Halogenated fullerene pyrrolidine derivative as well as preparation method and application thereof

Abstract

The invention provides a halogenated fullerene pyrrolidine derivative as well as a preparation method and application thereof. The halogenated fullerene pyrrolidine derivative has a structural general formula I, and a fullerene ring comprises a fullerene ring of C28-C120; each X is independently any one of a halogen atom and a C1-C3 halogenated alkyl group; n is an integer from 1 to 5; r comprises any one of substituted or unsubstituted C6-C20 aryl, 5-to 20-membered heteroaryl and C1-C6 alkyl, a substituent group of R comprises any one of halogen,-SH, C1-C6 alkyl or halogenated alkyl, 5-to 10-membered heteroaryl,-C (O) O (C1-C6) alkyl,-NR1R2,-P (O) (OR3) 2,-Si-(OR4) 3, 12-to 20 crown ether and 12-to 20 hetero-crown ether, and R1, R2, R3 and R4 are respectively and independently selected from any one of H, C1-C6 alkyl and t-butyloxycarboryl. # imgabs0 #

Description

Technical Field

[0001] The present application relates to the technical field of photoelectric conversion materials, and in particular to a halogenated fullerene pyrrolidine derivative, and a preparation method and application thereof. Background Art

[0002] Since its launch in 2009, the photoelectric conversion efficiency of perovskite solar cells has achieved rapid growth, catching up with the efficiency level of silicon-based solar cells. The device structure of perovskite solar cells is mainly divided into nip configuration and pin configuration. Although the nip configuration cell performs well in terms of photoelectric conversion efficiency, its stability limitations constitute an obstacle to the expansion of applications. On the contrary, although the pin configuration has a slightly lower photoelectric conversion efficiency, it has become the focus of academic and industrial attention due to its convenience of low-temperature solution processing, excellent long-term stability, and high adaptability to stacked cell design.

[0003] Traditional C 60 The evaporation method can achieve excellent performance layer construction, but its high cost and adverse effects on industrial large-scale manufacturing cannot be underestimated. In contrast, although the solution method still has room for improvement in several performance parameters, it has opened up broader practical and commercial prospects for perovskite solar cell technology due to its simple preparation process, significant cost-effectiveness, and flexibility to modify materials to meet specific needs. This method is not only highly coordinated with large-scale manufacturing systems, but also provides a practical strategic path for continuously optimizing material performance and enhancing the overall stability of devices.

[0004] In this context, fullerene, as an electron transport layer material, plays a key role in promoting the performance optimization of pin-type perovskite solar cells. 60 Derivative PCBM ([6,6]-phenyl-C 61 -Methyl butyrate) is still the mainstream choice for perovskite electron transport layer, but its synthesis is complex and costly. Therefore, designing and synthesizing new fullerene derivatives that can replace PCBM is a key technology for high-efficiency and low-cost perovskite solar cell materials. Summary of the invention

[0005] In order to reduce the preparation cost of electron transport layer materials for perovskite solar cells and achieve high electron transport efficiency, the present application provides a halogenated fullerene pyrrolidine derivative, and a preparation method and application thereof.

[0006] The first aspect of the present application provides a halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof. The halogenated fullerene pyrrolidine derivative has a general structural formula I:

[0007]

[0008] Wherein, the fullerene ring includes a C28-C120 fullerene ring; each X is independently any one of a halogen atom and a C1-C3 haloalkyl group; n is any integer from 1 to 5; R includes any one of a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted 5-20-membered heteroaryl group, and a substituted or unsubstituted C1-C6 alkyl group, and the substituent of R includes halogen, -SH, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a 5-10-membered heteroaryl group, a -C(O)O(C1-C6) alkyl group, -NR 1 R 2 、-P(O)(OR 3 )2、-Si-(OR 4 )3, any one of 12-20 crown ethers and 12-20 heterocrown ethers, R 1 , R 2 , each R 3 , each R 4 Each is independently selected from any one of H, C1-C6 alkyl and tert-butoxycarbonyl.

[0009] The structure of the fullerene and pyrrole ring coupling of the halogenated fullerene pyrrolidine derivative provided in the present application makes the halogenated fullerene pyrrolidine derivative have excellent structural stability; and the benzene ring connected to the pyrrole ring in the para position is substituted by a halogen-containing substituent X, and the presence of the halogen can improve the solubility by increasing the polarity between molecules. In addition, due to the strong electronegativity of the halogen, the electron affinity of the halogenated fullerene pyrrolidine derivative can be reduced, so that its ability to attract and transfer electrons can be further improved, and it can be used as a more efficient electron transport material.

[0010] When applied to perovskite solar cells, the photoelectric conversion efficiency (PCE) of perovskite cells can be improved, and the photoelectric performance is comparable to that of PCBM. In addition, the raw materials used to generate the above-mentioned halogenated fullerene pyrrolidine derivatives are easy to obtain, and the reaction also has the cost advantage of not requiring a metal catalyst and simple conditions.

[0011] In any embodiment of the first aspect, the fullerene ring is a C60 fullerene ring or a C70 fullerene ring.

[0012] In any embodiment of the first aspect, each X is independently any one of F, Cl, Br or C1-C3 haloalkyl, and can be selected from F, Cl, Br or trifluoromethyl, and can be further selected from F or Br; n is 1 or 2, and can be selected from 1.

[0013] In any embodiment of the first aspect, R includes any one of substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 5-10 membered heteroaryl, and C1-C3 alkyl substituted with 5-10 membered heteroaryl, and the substituents of the substituted C6-C10 aryl and substituted 5-10 membered heteroaryl in R include halogen, -SH, C1-C3 alkyl, C1-C3 haloalkyl, -C(O)O(C1-C3)alkyl, -NR 1 R 2 、-P(O)(OR 3 )2、-Si-(OR 4 )3, any one of 15-18 crown ether and 15-18 hetero crown ether, R 1 , R 2 , each R 3 , each R 4 Each is independently selected from any one of H, C1-C3 alkyl and tert-butyloxycarbonyl.

[0014] In any embodiment of the first aspect, the aryl group in the substituted or unsubstituted C6-C10 aryl group is a phenyl group.

[0015] In any embodiment of the first aspect, the heteroaryl in the substituted or unsubstituted 5-10 membered heteroaryl is any one of thienyl, furanyl, thiazolyl, pyridyl, pyrimidinyl, oxazolyl or imidazolyl, and can be optionally thiazolyl or pyridyl.

[0016] In any embodiment of the first aspect, the alkyl group in the C1-C3 alkyl group substituted with a 5-10 membered heteroaryl group is selected from methyl or ethyl, and the 5-10 membered heteroaryl group is selected from pyridyl or pyrimidinyl.

[0017] In any embodiment of the first aspect, R is selected from phenyl, thiazolyl or pyridyl, pyridyl is optionally 2-pyridyl, 3-pyridyl or 4-pyridyl, pyridyl is optionally 3-pyridyl or 4-pyridyl.

[0018] In any embodiment of the first aspect, the substituents of the substituted C6-C10 aryl and the substituted 5-10 membered heteroaryl in R include any one of halogen, -SH, methyl, ethyl, propyl, trifluoromethyl, -C(O)OCH3, -C(O)OCH2CH3, -NH2, -NHBoc, -P(O)(OH)2, -P(O)(OCH2CH3)2, -Si-(OCH3)3, 15-18 crown ether, 15-18 aza crown ether, and 15-18 nitrogen-sulfur co-crown ether.

[0019] In any embodiment of the first aspect, the substituent of the substituted C6-C10 aryl or substituted 5-10 membered heteroaryl in R is selected from ethyl or -C(O)OCH2CH3.

[0020] In any embodiment of the first aspect, the number of substituents of R is 0, 1, 2, 3, 4 or 5, and can be optionally 0 or 1.

[0021] In any embodiment of the first aspect, the halogenated fullerene pyrrolidine derivative has the following structural formula II:

[0022]

[0023] In any embodiment of the first aspect, the halogenated fullerene pyrrolidine derivative has the following structural formula III:

[0024]

[0025] In any embodiment of the first aspect, the halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof are selected from any one or more of the following compounds:

[0026]

[0027]

[0028]

[0029]

[0030] The second aspect of the present application provides a method for preparing a halogenated fullerene pyrrolidine derivative, which can prepare the halogenated fullerene pyrrolidine derivative in any embodiment of the first aspect, wherein the preparation method comprises: reacting fullerene, halogen-substituted N-phenylglycine, and a derivative of an aromatic aldehyde in a solvent to obtain a halogenated fullerene pyrrolidine derivative;

[0031] Halogen-substituted N-phenylglycine has the structural formula IV:

[0032]

[0033] Derivatives of aromatic aldehydes have the structural formula V:

[0034]

[0035] The definitions of X and n in structural formula IV and R in structural formula V are the same as those in the first aspect of the present application.

[0036] In any embodiment of the second aspect, the above reaction satisfies one or more of the following conditions: 1) the molar ratio of fullerene, halogen-substituted N-phenylglycine, and aromatic aldehyde derivatives is 1:(4-15):(2-15), optionally 1:(2-10):(2-10); 2) the reaction temperature is 60°C-150°C; 3) the solvent includes o-dichlorobenzene or chlorobenzene; 4) the reaction is carried out under the protection of nitrogen or an inert gas.

[0037] In any embodiment of the second aspect, the preparation method also includes a process of purifying the halogenated fullerene pyrrolidine derivative, and the eluent used for purification includes a mixture of one or more of CS2, petroleum ether and toluene, and optionally the eluent includes a mixture of petroleum ether and toluene in a volume ratio of 1:1 to 10:1.

[0038] The third aspect of the present application provides a use of a halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof in any embodiment of the first aspect in a battery.

[0039] The fourth aspect of the present application provides a perovskite solar cell, comprising an electron transport layer, the electron transport layer comprising a fullerene derivative, wherein the fullerene derivative comprises a halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof in any embodiment of the first aspect.

[0040] A fifth aspect of the present application provides a fuel cell, comprising an electrode assembly, wherein the electrode assembly comprises a fullerene derivative, wherein the fullerene derivative comprises a halogenated fullerene pyrrolidine derivative in any embodiment of the first aspect and a chemically acceptable salt thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the specific embodiments of the present invention, the drawings required for use in the specific embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0042] Figure 1 The fullerene pyrrolidine derivative L-6 synthesized in Synthesis Example 1 is shown. 1 HNMR spectrum;

[0043] Figure 2 The fullerene pyrrolidine derivative L-17 synthesized in Synthesis Example 2 is shown. 1 HNMR spectrum;

[0044] Figure 3 The fullerene pyrrolidine derivative L-56 synthesized in Synthesis Example 3 is shown. 1 HNMR spectrum;

[0045] Figure 4 The fullerene pyrrolidine derivative L-53 synthesized in Synthesis Example 4 is shown. 1 HNMR spectrum;

[0046] Figure 5 The fullerene pyrrolidine derivative L-51 synthesized in Synthesis Example 5 is shown. 1 HNMR spectrum;

[0047] Figure 6 The fullerene pyrrolidine derivative L-52 synthesized in Synthesis Example 6 is shown. 1 HNMR spectrum;

[0048] Figure 7 The fullerene pyrrolidine derivative L-40 synthesized in Synthesis Example 7 is shown. 1 HNMR spectrum;

[0049] Figure 8 The fullerene pyrrolidine derivative L-50 synthesized in Synthesis Example 8 is shown. 1 HNMR spectrum;

[0050] Fig. 9 The fullerene pyrrolidine derivative L-66 synthesized in Synthesis Example 9 is shown. 1 HNMR spectrum;

[0051] Fig.10 The fullerene pyrrolidine derivative L-69 synthesized in Synthesis Example 10 is shown. 1 H NMR spectrum;

[0052] Fig.11 The fullerene pyrrolidine derivative L-74 synthesized in Synthesis Example 11 is shown. 1 H NMR spectrum;

[0053] Fig.12 shows the mass spectrum of the fullerene pyrrolidine derivative L-74 synthesized in Synthesis Example 11;

[0054] Fig.13 The fullerene pyrrolidine derivative L-75 synthesized in Synthesis Example 12 is shown. 1 H NMR spectrum;

[0055] Fig.14 shows the mass spectrum of the fullerene pyrrolidine derivative L-75 synthesized in Synthesis Example 12;

[0056] Fig.15 The fullerene pyrrolidine derivative L-76 synthesized in Synthesis Example 13 is shown. 1 H NMR spectrum;

[0057] Fig.16 shows the mass spectrum of the fullerene pyrrolidine derivative L-76 synthesized in Synthesis Example 13;

[0058] Fig.17 The fullerene pyrrolidine derivative L-22 synthesized in Synthesis Example 14 is shown. 1 H NMR spectrum;

[0059] Fig.18 The fullerene pyrrolidine derivative L-67 synthesized in Synthesis Example 15 is shown. 1 H NMR spectrum;

[0060] Fig.19 The fullerene pyrrolidine derivative L-11 synthesized in Synthesis Example 16 is shown. 1 H NMR spectrum;

[0061] Fig. 20 The fullerene pyrrolidine derivative L-15 synthesized in Synthesis Example 17 is shown. 1 H NMR spectrum;

[0062] Fig.21 The fullerene pyrrolidine derivative L-16 synthesized in Synthesis Example 18 is shown. 1 H NMR spectrum;

[0063] Fig. 22 The fullerene pyrrolidine derivative L-78 synthesized in Synthesis Example 19 is shown. 1 H NMR spectrum;

[0064] Fig.23 The fullerene pyrrolidine derivative L-79 synthesized in Synthesis Example 20 is shown. 1 H NMR spectrum;

[0065] Fig.24 The JV curves of the photovoltaic device based on the fullerene pyrrolidine derivative L-22 in Application Example A1 and the photovoltaic device based on the non-halogenated fullerene pyrrolidine derivative F1 in Application Comparative Example 1 are shown;

[0066] Fig.25 shows the JV curve of the photovoltaic device based on the fullerene pyrrolidine derivative L-17 in Application Example A2;

[0067] Fig.26 shows the JV curve of the photovoltaic device based on the fullerene pyrrolidine derivative L-11 in Application Example A3;

[0068] Fig. 27 shows the JV curve of the photovoltaic device based on the fullerene pyrrolidine derivative L-15 in Application Example A4;

[0069] Fig.28 shows the JV curve of the photovoltaic device based on the fullerene pyrrolidine derivative L-16 in Application Example A5;

[0070] Fig.29 shows the JV curve of the photovoltaic device based on the fullerene pyrrolidine derivative L-78 in Application Example A6;

[0071] Fig.30 shows the JV curve of the photovoltaic device based on the fullerene pyrrolidine derivative L-79 in Application Example A7;

[0072] Fig.31 The JV curve of the photovoltaic device based on the fullerene derivative PCBM in Comparative Example 2 is shown;

[0073] Fig.32 The polarization curve and power density curve of the H2-O2 fuel cell based on the fullerene pyrrolidine derivative L-15 in Application Example B1 are shown;

[0074] Fig.33 The polarization curve and power density curve of the H2-Air fuel cell based on the fullerene pyrrolidine derivative L-15 in Application Example B1 are shown. DETAILED DESCRIPTION

[0075] The following embodiments further describe the implementation of the present application in detail. The detailed description of the following embodiments is used to illustrate the principle of the present application, but cannot be used to limit the scope of the present application, that is, the present application is not limited to the described embodiments.

[0076] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0077] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0078] Among the many fullerene derivatives, fullerene pyrrolidine derivatives have become the focus of current fullerene derivative research due to their ease of synthesis and high flexibility in structural modification. However, the synthesis of current fullerene pyrrolidine derivatives is complex and the preparation cost is high. In order to improve the electron transfer efficiency of fullerene pyrrolidine derivatives on the basis of reducing costs, the first embodiment of the present application provides a halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof, wherein the halogenated fullerene pyrrolidine derivative has a general structural formula I:

[0079]

[0080] Wherein, the fullerene ring includes a C28-C120 fullerene ring; each X is independently a halogen atom or a C1-C3 halogenated alkyl group; n is any integer from 1 to 5; and R includes a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted 5-20-membered heteroaryl group, or a substituted or unsubstituted C1-C6 alkyl group, and the substituent of R includes a halogen, -SH, a C1-C6 alkyl group, a C1-C6 halogenated alkyl group, a 5-10-membered heteroaryl group, a -C(O)O(C1-C6) alkyl group, or a -NR 1 R 2 、-P(O)(OR 3 )2、-Si-(OR 4 )3, any one of 12-20 crown ethers and 12-20 heterocrown ethers, R 1 , R 2 , each R 3 , each R 4 Each is independently selected from any one of H, C1-C6 alkyl and tert-butoxycarbonyl.

[0081] The structure of the fullerene and pyrrole ring coupling of the halogenated fullerene pyrrolidine derivative provided in the present application makes the halogenated fullerene pyrrolidine derivative have excellent structural stability; and the benzene ring connected to the pyrrole ring in the para position is substituted by a halogen-containing substituent X, and the presence of the halogen can improve the solubility by increasing the polarity between molecules. In addition, due to the strong electronegativity of the halogen, the electron affinity of the halogenated fullerene pyrrolidine derivative can be reduced, so that its ability to attract and transfer electrons can be further improved, and it can be used as a more efficient electron transport material.

[0082] When applied to perovskite solar cells, the photoelectric conversion efficiency (PCE) of perovskite cells can be improved, and the photoelectric performance is comparable to that of PCBM. In addition, the raw materials used to generate the above-mentioned halogenated fullerene pyrrolidine derivatives are easy to obtain, and the reaction also has the cost advantage of not requiring a metal catalyst and simple conditions.

[0083] In the above-mentioned halogenated fullerene pyrrolidine derivatives, the fullerene ring can be a C28-C120 fullerene ring, such as C28, C34, C60, C70, C84, C90, C104 or C120. Fullerene itself is a typical electron-deficient conjugated system, with properties similar to aromatic hydrocarbons, and can undergo a variety of chemical reactions such as cycloaddition, nucleophilic addition, electrophilic addition, free radical addition, photochemistry, and redox with certain substances. Based on the 1,3-dipolar cycloaddition mechanism of azomethine ylide intermediates, a series of fullerene pyrrolidines with high stereoselectivity can be prepared by cycloaddition of Schiff base intermediates synthesized from aldehydes, amines or amino acids with fullerenes.

[0084] The difference in the number of carbon atoms contained in the fullerene molecule is accompanied by the diversity of geometric structures. On this basis, fullerene molecules with different geometric structures have different stability. In some embodiments, the fullerene ring in the halogenated fullerene pyrrolidine derivative is C 60 Fullerene ring or C 70 Fullerene ring.

[0085] C 60 For example, it is generally composed of 12 five-membered rings and 20 six-membered rings, and each carbon atom adopts a similar sp 2 Hybridization, there is p orbital overlap between adjacent carbon atoms, forming a total of 30 C=C bonds, and all double bonds are alternately conjugated to form a highly delocalized large conjugated π system with good electron-accepting properties and high electron mobility.

[0086] C 70 Fullerene and C 60 Fullerenes have similar physical and chemical properties, and are composed of sp 2 The zero-dimensional conjugated spherical molecule composed of hybridized carbon atoms is composed of five-membered rings and six-membered rings, and conforms to the isolated pentagonal rule, with high conductivity. Compared with fullerene molecules with other carbon atoms, C 60 and C 70 It is more readily available and has a more stable nature.

[0087] The inventors have found through a large number of experimental preparations and test analyses that the halogenated fullerene pyrrolidine derivatives having the following side chain R composition have a relatively high yield.

[0088] In some embodiments, R includes any one of substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 5-10 membered heteroaryl, and C1-C3 alkyl substituted by 5-10 membered heteroaryl, and the substituents of the substituted C6-C10 aryl and substituted 5-10 membered heteroaryl in R include halogen, -SH, C1-C3 alkyl, C1-C3 haloalkyl, -C(O)O(C1-C3)alkyl, -NR 1 R 2 、-P(O)(OR 3 )2、-Si-(OR 4 )3, any one of 15-18 crown ether and 15-18 hetero crown ether, R 1 , R 2 , each R 3 , each R 4 Each is independently selected from any one of H, C1-C3 alkyl and tert-butyloxycarbonyl.

[0089] In some embodiments, in the substituted or unsubstituted C6-C10 aryl group included in R, the aryl group is phenyl;

[0090] In some embodiments, in the substituted or unsubstituted 5-10 membered heteroaryl group included in R, the heteroaryl group is any one of thienyl, furanyl, thiazolyl, pyridyl, pyrimidinyl, oxazolyl or imidazolyl, preferably thiazolyl or pyridyl;

[0091] In some embodiments, R includes a substituted or unsubstituted C1-C3 alkyl group, wherein the alkyl group is selected from methyl or ethyl;

[0092] In some embodiments, R is selected from phenyl, thiazolyl or pyridyl, pyridyl is optionally 2-pyridyl, 3-pyridyl or 4-pyridyl, pyridyl is optionally 3-pyridyl or 4-pyridyl;

[0093] In some embodiments, the substituents of the substituted C6-C10 aryl and substituted 5-10 membered heteroaryl in R include any one of halogen, -SH, methyl, ethyl, propyl, trifluoromethyl, -C(O)OCH3, -C(O)OCH2CH3, -NH2, -NHBoc, -P(O)(OH)2, -P(O)(OCH2CH3)2, -Si-(OCH3)3, 15-18 crown ether, 15-18 aza crown ether, and 15-18 aza-sulfur co-crown ether;

[0094] In some embodiments, the substituents of the substituted C6-C10 aryl and substituted 5-10 membered heteroaryl in R are selected from ethyl or -C(O)OCH2CH3;

[0095] In some embodiments, the number of substituents of R is 0, 1, 2, 3, 4 or 5, and can be optionally 0 or 1.

[0096] In some embodiments, each X in the general structural formula I is independently any one of F, Cl, Br or C1-C3 halogenated alkyl, and may be F, Cl, Br or trifluoromethyl, and may be further selected as F or Br; n is 1 or 2, and may be selected as 1, so that the effect of the halogen can be fully exerted.

[0097] In some embodiments, the halogenated fullerene pyrrolidine derivative has the following structural formula II:

[0098]

[0099] Although the mechanism is not yet clear, the inventors have found through a large number of experiments and tests that when X in the halogenated fullerene pyrrolidine derivative is in the para-N position, the electron transport performance is better.

[0100] In some embodiments, the halogenated fullerene pyrrolidine derivative has the following structural formula III:

[0101]

[0102] In some embodiments, the halogenated fullerene pyrrolidine derivative and its chemically acceptable salt are selected from any one or more of the following compounds:

[0103]

[0104]

[0105]

[0106] The second embodiment of the present application provides a method for preparing a halogenated fullerene pyrrolidine derivative, which can be used to prepare any one of the halogenated fullerene pyrrolidine derivatives in the first embodiment. The preparation method comprises: reacting fullerene, halogen-substituted N-phenylglycine, and a derivative of an aromatic aldehyde in a solvent to obtain a halogenated fullerene pyrrolidine derivative; the halogen-substituted N-phenylglycine has a structural formula IV:

[0107]

[0108] Derivatives of aromatic aldehydes have the structural formula V:

[0109]

[0110] The definitions of X and n in Structural Formula IV and R in Structural Formula V are consistent with those in the first embodiment and are not repeated here.

[0111] The present application utilizes the Prato reaction to synthesize halogenated fullerene pyrrolidine derivatives in one step to obtain a single [6,6] closed-ring product. Most of the precursors required for the reaction are commercially available or easy to prepare, so the preparation cost is low. Two substituents can be simultaneously introduced into the pyrrole ring to achieve product diversification.

[0112] Fullerene reacts with halogen-substituted amino acids and corresponding aldehydes under heating conditions to obtain halogenated fullerene pyrrolidine derivatives. The raw materials involved in the preparation method are cheap and easy to obtain, there is no metal catalyst, the generality is strong, the product yield is excellent, and the product halogenated fullerene pyrrolidine derivative is used as an electron transport material for perovskite solar cells, and has excellent performance.

[0113] In some embodiments, Select one of the following structural formulas:

[0114]

[0115] In some embodiments, Select one of the following structural formulas:

[0116]

[0117] In some embodiments, the above reaction satisfies one or more of the following conditions: 1) the molar ratio of fullerene, halogen-substituted N-phenylglycine, and aromatic aldehyde derivatives is 1: (4-15): (2-15), optionally 1: (2-10): (2-10); 2) the reaction temperature is 60°C to 150°C; 3) the solvent includes o-dichlorobenzene or chlorobenzene; 4) the reaction is carried out under the protection of nitrogen or an inert gas. Under the above reaction conditions, the synthesis efficiency is high, and a high reaction yield and product purity can be obtained. The specific raw materials, reaction conditions, etc. of the reaction can be flexibly adjusted by those skilled in the art based on the above description, and this application does not make any special restrictions. Exemplarily, the preparation method of halogenated fullerene pyrrolidine derivatives can be achieved by the following method: under the protection of N2 or an inert gas, add fullerene (for example, C 60 or C 70 ), halogen-substituted N-phenylglycine and the corresponding aromatic aldehyde derivatives, and then add o-dichlorobenzene (or chlorobenzene) thereto, ultrasonicate the reaction solution to completely dissolve it, and then place it in an oil bath at 60°C to 150°C and heat it until the reaction is completed.

[0118] In some embodiments, the preparation method further comprises a process of purifying the halogenated fullerene pyrrolidine derivative, wherein the eluent used for purification comprises a mixture of one or more of CS2, petroleum ether and toluene, and optionally the eluent comprises a mixture of petroleum ether and toluene in a volume ratio of 1:1 to 10:1.

[0119] In some embodiments, the purification process includes cooling the reaction solution to room temperature and then performing multiple separation and purification. First, the reaction product obtained by the reaction is filtered through a short silica gel column to remove insoluble matter, and the solvent is removed by rotary evaporation to obtain a crude product; the crude product is dissolved with CS2, and a long thin layer chromatography silica gel column is used for further separation and purification, and CS2 is first used as an eluent to recover unreacted fullerenes, and then the volume ratio of petroleum ether and toluene in the eluent is adjusted according to the polarity difference of the fullerene derivatives, and then elution is performed to obtain the target product halogenated fullerene pyrrolidine derivatives. The above purification process can be used as a reference for the purification process of conventional fullerene pyrrolidine derivatives, which will not be repeated here.

[0120] The third embodiment of the present application provides the use of any one of the halogenated fullerene pyrrolidine derivatives and chemically acceptable salts thereof in the first embodiment in a battery. The battery includes but is not limited to an organic solar cell, a perovskite solar cell, and a fuel cell.

[0121] The halogenated fullerene pyrrolidine derivatives are used as efficient electron transport materials in the above-mentioned batteries to improve the photoelectric conversion efficiency or the conversion efficiency of chemical energy into electrical energy.

[0122] The fourth embodiment of the present application provides a perovskite solar cell, comprising an electron transport layer, wherein the electron transport layer comprises a fullerene derivative, wherein the “fullerene derivative” herein comprises any one of the halogenated fullerene pyrrolidine derivatives and chemically acceptable salts thereof in the first embodiment.

[0123] In perovskite solar cells with organic metal halides as light-absorbing layers, considering that the solvent used to dissolve PbI2 is destructive to the structure of the organic electron transport layer, halogenated fullerene pyrrolidine derivatives and their chemically acceptable salts are mostly used in inverted (pin-type) structure devices, that is, deposited on the perovskite photoactive layer. The photoelectric performance of the halogenated fullerene pyrrolidine derivatives of the present application can reach a level comparable to that of PCBM, and the synthesis and separation process is extremely simple and easy, and can be used as an electron transport material to replace PCBM for the preparation of photovoltaic devices such as perovskite solar cells.

[0124] The fifth embodiment of the present application provides a fuel cell, including an electrode assembly, the electrode assembly including a fullerene derivative, wherein the "fullerene derivative" includes any one of the halogenated fullerene pyrrolidine derivatives and chemically acceptable salts thereof in the first embodiment. Compared with the electrode assembly of a conventional fuel cell, when the composition of the electrode assembly includes a halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof, the power density of the fuel cell can be significantly improved, thereby enhancing the power output capacity of the fuel cell.

[0125] The beneficial effects of the present application will be further illustrated below in combination with examples and comparative examples, but the scope of the present invention is not limited to these examples.

[0126] Unless otherwise specified, the raw materials and reagents used in the following examples and comparative examples can be purchased from commercial sources.

[0127] Synthesis Example 1

[0128] Synthesis and characterization of fullerene pyrrolidine derivative L-6:

[0129]

[0130] The specific synthesis steps are:

[0131] Weigh C 60(144.0 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.3 mg, 0.8 mmol) and 4-thiazolecarboxaldehyde (90.5 mg, 0.8 mmol) were dissolved in 20 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 2 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used to elute to remove the unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 5:1 as eluent to obtain a brown solid L-6 (84.5 mg, yield 45%).

[0132] like Figure 1 As shown, L-6 1 H NMR spectrum (500 MHz, CS2 / DMSO): δ8.87 (s, 1H), 8.24 (s, 1H), 7.51-7.50 (m, 2H), 7.11 (t, J=7.5 Hz, 2H), 6.92 (s, 1H), 5.50 (d, J=10.0 Hz, 1H), 5.14 (d, J=10.0 Hz, 1H).

[0133] APCI-MS: [M] - m / z = 939.3 (measured value), 940.05 (calculated value).

[0134] Synthesis Example 2

[0135] Synthesis and characterization of fullerene pyrrolidine derivative L-17:

[0136]

[0137] Weigh C 60 (144.0 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.3 mg, 0.8 mmol) and 4-propylthiazolecarboxaldehyde (31.1 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene, and the mixture was completely dissolved by sonication with an ultrasonicator; then, the mixture was stirred at 120°C for 1.5 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used to elute to remove unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 8:1 as eluent to obtain a brown solid L-17 (81.0 mg, yield 41%).

[0138] like Figure 2 As shown, L-17 1H NMR spectrum (500MHz, CS2 / DMSO): δ7.95(s,1H),7.49-7.47(m,2H),7.10(t,J=10.0Hz,2H),6.77(s,1H),5.46(d ,J=10.0Hz,1H),5.12(d,J=10.0Hz,1H),2.92(t,J=5.0Hz,2H),1.84-1.77(m,2H),0.99(t,J=7.5Hz,3H).

[0139] APCI-MS: [M] - m / z = 981.4 (measured value), 982.09 (calculated value).

[0140] Synthesis Example 3

[0141] Synthesis and characterization of fullerene pyrrolidine derivative L-56:

[0142]

[0143] Weigh C 60 (144.0 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.3 mg, 0.8 mmol) and oxazolecarboxaldehyde (0.06 mL, 0.8 mmol) were dissolved in 30 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 2.5 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 4:1 as eluent to obtain brown solid L-17 (81.0 mg, yield 41%).

[0144] like Figure 3 As shown, L-56 1 H NMR spectrum (500 MHz, CS2 / DMSO): δ8.14 (s, 1H), 7.46 (s, 1H), 7.36-7.35 (m, 2H), 7.14-7.09 (m, 3H), 5.56 (d, J=5.0 Hz, 1H), 5.42 (d, J=5.0 Hz, 1H).

[0145] APCI-MS: [M] - m / z = 925.8 (measured value), 924.07 (calculated value).

[0146] Synthesis Example 4

[0147] Synthesis and characterization of fullerene pyrrolidine derivative L-53:

[0148]

[0149] Weigh C 60 (144.0 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.3 mg, 0.8 mmol) and 4-formylphenyl ethyl phosphate (134.5 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 7 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 6:1 as eluent to obtain a brown solid L-53 (70.6 mg, 33%).

[0150] like Figure 4 As shown, L-53 1 H NMR spectrum (500 MHz, CS2 / DMSO): δ7.94-7.93 (m, 2H), 7.74-7.69 (m, 2H), 7.46-7.43 (m, 2H), 7.10 (t, J = 10 Hz, 2H), 6.24 (s, 1H), 5.68 (d, J = 10.0 Hz, 1H), 5.02 (d, J = 10.0 Hz, 1H), 4.02-3.93 (m, 4H), 1.29-1.26 (m, 6H).

[0151] APCI-MS: [M] - m / z = 1068.4 (measured value), 1069.12 (calculated value).

[0152] Synthesis Example 5

[0153] Synthesis and characterization of fullerene pyrrolidine derivative L-51:

[0154]

[0155] Weigh C 60 (144.0mg, 0.2mmol), 2-((4-fluorophenyl)amino)acetic acid (135.3mg, 0.8mmol) and thiophene carboxaldehyde (0.072mL, 0.8mmol) were dissolved in 30mL chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 2.5 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 Then petroleum ether and toluene in a volume ratio of 8:1 were used as eluent to obtain brown solid L-51 (81.6 mg, 44%).

[0156] like Figure 5 As shown, L-51 1 H NMR spectrum (500 MHz, CDCl3): δ7.41 (d, J = 5.0 Hz, 1H), 7.37 (s, 1H), 7.34 (d, J = 5.0 Hz, 3H), 7.30-7.29 (m, 1H), 7.00-6.99 (m, 1H), 6.56 (s, 1H), 5.57 (d, J = 10 Hz, 1H), 5.09 (d, J = 10.0 Hz, 1H).

[0157] APCI-MS: [M] - m / z = 954.8 (measured value), 955.02 (calculated value).

[0158] Synthesis Example 6

[0159] Synthesis and characterization of fullerene pyrrolidine derivative L-52:

[0160]

[0161] Weigh C 60 (144.0 mg, 0.2 mmol), 2-((4-chlorophenyl)amino)acetic acid (150.0 mg, 0.8 mmol) and 4-trifluoromethyl-2-pyridinecarboxaldehyde (140.1 mg, 0.8 mmol) were dissolved in 20 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 3.5 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 Then petroleum ether and toluene in a volume ratio of 4:1 were used as eluent to obtain brown solid L-52 (71.3 mg, 35%).

[0162] like Figure 6 As shown, L-52 1 H NMR spectrum (500MHz, CDCl3): δ8.95(s,1H),7.93(s,2H),7.34(d,J=10.0Hz,2H),7.2 0(d,J=10.0Hz,2H),6.55(s,1H),5.82(d,J=10Hz,2H),5.18(d,J=10.0Hz,1H).

[0163] APCI-MS: [M] - m / z = 1017.6 (measured value), 1018.05 (calculated value).

[0164] Synthesis Example 7

[0165] Synthesis and characterization of fullerene pyrrolidine derivative L-40:

[0166]

[0167] Weigh C 60 (144.0 mg, 0.2 mmol), 2-((4-bromophenyl)amino)acetic acid (184.2 mg, 0.8 mmol) and 4-bromo-3-pyridinebenzaldehyde (149.1 mg, 0.8 mmol) were dissolved in 20 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 4 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 Then petroleum ether and toluene in a volume ratio of 5:1 were used as eluent to obtain brown solid L-40 (73.1 mg, 34%).

[0168] like Figure 7 As shown, L-40 1 H NMR spectrum (500 MHz, CDCl3): δ8.80 (s, 1H), 7.98 (d, J = 10.0 Hz, 1H), 7.46 (d, J = 10.0 Hz, 1H), 7.38-7.35 (m, 2H), 7.11 (t, J = 7.5 Hz, 2H), 5.99 (s, 1H), 5.50 (d, J = 10.0 Hz, 1H), 4.89 (d, J = 10.0 Hz, 1H).

[0169] APCI-MS: [M] - m / z = 1071.4 (measured value), 1071.92 (calculated value).

[0170] Synthesis Example 8

[0171] Synthesis and characterization of fullerene pyrrolidine derivative L-50:

[0172]

[0173] Weigh C 60 (144.0 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.1 mg, 0.8 mmol) and 4-trifluoromethylpyridinecarboxaldehyde (140.1 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 8 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60Then petroleum ether and toluene in a volume ratio of 4:1 were used as eluent to obtain brown solid L-50 (70.1 mg, 29%).

[0174] like Figure 8 As shown, L-50 1 H NMR spectrum (500 MHz, CDCl3): δ8.98 (s, 1H), 8.11 (d, J = 10.0 Hz, 1H), 8.04 (d, J = 10.0 Hz, 1H), 7.33-7.31 (m, 2H), 7.06 (t, J = 7.5 Hz, 1H), 6.86 (s, 1H), 5.98 (d, J = 10.0 Hz, 1H), 5.28 (d, J = 10.0 Hz, 1H).

[0175] APCI-MS: [M] - m / z = 1001.3 (measured value), 1002.08 (calculated value).

[0176] Synthesis Example 9

[0177] Synthesis and characterization of fullerene pyrrolidine derivative L-66:

[0178]

[0179] Weigh C 60 (144.0 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.3 mg, 0.8 mmol) and pentafluorobenzaldehyde (272.1 mL, 0.8 mmol) were dissolved in 30 mL of chlorobenzene, and the mixture was completely dissolved by sonication using an ultrasonic device; then, the mixture was stirred at 120° C. for 10 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 10:1 as eluent to obtain a brown solid L-66 (70.1 mg, 31%).

[0180] like Fig. 9 As shown, L-66 1 H NMR spectrum (500 MHz, CDCl3): δ7.31-7.29 (m, 2H), 7.15 (t, J = 7.5 Hz, 2H), 7.04 (s, 1H), 5.58 (d, J = 10.0 Hz, 1H), 5.30 (dd, J = 5.0, 10.0 Hz, 1H).

[0181] APCI-MS: [M] - m / z = 1022.7 (measured value), 1023.05 (calculated value).

[0182] Synthesis Example 10

[0183] Synthesis and characterization of fullerene pyrrolidine derivative L-69:

[0184]

[0185] Weigh C 60 (144.0 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.3 mg, 0.8 mmol) and 4'-formylbenzo-18-crown-6 (272 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene, and the mixture was completely dissolved by sonication using an ultrasonicator; then, the mixture was stirred at 120°C for 10 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 5:1 as eluent to obtain brown solid L-69 (77.1 mg, 33%).

[0186] like Fig.10 As shown, L-66 1 H NMR spectrum (500MHz, CDCl3): δ7.45-7.42(m,2H),7.32-7.31(m,2H),7.11(t,J=7.5Hz,2H),6.85(d,J=10.0Hz,1H),6.03(s,1H),5.66(d,J=10.0Hz,1H), 4.96(d,J=10.0Hz,1H),4.08-4.04(m,3H),3.99-3.95(m,1H),3.81(t,J= 5.0Hz, 2H), 3.73 (t, J = 5.0Hz, 2H), 3.68-3.65 (m, 2H), 3.63-3.55 (m, 12H).

[0187] APCI-MS: [M] - m / z = 1167.1 (measured value), 1167.21 (calculated value).

[0188] Synthesis Example 11

[0189] Synthesis and characterization of fullerene pyrrolidine derivative L-74:

[0190]

[0191] Weigh C 70(188.0 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.32 mg, 0.8 mmol) and 4-pyridinecarboxaldehyde (0.075 mL, 0.8 mmol) were dissolved in 30 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 10 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used to elute to remove unreacted C 70 , and then using petroleum ether and toluene in a volume ratio of 6:1 as eluent to obtain a brown solid L-74 (78.0 mg, 37%).

[0192] like Fig.11 As shown, L-74 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ15.57 (s, 1H), 4.89 (d, J = 10.0Hz, 1H), 4.73 (d, J = 10.0Hz, 1H); δ2 5.47(s,1H),4.28(d,J=10.0Hz,1H),4.19(d,J=10.0Hz,1H); δ3 5.37(s,1H),5.33(d,J=10.0Hz,1H),4.43(d,J=10.0Hz,1H); δ4 5.13(s,1H),4.95(d,J=10.0Hz,1H),3.99(d,J=10.0Hz,1H). L-74 is composed of 4 isomers, and the ratio of the isomers is obtained by integrating the signal peaks in the pyrrolidine region, which is 0.23:0.22:0.42:0.13.

[0193] like Fig.12 As shown, APCI-MS: [M] - m / z = 1053.35 (measured value), 1054.09 (calculated value).

[0194] Synthesis Example 12

[0195] Synthesis and characterization of fullerene pyrrolidine derivative L-75:

[0196]

[0197] Weigh C 70(188.0 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.32 mg, 0.8 mmol) and 2-aminopyrimidinecarboxaldehyde (197 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 10 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 70 , and then using petroleum ether and toluene in a volume ratio of 4:1 as eluent to obtain a brown solid L-75 (72.8 mg, 34%).

[0198] like Fig.13 As shown, L-75 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ15.42(s,1H),4.76(d,J=10.0Hz,1H),4.12(d,J =10.0Hz,1H); δ25.30(s,1H),4.81(d,J=10.0Hz,1H),4.19(d,J=10.0Hz,1H); δ3 5.20(d,J=10.0Hz,1H),5.18(s,1H),4.33(d,J=10.0Hz,1H); δ4 4.96(s,1H),4.59(d,J=10.0Hz,1H),3.90(d,J=10.0Hz,1H). L-75 is composed of 4 isomers, and the ratio of the isomers is obtained by integrating the signal peaks in the pyrrolidine region, which is 0.26:0.21:0.36:0.17.

[0199] like Fig.14 As shown, APCI-MS: [M] - m / z = 1069.30 (measured value), 1070.10 (calculated value).

[0200] Synthesis Example 13

[0201] Synthesis and characterization of fullerene pyrrolidine derivative L-76:

[0202]

[0203] Weigh C 70(188.0 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.32 mg, 0.8 mmol) and 4'-formylbenzo-18-crown-6 (272 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene, and the mixture was completely dissolved by sonication using an ultrasonicator; then, the mixture was stirred at 120°C for 10 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used to elute to remove the unreacted C 70 , and then using petroleum ether and toluene in a volume ratio of 4:1 as eluent to obtain a brown solid L-76 (92.8 mg, 36%).

[0204] like Fig.15 As shown, L-76 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ1 5.38(s,1H),4.88(d,J=10.0Hz,1H),4.72(d,J=10.0Hz,1H); δ25.34(d,J=10.0Hz,1H),5.18(s,1H),4.36(d,J=10.0Hz,1H); δ3 5.29 (s, 1H), 4.88 (d, J = 10.0Hz, 1H), 4.72 (d, J = 10.0Hz, 1H); δ 44.96 (s, 1H), 4.94 (d, J = 10.0Hz, 1H), 4.21-4.19 (m, 1H). L-76 is composed of 4 isomers, and the ratio of the isomers is obtained by integrating the signal peaks in the pyrrolidine region, which is 0.25:0.24:0.34:0.17.

[0205] like Fig.16 As shown, APCI-MS: [M] - m / z = 1287.20 (measured value), 1287.21 (calculated value).

[0206] Synthesis Example 14

[0207] Synthesis and characterization of fullerene pyrrolidine derivative L-22:

[0208]

[0209] Weigh C 60(144 mg, 0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.32 mg, 0.8 mmol) and ethyl 4-formylbenzoate (62.5 μL, 0.8 mmol) were dissolved in 20 mL of chlorobenzene, and the mixture was completely dissolved by sonication using an ultrasonicator; then, the mixture was stirred and reacted at 120° C. for 6 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 5:1 as eluent to obtain a brown solid L-22 (83 mg, yield 41%).

[0210] like Fig.17 As shown, L-22 1 H NMR spectrum (500MHz, CDCl3): δ8.03(d,J=5.0Hz,2H),7.89(d,J=10.0Hz,2H),7.38~7.30(m,2H),7.08(t,J=5.0Hz, 2H), 6.13 (s, 1H), 5.68 (d, J = 10.0Hz, 1H), 5.0 (d, J = 10.0Hz, 1H), 4.33 (q, J = 8.3Hz, 2H), 1.35 (t, J = 7.5Hz, 3H).

[0211] APCI-MS: [M] - m / z = 1004.6 (measured value), 1005.12 (calculated value).

[0212] Synthesis Example 15

[0213] Synthesis and characterization of fullerene pyrrolidine derivative L-67:

[0214]

[0215] Weigh C 60 (144 mg, 0.2 mmol), 2-((4-trifluoromethylphenyl)amino)acetic acid (175.33 mg, 0.8 mmol) and 4-pyridinecarboxaldehyde (0.075 mL, 0.8 mmol) were dissolved in 20 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 6 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 5:1 as eluent to obtain a brown solid L-67 (68.9 mg, yield 35%).

[0216] like Fig.18 As shown, L-671 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ8.62(d,J=5.0Hz,2H),7.77(d,J=10.0Hz,2H),7.62(d,J=10. 0Hz, 2H), 7.42 (d, J = 5.0Hz, 2H), 6.62 (s, 1H), 5.93 (d, J = 10.0Hz, 1H), 5.41 (d, J = 15.0Hz, 1H).

[0217] APCI-MS: [M] - m / z = 983.8 (measured value), 984.09 (calculated value).

[0218] Synthesis Example 16

[0219] Synthesis and characterization of fullerene pyrrolidine derivative L-11:

[0220]

[0221] Weigh C 60 (288 mg, 0.4 mmol), 2-((4-fluorophenyl)amino)acetic acid (270.6 mg, 1.6 mmol) and 2-pyridinecarboxaldehyde (0.15 mL, 1.6 mmol) were dissolved in 20 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 6 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 5:1 as eluent to obtain a brown solid L-11 (138.2 mg, yield 37%).

[0222] like Fig.19 As shown, L-11 1 H NMR spectrum (500 MHz, CS2 / DMSO-d6): δ8.71 (d, J=5.0 Hz, 1H), 7.84 (d, J=10.0 Hz, 1H), 7.74-7.71 (m, 1H), 7.32-7.25 (m, 3H), 7.05 (t, J=10.0 Hz, 2H), 6.64 (s, 1H), 5.98 (d, J=5.0 Hz, 1H), 5.24 (d, J=5.0 Hz, 1H).

[0223] APCI-MS: [M] - m / z = 933.3 (measured value), 934.09 (calculated value).

[0224] Synthesis Example 17

[0225] Synthesis and characterization of fullerene pyrrolidine derivative L-15:

[0226]

[0227] Weigh C 60 (288 mg, 0.4 mmol), 2-((4-fluorophenyl)amino)acetic acid (270.6 mg, 1.6 mmol) and 3-pyridinecarboxaldehyde (0.15 mL, 1.6 mmol) were dissolved in 20 mL of chlorobenzene, and the mixture was completely dissolved by sonication with an ultrasonicator; then, the mixture was stirred at 120°C for 6 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 5:1 as eluent to obtain a brown solid L-15 (153.2 mg, yield 41%).

[0228] like Fig. 20 As shown, L-15 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ9.03(d,J=5.0Hz,1H),8.50(d,J=5.0Hz,1H),8.12(d,J=10.0Hz,1H),7.49-7.46 (m,2H),7.31-7.28(m,1H),7.11(t,J=10.0Hz,2H),6.26(s,1H),5.64(d,J=10.0Hz,1H),5.02(d,J=10.0Hz,1H).

[0229] APCI-MS: [M] - m / z = 933.3 (measured value), 934.09 (calculated value).

[0230] Synthesis Example 18

[0231] Synthesis and characterization of fullerene pyrrolidine derivative L-16:

[0232]

[0233] Weigh C 60 (288 mg, 0.4 mmol), 2-((4-fluorophenyl)amino)acetic acid (270.6 mg, 1.6 mmol) and 4-pyridinecarboxaldehyde (0.15 mL, 1.6 mmol) were dissolved in 20 mL of chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 5 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60, and then using petroleum ether and toluene in a volume ratio of 5:1 as eluent to obtain a brown solid L-16 (160.7 mg, yield 43%).

[0234] like Fig.21 As shown, L-16 1 H NMR spectrum (500 MHz, CS2 / DMSO-d6): δ8.56 (t, J=5.0 Hz, 2H), 7.74 (d, J=5.0 Hz, 2H), 7.45-7.42 (m, 2H), 7.11 (t, J=10.0 Hz, 3H), 6.21 (s, 1H), 5.67 (d, J=10.0 Hz, 1H), 5.02 (d, J=10.0 Hz, 1H).

[0235] APCI-MS: [M] - m / z = 933.3 (measured value), 934.09 (calculated value).

[0236] Synthesis Example 19

[0237] Synthesis and characterization of fullerene pyrrolidine derivative L-78:

[0238]

[0239] Weigh C 60 (288mg, 0.4mmol), 2-((4-chlorophenyl)amino)acetic acid (297mg, 1.6mmol) and 4-pyridinecarboxaldehyde (0.15mL, 1.6mmol) were dissolved in 20mL chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 6 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 6:1 as eluent to obtain a brown solid L-78 (148.2 mg, yield 39%).

[0240] like Fig. 22 As shown, L-78 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ8.59 (d, J = 5.0 Hz, 2H), 7.73 (d, J = 5.0 Hz, 1H), 7.34 (s, 4H), 6.29 (s, 1H), 5.76 (d, J = 10.0 Hz, 1H), 5.11 (d, J = 10.0 Hz, 1H).

[0241] APCI-MS: [M] - m / z = 949.6 (measured value), 950.06 (calculated value).

[0242] Synthesis Example 20

[0243] Synthesis and characterization of fullerene pyrrolidine derivative L-79:

[0244]

[0245] Weigh C 60 (288mg, 0.4mmol), 2-((4-bromophenyl)amino)acetic acid (360mg, 1.6mmol) and 4-pyridinecarboxaldehyde (0.15mL, 1.6mmol) were dissolved in 20mL chlorobenzene, and the mixture was completely dissolved by ultrasonication; then, the mixture was stirred at 120°C for 5 hours under N2 protection; after the reaction, the reaction solution was cooled to room temperature and then concentrated in vacuo, and then separated by column chromatography, and CS2 was used for elution to remove unreacted C 60 , and then using petroleum ether and toluene in a volume ratio of 6:1 as eluent to obtain a brown solid L-79 (147.1 mg, yield 37%).

[0246] like Fig.23 As shown, L-79 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ8.59(d,J=5.0Hz,2H),7.73(d,J=5.0Hz,2H),7.48(d,J=5.0 Hz, 2H), 7.29 (d, J = 5.0 Hz, 2H), 6.30 (s, 1H), 5.77 (d, J = 10.0 Hz, 1H), 5.13 (d, J = 10.0 Hz, 1H).

[0247] APCI-MS: [M] - m / z = 993.5 (measured value), 994.01 (calculated value).

[0248] Application Example A1: Application of halogenated fullerene pyrrolidine derivative L-22 in perovskite solar cells

[0249]

[0250] Perovskite solar cells are prepared as follows:

[0251] (1) Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) was dissolved in chlorobenzene at a concentration of 2 mg / mL, and the resulting solution was spin-coated on a pre-cleaned indium tin oxide (ITO) conductive glass and annealed at 100°C for 10 min. Formamidine iodide (FAI), methylamine iodide (MAI), cesium iodide (CsI), lead iodide (PbI2), and lead bromide (PbBr2) powders were prepared according to (FAI)0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 )3 components are mixed and dissolved in a mixed solvent of N,N-dimethylacetamide / dimethyl sulfoxide with a volume ratio of 4:1 to prepare a perovskite precursor solution with a concentration of 1.4 mol / L. The pre-prepared perovskite precursor solution is then spin-coated on a PTAA substrate and annealed at 110°C for 30 minutes to obtain a perovskite photoactive layer;

[0252] (2) fully dissolving the halogenated fullerene pyrrolidine derivative L-22 in o-dichlorobenzene at a concentration of 20 mg / mL, and spin-coating the solution on the perovskite photoactive layer as a fullerene electron transport layer;

[0253] (3) dissolving 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in isopropanol at a concentration of 0.5 mg / mL, and spin-coating the resulting solution on the fullerene electron transport layer as a hole blocking layer;

[0254] (4) 100 nm of Ag was evaporated onto the hole blocking layer to prepare a silver electrode, thereby obtaining a photovoltaic device (perovskite solar cell) based on L-22.

[0255] The photovoltaic performance of the above perovskite solar cells was measured:

[0256] At a light intensity of 100 mW / cm 2 The open circuit voltage, short circuit current density, fill factor, and photoelectric conversion efficiency of the L-22-based perovskite solar cell were measured under AM 1.5G simulated sunlight. The current density-voltage (JV) characteristic curve of the photovoltaic device is shown in Figure 2. Fig.24 shown.

[0257] Application Example A2:

[0258] The halogenated fullerene pyrrolidine derivative L-17 was used to replace the halogenated fullerene pyrrolidine derivative L-22 in Application Example A1, and the rest was the same as Application Example A1.

[0259]

[0260] At a light intensity of 100 mW / cm 2 The open circuit voltage, short circuit current density, fill factor, and photoelectric conversion efficiency of the L-17-based perovskite solar cell were measured under AM 1.5G simulated sunlight. The current density-voltage (JV) characteristic curve of the photovoltaic device is shown in Figure 2. Fig.25 shown.

[0261] Application Example A3

[0262] The halogenated fullerene pyrrolidine derivative L-11 was used to replace the halogenated fullerene pyrrolidine derivative L-22 in Application Example A1, and the rest was the same as Application Example A1.

[0263]

[0264] The photovoltaic performance of the above perovskite solar cells was measured:

[0265] At a light intensity of 100 mW / cm 2 The open circuit voltage, short circuit current density, fill factor, and photoelectric conversion efficiency of the L-11-based perovskite solar cell were measured under AM 1.5G simulated sunlight. The current density-voltage (JV) characteristic curve of the photovoltaic device is shown in Figure 2. Fig.26 shown.

[0266] Application Example A4:

[0267] The halogenated fullerene pyrrolidine derivative L-15 was used to replace the halogenated fullerene pyrrolidine derivative L-22 in Application Example A1, and the rest was the same as Application Example A1.

[0268]

[0269] The photovoltaic performance of the above perovskite solar cells was measured:

[0270] At a light intensity of 100 mW / cm 2 The open circuit voltage, short circuit current density, fill factor, and photoelectric conversion efficiency of the L-15-based perovskite solar cell were measured under AM 1.5G simulated sunlight. The current density-voltage (JV) characteristic curve of the photovoltaic device is shown in Figure 2. Fig. 27 shown.

[0271] Application Example A5:

[0272] The halogenated fullerene pyrrolidine derivative L-16 was used to replace the halogenated fullerene pyrrolidine derivative L-22 in Application Example A1, and the rest was the same as Application Example A1.

[0273]

[0274] The photovoltaic performance of the above perovskite solar cells was measured:

[0275] At a light intensity of 100 mW / cm 2The open circuit voltage, short circuit current density, fill factor, and photoelectric conversion efficiency of the L-16-based perovskite solar cell were measured under AM 1.5G simulated sunlight. The current density-voltage (JV) characteristic curve of the photovoltaic device is shown in Fig.28 shown.

[0276] Application Example A6:

[0277] The halogenated fullerene pyrrolidine derivative L-78 was used to replace the halogenated fullerene pyrrolidine derivative L-22 in Application Example A1, and the rest was the same as Application Example A1.

[0278]

[0279] The photovoltaic performance of the above perovskite solar cells was measured:

[0280] At a light intensity of 100 mW / cm 2 The open circuit voltage, short circuit current density, fill factor, and photoelectric conversion efficiency of the L-78-based perovskite solar cell were measured under AM 1.5G simulated sunlight. The current density-voltage (JV) characteristic curve of the photovoltaic device is shown in Figure 2. Fig.29 shown.

[0281] Application Example A7:

[0282] The halogenated fullerene pyrrolidine derivative L-79 was used to replace the halogenated fullerene pyrrolidine derivative L-22 in Application Example A1, and the rest was the same as Application Example A1.

[0283]

[0284] The photovoltaic performance of the above perovskite solar cells was measured:

[0285] At a light intensity of 100 mW / cm 2 The open circuit voltage, short circuit current density, fill factor, and photoelectric conversion efficiency of the L-79-based perovskite solar cell were measured under AM 1.5G simulated sunlight. The current density-voltage (JV) characteristic curve of the photovoltaic device is shown in Fig.30 shown.

[0286] Application Comparative Example 1:

[0287] The non-halogenated fullerene pyrrolidine derivative F1 was used to replace the halogenated fullerene pyrrolidine derivative L-22 in Application Example A1, and the rest was the same as Application Example A1.

[0288] The molecular structure of the non-halogenated fullerene pyrrolidine derivative F1 is:

[0289]

[0290] The photovoltaic performance of the above perovskite solar cells was measured:

[0291] At a light intensity of 100 mW / cm 2 The open circuit voltage, short circuit current density, fill factor, and photoelectric conversion efficiency of the F1-based perovskite solar cell were measured under AM 1.5G simulated sunlight. The current density-voltage (JV) characteristic curve of the photovoltaic device is shown in Figure 2. Fig.24 shown.

[0292] Application Comparative Example 2:

[0293] The fullerene derivative PCBM was used to replace the halogenated fullerene pyrrolidine derivative L-22 in Application Example A1, and the rest was the same as in Application Example A1.

[0294] The molecular structure of fullerene derivative PCBM is as follows:

[0295]

[0296] Perovskite solar cells are prepared as follows:

[0297] The photovoltaic performance of the above perovskite solar cells was measured:

[0298] At a light intensity of 100 mW / cm 2 Under AM 1.5G simulated sunlight, the open circuit voltage, short circuit current density, fill factor, and photoelectric conversion efficiency of the PCBM-based perovskite solar cell were measured. The current density-voltage (JV) characteristic curve of the photovoltaic device is shown in Fig.31 shown.

[0299] According to the current density-voltage (JV) characteristic curve, the open circuit voltage, short circuit current density and fill factor can be obtained. The intersection of the JV curve and the horizontal axis of the coordinate axis corresponds to the open circuit voltage (V oc ), the unit is V; the value corresponding to the intersection of the JV curve and the vertical axis of the coordinate axis is the short-circuit current density (J sc ), unit is mA / cm 2 ; The point in the JV curve corresponding to the maximum power of the perovskite solar cell is P max (V max ,J max ), the fill factor (FF) can be calculated as follows: FF = (V max ·J max ) / (V oc ·J sc); Photovoltaic conversion efficiency (PCE) refers to the efficiency of perovskite solar cells in converting solar energy into electrical energy, which can be calculated as follows: PCE = (V oc ·J sc FF) / P in , where P in The irradiance power of AM 1.5G simulated sunlight is 100mW / cm 2 .

[0300] The open circuit voltage, short circuit current density, fill factor, and photoelectric conversion efficiency of the above application examples A1 to A7 and application comparative examples 1 and 2 are recorded in Table 1.

[0301] Table 1

[0302]

[0303] It can be seen that the photoelectric conversion performance of the above-mentioned halogenated fullerene pyrrolidine derivatives L-22, L-17, L-11, L-15, L-16, L-78 and L-79 is comparable to that of PCBM, and the synthesis and separation process is extremely simple and easy. The halogenated fullerene pyrrolidine derivatives of the present invention can be used as electron transport materials to replace PCBM for the preparation of photovoltaic devices such as perovskite solar cells. Moreover, compared with the non-halogenated fullerene pyrrolidine derivative F1, the photoelectric conversion efficiency of the perovskite solar cell made of the halogenated fullerene pyrrolidine derivative L-22 of the present invention is significantly higher.

[0304] Application Example B1: Application of halogenated fullerene pyrrolidine derivative L-15 in fuel cells

[0305] The preparation method of fuel cell with L-15 as electrode additive is as follows:

[0306] Commercial Pt / C, Nafion and homemade fullerene were dissolved in isopropanol to prepare ink.

[0307] The prepared ink was sprayed on both sides of the proton exchange membrane (Gore, thickness 12 μm) to form an electrode area of ​​5 cm 2 Catalyst coated membrane (CCM);

[0308] The obtained CCM was placed between two sheets of carbon paper to make a membrane electrode assembly (MEA);

[0309] The above membrane electrode assemblies were assembled into H2-O2 fuel cells and H2-Air fuel cells, respectively, wherein the flow rates of H2 and O2 / Air gas were both 1000 sccm / 1000 sccm (2000 sccm), the back pressure was 100 KPa, and the loading amounts of noble metals at the anode and cathode were both 0.1 mg·cm -2 .

[0310] The H2-O2 fuel cell was tested using an 850E Multi Range fuel cell test station at a cell temperature of 80°C. After the introduction of the halogenated fullerene pyrrolidine derivative L-15, the power density increased from 1.87 W cm -2 Increased to 2.83W·cm -2 The polarization curve and power density curve of the fuel cell with L-15 as an electrode additive are shown in Fig.32 shown.

[0311] The H2-Air fuel cell was tested using an 850E Multi Range fuel cell test station at a cell temperature of 80°C. After the introduction of the halogenated fullerene pyrrolidine derivative L-15, the power density increased from 0.84 W·cm -2 Increased to 1.6W·cm -2 The polarization curve and power density curve of the fuel cell with L-15 as an electrode additive are shown in Fig.33 shown.

[0312] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof, wherein the halogenated fullerene pyrrolidine derivative has a general structural formula I: in, Fullerene rings include C28-C120 fullerene rings; Each X is independently any one of a halogen atom and a C1-C3 haloalkyl group; n is any integer from 1 to 5; R includes any one of substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 5-20-membered heteroaryl, substituted or unsubstituted C1-C6 alkyl, and the substituent of R includes halogen, -SH, C1-C6 alkyl, C1-C6 haloalkyl, 5-10-membered heteroaryl, -C(O)O(C1-C6)alkyl, -NR 1 R 2 、-P(O)(OR 3 )2、-Si-(OR 4 )3, any one of 12-20 crown ethers and 12-20 heterocrown ethers, R 1 , R 2 , each R 3 , each R 4 Each is independently selected from any one of H, C1-C6 alkyl and tert-butoxycarbonyl.

2. The halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof according to claim 1, wherein: The fullerene ring is a C60 fullerene ring or a C70 fullerene ring.

3. The halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof according to claim 1 or 2, wherein: Each X is independently any one of F, Cl, Br or C1-C3 haloalkyl, and may be F, Cl, Br or trifluoromethyl, and may be further F or Br; n is 1 or 2, and can be 1 if desired.

4. The halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof according to any one of claims 1 to 3, wherein: The R includes any one of substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 5-10 membered heteroaryl, and C1-C3 alkyl substituted with 5-10 membered heteroaryl. The substituents of the substituted C6-C10 aryl and substituted 5-10 membered heteroaryl in R include halogen, -SH, C1-C3 alkyl, C1-C3 haloalkyl, -C(O)O(C1-C3)alkyl, -NR 1 R 2 、-P(O)(OR 3 )2、-Si-(OR 4 )3, any one of 15-18 crown ether and 15-18 hetero crown ether, R 1 , R 2 , each R 3 , each R 4 Each is independently selected from any one of H, C1-C3 alkyl, and tert-butyloxycarbonyl; Optionally, the aryl group in the substituted or unsubstituted C6-C10 aryl group is phenyl; Optionally, the heteroaryl in the substituted or unsubstituted 5-10-membered heteroaryl is any one of thienyl, furanyl, thiazolyl, pyridyl, pyrimidinyl, oxazolyl or imidazolyl, and may be thiazolyl or pyridyl; Optionally, the alkyl group in the C1-C3 alkyl group substituted with a 5-10 membered heteroaryl group is selected from methyl or ethyl, and the 5-10 membered heteroaryl group is selected from pyridyl or pyrimidinyl; Optionally, the R is selected from phenyl, thiazolyl or pyridyl, the pyridyl is optionally 2-pyridyl, 3-pyridyl or 4-pyridyl, the pyridyl is optionally 3-pyridyl or 4-pyridyl; Optionally, the substituents of the substituted C6-C10 aryl and substituted 5-10 membered heteroaryl in R include any one of halogen, -SH, methyl, ethyl, propyl, trifluoromethyl, -C(O)OCH3, -C(O)OCH2CH3, -NH2, -NHBoc, -P(O)(OH)2, -P(O)(OCH2CH3)2, -Si-(OCH3)3, 15-18 crown ether, 15-18 aza crown ether, and 15-18 nitrogen-sulfur co-crown ether; Optionally, the substituent of the substituted C6-C10 aryl or substituted 5-10 membered heteroaryl in R is selected from ethyl or -C(O)OCH2CH3. Optionally, the number of substituents of R is 0, 1, 2, 3, 4 or 5, and can be 0 or 1.

5. The halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof according to any one of claims 1 to 4, wherein: The halogenated fullerene pyrrolidine derivative has the following general structural formula II:

6. The halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof according to any one of claims 1 to 4, wherein: The halogenated fullerene pyrrolidine derivative has the following general structural formula III:

7. The halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof according to claim 1, wherein: The halogenated fullerene pyrrolidine derivative and its chemically acceptable salt are selected from any one or more of the following compounds:

8. A method for preparing a halogenated fullerene pyrrolidine derivative according to any one of claims 1 to 7, wherein: The preparation method comprises: reacting fullerene, halogen-substituted N-phenylglycine, and a derivative of an aromatic aldehyde in a solvent to obtain the halogenated fullerene pyrrolidine derivative; The halogen-substituted N-phenylglycine has the structural formula IV: The aromatic aldehyde derivative has the structural formula V: The definitions of X and n in the structural formula IV and R in the structural formula V are the same as those in any one of claims 1 to 7.

9. The preparation method according to claim 8, wherein: The reaction satisfies one or more of the following conditions: 1) The molar ratio of the fullerene, the halogen-substituted N-phenylglycine, and the aromatic aldehyde derivative is 1:(4-15):(2-15), or optionally 1:(2-10):(2-10); 2) The reaction temperature is 60°C-150°C; 3) The solvent includes o-dichlorobenzene or chlorobenzene; 4) The reaction is carried out under the protection of nitrogen or inert gas.

10. The preparation method according to claim 8 or 9, wherein: The preparation method also includes a process of purifying the halogenated fullerene pyrrolidine derivative, wherein the eluent used for purification includes a mixture of one or more of CS2, petroleum ether and toluene, and optionally the eluent includes a mixture of petroleum ether and toluene in a volume ratio of 1:1 to 10:

1.

11. Use of the halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof according to any one of claims 1 to 7 in a battery.

12. A perovskite solar cell comprising an electron transport layer, the electron transport layer comprising a fullerene derivative, wherein the fullerene derivative comprises the halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof according to any one of claims 1 to 7.

13. A fuel cell comprising an electrode assembly, the electrode assembly comprising a fullerene derivative, wherein the fullerene derivative comprises the halogenated fullerene pyrrolidine derivative and a chemically acceptable salt thereof according to any one of claims 1 to 7.

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