Amino fullerene derivatives, methods for their preparation and use in perovskite electron transport layers

Abstract

The present disclosure relates to the technical field of organic photovoltaics, in particular to an amino-fullerene derivative, a preparation method thereof and application thereof in a perovskite electron transport layer. The present disclosure has the following advantages: the present disclosure uses an amino-fullerene derivative as an electron transport layer of a perovskite solar cell, and can significantly improve energy conversion efficiency.

Description

Technical Field

[0001] This disclosure relates to the field of organic photovoltaic technology, specifically to aminofullerene derivatives, their preparation methods, and their application in perovskite electron transport layers. Background Technology

[0002] Fullerenes are a series of carbon-based molecules with cage-like fused-ring structures. Their high electron affinity, excellent electron mobility, and good energy level matching make them key materials in perovskite solar cells (PSCs). The numerous active sites on the carbon cage surface can react with various functional groups to generate fullerene derivatives, achieving functionalization and allowing for precise control over their solubility, thin-film formation properties, and interfacial interaction characteristics—crucial for overcoming core bottlenecks such as poor stability and severe interfacial charge recombination in perovskite solar cells. Currently, most fullerene derivatization reactions suffer from long reaction cycles, low yields, and poor product structural uniformity, leading to unstable performance in perovskite devices and hindering further breakthroughs in device efficiency and stability. Therefore, developing efficient and rapid methods for synthesizing fullerene derivatives with well-defined molecular structures is crucial for optimizing the performance and industrialization of perovskite solar cells.

[0003] Hexachlorofullerene (C 60 Cl6) is a structurally well-defined fullerene derivative, similar to the original C16. 60 In comparison, C 60 The strong electron-withdrawing effect of the chlorine atom in Cl6 significantly enhances the electrophilic activity of the carbon cage, while the steric hindrance of the chlorine atom gives it superior reaction selectivity, effectively avoiding side reactions. As an important intermediate in fullerene synthesis, C... 60 Cl6 can undergo substitution reactions with various nucleophiles such as amino, mercapto, and alkoxy groups to precisely construct functionalized fullerene derivatives with well-defined structures. These derivatives show great potential in perovskite solar cells for interface modification and transport layer modification.

[0004] In the prior art, the epoxidation reaction of primary amine compounds with chlorinated fullerene solution (hexachlorofullerene) typically only yields pentaaddition epoxide products (pentasubstituted aminofullerene derivatives), and the synthesis of tetraaddition epoxide products (tetrasubstituted aminofullerene derivatives) has not been reported. This disclosure unexpectedly discovers that, under the synergistic effect of cumene hydroperoxide and triethylamine, a significant shift in the epoxidation reaction pathway of primary amine compounds with chlorinated fullerene solution (hexachlorofullerene) can be induced, thereby achieving for the first time the selective synthesis of tetraaddition epoxide products (tetrasubstituted aminofullerene derivatives), filling a technological gap in this field.

[0005] However, there are currently no reports on the preparation of tetrasubstituted aminofullerene derivatives by reacting fullerene chloride solution (hexachlorofullerene) with primary amine compounds and using them for perovskite electron transport layers. Summary of the Invention

[0006] This disclosure aims to provide aminofullerene derivatives, their preparation methods, and their applications in perovskite electron transport layers. This disclosure uses C... 60 Cl6 was used as a precursor for the synthesis of aminofullerene derivatives, via primary amine compounds to target C. 60 The nucleophilic substitution reaction of Cl6 enables controllable amino modification of fullerenes, yielding a series of amino-fullerene derivatives with well-defined molecular structures. These derivatives are then used as perovskite electron transport layers, significantly improving energy conversion efficiency.

[0007] To achieve the above-mentioned technical objectives, the technical solution adopted in this disclosure is as follows: On the one hand, this disclosure provides a method for preparing an aminofullerene derivative or its stereoisomer, optical isomer, deuterated derivative, or solvate, comprising the following steps: An amine compound was added to a solution of chlorinated fullerene and stirred at room temperature to react. After the reaction was completed, an aminofullerene derivative was obtained. The amine compounds are primary amine compounds; The fullerene is selected from at least one of hollow fullerene, metallogenic fullerene, heterocyclic fullerene, and endogenous fullerene.

[0008] In some embodiments, the preparation method further includes the step of adding a tertiary amine compound to a fullerene chloride solution.

[0009] In some embodiments, the tertiary amine compound is NR. 3 R 4 R 5 , where R 3 R 4 R 5 Each is independently selected from -C1-C6 alkyl groups.

[0010] In some implementation schemes, R 3 R 4 R 5 Each is independently selected from -C1-C5 alkyl groups.

[0011] In some implementation schemes, R 3 R 4 R 5 Each is independently selected from -C1-C3 alkyl groups.

[0012] In some embodiments, the tertiary amine is triethylamine.

[0013] In some embodiments, the fullerene is selected from C 2n M@C 2n M2@C 2n MA@C 2n M3N@C 2n M2C2@C 2n M2S@C 2n M2O@C 2n and M x A 3-x N@C 2n Any one or a mixture thereof, wherein M and A are both metallic elements, and both M and A are selected from any one of Sc, Y and lanthanide metals.

[0014] In some embodiments, the fullerene is selected from C-containing... 2n One or more fullerene molecules, wherein 2n is the number of carbon atoms, and 30≤n≤60.

[0015] In some embodiments, the fullerene is selected from C 60 C 70 C 76 C 78 C 84 One or more thereof; more preferably, the fullerene is C10. 60 .

[0016] In some implementation schemes, the synthetic route is as follows: The amine compound and cumene hydroperoxide were added to the fullerene chloride solution, and the mixture was stirred at room temperature to react. After the reaction was completed, an aminofullerene derivative was obtained.

[0017] In some embodiments, the aminofullerene derivative is a tetrasubstituted aminofullerene derivative. In some embodiments, the molar ratio of the chlorinated fullerene to the primary amine compound is 1:(1-20), preferably 1:(1-10), preferably 1:(1-5), preferably 1:(1-3), preferably 1:(1-2), and preferably 1:(1.2-1.8).

[0018] In some embodiments, the molar ratio of the fullerene chloride, the primary amine compound, and the cumene hydroperoxide is (1-5):(1-20):(1-5), preferably (1-5):(1-10):(1-5), preferably (1-3):(1-5):(1-5), preferably (1-2):(1-3):(1-3), and preferably (1-1.5):(1-2):(1-2).

[0019] In some embodiments, the molar ratio of the fullerene chloride, the primary amine compound, the tertiary amine compound, and the cumene hydroperoxide is (1-5):(1-20):(1-5):(1-5), preferably (1-5):(1-10):(1-5):(1-5), preferably (1-3):(1-5):(1-5):(1-5), preferably (1-2):(1-3):(1-3):(1-3), and preferably (1-1.5):(1-2):(1-2):(1-2).

[0020] In some embodiments, the stirring time at room temperature is 0.6h-1h, preferably 1h.

[0021] In some embodiments, the chlorinated fullerene solution is obtained by dissolving chlorinated fullerene in an organic solvent, wherein the organic solvent is selected from toluene or chlorobenzene.

[0022] In some embodiments, the organic solvent is toluene.

[0023] In some embodiments, the amine compound NH2R is NH2CR. 1 R 2 Wherein, the amine compound NH2R is NH2CR 1 R 2 , where R 1 R 2 Each group is independently selected from aryl, heteroaryl, ester, or phosphate groups.

[0024] In some implementation schemes, R 1 R 2 Each is independently selected from phenyl, thienyl, C1-C6 alkoxycarbonyl, or C1-C6 alkoxyphosphoryl.

[0025] In some implementation schemes, R 1 R 2 Each is independently selected from phenyl, methylphenyl, thiophene, methoxycarbonyl, ethoxycarbonyl, dimethoxyphosphoryl or diethoxyphosphoryl.

[0026] In some embodiments, the amine compound is selected from... , , , , , One or more of them.

[0027] In some embodiments, the aminofullerene derivative has the structure shown in formula (I): (I); In equation (Ⅰ), R is CR1 R 2 , where R 1 R 2 Each group is independently selected from aryl, heteroaryl, ester, or phosphate groups.

[0028] In some implementations, the synthetic route of formula (Ⅰ) is as follows: Where R is CR 1 R 2 R 1 R 2 As mentioned above.

[0029] In some implementations, the synthetic route of formula (Ⅰ) is as follows: .

[0030] In some implementation schemes, R 1 R 2 Each is independently selected from phenyl, thienyl, C1-C6 alkoxycarbonyl, or C1-C6 alkoxyphosphoryl.

[0031] In some implementation schemes, R 1 R 2 Each is independently selected from phenyl, methylphenyl, thiophene, methoxycarbonyl, ethoxycarbonyl, dimethoxyphosphoryl or diethoxyphosphoryl.

[0032] In some implementations, -NHR is selected from , , , , , One or more of them, wherein " " " indicates a connection point.

[0033] In some embodiments, the aminofullerene derivative has the following structure: , , , , , .

[0034] On the other hand, this disclosure provides aminofullerene derivatives or their stereoisomers, optical isomers, deuterated derivatives or solvates prepared by the preparation method described above.

[0035] On the other hand, this disclosure provides an aminofullerene derivative or its stereoisomer, optical isomer, deuterated derivative or solvate thereof, wherein the aminofullerene derivative has the structure shown in formula (I): (I); In equation (Ⅰ), R is CR 1 R 2 , where R 1 R 2 Each group is independently selected from aryl, heteroaryl, ester, or phosphate groups.

[0036] In some implementation schemes, R 1 R 2 Each is independently selected from phenyl, thienyl, C1-C6 alkoxycarbonyl, or C1-C6 alkoxyphosphoryl; In some implementation schemes, R 1 R 2 Each is independently selected from phenyl, methylphenyl, thiophene, methoxycarbonyl, ethoxycarbonyl, dimethoxyphosphoryl or diethoxyphosphoryl; In some implementations, -NHR is selected from , , , , , One or more of them, wherein " "Indicates a connection site; In some embodiments, the aminofullerene derivative has the following structure: , , , , , .

[0037] On the other hand, this disclosure provides compositions comprising an aminofullerene derivative or its stereoisomer, optical isomer, deuterated derivative or solvate prepared by the preparation method described above, or the aminofullerene derivative or its stereoisomer, optical isomer, deuterated derivative or solvate described above.

[0038] On the other hand, this disclosure provides the use of aminofullerene derivatives or their stereoisomers, optical isomers, deuterated derivatives or solvates prepared by the preparation method described above, or the aminofullerene derivatives or their stereoisomers, optical isomers, deuterated derivatives or solvates described above, or the compositions described above, in batteries.

[0039] On the other hand, this disclosure provides the application of aminofullerene derivatives or their stereoisomers, optical isomers, deuterated derivatives or solvates prepared by the preparation method described above, or the aminofullerene derivatives or their stereoisomers, optical isomers, deuterated derivatives or solvates described above, or the compositions described above, in solar cells.

[0040] On the other hand, this disclosure provides the application of aminofullerene derivatives or their stereoisomers, optical isomers, deuterated derivatives or solvates prepared by the preparation method described above, or the aminofullerene derivatives or their stereoisomers, optical isomers, deuterated derivatives or solvates described above, or the compositions described above, in perovskite solar cells.

[0041] On the other hand, this disclosure provides the use of aminofullerene derivatives or their stereoisomers, optical isomers, deuterated derivatives or solvates prepared by the preparation method described above, or the aminofullerene derivatives or their stereoisomers, optical isomers, deuterated derivatives or solvates described above, or the compositions described above, in the electron transport layer of perovskite solar cells.

[0042] In some embodiments, the perovskite solar cell includes an electron transport layer.

[0043] In some implementations, the electron transport layer significantly enhances the overall performance of the perovskite solar cell.

[0044] The aminofullerene derivatives disclosed herein can be used as electron transport layers in perovskite solar cells. Thanks to the unique structure of these molecules and the different functional groups connected to them, the aminofullerene derivatives disclosed herein have better photovoltaic performance, such as higher short-circuit circuit, open-circuit voltage, fill factor and energy conversion efficiency, compared with the conventional solution spin-coated electron transport layer material methyl phenyl-C61-butyrate (PCBM).

[0045] This disclosure has the following advantages: (1) This disclosure provides aminofullerene derivatives, which are rapidly synthesized by a nucleophilic substitution reaction of hexachlorofullerene with a specific primary amine compound; the resulting aminofullerene derivatives have a well-defined structure and high purity.

[0046] (2) The present disclosure uses aminofullerene derivatives as the electron transport layer of perovskite solar cells, which can significantly improve the energy conversion efficiency.

[0047] (3) This disclosure provides aminofullerene derivatives, which are expected to provide a new strategy for the electron transport layer of perovskite solar cells. Attached Figure Description

[0048] To more clearly illustrate the technical solutions in the specific embodiments of this disclosure or the prior art, the accompanying drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this disclosure. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. The accompanying drawings are incorporated in and constitute a part of this specification, illustrating embodiments consistent with this specification, and are used together with the specification to explain the principles of this specification.

[0049] Figure 1 The molecular structure (left) and high-resolution mass spectra (right) of aminofullerene TDTMC in Example 1 are shown.

[0050] Figure 2 The high-performance liquid chromatography of the aminofullerene molecule TDTMC in Example 1 is shown.

[0051] Figure 3 The 1H NMR spectrum of aminofullerene TDTMC in Example 1 is shown.

[0052] Figure 4 The carbon NMR spectrum of aminofullerene TDTMC in Example 1 is shown.

[0053] Figure 5 The molecular structure (left) and high-resolution mass spectra (right) of aminofullerene THFAC in Example 2 are shown.

[0054] Figure 6 The high-performance liquid chromatography of the aminofullerene molecule THFAC in Example 2 is shown.

[0055] Figure 7 The 1H NMR spectrum of aminofullerene THFAC in Example 2 is shown.

[0056] Figure 8 The carbon NMR spectrum of aminofullerene THFAC in Example 2 is shown.

[0057] Figure 9 The molecular structure (left) and high-resolution mass spectrum (right) of aminofullerene TDPAC in Example 3 are shown.

[0058] Figure 10 The high-performance liquid chromatography of the aminofullerene molecule TDPAC in Example 3 is shown.

[0059] Figure 11 The 1H NMR spectrum of aminofullerene TDPAC in Example 3 is shown.

[0060] Figure 12The carbon NMR spectrum of aminofullerene TDPAC in Example 3 is shown.

[0061] Figure 13 The molecular structure (left) and high-resolution mass spectra (right) of aminofullerene TATPC in Example 4 are shown.

[0062] Figure 14 The high-performance liquid chromatography of the aminofullerene molecule TATPC in Example 4 is shown.

[0063] Figure 15 The 1H NMR spectrum of aminofullerene TATPC in Example 4 is shown.

[0064] Figure 16 The carbon NMR spectrum of aminofullerene TATPC in Example 4 is shown.

[0065] Figure 17 The molecular structure (left) and high-resolution mass spectra (right) of aminofullerene TDAMC in Example 5 are shown.

[0066] Figure 18 The high-performance liquid chromatography of the aminofullerene molecule TDAMC in Example 5 is shown.

[0067] Figure 19 The 1H NMR spectrum of aminofullerene TDAMC in Example 5 is shown.

[0068] Figure 20 The carbon NMR spectrum of aminofullerene TDAMC in Example 5 is shown.

[0069] Figure 21 The molecular structure (left) and high-resolution mass spectrum (right) of aminofullerene TTAPC in Example 6 are shown.

[0070] Figure 22 The high-performance liquid chromatography of the aminofullerene molecule TTAPC in Example 6 is shown.

[0071] Figure 23 The 1H NMR spectrum of aminofullerene TTAPC in Example 6 is shown.

[0072] Figure 24 The carbon NMR spectrum of aminofullerene TTAPC in Example 6 is shown.

[0073] Figure 25 The current density-voltage curves of aminofullerene TMPC, TATPC, TDAMC, and TTAPC in Example 7 are shown. Detailed Implementation

[0074] Definitions and Explanations To facilitate understanding of this disclosure, certain technical and scientific terms are specifically defined below. In this disclosure, unless otherwise stated, the scientific and technical terms used herein have meanings commonly understood by those skilled in the art. Furthermore, the cell and tissue culture, microbiology-related terms, and laboratory procedures used herein are all widely used terms and routine procedures in their respective fields. Meanwhile, to better understand this disclosure, definitions and explanations of relevant terms are provided below. It should be understood that this disclosure is not limited to specific methods, reagents, compounds, compositions, or biological systems, and variations thereof are certainly possible. It should also be understood that the terminology used in this application is for describing specific embodiments only and is not intended to be limiting.

[0075] Unless otherwise expressly stated, the terms “a,” “an,” and “the” as used in this specification and the appended claims cover one or more types.

[0076] As used herein, the terms “comprising” and “having”, and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, apparatus, product, or device that includes a series of steps is not limited to the steps or modules listed, but may optionally include steps not listed, or may optionally include other steps inherent to such process, method, product, or device.

[0077] In the description herein, references to “some embodiments,” “some implementations,” or “some implementation schemes” describe a subset of all possible embodiments. However, it is understood that “some embodiments” may be the same subset or different subsets of all possible embodiments and may be combined with each other without conflict.

[0078] In this invention, the disclosure of all ranges should be regarded as a disclosure of all sub-ranges and all point values ​​within the range. For example, the disclosure of 0.5-1h should be regarded as also disclosing ranges such as 0.6-1h and 0.7-0.9h, as well as point values ​​such as 0.8 and 0.85.

[0079] The term "alkyl" refers to a saturated aliphatic hydrocarbon group, including straight-chain or branched saturated hydrocarbon groups having the indicated number of carbon atoms. For example, the term "C1-C6 alkyl" includes C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl, examples of which include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, n-hexyl, 2-hexyl, 3-hexyl, etc.

[0080] As used herein, the term "fullerene" is a series of spherical cluster molecules consisting of an even number of carbon atoms, with 12 five-membered rings and the remainder being six-membered rings. Fullerenes include hollow fullerenes and endohedral fullerenes, wherein the endohedral fullerene is a fullerene whose carbon cage structure contains a metal or a cluster of metal atoms.

[0081] The terms "metal fullerene" and "endo-fullerene" refer to compounds with special structures and properties formed by incorporating various metals or metal atom clusters into the carbon cage structure of fullerenes. These compounds are usually called endohedral fullerenes and are generally represented in the form M@C2n, where M represents a metal element.

[0082] The term "chlorinated fullerene" refers to a fullerene derivative obtained by combining one or more carbon atoms of a fullerene with chlorine.

[0083] The term "aminofullerene derivative" refers to a fullerene that has been aminated, resulting in a fullerene containing one or more identical or different amino groups on its exterior.

[0084] J SC This refers to the short-circuit current density, measured in milliamperes per square centimeter (mA / cm²). 2 ); J SC This represents the photocurrent generated per unit area of ​​the battery under short-circuit conditions. The higher the value, the stronger the light conversion capability.

[0085] FF stands for fill factor, and its unit is percentage (%). FF measures how close the actual maximum power output of a battery is to its theoretical limit power. The higher the value, the smaller the series resistance of the battery and the better its performance.

[0086] PCE refers to power conversion efficiency, expressed as a percentage (%). PCE is the most critical indicator of a solar cell, directly reflecting its ability to convert light energy into electrical energy.

[0087] Device area refers to the actual effective area of ​​the solar cell used for testing, measured in cm². 2 .

[0088] Example To make the objectives, technical solutions, and advantages of the embodiments of this disclosure clearer, the technical solutions of the embodiments of this disclosure will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this disclosure, not all embodiments. The following is merely a further description of this disclosure, and the scope of protection of this disclosure is not limited thereto. In the embodiments and experimental examples of this disclosure, the technical means or methods, etc., not specifically described, are conventional technical means or methods in the art. Unless otherwise specified, the materials, reagents, experimental equipment, etc., used in the embodiments and experimental examples of this disclosure can all be obtained commercially.

[0089] Example 1: Preparation of aminofullerene molecule TDTMC Synthesis method: 1g C 60 Cl6 was dissolved in 1000 mL of toluene, and 1.69 g of di-p-toluylmethylamine, 1.2 mL of cumene hydroperoxide (80%), and 1.14 mL of triethylamine were added. The mixture was stirred at room temperature (550 rpm) for 1 h. The reaction solution was analyzed by HPLC. The reaction was complete, and the reaction was stopped. The reaction solution was washed successively with 500 mL of saturated ammonium chloride solution and 500 mL of saturated sodium bicarbonate solution. The organic layer was dried with anhydrous sodium sulfate and concentrated at 40 °C to dryness, yielding a reddish-brown solid.

[0090] The reaction product was dissolved in toluene and then processed using a rapid preparative liquid chromatograph (SepaBean). TM machine), positive phase silicone column (September Flash Technology) ® A standard rapid separation column (S-8101-0120, pre-packed with normal-phase silica gel, particle size 40-63 μm, pore size 60 Å, packing amount 120 g) was used for column chromatography separation. Pure toluene was used as the eluent, the flow rate was 25 mL / min, and a UV detector was used (detection wavelength: 310 nm, collection wavelength: 320 nm). The obtained product was concentrated and evaporated to dryness at 40 °C to obtain a reddish-brown solid, namely aminofullerene molecule TDTMC.

[0091] Structural characterization: Molecular weight was determined using electrospray ionization mass spectrometry (ESI-MS, Thermo Scientific Exactive, positive ion mode). Figure 1 The purity was determined using high-performance liquid chromatography (HPLC, LC-2030, Shimadzu), a C18 column (Agilent, Eclipse XDB-C18, 4.6*250mm, packing particle size 5μm), toluene-acetonitrile as the mobile phase (Table 1), a UV detector (detection wavelength: 310nm), and a flow rate of 1mL / min. Figure 2); using nuclear magnetic resonance (Bruker Avance III 400HD, 400MHz), the sample was dissolved in deuterated o-dichlorobenzene for proton NMR spectroscopy (NMR spectroscopy). Figure 3 ) and carbon spectrum ( Figure 4 ) Detection and analysis of product structure.

[0092] Table 1 shows the toluene-acetonitrile ratio gradient method in high performance liquid chromatography, as follows: Table 1. High Performance Liquid Chromatography (HPLC) Toluene-Acetonitrile Ratio Gradient Method Conclusion: The molecular weight detected by ESI-MS is completely consistent with the theoretical molecular weight of TDTMC, the purity detected by HPLC is above 95%, and the hydrogen atom shift and integral identification of the proton NMR spectrum and the carbon atom shift identification of the carbon NMR spectrum are consistent with the TDAD structure.

[0093] Example 2: Preparation of aminofullerene molecule THFAC Synthesis method: 1g C 60 Cl6 was dissolved in 1000 mL of toluene, and 1.45 g of 9-aminofluorene, 1.2 mL of cumene hydroperoxide (80%), and 1.14 mL of triethylamine were added. The mixture was stirred at room temperature (550 rpm) for 1 h. The reaction solution was analyzed by HPLC. The reaction was complete, and the reaction was stopped. The reaction solution was washed successively with 500 mL of saturated ammonium chloride solution and 500 mL of saturated sodium bicarbonate solution. The organic layer was dried with anhydrous sodium sulfate and concentrated at 40 °C to obtain a reddish-brown solid.

[0094] The reaction product was dissolved in toluene and then processed using a rapid preparative liquid chromatograph (SepaBean). TM machine), positive phase silicone column (September Flash Technology) ® A standard rapid separation column (S-8101-0120, pre-packed with normal-phase silica gel, particle size 40-63 μm, pore size 60 Å, packing amount 120 g) was used for column chromatography separation. Pure toluene was used as the eluent, the flow rate was 25 mL / min, and a UV detector was used (detection wavelength: 310 nm, collection wavelength: 320 nm). The obtained product was concentrated and evaporated to dryness at 40 °C to obtain a reddish-brown solid, namely aminofullerene molecule THFAC.

[0095] Structural characterization: Molecular weight was determined using electrospray ionization mass spectrometry (ESI-MS, Thermo Scientific Exactive, positive ion mode). Figure 5The purity was determined using high-performance liquid chromatography (HPLC, LC-2030, Shimadzu), a C18 column (Agilent, Eclipse XDB-C18, 4.6*250mm, packing particle size 5μm), toluene-acetonitrile as the mobile phase (Table 1), a UV detector (detection wavelength: 310nm), and a flow rate of 1mL / min. Figure 6 ); using nuclear magnetic resonance (Bruker Avance III 400HD, 400MHz), the sample was dissolved in deuterated chloroform for proton NMR spectroscopy (NMR). Figure 7 ) and carbon spectrum ( Figure 8 ) Detection and analysis of product structure.

[0096] Conclusion: The molecular weight detected by ESI-MS is completely consistent with the theoretical molecular weight of THFAC, the purity detected by HPLC is above 95%, and the hydrogen atom shift and integral identification of the proton NMR spectrum and the carbon atom shift identification of the carbon NMR spectrum are consistent with the structure of THFAC.

[0097] Example 3: Preparation of aminofullerene molecule TDPAC Synthesis method: 1g C 60 Cl6 was dissolved in 1000 mL of toluene, and 1.69 g of 1,3-diphenylprop-2-amine, 1.2 mL of cumene hydroperoxide (80%), and 1.14 mL of triethylamine were added. The mixture was stirred at room temperature (550 rpm) for 1 h. The reaction solution was analyzed by HPLC. The reaction was complete, and the reaction was stopped. The reaction solution was washed successively with 500 mL of saturated ammonium chloride solution and 500 mL of saturated sodium bicarbonate solution. The organic layer was dried with anhydrous sodium sulfate and concentrated at 40 °C to dryness, yielding a reddish-brown solid.

[0098] The reaction product was dissolved in toluene and then processed using a rapid preparative liquid chromatograph (SepaBean). TM machine), positive phase silicone column (September Flash Technology) ® A standard rapid separation column (S-8101-0120, pre-packed with normal-phase silica gel, particle size 40-63 μm, pore size 60 Å, packing amount 120 g) was used for column chromatography separation. Pure toluene was used as the eluent, the flow rate was 25 mL / min, and a UV detector was used (detection wavelength: 310 nm, collection wavelength: 320 nm). The obtained product was concentrated and evaporated to dryness at 40 °C to obtain a reddish-brown solid, namely the aminofullerene molecule TDPAC.

[0099] Structural characterization: Molecular weight was determined using electrospray ionization mass spectrometry (ESI-MS, Thermo Scientific Exactive, positive ion mode). Figure 9The purity was determined using high-performance liquid chromatography (HPLC, LC-2030, Shimadzu), a C18 column (Agilent, Eclipse XDB-C18, 4.6*250mm, packing particle size 5μm), toluene-acetonitrile as the mobile phase (Table 1), a UV detector (detection wavelength: 310nm), and a flow rate of 1mL / min. Figure 10 ); using nuclear magnetic resonance (Bruker Avance III 400HD, 400MHz), the sample was dissolved in deuterated o-dichlorobenzene for proton NMR spectroscopy (NMR spectroscopy). Figure 11 ) and carbon spectrum ( Figure 12 ) Detection and analysis of product structure.

[0100] Conclusion: The molecular weight detected by ESI-MS is completely consistent with the theoretical molecular weight of TDPAC, the purity detected by HPLC is above 95%, and the hydrogen atom shift and integral identification of the proton NMR spectrum and the carbon atom shift identification of the carbon NMR spectrum are consistent with the structure of TDPAC.

[0101] Example 4: Preparation of aminofullerene molecule TATPC Synthesis method: 1g C 60 Cl6 was dissolved in 1000 mL of toluene, and 1.47 g of methyl 3-amino-3-(thiophen-2-yl)propionate, 1.2 mL of cumene hydroperoxide (80%), and 1.14 mL of triethylamine were added. The mixture was stirred at room temperature (550 rpm) for 1 h. The reaction solution was analyzed by HPLC. The reaction was complete, and the reaction was stopped. The reaction solution was washed successively with 500 mL of saturated ammonium chloride solution and 500 mL of saturated sodium bicarbonate solution. The organic layer was dried with anhydrous sodium sulfate and concentrated at 40 °C to obtain a reddish-brown solid.

[0102] The reaction product was dissolved in toluene and then processed using a rapid preparative liquid chromatograph (SepaBean). TM machine), positive phase silicone column (September Flash Technology) ® A standard rapid separation column (S-8101-0120, pre-packed with normal-phase silica gel, particle size 40-63 μm, pore size 60 Å, packing weight 120 g) was used for column chromatography separation. The eluent was ethyl acetate / toluene, with ethyl acetate accounting for 5% by volume. The flow rate was 25 mL / min, and a UV detector was used (detection wavelength: 310 nm, collection wavelength: 320 nm). The obtained product was concentrated and evaporated to dryness at 40 °C to obtain a brown solid, namely aminofullerene molecule TATPC.

[0103] Structural characterization: Molecular weight was determined using electrospray ionization mass spectrometry (ESI-MS, Thermo Scientific Exactive, positive ion mode). Figure 13The purity was determined using high-performance liquid chromatography (HPLC, LC-2030, Shimadzu), with an Agilent Eclipse XDB-C18 column (4.6*250mm, packing particle size 5μm, toluene-acetonitrile as the mobile phase (Table 1), a UV detector (detection wavelength: 310nm), and a flow rate of 1mL / min. Figure 14 ); using nuclear magnetic resonance (Bruker Avance III 400HD, 400MHz), the sample was dissolved in deuterated chloroform for proton NMR spectroscopy (NMR). Figure 15 ) and carbon spectrum ( Figure 16 ) Detection and analysis of product structure.

[0104] Conclusion: The molecular weight detected by ESI-MS is completely consistent with the theoretical molecular weight of TATPC, the purity detected by HPLC is above 95%, and the hydrogen atom shift and integral identification of the proton NMR spectrum and the carbon atom shift identification of the carbon NMR spectrum are consistent with the structure of TATPC.

[0105] Example 5: Preparation of aminofullerene molecule TDAMC Synthesis method: 1g C 60 Cl6 was dissolved in 1000 mL of toluene, and 1.40 g of diethyl 2-aminomalonate, 1.2 mL of cumene hydroperoxide (80%), and 1.14 mL of triethylamine were added. The mixture was stirred at room temperature (550 rpm) for 1 h. The reaction solution was analyzed by HPLC. The reaction was complete, and the reaction was stopped. The reaction solution was washed successively with 500 mL of saturated ammonium chloride solution and 500 mL of saturated sodium bicarbonate solution. The organic layer was dried with anhydrous sodium sulfate and concentrated at 40 °C to dryness, yielding a reddish-brown solid.

[0106] The reaction product was dissolved in toluene and then processed using a rapid preparative liquid chromatograph (SepaBean). TM machine), positive phase silicone column (September Flash Technology) ® A standard rapid separation column (S-8101-0120, pre-packed with normal-phase silica gel, particle size 40-63 μm, pore size 60 Å, packing weight 120 g) was used for column chromatography separation. The eluent was ethyl acetate / toluene, with ethyl acetate accounting for 20% by volume. The flow rate was 25 mL / min, and a UV detector was used (detection wavelength: 310 nm, collection wavelength: 320 nm). The obtained product was concentrated and evaporated to dryness at 40 °C to obtain a reddish-brown solid, namely aminofullerene molecule TDAMC.

[0107] Structural characterization: Molecular weight was determined using electrospray ionization mass spectrometry (ESI-MS, Thermo Scientific Exactive, positive ion mode). Figure 17The purity was determined using high-performance liquid chromatography (HPLC, LC-2030, Shimadzu), a C18 column (Agilent, Eclipse XDB-C18, 4.6*250mm, packing particle size 5μm), toluene-acetonitrile as the mobile phase (Table 1), a UV detector (detection wavelength: 310nm), and a flow rate of 1mL / min. Figure 18 ); using nuclear magnetic resonance (Bruker Avance III 400HD, 400MHz), the sample was dissolved in deuterated chloroform for proton NMR spectroscopy (NMR). Figure 19 ) and carbon spectrum ( Figure 20 ) Detection and analysis of product structure.

[0108] Conclusion: The molecular weight detected by ESI-MS is completely consistent with the theoretical molecular weight of TDAMC, the purity detected by HPLC is above 95%, and the hydrogen atom shift and integral identification of the proton NMR spectrum and the carbon atom shift identification of the carbon NMR spectrum are consistent with the structure of TDAMC.

[0109] Example 6: Preparation of aminofullerene molecule TTAPC Synthesis method: 1g C 60 Cl6 was dissolved in 1000 mL of toluene, and 2.43 g of tetraethyl(aminomethylene)bis(phosphonate), 1.2 mL of cumene hydroperoxide (80%), and 1.14 mL of triethylamine were added. The mixture was stirred at room temperature (550 rpm) for 1 h. The reaction solution was analyzed by HPLC. The reaction was complete, and the reaction was stopped. The reaction solution was washed successively with 500 mL of saturated ammonium chloride solution and 500 mL of saturated sodium bicarbonate solution. The organic layer was dried with anhydrous sodium sulfate and concentrated at 40 °C to dryness, yielding a reddish-brown solid.

[0110] The reaction product was dissolved in toluene and then processed using a rapid preparative liquid chromatograph (SepaBean). TM machine), positive phase silicone column (September Flash Technology) ® A standard rapid separation column (S-8101-0120, pre-packed with normal-phase silica gel, particle size 40-63 μm, pore size 60 Å, packing weight 120 g) was used for column chromatography. The eluent was ethyl acetate / toluene, with ethyl acetate accounting for 40% by volume. The flow rate was 25 mL / min, and a UV detector was used (detection wavelength: 310 nm, collection wavelength: 320 nm). The obtained product was concentrated and evaporated to dryness at 40 °C to obtain a brown solid, namely aminofullerene molecule TTAPC.

[0111] Structural characterization: Molecular weight was determined using electrospray ionization mass spectrometry (ESI-MS, Thermo Scientific Exactive, positive ion mode). Figure 21The purity was determined using high-performance liquid chromatography (HPLC, LC-2030, Shimadzu), a C18 column (Agilent, Eclipse XDB-C18, 4.6*250mm, packing particle size 5μm), toluene-acetonitrile as the mobile phase (Table 1), a UV detector (detection wavelength: 310nm), and a flow rate of 1mL / min. Figure 22 ); using nuclear magnetic resonance (Bruker Avance III 400HD, 400MHz), the sample was dissolved in deuterated chloroform for proton NMR spectroscopy (NMR). Figure 23 ) and carbon spectrum ( Figure 24 ) Detection and analysis of product structure.

[0112] Conclusion: The molecular weight detected by ESI-MS is completely consistent with the theoretical molecular weight of TTAPC, the purity detected by HPLC is above 95%, and the hydrogen atom shift and integral identification of the proton NMR spectrum and the carbon atom shift identification of the carbon NMR spectrum are consistent with the structure of TTAPC.

[0113] Example 7: Aminofullerene molecules TMPC, TATPC, TDAMC, and TTAPC used as electron transport layers in perovskite solar cells (1) Device fabrication: The glass / indium tin oxide (ITO) substrate was ultrasonically cleaned for 15 min each in detergent solution, distilled water, and anhydrous ethanol. The substrate was then dried with nitrogen gas and subsequently cleaned with ultraviolet ozone for 30 min before use.

[0114] (2) The preparation process of the self-assembled molecular (SAM) layer is as follows: A 0.5 mg / mL solution of [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid (4PADCB) in ethanol is spin-coated onto an ITO glass substrate. The spin-coating parameters are 3000 rpm and 30 s. After spin-coating, the substrate is annealed at 100°C for 10 min.

[0115] 1.5M FA 0.95 Cs 0.05 The PbI3 perovskite precursor solution was prepared by dissolving 1.53 mmol lead iodide (PbI2), 1.425 mmol formamidinium iodide (FAI), 0.075 mmol cesium iodide (CsI), and 0.075 mmol methylamine chloride (MACl) in a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 5:1.

[0116] (3) Spin coating process of perovskite thin film: 80 μL of precursor solution was dropped onto the substrate surface. The spin coating parameters were set as follows: rotation speed 4000 rpm, time 50 s, and acceleration 1000 rpm. -1During the last 20 seconds of the spin coating process, 350 μL of chlorobenzene (CB) was rapidly added dropwise to the substrate surface at 1-second intervals. After spin coating, the substrate was immediately placed on a 100°C heating stage for annealing for 30 minutes.

[0117] (4) Preparation of passivation layer: 0.4 mg / mL of the passivation layer was prepared. -1 A 1,3-diaminopropane dihydroiodate (PDADI) isopropanol solution was spin-coated onto the surface of a perovskite film at 3000 rpm for 30 s, followed by annealing at 100°C for 5 min.

[0118] (5) Preparation of electron transport layer (ETL): Electron transport layer solutions based on different aminofullerene derivatives TMPC, TATPC, TDAMC and TTAPC were prepared respectively.

[0119] For TATPC: Dissolve a mixture of methyl phenyl-C61-butyrate (PCBM) and TATPC in chlorobenzene at mass ratios of 20:0, 19:1, 9:1, 4:1, and 0:20 to prepare a solution with a total concentration of 20 mg / mL. -1 The solution.

[0120] For TMPC, TDAMC, and TTAPC: Following the preparation method for the electron transport layer solution of TATPC, PCBM was mixed with TMPC, TDAMC, and TTAPC respectively at the above mass ratios (20:0, 19:1, 9:1, 4:1, 0:20), and dissolved in chlorobenzene to prepare solutions with a total concentration of 20 mg / mL. -1 The solution.

[0121] Each of the above solutions was spin-coated onto the surface of a perovskite film at 3000 rpm for 30 s, and then annealed at 70°C for 10 min.

[0122] (6) Preparation of BCP (Boiled Copper Plating) Thin Film: A saturated isopropanol solution of BCP was spin-coated onto the surface of the electron transport layer at 5000 rpm for 30 s, followed by annealing at 70°C for 10 min. Finally, the film was annealed in a high vacuum environment (vacuum degree < 5 × 10⁻⁶). -4 Under the condition of Pa), silver (Ag) electrodes with a thickness of 100 nm were sequentially deposited by thermal evaporation.

[0123] (7) Device testing: Device current-voltage ( J - V The curves were tested using a Keithley 2400 source meter and a solar simulator (Oriel, model 9119) equipped with an AM 1.5G standard solar spectrum. Light intensity was calibrated to 100 mW·cm² using a certified WPVS standard silicon reference cell (Enlitech).-2 The effective area of ​​the device is defined by a light-shielding mask with a size of 0.0586 cm². 2 and 1.04cm 2 The short-circuit density was obtained through testing. J SC ), open circuit voltage ( V OC ), fill factor (FF) and power conversion efficiency (PCE). Figure 25 The current density-voltage curves of the electron transport layers of aminofullerene molecules TMPC, TATPC, TDAMC, and TTAPC are shown.

[0124] Depend on Figure 25 It can be seen that, compared with the control group using only PCBM (PCE approximately 25.60%), the performance indicators of the device were improved after PCBM was blended with aminofullerene molecules TMPC, TATPC, TDAMC, and TTAPC as electron transport layers, with PCE reaching between 25.81% and 26.44%. This demonstrates that the aminofullerene derivatives disclosed herein, as additives, significantly improve the energy conversion efficiency of the electron transport layer compared to traditional PCBM materials, and can effectively enhance the photoelectric conversion performance of perovskite solar cells.

[0125] The foregoing description of specific exemplary embodiments of this disclosure is for illustrative and explanatory purposes. These descriptions are not intended to limit this disclosure to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of this disclosure and their practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of this disclosure, as well as various different choices and variations. The scope of this disclosure is intended to be defined by the claims and their equivalents.

Claims

1. A method for preparing an aminofullerene derivative or its stereoisomer, optical isomer, deuterated derivative, or solvate, comprising the following steps: An amine compound was added to a solution of chlorinated fullerene and stirred at room temperature to react. After the reaction was completed, an aminofullerene derivative was obtained. The amine compounds are primary amine compounds; The fullerene is selected from at least one of hollow fullerene, metallogenic fullerene, heterocyclic fullerene, and endogenous fullerene.

2. The preparation method according to claim 1, characterized in that, The preparation method further includes the step of adding a tertiary amine compound to a fullerene chloride solution; Preferably, the tertiary amine compound is NR. 3 R 4 R 5 , where R 3 R 4 R 5 Each is independently selected from -C1-C6 alkyl groups; Preferably, R 3 R 4 R 5 Each is independently selected from -C1-C5 alkyl groups; Preferably, R 3 R 4 R 5 Each is independently selected from -C1-C3 alkyl groups; Preferably, the tertiary amine is triethylamine.

3. The preparation method according to claim 1, characterized in that, The fullerene is selected from C 2n M@C 2n M2@C 2n MA@C 2n M3N@C 2n M2C2@C 2n M2S@C 2n M2O@C 2n and M x A 3-x N@C 2n M and A are either one or a mixture thereof, wherein M and A are both metallic elements, and M and A are each selected from Sc, Y and lanthanide metals. Preferably, the fullerene is selected from C-containing... 2n One or more fullerene molecules, wherein 2n is the number of carbon atoms, and 30≤n≤60; Preferably, the fullerene is selected from C 60 C 70 C 76 C 78 C 84 One or more thereof; more preferably, the fullerene is C10. 60 .

4. The preparation method according to any one of claims 1-3, characterized in that, The synthetic route is as follows: The amine compound and cumene hydroperoxide were added to the fullerene chloride solution, and the mixture was stirred at room temperature. After the reaction was completed, an aminofullerene derivative was obtained. Preferably, the aminofullerene derivative is a tetrasubstituted aminofullerene derivative; Preferably, the molar ratio of the fullerene chloride to the primary amine compound is 1:(1-20), more preferably 1:(1-10), more preferably 1:(1-5), more preferably 1:(1-3), more preferably 1:(1-2), and more preferably 1:(1.2-1.8). Preferably, the molar ratio of the fullerene chloride, the primary amine compound, and the cumene hydroperoxide is (1-5):(1-20):(1-5), more preferably (1-5):(1-10):(1-5), more preferably (1-3):(1-5):(1-5), more preferably (1-2):(1-3):(1-3), and more preferably (1-1.5):(1-2):(1-2). Preferably, the molar ratio of the fullerene chloride, the primary amine compound, the tertiary amine compound, and the cumene hydroperoxide is (1-5):(1-20):(1-5):(1-5), more preferably (1-5):(1-10):(1-5):(1-5), more preferably (1-3):(1-5):(1-5):(1-5), more preferably (1-2):(1-3):(1-3):(1-3), more preferably (1-1.5):(1-2):(1-2):(1-2); Preferably, the stirring time at room temperature is 0.6 h - 1 h; more preferably, it is 1 h. Preferably, the fullerene chloride solution is obtained by dissolving fullerene chloride in an organic solvent, wherein the organic solvent is selected from toluene or chlorobenzene; Preferably, the organic solvent is toluene.

5. The preparation method according to any one of claims 1-4, characterized in that, The amine compound NH2R is NH2CR. 1 R 2 Wherein, the amine compound NH2R is NH2CR 1 R 2 , where R 1 R 2 Each group is independently selected from aryl, heteroaryl, ester, or phosphate ester groups; Preferably, R 1 R 2 Each is independently selected from phenyl, thienyl, C1-C6 alkoxycarbonyl, or C1-C6 alkoxyphosphoryl; Preferably, R 1 R 2 Each is independently selected from phenyl, methylphenyl, thiophene, methoxycarbonyl, ethoxycarbonyl, dimethoxyphosphoryl or diethoxyphosphoryl; Preferably, the amine compound is selected from... , , , , , One or more of them.

6. The preparation method according to any one of claims 1-5, characterized in that, The aminofullerene derivative has the structure shown in formula (Ⅰ): （Ⅰ）； In equation (Ⅰ), R is CR 1 R 2 , where R 1 R 2 Each group is independently selected from aryl, heteroaryl, ester, or phosphate ester groups; Preferably, R 1 R 2 Each is independently selected from phenyl, thienyl, C1-C6 alkoxycarbonyl, or C1-C6 alkoxyphosphoryl; Preferably, R 1 R 2 Each is independently selected from phenyl, methylphenyl, thiophene, methoxycarbonyl, ethoxycarbonyl, dimethoxyphosphoryl or diethoxyphosphoryl; Preferably, -NHR is selected from , , , , , One or more of them, wherein " "Indicates a connection site; Preferably, the aminofullerene derivative has the following structure: 、 、 、 、 、 。 7. The aminofullerene derivative or its stereoisomer, optical isomer, deuterated product or solvate prepared by the preparation method of any one of claims 1-6.

8. An aminofullerene derivative or its stereoisomer, optical isomer, deuterated derivative or solvate, characterized in that, The aminofullerene derivative has the structure shown in formula (Ⅰ): （Ⅰ）； In equation (Ⅰ), R is CR 1 R 2 , where R 1 R 2 Each group is independently selected from aryl, heteroaryl, ester, or phosphate ester groups; Preferably, R 1 R 2 Each is independently selected from phenyl, thienyl, C1-C6 alkoxycarbonyl, or C1-C6 alkoxyphosphoryl; Preferably, R 1 R 2 Each is independently selected from phenyl, methylphenyl, thiophene, methoxycarbonyl, ethoxycarbonyl, dimethoxyphosphoryl or diethoxyphosphoryl; Preferably, -NHR is selected from , , , , , One or more of them, wherein " "Indicates a connection site; Preferably, the aminofullerene derivative has the following structure: 、 、 、 、 、 。 9. A composition comprising an aminofullerene derivative or its stereoisomer, optical isomer, deuterated derivative or solvate prepared by the preparation method of any one of claims 1-6, or an aminofullerene derivative or its stereoisomer, optical isomer, deuterated derivative or solvate as described in claim 7 or 8.

10. The application of the aminofullerene derivative or its stereoisomer, optical isomer, deuterated product or solvate prepared by the preparation method of any one of claims 1-6, the aminofullerene derivative or its stereoisomer, optical isomer, deuterated product or solvate of claim 7 or 8, or the composition of claim 9 in a battery; Alternatively, the application of the aminofullerene derivative or its stereoisomer, optical isomer, deuterated product or solvate prepared by the preparation method of any one of claims 1-6, the aminofullerene derivative or its stereoisomer, optical isomer, deuterated product or solvate of claim 7 or 8, or the composition of claim 9 in a solar cell. Alternatively, the application of the aminofullerene derivative or its stereoisomer, optical isomer, deuterated product or solvate prepared by the preparation method of any one of claims 1-6, the aminofullerene derivative or its stereoisomer, optical isomer, deuterated product or solvate of claim 7 or 8, or the composition of claim 9 in perovskite solar cells. Alternatively, the application of the aminofullerene derivative or its stereoisomer, optical isomer, deuterated product or solvate prepared by the preparation method of any one of claims 1-6, the aminofullerene derivative or its stereoisomer, optical isomer, deuterated product or solvate of claim 7 or 8, or the composition of claim 9 in the electron transport layer of a perovskite solar cell. Preferably, the perovskite solar cell includes an electron transport layer; Preferably, the electron transport layer significantly improves the overall performance of the perovskite solar cell.

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