CN114031737A - Large-size melamine-based covalent organic framework material, and preparation method and application thereof - Google Patents
Large-size melamine-based covalent organic framework material, and preparation method and application thereof Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 80
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 58
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 27
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims abstract description 26
- 239000002608 ionic liquid Substances 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- UJCACAOPZBJKIW-UHFFFAOYSA-N 2-(4-formylpyridin-2-yl)pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC(C=2N=CC=C(C=O)C=2)=C1 UJCACAOPZBJKIW-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 239000002262 Schiff base Substances 0.000 claims abstract description 4
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007772 electrode material Substances 0.000 claims description 15
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 14
- 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 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 9
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- 238000001035 drying Methods 0.000 claims description 8
- 238000000944 Soxhlet extraction Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
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- -1 1-ethyl-3-methylimidazole tetrafluoroborate Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 3
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- 239000000243 solution Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
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- 238000010923 batch production Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 16
- 239000003990 capacitor Substances 0.000 description 12
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- 238000004108 freeze drying Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- WYLKURXIYWTCJC-UHFFFAOYSA-L 1-ethyl-3-methylimidazol-3-ium trifluoromethanesulfonate Chemical compound FC(S(=O)(=O)[O-])(F)F.C(C)[N+]1=CN(C=C1)C.FC(S(=O)(=O)[O-])(F)F.C(C)[N+]1=CN(C=C1)C WYLKURXIYWTCJC-UHFFFAOYSA-L 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000013474 COF-1 Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- IQDQMRZGMILNMQ-UHFFFAOYSA-N naphthalene-2,6-dicarbaldehyde Chemical compound C1=C(C=O)C=CC2=CC(C=O)=CC=C21 IQDQMRZGMILNMQ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- 239000013384 organic framework Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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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
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention relates to a large-size melamine-based covalent organic framework material, a preparation method and application thereof, belonging to the technical field of preparation of energy storage materials. The invention solves the technical problem of providing a large-size melamine-based covalent organic framework material. The melamine-based covalent organic framework material is prepared by reacting melamine with a dialdehyde ligand through Schiff base; wherein the dialdehyde ligand is 2,2 ' -bipyridine-4, 4' -dicarboxaldehyde, 2, 6-naphthaldehyde or 4,4' -biphenyldicarboxaldehyde material. The invention adopts melamine as COF building block, adopts specific dialdehyde ligand to prepare covalent organic framework material, has low cost, high nitrogen content and micropore size larger than 1.5nm, and can realize high specific volume of ionic liquid electrolyte. The invention adopts solvothermal synthesis, has simple synthesis method and is easy for batch production.
Description
Technical Field
The invention relates to a large-size melamine-based covalent organic framework material, a preparation method and application thereof, belonging to the technical field of preparation of energy storage materials.
Background
The super capacitor is composed of an electrode material, electrolyte, a diaphragm and a current collector, wherein the electrode material and the electrolyte have great influence on the electrochemical performance of the super capacitor. The super capacitor not only has the rapid charge and discharge performance of a conventional capacitor, but also has the energy storage characteristic of a secondary battery, and is an ideal novel energy storage device. Supercapacitors can be divided into aqueous, organic solvent, and ionic liquid systems, depending on the electrolyte. The super capacitor with the water system electrolyte needs to solve the problem of low energy density caused by narrow voltage window; the organic solvent system is highly toxic, flammable and volatile. The ionic liquid electrolyte has the advantages of wide voltage window, non-volatility and flame retardance, and can be used for preparing super capacitors with ultrahigh energy density and high safety.
However, in contrast to conventional electrolyte ions (e.g. Li)+，Cl-,H+,SO4 2-) The ionic liquid has a large ionic radius (Emim)2+,TFSI-,BF4 -) The conventional electrode material has difficulty in exerting the performance of the improved electrolyte. Moreover, the ionic liquid system can only have the electric double layer capacitance characteristic, so that the electrode material needs to have a proper pore size to effectively exert the performance of the ionic liquid system supercapacitor.
A Covalent Organic Framework (COF) is a novel crystal form organic porous material, is synthesized for the first time in 2005, and has chemical uniqueness, regular pore junctions, a new structure and new application which are gradually expanded. In addition, the pore diameter structure of the COF material can be regulated and controlled through structural design, and the electrode material with a reasonable pore diameter size is prepared. COF materials developed to date tend to develop smaller pores (< 1nm) to extend their pseudocapacitive properties. This type of COF material is not suitable for new ionic liquid electrolyte systems.
Disclosure of Invention
In view of the above disadvantages, the technical problem to be solved by the present invention is to provide a large-sized (i.e. single pore diameter > 2nm) melamine-based covalent organic framework material, which is suitable for ionic liquid electrolyte systems.
The large-size melamine-based covalent organic framework material is prepared by reacting melamine with a dialdehyde ligand through Schiff base; wherein the dialdehyde ligand is 2,2 ' -bipyridine-4, 4' -dicarboxaldehyde, 2, 6-naphthaldehyde or 4,4' -biphenyldicarboxaldehyde material.
In one embodiment of the invention, the single pore size of the large size melamine based covalent organic framework material is > 2 nm.
In one embodiment of the invention, the specific surface area of the large-size melamine-based covalent organic framework material is 1120-1400 m2/g。
The second technical problem solved by the invention is to provide a preparation method of a large-size melamine-based covalent organic framework material.
The preparation method of the large-size melamine-based covalent organic framework material comprises the following steps: mixing melamine and a dialdehyde ligand, adding mesitylene and an acetic acid aqueous solution, uniformly mixing, freezing and thawing for deoxidation, reacting at 140-160 ℃ for 24-72 h, purifying, and drying to obtain the large-size melamine-based covalent organic framework material.
In one embodiment of the invention, the molar ratio of the melamine to the dialdehyde ligand is 1.5-2.5: 3. In a preferred embodiment of the invention, the molar ratio of melamine to dialdehyde ligands is 2: 3.
In one embodiment of the invention, the weight ratio of the monomer, the mesitylene and the acetic acid aqueous solution is 0.6-1.4 g: 25-45 g: 0.1-1 g based on the concentration of the acetic acid aqueous solution being 3M, wherein the monomer is melamine and a dialdehyde ligand.
In a preferred embodiment of the invention, the weight ratio of the monomer, mesitylene and aqueous acetic acid is 1.09g to 35g to 0.5 g.
In a preferred embodiment of the invention, the reaction is carried out for 48h at 160 ℃.
In a specific embodiment of the invention, the purification is performed by respective Soxhlet extraction with ethanol, acetone and water as solvents for 8-12 h.
The invention also provides application of the large-size melamine-based covalent organic framework material in preparation of electrode materials of a super capacitor, wherein the super capacitor is a super capacitor with ionic liquid electrolyte.
The large-size melamine-based covalent organic framework material can be prepared into an electrode material by adopting a conventional method and applied to a super capacitor of an ionic liquid electrolyte.
In one embodiment of the invention, the ionic liquid electrolyte is 1-ethyl-3-methylimidazolium tetrafluoroborate or 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonate.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts melamine as COF building block, adopts specific dialdehyde ligand to prepare covalent organic framework material, has low cost, high nitrogen content and micropore size larger than 1.5nm, and can realize high specific volume of ionic liquid electrolyte.
2. The invention adopts solvothermal synthesis, has simple synthesis method and is easy for batch production.
Drawings
FIG. 1 is a scanning electron micrograph of a covalent organic framework material prepared according to example 1.
Figure 2 is an XRD diffractogram of the covalent organic framework material prepared in example 1.
FIG. 3 is a calculation chart of pore structure simulation for the covalent organic framework material prepared in example 1.
FIG. 4 is a scanning electron micrograph of the covalent organic framework material prepared in example 2.
Figure 5 is an XRD diffractogram of the covalent organic framework material prepared in example 2.
Fig. 6 is a calculation chart for pore structure simulation of the covalent organic framework material prepared in example 2.
FIG. 7 is a scanning electron micrograph of a covalent organic framework material prepared according to example 3.
Figure 8 is an XRD diffractogram of the covalent organic framework material prepared in example 3.
Fig. 9 is a calculation chart for pore structure simulation of the covalent organic framework material prepared in example 3.
Detailed Description
The large-size melamine-based covalent organic framework material is prepared by reacting melamine with a dialdehyde ligand through Schiff base; wherein the dialdehyde ligand is 2,2 ' -bipyridine-4, 4' -dicarboxaldehyde, 2, 6-naphthaldehyde or 4,4' -biphenyldicarboxaldehyde material.
According to the invention, melamine is used as one of ligands of the COF material and matched with a specific dialdehyde ligand, the COF with high specific surface area and single aperture larger than 2nm can be obtained, the anion shuttle and the cation shuttle of the ionic liquid are met, and the super capacitor with ultrahigh energy density (the energy density is larger than 100Wh/kg) can be prepared.
The porous material of the microporous covalent organic framework material has the structural formula as follows:
wherein, COF-1 is 2,2 ' -bipyridine-4, 4' -dicarboxaldehyde as a dialdehyde ligand, COF-2 is 4,4' -biphenyldicarboxaldehyde as a dialdehyde ligand, and COF-3 is 2, 6-naphthaldehyde as a dialdehyde ligand.
The large size of the large-size melamine-based covalent organic framework material of the present invention refers to a large pore size, and in one embodiment of the present invention, the single pore size of the material is greater than 2 nm.
In one embodiment of the invention, the specific surface area of the large-size melamine-based covalent organic framework material is 1120-1400 m2/g。
The preparation method of the large-size melamine-based covalent organic framework material comprises the following steps: mixing melamine with a dialdehyde ligand, adding mesitylene and an acetic acid aqueous solution, performing ultrasonic dispersion, performing freeze thawing and deoxidation, reacting at 140-160 ℃ for 24-72 h, purifying, and drying to obtain the covalent organic framework material.
The method adopts mesitylene as a reaction medium, has high melting point and good thermal stability, and the amino and aldehyde groups are condensed in the synthesis process of the covalent organic framework material.
In one embodiment of the invention, the molar ratio of the melamine to the dialdehyde ligand is 1.5-2.5: 3. In a preferred embodiment of the invention, the molar ratio of melamine to dialdehyde ligands is 2: 3.
In one embodiment of the invention, the weight ratio of the monomer, the mesitylene and the acetic acid aqueous solution is 0.6-1.4 g: 25-45 g: 0.1-1 g based on the concentration of the acetic acid aqueous solution being 3M, wherein the monomer is melamine and a dialdehyde ligand.
In a preferred embodiment of the invention, the weight ratio of the monomer, mesitylene and aqueous acetic acid is 1.09g to 35g to 0.5 g.
In a preferred embodiment of the invention, the reaction is carried out for 48h at 160 ℃.
The blending of the invention can adopt the conventional method in the field, and only needs to fully blend the reactants. In one embodiment of the invention, ultrasonic dispersion is used. In a specific embodiment, the ultrasound is dispersed for 10 min.
The freeze-thaw deoxidation of the invention can adopt the conventional method in the field, namely freezing and unfreezing. The purpose of which is to carry away oxygen. In one embodiment of the invention, the freeze-thaw is deoxygenated 3 times in order to adequately remove oxygen.
The purification can be performed by a conventional method, and in a specific embodiment of the invention, the purification is performed by respectively performing Soxhlet extraction for 8-12 hours by using ethanol, acetone and water as solvents. The extraction time is 8-12 h, namely the solid is extracted by ethanol for 8-12 h, then the solid is extracted by acetone for 8-12 h, and finally the solid is extracted by water for 8-12 h.
In one embodiment of the invention, the extraction time is 10 h.
Drying after purification, drying methods commonly used in the art are all suitable for the present invention, such as oven drying, freeze drying, etc.
The large-size melamine-based covalent organic framework material can be prepared into an electrode material by adopting a conventional method and applied to a super capacitor of an ionic liquid electrolyte.
In a specific embodiment, the electrode material of the supercapacitor is prepared by adopting the following method: and grinding and dispersing the covalent organic framework material, the conductive carbon black and the PVDF by using N-methyl pyrrolidone according to the weight ratio of 6:3:1, uniformly coating the mixture on the surface of the current collector, and drying to obtain the conductive carbon black.
In one embodiment of the invention, the ionic liquid electrolyte is 1-ethyl-3-methylimidazolium tetrafluoroborate or 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonate. The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
The raw material sources in the examples are: melamine (mca, 99%) was purchased from Aladdin chemistry,2,2 '-bipyridine-4, 4' -dicarboxaldehyde (bpd, 99%), 2, 6-naphthalenedicarboxaldehyde (nd, 99%), 4 '-biphenyldicarboxaldehyde (bd, 99%) was purchased from Viller's organic. 1-Ethyl-3-methylimidazolium tetrafluoroborate (EmimBF4), 1-Ethyl-3-methylimidazolium bistrifluoromethanesulfonate (EmimTFSI), commercially available from TCI.
Example 1
The covalent organic framework material is prepared by the following method, and the name of the material is COF-1:
0.37g of melamine and 0.95g of 2,2 '-bipyridine-4, 4' -diformaldehyde are added into a reaction bottle, 30g of mesitylene and 0.5g of 3M acetic acid aqueous solution are added and ultrasonically dispersed for 10min, and then after 3 times of freeze thawing and deoxidation, the mixture is ultrasonically dispersed for 10min with stirring. And sealing the system in a hydrothermal reaction kettle, reacting at 140 ℃ for 72 hours, performing Soxhlet extraction on the solid material with ethanol, acetone and water for 10 hours respectively, and finally freeze-drying the solid to obtain the covalent organic framework load material.
A scanning electron micrograph of the covalent organic framework support material is shown in figure 1. The independent rod-shaped COF crystal is observed under a field emission scanning electron microscope, and the BET represents that the specific surface area of the material is 1140m2(ii) in terms of/g. The XRD diffraction data curve of the covalent organic framework support material is shown in fig. 2. From the XRD diffraction pattern of the material, the material can be found to have a strong diffraction peak at 3.1 degrees, the crystal structure of the material is proved, and the aperture of the material is 2.8nm through material studio simulation calculation, as shown in figure 3.
Example 2
The covalent organic framework material is prepared by adopting the following method, and is named as COF-2:
0.31g of melamine and 0.78g of 4,4' -biphenyldicarboxaldehyde are added into a reaction bottle, 35g of mesitylene and 0.5g of 3M acetic acid aqueous solution are added and ultrasonically dispersed for 10min, and then after 3 times of freeze thawing and deoxidation, ultrasonic and stirring dispersion are carried out for 10 min. And sealing the system in a hydrothermal reaction kettle, reacting for 48 hours at 160 ℃, performing Soxhlet extraction on the solid material with ethanol, acetone and water for 10 hours respectively, and finally freeze-drying the solid to obtain the covalent organic framework load material.
A scanning electron micrograph of the covalent organic framework material is shown in FIG. 4. COF crystals of sea urchin-like structure were observed under a field emission scanning electron microscope. BET characterisation the specific surface area of the material is 1200m2(ii) in terms of/g. The XRD diffraction data curve of the covalent organic framework loading material is shown in figure 5, the material can be found to have a stronger diffraction peak at 3.5 degrees from the XRD diffraction pattern of the material, the crystal structure of the material is proved, and the aperture of the material is 2.5nm through material studio simulation calculation, which is shown in figure 6.
Example 3
The covalent organic framework material is prepared by the following method, and the name of the material is COF-3:
0.28g of melamine and 0.61g of 2, 6-naphthalenedicarboxaldehyde are added into a reaction flask, an aqueous solution containing 35g of mesitylene and 0.6g of 3M acetic acid is added and ultrasonically dispersed for 10min, and then, after 3 times of freeze thawing and deoxidation, ultrasonic and stirring dispersion are carried out for 10 min. And sealing the system in a hydrothermal reaction kettle, reacting for 48 hours at 160 ℃, performing Soxhlet extraction on the solid material with ethanol, acetone and water for 10 hours respectively, and finally freeze-drying the solid to obtain the covalent organic framework load material.
A scanning electron micrograph of the covalent organic framework material is shown in FIG. 7. Needle-shaped COF crystals are observed under a field emission scanning electron microscope, and the BET represents that the specific surface area of the material is 1400m2The XRD diffraction data curve of the covalent organic framework loading material is shown in figure 8, a stronger diffraction peak of the material at 3.8 ℃ can be found from the XRD diffraction pattern of the material, the crystal structure of the material is proved, and the pore diameter of the material is 2.3nm through the calculation of material studio simulation, and is shown in figure 9.
Example 4
The covalent organic framework electrode material is prepared by the following method:
and (2) grinding and dispersing the covalent organic framework material, the conductive carbon black and the PVDF by using N-methyl pyrrolidone according to the mass ratio of 6:3:1, uniformly coating the mixture on the surface of the current collector, and drying the mixture at the temperature of 80 ℃ for 24 hours to obtain the required electrode.
Example 5
The specific capacitance of the electrode material is measured in the ionic liquid of the double-electrode system. The covalent organic framework materials are respectively prepared from the materials prepared in examples 1-3, and the measurement results are shown in Table 1.
Comparative example 1
The conventional small-hole covalent organic framework material is prepared by the following method:
adding 0.47g of melamine and 0.76g of terephthalaldehyde into a reaction bottle, adding 30g of mesitylene and 0.5g of 3M acetic acid aqueous solution, performing ultrasonic dispersion for 10min, performing freeze thawing for 3 times for deoxidation, and performing ultrasonic dispersion for 10min under stirring. And sealing the system in a hydrothermal reaction kettle, reacting at 140 ℃ for 72 hours, performing Soxhlet extraction on the solid material with ethanol, acetone and water for 10 hours respectively, and finally freeze-drying the solid to obtain the covalent organic framework load material. And (2) grinding and dispersing the covalent organic framework material, the conductive carbon black and the PVDF by using N-methyl pyrrolidone according to the mass ratio of 6:3:1, uniformly coating the mixture on the surface of the current collector, and drying the mixture at the temperature of 80 ℃ for 24 hours to obtain the required electrode.
BET characterization of the covalent organic framework Supported Material the specific surface area of the material was 1440m2The pore diameter of the material is 1.6nm calculated by the material intuio simulation. The specific capacitance of the electrode material was measured in a two-electrode ionic liquid, and the measurement results are shown in table 1.
Comparative example 2
The organic framework material was replaced with a commercially available activated carbon material, model yp50f, as in example 4. The specific capacitance of the electrode material was measured in a two-electrode ionic liquid, and the measurement results are shown in table 1.
TABLE 1
Therefore, the large-size melamine-based covalent organic framework material can realize the high specific volume of the ionic liquid electrolyte.
Claims (10)
1. The large-size melamine-based covalent organic framework material is characterized in that: prepared by reacting melamine with a dialdehyde ligand through Schiff base; wherein the dialdehyde ligand is 2,2 ' -bipyridine-4, 4' -dicarboxaldehyde, 2, 6-naphthaldehyde or 4,4' -biphenyldicarboxaldehyde material.
2. The large-size melamine-based covalent organic framework material of claim 1, wherein: the single aperture of the large-size melamine-based covalent organic framework material is larger than 2 nm.
3. The large-sized melamine-based covalent-organic framework of claim 1The frame material is characterized in that: the specific surface area of the large-size melamine-based covalent organic framework material is 1120-1400 m2/g。
4. The method for preparing a large-size melamine-based covalent organic framework material according to any one of claims 1 to 3, comprising the steps of:
mixing melamine and a dialdehyde ligand, adding mesitylene and an acetic acid aqueous solution, uniformly mixing, freezing and thawing for deoxidation, reacting at 140-160 ℃ for 24-72 h, purifying, and drying to obtain the large-size melamine-based covalent organic framework material.
5. The method of preparing a large-sized melamine-based covalent organic framework material of claim 4, wherein: the molar ratio of the melamine to the dialdehyde ligand is 1.5-2.5: 3; preferably, the molar ratio of melamine to dialdehyde ligands is 2: 3.
6. The method of preparing a large-sized melamine-based covalent organic framework material of claim 4, wherein: the weight ratio of the monomer, the mesitylene and the acetic acid aqueous solution is 0.6-1.4 g, 25-45 g, 0.1-1 g, wherein the monomer is melamine and a dialdehyde ligand, and the concentration of the acetic acid aqueous solution is 3M; the weight ratio of the monomer, mesitylene and aqueous acetic acid solution is preferably 1.09g to 35g to 0.5 g.
7. The method of preparing a large-sized melamine-based covalent organic framework material of claim 4, wherein: the reaction is carried out for 48h at 160 ℃.
8. The method of preparing a large-sized melamine-based covalent organic framework material of claim 4, wherein: the purification is that ethanol, acetone and water are used as solvents to perform Soxhlet extraction for 8-12 hours respectively.
9. The use of the large-size melamine-based covalent organic framework material according to any one of claims 1 to 3 for the preparation of an electrode material of a supercapacitor, wherein the supercapacitor is a supercapacitor of ionic liquid electrolyte.
10. The use of a large size melamine based covalent organic framework material according to claim 9 for the preparation of supercapacitor electrode materials, wherein: the ionic liquid electrolyte is 1-ethyl-3-methylimidazole tetrafluoroborate or 1-ethyl-3-methylimidazole bistrifluoromethanesulfonic acid imine salt.
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