CN114590796A - Method for purifying carbon nano tube and method for preparing carbon nano tube slurry - Google Patents
Method for purifying carbon nano tube and method for preparing carbon nano tube slurry Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 123
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000002002 slurry Substances 0.000 title claims abstract description 21
- 238000000746 purification Methods 0.000 claims abstract description 60
- 239000000460 chlorine Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 19
- 238000005469 granulation Methods 0.000 claims description 18
- 230000003179 granulation Effects 0.000 claims description 18
- 239000012159 carrier gas Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 238000007906 compression Methods 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005054 agglomeration Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005243 fluidization Methods 0.000 claims description 3
- 238000010902 jet-milling Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 8
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052755 nonmetal Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C01B32/17—Purification
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a purification method of a carbon nano tube and a preparation method of carbon nano tube slurry. In a first aspect of the present application, there is provided a method for purifying carbon nanotubes, the method comprising the steps of: and (3) carrying out contact reaction on the carbon nano tube and chlorine at the temperature of 950-1050 ℃. The purification method provided by the embodiment of the application has at least the following beneficial effects: according to the scheme, the temperature of the reaction environment is directly raised to 950-1050 ℃ before purification, under the condition, the reaction of metal impurities in the carbon nano tube and chlorine and the discharge of metal chlorides with low boiling points after the reaction are carried out simultaneously, the purification effect is greatly improved, the purity of the carbon nano tube can reach 99.999 +%, and compared with the purification method in the prior art, the purification method has the advantages of higher purification efficiency, lower cost and simplicity and convenience in operation and can be operated continuously.
Description
Technical Field
The present disclosure relates to the field of carbon nanotube technology, and more particularly, to a method for purifying carbon nanotubes and a method for preparing carbon nanotube slurry.
Background
In recent years, the demand of lithium ion batteries is increasing, and particularly, the market demand of high-power and high-energy-density lithium ion batteries is great. Compared with the traditional conductive agents such as Super P and graphite, the carbon nano tube has the advantages of ultrahigh length-diameter ratio and high conductivity, and an efficient three-dimensional high-conductivity network can be built in the electrode only by a small amount of addition, so that the purpose of improving the energy density of the battery is achieved. Carbon nanotubes have been recognized as the best conductive agent for enhancing the high rate and long cycle performance of lithium ion batteries. However, in the process of preparing the carbon nanotube, excessive metal impurities are often left, and there are safety problems such as reduction in thermal stability, reduction in chemical stability, and short-circuiting of the battery in the use process of the lithium ion battery. Therefore, it is necessary to purify carbon nanotubes to improve the purity of the carbon nanotubes, thereby reducing the problems caused by excessive metal impurities during the use of the lithium ion battery.
The existing purification method mainly adopts a chemical method, and comprises acid treatment, a complexation method and high-temperature vacuum purification. When acid is used for treatment, only metal impurities exposed on the surface of the carbon nano tube can be removed, the removal effect on the metal impurities at the end port of the carbon nano tube and in the cavity is very small, the purification effect is limited, and the problems of environmental pollution caused by waste acid and waste acid treatment can also exist; when the complexing reaction is adopted, although the method cannot cause the damage of the carbon nano tube structure, the complexing agent has higher cost and complex process and is not suitable for industrial mass production; the purification can also be carried out by high-temperature vacuum purification, but the energy consumption is high, the reaction time is long, the continuous operation cannot be carried out, and the method has great limitation. Therefore, it is necessary to provide a method for purifying carbon nanotubes, which has high purification efficiency, little environmental pollution, low cost, simple operation, and continuous operation.
Disclosure of Invention
The present application is directed to solving at least one of the problems in the prior art. Therefore, the application provides a carbon nanotube purification method and a carbon nanotube slurry preparation method which have the advantages of high purification efficiency, small environmental pollution, low cost and simple and convenient operation and can be operated continuously.
In a first aspect of the present application, there is provided a method for purifying carbon nanotubes, the method comprising the steps of: and (3) carrying out contact reaction on the carbon nano tube and chlorine at the temperature of 950-1050 ℃.
The purification method provided by the embodiment of the application has at least the following beneficial effects:
according to the scheme, the temperature of the reaction environment is directly raised to 950-1050 ℃ before purification, under the condition, the reaction of metal impurities in the carbon nano tube and chlorine and the discharge of metal chlorides with low boiling points after the reaction are carried out simultaneously, the purification effect is greatly improved, the purity of the carbon nano tube can reach 99.999 +%, and compared with the purification method in the prior art, the purification method has the advantages of higher purification efficiency, lower cost and simplicity and convenience in operation and can be operated continuously.
In some embodiments of the present application, the carbon nanotubes are placed on a porous substrate, and chlorine gas is contacted and reacted with the carbon nanotubes from the lower direction of the porous substrate at a temperature of 950 to 1050 ℃. The carbon nano tube is arranged on the porous substrate, and chlorine gas passes upwards from the lower part, so that the chlorine gas can be fully contacted with the carbon nano tube, and the purification is more thorough.
In some embodiments of the present application, the carbon nanotubes are compressed and formed into carbon nanotube particles prior to contact reaction with chlorine gas. The fluffy carbon nano tube powder is made into stable particles, thereby reducing the flying dust pollution of the powder, increasing the volume and the quality of the powder and being convenient for storage and transportation. Meanwhile, the compressed carbon tubes are used for purification, so that the space-time yield can be effectively improved, and a certain purification effect is achieved.
In some embodiments of the present application, the carbon nanotube particles have a size of 1 to 20 mm. The size of the carbon nano tube particles comprises the length and the diameter of the carbon nano tube particles, preferably, the length is 1-20 mm, and the diameter is 1-10 mm.
In some embodiments of the present application, the method of forming carbon nanotube particles is at least one of compression granulation, extrusion granulation, agglomeration granulation, fluidization granulation, spray granulation. It can be understood that compression granulation and extrusion granulation have introduced compression treatment in the granulation process, so as to increase the apparent specific gravity; when agglomeration granulation, fluidization granulation, spray granulation and other methods are adopted, a compression step can be additionally introduced in order to further increase the volume and the mass.
In some embodiments of the present disclosure, the ratio of the amount of chlorine gas to the mass of the carbon nanotubes is 1 to 100 sccm/g. By adjusting the proportion of the chlorine gas and the carbon nano tube, metal impurities in the carbon tube can be removed more effectively, and the purification efficiency and the purification effect are ensured.
In some embodiments of the present application, a ratio of a ventilation amount of chlorine gas to a mass of the carbon nanotubes is 20 to 100 sccm/g.
In some embodiments of the present application, the holding time at 950 to 1050 ℃ is 10 to 240 min. The generated metal chloride can be removed in time by controlling the heat preservation time.
In some embodiments of the present application, the holding time at 950 to 1050 ℃ is 30 to 150 min.
In some embodiments of the present application, the position of the reactor where the porous substrate is located constitutes a heating portion of the reactor, and the heating portion is further provided with a porous baffle plate along the end where the gas flows, so as to ensure normal circulation of the gas while blocking the outflow of the carbon nanotubes.
In some embodiments of the present application, the reactor is further provided with a recovery section at the end along the gas flow path for recovering the gasified metal chloride, in particular at least one collection and storage vessel.
In some embodiments of the present application, the carrier gas used in the contact reaction with chlorine gas is at least one of nitrogen, helium, and argon.
In some embodiments of the present application, the volume ratio of chlorine gas to carrier gas is 1: (10-1).
In some embodiments of the present application, the volume ratio of chlorine gas to carrier gas is 1: (5-1).
In some embodiments of the application, an atomization device or a heating jacket is arranged at the connecting position of the chlorine gas cylinder and the reactor, so that liquid chlorine is gasified more easily, and the air inflow of chlorine gas is ensured.
In some embodiments of the present application, when chlorine gas and carbon nanotubes are purified, the purification may be performed by using a fixed method or a suspension method according to the magnitude of the gas flow.
In a second aspect of the present application, there is provided a method for preparing a carbon nanotube slurry, the method comprising: and purifying the carbon nano tube according to the purification method, and dispersing the purified carbon nano tube to obtain carbon nano tube slurry.
In some embodiments of the present application, the means of dispersing comprises at least one of sanding, microfluidization, homogenization, jet milling, ball milling, and comminution.
In some embodiments of the present application, the purified carbon nanotubes are mixed with a solvent, a dispersant and a viscosity reducer and then dispersed to obtain a carbon nanotube slurry.
In some embodiments of the present application, the solvent is water or an organic solvent. Among them, the organic solvent includes, but is not limited to, N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), acetone, etc.
In some embodiments of the present application, the dispersing agent includes, but is not limited to, polyvinylpyrrolidone, carboxymethylcellulose (CMC), polyethylene glycol (PEG), polyvinyl alcohol (PVA), and the like.
In some embodiments herein, viscosity reducing agents include, but are not limited to, ethanolamines, piperazines, and the like.
The chlorination purification method provided by the embodiment of the application has the advantages of high purification efficiency, small environmental pollution, low cost, simple and convenient operation and continuous operation, and is suitable for industrial large-scale production. The carbon nano tube conductive slurry prepared by the method has the advantages of high performance, easy storage and high purity. The total content of metal impurities (including iron, cobalt, nickel, zinc, copper and chromium) contained in the conductive carbon paste is less than 5ppm, so that the impurities are effectively removed, and the problems of low thermal stability, low chemical stability, short circuit of the battery and the like of the conventional conductive carbon paste when the conductive carbon paste is applied to the lithium ion battery are greatly solved. Therefore, the lithium ion battery can be applied to lithium ion batteries, solid-state batteries, lithium metal batteries, sodium ion batteries, lithium sulfur batteries, fuel batteries, lithium air batteries and the like.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Detailed Description
The conception and the resulting technical effects of the present application will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
The following detailed description of embodiments of the present application is provided for illustrative purposes only and is not intended to be limiting of the present application.
In the description of the present application, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present number, and the above, below, within, etc. are understood as including the present number. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated. About is understood to mean floating up and down within the range of + -20%, + -15%, + -10%, + -8%, + -5%, + -3%, + -2%, + -1%, + -0.5%, + -0.2%, + -0.1% of the point values.
In the description of the present application, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The reactors used in the chlorination purification process of the examples are briefly described below, and it will be understood that other reactors capable of performing substantially the same function are also suitable for use in the purification step of the present scheme.
The reactor used in the following embodiments is a vertical quartz reactor, which includes a chlorine inlet, a carrier gas inlet, a heating portion, and a recovery portion from bottom to top along the inlet and outlet flow direction of gas, the heating portion is provided with at least one reaction chamber, the reaction chamber includes a porous substrate and a porous baffle plate from bottom to top along the flow direction of gas, and the recovery portion is provided with a metal chloride storage tank. The carbon nanotubes are placed on a porous substrate during the purification process. The porous substrate and the porous baffle have pore sizes configured to block carbon nanotubes from passing through and allow gas to pass through.
Example 1
The embodiment provides a method for purifying carbon nanotubes, which comprises the following steps:
(1) putting the carbon nano tube raw powder into a double-screw extruder, and compressing and granulating, wherein the particle size of the compressed carbon nano tube is as follows: length 5mm, diameter 5 mm.
(2) 50g of compressed carbon nano tube particles are loaded on a high-temperature resistant nonmetal filter element of a high-temperature furnace in a vertical quartz reactor, a chlorine gas cylinder and a nitrogen gas cylinder are connected, and 1000sccm N is firstly introduced from the bottom of the quartz reactor2And keeping for 15min to exhaust air in the device. Then the temperature of the high-temperature furnace is raised from room temperature to 1000 ℃, and 500sccm Cl is introduced2Hold for 120min, then close Cl2And reducing the temperature of the high-temperature furnace to room temperature. Wherein, throughout the purification process, 1000sccm N is introduced2As a carrier gas. And after the high-temperature furnace is cooled to room temperature, wiping the pipe orifice of the quartz reactor with alcohol, and taking out the purified carbon nano tube.
The embodiment also relates to a preparation method of the carbon nanotube conductive paste, which comprises the following steps:
and taking 10g of the purified carbon nano tube obtained by the purification method, adding 1g of polyvinylpyrrolidone, 5g of ethanolamine and 84g of N-methyl pyrrolidone, mixing, and dispersing by microjet to obtain the high-purity carbon nano tube conductive slurry.
Example 2
The embodiment provides a method for purifying carbon nanotubes, which comprises the following steps:
(1) putting the carbon nano tube raw powder into a double-screw extruder, and compressing and granulating, wherein the particle size of the compressed carbon nano tube is as follows: length 5mm, diameter 5 mm.
(2) 50g of compressed carbon nano tube particles are loaded on a high-temperature resistant nonmetal filter element of a high-temperature furnace in a vertical quartz reactor, a chlorine gas cylinder and a nitrogen gas cylinder are connected, and 1000sccm N is firstly introduced from the bottom of the quartz reactor2And keeping for 15min to exhaust the air in the device. Then the temperature of the high-temperature furnace is raised from room temperature to 1000 ℃, and 200sccm Cl is introduced2Hold for 120min, then close Cl2And reducing the temperature of the high-temperature furnace to room temperature. Wherein, throughout the purification process, 1000sccm N is introduced2As a carrier gas. And after the high-temperature furnace is cooled to room temperature, wiping the pipe orifice of the quartz reactor with alcohol, and taking out the purified carbon nano tube.
The embodiment also relates to a preparation method of the carbon nanotube conductive paste, which comprises the following steps:
and taking 10g of the purified carbon nano tube obtained by the purification method, adding 1g of polyvinylpyrrolidone, 5g of ethanolamine and 84g of N-methyl pyrrolidone, mixing, and dispersing by microjet to obtain the high-purity carbon nano tube conductive slurry.
Example 3
The embodiment provides a method for purifying carbon nanotubes, which comprises the following steps:
(1) putting the carbon nano tube raw powder into a double-screw extruder, and compressing and granulating, wherein the particle size of the compressed carbon nano tube is as follows: length 5mm, diameter 5 mm.
(2) 50g of compressed carbon nano tube particles are loaded on a high-temperature resistant nonmetal filter element of a high-temperature furnace in a vertical quartz reactor, a chlorine gas cylinder and a nitrogen gas cylinder are connected, and 1000sccm N is firstly introduced from the bottom of the quartz reactor2And keeping for 15min to exhaust the air in the device. Then the temperature of the high-temperature furnace is raised to 1000 ℃ from room temperature, and 800sccm Cl is introduced2Hold for 120min, then close Cl2And reducing the temperature of the high-temperature furnace to room temperature. Wherein, throughout the purification process, 1000sccm N is introduced2As a carrier gas. And after the high-temperature furnace is cooled to room temperature, wiping the pipe orifice of the quartz reactor with alcohol, and taking out the purified carbon nano tube.
The embodiment also relates to a preparation method of the carbon nanotube conductive paste, which comprises the following steps:
and taking 10g of the purified carbon nano tube obtained by the purification method, adding 1g of polyvinylpyrrolidone, 5g of ethanolamine and 84g of N-methyl pyrrolidone, mixing, and dispersing by microjet to obtain the high-purity carbon nano tube conductive slurry.
Example 4
The embodiment provides a method for purifying carbon nanotubes, which comprises the following steps:
(1) 5g of carbon nano tube raw powder is loaded on a high-temperature resistant nonmetal filter element of a high-temperature furnace in a vertical quartz reactor, a chlorine gas cylinder and a nitrogen gas cylinder are connected, and 1000sccm N is firstly introduced from the bottom of the quartz reactor2And keeping for 15min to exhaust air in the device. Then the temperature of the high-temperature furnace is raised to 1000 ℃ from room temperature, and 500sccm Cl is introduced2Hold for 120min, then close Cl2And reducing the temperature of the high-temperature furnace to room temperature. Wherein, throughout the purification process, 1000sccm N is introduced2As a carrier gas. And after the high-temperature furnace is cooled to room temperature, wiping the pipe orifice of the quartz reactor with alcohol, and taking out the purified carbon nano tube.
The embodiment also relates to a preparation method of the carbon nanotube conductive paste, which comprises the following steps:
and taking 10g of the purified carbon nano tube obtained by the purification method, adding 1g of polyvinylpyrrolidone, 5g of ethanolamine and 84g of N-methyl pyrrolidone, mixing, and dispersing by microjet to obtain the high-purity carbon nano tube conductive slurry.
Example 5
The embodiment provides a method for purifying carbon nanotubes, which comprises the following steps:
(1) putting the carbon nano tube raw powder into a double-screw extruder, and compressing and granulating, wherein the particle size of the compressed carbon nano tube is as follows: length 5mm, diameter 5 mm.
(2) 20g of compressed carbon nano tube particles are put into a high-temperature resistant nonmetal filter element of a high-temperature furnace in a vertical quartz reactor and connected with chlorine gasIntroducing 1000sccm N into a gas cylinder and a nitrogen gas cylinder2And keeping for 15min to exhaust the air in the device. Then the temperature of the high-temperature furnace is raised to 1000 ℃ from room temperature, and 500sccm Cl is introduced2Hold for 180min, then close Cl2And reducing the temperature of the high-temperature furnace to room temperature. Wherein, throughout the purification process, 1000sccm N is introduced2As a carrier gas. And after the high-temperature furnace is cooled to room temperature, wiping the pipe orifice of the quartz reactor with alcohol, and taking out the purified carbon nano tube.
The embodiment also relates to a preparation method of the carbon nanotube conductive paste, which comprises the following steps:
and taking 10g of the purified carbon nano tube obtained by the purification method, adding 1g of polyvinylpyrrolidone, 5g of ethanolamine and 84g of N-methyl pyrrolidone, mixing, and dispersing by microjet to obtain the high-purity carbon nano tube conductive slurry.
Example 6
The embodiment provides a method for purifying carbon nanotubes, which comprises the following steps:
(1) putting the carbon nano tube raw powder into a double-screw extruder, and compressing and granulating, wherein the particle size of the compressed carbon nano tube is as follows: length 5mm, diameter 5 mm.
(2) 20g of compressed carbon nano tube particles are put on a high-temperature resistant nonmetal filter element of a high-temperature furnace in a vertical quartz reactor, a chlorine gas cylinder and a nitrogen gas cylinder are connected, and 1000sccm N is firstly introduced2And keeping for 15min to exhaust the air in the device. Then the temperature of the high-temperature furnace is increased from room temperature to 900 ℃, and 500sccm Cl is introduced2Hold for 120min, then close Cl2And reducing the temperature of the high-temperature furnace to room temperature. Wherein, 1000sccm N is introduced all the time in the whole purification process2As a carrier gas. And after the high-temperature furnace is cooled to room temperature, wiping the pipe orifice of the quartz reactor with alcohol, and taking out the purified carbon nano tube.
The embodiment also relates to a preparation method of the carbon nanotube conductive paste, which comprises the following steps:
and taking 10g of the purified carbon nano tube obtained by the purification method, adding 1g of polyvinylpyrrolidone, 5g of ethanolamine and 84g of N-methyl pyrrolidone, mixing, and dispersing by microjet to obtain the high-purity carbon nano tube conductive slurry.
Comparative test
The carbon nanotubes purified in examples 1 to 6 were calcined in a muffle furnace at 950 ℃ for 2 hours to test ash content, and the results are shown in table 1.
The carbon nanotube conductive slurry prepared in examples 1 to 6 was taken, and the contents of six elements, i.e., iron, cobalt, nickel, zinc, copper, and chromium, in the slurry were measured by ICP-OES (inductively coupled plasma emission spectrometer). The results are shown in Table 2.
TABLE 1 data table of ash content of carbon nanotubes after chlorination purification
| Examples | Cl2Introduction amount/sccm | Purification time/min | Purification temperature/. degree.C | Purity/%) |
| Example 1 | 500 | 120 | 1000 | 99.999+％ |
| Example 2 | 100 | 120 | 1000 | 99.9+％ |
| Example 3 | 800 | 120 | 1000 | 99.999+％ |
| Example 4 | 500 | 120 | 1000 | 99.999+％ |
| Example 5 | 500 | 180 | 1000 | 99.999+％ |
| Example 6 | 500 | 120 | 900 | 99.8+％ |
In the above embodiment, the purity of the carbon nanotube before chlorination purification is about 94.5%, and it can be seen by combining the above embodiments that the purity of the carbon nanotube after purification in the present application is all above 99.8%, and some embodiments can reach above 99.999%, and the purification effect is significant. In contrast to example 4, in which example 1 and example 4 were compared, only 5g of carbon nanotubes were purified at a time without compression when chlorination purification was performed, in example 1, 50g of carbon nanotubes were purified at a time by compression granulation, but the purity was maintained at 99.999 +%. Thus, the pretreatment step of example 1 by compression granulation leads to a significant increase in the space-time yield of the purification compared to example 4.
TABLE 2 data table of contents of metallic impurities in the high purity carbon nanotube conductive paste
Wherein, the N.D. indicates that the result is less than the detection limit. From the detection results in table 2, the content of possible catalyst metals such as iron, cobalt, nickel, zinc, copper, chromium and the like is greatly reduced after the carbon nanotubes are chloridized and purified in the slurry prepared in examples 1 to 6.
The present application has been described in detail with reference to the embodiments, but the present application is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
Claims (10)
1. The method for purifying the carbon nano tube is characterized by comprising the following steps of: and (3) carrying out contact reaction on the carbon nano tube and chlorine at the temperature of 950-1050 ℃.
2. The purification method according to claim 1, wherein the contact reaction is specifically: and placing the carbon nano tube on a porous substrate, and enabling chlorine to contact and react with the carbon nano tube from the lower direction of the porous substrate at the temperature of 950-1050 ℃.
3. The purification method according to claim 1, wherein the carbon nanotubes are compressed and formed into carbon nanotube particles before being reacted in contact with chlorine gas;
preferably, the size of the carbon nano tube particles is 1-20 mm.
4. The purification method according to claim 3, wherein the carbon nanotube particles are formed by at least one of compression granulation, extrusion granulation, agglomeration granulation, fluidization granulation, and spray granulation.
5. The purification method according to claim 1, wherein the ratio of the amount of chlorine gas introduced to the mass of the carbon nanotubes is 1 to 100 sccm/g;
preferably, the ratio of the amount of chlorine gas introduced to the mass of the carbon nanotubes is 20 to 100 sccm/g.
6. The purification method according to any one of claims 1 to 5, wherein the holding time at 950 to 1050 ℃ is 10 to 240 min.
7. The purification process according to any one of claims 1 to 5, wherein the carrier gas used in the contact reaction with chlorine gas is at least one or more of nitrogen, helium, argon;
preferably, the volume ratio of chlorine gas to carrier gas is 1: (10-1);
preferably, the volume ratio of chlorine gas to carrier gas is 1: (5-1).
8. The method for preparing carbon nanotube slurry, characterized by comprising purifying carbon nanotubes by the purification method according to any one of claims 1 to 7, and dispersing the purified carbon nanotubes to obtain the carbon nanotube slurry.
9. The method of claim 8, wherein the dispersing step comprises at least one of sand milling, micro-jet milling, homogenizing, air jet milling, ball milling, and pulverizing.
10. The method of claim 8, wherein the carbon nanotubes are dispersed after being mixed with a solvent, a dispersant and a viscosity reducer to obtain the carbon nanotube slurry.
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