CN115799503A - Covalent organic framework materials and their use in organic photorechargeable batteries - Google Patents
Covalent organic framework materials and their use in organic photorechargeable batteries Download PDFInfo
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Abstract
The invention discloses a covalent organic framework material and application thereof in an organic light charging battery. The covalent organic framework material comprises photoresponsive active sites, wherein the active sites can be excited by light to carry out anion and/or cation de-intercalation; the active sites include at least active sites available for intercalation of anions and/or active sites available for intercalation of cations. The invention also provides an organic light charging bi-ion battery based on the covalent organic framework material. The covalent organic framework material is coupled with anion and cation de-intercalation active sites, and the flow of photo-generated carriers between the anode and the cathode of the light charging battery is directionally regulated by compounding an electron transport layer material/a hole transport layer material, and the organic light charging battery is assembled under the infiltration of an organic electrolyte, so that the efficient storage and conversion from solar energy to electrochemical energy can be realized.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a covalent organic framework material and application thereof in an organic light charging bi-ion battery.
Background
Photoelectrochemical energy storage and conversion, as an important technology in the emerging energy field, has made tremendous progress. The photoelectrochemical energy storage technology can reduce the influence of sunlight intermittency, namely, the solar cell and an energy storage system are integrated, so that the daytime (illumination) production and the nighttime (dark field) requirements are balanced, and the day and night alternate circulation of solar energy conversion is realized.
The organic light rechargeable battery is considered to be a light-responsive energy storage device with great application potential by virtue of the stable electrochemical window and high light-responsive voltage. Currently, lithium ion batteries have been implemented as the most widely used organic batteries to supply power to small portable electronic devices and large electric vehicles. Nevertheless, the limited natural resources of lithium minerals still hinder the further widespread use of lithium ion batteries. Further, the problems of dendrite growth, solid electrolyte interface corrosion, and the like, which are present in the use of a metal lithium electrode, are not negligible. Therefore, coupling the lithium ion battery structure and the photoresponsive material together is not an optimal practical way, and how to reasonably design and construct a novel efficient metal-free lithium organic light rechargeable battery becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to improve the technical problem, the invention is realized by the following technical scheme:
a covalent organic framework material having photoresponsive ionic deintercalation active sites having at least one, two or more photoresponsive anionic deintercalation activities and/or photoresponsive cationic deintercalation activities.
Preferably, the active sites available for anion intercalation are selected from at least one of nitrogen cations and nitro groups.
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, triazinyl.
According to an embodiment of the invention, the covalent organic framework material is obtained by synthesis of monomer B and monomer a.
Preferably, in the covalent organic framework material, the active sites are obtained by alternating coupling between the monomer B and the monomer A, so that anion and/or cation are/is deintercalated.
According to an embodiment of the invention, the monomer a is selected from 4,4 '-4 "-triaminotriphenylamine, N' -tetrakis (p-aminophenyl) p-phenylenediamine, 3,3',6,6' -tetraamino-9,9 '-binaphthylfluorene, 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.
Preferably, 5,10,15,20-tetrakis (4-aminophenyl) -21h, 23h-metalloporphyrin has a structure represented by the following formula (1), wherein M is at least one metal selected from iron, cobalt, nickel, ruthenium and the like.
According to an embodiment of the invention, the monomer B is selected from the group consisting of 4,4 '4' -trialdehyde triphenylamine, N, N, N ', N' -tetra (p-aldehydic phenyl) p-phenylenediamine, 3,3',6,6' -tetra aldehydic-9,9 '-bi-spirofluorene, 2,2',7,7 '-tetra [ N, N-di (4-aldehydic phenyl) amino ] -9,9' -spirobifluorene, 5,10,15,20-tetra (4-aldehydic benzene) -21H, 23H-porphyrin, 5,10,15,20-tetra (4-aldehydic phenyl) -21H, 23H-metalloporphyrin, pyromellitic dianhydride, 3,4,9,10-naphthalene tetracarboxylic anhydride and 3,4,9,10 perylene tetracarboxylic anhydride.
Preferably, 5,10,15,20-tetrakis (4-formylphenyl) -21h, 23h-metalloporphyrin has a structure represented by the following formula (2), wherein M is at least one selected from metals such as iron, cobalt, nickel and ruthenium.
According to an embodiment of the invention, the molar ratio of the monomers a and B in the covalent organic framework material is 1:3-3:1, such as 1:1, 1.5, 2:1, 3:1.
According to embodiments of the present invention, the covalent organic framework material may be prepared using methods known in the art.
According to an embodiment of the invention, the covalent organic framework material is prepared as follows: dissolving the reaction precursor in a reaction solvent, and reacting at a certain temperature to obtain the covalent organic framework material. Furthermore, the covalent organic framework material also needs to be subjected to suction filtration, washing and drying.
Preferably, the reaction precursor is selected from monomers a and B, which have the meaning as described above.
Further, the molar ratio of the monomers A to B is 1:3 to 3:1, and examples are 1:1, 1.5, 2:1 and 3:1.
Preferably, the reaction solvent includes an organic solvent and water. Further, the organic solvent includes at least one of the following compounds: dichlorobenzene, methanol, ethanol, N-dimethylformamide, methylpyrrolidone and tetrahydrofuran.
According to the embodiment of the invention, in the preparation method of the covalent organic framework material, the reaction includes but is not limited to one of a hydrothermal method, a solvothermal method, a melting method, a vacuum tube sealing method and the like, and is preferably a hydrothermal method. Preferably, the conditions of the hydrothermal process include: the reaction temperature is 150 to 240 ℃, illustratively 160 ℃, 180 ℃, 200 ℃, 240 ℃; the reaction time is 48 to 240 hours, illustratively 48 hours, 72 hours and 160 hours. The crystallization of the covalent organic framework material can be promoted within the reaction temperature range; in the above reaction time, the reaction can be more sufficient.
The invention also provides the use of the covalent organic framework material as an electrode material for converting solar energy into electrical and electrochemical energy, preferably for use in a photovoltaic cell.
According to embodiments of the present invention, the photovoltaic rechargeable battery is capable of converting light energy directly into electrochemical energy for energy storage.
The invention also provides an electrode material, which at least comprises the covalent organic framework material.
According to an embodiment of the invention, the electrode material further comprises an electron transport material and/or a hole transport material.
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 tubes, single-arm carbon tubes, graphene, and the like, preferably silver.
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, indium vanadate, and the like, and preferably titanium dioxide.
According to a preferred embodiment of the present invention, the electrode material comprises the covalent organic framework material and the electron transport material, and the mass ratio of the covalent organic framework material to the electron transport material is 1:1-10, for example, 1:1, 2:1, 3.
According to a preferred embodiment of the present invention, the electrode material comprises the covalent organic framework material and the hole transport material, and the mass ratio of the covalent organic framework material to the hole transport material is 1:1-10, for example 1:1, 2:1, 3.
The invention also provides a positive electrode material comprising a covalent organic framework material and an electron transport material, the covalent organic framework material and the electron transport material having the meanings as described above.
According to an embodiment of the invention, in the positive electrode material, the mass ratio of the covalent organic framework material to the electron transport material is 1:1-10, for example, 1:1, 2:1, 3.
The invention also provides an anode material comprising a covalent organic framework material and a hole transport material, the covalent organic framework material and the hole transport material having the meaning as described above.
According to the embodiment of the invention, the mass ratio of the covalent organic framework material to the hole transport material in the anode material is 1:1-10, such as 1:1, 2:1, 3, 6:1, 8:3, 10.
The invention also provides application of the electrode material, the positive electrode material and/or the negative electrode material, preferably to a light charging battery, more preferably to an organic light charging battery, wherein the light charging battery can directly convert light energy into electrochemical energy for energy storage.
The invention also provides a light charging battery, which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the positive electrode comprises the positive electrode material, and the negative electrode comprises the negative electrode material.
According to an embodiment of the present invention, the organic electrolytic solution includes an electrolyte and a solvent.
According to an embodiment of the present invention, the electrolyte includes, but is not limited to, lithium bistrifluoromethanesulfonimide, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonimide, lithium nitrate, lithium perchlorate, lithium sulfate, and the like, preferably lithium bistrifluoromethanesulfonimide.
According to an embodiment of the present invention, the concentration of the electrolyte in the organic electrolytic solution may be 0.01 to 5mol/L, and exemplary are 0.1mol/L, 0.5mol/L, 2mol/L, 4mol/L, 5mol/L.
According to an embodiment 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-methylimidazolium bistrifluoromethylsulfonimide, etc., preferably 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonimide.
The invention also provides a construction method of the light charging battery, which comprises the following steps:
(1) Manufacturing a positive electrode and a negative electrode: respectively coating the positive electrode material and the negative electrode material on the surfaces of a positive current collector and a negative current collector to obtain a positive electrode and a negative electrode;
(2) Fixedly assembling the positive electrode and the negative electrode into a battery shell, and additionally arranging a battery diaphragm between the positive electrode and the negative electrode;
(3) And injecting an electrolyte into the battery shell, fully soaking and packaging to obtain the light rechargeable battery.
According to an embodiment of the present invention, the positive and negative current collectors may be made of a material known in the art, and are, for example, independently selected from the substrates.
According to the embodiment of the invention, in the step (1), the positive electrode and the negative electrode are respectively provided with a positive electrode tab and a negative electrode tab, and the positive electrode current collector and the negative electrode current collector are respectively led out of the battery shell through the positive electrode tab and the negative electrode tab.
According to an embodiment of the present invention, in the step (2), the fixing refers to fixing the positive electrode and the negative electrode to a positive current collecting fixing plate and a negative current collecting fixing plate, respectively.
According to an embodiment of the present invention, the current collecting fixing plate of the positive electrode and the current collecting fixing plate of the negative electrode independently include a transparent glass and a metal plate.
According to an embodiment of the present invention, in the step (3), the encapsulation may be performed by a method known in the art.
The invention also provides the use of the above-described light rechargeable battery, for example for light-responsive energy storage.
According to an embodiment of the present invention, the photo-rechargeable battery converts solar energy into electrochemical energy under uv-visible light irradiation, thereby achieving photo-responsive energy storage.
Preferably, the light charging battery can realize a discharge platform of more than 1.5V, and the photoelectrochemical energy conversion efficiency is more than 15%.
According to an embodiment of the present invention, the light charging cells are connected in series and/or in parallel according to power supply requirements.
According to embodiments of the present invention, the uv-vis light is provided by a light source including, but not limited to, at least one of a 300W xenon lamp, an LED lamp, natural light, and the like.
According to an embodiment of the present invention, the time of the light irradiation is 1min to 600min, such as 1min, 50min, 200min and 600min.
The invention has the beneficial effects that:
(1) The invention designs an organic light charging double-ion battery based on a covalent organic framework material, which realizes light field charging by the de-intercalation reaction of anions and cations on electrodes. The positive electrode and the negative electrode of the battery do not need to use metal lithium sheets, so that the problems of dendritic crystal growth and solid electrolyte interface corrosion are avoided, and the types of the organic light charging battery are expanded. The covalent organic framework material is coupled with anion and cation de-intercalation active sites, and directionally adjusts the flow of photo-generated carriers between the anode and the cathode of the photo-charging battery through the composite electron transport layer material/hole transport layer material, thereby realizing the efficient storage and conversion from solar energy to electrochemical energy under the infiltration of organic electrolyte.
(2) The organic light charging battery based on the covalent organic framework material has the advantages of simple preparation process, low cost and high photoelectric conversion efficiency, and is suitable for industrial popularization.
(3) The invention provides a high-efficiency high-voltage organic light rechargeable battery based on double-ion de-intercalation. The use of metal lithium sheets is avoided, so that the problems of dendritic crystal growth, solid electrolyte interface corrosion and the like are solved, and the variety of the organic light charging battery is expanded.
(4) The invention provides a secondary battery capable of being directly charged and discharged under the irradiation of sunlight, and the secondary battery can maximally realize the light charging voltage of more than 1.5V under the light radiation of a 300W xenon lamp (simulated sunlight, AM 1.5). When the light source is removed, dark field discharge can be realized, and the maximum photoelectric storage efficiency is more than 15%. The invention realizes the construction of a high-efficiency solar-to-electrochemical energy storage system and reduces the influence of solar radiation intermittency in energy utilization. Compared with the conventional aqueous acidic light rechargeable battery, the organic light rechargeable battery has the advantages of high charge and discharge voltage, wider applicability, high photoelectric conversion efficiency, environmental friendliness, no pollution and the like, and is suitable for the concept of green continuous development.
Drawings
FIG. 1 is a schematic structural diagram of a covalent organic framework material prepared in example 1 of the present invention.
FIG. 2 is an X-ray powder diffraction pattern of the covalent organic framework material prepared in example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of a covalent organic framework material prepared according to example 1 of the present invention.
FIG. 4 is a physical representation of the covalent organic framework material prepared in example 1 of the present invention.
FIG. 5 is a graph comparing the performance of examples 1, 2 and 3 of the present invention, comparative example 1 and comparative example 2.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In the invention, a monomer A and a monomer B shown in Table 1 are respectively selected, and a covalent organic framework material is prepared by a hydrothermal method, wherein the covalent organic framework material is specifically listed in Table 1, the structures of the monomer A and the monomer B are shown, and M is selected from at least one of metals such as iron, cobalt, nickel, ruthenium and the like.
In the present invention, the covalent organic framework material portions constituting the positive electrode and the negative electrode of the electrode may be at least one, two or more covalent organic framework materials synthesized by the structure shown in table 1.
TABLE 1
Example 1
The preparation method of the covalent organic framework material COF-43 comprises the following steps:
selecting monomer B3,4,9,10-tetracarboxylic anhydride and monomer A4, 4 '-4' -triaminotriphenylamine as a building unit, and preparing by a hydrothermal method, wherein the method comprises the following steps: 0.75mmol of 3,4,9,10-tetracarboxylic acid anhydride and 0.5mmol of 4,4' -triaminotriphenylamine were dissolved in 10mL of ultra-dry N, N-dimethylformamide, the reaction solution was transferred to a 15mL polytetrafluoroethylene liner, and the apparatus was heated in a hydrothermal kettle at 180 ℃ for 72h to give a solid. The crystalline solid was heated to reflux at 80 ℃ and solvent exchanged. The specific operation is to reflux in ultra-dry N, N-dimethylformamide at 80 ℃ for 48h, and then soak in absolute ethyl alcohol for reflux for 120h. And after the solvent exchange, carrying out suction filtration to obtain a crystalline solid, namely COF-43.
Example 2
The preparation method of the covalent organic framework material COF-50 comprises the following steps:
referring to table 1, the monomer B3,4,9,10 perylene tetracarboxylic anhydride and the monomer A N, N' -tetrakis (p-aminophenyl) p-phenylenediamine are selected as building units, and prepared by a hydrothermal method, which comprises the following steps: 0.75mmol of 3,4,9,10-perylene tetracarboxylic anhydride, 0.5mmol of N, N, N ', N' -tetra (p-aminophenyl) p-phenylenediamine and 10g of imidazole are dissolved in 10mL of ultra-dry N, N-dimethylformamide, the reaction liquid is displaced into 15mL of polytetrafluoroethylene lining, and the mixture is heated and reacted for 72 hours in a hydrothermal kettle at 190 ℃ to obtain a solid. The crystalline solid was heated to reflux at 100 ℃ and solvent exchanged. The specific operation is to reflux in ultra-dry N, N-dimethylformamide for 48h at 100 ℃, and then soak in absolute ethyl alcohol for 120h. And after the solvent exchange, carrying out suction filtration to obtain a crystalline solid, namely COF-50.
Application example 1
The design of the organic light rechargeable battery comprises the following steps:
(1) The preparation process of the positive electrode of the organic light rechargeable battery comprises the following steps: 70mg of the COF-43 covalent organic framework material prepared in example 1, 10mg of commercially available nano-Ag particles, 40mg of single-armed carbon nanotubes, and 20mg of PTFE were weighed out and dispersed in 4mL of isopropanol solution. And (3) treating the mixed solution for 30min by using a shearing machine, rolling and pressing the mixed solution on a titanium net, and naturally drying to obtain the anode of the organic light rechargeable battery for later use. And a positive pole lug which is not coated with a positive pole material is arranged on the titanium mesh.
(2) The preparation process of the negative electrode of the organic light rechargeable battery comprises the following steps: 70mg of the COF-43 covalent organic framework material prepared in example 1, 70mg of commercially available nano-titania (anatase), 40mg of superconducting carbon black, and 20mg of PTFE were weighed out and dispersed in 4mL of isopropanol solution. And (3) treating the mixed solution for 30min by using a shearing machine, then rolling and pressing the mixed solution on a titanium net, and naturally drying to obtain the cathode of the organic light rechargeable battery for later use. And a negative electrode tab which is not coated with a negative electrode material is arranged on the titanium sheet.
(3) The preparation process of the electrolyte of the organic light rechargeable battery comprises the following steps: weighing 2.87g of lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) in a glove box, dissolving in a mixed solvent of 5mL of Ethylene Carbonate (EC) and 5mL of diethyl carbonate (DEC), and obtaining an electrolyte solution 1M LiTFSI/EC + DEC after complete dissolution.
(4) Assembling the organic light charging battery:
(a) And (3) respectively connecting the anode in the step (1) and the cathode in the step (2) with a current collecting fixed plate of the anode and a current collecting fixed plate of the cathode, wherein the current collecting fixed plate comprises transparent glass and a perforated metal plate.
(b) And fixing the positive electrode and the negative electrode, then assembling the fixed positive electrode and the fixed negative electrode into an organic battery shell, and leading the positive electrode current collector and the negative electrode current collector out of the battery shell through a positive electrode tab and a negative electrode tab respectively.
(c) And (3) additionally arranging a battery diaphragm between the anode and the cathode, and injecting the electrolyte in the step (3) into the shell to fully soak the battery diaphragm and the battery.
(d) And packaging the positive plate and the negative plate and welding a shell to assemble the light-permeable light charging organic battery.
(5) The successfully assembled organic light rechargeable battery is placed under a 300W xenon lamp (full spectrum, incident light wavelength is 200-1000 nm), and a light source is directly opposite to the opening of the battery shell for illumination.
The experimental result shows that the organic light charging battery prepared in the example 1 can realize the photoresponse charging voltage of more than 1.5V within 20min under the light radiation of a 300W xenon lamp. Dark field discharge can be realized after the light source is removed, the discharge platform is 1.2V, and the maximum photoelectric efficiency is more than 10%.
Application example 2
The method steps for preparing the organic light rechargeable battery in the application example 2 are basically the same as the application example 1, except that:
in the steps (1) and (2), the covalent organic framework material 1 is replaced by the COF-50 type covalent organic framework material prepared in the example 2;
the remaining steps were the same as in application example 1.
The experimental result shows that the organic light charging battery prepared in the application example 2 can realize the photoresponse charging voltage of more than 1.2V within 20min under the light radiation of a 300W xenon lamp. Dark field discharge can be realized after the light source is removed, the discharge platform is 1.0V, and the maximum photoelectric efficiency is more than 10%.
Application example 3
The method steps for preparing the organic light rechargeable battery in the application example 2 are basically the same as the application example 1, except that:
in the step (3), the solvent in the preparation process of the electrolyte of the organic light charging battery is changed into 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide;
the remaining steps were the same as in application example 1.
The experimental result shows that the organic light charging battery prepared in the application example 2B can realize the photoresponse charging voltage of more than 1.6V within 20min under the light radiation of a 300W xenon lamp. Dark field discharge can be realized after the light source is removed, the discharge platform is 1.5V, and the maximum photoelectric efficiency is more than 15%.
Comparative application example 1
The steps of the method for preparing the organic light rechargeable battery in the comparative application example are basically the same as those in the application example 1, except that: when preparing the electrode slice slurry in the steps (1) and (2), adding no covalent organic framework material; the remaining steps were the same as in application example 1.
The experimental results showed that the photo-charging cell prepared in comparative example 1 had substantially no photo-charging activity under light irradiation from a 300W xenon lamp. Comparative example 1 shows that the incorporation of a covalent organic framework material is a prerequisite for achieving an efficient photo-charging function.
Comparative application example 2
The procedure of the method for preparing a photo-rechargeable battery according to this comparative application example was substantially the same as in application example 1, except that: and (5) not illuminating the assembled light rechargeable battery.
The experimental results showed that the voltage of the organic light rechargeable battery of comparative application example 2 remained stable, and no voltage increase such as self-charging was observed. It is proved that the photo-electrochemical energy conversion process can be induced to realize the illumination charging phenomenon only when the light energy radiation is continued.
In addition, the performance of the organic light charging battery prepared by using other covalent organic framework materials in table 1 is basically the same as that of the organic light charging battery prepared by using the covalent organic framework materials in examples 1 and 2, and the light response charging voltage of more than 1V can be realized within 20 min. Dark field discharge above a 0.8V platform can be realized after the light source is removed, and the photoelectric efficiency is more than 5%.
The above description is directed to exemplary embodiments of the present invention. However, the scope of protection of the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement and the like made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. A covalent organic framework material comprising photoresponsive ionic deintercalation active sites having at least one, two or more photoresponsive anionic deintercalation activities and/or photoresponsive cationic deintercalation activities.
2. The covalent organic framework material of claim 1, wherein the anionic active sites are selected from at least one of nitrogen cations and nitro groups.
Preferably, the cationic active site is selected from at least one of carbonyl/hydroxyl, porphyrin nitrogen, pyridine nitrogen, imine, azo, nitroxide radical, triazine group.
Preferably, the covalent organic framework material is synthesized from monomer B and monomer a.
Preferably, in the covalent organic framework material, the active sites are obtained by alternating coupling between the monomer B and the monomer A, so that anion and/or cation are/is deintercalated.
Preferably, the monomer A is selected from 4,4' triaminotriphenylamine, N, N, N ', N ' -tetrakis (p-aminophenyl) p-phenylenediamine, 3,3',6,6' -tetraamino-9,9 ' -bi-spirofluorene, 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.
Preferably, 5,10,15,20-tetrakis (4-aminophenyl) -21h, 23h-metalloporphyrin has a structure represented by the following formula (1), wherein M is selected from at least one of iron, cobalt, nickel and ruthenium.
Preferably, the monomer B is selected from 4,4' trialdehyde triphenylamine, N, N, N ', N ' -tetra (p-aldehydiphenyl) p-phenylenediamine, 3,3',6,6' -tetra aldehydic-9,9 ' -bi-spirofluorene, 2,2',7,7' -tetra [ N, N-di (4-aldehydiphenyl) amino ] -9,9' -spirobifluorene, 5,10,15,20-tetra (4-aldehydiphenyl) -21H, 23H-porphyrin, 5,10,15,20-tetra (4-aldehydiphenyl) -2H, 23H-metalloporphyrin, pyromellitic dianhydride, 3,4,9,10-naphthalene tetracarboxylic anhydride and 3,4,9,10 perylene tetracarboxylic anhydride.
Preferably, 5,10,15,20-tetrakis (4-aldehyde-phenyl) -21h, 23h-metalloporphyrin has the structure shown in formula (2) below, wherein M is selected from at least one of iron, cobalt, nickel and ruthenium.
Preferably, in the covalent organic framework material, the molar ratio of the monomer A to the monomer B is 1:3-3:1.
3. Use of the covalent organic framework material of claim 1 or 2 as electrode material for the conversion of solar energy into electrical and electrochemical energy.
4. An electrode material, characterized in that it comprises at least a covalent organic framework material according to claim 1 or 2.
Preferably, the electrode material further comprises an electron transport material and/or a hole transport material.
Preferably, the electron transport material is selected from at least one of cuprous oxide, selenium, silver, multi-arm carbon tubes, single-arm carbon tubes, and graphene.
Preferably, the hole 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.
5. A positive electrode material comprising the covalent organic framework material of claim 1 or 2 and the electron transport material of claim 4.
Preferably, in the positive electrode material, the mass ratio of the covalent organic framework material to the electron transport material is 1:1-10.
6. An anode material, characterized in that it comprises a covalent organic framework material according to claim 1 or 2 and a hole transport material according to claim 4.
Preferably, in the anode material, the mass ratio of the covalent organic framework material to the hole transport material is 1:1-10.
7. Use of the electrode material of claim 4, the positive electrode material of claim 5 and/or the negative electrode material of claim 6.
8. A light charging battery is characterized in that the light charging battery comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm; wherein the positive electrode comprises the positive electrode material of claim 5, the negative electrode comprises the negative electrode material of claim 6, and the electrolyte comprises lithium bistrifluoromethanesulfonylimide, lithium hexafluorophosphate, lithium bisfluorosulfonylimide, lithium nitrate, lithium perchlorate, and lithium sulfate.
9. The method of assembling a rechargeable battery of claim 8, wherein:
(1) Manufacturing a positive electrode and a negative electrode: respectively coating the positive electrode material and the negative electrode material on the surfaces of a positive electrode current collector and a negative electrode current collector to obtain a positive electrode and a negative electrode;
(2) Fixedly assembling the positive electrode and the negative electrode into a battery shell, and additionally arranging a battery diaphragm between the positive electrode and the negative electrode;
(3) And injecting an electrolyte into the battery shell, fully soaking and packaging to obtain the light rechargeable battery.
10. Use of the light rechargeable battery of claim 8, for example for light responsive energy storage.
Preferably, the photo-charged cell converts solar energy into electrochemical energy under uv-vis illumination, thereby enabling photoresponsive energy storage.
Preferably, the light charging battery can realize a discharge platform of more than 1.5V, and the photoelectrochemical energy conversion efficiency is more than 15%.
Preferably, the light charging batteries are connected in series and/or in parallel according to power supply requirements.
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2022
- 2022-11-18 CN CN202211449850.0A patent/CN115799503A/en active Pending
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