CN116925311A - Carbon nano tube/phthalocyanine composite material, preparation method and application - Google Patents
Carbon nano tube/phthalocyanine composite material, preparation method and application Download PDFInfo
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- CN116925311A CN116925311A CN202311190399.XA CN202311190399A CN116925311A CN 116925311 A CN116925311 A CN 116925311A CN 202311190399 A CN202311190399 A CN 202311190399A CN 116925311 A CN116925311 A CN 116925311A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 97
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 97
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000008367 deionised water Substances 0.000 claims abstract description 48
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000013317 conjugated microporous polymer Substances 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 238000004140 cleaning Methods 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000007772 electrode material Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 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
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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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
- H01M4/362—Composites
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
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- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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Abstract
The invention provides a carbon nano tube/phthalocyanine composite material, a preparation method and application thereof, comprising the following steps: step one, synthesizing tetraminocobalt phthalocyanine; step two, synthesizing a tetra-amino cobalt phthalocyanine conjugated microporous polymer; step three, modifying the carbon nano tube; step four, preparing a carbon nano tube/phthalocyanine composite material: adding the modified carbon nano tube and tetra-amino cobalt phthalocyanine conjugated microporous polymer into a container according to a proportion, adding a proper amount of deionized water, then dripping a proper amount of 4-dimethylamino pyridine, heating to 80-100 ℃, reacting for 12-24 hours, filtering after the reaction is finished, cleaning with methanol and deionized water in sequence, adding the cleaned carbon nano tube and nano silicon dioxide into the deionized water together, carrying out ultrasonic treatment for 6-8 hours, filtering, and cleaning with deionized water to obtain the carbon nano tube/phthalocyanine composite material. The material prepared by the invention can be used as an electrode material, and has higher conductivity, high capacity retention rate and good stability.
Description
Technical Field
The invention relates to the technical field of carbon nanotubes, in particular to a carbon nanotube/phthalocyanine composite material, a preparation method and application thereof.
Background
The carbon nano tube is used as a one-dimensional nano material, has light weight, perfect hexagonal structure connection and a plurality of abnormal mechanical, electrical and chemical properties, and has wide application prospect along with the deep research of the carbon nano tube and the nano material in recent years.
The carbon nanotube, also called Baki tube, is a one-dimensional quantum material with special structure (the radial dimension is nanometer order, the axial dimension is micrometer order, the two ends of the tube are basically sealed), the carbon nanotube mainly comprises a plurality of layers to tens of layers of coaxial round tubes by carbon atoms arranged in a hexagonal shape, the distance between the layers is kept to be fixed, the diameter is generally 2-60 nm, and the carbon nanotube can be divided into three types of zigzag, armchair type and spiral type according to different orientations of the carbon hexagon along the axial direction, wherein the spiral type carbon nanotube has chirality, and the zigzag type and armchair type carbon nanotube have no chirality.
The carbon nano tube has better conductive performance, so that the carbon nano tube can be used as a conductive material of a lithium battery, however, with the development of technology, the conductive performance of a single carbon nano tube material cannot meet the use requirement, and therefore, the invention provides a carbon nano tube/phthalocyanine composite material, a preparation method and application.
Disclosure of Invention
The invention aims to provide a carbon nano tube/phthalocyanine composite material, a preparation method and application thereof, so as to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: the first aspect of the present invention provides a method for preparing a carbon nanotube/phthalocyanine composite material, comprising the steps of:
step one, synthesizing tetraminocobalt phthalocyanine:
adding 4-nitrophthalonitrile, cobalt chloride and urea into a three-mouth bottle according to a specific proportion, adding a proper amount of ammonium molybdate, carrying out reflux reaction for 5-6 h, and carrying out post-treatment to obtain tetranitrocobalt phthalocyanine, wherein the structural formula is as follows:sodium sulfide is used as a reducing agent, DMF is used as a solvent, tetranitryl cobalt phthalocyanine is reduced, the reduction reaction time is 2-3 h, the reaction temperature is 60-70 ℃, then the tetranitryl cobalt phthalocyanine is filtered, washed by deionized water and dried, and the tetranitryl cobalt phthalocyanine is prepared, wherein the structural formula is as follows: />Step two, synthesizing a tetra-amino cobalt phthalocyanine conjugated microporous polymer:
according to the mol ratio (1-2): (2-3) weighing tetra-amino cobalt phthalocyanine and terephthalaldehyde, adding the tetra-amino cobalt phthalocyanine and terephthalaldehyde into a three-mouth bottle, then adding a proper amount of N, N-dimethylacetamide as a solvent, carrying out reflux reaction under the protection of nitrogen, and purifying after the reaction is finished to obtain the tetra-amino cobalt phthalocyanine conjugated microporous polymer with the following structural formula:step three, modifying the carbon nano tube:
weighing carbon nanotubes, adding the carbon nanotubes into a mixed solution of concentrated sulfuric acid and concentrated nitric acid, carrying out ultrasonic treatment for 2-3 hours at room temperature, filtering, placing the carbon nanotubes in a cleaning device, washing the carbon nanotubes with deionized water to be neutral, and drying the carbon nanotubes for later use;
step four, preparing a carbon nano tube/phthalocyanine composite material:
adding the modified carbon nano tube and tetra-amino cobalt phthalocyanine conjugated microporous polymer into a container according to a proportion, adding a proper amount of deionized water, then dripping a proper amount of 4-dimethylamino pyridine, heating to 80-100 ℃, reacting for 12-24 hours, filtering after the reaction is finished, cleaning with methanol and deionized water in sequence, adding the cleaned carbon nano tube and nano silicon dioxide into the deionized water together, carrying out ultrasonic treatment for 6-8 hours, filtering, and cleaning with deionized water to obtain the carbon nano tube/phthalocyanine composite material.
Preferably, in the first step, the molar ratio of 4-nitrophthalonitrile, cobalt chloride and urea is 4 (1-1.5) (35-40).
Preferably, the post-treatment step of tetranitrocobalt phthalocyanine in the step one is as follows: after the reaction is finished, filtering, adding the crude product into deionized water, firstly dropwise adding a proper amount of dilute hydrochloric acid solution until the pH value is acidic, magnetically stirring for 2-3 h, then dropwise adding a proper amount of sodium hydroxide solution until the pH value is alkaline, magnetically stirring for 1-2 h, finally filtering, washing with deionized water until the pH value is neutral, and drying for later use.
Preferably, the reaction temperature of the di-tetra-amino cobalt phthalocyanine conjugated microporous polymer in the step is 120-200 ℃ and the reaction time is 60-72 h.
Preferably, in the third step, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution of the concentrated sulfuric acid and the concentrated nitric acid is (5-6): 1.
preferably, the purity of the carbon nano tube in the third step is more than or equal to 90%, the diameter is 5-60 nm, and the length is less than or equal to 50 mu m.
Preferably, in the fourth step, the molar ratio of the carbon nanotube, the tetra-amino cobalt phthalocyanine conjugated microporous polymer and the nano-silica is (40-50): (6-12): (0.5-2).
Preferably, the cleaning device in the third step comprises a barrel body, a cover plate is arranged at the top of the barrel body, a micro motor is arranged on the top surface of the cover plate, a rotating shaft is arranged at the output end of the micro motor, the rotating shaft penetrates through the cover plate and extends to the inside of the barrel body, a limit column is arranged in the barrel body, a limit column is sleeved outside the rotating shaft, a door-shaped support is sleeved above the limit column, filter cartridges are arranged on two sides of the door-shaped support, and bolts are jointly penetrated between the side wall of the cover plate and the side wall of the barrel body.
In a second aspect, the present invention provides a carbon nanotube/phthalocyanine composite produced by the method of the first aspect of the present invention.
In a third aspect, the present invention provides an application of the carbon nanotube/phthalocyanine composite material according to the second aspect of the present invention, wherein the carbon nanotube/phthalocyanine composite material can be used as an electrode material.
The invention has at least the following beneficial effects:
(1) According to the carbon nano tube/phthalocyanine composite material, the preparation method and the application, more lithium storage sites can be provided by introducing the tetra-amino cobalt phthalocyanine conjugated microporous polymer, and electron transfer is performed between the phthalocyanine and the carbon nano tube through an amide bond, so that the electron transfer efficiency is higher, and the carbon nano tube and the tetra-amino cobalt phthalocyanine conjugated microporous polymer are high in stability, so that the prepared material can be used as an electrode material, and has higher conductivity, high capacity retention rate and good stability;
(2) Compared with the existing method of carrying out suction filtration and flushing by adopting deionized water, the carbon nano tube/phthalocyanine composite material, the preparation method and the application thereof provided by the invention have the advantages that the water consumption is greatly saved, the cleaning time is longer, and the cleaning effect is good.
Drawings
FIG. 1 is a synthetic route diagram of a carbon nanotube/phthalocyanine composite material according to the present invention;
fig. 2 is a structural view of a cleaning apparatus according to the present invention.
In the reference numerals: 1. a tub body; 2. a cover plate; 3. a micro motor; 4. a rotating shaft; 5. a limit column; 6. a door-shaped bracket; 7. a filter cartridge; 8. a bolt.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a carbon nano tube/phthalocyanine composite material comprises the following steps:
step one, synthesizing tetraminocobalt phthalocyanine:
adding 4-nitrophthalonitrile, cobalt chloride and urea into a three-mouth bottle according to the molar ratio of 4:1:35, adding a proper amount of ammonium molybdate, carrying out reflux reaction for 5 hours, and carrying out aftertreatment to obtain tetranitrocobalt phthalocyanine;
the post-treatment steps of tetranitrocobalt phthalocyanine are as follows: after the reaction is finished, filtering, adding the crude product into deionized water, firstly dropwise adding a proper amount of dilute hydrochloric acid solution until the pH value is acidic, magnetically stirring for 2 hours, then dropwise adding a proper amount of sodium hydroxide solution until the pH value is alkaline, magnetically stirring for 1 hour, filtering, washing with deionized water until the solution is neutral, and drying for later use;
tetranitrocobalt phthalocyanine has the structural formula:sodium sulfide is used as a reducing agent, DMF is used as a solvent, tetranitro cobalt phthalocyanine is reduced, the reduction reaction time is 2 hours, the reaction temperature is 60 ℃, then the tetranitro cobalt phthalocyanine is filtered, washed by deionized water and dried, and the tetraamino cobalt phthalocyanine is prepared, wherein the structural formula is as follows: />Step two, synthesizing a tetra-amino cobalt phthalocyanine conjugated microporous polymer:
according to the mole ratio of 1:2 weighing tetra-amino cobalt phthalocyanine and terephthalaldehyde, adding the tetra-amino cobalt phthalocyanine and terephthalaldehyde into a three-mouth bottle, then adding a proper amount of N, N-dimethylacetamide as a solvent, carrying out reflux reaction under the protection of nitrogen, wherein the reflux reaction temperature is 120 ℃, the reaction time is 72 hours, and purifying after the reaction is finished to obtain the tetra-amino cobalt phthalocyanine conjugated microporous polymer with the following structural formula:step three, modifying the carbon nano tube:
weighing carbon nanotubes (the purity is more than or equal to 90%, the diameter is 5-10 nm, the length is less than or equal to 50 mu m), adding the carbon nanotubes into a mixed solution of concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 5:1), carrying out ultrasonic treatment for 2 hours at room temperature, filtering, placing the carbon nanotubes in a cleaning device, washing the carbon nanotubes to be neutral by deionized water, and drying the carbon nanotubes for later use;
step four, preparing a carbon nano tube/phthalocyanine composite material:
adding the modified carbon nano tube and tetra-amino cobalt phthalocyanine conjugated microporous polymer into a container according to a proportion, adding a proper amount of deionized water, then dripping a proper amount of 4-dimethylamino pyridine, heating to 80 ℃, reacting for 12 hours, filtering after the reaction is finished, cleaning sequentially by methanol and deionized water, adding the cleaned carbon nano tube and nano silicon dioxide into the deionized water together, carrying out ultrasonic treatment for 6 hours, filtering, and cleaning by deionized water to obtain the carbon nano tube/phthalocyanine composite material;
wherein, the molar ratio of the carbon nano tube, the tetra-amino cobalt phthalocyanine conjugated microporous polymer and the nano silicon dioxide is 40:6:0.5.
example 2
A preparation method of a carbon nano tube/phthalocyanine composite material comprises the following steps:
step one, synthesizing tetraminocobalt phthalocyanine:
adding 4-nitrophthalonitrile, cobalt chloride and urea into a three-mouth bottle according to the molar ratio of 4:1.2:38, adding a proper amount of ammonium molybdate, carrying out reflux reaction for 5.5h, and carrying out post-treatment to obtain tetranitrocobalt phthalocyanine;
the post-treatment steps of tetranitrocobalt phthalocyanine are as follows: after the reaction is finished, filtering, adding the crude product into deionized water, firstly dropwise adding a proper amount of dilute hydrochloric acid solution until the pH value is acidic, magnetically stirring for 2.5 hours, then dropwise adding a proper amount of sodium hydroxide solution until the pH value is alkaline, magnetically stirring for 1.5 hours, filtering, washing with deionized water to be neutral, and drying for later use;
tetranitrocobalt phthalocyanine has the structural formula:sodium sulfide as reductionReducing tetranitryl cobalt phthalocyanine by using DMF as a solvent, wherein the reduction reaction time is 2.5h, the reaction temperature is 60 ℃, filtering, washing with deionized water, and drying to obtain tetraminocobalt phthalocyanine, wherein the structural formula is as follows:step two, synthesizing a tetra-amino cobalt phthalocyanine conjugated microporous polymer:
according to the mole ratio of 2:2 weighing tetra-amino cobalt phthalocyanine and terephthalaldehyde, adding the tetra-amino cobalt phthalocyanine and terephthalaldehyde into a three-mouth bottle, then adding a proper amount of N, N-dimethylacetamide as a solvent, carrying out reflux reaction under the protection of nitrogen, wherein the reflux reaction temperature is 180 ℃, the reaction time is 72 hours, and purifying after the reaction is finished to obtain the tetra-amino cobalt phthalocyanine conjugated microporous polymer with the following structural formula:step three, modifying the carbon nano tube:
weighing carbon nanotubes (the purity is more than or equal to 90%, the diameter is 10-30 nm, the length is less than or equal to 50 mu m), adding the carbon nanotubes into a mixed solution of concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 5.5:1), performing ultrasonic treatment for 2.5 hours at room temperature, filtering, placing the carbon nanotubes in a cleaning device, washing the carbon nanotubes with deionized water to be neutral, and drying the carbon nanotubes for later use;
step four, preparing a carbon nano tube/phthalocyanine composite material:
adding the modified carbon nano tube and tetra-amino cobalt phthalocyanine conjugated microporous polymer into a container according to a proportion, adding a proper amount of deionized water, then dripping a proper amount of 4-dimethylamino pyridine, heating to 90 ℃, reacting for 18 hours, filtering after the reaction is finished, cleaning with methanol and deionized water in sequence, adding the cleaned carbon nano tube and the nano silicon dioxide into the deionized water together, carrying out ultrasonic treatment for 7 hours, filtering, and cleaning with deionized water to obtain the carbon nano tube/phthalocyanine composite material;
wherein, the molar ratio of the carbon nano tube, the tetra-amino cobalt phthalocyanine conjugated microporous polymer and the nano silicon dioxide is 45:10:1.
example 3
A preparation method of a carbon nano tube/phthalocyanine composite material comprises the following steps:
step one, synthesizing tetraminocobalt phthalocyanine:
adding 4-nitrophthalonitrile, cobalt chloride and urea into a three-mouth bottle according to the molar ratio of 4:1.5:40, adding a proper amount of ammonium molybdate, carrying out reflux reaction for 6 hours, and carrying out aftertreatment to obtain tetranitrocobalt phthalocyanine;
the post-treatment steps of tetranitrocobalt phthalocyanine are as follows: after the reaction is finished, filtering, adding the crude product into deionized water, firstly dropwise adding a proper amount of dilute hydrochloric acid solution until the pH value is acidic, magnetically stirring for 3 hours, then dropwise adding a proper amount of sodium hydroxide solution until the pH value is alkaline, magnetically stirring for 2 hours, filtering, washing with deionized water until the solution is neutral, and drying for later use;
tetranitrocobalt phthalocyanine has the structural formula:sodium sulfide is used as a reducing agent, DMF is used as a solvent, tetranitro cobalt phthalocyanine is reduced, the reduction reaction time is 3 hours, the reaction temperature is 60 ℃, then the tetranitro cobalt phthalocyanine is filtered, washed by deionized water and dried, and the tetraamino cobalt phthalocyanine is prepared, wherein the structural formula is as follows: />Step two, synthesizing a tetra-amino cobalt phthalocyanine conjugated microporous polymer:
according to the mole ratio of 2: weighing tetra-amino cobalt phthalocyanine and terephthalaldehyde, adding the tetra-amino cobalt phthalocyanine and terephthalaldehyde into a three-mouth bottle, then adding a proper amount of N, N-dimethylacetamide as a solvent, carrying out reflux reaction under the protection of nitrogen, wherein the reflux reaction temperature is 200 ℃, the reaction time is 72 hours, and purifying after the reaction is finished to obtain the tetra-amino cobalt phthalocyanine conjugated microporous polymer with the following structural formula:step three, modifying the carbon nano tube:
weighing carbon nanotubes (the purity is more than or equal to 90%, the diameter is 30-60 nm, the length is less than or equal to 50 mu m), adding the carbon nanotubes into a mixed solution of concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 6:1), carrying out ultrasonic treatment for 3 hours at room temperature, filtering, placing the carbon nanotubes in a cleaning device, washing the carbon nanotubes to be neutral by deionized water, and drying the carbon nanotubes for later use;
step four, preparing a carbon nano tube/phthalocyanine composite material:
adding the modified carbon nano tube and tetra-amino cobalt phthalocyanine conjugated microporous polymer into a container according to a proportion, adding a proper amount of deionized water, then dripping a proper amount of 4-dimethylamino pyridine, heating to 100 ℃, reacting for 24 hours, filtering after the reaction is finished, cleaning sequentially by methanol and deionized water, adding the cleaned carbon nano tube and nano silicon dioxide into the deionized water together, carrying out ultrasonic treatment for 8 hours, filtering, and cleaning by deionized water to obtain the carbon nano tube/phthalocyanine composite material;
wherein, the molar ratio of the carbon nano tube, the tetra-amino cobalt phthalocyanine conjugated microporous polymer and the nano silicon dioxide is 50:12:2.
according to the invention, more lithium storage sites can be provided by introducing the tetra-amino cobalt phthalocyanine conjugated microporous polymer, and electron transfer is performed between the phthalocyanine and the carbon nano tube through an amide bond, so that the electron transfer efficiency is higher, and the stability of the carbon nano tube and the tetra-amino cobalt phthalocyanine conjugated microporous polymer is high. In addition, the conductivity can be further improved by introducing nanosilica.
Grinding and dispersing the materials obtained in the examples 1-3 with PVP and a dispersing aid by taking NMP as a solvent, mixing the materials with acetylene carbon black serving as a conductive agent, PVDF serving as an adhesive and NCM serving as a main material in proportion after full dispersion, adding a proper amount of NMP for full dispersion, uniformly coating the mixture on the surface of an aluminum foil, drying the mixture to prepare a wafer with the thickness of 12mm and 1mg, taking a metal lithium sheet as a counter electrode, and adopting 1mol/L LiPF as an electrolyte 6 And (3) dissolving the membrane in an EC/EDC mixed solution with the volume ratio of 1:1, and assembling the button cell by using a Celgard microporous membrane as a diaphragm to perform performance test.
The materials prepared in examples 1 to 3 above were subjected to the relevant tests, and the results are shown in the following table:
as shown in the table, the material obtained by the invention has higher conductivity, high capacity retention rate and wide application prospect.
The third embodiment 1-3 provides a cleaning device, which comprises a barrel body 1, the top of the barrel body 1 is provided with a cover plate 2, the top surface of the cover plate 2 is provided with a micro motor 3, the micro motor 3 is fixedly connected with the cover plate 2, the output end of the micro motor 3 is provided with a rotating shaft 4, the rotating shaft 4 is fixedly connected with the output end of the micro motor 3, the rotating shaft 4 penetrates through the cover plate 2 and extends to the inside of the barrel body 1, the rotating shaft 4 is rotatably connected with the cover plate 2, a limit post 5 is arranged in the inside of the barrel body 1, the bottom of the limit post 5 is fixedly connected with the bottom wall of the barrel body 1, the limit post 5 is sleeved outside the rotating shaft 4, the rotating shaft 4 is slidably connected with the limit post 5, a door-shaped bracket 6 is sleeved above the limit post 5, the door-shaped bracket 6 is fixedly connected with the rotating shaft 4, filter cylinders 7 are arranged on two sides of the door-shaped bracket 6, the side walls of the cover plate 2 are fixedly connected with the door-shaped bracket 6 through connecting rods, and 8 are jointly penetrated between the side walls of the cover plate 2 and the side walls of the barrel body 1, and the side walls of the barrel body 2 are slidably connected with the side walls of the barrel body 1.
The working flow of the cleaning device is as follows: when the novel water purifier works, the plug pins 8 are pulled out, the cover plate 2 is lifted upwards, the cover plate 2 drives the rotating shaft 4 to lift upwards, the rotating shaft 4 moves upwards stably along the limiting columns 5 to drive the filter drum 7 to move upwards, when the filter drum 7 moves to the top of the barrel body 1, filter paper is filled in the filter drum 7, then coarse products which need to be washed by deionized water are placed in the filter paper, the deionized water is injected into the barrel body 1, then the cover plate 2 is slowly moved downwards, when the cover plate 2 is overlapped with the top of the barrel body 1, the plug pins 8 are inserted into the cover plate 2 and the barrel body 1, the cover plate 2 is fixed, the micro motor 3 is started, the rotating shaft 4 is driven to rotate, and the filter drum 7 is driven to rotate for washing.
Because the existing cleaning mode adopts deionized water for suction filtration and flushing, the water consumption is high, the resource is wasted, the flushing time is short, and the flushing effect is poor.
While the fundamental principles, principal features, and advantages of the present invention have been shown and described, it will be apparent to those skilled in the art that the present invention is not limited to the details of the foregoing exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the carbon nano tube/phthalocyanine composite material is characterized by comprising the following steps of:
step one, synthesizing tetraminocobalt phthalocyanine:
adding 4-nitrophthalonitrile, cobalt chloride and urea into a three-mouth bottle according to a specific proportion, adding a proper amount of ammonium molybdate, carrying out reflux reaction for 5-6 h, and carrying out post-treatment to obtain tetranitrocobalt phthalocyanine, wherein the structural formula is as follows:sodium sulfide is used as a reducing agent, DMF is used as a solvent, tetranitryl cobalt phthalocyanine is reduced, the reduction reaction time is 2-3 h, the reaction temperature is 60-70 ℃, then the tetranitryl cobalt phthalocyanine is filtered, washed by deionized water and dried, and the tetranitryl cobalt phthalocyanine is prepared, wherein the structural formula is as follows:
step two, synthesizing a tetra-amino cobalt phthalocyanine conjugated microporous polymer:
according to the mol ratio (1-2): (2-3) weighing tetra-amino cobalt phthalocyanine and terephthalaldehyde, adding the tetra-amino cobalt phthalocyanine and terephthalaldehyde into a three-mouth bottle, then adding a proper amount of N, N-dimethylacetamide as a solvent, carrying out reflux reaction under the protection of nitrogen, and purifying after the reaction is finished to obtain the tetra-amino cobalt phthalocyanine conjugated microporous polymer with the following structural formula:
step three, modifying the carbon nano tube:
weighing carbon nanotubes, adding the carbon nanotubes into a mixed solution of concentrated sulfuric acid and concentrated nitric acid, carrying out ultrasonic treatment for 2-3 hours at room temperature, filtering, placing the carbon nanotubes in a cleaning device, washing the carbon nanotubes with deionized water to be neutral, and drying the carbon nanotubes for later use;
step four, preparing a carbon nano tube/phthalocyanine composite material:
adding the modified carbon nano tube and tetra-amino cobalt phthalocyanine conjugated microporous polymer into a container according to a proportion, adding a proper amount of deionized water, then dripping a proper amount of 4-dimethylamino pyridine, heating to 80-100 ℃, reacting for 12-24 hours, filtering after the reaction is finished, cleaning with methanol and deionized water in sequence, adding the cleaned carbon nano tube and nano silicon dioxide into the deionized water together, carrying out ultrasonic treatment for 6-8 hours, filtering, and cleaning with deionized water to obtain the carbon nano tube/phthalocyanine composite material.
2. The method for preparing a carbon nanotube/phthalocyanine composite material according to claim 1, wherein the molar ratio of 4-nitrophthalonitrile, cobalt chloride and urea in the step one is 4 (1-1.5) (35-40).
3. The method for preparing a carbon nanotube/phthalocyanine composite material according to claim 1, wherein the post-treatment step of tetranitrocobalt phthalocyanine in the step one is as follows: after the reaction is finished, filtering, adding the crude product into deionized water, firstly dropwise adding a proper amount of dilute hydrochloric acid solution until the pH value is acidic, magnetically stirring for 2-3 h, then dropwise adding a proper amount of sodium hydroxide solution until the pH value is alkaline, magnetically stirring for 1-2 h, finally filtering, washing with deionized water until the pH value is neutral, and drying for later use.
4. The method for preparing a carbon nanotube/phthalocyanine composite material according to claim 1, wherein the reaction temperature of the step di-tetra-amino cobalt phthalocyanine conjugated microporous polymer is 120-200 ℃ and the reaction time is 60-72 h.
5. The method for preparing a carbon nanotube/phthalocyanine composite material according to claim 1, wherein in the third step, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution of the concentrated sulfuric acid and the concentrated nitric acid is (5-6): 1.
6. the method for preparing a carbon nanotube/phthalocyanine composite material according to claim 1, wherein the purity of the carbon nanotubes in the third step is not less than 90%, the diameter is 5-60 nm, and the length is not more than 50. Mu.m.
7. The method for preparing a carbon nanotube/phthalocyanine composite material according to claim 1, wherein in the fourth step, the molar ratio of carbon nanotubes, tetra-amino cobalt phthalocyanine conjugated microporous polymer and nano-silica is (40-50): (6-12): (0.5-2).
8. The preparation method of the carbon nanotube/phthalocyanine composite material according to claim 1, wherein the cleaning device in the third step comprises a barrel body (1), a cover plate (2) is arranged at the top of the barrel body (1), a micro motor (3) is arranged on the top surface of the cover plate (2), a rotating shaft (4) is arranged at the output end of the micro motor (3), the rotating shaft (4) penetrates through the cover plate (2) and extends to the inside of the barrel body (1), a limit column (5) is arranged in the barrel body (1), the limit column (5) is sleeved outside the rotating shaft (4), a door-shaped bracket (6) is sleeved above the limit column (5) by the rotating shaft (4), a filter cartridge (7) is arranged on two sides of the door-shaped bracket (6), and a bolt (8) is jointly arranged between the side wall of the cover plate (2) and the side wall of the barrel body (1).
9. A carbon nanotube/phthalocyanine composite, characterized in that it is produced by the method of any one of claims 1 to 8.
10. Use of the carbon nanotube/phthalocyanine composite according to claim 9 as an electrode material.
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