CN116874775A - Conjugated organic material BQBQ-COF, preparation method, positive electrode material, preparation method and application - Google Patents
Conjugated organic material BQBQ-COF, preparation method, positive electrode material, preparation method and application Download PDFInfo
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- 239000011368 organic material Substances 0.000 title claims abstract description 67
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- DNHCPEFCQYRQQN-UHFFFAOYSA-N 2,3,5,6-tetraaminocyclohexa-2,5-diene-1,4-dione Chemical compound NC1=C(N)C(=O)C(N)=C(N)C1=O DNHCPEFCQYRQQN-UHFFFAOYSA-N 0.000 claims abstract description 14
- RRFZCJGLIHVKTK-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexol;hydrate Chemical compound O.C12=CC(O)=C(O)C=C2C2=CC(O)=C(O)C=C2C2=C1C=C(O)C(O)=C2 RRFZCJGLIHVKTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 20
- 239000007772 electrode material Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- -1 stirring Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000006255 coating slurry Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 12
- 239000011701 zinc Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
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- 239000007779 soft material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The conjugated organic material BQBQ-COF provided by the application adopts a method of condensing and refluxing 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate and 2,3,5, 6-tetra (amino) p-benzoquinone in an organic solvent, and the organic material BQBQ-COF with multiple active sites, which is highly conjugated, is obtained after dehydration and condensation of organic molecules in an acetic acid solution. In addition, the application also provides a preparation method of the conjugated organic material BQBQ-COF, a positive electrode material, a preparation method and application.
Description
Technical Field
The application relates to the technical field of battery materials, in particular to a conjugated organic material BQBQ-COF, a preparation method, a positive electrode material, a preparation method and application.
Background
The water-based zinc ion battery has the advantages of high safety, low raw material cost, abundant zinc resources, environmental friendliness and the like. Meanwhile, the zinc metal cathode also has the advantages of high specific capacity (820 mAh/g), low oxidation-reduction potential (-0.76V vs. standard hydrogen electrode) and the like, so the water-based zinc ion battery has the characteristics of high safety, low cost and high energy density, has strong competitive advantage in the field of large-scale energy storage batteries, and is expected to solve the problem of unbalanced development of the current power generation end and the energy storage end. The choice of electrode materials has an important influence on the development of aqueous zinc ion batteries and the improvement of electrochemical performance. Over several decades, zinc ion batteries have been developed with a variety of inorganic positive electrode materials, such as manganese oxides, vanadium oxides, prussian blue analogues, and the like. However, electrochemical processes of these inorganic materials are often accompanied by lattice evolution or deposition/dissolution, resulting in low practical specific capacity, rapid decay, poor rate performance and cycling stability of these materials, and difficult to expect electrochemical performance. In addition, the traditional inorganic positive electrode contains a large amount of expensive metal elements, which are not in line with the low-cost requirements in large-scale energy storage, and the development of the water-based zinc ion battery is limited to a certain extent.
The organic material has the characteristics of rich elements in nature, sustainable development and high reversible electrochemistry, is suitable for being applied to a large-scale energy storage system and has extremely strong competitive advantage. The development of the electrode materials of the organic batteries is rapid in the last decades, mainly because the structure of the organic molecules is adjustable, the oxidation-reduction reaction potential of the organic molecules can be changed through the adjustment of active groups and frameworks, and the improvement of the voltage and specific capacity of the batteries is realized. In addition, the covalent organic framework material is a layered soft material with through holes, weak intermolecular forces and the characteristics of the soft material, which are favorable for the combination with large-size or multivalent metal ions; the hollow pore structure facilitates rapid diffusion of ions, which makes covalent organic framework materials suitable for use in aqueous zinc ion batteries.
However, at present, the application of the organic electrode material to the field of the water-based zinc ion battery is still in an initial stage, a plurality of problems still remain unsolved, the influence of the structure of the organic electrode material on the ion storage mechanism is not clearly determined, and the existing organic small-molecule electrode material has the advantages of easy synthesis, mass production and lower application cost, but has high solubility in electrolyte, so that the shuttle of the active material, the rapid decay of the battery capacity and short cycle life. In addition, the insufficient conductivity of the organic material results in poor reaction kinetics, and it is difficult to improve the rate performance. It is therefore necessary to develop and design novel organic molecules with multiple active sites, exploring their use in aqueous zinc ion batteries.
Disclosure of Invention
In view of this, it is necessary to provide a conjugated organic material BQBQ-COF, a preparation method, a positive electrode material, a preparation method and applications, which are not easily dissolved in water, have good conductivity and are rich in redox active sites, aiming at the technical defects existing in the prior art.
In order to solve the problems, the application adopts the following technical scheme:
the application provides a conjugated organic material BQBQ-COF, which has the following structural formula:
the second object of the application is to provide a preparation method of the conjugated organic material BQBQ-COF, which comprises the following steps:
2,3,6,7,10, 11-hexahydroxy triphenylene hydrate and 2,3,5, 6-tetra (amino) p-benzoquinone are dissolved in an organic solvent to obtain a mixed solution;
heating the mixed solution under the protection of inert gas for reaction;
and washing and drying the crude product obtained after the reaction to obtain the conjugated organic material BQBQ-COF.
In some embodiments, in the step of dissolving 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate and 2,3,5, 6-tetra (amino) p-benzoquinone in an organic solvent to obtain a mixed solution, the molar ratio of 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate to 2,3,5, 6-tetra (amino) p-benzoquinone is from 1:2 to 2:3.
In some embodiments, in the step of dissolving 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate and 2,3,5, 6-tetra (amino) p-benzoquinone in an organic solvent to obtain a mixed solution, the organic solvent is a mixed solution of acetic acid and ethanol, and the volume ratio of the mixed solution is 3-6:1-2.
In some of these embodiments, in the step of heating the mixed solution under the protection of an inert gas, the inert gas is Ar or N 2 。
In some embodiments, in the step of heating the mixed solution under the protection of inert gas for reaction, the heating temperature is 120-160 ℃ and the reaction time is 12-48 hours.
In some embodiments, the step of washing and drying the crude product obtained after the reaction to obtain the conjugated organic material BQBQ-COF specifically includes the following steps: the crude product obtained after the reaction is washed in acetic acid, ethanol and water in this order and freeze-dried for 24 to 36 hours.
The application further provides a positive electrode material, which comprises the conjugated organic material BQBQ-COF, conductive carbon and a binder, wherein the conjugated organic material BQBQ-COF, the conductive carbon and the binder are in the following mass percent of 6:3:1-8:1:1.
The application provides a preparation method of the positive electrode material, which comprises the following steps:
and mixing and grinding BQBQ-COF, conductive carbon and a binder according to the mass ratio of 6:3:1-8:1:1 to obtain electrode material powder, dissolving the electrode material powder in an organic solvent, stirring, coating slurry on a current collector carbon cloth, carrying out forced air drying on the current collector carbon cloth at 60-110 ℃ for 2-4 hours, and carrying out vacuum drying at 90-120 ℃ for 10-12 hours to obtain the anode material.
The fifth object of the present application is to provide a battery comprising a positive electrode comprising the positive electrode material.
The application aims at providing an application of the conjugated organic material BQBQ-COF as a positive electrode active material of a water-based zinc ion battery.
By adopting the technical scheme, the application has the following beneficial effects:
the conjugated organic material BQBQ-COF provided by the application adopts a method of condensing and refluxing 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate and 2,3,5, 6-tetra (amino) p-benzoquinone in an organic solvent, and the organic material BQBQ-COF with multiple active sites, which is highly conjugated, is obtained after dehydration and condensation of organic molecules in an acetic acid solution, is introduced with abundant active sites through polymerization reaction, and a formed conjugated framework inhibits the dissolution of the organic material in water, and simultaneously enhances the electron conduction capacity of the material, so that the multiplying power performance and long-cycle stability of the organic material are effectively improved; the multi-active-site conjugated organic material BQBQ-COF is applied to a water-based zinc ion battery, realizes the electrochemical property of stable long circulation under high multiplying power, and has wide application prospect in the aspect of zinc ion storage.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly explain the embodiments of the present application or the drawings used in the description of the prior art, and it is obvious that the drawings described below are only some embodiments of the present application, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of steps of a preparation method of a conjugated organic material BQBQ-COF provided by the application;
FIG. 2 is an XRD pattern of the organic material BQBQ-COF provided in example 1 of the present application;
FIG. 3 is a FT-IR chart of the organic material BQBQ-COF provided in example 1 of the application;
FIG. 4 shows an organic material BQBQ-COF according to example 1 of the present application 13 C nuclear magnetic resonance spectrogram;
FIG. 5 is a graph showing the rate performance of the aqueous zinc ion battery of the organic material BQBQ-COF electrode provided in example 2 of the present application;
fig. 6 is a charge-discharge curve of an aqueous zinc ion battery with an organic material BQBQ-COF electrode according to example 3 of the present application.
Detailed Description
Embodiments of the present application are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present application and should not be construed as limiting the application.
In the description of the present application, it should be understood that the directions or positional relationships indicated by the terms "upper", "lower", "horizontal", "inner", "outer", etc., are based on the directions or positional relationships shown in the drawings, are merely for convenience in describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present application.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent.
An embodiment of the present application provides a conjugated organic material BQBQ-COF (conjugated organic material benzoquinoxaline-benzoquinone), which has a molecular structural formula as follows:
the conjugated organic electrode material provided by the application comprises an organic compound which has a benzene ring structure, wherein ring-forming atoms contain nitrogen atoms besides carbon atoms, and the conjugated organic electrode material has multiple active sites, and the conjugated structure is favorable for efficient transmission of electrons in molecules and improves reaction kinetics; meanwhile, the polymerization of the organic small molecules increases the number of active groups in unit mass, the formed conjugated framework inhibits the dissolution of the organic material in water, and meanwhile, the electron conduction capacity of the material is enhanced, and the rate capability and long-cycle stability of the organic electrode material are effectively improved. The conjugated organic electrode material provided by the application has the advantages of difficult dissolution in water, good conductivity and rich redox active sites, so that the requirements of a high-performance water system zinc/organic battery in the future are met, and a wide development space is provided.
Referring to fig. 1, a step flow chart of a preparation method of the conjugated organic material BQBQ-COF according to another embodiment of the application includes the following steps S110 to S130, and the implementation manner of each step is described in detail below.
Step S110: 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate and 2,3,5, 6-tetra (amino) p-benzoquinone are dissolved in an organic solvent to obtain a mixed solution.
In this example, the molar ratio of 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate to 2,3,5, 6-tetra (amino) p-benzoquinone was 2:3.
In this embodiment, the organic solvent is a mixed solution of acetic acid and ethanol, and the volume ratio is 3:1.
Step S120: and heating the mixed solution under the protection of inert gas to react.
In the present embodiment, the inert gas is Ar or N 2 。
In this example, the heating temperature is 120-160 ℃, the reaction time is 12-48 hours, and the mixed solution is dark purple at this time, so that no obvious reaction phenomenon exists.
Step S130: and washing and drying the crude product obtained after the reaction to obtain the conjugated organic material BQBQ-COF.
In this embodiment, in the step of washing and drying the crude product obtained after the reaction to obtain the conjugated organic material BQBQ-COF, the method specifically includes the following steps: the crude product obtained after the reaction is washed in acetic acid, ethanol and water in this order and freeze-dried for 24 to 36 hours.
The preparation method of the conjugated organic material BQBQ-COF provided in the embodiment above has the following synthesis reaction formula:
according to the preparation method provided by the embodiment of the application, the method of condensing and refluxing 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate and 2,3,5, 6-tetra (amino) p-benzoquinone in an organic solvent is adopted, and after dehydration and condensation of organic molecules in an acetic acid solution, the highly conjugated organic matter BQBQ-COF with multiple active sites is obtained, and the conjugated structure is beneficial to efficient transmission of electrons in the molecules and improves reaction kinetics. Meanwhile, the polymerization of the organic small molecules increases the number of active groups in unit mass and inhibits the dissolution of the organic molecules in water; the multi-active-site conjugated organic material BQBQ-COF is applied to a water-based zinc ion battery, realizes the electrochemical property of stable long circulation under high multiplying power, and has wide application prospect in the aspect of zinc ion storage.
The preparation method of the conjugated organic material BQBQ-COF provided by the embodiment of the application has the advantages of simple process and mild synthesis conditions, and is suitable for industrial production.
The application also provides a positive electrode material, which comprises the conjugated organic material BQBQ-COF, conductive carbon and a binder, wherein the mass ratio of the conjugated organic material BQBQ-COF to the conductive carbon to the binder is 6:3:1-8:1:1.
The positive electrode material provided by the embodiment of the application comprises the conjugated organic material BQBQ-COF, and the conjugated organic material BQBQ-COF is the conjugated organic material benzo quinoxaline-benzoquinone (BQBQ-COF) with multiple active sites, so that abundant active sites are introduced through polymerization reaction, the formed conjugated framework inhibits the dissolution of the organic material in water, and simultaneously enhances the electron conduction capability of the material, thereby effectively improving the multiplying power performance and long-cycle stability of the organic material, and being applicable to the preparation of the positive electrode material of a battery.
The application also provides a preparation method of the positive electrode material, which comprises the following steps: and mixing and grinding BQBQ-COF, conductive carbon and a binder according to the mass ratio of 6:3:1-8:1:1 to obtain electrode material powder, dissolving the electrode material powder in an organic solvent, stirring, coating slurry on a current collector carbon cloth, carrying out forced air drying on the current collector carbon cloth at 60-110 ℃ for 2-4 hours, and then carrying out vacuum drying at 90-120 ℃ for 10-12 hours to obtain the anode material.
Another embodiment of the present application also provides a battery, including a positive electrode including the positive electrode material, and the positive electrode material includes a conjugated organic material BQBQ-COF. It can be understood that in practice, a sheet cutting machine is used to cut the sheet to a suitable size to serve as a positive electrode sheet of the battery, a zinc sheet is used as a negative electrode, and a suitable separator and electrolyte are selected to assemble the battery.
In this embodiment, the electrolyte is zinc sulfate, zinc trifluoromethane sulfonate, or the like. The electrolyte comprises aqueous electrolyte and organic electrolyte, and comprises water, acetonitrile, dimethyl carbonate, dimethyl sulfoxide and the like. The membrane is a cellulose membrane, a glass fiber membrane, a PP membrane and the like.
The battery provided by the embodiment of the application comprises the positive electrode material, wherein the positive electrode material comprises the conjugated organic material BQBQ-COF, and the conjugated organic material BQBQ-COF is the conjugated organic material benzo quinoxaline-benzoquinone (BQBQ-COF) with multiple active sites, rich active sites are introduced through polymerization reaction, so that the formed conjugated framework inhibits the dissolution of the organic material in water, simultaneously enhances the electron conduction capability of the material, effectively improves the rate capability and long-cycle stability of the organic material, and is applied to a water-based zinc ion battery, so that the stable long-cycle electrochemical property under high rate is realized, and the multi-active site conjugated organic material BQBQ-COF has wide application prospect in the aspect of zinc ion storage.
The above technical scheme of the present application will be described in detail with reference to specific embodiments.
Example 1
The preparation of the BQBQ-COF electrode with the multi-active-site conjugated organic material provided in the embodiment 1 comprises the following steps:
(1) 0.65g 2,3,6,7,10,11-hexahydroxytriphenylene hydrate (T-phenol, mw= 324.29 g/mol) was weighed into a mixed solution of 60mL acetic acid and 20mL absolute ethanol and sonicated for 5 minutes. Then, 0.54g of 2,3,5, 6-tetra (amino) p-benzoquinone (tab, mw= 168.15 g/mol) was added to the mixed solution, stirred at room temperature for 20 minutes and sonicated for 5 minutes to obtain a mixed solution with uniformly dispersed particles. The mixed solution was transferred to a three-necked flask and refluxed at 120℃for 48 hours under Ar atmosphere to obtain a black powder. And respectively using acetic acid, methanol, ethanol and deionized water to wash for a plurality of times, and freeze-drying to obtain the BQBQ-COF material. The organic material BQBQ-COF was subjected to X-ray diffraction, and the data is shown in FIG. 2. The infrared data, as shown in fig. 3, which contains c=o and c=n, indicate that the material has multiple active sites. BQBQ-COF 13 As shown in FIG. 4, the C-nuclear magnetic resonance spectrum showed that the carbonyl group was detected at 174.2ppm and the imine bond was detected at 145.5 ppm.
(2) The preparation method of the BQBQ-COF electrode with the multi-active-site conjugated organic material comprises the following steps: the BQBQ-COF material, the conductive carbon black and the adhesive polyvinylidene fluoride are respectively weighed according to the mass ratio of 6:3:1, placed in a mortar, added with an organic solvent N-methyl pyrrolidone and mixed into sticky slurry, coated on carbon cloth, dried by blowing at 120 ℃ for 3 hours, removed most of the organic solvent, and dried in vacuum at 90 ℃ for 12 hours. Cut it to 1cm using a cutter 2 The size is that the multi-active site conjugated organic material BQBQ-COF electrode is prepared.
Example 2
The application of the multi-active-site conjugated organic material BQBQ-COF electrode in the aqueous zinc ion battery and the performance test thereof are provided in the embodiment 2:
(1) And (3) battery assembly: the anode is a BQBQ-COF material electrode prepared by the application, the anode is zinc metal, the diaphragm is cellulose paper, and the electrolyte is 1mol/L zinc triflate aqueous solution, so as to assemble the CR2032 type button cell. The structure of the assembled battery is as follows: the positive electrode comprises a positive electrode cover, a positive electrode plate, electrolyte, a diaphragm, electrolyte, a zinc plate, a gasket, an elastic piece and a negative electrode cover.
(2) Electrochemical testing: under the condition of room temperature, the prepared button cell is subjected to charge and discharge test on a Xinwei cell test system, and the charge and discharge voltage interval is 0.1-1.3V (vs. Zn/Zn) 2+ ) The cycle-capacity diagram of the electrode material is tested at current densities of 0.5, 1, 5, 10, 15 and 20A/g, and the specific capacity of the electrode material can reach 92mAh/g at the current densities of 20A/g as shown in FIG. 5.
Example 3
The application of the multi-active-site conjugated organic material BQBQ-COF electrode in the aqueous zinc ion battery and the performance test thereof are provided in the embodiment 3:
the difference from example 2 is that the electrolyte is a test system consisting of a 2mol/L zinc sulfate aqueous solution. The charge-discharge voltage interval is 0-1.4V (vs. Zn/Zn) 2+ ) The charge and discharge tests were carried out at current densities of 0.5, 1, 2 and 5A/g, respectively, and the specific capacity of the electrode material can reach 151mAh/g at current densities of 5A/g as shown in FIG. 6.
It will be understood that the technical features of the above-described embodiments may be combined in any manner, and that all possible combinations of the technical features in the above-described embodiments are not described for brevity, however, they should be considered as being within the scope of the description provided in the present specification, as long as there is no contradiction between the combinations of the technical features.
The foregoing description of the preferred embodiments of the present application has been provided for the purpose of illustrating the general principles of the present application and is not to be construed as limiting the scope of the application in any way. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application, and other embodiments of the present application as will occur to those skilled in the art without the exercise of inventive faculty, are intended to be included within the scope of the present application.
Claims (11)
1. A conjugated organic material BQBQ-COF, characterized by the following structural formula:
2. a method for preparing the conjugated organic material BQBQ-COF according to claim 1, comprising the steps of:
2,3,6,7,10, 11-hexahydroxy triphenylene hydrate and 2,3,5, 6-tetra (amino) p-benzoquinone are dissolved in an organic solvent to obtain a mixed solution;
heating the mixed solution under the protection of inert gas for reaction;
and washing and drying the crude product obtained after the reaction to obtain the conjugated organic material BQBQ-COF.
3. The method for preparing a conjugated organic material BQBQ-COF of claim 2, wherein in the step of dissolving 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate and 2,3,5, 6-tetra (amino) p-benzoquinone in an organic solvent to obtain a mixed solution, the molar ratio of the 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate to the 2,3,5, 6-tetra (amino) p-benzoquinone is 1:2 to 2:3.
4. The method for preparing a conjugated organic material BQBQ-COF according to claim 2, wherein in the step of dissolving 2,3,6,7,10, 11-hexahydroxytriphenylene hydrate and 2,3,5, 6-tetra (amino) p-benzoquinone in an organic solvent to obtain a mixed solution, the organic solvent is a mixed solution of acetic acid and ethanol in a volume ratio of (3-6): 1-2.
5. The method for preparing a conjugated organic material BQBQ-COF according to claim 2, wherein in the step of heating the mixed solution under the protection of an inert gas, the inert gas is Ar or N 2 。
6. The method for preparing the conjugated organic material BQBQ-COF of claim 2, wherein in the step of heating the mixed solution under the protection of inert gas to react, the heating temperature is 120 to 160 ℃ and the reaction time is 12 to 48 hours.
7. The method for preparing the conjugated organic material BQBQ-COF according to claim 1, wherein the step of washing and drying the crude product obtained after the reaction to obtain the conjugated organic material BQBQ-COF specifically comprises the following steps: the crude product obtained after the reaction is washed in acetic acid, ethanol and water in this order and freeze-dried for 24 to 36 hours.
8. The positive electrode material is characterized by comprising the conjugated organic material BQBQ-COF, conductive carbon and a binder according to the mass ratio of 6:3:1-8:1:1.
9. A method for preparing the positive electrode material according to claim 8, comprising the steps of:
and mixing and grinding BQBQ-COF, conductive carbon and a binder according to the mass ratio of 6:3:1-8:1:1 to obtain electrode material powder, dissolving the electrode material powder in an organic solvent, stirring, coating slurry on a current collector carbon cloth, drying the current collector carbon cloth at 60-110 ℃ for 2-4 hours by blowing, and drying at 90-120 ℃ for 10-12 hours to obtain the positive electrode material.
10. A battery comprising a positive electrode comprising the positive electrode material of claim 8.
11. Use of the conjugated organic material BQBQ-COF according to claim 1 as a positive electrode active material of an aqueous zinc ion battery.
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