Covalent organic framework materials and their use in organic photo-charge cells

Abstract

This invention discloses covalent organic framework materials and their use in organic photovoltaic cells. The covalent organic framework materials of this invention include photoresponsive active sites, which can be photoexcited to perform anion and / or cation insertion / extraction; the active sites include at least active sites for anion insertion and / or active sites for cation insertion. This invention also provides an organic photovoltaic dual-ion battery based on covalent organic framework materials. The covalent organic framework materials of this invention couple anion and cation insertion / extraction active sites, and through composite electron transport layer materials / hole transport layer materials, the flow of photogenerated carriers between the positive and negative electrodes of the photovoltaic cell is directionally regulated. When assembled into an organic photovoltaic cell under the wetting of an organic electrolyte, it can achieve efficient storage and conversion of solar energy into electrochemical energy.

Description

Technical Field

[0001] This invention relates to the field of battery technology, and more specifically, to covalent organic framework materials and their use in organic photochargeable dual-ion batteries. Background Technology

[0002] Photoelectrochemical energy storage and conversion, as an important technology in the emerging energy field, has made great progress. Photoelectrochemical energy storage technology can reduce the impact of the intermittency of sunlight by integrating solar cells with energy storage systems to balance daytime (sunlight) production and nighttime (dark field) demand, realizing a day-night cycle of solar energy conversion.

[0003] Organic photocells, with their stable electrochemical window and high photoresponse voltage, are considered to be photoresponsive energy storage devices with great application potential. Currently, lithium-ion batteries, as the most widely used organic battery system, have already powered small portable electronic devices and large electric vehicles. However, the limited natural resources of lithium minerals still hinder the further widespread application of lithium-ion batteries. Furthermore, problems such as dendrite growth and solid electrolyte interface corrosion associated with using metallic lithium electrodes cannot be ignored. Therefore, coupling lithium-ion battery structures and photoresponsive materials together is not the most ideal approach for practical application. How to rationally design and construct efficient, lithium-free novel organic photocells has become an urgent technical problem to be solved. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention is achieved through the following technical solution:

[0005] A covalent organic framework material having photoresponsive ion intercalation / deintercalation active sites, wherein the active sites have at least one, two, or more photoresponsive anion intercalation / deintercalation activities and / or photoresponsive cation intercalation / deintercalation activities.

[0006] Preferably, the active site available for anion insertion is selected from at least one of nitrogen cations and nitro groups.

[0007] Preferably, the active site available for cation intercalation is selected from at least one of carbonyl / hydroxyl, porphyrin nitrogen, pyridine nitrogen, imine, azo, nitroxide radical, and triazine group.

[0008] According to an embodiment of the present invention, the covalent organic framework material is synthesized by monomer B and monomer A.

[0009] Preferably, in the covalent organic framework material, monomer B and monomer A are coupled alternately to obtain the active site, thereby achieving the insertion / extraction of anions and / or cations.

[0010] According to an embodiment of the present invention, the monomer A is selected from 4,4'4"-triaminotriphenylamine, N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine, 3,3',6,6'-tetraamino-9,9'-bispirofluorene, 2,2',7,7'-tetra[N,N-di(4-methylaminophenyl)amino]-9,9'-spirobisfluorene, 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin and 5,10,15,20-tetra(4-aminophenyl)-21H,23H-metalporphyrin.

[0011] Preferably, 5,10,15,20-tetra(4-aminophenyl)-21H,23H-metalporphyrin has the structure shown in formula (1), wherein M is selected from at least one of metals such as iron, cobalt, nickel and ruthenium.

[0012]

[0013] According to an embodiment of the present invention, the monomer B is selected from 4,4'4"-trialdehydetriphenylamine, N,N,N',N'-tetra(p-aldehydephenyl)p-phenylenediamine, 3,3',6,6'-tetraaldehyde-9,9'-bispirofluorene, 2,2',7,7'-tetra[N,N-di(4-aldehydephenyl)amino]-9,9'-spirobifluorene, 5,10,15,20-tetra(4-aldehydephenyl)-21H,23H-porphyrin, 5,10,15,20-tetra(4-aldehydephenyl)-21H,23H-metalporphyrin, pyromellitic dianhydride, 3,4,9,10-naphthalenetetracarboxylic anhydride, and 3,4,9,10 perylenetetracarboxylic anhydride.

[0014] Preferably, 5,10,15,20-tetra(4-aldehydebenzene)-21H,23H-metalporphyrin has the structure shown in formula (2), wherein M is selected from at least one of metals such as iron, cobalt, nickel and ruthenium.

[0015]

[0016] According to an embodiment of the present invention, in the covalent organic framework material, the molar ratio of monomer A to monomer B is 1:3 to 3:1, for example, 1:1, 1:1.5, 2:1, or 3:1.

[0017] According to an embodiment of the present invention, the covalent organic framework material can be prepared using methods known in the art.

[0018] According to an embodiment of the present invention, the covalent organic framework material is prepared as follows: a reaction precursor is dissolved in a reaction solvent, and the reaction is carried out at a certain temperature to obtain the covalent organic framework material. Further, the covalent organic framework material is subjected to filtration, washing, and drying.

[0019] Preferably, the reaction precursor is selected from monomer A and monomer B, wherein monomer A and monomer B have the meanings described above.

[0020] Furthermore, the molar ratio of monomer A to monomer B is 1:3 to 3:1, with examples being 1:1, 1:1.5, 2:1, and 3:1.

[0021] Preferably, the reaction solvent comprises an organic solvent and water. Further, the organic solvent comprises at least one of the following compounds: dichlorobenzene, methanol, ethanol, N,N-dimethylformamide, methylpyrrolidone, and tetrahydrofuran.

[0022] According to an embodiment of the present invention, in the preparation method of the covalent organic framework material, the reaction includes, but is not limited to, one of the following: hydrothermal method, solvothermal method, melting method, and vacuum sealing method, preferably the hydrothermal method. Preferably, the conditions for the hydrothermal method include: a reaction temperature of 150–240°C, exemplarily 160°C, 180°C, 200°C, and 240°C; and a reaction time of 48–240 h, exemplarily 48 h, 72 h, and 160 h. Within the above reaction temperature range, the crystallization of the covalent organic framework material can be promoted; within the above reaction time, the reaction can be made more complete.

[0023] The present invention also provides the use of the above-mentioned covalent organic framework material as an electrode material to convert solar energy into electrical energy and electrochemical energy, preferably for use in photovoltaic rechargeable batteries.

[0024] According to an embodiment of the present invention, the photo-rechargeable battery can directly convert light energy into electrochemical energy for energy storage.

[0025] The present invention also provides an electrode material, wherein the electrode material comprises at least the above-mentioned covalent organic framework material.

[0026] According to an embodiment of the present invention, the electrode material further includes an electron transport material and / or a hole transport material.

[0027] According to an embodiment of the present invention, the electron transport material is selected from at least one of cuprous oxide, selenium, silver, multi-arm carbon nanotubes, single-arm carbon nanotubes, graphene, etc., and is preferably silver.

[0028] According to an embodiment of the present invention, the hole transport material is selected from at least one of tin dioxide, tungsten oxide, silver iodide, molybdenum trioxide, α-iron oxide, titanium dioxide, and indium vanadate, preferably titanium dioxide.

[0029] According to a preferred embodiment of the present invention, the electrode material comprises the covalent organic framework material and the electron transport material, wherein the mass ratio is 1:1 to 10:1, for example, 1:1, 2:1, 3:1.25, 6:1, 8:3, or 10:1.

[0030] According to a preferred embodiment of the present invention, the electrode material comprises the covalent organic framework material and the hole transport material, with a mass ratio of 1:1 to 10:1, for example, 1:1, 2:1, 3:1.25, 6:1, 8:3, or 10:1.

[0031] The present invention also provides a cathode material, the cathode material comprising a covalent organic framework material and an electron transport material, wherein the covalent organic framework material and the electron transport material have the meanings described above.

[0032] According to an embodiment of the present invention, in the positive electrode material, the mass ratio of the covalent organic framework material to the electron transport material is 1:1 to 10:1, for example, 1:1, 2:1, 3:1.25, 6:1, 8:3, or 10:1.

[0033] The present invention also provides a negative electrode material, the negative electrode material comprising a covalent organic framework material and a hole transport material, wherein the covalent organic framework material and the hole transport material have the meanings described above.

[0034] According to an embodiment of the present invention, in the negative electrode material, the mass ratio of the covalent organic framework material to the hole transport material is 1:1 to 10:1, for example, 1:1, 2:1, 3:1.25, 6:1, 8:3, or 10:1.

[0035] The present invention also provides the use of the above-mentioned electrode materials, positive electrode materials and / or negative electrode materials, preferably for use in photovoltaic rechargeable batteries, more preferably for use in organic photovoltaic rechargeable batteries, wherein the photovoltaic rechargeable battery can directly convert light energy into electrochemical energy for energy storage.

[0036] The present invention also provides a photoelectric rechargeable battery, the photoelectric rechargeable battery comprising a positive electrode and a negative electrode, an electrolyte and a separator, wherein the positive electrode comprises the above-mentioned positive electrode material, and the negative electrode comprises the above-mentioned negative electrode material.

[0037] According to an embodiment of the present invention, the organic electrolyte comprises an electrolyte and a solvent.

[0038] According to embodiments of the present invention, the electrolyte includes, but is not limited to, lithium bis(trifluoromethanesulfonyl)imide, lithium hexafluorophosphate, lithium bis(fluoromethanesulfonyl)imide salt, lithium nitrate, lithium perchlorate, and lithium sulfate, and is preferably lithium bis(trifluoromethanesulfonyl)imide.

[0039] According to an embodiment of the present invention, the concentration of the electrolyte in the organic electrolyte can be 0.01 to 5 mol / L, for example 0.1 mol / L, 0.5 mol / L, 2 mol / L, 4 mol / L, and 5 mol / L.

[0040] According to embodiments of the present invention, the solvent includes, but is not limited to, at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, and 1-ethyl-3-methaneimidazole bis(trifluoromethanesulfonyl)imide, preferably 1-ethyl-3-methaneimidazole bis(trifluoromethanesulfonyl)imide.

[0041] The present invention also provides a method for constructing the above-mentioned photoelectric rechargeable battery, the method comprising the following steps:

[0042] (1) Fabrication of positive and negative electrodes: The above-mentioned positive and negative electrode materials are coated on the surfaces of the positive current collector and the negative current collector, respectively, to obtain the positive and negative electrodes;

[0043] (2) The positive and negative electrodes are fixedly assembled into the battery casing, and a battery separator is installed between the positive and negative electrodes;

[0044] (3) After injecting electrolyte into the battery casing, fully immerse it, and encapsulate it to obtain the photo-rechargeable battery.

[0045] According to an embodiment of the present invention, the positive current collector and the negative current collector may be selected from materials known in the art. For example, the positive current collector and the negative current collector are selected independently from the above-mentioned substrate.

[0046] According to an embodiment of the present invention, in step (1), the positive electrode and the negative electrode are respectively provided with positive electrode tabs and negative electrode tabs, and the positive electrode current collector and the negative electrode current collector are respectively led out of the battery casing through the positive electrode tabs and the negative electrode tabs.

[0047] According to an embodiment of the present invention, in step (2), the fixing refers to fixing the positive electrode and the negative electrode to the current collector fixing plate of the positive electrode and the current collector fixing plate of the negative electrode, respectively.

[0048] According to an embodiment of the present invention, the current collector fixing plate of the positive electrode and the current collector fixing plate of the negative electrode are independently composed of transparent glass and metal plates.

[0049] According to an embodiment of the present invention, in step (3), the encapsulation can be performed using methods known in the art.

[0050] The present invention also provides uses for the above-described photochargeable battery, such as for light-responsive energy storage.

[0051] According to an embodiment of the present invention, under ultraviolet-visible light irradiation, the photo-rechargeable battery converts solar energy into electrochemical energy, thereby realizing light-responsive energy storage.

[0052] Preferably, the photoelectric rechargeable battery can achieve a discharge platform of 1.5V or higher and a photoelectrochemical energy conversion efficiency of 15% or higher.

[0053] According to an embodiment of the present invention, the photovoltaic cells are connected in series and / or in parallel, depending on the power supply requirements.

[0054] According to an embodiment of the present invention, the ultraviolet-visible light is provided by a light source, which includes, but is not limited to, at least one of a 300W xenon lamp, an LED lamp, or natural light.

[0055] According to an embodiment of the present invention, the illumination time is from 1 min to 600 min, such as 1 min, 50 min, 200 min and 600 min.

[0056] The beneficial effects of this invention are:

[0057] (1) This invention designs an organic photoelectric rechargeable dual-ion battery based on a covalent organic framework material, which achieves photoelectric charging through the intercalation-deintercalation reaction of anions and cations on the electrodes. The positive and negative electrodes of the battery do not require lithium metal sheets, avoiding dendrite growth, solid electrolyte interface corrosion problems, and expanding the types of organic photoelectric rechargeable batteries. The covalent organic framework material of this invention couples the active sites for intercalation-deintercalation of anions and cations, and through a composite electron transport layer material / hole transport layer material, it directionally regulates the flow of photogenerated carriers between the positive and negative electrodes of the photoelectric rechargeable battery, achieving efficient storage and conversion of solar energy into electrochemical energy under the wetting of an organic electrolyte.

[0058] (2) The organic photoelectric rechargeable battery based on covalent organic framework material provided by the present invention has a simple preparation process, low cost, high photoelectric conversion efficiency, and is suitable for industrial promotion.

[0059] (3) This invention provides a type of high-efficiency, high-voltage organic photovoltaic cell based on dual-ion intercalation and deintercalation. It avoids the use of lithium metal sheets, thereby solving problems such as dendrite growth and solid electrolyte interface corrosion, and expanding the types of organic photovoltaic cells.

[0060] (4) This invention provides a type of secondary battery that can be directly charged and discharged under sunlight. Under the light radiation of a 300W xenon lamp (simulating sunlight, AM1.5), it can achieve a maximum photocharging voltage of over 1.5V. When the light source is removed, it can achieve dark-field discharge, with a maximum photoelectric storage efficiency of over 15%. This invention realizes the construction of a highly efficient solar-to-electrochemical energy storage system, reducing the impact of the intermittent nature of solar radiation in energy utilization. Compared with previous aqueous acidic photocharging batteries, the organic photocharging battery of this invention has advantages such as higher charging and discharging voltage, wider applicability, higher photoelectric conversion efficiency, and environmental friendliness, adapting to the concept of green and sustainable development. Attached Figure Description

[0061] Figure 1 This is a schematic diagram of the structure of the covalent organic framework material prepared in Example 1 of the present invention.

[0062] Figure 2 The image shows the X-ray powder diffraction pattern of the covalent organic framework material prepared in Example 1 of this invention.

[0063] Figure 3 This is a scanning electron microscope image of the covalent organic framework material prepared in Example 1 of the present invention.

[0064] Figure 4 This is a physical image of the covalent organic framework material prepared in Example 1 of the present invention.

[0065] Figure 5 The above are performance comparison charts for Embodiments 1, 2, and 3 of the present invention, as well as Comparative Examples 1 and 2. Detailed Implementation

[0066] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0067] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0068] In this invention, monomers A and B shown in Table 1 are selected respectively, and covalent organic framework materials are prepared by hydrothermal method. The specific covalent organic framework materials are listed in Table 1. In the structure of monomers A and B, M is selected from at least one of metals such as iron, cobalt, nickel and ruthenium.

[0069] In this invention, the covalent organic framework material components constituting the positive and negative electrodes can be selected from at least one, two, or more covalent organic framework materials synthesized according to the structures in Table 1.

[0070] Table 1

[0071]

[0072] Example 1

[0073] The preparation method of the covalent organic framework material COF-43 is as follows:

[0074] Monomers B (3,4,9,10-tetracarboxylic anhydride) and A (4,4'4"-triaminotriphenylamine) were selected as building blocks and prepared via a hydrothermal method. The specific method is as follows: 0.75 mmol of 3,4,9,10-tetracarboxylic anhydride and 0.5 mmol of 4,4'4"-triaminotriphenylamine were dissolved in 10 mL of ultra-dry N,N-dimethylformamide. The reaction solution was transferred to a 15 mL polytetrafluoroethylene liner and placed in a hydrothermal reactor, where it was heated at 180 °C for 72 h to obtain a solid. The crystalline solid was then refluxed at 80 °C for solvent exchange. Specifically, the solvent was refluxed in ultra-dry N,N-dimethylformamide at 80 °C for 48 h, followed by reflux in anhydrous ethanol for 120 h. After the solvent exchange, the solid was filtered to obtain the crystalline solid, which is COF-43.

[0075] Example 2

[0076] The preparation method of the covalent organic framework material COF-50 is as follows:

[0077] Referring to Table 1, monomers B 3,4,9,10-perylenetetracarboxylic anhydride and AN,N,N',N'-tetra(p-aminophenyl)-p-phenylenediamine were selected as building blocks and prepared via a hydrothermal method. The specific method is as follows: 0.75 mmol of 3,4,9,10-perylenetetracarboxylic anhydride, 0.5 mmol of N,N,N',N'-tetra(p-aminophenyl)-p-phenylenediamine, and 10 g of imidazole were dissolved in 10 mL of ultra-dry N,N-dimethylformamide. The reaction solution was transferred to a 15 mL polytetrafluoroethylene liner and placed in a hydrothermal reactor, where it was heated at 190 °C for 72 h to obtain a solid. The crystalline solid was then refluxed at 100 °C for solvent exchange. Specifically, the solid was refluxed at 100 °C for 48 h in ultra-dry N,N-dimethylformamide, followed by immersion in anhydrous ethanol under reflux for 120 h. After the above solvent exchange, the solid is obtained by vacuum filtration, which is COF-50.

[0078] Application Example 1

[0079] The design of organic photocells includes the following steps:

[0080] (1) Preparation process of the positive electrode of the organic photovoltaic cell: 70 mg of COF-43 covalent organic framework material prepared in Example 1, 10 mg of commercially available nano-Ag particles, 40 mg of single-arm carbon nanotubes, and 20 mg of PTFE were weighed and dispersed in 4 mL of isopropanol solution. After treating the mixed solution with a shearing machine for 30 min, it was rolled and pressed onto a titanium mesh and allowed to dry naturally to obtain the positive electrode of the organic photovoltaic cell for later use. A positive electrode tab without coating material was then placed on the titanium mesh.

[0081] (2) Preparation process of the negative electrode of the organic photovoltaic cell: 70 mg of COF-43 covalent organic framework material prepared in Example 1, 70 mg of commercially available nano-titanium dioxide (anatase type), 40 mg of superconducting carbon black, and 20 mg of PTFE were weighed and dispersed in 4 mL of isopropanol solution. After treating the mixed solution with a shearing machine for 30 min, it was rolled and pressed onto a titanium mesh and allowed to dry naturally to obtain the negative electrode of the organic photovoltaic cell for later use. A negative electrode tab without coating material was then placed on the titanium sheet.

[0082] (3) Preparation process of electrolyte for organic photoelectric rechargeable battery: 2.87g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was weighed in a glove box and dissolved in a mixed solvent of 5mL ethylene carbonate (EC) and 5mL diethyl carbonate (DEC). After complete dissolution, the electrolyte 1M LiTFSI / EC+DEC was obtained.

[0083] (4) Assembly of organic photocells:

[0084] (a) Connect the positive electrode of step (1) and the negative electrode of step (2) to the current collector fixing plate of the positive electrode and the current collector fixing plate of the negative electrode, respectively. The current collector fixing plate includes transparent glass and perforated metal plate.

[0085] (b) After fixing the positive and negative electrodes, assemble them into the organic battery casing, and lead the positive current collector and negative current collector out of the battery casing through the positive electrode tab and the negative electrode tab, respectively.

[0086] (c) Install a battery separator between the positive and negative electrodes, and inject the electrolyte from step (3) into the casing to fully wet the battery separator and the battery.

[0087] (d) The above positive and negative plates are encapsulated and the outer shell is welded to assemble a light-transmitting photochargeable organic battery.

[0088] (5) Place the assembled organic photocell under a 300W xenon lamp (full spectrum, incident light wavelength between 200-1000nm), with the light source pointing directly at the opening in the battery casing.

[0089] Experimental results show that the organic photorechargeable battery prepared using Example 1 can achieve a photoresponse charging voltage of over 1.5V within 20 minutes under the light radiation of a 300W xenon lamp. After the light source is removed, it can achieve dark-field discharge with a discharge plateau of 1.2V and a maximum photoelectric efficiency of over 10%.

[0090] Application Example 2

[0091] The method and steps for preparing the organic photoelectric rechargeable cell in Application Example 2 are basically the same as those in Application Example 1, except that:

[0092] In steps (1) and (2), covalent organic framework material 1 is replaced with the COF-50 type covalent organic framework material prepared in Example 2;

[0093] The remaining steps are the same as in Application Example 1.

[0094] Experimental results show that the organic photorechargeable battery prepared using Example 2 can achieve a photoresponse charging voltage of over 1.2V within 20 minutes under the light radiation of a 300W xenon lamp. After the light source is removed, it can achieve dark-field discharge with a discharge plateau of 1.0V and a maximum photoelectric efficiency of over 10%.

[0095] Application Example 3

[0096] The method and steps for preparing the organic photoelectric rechargeable cell in Application Example 2 are basically the same as those in Application Example 1, except that:

[0097] In step (3), the solvent used in the preparation of the electrolyte for the organic photoelectric rechargeable battery is replaced with 1-ethyl-3-methaneimidazolium bis(trifluoromethanesulfonyl)imide;

[0098] The remaining steps are the same as in Application Example 1.

[0099] Experimental results show that the organic photorechargeable battery prepared using Example 2B can achieve a photoresponse charging voltage of over 1.6V within 20 minutes under the light radiation of a 300W xenon lamp. After the light source is removed, it can achieve dark-field discharge with a discharge plateau of 1.5V and a maximum photoelectric efficiency greater than 15%.

[0100] Comparative Application Example 1

[0101] The method and steps for preparing organic photoelectric rechargeable cells in this comparative application example are basically the same as those in application example 1, except that: when preparing the electrode slurry in steps (1) and (2), no covalent organic framework material is added; the remaining steps are the same as those in application example 1.

[0102] Experimental results show that the photochargeable battery prepared in Comparative Example 1 exhibits virtually no photocharging activity under the light radiation of a 300W xenon lamp. Comparative Example 1 demonstrates that the introduction of covalent organic framework materials is a necessary condition for achieving effective photocharging functionality.

[0103] Comparative Application Example 2

[0104] The method and steps for preparing the photovoltaic cell in this comparative application example are basically the same as those in application example 1, except that the assembled photovoltaic cell is not exposed to light in step (5).

[0105] Experimental results show that, compared to application example 2, the organic photochargeable battery maintained a stable voltage, and no voltage increase was observed due to self-charging. This confirms that only under continuous light radiation can the photo-electrochemical energy conversion process be induced, achieving the photocharging phenomenon.

[0106] Furthermore, the organic photocells prepared using other covalent organic framework materials listed in Table 1 exhibit performance essentially the same as those prepared using the covalent organic framework materials of Examples 1 and 2, achieving a photoresponse charging voltage of over 1V within 20 minutes. After removing the light source, they achieve dark-field discharge with a plateau of over 0.8V, with photoelectric efficiencies all exceeding 5%.

[0107] The exemplary embodiments of the present invention have been described above. However, the scope of protection of this application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A photoelectric battery, characterized by comprising: The light charging battery comprises a positive electrode, a negative electrode, an electrolyte and a separator, wherein The positive electrode comprises a positive electrode material, and the positive electrode material comprises a covalent organic framework material and a hole transport material; The negative electrode comprises a negative electrode material, and the negative electrode material comprises a covalent organic framework material and an electron transport material; The covalent organic framework material has ion deintercalation active sites with light response, and the active sites have light response anion deintercalation activity and light response cation deintercalation activity; the anion active sites are selected from nitro groups; the cation active sites are selected from at least one of hydroxyl groups, porphyrin nitrogen, pyridine nitrogen, imine, azo and nitroxide radicals; The covalent organic framework material is prepared by hydrothermal reaction of monomer A and monomer B dissolved in a reaction solvent; the molar ratio of the monomer A to the monomer B is 1:3 to 3:1; the hydrothermal reaction conditions include a reaction temperature of 150 to 240 DEG C and a reaction time of 48 to 240 h; The monomer A is selected from 4,4'4''-triaminotriphenylamine, N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, 3,3',6,6'-tetraamino-9,9'-bifluorene, 2,2',7,7'-tetrakis[N,N-bis(4-methylaminophenyl)amino]-9,9'-spirobifluorene, 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin and 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-metalloporphyrin; The monomer B is selected from 4,4'4''-triformyltriphenylamine, N,N,N',N'-tetrakis(p-formylphenyl)-p-phenylenediamine, 3,3',6,6'-tetraformyl-9,9'-bifluorene, 2,2',7,7'-tetrakis[N,N-bis(4-formylphenyl)amino]-9,9'-spirobifluorene, 5,10,15,20-tetrakis(4-formylphenyl)-21H,23H-porphyrin, 5,10,15,20-tetrakis(4-formylphenyl)-21H,23H-metalloporphyrin, pyromellitic dianhydride, 3,4,9,10-naphthalenetetracarboxylic anhydride and 3,4,9,10-perylenetetracarboxylic anhydride; The reaction solvent comprises an organic solvent and water, and the organic solvent comprises at least one of dichlorobenzene, methanol, ethanol, N,N-dimethylformamide, methylpyrrolidone and tetrahydrofuran.

2. The photoelectric battery of claim 1, wherein In the covalent organic framework material, the active sites are obtained by alternating coupling between the monomer B and the monomer A, so as to realize deintercalation of anions and / or cations; 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-metalloporphyrin has the structure shown in the following formula (1), wherein M is selected from at least one of iron, cobalt, nickel and ruthenium; Formula (1) 5,10,15,20-tetrakis(4-formylphenyl)-21H,23H-metalloporphyrin has the structure shown in the following formula (2), wherein M is selected from at least one of iron, cobalt, nickel and ruthenium; Formula (2).

3. The photoelectric battery of claim 1, wherein The hole transport material is selected from at least one of cuprous oxide, selenium, silver, multi-walled carbon nanotubes, single-walled carbon nanotubes and graphene. The electron transport material is selected from at least one of tin dioxide, tungsten oxide, silver iodide, molybdenum trioxide, alpha-iron oxide, titanium dioxide and indium vanadate.

4. The photoelectric battery of claim 1, wherein The mass ratio of the covalent organic framework material to the hole transport material in the positive electrode material is 1:1-10:

1.

5. The photoelectric battery of claim 1, wherein The mass ratio of the covalent organic framework material to the electron transport material in the negative electrode material is 1:1-10:

1.

6. The photoelectric battery of claim 1, wherein The electrolyte comprises at least one of lithium bis-trifluoromethanesulfonimide, lithium hexafluorophosphate, lithium bis-fluorosulfonimide, lithium nitrate, lithium perchlorate and lithium sulfate.

7. The method for assembling the photo-charging battery according to any one of claims 1-6, wherein: (1) preparing the positive electrode and the negative electrode: coating the positive electrode material and the negative electrode material on the surface of the positive electrode current collector and the negative electrode current collector respectively to obtain the positive electrode and the negative electrode; (2) fixing and assembling the positive electrode and the negative electrode into the battery shell, and adding a battery separator between the positive electrode and the negative electrode; (3) after injecting the electrolyte into the battery shell, fully soaking and packaging to obtain the photo-charging battery.

8. The photo-charging battery according to any one of claims 1-7 is applied to light-responsive energy storage.

9. Use according to claim 8, wherein the compound is ###0002### Under ultraviolet-visible light irradiation, the photo-charging battery converts solar energy into electrochemical energy, thereby realizing light-responsive energy storage.

10. The use according to claim 8, wherein the compound is ###0002### The photo-charging battery can realize a discharge platform of 1.5 V or more, and the photoelectrochemical energy conversion efficiency is 15% or more.

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