CN116925308A - Covalent organic framework containing anthraquinone structure and application of covalent organic framework in water-based zinc ion battery - Google Patents
Covalent organic framework containing anthraquinone structure and application of covalent organic framework in water-based zinc ion battery Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 60
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 title claims abstract description 24
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical compound NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 9
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000944 Soxhlet extraction Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000005297 pyrex Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000010257 thawing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- KAPNIDMXEKQLMQ-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde Chemical compound OC1=C(C=O)C(O)=C(C=O)C(O)=C1C=O KAPNIDMXEKQLMQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 238000000746 purification Methods 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 7
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000010348 incorporation Methods 0.000 abstract 1
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000010354 integration Effects 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
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- 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 invention discloses an anthraquinone structure-containing covalent organic framework and application thereof in a water-based zinc ion battery, wherein 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde is taken as a node and 2, 6-diaminoanthraquinone is taken as an active monomer to synthesize a covalent organic framework material (TfDa-COF) which is connected by beta-keto-enamine bonds and contains a large number of active sites (C ═ O). The TfDa-COF is stably connected through covalent bonds, so that the TfDa-COF has excellent solubility resistance, and the battery cycle stability is effectively improved; ordered channels and pi conjugated structures enhance Zn 2+ And electron transmission capability, the charge and discharge efficiency of the battery is optimized; redox building blocks can be assembled reasonably to COFs at the molecular level, and the incorporation of anthraquinone carbonyl groups promotes optimal regulation of material activity. TfDa-COF shows higher performance when being used as a positive electrode material of a zinc ion batteryAnd exhibits an extremely long cycle stability and excellent coulombic efficiency.
Description
Technical Field
The invention belongs to the field of metal ion battery electrode materials, and particularly relates to an anthraquinone structure-containing covalent organic framework and application thereof in a water system zinc ion battery.
Background
Due to environmental pollutionThe urgency of dyeing, the urgent need for green renewable energy sources, and the positive response to dual carbon targets, the exploration and development of advanced electrochemical energy storage systems (EESs) have become an important focus of sustainable energy sources. Lithium ion batteries have been widely used for daily and commercial applications due to their high energy density, long cycle life, and light weight. However, developments in this area face inherent challenges of high cost, safety, and limited lithium resources. On this basis, aqueous Zinc Ion Batteries (ZIBs) are becoming extremely competitive and efficient energy storage devices due to their low cost, inherent safety and natural richness. In addition, its high theoretical capacity (820 mAhg -1 ) Low redox potential (-0.76vvs. She) and high volumetric energy density (5851 mAhcm) -3 ) The ZIBs have great potential for future development.
Suitable cathode materials are one of the key factors driving the development of ZIBs. Currently, the main cathodes are inorganic compounds such as manganese-based oxides, vanadium-based compounds, and prussian blue analogues, etc. However, problems of irreversible dissolution, volumetric structural strain, and slow kinetics of these materials during charge and discharge lead to battery capacity fade, rate performance non-idealities, and poor cycling performance. Furthermore, the presence of toxic elements in inorganic materials is contrary to the original goal of green and sustainable development of energy. Recently, organic materials have triggered the research trend of ZIBs due to their light weight, low toxicity and sustainability. In particular carbonyl compounds are sought after because of their presence with Zn 2+ The ability to reversibly coordinate and excellent electrochemical reversibility. However, their high solubility in electrolytes presents a significant challenge to improving battery performance.
Covalent Organic Frameworks (COFs) are a class of organic porous polymers with crystalline structures linked by covalent bonds. Its good crystallinity, high chemical stability, pore diameter designability, structural diversity and large pi conjugated structure give them great potential as electrode materials. First, the stable covalent bonds of COFs render them resistant to dissolution, effectively improving the cycling stability of the battery. In addition, the ordered channels and pi-conjugated structures respectively help to increase Zn 2+ And electron transport capability, thereby optimizing charge and discharge efficiency of the battery. More importantly, the redox building blocks can be assembled reasonably to COFs at the molecular level, thereby facilitating optimal regulation of material activity.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide an anthraquinone structure-containing covalent organic framework having a plurality of redox active sites, which has excellent electrochemical properties such as high reversible capacity and long cycle stability, and which can be used in aqueous zinc ion batteries.
The technical scheme adopted by the invention is as follows:
the covalent organic framework containing anthraquinone structure has the structural formula:
the synthesis method of the covalent organic framework containing the anthraquinone structure specifically comprises the following steps:
step 1: weighing 2,4, 6-trihydroxy-1, 3, 5-benzene tricarbaldehyde and 2, 6-diaminoanthraquinone, adding into a Pyrex tube containing N, N-dimethylacetamide and mesitylene, carrying out ultrasonic treatment for 4-6 min, slowly adding acetic acid, then carrying out three freeze-thawing circulation degassing, sealing, and reacting for 3d in a baking oven at 120 ℃;
step 2: stopping the reaction, cooling to room temperature, collecting precipitate, centrifugally washing with tetrahydrofuran and acetone for 5 times, and drying to obtain black-red powder;
step 3: purifying by Soxhlet extraction for 3d, extracting by tetrahydrofuran, washing, and vacuum drying at 100deg.C overnight to obtain final product, namely TfDa-COF.
Preferably, in the step 1, the molar ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde to the 2, 6-diaminoanthraquinone is 1:1-2.
Preferably, in the step 1, the total volume of the N, N-dimethylacetamide and the mesitylene is 1.2ml, and the volume ratio of the N, N-dimethylacetamide to the mesitylene is 2.5-3.5:1.
Preferably, in step 1, acetic acid is added in an amount of 6M,0.04 to 0.06ml.
The synthetic route of the invention is as follows:
the covalent organic framework containing the anthraquinone structure prepared by the method is applied to the anode material of the water-based zinc ion battery.
An application method of an anthraquinone structure-containing covalent organic framework in a water-based zinc ion battery anode material specifically comprises the following steps: taking a covalent organic framework containing an anthraquinone structure as an active material, mixing the active material with a conductive agent and a binder, placing the mixture in a mortar, adding an organic solvent to obtain uniform slurry, coating the uniform slurry on a stainless steel net, and drying the uniform slurry in vacuum at 80 ℃ overnight to obtain an anode electrode plate; and taking a zinc sheet as a negative electrode, and adding electrolyte and a diaphragm to assemble the water-based zinc ion battery.
Compared with the prior art, the invention has the beneficial effects that:
the invention synthesizes the covalent organic framework material (TfDa-COF) which is connected by beta-ketoenamine bond and contains a large number of active sites (C ═ O) by taking 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde as a node and 2, 6-diamino anthraquinone as an active monomer, and the synthesis method is simple. The redox building blocks can be reasonably assembled on the COFs on the molecular level, and the introduced anthraquinone carbonyl promotes the optimal regulation of the activity of the material, so that the higher battery capacity is ensured; the TfDa-COF orderly open channel is favorable for rapidly transmitting Zn < 2+ > to an active site, the pi conjugated structure is favorable for promoting electron transmission, and the charge and discharge efficiency of the battery is optimized; meanwhile, tfDa-COF is stably connected through covalent bonds, so that the TfDa-COF has excellent solubility resistance, and the battery cycle stability is effectively improved. TfDa-COF, when used as a positive electrode material of a zinc ion battery, shows higher reversible cycle capacity, ultra-long cycle stability and excellent coulombic efficiency.
Drawings
FIG. 1 is an infrared spectrum of TfDa-COF and raw materials according to example 1 of the present invention;
FIG. 2 is a powder X-ray diffraction pattern of TfDa-COF of example 1 of the present invention;
FIG. 3 shows that the TfDa-COF of example 1 of the present invention has a sweep rate of 0.5mVs as a positive electrode material for a water-based zinc-ion battery -1 Is a CV diagram of (c);
FIG. 4 shows that the TfDa-COF of example 1 of the present invention has a current density of 0.1Ag as a positive electrode material of a water-based zinc-ion battery -1 A charge-discharge curve graph of (2);
FIG. 5 shows the current densities of 0.1, 0.3, 0.5, 1,3 and 5Ag when TfDa-COF according to example 1 of the present invention was used as the positive electrode material of the aqueous zinc-ion battery -1 Is a ratio performance graph of (2);
FIG. 6 shows that the TfDa-COF of example 1 of the present invention has a current density of 2.5Ag as a positive electrode material of a water-based zinc-ion battery -1 Long cycle performance plots of (2).
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
The synthesis process of covalent organic frame containing anthraquinone structure includes the following steps:
step 1: weighing 0.096 mmole of 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde and 0.142 mmole of 2, 6-diaminoanthraquinone, adding into a Pyrex tube containing 0.9ml of N, N-dimethylacetamide and 0.3ml of mesitylene, carrying out ultrasonic treatment for 5min, slowly adding 0.05ml of 6M acetic acid, then carrying out three freeze-thawing cycle degassing, sealing, and reacting for 3d in a baking oven at 120 ℃;
step 2: stopping the reaction, cooling to room temperature, collecting precipitate, centrifugally washing with tetrahydrofuran and acetone for 5 times, and drying to obtain black-red powder;
step 3: purifying by Soxhlet extraction for 3d, extracting by tetrahydrofuran, washing, and vacuum drying at 100deg.C overnight to obtain final product, namely TfDa-COF.
FT-IR test of the product TfDa-COF obtained in example 1, as shown in FIG. 1, the FT-IR spectrum of TfDa-COF was found to be 1566cm -1 And 1259cm -1 Two prominent peaks, characteristic of the C ═ C and C-N bonds, are shown, indicating successful formation of the beta-ketoenamine linkage framework structure. C ═ O (1643 cm) in raw material 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde -1 ) And N-H (3424, 3334, 3211 cm) in 2, 6-diaminoanthraquinone -1 ) The disappearance of the characteristic peak indicates complete consumption of the reactant.
The powder of the product TfDa-COF obtained in example 1 was subjected to X-ray diffraction, as shown in fig. 2, with PXRD characteristics having peaks at 3.5 °, 5.9 °, 7.0 ° and 27 ° corresponding to (100), (110), (210) and (001) crystal planes, respectively, indicating ordered integration of building blocks and the presence of a crystalline framework structure.
The TfDa-COF obtained in example 1 was used as a positive electrode material for a water-based zinc-ion battery at a sweep rate of 0.5mVs -1 As shown in fig. 3, the CV diagram shows a pair of distinct redox peaks around 0.79/0.66V, indicating redox of the anthraquinone group.
The TfDa-COF obtained in example 1 was used as a positive electrode material of a water-based zinc-ion battery having a current density of 0.1Ag -1 As shown in FIG. 4, the charge-discharge curve is 0.1Ag -1 Shows 96.6mAhg at a current density of (C) -1 Is a high specific capacity of (a).
The current density of the TfDa-COF product obtained in example 1 as a positive electrode material of an aqueous zinc-ion battery was 0.1, 0.3, 0.5, 1,3 and 5Ag -1 As shown in FIG. 5, when the current density is from 5Ag -1 Gradually decrease to 0.1Ag -1 When the discharge capacity is restored to the initial value, the excellent rate performance of TfDa-COF is proved.
FIG. 5 shows that the TfDa-COF obtained in example 1 has a current density of 2.5Ag as a positive electrode material for a water-based zinc-ion battery -1 Long cycle performance plots of (2). TfDa-COF showed 39.6mAhg in 10000 cycles -1 While retaining approximately 98% of the original capacity. In addition, coulombic efficiency was kept around 100%, indicating stable cycling performance of TfDa-COF positive electrode during charge and discharge.
The reagents, materials and the like used in example 1 were all commercially available unless otherwise specified.
The cell performance test in example 1 used a Chenhua electrochemical workstation and a Xinwei cell test system.
The positive electrode material obtained in example 1, the conductive agent acetylene black and the binder PVDF were mixed in an amount of 70:30:10 in NMP solvent to obtain slurry, coating the slurry on stainless steel net to obtain working electrode, and preparing glass fiber diaphragm as 2MZnSO electrolyte 4 The zinc sheet is used as a negative electrode, and is assembled into a CR2032 type button cell in the air, and the test voltage range is 0.2-1.5Vvs. Zn2+/Zn.
Example 2
The synthesis process of covalent organic frame containing anthraquinone structure includes the following steps:
step 1: weighing 0.096 mmole of 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde and 0.192 mmole of 2, 6-diaminoanthraquinone, adding into a Pyrex tube containing 0.96ml of N, N-dimethylacetamide and 0.24ml of mesitylene, carrying out ultrasonic treatment for 6min, slowly adding 0.06ml of 6M acetic acid, then carrying out three freeze-thawing cycle degassing, sealing, and reacting for 4d in a baking oven at 120 ℃;
step 2: stopping the reaction, cooling to room temperature, collecting precipitate, centrifugally washing with tetrahydrofuran and acetone for 5 times, and drying to obtain black-red powder;
step 3: purifying by Soxhlet extraction for 3d, extracting by tetrahydrofuran, washing, and vacuum drying at 100deg.C overnight to obtain final product, namely TfDa-COF.
The positive electrode material obtained in example 2, the conductive agent acetylene black and the binder PVDF were mixed in an amount of 70:30:10 in NMP solvent to obtain slurry, coating the slurry on stainless steel net to obtain working electrode, and preparing glass fiber diaphragm as 2MZnSO electrolyte 4 The zinc sheet is used as a negative electrode, and is assembled into a CR2032 button cell in air, and the test voltage range is 0.2-1.5Vvs. Zn 2+ /Zn。
Example 3
The synthesis process of covalent organic frame containing anthraquinone structure includes the following steps:
step 1: weighing 0.096 mmole of 2,4, 6-trihydroxy-1, 3, 5-benzene tricarbaldehyde and 0.115 mmole of 2, 6-diaminoanthraquinone, adding into a Pyrex tube containing 0.8ml of N, N-dimethylacetamide and 0.4ml of mesitylene, carrying out ultrasonic treatment for 4min, slowly adding 0.04ml of 6M acetic acid, carrying out three freeze-thawing cycle degassing, sealing, and reacting for 4d in a baking oven at 120 ℃;
step 2: stopping the reaction, cooling to room temperature, collecting precipitate, centrifugally washing with tetrahydrofuran and acetone for 5 times, and drying to obtain black-red powder;
step 3: purifying by Soxhlet extraction for 3d, extracting by tetrahydrofuran, washing, and vacuum drying at 100deg.C overnight to obtain final product, namely TfDa-COF.
The positive electrode material obtained in example 2, the conductive agent acetylene black and the binder PVDF were mixed in an amount of 70:30:10 in NMP solvent to prepare slurry, then coating the slurry on a stainless steel net to prepare a working electrode, wherein the diaphragm is a glass fiber diaphragm, the electrolyte is 2MZnSO4, the zinc sheet is a negative electrode, and assembling the slurry into a CR2032 button cell in air, wherein the test voltage range is 0.2-1.5Vvs. Zn 2+ /Zn。
Claims (9)
1. A covalent organic framework comprising an anthraquinone structure, characterized in that: the structure is that
2. A method of synthesizing the anthraquinone structure-containing covalent organic framework of claim 1, wherein: the method comprises the following steps:
step 1: weighing 2,4, 6-trihydroxy-1, 3, 5-benzene tricarbaldehyde and 2, 6-diaminoanthraquinone, adding into a Pyrex tube containing solvents N, N-dimethylacetamide and mesitylene, ultrasonically treating for 4-6 min, slowly adding acetic acid, freezing-thawing, circularly degassing, sealing, and placing into a baking oven at 120 ℃ for reacting for 2-4 d;
step 2: taking out from the oven, cooling to room temperature, collecting precipitate, centrifugally washing with tetrahydrofuran and acetone, and drying to obtain black-red powder;
step 3: and (3) carrying out Soxhlet extraction and purification on the product obtained in the step (2) for 3d, carrying out Soxhlet extraction on tetrahydrofuran, washing, and drying in vacuum overnight to obtain the covalent organic framework containing the anthraquinone structure, namely TfDa-COF.
3. The method for synthesizing the anthraquinone structure-containing covalent organic framework according to claim 2, wherein: in the step 1, the molar ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzene tricaldehyde to the 2, 6-diaminoanthraquinone is 1:1-2.
4. A method of synthesizing an anthraquinone structure-containing covalent organic framework according to claim 2 or 3, characterized in that: in the step 1, the total volume of the N, N-dimethylacetamide and the mesitylene is 1.2ml, and the volume ratio of the N, N-dimethylacetamide to the mesitylene is 2-4:1.
5. The method for synthesizing the anthraquinone structure-containing covalent organic framework according to claim 4, wherein: in the step 1, the ultrasonic time is 4-6 min.
6. The method for synthesizing the anthraquinone structure-containing covalent organic framework according to claim 5, wherein: in the step 1, the amount of acetic acid added is 6M, 0.04-0.06 ml.
7. The method for synthesizing an anthraquinone structure-containing covalent organic framework according to claim 2, 3,5 or 6, characterized in that: in step 3, soxhlet extraction is performed for 3d.
8. Use of an anthraquinone structure-containing covalent organic framework prepared by the method of claim 7 in an aqueous zinc ion battery.
9. The use according to claim 8, characterized in that: taking a covalent organic framework containing an anthraquinone structure as an active material, mixing the active material with a conductive agent and a binder, placing the mixture in a mortar, adding an organic solvent to obtain uniform slurry, coating the uniform slurry on a stainless steel net, and drying the uniform slurry in vacuum at 80 ℃ overnight to obtain an anode electrode plate; and taking a zinc sheet as a negative electrode, and adding electrolyte and a diaphragm to assemble the water-based zinc ion battery.
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