CN116534846B - Preparation device and preparation method of carbon nanotube slurry - Google Patents
Preparation device and preparation method of carbon nanotube slurry Download PDFInfo
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- CN116534846B CN116534846B CN202310369976.5A CN202310369976A CN116534846B CN 116534846 B CN116534846 B CN 116534846B CN 202310369976 A CN202310369976 A CN 202310369976A CN 116534846 B CN116534846 B CN 116534846B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 134
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 80
- 239000002002 slurry Substances 0.000 title claims abstract description 57
- 239000006185 dispersion Substances 0.000 claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 32
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 32
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000001105 regulatory effect Effects 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005520 cutting process Methods 0.000 abstract description 5
- 238000010902 jet-milling Methods 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 238000000935 solvent evaporation Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- 238000002834 transmittance Methods 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/176—Cutting
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly discloses a preparation device and a preparation method of carbon nanotube slurry. Adopting jet milling and supercritical carbon dioxide to realize nondestructive dispersion of the carbon nano tubes; directly preparing the dispersed carbon nano tube into high-conductivity slurry by adopting supercritical nitrogen methyl pyrrolidone; avoiding the condition of cutting off and damaging the conductive network of the carbon nano tube in the prior art.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation device and a preparation method of carbon nanotube slurry.
Background
The carbon nano tube has a unique one-dimensional nano tube structure, and the sp is mainly used between carbon atoms 2 The hybrid mode forms delocalized pi bonds, and further exhibits excellent mechanical, electrical, magnetic and optical properties. The high-quality carbon nano tube with high length-diameter ratio can form pi-pi conjugation strong force besides intermolecular force between CNTs and tubes due to pi bond in the delocalization, so that the tubes of the carbon nano tube are mutually adhered or wound to form an aggregate. The physical and chemical properties of the polymer can be weakened, the polymer is difficult to disperse in a non-aromatic solvent, and the application of the polymer in the fields of battery conductive agents, antistatic coatings, hot spot coatings, cement and polymer composite materials and the like is limited to a great extent. In recent years, the market size of highly conductive carbon nanotube pastes has increased with rapid penetration of the carbon nanotube paste in the field of lithium conductive additives.
Carbon nanotube slurry preparation typically includes surface modification to reduce the degree of tube-to-tube adhesion and entanglement, and surface modification includes chemical modification and surfactant-assisted dispersion, which is typically employed because chemical modification can disrupt the conductivity of the carbon nanotubes. The disclosed preparation method of the carbon nano tube slurry comprises ball milling, mechanical stirring, ultrasonic, nano sand milling shearing, homogenizing shearing and the like, and as shown in the U.S. patent No. 2006039848, the method adopts high-frequency ultrasonic wave with the frequency of more than 20KHz to disperse the single-wall carbon nano tubes in the laboratory preparation level, and is not suitable for large-scale industrial production; chinese patent No. CN201610763172.3 discloses a high viscosity slurry ultrasonic strong dispersion apparatus, which comprises an ultrasonic dispersion device, an autoclave, a homogenizer and a low pressure autoclave; the Chinese patent No. 201310350352.5 discloses a method for preparing aqueous carbon nanotube slurry by stirring or sanding, wherein one or more of ultrasonic, nano sanding and homogenizing shearing are usually used in the method, and the method is often used for cutting off and damaging a conductive network of the carbon nanotubes in the process of dispersing the carbon nanotubes, so that the high conductivity of the prepared slurry is not easy to maintain.
Disclosure of Invention
The invention aims to provide a preparation device and a preparation method of carbon nanotube slurry, which are used for solving the problems that the traditional preparation method of the carbon nanotube slurry is often used for cutting off and damaging a conductive network of the carbon nanotube in the process of dispersing the carbon nanotube, and is not beneficial to maintaining the high conductivity of the prepared slurry.
In order to achieve the above purpose, the technical scheme of the invention is as follows: the preparation device of the carbon nano tube slurry comprises a dispersion system and a preparation system, wherein the dispersion system comprises a supercritical dispersion kettle, a first pressure regulating structure, a first pressure measuring structure, a first heating structure, a first temperature measuring structure and a first conveying structure, the preparation system comprises a second conveying structure, a third conveying structure, a supercritical preparation kettle, a second heating structure, a second temperature measuring structure, a second pressure regulating structure and a second pressure measuring structure, the first conveying structure is used for conveying carbon dioxide into the supercritical dispersion kettle, and the first pressure regulating structure and the first heating structure are respectively used for regulating the pressure and the temperature in the supercritical dispersion kettle to the supercritical condition of the carbon dioxide; the second conveying structure is used for conveying the carbon nanotubes after the dispersion in the supercritical dispersion kettle to a supercritical preparation kettle; the third conveying structure is used for conveying the nitrogen methyl pyrrolidone into the supercritical preparation kettle, and the second pressure regulating structure and the second heating structure are respectively used for regulating the pressure and the temperature in the supercritical preparation kettle to the supercritical conditions of the nitrogen methyl pyrrolidone; the first pressure measuring structure and the second pressure measuring structure are respectively used for detecting the pressure intensity in the supercritical dispersing kettle and the supercritical preparation kettle, and the first temperature measuring structure and the second temperature measuring structure are respectively used for detecting the temperature in the supercritical dispersing kettle and the supercritical preparation kettle.
Further, the supercritical dispersing kettle is located above the supercritical preparation kettle, a discharge port of the supercritical dispersing kettle is opposite to a feed port of the supercritical preparation kettle, and the second conveying structure is used for communicating and blocking the discharge port of the supercritical dispersing kettle and the feed port of the supercritical preparation kettle.
Further, the first heating structure and the second heating structure are both heating jackets, and the first heating structure and the second heating structure are respectively arranged outside the supercritical dispersing kettle and the supercritical preparation kettle.
Further, the dispersion system further comprises an air flow pulverizer and a fourth conveying structure, wherein the air flow pulverizer is used for pulverizing the carbon nanotube powder, and the fourth conveying structure is used for conveying the pulverized carbon nanotube powder into the supercritical dispersion kettle.
Further, the first pressure regulating structure and the second pressure regulating structure comprise a driving piece, a piston and a baffle; the baffle is arranged on the periphery of the piston, openings are formed in one side of the supercritical preparation kettle and one side of the supercritical dispersion kettle, and the baffle is in sliding connection with the openings; the driving piece is used for driving the piston to reciprocate.
Further, a sealing layer is arranged on one side of the baffle plate, which is contacted with the opening.
Further, the second conveying structure adopts an drift diameter ball valve.
Further, a collection system for collecting the prepared carbon nanotube slurry is also included, the collection system including a collection tank and a fifth conveying structure for transporting the carbon nanotube slurry in the supercritical preparation tank to the collection tank.
A method for preparing carbon nanotube slurry, comprising the steps of:
adding carbon nano tube powder into a jet mill, crushing for t1 time by the jet mill, opening a fourth conveying structure, conveying the crushed carbon nano tube powder to a supercritical dispersion kettle by the fourth conveying structure, and closing the fourth conveying structure when the volume of the carbon nano tube accounts for a certain proportion of the volume of the supercritical dispersion kettle;
opening a first conveying structure, injecting carbon dioxide into the supercritical dispersion kettle, and opening a first pressure regulating structure and a first heating structure until the temperature in the supercritical dispersion kettle is 500-750 ℃ and the pressure is 10-30Mpa, so that the carbon dioxide reaches a supercritical state; carbon dioxide in a supercritical state etches carbon nanotube impurities and disperses the carbon nanotubes, and after dispersing for t2 time, the first conveying structure is closed, and the supercritical dispersing kettle is cooled to room temperature;
after the supercritical dispersion kettle is cooled, opening a second conveying structure to enable the dispersed carbon nano tubes to enter a supercritical preparation kettle, then opening a third conveying structure, injecting nitrogen methyl pyrrolidone into the supercritical preparation kettle, opening a second pressure regulating structure and a second heating structure until the temperature in the supercritical preparation kettle is 445-750 ℃ and the pressure is 4.76-30Mpa, enabling the nitrogen methyl pyrrolidone to reach a supercritical state, maintaining t3 time, and preparing the carbon nano tubes into carbon nano tube slurry;
and opening a fifth conveying structure, and conveying the prepared carbon nano tube slurry to a collecting kettle for collecting.
Further, the ratio of the volume of the carbon nano tube to the volume of the supercritical dispersion kettle is 1/2-3/4.
The working principle of the technical scheme is as follows: the carbon nanotube powder is crushed by an air flow crusher and enters a supercritical dispersion kettle, impurities on the carbon nanotubes are etched by high-temperature supercritical carbon dioxide and dispersed, the dispersed carbon nanotubes are rapidly introduced into a supercritical preparation kettle after being cooled, the carbon nanotube dispersion is prepared into slurry by supercritical nitrogen methyl pyrrolidone, and finally the slurry is collected in a collection kettle.
The beneficial effects of this technical scheme lie in: the technical scheme adopts jet milling and supercritical carbon dioxide to realize nondestructive dispersion of the carbon nano tubes; directly preparing the dispersed carbon nano tube into high-conductivity slurry by adopting supercritical nitrogen methyl pyrrolidone; avoiding the condition of cutting off and damaging the conductive network of the carbon nano tube in the prior art. The technical scheme has simple equipment structure and can prepare high-conductivity carbon nano tube slurry in batches.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing a carbon nanotube slurry according to the present invention;
FIG. 2 is a schematic structural diagram of the supercritical dispersing vessel and the supercritical preparation vessel in FIG. 1;
FIG. 3 is a front view of FIG. 2;
FIG. 4 is a cross-sectional view taken along line A-A of FIG. 3;
FIG. 5 is a cross-sectional view B-B of FIG. 3;
FIG. 6 is a graph showing the transmittance of the carbon nanotube slurry according to the first embodiment;
FIG. 7 is a graph showing the transmittance of the carbon nanotube slurry according to the second embodiment;
FIG. 8 is a graph showing the transmittance of the carbon nanotube slurry in the third embodiment;
FIG. 9 is an X-ray diffraction chart of the carbon nanotube slurry of example I and comparative example I after solvent evaporation;
FIG. 10 is a Raman spectrum of the carbon nanotube slurry of example I and comparative example I after solvent evaporation.
Detailed Description
The following is a further detailed description of the embodiments:
reference numerals in the drawings of the specification include: the jet mill comprises a jet mill 1, a fourth conveying structure 2, a supercritical dispersion kettle 3, a first conveying structure 4, a second conveying structure 5, a first pressure regulating structure 6, a third conveying structure 7, a supercritical preparation kettle 8, a fifth conveying structure 9, a collecting kettle 10, a second pressure regulating structure 11, a driving piece 12, a baffle 13, a piston 14 and a heating jacket 15.
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described 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.
The embodiment is basically as shown in the accompanying figures 1-5: the preparation device of the carbon nano tube slurry comprises a dispersion system, a preparation system and a collection system, wherein the dispersion system comprises a jet mill 1, a fourth conveying structure 2, a supercritical dispersion kettle 3, a first pressure regulating structure 6, a first pressure measuring structure, a first heating structure, a first temperature measuring structure and a first conveying structure 4. The preparation system comprises a second conveying structure 5, a third conveying structure 7, a supercritical preparation kettle 8, a second heating structure, a second temperature measuring structure, a second pressure regulating structure 11 and a second pressure measuring structure, wherein the volume of the supercritical preparation kettle 8 is 10-200 times that of the supercritical dispersion kettle 3. The collecting system is used for collecting the prepared carbon nanotube slurry, and comprises a collecting kettle 10 and a fifth conveying structure 9, wherein the fifth conveying structure 9 is used for conveying the carbon nanotube slurry in the supercritical preparation kettle 8 to the collecting kettle 10. Each structure is supported and installed by adopting a bracket.
The jet mill 1 is used for smashing carbon nanotube powder, the fourth conveying structure 2 is used for conveying the smashed carbon nanotube powder into the supercritical dispersion kettle 3, the first conveying structure 4 is used for conveying carbon dioxide into the supercritical dispersion kettle 3, and the first pressure regulating structure 6 and the first heating structure are respectively used for regulating the pressure and the temperature in the supercritical dispersion kettle 3 to the supercritical condition of the carbon dioxide. The second conveying structure 5 is used for conveying the carbon nanotubes after the completion of dispersion in the supercritical dispersion kettle 3 into the supercritical preparation kettle 8, specifically, the supercritical dispersion kettle 3 is located above the supercritical preparation kettle 8, the discharge port of the supercritical dispersion kettle 3 is opposite to the feed port of the supercritical preparation kettle 8, the second conveying structure 5 is used for communicating and blocking the discharge port of the supercritical dispersion kettle 3 and the feed port of the supercritical preparation kettle 8, and the second conveying structure 5 adopts a drift diameter ball valve. The third conveying structure 7 is used for conveying the nitrogen methyl pyrrolidone into the supercritical preparation kettle 8, and the second pressure regulating structure 11 and the second heating structure are respectively used for regulating the pressure and the temperature in the supercritical preparation kettle 8 to the supercritical conditions of the nitrogen methyl pyrrolidone. The first pressure measuring structure and the second pressure measuring structure are respectively used for detecting the pressure intensity in the supercritical dispersion kettle 3 and the supercritical preparation kettle 8, and the pressure gauges can be adopted for the first pressure measuring structure and the second pressure measuring structure. The first temperature measuring structure and the second temperature measuring structure are respectively used for detecting the temperature in the supercritical dispersing kettle 3 and the supercritical preparation kettle 8, and thermocouples can be adopted for the first temperature measuring structure and the second temperature measuring structure. The first heating structure and the second heating structure are respectively arranged outside the supercritical dispersing kettle 3 and the supercritical preparation kettle 8 by adopting a heating jacket 15.
The first pressure regulating structure 6 and the second pressure regulating structure 11 comprise a driving piece 12, a piston 14 and a baffle 13; the baffle 13 is arranged on the periphery of the piston 14, openings are arranged on one side of the supercritical preparation kettle 8 and one side of the supercritical dispersion kettle 3, the baffle 13 is in sliding connection with the openings, and a sealing layer is arranged on one side of the baffle 13, which is in contact with the openings; the driving member 12 is used to drive the piston 14 back and forth.
Specifically, the fourth conveying structure 2, the first conveying structure 4, the third conveying structure 7 and the fifth conveying structure 9 all adopt conveying pump bodies, and the driving piece 12 adopts linear driving equipment such as a linear motor, a driving cylinder and the like.
The specific implementation process is as follows: the carbon nanotube powder is crushed by an air flow crusher 1 and enters a supercritical dispersion kettle 3, impurities on the carbon nanotubes are etched by high-temperature supercritical carbon dioxide and dispersed, the dispersed carbon nanotubes are rapidly introduced into a supercritical preparation kettle 8 after being cooled, the carbon nanotube dispersion is prepared into slurry by supercritical nitrogen methyl pyrrolidone, and finally the slurry is collected in a collection kettle 10.
A method for preparing carbon nanotube slurry, comprising the steps of:
s1: adding carbon nano tube powder into a jet mill 1, after the jet mill 1 is used for milling t1 (0.5 h in the embodiment), opening a discharge hole of the jet mill 1 and opening a fourth conveying structure 2, conveying the milled carbon nano tube powder to a supercritical dispersion kettle 3 by the fourth conveying structure 2, and closing the fourth conveying structure 2 when the volume of the carbon nano tube accounts for a certain proportion of the volume of the supercritical dispersion kettle 3, wherein the proportion of the volume of the carbon nano tube accounts for 1/2-3/4 of the volume of the supercritical dispersion kettle 3;
s2: opening a first conveying structure 4, injecting carbon dioxide into the supercritical dispersion kettle 3, and opening a first pressure regulating structure 6 and a first heating structure until the temperature in the supercritical dispersion kettle 3 is 500-750 ℃ and the pressure is 10-30Mpa, so that the carbon dioxide reaches a supercritical state; carbon dioxide in a supercritical state etches carbon nanotube impurities and disperses the carbon nanotubes, and after dispersing for t2 (0.5-4 h), the first conveying structure 4 is closed, and the supercritical dispersing kettle 3 is cooled to room temperature;
s3: after the supercritical dispersion kettle 3 is cooled, rapidly opening a second conveying structure 5 to enable the dispersed carbon nano-tubes to enter a supercritical preparation kettle 8 in a very short time, then opening a third conveying structure 7, injecting nitrogen methyl pyrrolidone into the supercritical preparation kettle 8, opening a second pressure regulating structure 11 and a second heating structure until the temperature in the supercritical preparation kettle 8 is 445-750 ℃ and the pressure is 4.76-30Mpa, enabling the nitrogen methyl pyrrolidone to reach a supercritical state, maintaining t3 (0.5-2 h) and preparing the carbon nano-tubes into carbon nano-tube slurry;
s4: the fifth conveying structure 9 is opened, and the prepared carbon nanotube slurry is conveyed to the collecting kettle 10 for collecting.
The technical scheme adopts jet milling and supercritical carbon dioxide to realize nondestructive dispersion of the carbon nano tubes; directly preparing the dispersed carbon nano tube into high-conductivity slurry by adopting supercritical nitrogen methyl pyrrolidone; avoiding the condition of cutting off and damaging the conductive network of the carbon nano tube in the prior art. The technical scheme has simple equipment structure and can prepare high-conductivity carbon nano tube slurry in batches.
The prepared carbon nanotube slurry was tested according to several specific examples:
embodiment one: firstly, carbon nano tube powder is introduced into a supercritical dispersion kettle 3 after being crushed for 0.5h by air flow, and a fourth conveying structure is closed when the volume of the carbon nano tube accounts for 2/3 of the volume of the supercritical dispersion kettle 3; introducing carbon dioxide into a supercritical dispersion kettle 3, regulating the temperature to 600 ℃ and the pressure to 20Mpa, enabling the carbon dioxide to be in a supercritical state, enabling the carbon dioxide to etch carbon nanotube impurities and disperse the carbon nanotubes for 1h, closing a first conveying structure of the carbon dioxide, quickly opening a drift diameter ball valve between the supercritical dispersion kettle 3 and a supercritical preparation kettle 8 after cooling to room temperature, enabling the dispersed carbon nanotubes to enter the supercritical preparation kettle 8 in a very short time, then injecting nitrogen methyl pyrrolidone, regulating the temperature to 600 ℃ and the pressure to 10Mpa, enabling the nitrogen methyl pyrrolidone to be in a supercritical state and maintaining the supercritical state for 1h, and preparing the carbon nanotube dispersion kettle into slurry. The slurry transmission detection diagram is shown in fig. 6, and has the advantages of complete structure, no obvious damage, maximum reservation of conductivity of the carbon tube, great reduction of winding degree of the carbon tube and complete compliance with requirements. And (3) evaporating the solvent in the carbon nanotube slurry prepared in the first embodiment, and analyzing the graphitization degree of the carbon nanotubes by adopting an X-ray diffractometer and a Raman spectrometer.
Embodiment two: firstly, carbon nano tube powder is introduced into a supercritical dispersion kettle 3 after being crushed for 0.5h by air flow, and a fourth conveying structure is closed when the volume of the carbon nano tube accounts for 1/2 of the volume of the supercritical dispersion kettle 3; introducing carbon dioxide into a supercritical dispersion kettle 3, regulating the temperature to 500 ℃ and the pressure to 30Mpa, enabling the carbon dioxide to be in a supercritical state, enabling the carbon dioxide to etch carbon nanotube impurities and disperse carbon nanotubes for 2h, closing a first conveying structure of the carbon dioxide, quickly opening a drift diameter ball valve between the supercritical dispersion kettle 3 and a supercritical preparation kettle 8 after cooling to room temperature, enabling the dispersed carbon nanotubes to enter the supercritical preparation kettle 8 in a very short time, then injecting nitrogen methyl pyrrolidone, regulating the temperature to 750 ℃ and the pressure to 30Mpa, enabling the nitrogen methyl pyrrolidone to be in a supercritical state and maintaining the supercritical state for 2h, and preparing the carbon nanotube dispersion kettle into slurry. The slurry detection chart is shown in fig. 7, and has complete structure, no obvious damage and the conductivity of the carbon tube is maintained to the greatest extent.
Embodiment III: firstly, carbon nano tube powder is introduced into a supercritical dispersion kettle 3 after being crushed for 0.5h by air flow, and a fourth conveying structure is closed when the volume of the carbon nano tube accounts for 3/4 of the volume of the supercritical dispersion kettle 3; introducing carbon dioxide into a supercritical dispersion kettle 3, regulating the temperature to 750 ℃ and the pressure to 10Mpa, enabling the carbon dioxide to be in a supercritical state, enabling the carbon dioxide to etch carbon nanotube impurities and disperse carbon nanotubes for 0.5h, then closing a first conveying structure of the carbon dioxide, quickly opening a drift diameter ball valve between the supercritical dispersion kettle 3 and a supercritical preparation kettle 8 after cooling to room temperature, enabling the dispersed carbon nanotubes to enter the supercritical preparation kettle 8 in a very short time, then injecting nitrogen methyl pyrrolidone, regulating the temperature to 500 ℃ and the pressure to 10Mpa, enabling the nitrogen methyl pyrrolidone to be in a supercritical state and maintaining the supercritical state for 2h, and preparing the carbon nanotube dispersion kettle into slurry. The slurry detection chart is shown in fig. 8, and has complete structure, no obvious damage and the conductivity of the carbon tube is maintained to the greatest extent.
Comparative example one: mixing carbon nano tube and dispersing agent according to the weight ratio of 1: adding nitrogen methyl pyrrolidone in a mass ratio, sealing and carrying out ultrasonic treatment for 2 hours, transferring to a nano sand mill for grinding for 1 hour, and transferring to a homogenizer for homogenizing for 1 hour to obtain carbon nanotube slurry; and (3) evaporating the solvent, and analyzing the graphitization degree of the carbon nano tube by adopting an X-ray diffractometer and a Raman spectrometer.
Fig. 9 is an X-ray diffraction pattern of the carbon nanotube slurry of example one and comparative example one after solvent evaporation, and it was found from fig. 9 that the comparative example one was broader in diffraction peak compared with example one (002) and showed peeling damage between the carbon nanotube graphite layers.
FIG. 10 is a Raman spectrum of the carbon nanotube slurry of example I and comparative example I after solvent evaporation, according to which FIG. 10 shows that comparative example I is compared with example I G /I D (area ratio) decreased, indicating that the graphitized structure portion of the carbon nanotube was destroyed.
Fig. 9 and 10 together illustrate that the physical shearing and stripping methods such as ultrasonic, sanding and homogenizing in the conventional preparation method of the carbon nanotube slurry can damage the microstructure of the carbon nanotubes, while the carbon nanotube structure in the slurry remains intact, so that the conductivity of the carbon nanotubes is maintained to the greatest extent.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The foregoing is merely an embodiment of the present invention, and a specific structure and characteristics of common knowledge in the art, which are well known in the scheme, are not described herein, so that a person of ordinary skill in the art knows all the prior art in the application day or before the priority date of the present invention, and can know all the prior art in the field, and have the capability of applying the conventional experimental means before the date, so that a person of ordinary skill in the art can complete and implement the present embodiment in combination with his own capability in the light of the present application, and some typical known structures or known methods should not be an obstacle for a person of ordinary skill in the art to implement the present application. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the structure of the present invention, and these should also be considered as the scope of the present invention, which does not affect the effect of the implementation of the present invention and the utility of the patent. The protection scope of the present application shall be subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (9)
1. A preparation method of carbon nano tube slurry is characterized in that: the method comprises the following steps:
adding carbon nano tube powder into a jet mill (1), crushing for 0.5h by the jet mill (1), opening a fourth conveying structure (2), conveying the crushed carbon nano tube powder to a supercritical dispersion kettle (3) by the fourth conveying structure (2), and closing the fourth conveying structure (2) when the volume of the carbon nano tube accounts for 1/2-3/4 of the volume of the supercritical dispersion kettle (3);
opening a first conveying structure (4), injecting carbon dioxide into the supercritical dispersion kettle (3), and opening a first pressure regulating structure (6) and a first heating structure until the temperature in the supercritical dispersion kettle (3) is 500-750 ℃ and the pressure is 10-30Mpa, so that the carbon dioxide reaches a supercritical state; carbon dioxide in a supercritical state etches carbon nanotube impurities and disperses the carbon nanotubes, after dispersing for 0.5-4h, the first conveying structure (4) is closed, and the supercritical dispersing kettle (3) is cooled to room temperature;
after the supercritical dispersion kettle (3) is cooled, a second conveying structure (5) is opened to enable the dispersed carbon nano-tubes to enter a supercritical preparation kettle (8), then a third conveying structure (7) is opened, nitrogen methyl pyrrolidone is injected into the supercritical preparation kettle (8), a second pressure regulating structure (11) and a second heating structure are opened until the temperature in the supercritical preparation kettle (8) is 445-750 ℃ and the pressure is 4.76-30Mpa, so that the nitrogen methyl pyrrolidone reaches a supercritical state, and the carbon nano-tubes are prepared into carbon nano-tube slurry for 0.5-2 h;
and opening a fifth conveying structure (9), and conveying the prepared carbon nano tube slurry to a collecting kettle (10) for collecting.
2. A carbon nanotube paste production apparatus for use in the process for producing a carbon nanotube paste according to claim 1, characterized in that: the device comprises a dispersing system and a preparation system, wherein the dispersing system comprises a supercritical dispersing kettle (3), a first pressure regulating structure (6), a first pressure measuring structure, a first heating structure, a first temperature measuring structure and a first conveying structure (4), the preparation system comprises a second conveying structure (5), a third conveying structure (7), a supercritical preparation kettle (8), a second heating structure, a second temperature measuring structure, a second pressure regulating structure (11) and a second pressure measuring structure, the first conveying structure (4) is used for conveying carbon dioxide into the supercritical dispersing kettle (3), and the first pressure regulating structure (6) and the first heating structure are respectively used for regulating the pressure and the temperature in the supercritical dispersing kettle (3) to supercritical conditions of the carbon dioxide; the second conveying structure (5) is used for conveying the carbon nanotubes after the dispersion in the supercritical dispersion kettle (3) is completed into a supercritical preparation kettle (8); the third conveying structure (7) is used for conveying the nitrogen methyl pyrrolidone into the supercritical preparation kettle (8), and the second pressure regulating structure (11) and the second heating structure are respectively used for regulating the pressure and the temperature in the supercritical preparation kettle (8) to the supercritical conditions of the nitrogen methyl pyrrolidone; the first pressure measuring structure and the second pressure measuring structure are respectively used for detecting the pressure intensity in the supercritical dispersing kettle (3) and the supercritical preparation kettle (8), and the first temperature measuring structure and the second temperature measuring structure are respectively used for detecting the temperature in the supercritical dispersing kettle (3) and the supercritical preparation kettle (8).
3. The apparatus for preparing a carbon nanotube paste according to claim 2, wherein: the supercritical dispersing kettle (3) is located above the supercritical preparation kettle (8), a discharge port of the supercritical dispersing kettle (3) is opposite to a feed port of the supercritical preparation kettle (8), and the second conveying structure (5) is used for communicating and blocking the discharge port of the supercritical dispersing kettle (3) and the feed port of the supercritical preparation kettle (8).
4. The apparatus for preparing a carbon nanotube paste according to claim 2, wherein: the first heating structure and the second heating structure are both provided with heating jackets (15), and the first heating structure and the second heating structure are respectively arranged outside the supercritical dispersing kettle (3) and the supercritical preparation kettle (8).
5. The apparatus for preparing a carbon nanotube paste according to claim 2, wherein: the dispersing system further comprises an air flow pulverizer (1) and a fourth conveying structure (2), wherein the air flow pulverizer (1) is used for pulverizing the carbon nanotube powder, and the fourth conveying structure (2) is used for conveying the pulverized carbon nanotube powder into a supercritical dispersing kettle (3).
6. The apparatus for preparing a carbon nanotube paste according to claim 2, wherein: the first pressure regulating structure (6) and the second pressure regulating structure (11) comprise a driving piece (12), a piston (14) and a baffle plate (13); the baffle (13) is arranged on the periphery of the piston (14), openings are formed in one side of the supercritical preparation kettle (8) and one side of the supercritical dispersion kettle (3), and the baffle (13) is in sliding connection with the openings; the driving member (12) is used for driving the piston (14) to reciprocate.
7. The apparatus for preparing a carbon nanotube paste according to claim 6, wherein: a sealing layer is arranged on one side of the baffle plate (13) contacted with the opening.
8. A device for preparing a carbon nanotube paste according to claim 3, wherein: and the second conveying structure (5) adopts a drift diameter ball valve.
9. The apparatus for preparing a carbon nanotube paste according to claim 2, wherein: the system further comprises a collecting system for collecting the prepared carbon nanotube slurry, wherein the collecting system comprises a collecting kettle (10) and a fifth conveying structure (9), and the fifth conveying structure (9) is used for conveying the carbon nanotube slurry in the supercritical preparation kettle (8) to the collecting kettle (10).
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| KR20110109730A (en) * | 2010-03-31 | 2011-10-06 | 세종대학교산학협력단 | Method for purifying carbon nanotubes, method for dispersing carbon nanotubes, and apparatus for purifying or dispersing carbon nanotubes |
| JP2015006963A (en) * | 2013-06-25 | 2015-01-15 | 帝人株式会社 | Method for producing metal or semiconductor carbon nanotube-enriched product |
| CN104766645A (en) * | 2015-03-24 | 2015-07-08 | 中国石油大学(北京) | Carbon nanotube-graphene composite electric conduction slurry and preparation method and application thereof |
| CN106102889A (en) * | 2014-02-26 | 2016-11-09 | 株式会社东进世美肯 | Method for producing carbon material using subcritical or supercritical fluid |
| CN108636526A (en) * | 2018-04-24 | 2018-10-12 | 北京协同创新食品科技有限公司 | It is a kind of in supercriticality or using liquid gas as milling apparatus of decentralized medium and products thereof |
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Patent Citations (5)
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| KR20110109730A (en) * | 2010-03-31 | 2011-10-06 | 세종대학교산학협력단 | Method for purifying carbon nanotubes, method for dispersing carbon nanotubes, and apparatus for purifying or dispersing carbon nanotubes |
| JP2015006963A (en) * | 2013-06-25 | 2015-01-15 | 帝人株式会社 | Method for producing metal or semiconductor carbon nanotube-enriched product |
| CN106102889A (en) * | 2014-02-26 | 2016-11-09 | 株式会社东进世美肯 | Method for producing carbon material using subcritical or supercritical fluid |
| CN104766645A (en) * | 2015-03-24 | 2015-07-08 | 中国石油大学(北京) | Carbon nanotube-graphene composite electric conduction slurry and preparation method and application thereof |
| CN108636526A (en) * | 2018-04-24 | 2018-10-12 | 北京协同创新食品科技有限公司 | It is a kind of in supercriticality or using liquid gas as milling apparatus of decentralized medium and products thereof |
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