CN114014300A - Carbon nanotube and method for purifying the same - Google Patents
Carbon nanotube and method for purifying the same Download PDFInfo
- Publication number
- CN114014300A CN114014300A CN202111408353.1A CN202111408353A CN114014300A CN 114014300 A CN114014300 A CN 114014300A CN 202111408353 A CN202111408353 A CN 202111408353A CN 114014300 A CN114014300 A CN 114014300A
- Authority
- CN
- China
- Prior art keywords
- nano tube
- carbon nano
- carbon
- carbon nanotube
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 206
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 206
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 60
- 239000000725 suspension Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 69
- 239000002109 single walled nanotube Substances 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 27
- 239000003929 acidic solution Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004108 freeze drying Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 description 47
- 229910052751 metal Inorganic materials 0.000 description 28
- 239000002184 metal Substances 0.000 description 28
- 229910044991 metal oxide Inorganic materials 0.000 description 15
- 150000004706 metal oxides Chemical class 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002048 multi walled nanotube Substances 0.000 description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
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
-
- 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
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/24—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/30—Purity
Abstract
The application belongs to the technical field of materials, and particularly relates to a carbon nanotube and a purification method thereof. The purification method of the carbon nano tube comprises the following steps: preparing a carbon nano tube suspension; mixing the carbon nano tube suspension with an alkaline substance, and drying to obtain a mixture of the carbon nano tube and the alkaline substance; calcining the mixture in an inert atmosphere to obtain a calcined carbon nanotube; and mixing the calcined carbon nano tube with an acid solution, and separating to obtain the purified carbon nano tube. The purification method of the carbon nano tube in the embodiment of the application has a good purification effect on the crude sample of the carbon nano tube, the purity of the purified carbon nano tube can reach 95%, the physicochemical property of the carbon nano tube cannot be damaged in the treatment process, the carbon nano tube can still maintain good electrical property and thermal property, and the stability of the carbon nano tube is improved.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to a carbon nanotube and a purification method thereof.
Background
Since the discovery of carbon nanotubes, especially single-walled carbon nanotubes (SWCNTs), much attention has been paid to research on the preparation, purification, and structural characterization of single-walled carbon nanotubes. In addition to large-scale preparation techniques, purification is the biggest problem affecting its application. After the carbon nanotubes are prepared, a large amount of impurities are often contained, and the impurities mainly comprise two types of carbon impurities and metal impurities. Wherein the carbon impurities mainly comprise amorphous carbon, fullerene, graphite particles and other carbon nano-particles; the metal impurities typically originate from the metal catalyst. The existence of impurities in the carbon nano tube limits the application of the carbon nano tube, and the purification of the carbon nano tube becomes a technical problem which is urgently needed to be solved at present.
The conventional carbon nanotube purification method includes: acidification, oxidation, annealing, ultrasonication, centrifugation, magnetic adsorption, and cutting. However, for carbon nanotubes, it is difficult to completely remove impurities from carbon nanotubes, especially single-walled carbon nanotubes, by a single purification method. The single-walled carbon nanotubes grow more densely than multi-walled carbon nanotubes, and a large amount of metal catalysts are distributed among the single-walled carbon nanotubes to firmly adhere the carbon tubes together, so that the yield of the single-walled carbon nanotubes is far lower than that of the multi-walled carbon nanotubes. At present, the purity of the single-walled carbon nanotube purified by a common treatment method is not high, and the application of the single-walled carbon nanotube is limited.
Disclosure of Invention
The application aims to provide a carbon nanotube and a purification method thereof, and aims to solve the problems of low purification efficiency and poor effect of the existing carbon nanotube, especially a single-walled carbon nanotube to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for purifying carbon nanotubes, comprising the steps of:
preparing a carbon nano tube suspension;
mixing the carbon nano tube suspension with an alkaline substance, and drying to obtain a mixture of the carbon nano tube and the alkaline substance;
calcining the mixture in an inert atmosphere to obtain a calcined carbon nanotube;
and mixing the calcined carbon nano tube with an acid solution, and separating to obtain the purified carbon nano tube.
Further, the carbon nanotubes are selected from single-walled carbon nanotubes.
Further, the step of preparing the carbon nanotube suspension comprises: and dispersing the carbon nano tube rough sample into an alcohol solution, and grinding for 0.3-6 hours under the condition of containing a magnet to obtain the carbon nano tube suspension.
Further, the mass percentage of water in the alcohol solution is 10-90%, and the alcohol solution comprises at least one of ethanol, ethylene glycol and methanol.
Further, the mass ratio of the carbon nanotube crude sample to the alcoholic solution is 1: (20-200).
Further, the step of mixing the carbon nanotube suspension with an alkaline substance includes: and mixing the carbon nano tube suspension with the solution of the alkaline substance, and stirring for 10-60 minutes at the rotating speed of 100-300 r/min.
Further, the drying treatment is selected from freeze drying.
Further, the alkaline substance comprises at least one of sodium hydroxide and potassium hydroxide.
Further, the solution concentration of the alkaline substance is 0.1-5 mol/L; the mass ratio of the carbon nanotube suspension to the solution of the alkaline substance is 1: (1-5).
Further, the step of subjecting the mixture to a calcination treatment comprises: calcining the mixture for 15-60 minutes under an inert atmosphere with the temperature of 600-1000 ℃ and the gas flow rate of 0.1-20 mL/min.
Further, the step of mixing the calcined carbon nanotube with an acidic solution comprises: and dispersing the calcined carbon nano tube in an acid solution, and stirring for 10-60 minutes at the rotating speed of 100-300 r/min.
Further, the step of separating comprises: and sequentially filtering the mixed products, washing until the pH value is neutral, dispersing the carbon nano tube in a solvent, and freeze-drying to obtain the purified carbon nano tube.
Further, the acidic solution includes at least one of hydrochloric acid, nitric acid, and sulfuric acid.
Further, the concentration of the acidic solution is 0.1-5 mol/L; the mass ratio of the calcined carbon nanotube to the acidic solution is 1: (10-1000).
In a second aspect, the present application provides a carbon nanotube purified by the above method.
In the method for purifying the nanotube provided by the first aspect of the present application, a carbon nanotube crude sample is first dispersed in a solution to prepare a carbon nanotube suspension; then, mixing the dispersed carbon nano tube suspension with an alkaline substance, drying and then contacting and mixing the alkaline substance with the carbon nano tube and metal impurities in the carbon nano tube at a molecular level. Then, the mixture is calcined in inert atmosphere, the alkaline substance reacts with the metal impurities in the carbon nano tube in the calcining process to convert the metal impurities into metal oxides, and simultaneously, the carbon impurities in the carbon nano tube crude sample are oxidized, and the defects in the carbon nano tube can be modified in the high-temperature calcining process to improve the quality of the carbon nano tube. And mixing the calcined carbon nano tube in an acid solution to dissolve impurities such as metal oxide impurities, metal simple substances and the like in the carbon nano tube in the acid solution, and separating the carbon nano tube from the solution to obtain the purified carbon nano tube.
The carbon nanotube that this application second aspect provided, through foretell purification treatment back, impurity composition is few, and carbon nanotube purity is high, and its purity can reach more than 95%, and carbon nanotube structure integrity is high, has good calorifics performance and electrical property, and stability is high, has improved carbon nanotube's application prospect.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for purifying carbon nanotubes provided in an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a method for purifying carbon nanotubes, including the following steps:
s10, preparing a carbon nano tube suspension;
s20, mixing the carbon nanotube suspension with an alkaline substance, and drying to obtain a mixture of the carbon nanotube and the alkaline substance;
s30, calcining the mixture in an inert atmosphere to obtain a calcined carbon nano tube;
and S40, mixing the calcined carbon nano tube with an acid solution, and separating to obtain the purified carbon nano tube.
In the method for purifying nanotubes provided in the first aspect of the embodiment of the present application, first, a carbon nanotube crude sample is dispersed in a solution to prepare a carbon nanotube suspension; then, mixing the dispersed carbon nano tube suspension with an alkaline substance, drying and then contacting and mixing the alkaline substance with the carbon nano tube and metal impurities in the carbon nano tube at a molecular level. Then, the mixture is calcined in inert atmosphere, the alkaline substance reacts with the metal impurities in the carbon nano tube in the calcining process to convert the metal impurities into metal oxides, and simultaneously, the carbon impurities in the carbon nano tube crude sample are oxidized, and the defects in the carbon nano tube can be modified in the high-temperature calcining process to improve the quality of the carbon nano tube. And mixing the calcined carbon nano tube in an acid solution to dissolve impurities such as metal oxide impurities, metal simple substances and the like in the carbon nano tube in the acid solution, and separating the carbon nano tube from the solution to obtain the purified carbon nano tube. The purification method of the carbon nano tube in the embodiment of the application has a good purification effect on the crude sample of the carbon nano tube, the purity of the purified carbon nano tube can reach 95%, the physicochemical property of the carbon nano tube cannot be damaged in the treatment process, the carbon nano tube can still maintain good electrical property and thermal property, and the stability of the carbon nano tube is improved.
In some embodiments, the carbon nanotubes are selected from single-walled carbon nanotubes. The single-walled carbon nanotube grows more compactly than a multi-walled carbon nanotube, the metal catalyst is distributed among the single-walled carbon nanotubes in a large amount, the carbon tubes are firmly adhered together, and the yield of the carbon nanotube is far lower than that of the multi-walled carbon nanotube.
In some embodiments, in the step S10, the step of preparing the carbon nanotube suspension includes: and dispersing the carbon nano tube rough sample into an alcohol solution, and grinding for 0.3-6 hours under the condition of containing a magnet to obtain a carbon nano tube suspension. The embodiment of the application adopts the alcoholic solution as the dispersion liquid of the carbon nano tube rough sample, can improve the dispersion effect of the carbon nano tube, and is ground under the condition of containing a magnet, on one hand, the carbon nano tubes which are tightly intertwined together are separated by a physical cutting mode, and the dispersion effect of the carbon nano tube rough sample in the solution is improved; on the other hand, the magnet can adsorb the larger metal catalyst impurities in the carbon nanotube crude sample in the grinding process, so that the larger metal catalyst impurities are removed in a physical mode, and the subsequent chemical impurity removal efficiency is improved. And grinding for 0.3-6 hours, so that the dispersing effect of the carbon nanotube crude sample in a solvent is ensured, and the carbon nanotube is prevented from being cut and broken in a transitional manner in the grinding process, so that the physical and chemical properties such as the electrical property and the thermal property of the carbon nanotube material are reduced. In some embodiments, the carbon nanotubes are dispersed in the alcohol solution in a coarse form, and milled in the presence of a magnet for 0.3 to 6 hours, further milled for 0.5 to 5 hours, further milled for 1 to 4 hours, and further milled for 2 to 3 hours.
In some embodiments, the water content in the alcohol solution is 10-90% by mass, and the alcohol solution comprises at least one of ethanol, ethylene glycol and methanol. The alcohol solutions adopted in the embodiment of the application are beneficial to improving the dispersion effect of the carbon nanotubes, the dispersion performance of the carbon nanotubes is reduced along with the increase of the water content in the alcohol solutions, but if the alcohol solvents are completely adopted, the too fast volatilization of the alcohol solvents can also reduce the dispersion stability of the carbon nanotubes, and the risk of causing combustion exists. In some embodiments, the water in the alcohol solution includes, but is not limited to, 10-90% by mass, further 20-80% by mass, further 30-70% by mass, and further 40-60% by mass.
In some embodiments, the mass ratio of the carbon nanotube crude to the alcoholic solution is 1: (20-200), the proportion can fully disperse the carbon nano tube crude sample in the solution, if the proportion of the alcohol solution is too low, the carbon nano tube is not favorably and uniformly dispersed in the solution, and the viscosity of the dispersion is too high, so that the subsequent treatment is not easy to perform; if the alcohol solution ratio is too high, the production efficiency will be reduced. In some embodiments, the mass ratio of the carbon nanotube crude to the alcoholic solution includes, but is not limited to, 1: (20-200), and further the mass ratio is 1: (50-150), and further the mass ratio is 1: (80-120).
In some embodiments, in the step S20, the step of mixing the carbon nanotube suspension with the alkaline substance includes: mixing the carbon nano tube suspension with a solution of an alkaline substance, and stirring for 10-60 minutes at a rotating speed of 100-300 r/min; so that the alkaline substance and the carbon nano tube are fully and uniformly mixed. In some embodiments, the rotation speed includes, but is not limited to, 100 to 300r/min, further 150 to 250r/min, and further 200 to 250 r/min.
In some embodiments, the drying process is selected from freeze drying, wherein a mixed solution of the carbon nanotubes and the alkaline substance, which is well dispersed uniformly, is dried by freezing, so that the solvent component in the mixed solution is removed while the loose dispersion state of the carbon nanotubes is maintained, and the shrinkage and agglomeration of the carbon nanotubes caused by drying methods such as heating are avoided. The obtained mixture of the alkaline substance, the carbon nano tube and the metal impurities in the carbon nano tube in contact and mixing at the molecular level is beneficial to the uniform and sufficient reaction of the alkaline substance with the impurities such as the metal catalyst and the like in the subsequent purification treatment process.
In some embodiments, the alkaline substance comprises at least one of sodium hydroxide, potassium hydroxide; the alkaline substances can react with impurity components such as metal catalysts and the like in the subsequent calcining process to convert the metal catalysts into metal oxides, so that the subsequent dissolution in an acidic solution is facilitated, and the impurity components such as the metal catalysts and the like are separated and removed. In addition, during the calcination reaction process of the alkaline substances, elements such as sodium, potassium, hydrogen and the like can be volatilized and removed in the gas formation process, and the elements cannot remain in the carbon nano tube, so that the introduction of impurity components into the carbon nano tube is avoided, and the purification effect of the carbon nano tube is improved.
In some embodiments, the concentration of the alkaline substance in the solution is 0.1-5 mol/L; and the mass ratio of the carbon nano tube suspension to the solution of the alkaline substance is 1: (1-5). The concentration of the solution of the alkaline substance and the proportion of the solution of the alkaline substance and the carbon nanotube suspension fully ensure that the alkaline substance and the carbon nanotube in the carbon nanotube suspension have a better mixing effect, and the concentration of the alkaline substance is too high or too low, so that the alkaline substance is not beneficial to being fully and uniformly dispersed into the carbon nanotube. If the concentration of the alkaline substance is less than 0.1mol/L, the alkaline substance is not sufficiently dispersed in the carbon nanotube; if the concentration of the basic substance is higher than 5mol/L, the basic substance is difficult to be uniformly dispersed in the carbon nanotube, and the basic substance is likely to agglomerate, failing to provide a molecular-level dispersing effect. The solution ratio of the alkaline substance also affects the binding effect of the alkaline substance and the carbon nanotube. In some embodiments, the concentration of the solution of the basic substance includes, but is not limited to, 0.1mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, etc., and the mass ratio of the carbon nanotube suspension to the solution of the basic substance includes, but is not limited to, 1:1, 1:2, 1:3, 1:4, 1:5, etc.
In some embodiments, in the step S30, the step of calcining the mixture includes: calcining the mixture for 15-60 minutes under an inert atmosphere with the temperature of 600-1000 ℃ and the gas flow rate of 0.1-20 mL/min. The calcination temperature fully ensures that alkaline substances react with metal impurities to generate metal oxides, simultaneously converts alkaline metals such as sodium, potassium and the like, hydrogen elements and the like into gaseous state to be volatilized and removed, simultaneously oxidizes amorphous carbon and other impurity components in the carbon nano tube, and the defects in the carbon nano tube can be optimized in a high-temperature environment to improve the quality of the carbon nano tube. If the temperature is too low, the reaction between alkaline substances and metal impurities is not facilitated, and the optimization of defects in the carbon nano tube is also not facilitated; if the temperature is too high, there is a risk of damaging the carbon nanotubes. In addition, the inert atmosphere is favorable for preventing the carbon nano tube from being oxidized under the high-temperature condition, so that the structure of the carbon nano tube is damaged. The reaction effect of the alkaline substance and the impurity components such as the metal catalyst in the carbon nanotube can be influenced by factors such as the length of the calcination time. In addition, if the gas flow rate is too fast, the carbon nanotubes will float in the tube furnace, and waste will be generated; if the gas flow rate is too low, the side reaction products formed by the reaction of the catalyst and the hydroxide cannot be carried away, resulting in a decrease in the purity of the carbon nanotubes. In some embodiments, the calcination temperature may be 600-700 ℃, 700-800 ℃, 800-900 ℃, or 900-1000 ℃; the gas flow rate can be 0.1-1 mL/min, 1-5 mL/min, 5-10 mL/min, 10-15 mL/min, 15-20 mL/min, etc.; the inert atmosphere contains nitrogen, argon, helium, etc.
In some embodiments, in the step S40, the step of mixing the calcined carbon nanotube with the acidic solution includes: dispersing the calcined carbon nano tube in an acid solution, and stirring for 10-60 minutes at the rotating speed of 100-300 r/min. The metal impurity components in the calcined carbon nano tube mainly exist in the form of metal oxides, the metal oxides are high in dissolving efficiency in an acid solution relative to metal simple substances, and the metal oxides can be quickly and efficiently dissolved in the acid solution after being mixed with the acid solution. Stirring for 10-60 minutes at a rotating speed of 100-300 r/min to fully ensure that metal oxides, metal simple substances, amorphous carbon and other impurity components in the carbon nano tube are dissolved and dispersed in the acidic solution. And then the impurity components in the carbon nano tube can be efficiently separated through separation treatment, so that the high-purity carbon nano tube is obtained. In some embodiments, the rotation speed of the mixing process includes, but is not limited to, 100 to 300r/min, further 150 to 250r/min, and further 200 to 250 r/min. The stirring time can be 10-20 minutes, 20-30 minutes, 30-40 minutes, 40-50 minutes, 50-60 minutes and the like.
In some embodiments, the step of separating comprises: and sequentially filtering the mixed products, analyzing the acidic solution in which impurities such as metal oxides are dissolved and the carbon nano tubes, washing the carbon nano tubes until the pH value is neutral, removing residual impurity components in the carbon nano tubes, re-dispersing the carbon nano tubes in a solvent, dispersing for 10-60 minutes in an ultrasonic dispersion mode if necessary, and freeze-drying to keep the carbon nano tubes in a fluffy state without forming serious agglomeration so as to avoid carbon nano tube shrinkage and agglomeration caused by drying modes such as direct heating and the like to obtain the purified carbon nano tubes.
In some embodiments, the acidic solution comprises at least one of hydrochloric acid, nitric acid, sulfuric acid; these acidic solutions have a good dissolving and dispersing effect on the impurity components such as metal oxides in the carbon nanotubes, and can dissolve the impurity components such as metal oxides in the calcined carbon nanotubes into the solution, thereby removing the impurity components in the carbon nanotubes.
In some embodiments, the concentration of the acidic solution is 0.1-5 mol/L; the mass ratio of the calcined carbon nanotube to the acidic solution is 1: (10-1000). The concentration of the acidic solution and the ratio of the acidic solution to the calcined carbon nanotubes affect the dissolution and removal effects of metal oxides and other impurities in the carbon nanotubes. If the concentration of the acidic solution is too low or the ratio of the acidic solution to the carbon nano tube is too low, the acidic solution is not favorable for sufficiently dissolving and removing impurity components such as metal oxides and the like in the calcined carbon nano tube; if the concentration of the acidic solution is too high, the structure of the carbon nanotube may be damaged, and the electrical and thermal properties of the carbon nanotube may be affected. In some embodiments, the concentration of the acidic solution includes, but is not limited to, 0.1-1 mol/L, 1-2 mol/L, 2-3 mol/L, 3-4 mol/L, 4-5 mol/L, and the like; the mass ratio of the calcined carbon nanotubes to the acidic solution includes, but is not limited to, 1: (10-100), 1: (100-200), 1: (200-300), 1: (300-500), 1: (500-800), 1: (800-1000) and the like.
In a second aspect, the present embodiments provide a carbon nanotube, which is purified by the above method.
According to the carbon nanotube provided by the second aspect of the embodiment of the application, after the purification treatment, the impurity components are few, the purity of the carbon nanotube is high, the purity can reach more than 95%, the structural integrity of the carbon nanotube is high, the carbon nanotube has good thermal performance and electrical performance, the stability is high, and the application prospect of the carbon nanotube is improved.
In some embodiments, the carbon nanotubes of the present embodiments include, but are not limited to, single-walled carbon nanotubes, multi-walled carbon nanotubes, and the like, preferably single-walled carbon nanotubes.
In order to make the above-mentioned implementation details and operations of the present application clearly understood by those skilled in the art and to make the progress of the carbon nanotubes and the preparation method thereof obvious in the embodiments of the present application, the above-mentioned technical solutions are illustrated by a plurality of examples below.
Example 1
A purification process for single-walled carbon nanotubes comprises the steps of:
putting 1g of the single-walled carbon nanotube crude sample with the purity of 50 percent and 200g of deionized water into a sand mill for sand milling, arranging a permanent magnet in a high-speed dispersion cavity, and grinding for 3 hours to obtain a ground single-walled carbon nanotube suspension.
Secondly, mixing and stirring the ground single-walled carbon nanotube suspension with 300g of 0.5mol/L sodium hydroxide solution at the stirring speed of 100r/min for 10min, and freeze-drying after stirring to obtain a mixture of the single-walled carbon nanotube and the alkaline hydroxide.
Thirdly, under the protection of nitrogen, the gas flow rate of the mixture of 1g of single-walled carbon nanotube and alkaline hydroxide is 0.1mL/min, the mixture is burned at the high temperature of 600 ℃ for 15min, and after the mixture is cooled, the single-walled carbon nanotube subjected to oxidation treatment is obtained.
And fourthly, mixing and stirring 0.5g of the single-walled carbon nanotube subjected to oxidation treatment with 50g of 0.5mol/L hydrochloric acid solution at the stirring speed of 100r/min for 10min, then filtering and washing, washing with deionized water until the pH value of a washing solution is neutral, then washing with ethanol for 2 times, re-dispersing the washed single-walled carbon nanotube in the deionized water, ultrasonically dispersing for 20min, and then freeze-drying to obtain the purified single-walled carbon nanotube.
Example 2
A purification process for single-walled carbon nanotubes comprises the steps of:
putting 1g of the single-walled carbon nanotube crude sample with the purity of 50 percent and 200g of deionized water into a sand mill for sand milling, arranging a permanent magnet in a high-speed dispersion cavity, and grinding for 5 hours to obtain a ground single-walled carbon nanotube suspension.
Secondly, mixing and stirring the ground single-walled carbon nanotube suspension with 300g of 1mol/L sodium hydroxide solution at the stirring speed of 200r/min for 30min, and freeze-drying after stirring to obtain a mixture of the single-walled carbon nanotube and the alkaline hydroxide.
Thirdly, under the protection of nitrogen, the gas flow rate of the mixture of 1g of single-walled carbon nanotube and alkaline hydroxide is 1mL/min, the mixture is burned at the high temperature of 800 ℃ for 30min, and after the mixture is cooled, the single-walled carbon nanotube subjected to oxidation treatment is obtained.
And fourthly, mixing and stirring 0.5g of the single-walled carbon nanotube subjected to oxidation treatment with 50g of 1mol/L hydrochloric acid solution at the stirring speed of 200r/min for 10min, then filtering and washing, washing with deionized water until the pH value of the washing solution is neutral, then washing with ethanol for 2 times, re-dispersing the washed single-walled carbon nanotube in the deionized water, ultrasonically dispersing for 20min, and then freeze-drying to obtain the purified single-walled carbon nanotube.
Example 3
A purification process for single-walled carbon nanotubes comprises the steps of:
putting 1g of the single-walled carbon nanotube crude sample with the purity of 50 percent and 200g of deionized water into a sand mill for sand milling, arranging a permanent magnet in a high-speed dispersion cavity, and grinding for 6 hours to obtain a ground single-walled carbon nanotube suspension.
Secondly, mixing and stirring the ground single-walled carbon nanotube suspension with 300g of 5mol/L sodium hydroxide solution at the stirring speed of 300r/min for 60min, and freeze-drying after stirring to obtain a mixture of the single-walled carbon nanotube and the alkaline hydroxide.
Thirdly, under the protection of nitrogen, the gas flow rate of the mixture of 1g of single-walled carbon nanotube and alkaline hydroxide is 1mL/min, the mixture is burned at the high temperature of 1000 ℃ for 60min, and the single-walled carbon nanotube after oxidation treatment is obtained after the mixture is cooled.
And fourthly, mixing and stirring 0.5g of the single-walled carbon nanotube subjected to oxidation treatment with 50g of 5mol/L hydrochloric acid solution at the stirring speed of 300r/min for 60min, then filtering and washing, washing with deionized water until the pH value of the washing solution is neutral, then washing with ethanol for 2 times, re-dispersing the washed single-walled carbon nanotube in the deionized water, ultrasonically dispersing for 20min, and then freeze-drying to obtain the purified single-walled carbon nanotube.
Comparative example 1
A purification process for single-walled carbon nanotubes comprises the steps of:
1g of single-walled carbon nanotube crude sample with the purity of 50 percent is mixed and stirred with 50g of 0.5mol/L hydrochloric acid solution, the stirring speed is 100r/min, the stirring time is 10min, then filtration and washing are carried out, deionized water is firstly used for washing until the pH value of a washing liquid is neutral, then ethanol is used for 2 times, and then high-temperature drying is carried out, so that the purified single-walled carbon nanotube is obtained.
Comparative example 2
A purification process for single-walled carbon nanotubes comprises the steps of:
under the protection of nitrogen, 1g of single-walled carbon nanotube with the purity of 50 percent is burned at the high temperature of 600 ℃ for 1min at the gas flow rate of 0.1mL/min and oxygen is introduced for 2min, the gas flow rate is 0.05mL/min, the oxygen is stopped, the nitrogen is continuously introduced, the burning time is 15min, and the single-walled carbon nanotube subjected to oxygen oxidation treatment is obtained after the single-walled carbon nanotube is cooled. 0.5g of single-walled carbon nanotube after oxidation treatment, 20g of 0.5mol/L hydrochloric acid solution and 10g of 0.5mol/L hydrogen peroxide solution are mixed and stirred, the stirring speed is 50r/min, the stirring time is 10min, then filtration washing is carried out, deionized water is used for washing until the pH value of the washing liquid is neutral, then ethanol is used for 2 times, and the single-walled carbon nanotube purified by the oxygen oxidation treatment method is obtained after drying.
Further, in order to verify the advancement of the embodiment of the present application, the purity of the single-walled carbon nanotubes purified in examples 1 to 3 and comparative examples 1 to 2 was respectively tested by burning the carbon nanotubes in a thermal weight loss tester at 800 ℃ in an air atmosphere and calculating the purity of the carbon nanotubes by the weight of the burning residue, and the test results are shown in table 1 below:
TABLE 1
According to the test results, the purity of the single-walled carbon nanotube purified by the method in the embodiment 1-3 can reach more than 95%, the impurities such as the metal catalyst and the amorphous carbon in the coarse sample of the single-walled carbon nanotube can be basically removed, the high-purity single-walled carbon nanotube is obtained, and the application of the single-walled carbon nanotube is facilitated. And the single-wall carbon nano tube crude sample of the comparative example 1 is only subjected to acidification treatment, so that the purity of the obtained single-wall carbon nano tube is only 65%, a large amount of impurities are still contained, and the purification effect is poor. Comparative example 2 the crude sample of the single-walled carbon nanotube is calcined and then acidified, the purity of the obtained single-walled carbon nanotube is only 85%, and the single-walled carbon nanotube product also contains a large amount of impurity components, so that the purity is not high, and the application effect of the subsequent carbon nanotube is influenced.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method for purifying carbon nanotubes, comprising the steps of:
preparing a carbon nano tube suspension;
mixing the carbon nano tube suspension with an alkaline substance, and drying to obtain a mixture of the carbon nano tube and the alkaline substance;
calcining the mixture in an inert atmosphere to obtain a calcined carbon nanotube;
and mixing the calcined carbon nano tube with an acid solution, and separating to obtain the purified carbon nano tube.
2. The method for purifying carbon nanotubes according to claim 1, wherein the carbon nanotubes are selected from single-walled carbon nanotubes.
3. The method for purifying carbon nanotubes according to claim 1 or 2, wherein the step of preparing the carbon nanotube suspension comprises: and dispersing the carbon nano tube rough sample into an alcohol solution, and grinding for 0.3-6 hours under the condition of containing a magnet to obtain the carbon nano tube suspension.
4. The method for purifying carbon nanotubes, according to claim 3, wherein the water content in the alcohol solution is 10 to 90% by mass, and the alcohol solution comprises at least one of ethanol, ethylene glycol and methanol;
and/or the mass ratio of the carbon nano tube crude sample to the alcoholic solution is 1: (20-200).
5. The method for purifying carbon nanotubes according to claim 1 or 4, wherein the step of mixing the carbon nanotube suspension with an alkaline substance comprises: mixing the carbon nano tube suspension with the solution of the alkaline substance, and stirring for 10-60 minutes at the rotating speed of 100-300 r/min;
and/or the drying treatment mode is selected from freeze drying.
6. The method for purifying carbon nanotubes according to claim 5, wherein the basic substance comprises at least one of sodium hydroxide and potassium hydroxide;
and/or the concentration of the solution of the alkaline substance is 0.1-5 mol/L; the mass ratio of the carbon nanotube suspension to the solution of the alkaline substance is 1: (1-5).
7. The method for purifying carbon nanotubes according to claim 1 or 6, wherein the step of subjecting the mixture to a calcination treatment comprises: calcining the mixture for 15-60 minutes under an inert atmosphere with the temperature of 600-1000 ℃ and the gas flow rate of 0.1-20 mL/min.
8. The method for purifying carbon nanotubes according to claim 7, wherein the step of mixing the calcined carbon nanotubes with an acidic solution comprises: dispersing the calcined carbon nano tube in an acid solution, and stirring for 10-60 minutes at a rotating speed of 100-300 r/min;
and/or, the step of separating comprises: and sequentially filtering the mixed products, washing until the pH value is neutral, dispersing the carbon nano tube in a solvent, and freeze-drying to obtain the purified carbon nano tube.
9. The method for purifying carbon nanotubes according to claim 8, wherein the acidic solution comprises at least one of hydrochloric acid, nitric acid, and sulfuric acid;
and/or the concentration of the acidic solution is 0.1-5 mol/L; the mass ratio of the calcined carbon nanotube to the acidic solution is 1: (10-1000).
10. A carbon nanotube purified by the method according to any of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111408353.1A CN114014300A (en) | 2021-11-24 | 2021-11-24 | Carbon nanotube and method for purifying the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111408353.1A CN114014300A (en) | 2021-11-24 | 2021-11-24 | Carbon nanotube and method for purifying the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114014300A true CN114014300A (en) | 2022-02-08 |
Family
ID=80066203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111408353.1A Pending CN114014300A (en) | 2021-11-24 | 2021-11-24 | Carbon nanotube and method for purifying the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114014300A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403034A (en) * | 2022-09-26 | 2022-11-29 | 深圳市飞墨科技有限公司 | Method for purifying single-walled carbon nanotube with high purity and high conversion rate |
| CN115715824A (en) * | 2022-10-12 | 2023-02-28 | 杭州洛兮生物科技有限公司 | Bone scaffold material based on modified single-walled carbon nanotubes and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10120409A (en) * | 1996-10-17 | 1998-05-12 | Toyo Tanso Kk | Separation and purification of monolayered nanotube and separation ad purification of metal-including nanocapsule |
| JP2005015252A (en) * | 2003-06-24 | 2005-01-20 | Petroleum Energy Center | Method of purifying carbon nanotube |
| JP2007176767A (en) * | 2005-12-28 | 2007-07-12 | Toray Ind Inc | Purifying method for composition containing carbon nanotube |
| CN101289569A (en) * | 2008-06-16 | 2008-10-22 | 南昌大学 | Method for preparing multi-wall carbon nano-tube/epoxide resin wave- absorbing and camouflage composite material |
| JP2008290886A (en) * | 2007-05-22 | 2008-12-04 | National Institute Of Advanced Industrial & Technology | Cleaning agent for carbon nanotube, and method for purifying carbon nanotube using the same |
| CN101780951A (en) * | 2010-03-09 | 2010-07-21 | 北京大学 | Purification method for obtaining high-purity carbon nano tube |
| US20120083408A1 (en) * | 2009-06-11 | 2012-04-05 | Tohoku University | Carbon nanotube and method for producing same |
| US20160167966A1 (en) * | 2013-07-24 | 2016-06-16 | Covestro Deutschland Ag | Method for cleaning carbon nanotubes and carbon nanotube substrate and uses therefor |
| CN107634224A (en) * | 2017-09-14 | 2018-01-26 | 辽宁兰晶科技有限公司 | A kind of preparation method of the outer wall fluorination multi-walled carbon nanotube of the thing of intercalation containing ferric flouride |
| CN110662715A (en) * | 2017-03-31 | 2020-01-07 | 魁北克电力公司 | Method for purifying crude carbon nano tube |
-
2021
- 2021-11-24 CN CN202111408353.1A patent/CN114014300A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10120409A (en) * | 1996-10-17 | 1998-05-12 | Toyo Tanso Kk | Separation and purification of monolayered nanotube and separation ad purification of metal-including nanocapsule |
| JP2005015252A (en) * | 2003-06-24 | 2005-01-20 | Petroleum Energy Center | Method of purifying carbon nanotube |
| JP2007176767A (en) * | 2005-12-28 | 2007-07-12 | Toray Ind Inc | Purifying method for composition containing carbon nanotube |
| JP2008290886A (en) * | 2007-05-22 | 2008-12-04 | National Institute Of Advanced Industrial & Technology | Cleaning agent for carbon nanotube, and method for purifying carbon nanotube using the same |
| CN101289569A (en) * | 2008-06-16 | 2008-10-22 | 南昌大学 | Method for preparing multi-wall carbon nano-tube/epoxide resin wave- absorbing and camouflage composite material |
| US20120083408A1 (en) * | 2009-06-11 | 2012-04-05 | Tohoku University | Carbon nanotube and method for producing same |
| CN101780951A (en) * | 2010-03-09 | 2010-07-21 | 北京大学 | Purification method for obtaining high-purity carbon nano tube |
| US20160167966A1 (en) * | 2013-07-24 | 2016-06-16 | Covestro Deutschland Ag | Method for cleaning carbon nanotubes and carbon nanotube substrate and uses therefor |
| CN110662715A (en) * | 2017-03-31 | 2020-01-07 | 魁北克电力公司 | Method for purifying crude carbon nano tube |
| US20210107791A1 (en) * | 2017-03-31 | 2021-04-15 | HYDRO-QUéBEC | Method for the purification of raw carbon nanotubes |
| CN107634224A (en) * | 2017-09-14 | 2018-01-26 | 辽宁兰晶科技有限公司 | A kind of preparation method of the outer wall fluorination multi-walled carbon nanotube of the thing of intercalation containing ferric flouride |
Non-Patent Citations (1)
| Title |
|---|
| 赵江: ""高质量多壁碳纳米管的制备方法和应用研究"", 《中国优秀博士论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403034A (en) * | 2022-09-26 | 2022-11-29 | 深圳市飞墨科技有限公司 | Method for purifying single-walled carbon nanotube with high purity and high conversion rate |
| CN115715824A (en) * | 2022-10-12 | 2023-02-28 | 杭州洛兮生物科技有限公司 | Bone scaffold material based on modified single-walled carbon nanotubes and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114014300A (en) | Carbon nanotube and method for purifying the same | |
| CN101780951B (en) | Purification method for obtaining high-purity carbon nano tube | |
| US20170050850A1 (en) | Single wall carbon nanotube purification process and improved single wall carbon nanotubes | |
| CN101164874B (en) | Method for purifying multi-wall carbon nano pipe | |
| CN111606405A (en) | Method for degrading organic pollutants in water by activating peracetic acid through nitrogen-doped carbon material | |
| WO2012083511A1 (en) | Preparation method and use of manganese dioxide nano-rod | |
| CN103407984A (en) | Carbon nano-tube purification method based on weak oxidizing atmosphere oxidation assisted acid treatment | |
| CN108529606B (en) | High-stability graphene slurry and preparation method thereof | |
| CN112265981A (en) | Method for preparing carbon nano tube by lignin nano micelle | |
| CN109650379A (en) | A kind of single-walled carbon nanotube graded oxidation purification process | |
| CN113860289A (en) | Method for purifying carbon nano tube | |
| CN114314566A (en) | Separation and purification method of carbon nano tube | |
| CN113443620B (en) | Preparation method and application of few-layer graphene powder | |
| CN109277096B (en) | Nano Ti loaded on carbon nano tube4O7Composite material and preparation method and application thereof | |
| CN113336221B (en) | Preparation method of porous graphene dispersion liquid attached with oxygen-containing group | |
| CN110950322B (en) | Method for preparing carbon nanotube composite carbon material by utilizing red mud and raw coal | |
| CN111874899A (en) | Washing method of graphene oxide | |
| CN112479207A (en) | Method for recycling activated carbon, double-electric-layer capacitor comprising activated carbon recycled by method and preparation method of double-electric-layer capacitor | |
| WO2024066182A1 (en) | Prussian-type sodium ion positive electrode material and recycling method therefor | |
| CN102515142A (en) | Method for purification of low-purity single-wall carbon nano-tubes | |
| KR101738343B1 (en) | Nano ring carbon nano tube using nano oxide particle-template and fabrication method of the same | |
| CN115254000B (en) | Synthesis method and application of magnetic coal gas slag-based magnesium adsorbent | |
| CN116139823A (en) | MXene composite material and preparation method and application thereof | |
| CN106379896B (en) | A kind of graphene and preparation method thereof | |
| CN115231555A (en) | Arc method single-walled carbon nanotube green purification method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220208 |