvent. The mixture was extracted repeatedly with saturated brine and dichloromethane. The oil phase was combined and concentrated, and the product was purified by column chromatography (mobile phase: ethyl acetate / n-hexane = 1:10, volume ratio) to obtain the product. The product was dried under vacuum at room temperature for 16 hours to obtain the hydrazine-modified phosphatidylcholine. Compound testing and structural analysis confirmed the presence of the compound with the structure shown in Su1, designated as Compound Su1.

[0374] Preparation Example 2. Preparation of thiol-modified lecithin (Su2)

[0375] The thiol-modified lecithin was synthesized by the same method as in Preparation Example 1, except that in step 2:

[0376] The bromo-lecithin of 0.05mol and the thiocarbamide of 0.052mol are dissolved in the 95% ethanol of 50mL, reaction mixture is refluxed and stirred 3 hours.Then the 2.5mol / L sodium hydroxide solution of 30mL is added in the reaction mixture, and continued to reflux 2 hours.Separate water layer and by adding dilute hydrochloric acid acidifying (pH 1).Use petroleum ether extraction acidic solution twice then.Merge organic phase and use salt water washing.Organic phase is with dried over sodium sulfate after, removes petroleum ether solvent by distillation, product is separated by column chromatography, and at room temperature vacuum-drying products therefrom 8 hours, obtains sulfhydryl-modified lecithin, through compound test and structural analysis, confirms to obtain structural compound shown in Su2, is designated as compound Su2.

[0377] Here, 95% ethanol refers to a mixture of ethanol and water in a volume ratio of 95%:5%.

[0378] Preparation Example 3. Preparation of hydrazine-modified sodium dodecylbenzenesulfonate (Su3)

[0379] Hydrazine-modified sodium dodecylbenzenesulfonate was synthesized using essentially the same method as in Preparation Example 1, except that lecithin was replaced with sodium dodecylbenzenesulfonate in Step 1. Compound testing and structural analysis confirmed the formation of a compound with the structure Su3, designated as Compound Su3.

[0380] Preparation Example 4. Preparation of hydrazine-modified sodium lauroyl glutamate (Su4)

[0381] Hydrazine-modified sodium lauroyl glutamate was synthesized using a method substantially identical to that of Preparation Example 1, except that lecithin was replaced with sodium lauroyl glutamate in step 1. Compound testing and structural analysis confirmed the formation of a compound represented by the structure Su4, designated as compound Su4.

[0382] Preparation Example 5. Preparation of dithiol-modified lecithin (Su5)

[0383] A bis-thiol-modified lecithin was synthesized using essentially the same method as in Preparation Example 2, except that the amount of NBS in step 1 was doubled (to 10.8 g), and the amount of brominated lecithin in step 2 was reduced to half its original amount, i.e., 0.025 mol. Compound testing and structural analysis confirmed the formation of a compound with the structure Su5, designated as compound Su5.

[0384] Preparation Example 6. Preparation of hydrazine- and sulfhydryl-modified lecithin (Su6)

[0385] The hydrazine- and thiol-modified lecithin was synthesized using a method substantially the same as that in Preparation Example 1, except that step 3 was added after step 2 in Preparation Example 1:

[0386] The thiocarbamide of 0.05mol hydrazino modified lecithin and 0.052mol was dissolved in 95% ethanol of 50mL, reaction mixture was refluxed and stirred 3 hours. Then 30mL of 2.5mol / L sodium hydroxide solution was added in the reaction mixture, and continued to reflux 2 hours. The separated water layer was acidified (pH 1) by adding dilute hydrochloric acid. The petroleum ether extraction acid solution was then used twice. The organic phase was merged and washed with salt water. After the organic phase was dried over sodium sulfate, the petroleum ether solvent was removed by distillation. The product was separated by column chromatography, and at room temperature vacuum-drying products therefrom 8 hours, obtained the lecithin of hydrazino and sulfhydryl modification, and through compound test and structural analysis, confirmed that the structural compound shown in Su6 is obtained, which is designated as Su6.

[0387] Preparation Example 7. Preparation of hydrazine- and sulfhydryl-modified lecithin (Su7)

[0388] Step 1: Synthesis of brominated phosphatidylcholine

[0389] Take a clean and dry round-bottom flask, add 5.4g of NBS, 0.03mol of AuCl3, 60mL of dichloroethane, 0.06mol of lecithin (CAS: 8002-43-5) and a magnet, react at 80℃ for 11 hours, monitor the reaction process by liquid chromatography, if there is still raw material remaining after 11 hours, appropriately extend the reaction time, when the reaction is complete, filter to remove insoluble matter, concentrate the mother liquor by vacuum distillation, and obtain brominated lecithin by column chromatography (mobile phase is petroleum ether / ethyl acetate 20:1, volume ratio).

[0390] Step 2: Synthesis of hydrazine-modified lecithin

[0391] In a clean, dry round-bottom flask, add 0.07 mol of K2CO3, 0.07 mol of NaI, and 0.07 mol of hydrazine hydrate to 0.007 mol of bromophosphatidylcholine (prepared in Step 1). Then, add 100 mL of DMF and a magnetic stirrer and stir to obtain a suspension. The mixture is heated to 80°C for 24 hours, filtered, and concentrated to remove the solvent. Extract the mixture repeatedly with saturated brine and dichloromethane. The oil phase is combined and concentrated, and the product is purified by column chromatography (mobile phase: ethyl acetate / n-hexane = 1:10, volume ratio) to obtain the product. The product is then dried under vacuum at room temperature for 16 hours to yield hydrazine-modified phosphatidylcholine IM7b.

[0392] Step 3: Synthesis of BMPO Ligand: Accurately weigh 5 mmol of 2,6-dimethylaniline and dissolve it in 10 mL of THF (tetrahydrofuran). Add 10.5 mmol of triethylamine sequentially, stirring. Slowly add 10 mmol of oxalyl chloride in an ice-water bath. Stir the mixture at room temperature for 3 hours and then concentrate under vacuum to remove residual solvent. Dissolve the mixture in water and filter to remove Et3N·HCl (triethylamine hydrochloride). Wash the filtrate with water and petroleum ether and dry it under vacuum to obtain the BMPO ligand.

[0393] Step 4: A mixture of IM7b (4 mmol), LiBr (40 mmol), CF3CO2H (12 mmol), and a Cu complex (8 mol% CuI, 8 mol% BMPO, 16 mol% CTAB (hexadecyltrimethylammonium bromide)) in CH3NO2 (10 mL) was placed in a reaction tube and heated at 60°C under an oxygen atmosphere for 20 hours. The mixture was filtered and concentrated to remove the solvent. The product was extracted repeatedly with saturated brine and dichloromethane. The oil phase was combined, concentrated, and purified by column chromatography (mobile phase: ethyl acetate / n-hexane = 1:10, volume ratio) to obtain the product IM7c.

[0394] Step 5: 5mmol of step 3 product IM7c and 0.052mol of thiourea were dissolved in 50mL of 95% ethanol, and the reaction mixture was refluxed and stirred for 3 hours. Then 30mL of 2.5mol / L sodium hydroxide solution was added to the reaction mixture and refluxed for 2 hours. The aqueous layer was separated and acidified (pH 1) by adding dilute hydrochloric acid. The acidic solution was then extracted twice with petroleum ether. The organic phases were combined and washed with salt water. After the organic phases were dried over sodium sulfate, the petroleum ether solvent was removed by distillation. The product was separated by column chromatography and dried under vacuum for 8 hours at room temperature to obtain phosphatidylcholine modified with hydrazine and sulfhydryl groups. After compound testing and structural analysis, it was confirmed that the structural compound shown in Su7 was obtained, which was designated as compound Su7.

[0395] Among them, CF3CO2H is trifluoroacetic acid.

[0396] Preparation Example 8. Preparation of hydrazine-modified lecithin (Su8)

[0397] Step 1: Preparation of 2-((((2S)-2-(((E)-9-bromooctadec-12-enoyl)oxy)-2-(palmitoyloxy)ethoxy)(hydroxy)phosphoryl)oxy)-N,N,N-trimethylethane-1-amine (Preparation of bromophosphatidylcholine)

[0398] To a clean, dry, three-necked round-bottom flask, insert a thermometer and condenser, add 5 mmol of phosphatidylcholine (CAS: 8002-43-5), cool to -5°C, and dropwise add 10 mmol of hydrobromic acid, maintaining a temperature of 0-5°C. After the addition is complete, continue the reaction for 1 hour. Then, distill under reduced pressure to obtain brominated phosphatidylcholine P8a. The product is concentrated and purified by column chromatography (ethyl acetate / n-hexane = 1:20, volume ratio) and dried under vacuum at 50°C for 12 hours. Structural analysis confirms the synthesis of the following brominated compound, P8a.

[0399] Step 2: Synthesis of BMPO Ligand: Accurately weigh 5 mmol of 2,6-dimethylaniline and dissolve it in 10 mL of THF (tetrahydrofuran). Add 10.5 mmol of triethylamine sequentially, stirring. Slowly add 10 mmol of oxalyl chloride in an ice-water bath. Stir the mixture at room temperature for 3 hours and then concentrate under vacuum to remove residual solvent. Dissolve the mixture in water and filter to remove Et3N·HCl (triethylamine hydrochloride). Wash the filtrate with water and petroleum ether, then dry it under vacuum to obtain the BMPO ligand.

[0400] Step 3: In a clean, dry round-bottom flask, add 0.6 mmol of the brominated compound P8a, 8 mol% of CuI, 8 mol% of BMPO, and 16 mol% of CTAB (cetyltrimethylammonium bromide) in sequence. Dissolve the mixture in 0.6 mL of water. Add 0.12 mmol of K₃PO₄ first, stir with a magnetic stirrer at 80°C for 15 minutes, then add the remaining 0.6 mmol of K₃PO₄ and 0.6 mmol of hydrazine in water. Purge the mixture with nitrogen for 10-15 minutes, heat in an oil bath at 80°C, seal the flask, and react for 8 hours. Cool to room temperature, dilute with dichloromethane, filter, and extract with saturated brine. Separate the organic layer, acidify with 37% hydrochloric acid to pH 3.4, filter the precipitate, wash with dichloromethane, and combine the oily phases, concentrate, and purify the product by column chromatography (ethyl acetate / n-hexane = 1:10). Dry the resulting product in vacuo at room temperature for 16 hours. Compound testing and structural analysis confirmed the formation of the compound with the structure shown in Su8.

[0401] Example 1. Preparation of perovskite cells

[0402] Taking an inverse perovskite cell as a non-limiting example, the scoring method shown in Figure 1 is used. For the scoring areas P1, P2, and P3, the width of P1 is approximately 30 μm, the width of P2 is 150 μm, and the depth is etched to the FTO layer; the spacing between P2 and P1 is 20 μm; the width of P3 is 15 μm, and the depth is etched to the FTO layer, and the spacing between P3 and P2 is 20 μm.

[0403] 1.1. Take a set of 10 cm × 10 cm FTO conductive glass (as the first electrode), etch it to form the P1 notch area, clean it with a detergent, and then ultrasonicate it in deionized water, ethanol, and acetone for 10 minutes. After ultrasonication, blow dry it with nitrogen and set aside.

[0404] 1.2. Take a piece of FTO conductive glass prepared in step 1.1 above and prepare a 10 nm thick nickel oxide layer (hole transport layer as the first transport layer) by magnetron sputtering.

[0405] 1.3. Preparation of perovskite layer

[0406] Preparation of perovskite precursor solution: A solution of perovskite metal halide FAPbI3 (1 mol / L) was prepared using a mixed solvent of DMF and DMSO in a volume ratio of 4:1. Surfactants were added according to the type and amount listed in Table 1 based on the molar percentage of surfactant relative to Pb to obtain a perovskite precursor solution.

[0407] A wet perovskite film was coated onto the nickel oxide layer using the prepared perovskite precursor solution. The film was then transferred to a vacuum pump and evacuated for 60 seconds at a pressure of 15 Pa. The evacuated wafer was then annealed on a 120°C hot plate for 40 minutes to form a 500nm thick perovskite layer. The resulting perovskite layer was then etched to form the P2 notched area.

[0408] 1.4. Preparation of C60 / BCP electron transport layer (second transport layer) and second electrode

[0409] The prepared perovskite wafer is placed in an evaporation device, and 25nm C60, 5nm thick BCP (bathcopper ion) and 100nm Cu are evaporated in sequence; after forming the Cu electrode, the P3 notched area is etched to obtain a perovskite device.

[0410] Examples 2 to 8 adopt substantially the same method as Example 1, except that the types and / or amounts of surfactants are different, see Table 1.

[0411] Comparative Example 1 adopts substantially the same method as Example 1, except that lecithin is used as the surfactant.

[0412] Comparative Example 2 uses a method substantially the same as Example 3, except that sodium dodecylbenzenesulfonate is used as a surfactant.

[0413] Comparative Example 3 adopts a method substantially the same as Example 4, except that sodium lauroyl glutamate is used as a surfactant.

[0414] Comparative Example 4 adopts the method substantially the same as Comparative Example 1, except that hydrazine hydrate is further added in an amount equimolar to that of lecithin.

[0415] Comparative Example 5 adopts substantially the same method as Comparative Example 1, except that thioglycolic acid is further added in an amount equimolar to that of lecithin.

[0416] Comparative Example 6 adopts a method basically the same as Example 1, except that no surfactant is added, and a DMF / DMSO solution of FAPbI3 is used as a precursor solution to prepare the perovskite film.

[0417] Table 1.

[0418] Test Method

[0419] 1. Morphology of perovskite films

[0420] Testing methods: thickness measurement using a step profiler (Bruker DektakXT, resolution 10 nm) and scanning electron microscopy (Zeiss Sigma300; resolution 1 nm).

[0421] A step profiler test can determine whether the film thickness is uniform, and a scanning electron microscope can observe whether the grain size is uniform. A thickness deviation of <5% is considered good uniformity, and a grain size of ±50nm is considered uniform.

[0422] 2. Energy conversion efficiency and battery stability

[0423] In standard simulated sunlight (AM 1.5G, 100mW / cm 2 The energy conversion efficiency of the battery was tested under irradiation with a 2% RH (RH < 2%) irradiation. The initial efficiency and the efficiency after 800 hours in the dark state were measured. The percentage of the efficiency after 800 hours relative to the initial efficiency was recorded as battery stability. The test results can be found in Table 2.

[0424] Test results

[0425] According to the test results, it can be seen that the surfactant provided in this application is used to prepare a perovskite precursor solution, and then to prepare a perovskite film and a perovskite battery (see Examples 1-8). Compared with Comparative Examples 1-6, the perovskite batteries prepared in Examples 1-8 have significantly improved energy conversion efficiency and battery stability. In addition, all obtained perovskite films with good uniformity and uniform grain size. This is because the surfactant provided in this application significantly improves the uniformity of the perovskite film. Among them, Comparative Example 6 does not add a surfactant, Comparative Examples 1-3 use a common surfactant, and Comparative Examples 4-5 use a combination of a common surfactant and a functionalized small molecule with a lone pair of electrons.

[0426] Table 2.

[0427] 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.

[0428] 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 a surfactant; the surfactant comprises a hydrophilic group, a hydrophobic group and a first functional group, wherein: The first functional group is a Lewis basic group containing a lone pair of electrons, and the lone pair of electrons exists in at least one of the N atom and the S atom; the first functional group, the hydrophilic group and the hydrophobic group are different from each other.

2. The perovskite precursor solution according to claim 1, wherein: The first functional group includes -NR 11 -NR 12 R 13 and -SH; wherein R 11 and R 12 Each independently is H or a hydrocarbon group; R 13 is H, a hydrocarbon group or a hydrocarbon group substituted with a monovalent hydrophilic group; Optionally, R 11 and R 12 are each independently H or alkyl, further optionally, R 11 and R 12 Each independently is H or C 1- 6 alkyl, further optionally, R 11 and R 12 Each independently is H or C 1-3 Alkyl; further optionally, R 11 and R 12 are each independently H or methyl; further optionally, R 11 and R 12 All are H; Optionally, R 13 is H, an alkyl group or an alkyl group substituted with a monovalent hydrophilic group, and further optionally, the alkyl groups in the alkyl group or the alkyl group substituted with a monovalent hydrophilic group are each independently C 1-20 Alkyl, further optionally C 1-18 Alkyl, further optionally C 1-15 Alkyl, further optionally C 1-12 Alkyl, further optionally C 1-10 Alkyl, further 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; Optionally, R 13 is H or a hydrocarbon group, further optionally H or an alkyl group, further optionally H or C 1-20 Alkyl, further optionally H or C 1-18 Alkyl, further optionally H or C 1-15 Alkyl, further optionally H or C 1-12 Alkyl, further optionally H or C 1-10 Alkyl, further optionally H or C 1-8 Alkyl, further optionally H or C 1-6 Alkyl, further optionally H or C 1-4 Alkyl, further optionally H or C 1-3 Alkyl, further optionally H or methyl; Optionally, examples of the monovalent hydrophilic group may include, but are not limited to, one or more of: carboxyl, sulfonic acid, sulfonic acid salt, sulfate, sulfate salt, phosphate, phosphate salt, monohydrogen phosphate, monohydrogen phosphate salt, primary amino, primary amino salt, secondary amino, secondary amino salt, quaternary ammonium salt, -CONH2, and hydroxyl; Optionally, R 11 , R 12 and R 13 All are H; further optionally, the first functional group is selected from one or both of -NH-NH2 and -SH.

3. The perovskite precursor solution according to claim 1 or 2, wherein: The hydrophilic group includes one or more of a carboxyl group, a sulfonic acid group, a sulfonic acid salt, a sulfate group, a sulfate salt, a phosphate group, a phosphate salt, a monohydrogen phosphate ester group, a monohydrogen phosphate ester salt, a primary amino group, a primary amino salt, a secondary amino group, a secondary amino salt, a divalent tertiary amino group, a quaternary ammonium salt, -CONH2, a hydroxyl group, an ether group, an ester group, -CONH- and a divalent phosphate ester group; Optionally, the sulfonic acid salt, sulfate salt, phosphate salt and monohydrogen phosphate salt are alkali metal salts of the corresponding acids; Optionally, the primary amino salt and the secondary amino salt are salts formed by corresponding amines and acids; optionally, the acid is an organic acid or an inorganic acid; the organic acid includes one or more of carboxylic acid, phosphonic acid and sulfonic acid; the inorganic acid includes one or more of hydrohalic acid, phosphoric acid and sulfuric acid, and optionally, the inorganic acid includes one or more of hydrochloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid and sulfuric acid; Optionally, the hydrophilic group includes at least one of a quaternary ammonium ion and an alkali metal ion.

4. The perovskite precursor solution according to any one of claims 3, wherein: The hydrophilic groups include *-COOH, *-S(=O)2OH, *-S(=O)2OM, *-OS(=O)2OH, *-OS(=O)2OM, *-O-(O=)P(OH)2, *-NH2, *-NH2·n2A cd 、*-NHR0、*-NHR0·n1A cd , One or more of *-CONH2, *-OH and a hydrophilic linking group L0; wherein the hydrophilic linking group L0 includes *-CONH-*, *-NHCO-*, *-C(=O)O-*, *-OC(=O)-*, *-O-(O=)P(OM 01 )-O-*, *-NH-*, and *-O-*; Wherein, any "*" represents a connection site to a carbon atom; Any M is independently an alkali metal ion; Any M1 and any M2 are each independently an alkali metal ion; Any R 10 are independently a hydrocarbon group; Any A cd is independently an acid molecule; n2 is 1 or 2; n1 is 1; Any R0 is independently a hydrocarbon group or a substituted hydrocarbon group; the substituted hydrocarbon group is substituted by one or more hydrophilic groups; R 01 is an alkyl group; R 02 is a hydrocarbon group; R 03 is an alkyl group; M 01 It is absent or is H or an alkali metal ion.

5. The perovskite precursor solution according to claim 4, wherein: The surfactant satisfies any one or more of the following characteristics: Any M is independently lithium, sodium or potassium; Any one M1 and any one M2 are each independently lithium, sodium or potassium; Any R 10 Independently for C 1-10 Alkyl, optionally C 1-8 Alkyl, further optionally C 1-6 Alkyl, further optionally C 1-4 Alkyl, further optionally C 1-3 alkyl; Any A cd is independently an organic acid or an inorganic acid molecule; the organic acid comprises one or more of carboxylic acid, phosphoric acid and sulfonic acid; the inorganic acid comprises one or more of hydrohalic acid and sulfuric acid, and optionally, the inorganic acid comprises one or more of hydrochloric acid, hydroiodic acid, hydrobromic acid, hydrofluoric acid and sulfuric acid; Any R0 is independently alkyl; optionally, any R0 is independently C 1-3 Alkyl; further optionally, R0 is methyl; R 01 C 1-3 alkyl; optionally, R 01 is methyl; R 02 C 1-8 Alkyl or benzene substituted C 1-3 Alkylene, the benzene ring is phenyl or is surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl; R 03 C 1-3 alkyl; optionally, R 03 is methyl; M 01 Absent or H, lithium, sodium or potassium; At least one side of the hydrophilic linking group L0 is connected to a monovalent hydrophilic group.

6. The perovskite precursor solution according to any one of claims 1 to 5, wherein: The hydrophobic group includes C 8-20 Carbon chain; Optionally, the C 8-20 The carbon chain is a straight chain or branched structure; Optionally, the C 8-20 The main chain atom length of the carbon chain is 6 to 20; further optionally, the C 8-20 The main chain atom length of the carbon chain is 8 to 20; further optionally, the C 8-20 The main chain atom length of the carbon chain is 8 to 18; further optionally, the C 8-20 The carbon chain is a carbon with a main chain length of 10 to 18 atoms. 10-20 Carbon chain; Optionally, the C 8-20 The carbon chain is a saturated or unsaturated structure; Optionally, the C 8-20 The carbon chain is either aromatic or aliphatic; Optionally, the surfactant includes one or more C 8-20 Carbon chain.

7. The perovskite precursor solution according to claim 6, wherein: The hydrophobic group further comprises one or more of an arylene group Ar0 and an aralkyl group ArA; Optionally, the arylene group Ar0 is C 6-18 Arylene, further optionally, the arylene Ar0 is phenylene or one or more C 1-3 Alkyl-substituted phenylene; Optionally, the aralkyl group ArA is a C 1-18 Alkyl, wherein any of the aromatic groups Ar1 is independently phenyl or is replaced by one or more C 1-4 Alkyl-substituted phenyl; further optionally, any of the aryl groups Ar1 is independently phenyl or substituted by one or more C 1-3 Alkyl-substituted phenyl; further optionally, any one of the aryl groups Ar1 is independently phenyl or benzyl; further optionally, the aralkyl group ArA is benzyl.

8. The perovskite precursor solution according to any one of claims 1 to 7, wherein: In one molecule of the surfactant, the number of the hydrophilic group, the hydrophobic group and the first functional group is independently 1 or more; Optionally, in one molecule of the surfactant, the number of the first functional groups is 1 or 2 to 5; Optionally, in one molecule of the surfactant, the number of the hydrophilic groups is 1 or 2 to 5.

9. The perovskite precursor solution according to any one of claims 1 to 8, wherein: The molar percentage of the first functional group relative to the divalent metal ions in the perovskite precursor material is 0.001 mol% to 5 mol%; Optionally, the molar percentage of the first functional group relative to the divalent metal ions in the perovskite precursor material is 0.1 mol% to 2.5 mol%.

10. The perovskite precursor solution according to any one of claims 1 to 9, wherein: The first functional group and the hydrophilic group are each independently connected to the carbon atom of the hydrophobic group.

11. The perovskite precursor solution according to any one of claims 1 to 10, wherein: The surfactant includes one or more of the following compounds: In formula (I-1), q1 and q2 are each independently 0 or a positive integer, and q1+q2≥1, L 21 and L 22 Each is independently a polyvalent hydrocarbon group having a main chain length of 8 to 20 atoms; 01 and Z 02 Each is independently a covalent bond, a carbonyl group or -NHC(=O)-*, wherein * points to U 03 ; U 03 is a trivalent hydrocarbon group; M 01 Not present or H or alkali metal ion; L 10 C 1-6 Alkylene; R 01 is an alkyl group; R 02 is a hydrocarbon group; in one molecule, F 01 and F 02 At least one of them is the first functional group, and the other one is independently H or the first functional group; In formula (I-2), M 02 is an alkali metal ion; In formula (I-3), Z1 is a covalent bond or a linking group Z 10 , where Z 10 Any one selected from the group consisting of -CO-NH, -NH-CO-, -C(=O)-O-, -OC(=O)-, -NH-C(=O)-O-, -OC(=O)-NH-, and -O-; U N is a j+1 valence group; j is a positive integer; any Q 01 are independently -OH or -COOM 03 , M 03 is H or alkali metal ion; In formula (I-4), R 01 is an alkyl group; R 02 is a hydrocarbon group; In formula (I-2), formula (I-3), formula (I-4) and formula (I-5), F 03 are independently the first functional group; In formula (I-2), formula (I-3), formula (I-4) and formula (I-5), q3 is independently an integer ≥ 1, L 23 Each independently is a polyvalent hydrocarbon group having a main chain atom length of 8 to 20.

12. The perovskite precursor solution according to claim 11, wherein: The surfactant meets one or more of the following characteristics: In formula (I-1), L 21 and L 22 Each independently is a straight chain or branched type; optionally, L 21 and L 22 Each independently is a straight chain C 8-20 Alkylene or branched C 8-20 A polyvalent hydrocarbon group; further optionally, L 21 and L 22 Each independently is a straight chain C 8-20 Alkylene; further optionally, L 21 and L 22 Each independently is a straight chain C 8-20 Alkylene or linear C 8-20 Alkenylene; further optionally, L 21 and L 22 Each independently is a straight chain C 10-18 Alkylene or linear C 10-18 Alkenylene; further optionally, L 21 and L 22 Each independently is a straight chain C 12-18 Alkylene or linear C 12-18 alkenylene; In formula (I-1), U 03 A trivalent alkyl group or R 21 , R 22 and R 23 Each is independently an alkylene group; optionally, U 03 For trivalent C 2-10 Alkyl or trivalent C 3-10 A tertiary amino group, further optionally, U 03 -CH 2- CR 04 (-)-CH2-, >CH-L 04 -, or N(-CH2CH2-)3, R 04 H or C 1-4 Alkyl (R 04 further optionally H, methyl or ethyl, further optionally H), L 04 C 1-6 Alkylene (L 04 Further optional C 1-4 Alkylene, further optionally C 1-4 alkylene, further optionally methylene, 1,2-ethylene, 1,3-propylene or 1,4-butylene); optionally, R 21 , R 22 and R 23 Each independently is C 1-4 Alkylene, further optionally, R 21 , R 22 and R 23 Each independently is C 1-3 Alkylene, further optionally, R 21 , R 22 and R 23 are each independently methylene or ethylene, and further optionally, R 21 , R 22 and R 23 All are ethylene; In formula (I-1), M 01 Absent or H, lithium, sodium or potassium ions; In formula (I-1), L 10 C 1-4 Alkylene, which may be ethylene or propylene, may further be ethylene; In formula (I-1), R 01 C 1-3 alkyl; optionally, R 01 is methyl; In formula (I-1), R 02 C 1-8 Alkyl or benzene substituted C 1-3 Alkylene, the benzene ring is phenyl or is surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl; In formula (I-2), M 02 is H, lithium ion, sodium ion or potassium ion; In formula (I-3), U N Contains 0, 1 or more hydrophilic linking groups L 01 A polyvalent hydrocarbon group, optionally, U N Contains 0, 1 or more hydrophilic linking groups L 01 A polyvalent saturated hydrocarbon group, any one of the hydrophilic linking groups L 01 are independently *-CONH-*, *-NHCO-*, *-C(=O)O-*, *-OC(=O)-*, *-O-(O=)P(OM 01 )-O-* or *-O-*, wherein * indicates the connection site to the carbon atom, M 01 Absent or H, lithium, sodium or potassium; or, U N is a trivalent alkyl group or a tetravalent alkyl group, optionally, U N The number of carbon atoms is 3 to 10, further optionally 3 to 6, further optionally 3, 4 or 5, and further Optionally, U N -CH 2- CR 05 (-)-CH2-,R 05 is H, methyl or ethyl, and further optionally, R 05 H; or, U N It is a trivalent tertiary amino group, which can be a trivalent C 3-10 A tertiary amino group may further be N(-CH2CH2-)3; In formula (I-3), U N The number of non-hydrogen atoms is 2 to 40, preferably 2 to 30, further preferably 2 to 25, further preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 15, further preferably 2 to 12, further preferably 2 to 10, further preferably 2 to 8, further preferably 2 to 6, further preferably 2, 3, 4 or 5; In formula (I-3), j is an integer selected from 1 to 5, and may be an integer selected from 1 to 4, and may be 1, 2 or 3; In formula (I-4), R 01 C 1-3 alkyl; optionally, R 01 is methyl; In formula (I-4), R 02 C 1-8 Alkyl or benzene substituted C 1-3 Alkylene, the benzene ring is phenyl or is surrounded by 1 to 4 C 1-3 Alkyl-substituted phenyl; optionally, R 02 is methyl or benzyl; In formula (I-2), formula (I-3) and formula (I-4), L 23 are independently linear or branched; optionally, L 23 Each independently is a straight chain C 8-20 Alkylene or branched C 8-20 A polyvalent hydrocarbon group; further optionally, L 23 Each independently is a straight chain C 8-20 Alkylene or linear C 8-20 Alkenylene; further optionally, L 23 Each independently is a straight chain C 10-18 Alkylene or linear C 10-18 Alkenylene; further optionally, L 23 Each independently is a straight chain C 12-18 Alkylene or linear C 12-18 Alkenylene.

13. The perovskite precursor solution according to claim 1, wherein: The surfactant includes one or more of the following compounds: Among them, M 01 It is absent or is H or an alkali metal ion.

14. The perovskite precursor solution according to any one of claims 1 to 13, wherein: The molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.001 mol% to 5 mol%; Optionally, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.001% to 2.5%; Further optionally, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.01% to 1%; Further optionally, the molar percentage of the surfactant relative to the divalent metal ions in the perovskite precursor material is 0.01% to 0.5%.

15. The perovskite precursor solution according to any one of claims 1 to 14, wherein: The solvent includes a first solvent and a second solvent, and the boiling point of the first solvent is lower than the boiling point of the second solvent.

16. The perovskite precursor solution according to claim 15, wherein: The first solvent includes one or more of N,N-dimethylformamide, 2-methoxyethanol and acetonitrile; The second solvent includes one or more of N-methylpyrrolidone, diphenyl sulfoxide and dimethylpropylene urea.

17. The perovskite precursor solution according to claim 15 or 16, wherein: The volume ratio of the first solvent to the second solvent is 3 to 10; Optionally, the volume ratio of the first solvent to the second solvent is 3-5.

18. A perovskite film, which is prepared by coating and annealing the perovskite precursor solution of any one of claims 1 to 17, or at least comprises the non-solvent component in the perovskite precursor solution of any one of claims 1 to 16.

19. The perovskite film according to claim 18, wherein: The area of ​​the perovskite film is ≥1cm 2 ; Optionally, the area of ​​the perovskite film is ≥4 cm 2 .

20. A perovskite battery comprising the perovskite film according to claim 18 or 19.

21. An electrical device comprising the perovskite battery according to claim 20.

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