CN113860289A - Method for purifying carbon nano tube - Google Patents
Method for purifying carbon nano tube Download PDFInfo
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- CN113860289A CN113860289A CN202111229630.2A CN202111229630A CN113860289A CN 113860289 A CN113860289 A CN 113860289A CN 202111229630 A CN202111229630 A CN 202111229630A CN 113860289 A CN113860289 A CN 113860289A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 177
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 33
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- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 4
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- 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 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- 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
- C01B32/159—Carbon nanotubes single-walled
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/04—Nanotubes with a specific amount of walls
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- C01B2202/00—Structure or properties of carbon nanotubes
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- C01B2202/00—Structure or properties of carbon nanotubes
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- C01B2202/22—Electronic properties
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/30—Purity
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- 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
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Abstract
The invention relates to the technical field of carbon nanotube purification, and particularly discloses a method for purifying a carbon nanotube, which comprises the steps of mixing the carbon nanotube, an oxidant and dilute acid for reaction, wherein (6 multiplied by 10) is added into each 1g of the carbon nanotube‑3~32×10‑3) Oxidant of mol and 150-600g H+Diluted acid with the concentration of 1.8-20mol/L is subjected to post-treatment after the reaction is finished to obtain the purified carbon nano tube. The method for purifying the carbon nano tube not only can effectively improve the purity of the carbon nano tube, but also has small influence on the surface structure of the carbon nano tube, has simple integral purification process and is beneficial to improving the dispersibility of the carbon nano tube.
Description
Technical Field
The invention relates to the technical field of carbon nanotube purification, in particular to a method for purifying a carbon nanotube.
Background
In industrial production, a transition metal (Fe, Co, Ni, etc.) or a compound thereof is generally required as a catalyst to produce a carbon nanotube, and a large amount of transition metal impurities remain in the carbon nanotube produced by the catalyst. To remove these transition metal impurities, there are generally two purification methods. One is high-temperature heat treatment at 2500 ℃ or so, and the other is to perform oxidation treatment on the carbon nano tube at 300-900 ℃ and then perform purification treatment by using a dilute hydrochloric acid solution.
In recent years, many literature documents select concentrated nitric acid or concentrated sulfuric acid system for treating carbon nanotubes, for example, CN113003565A shows that concentrated nitric acid or concentrated sulfuric acid system is used as a treating solution for purifying carbon nanotubes, although the above method has simple process and improves the purity of carbon nanotubes to some extent, the strong oxidation treatment damages the surface structure of carbon nanotubes more seriously and leads to the decrease of conductivity of carbon nanotubes. CN109650379B is able to improve the purity of the carbon nanotubes and prevent the surface structure of the carbon nanotubes from being damaged by purifying the single-walled carbon nanotubes by gradient oxidation and acid washing, but the overall process conditions are complicated and the purification cost is high, so there is room for improvement.
In view of the above, the inventors of the present invention have considered that it is necessary to provide a method for purifying carbon nanotubes, which can effectively improve the purity of carbon nanotubes, has little influence on the surface structure of carbon nanotubes, and has a simple overall process.
Disclosure of Invention
In order to solve the problem of complicated carbon nanotube purification process, the inventors thought that it is necessary to provide a method for purifying carbon nanotubes, which can effectively improve the purity of carbon nanotubes, has little influence on the surface structure of carbon nanotubes, has a simple overall process, and is also advantageous for improving the dispersibility of carbon nanotubes.
In a first aspect, the present application provides a method for purifying carbon nanotubes, which adopts the following technical scheme:
a method for purifying carbon nanotubes comprises the following steps: mixing carbon nano-particlesMixing tube, oxidant and dilute acid, adding (6X 10) per 1g carbon nano tube-3～32×10-3) Oxidant of mol and 150-600g H+Diluted acid with the concentration of 1.8-20mol/L is subjected to post-treatment after the reaction is finished to obtain the purified carbon nano tube.
In the purification reaction process of the carbon nano tube, the oxidation degree of the carbon nano tube is controlled by controlling the reaction of the diluted acid and the oxidant with the carbon nano tube in a specific mass ratio, and the structure of the carbon nano tube is slightly damaged under the oxidation degree, so that the transition metal impurities coated in the carbon nano tube are in contact reaction with the diluted acid solution, and the purification effect of the carbon nano tube is better; in addition, since the diluted acid and the oxidant are compounded according to a specific mass ratio in the purification process, the oxidation degree of the carbon nano tube is low, so that the damage degree of the structure of the carbon nano tube is small, and the conductivity of the carbon nano tube is not obviously changed, therefore, the defect that the conductivity of the carbon nano tube is easy to reduce after the carbon nano tube is purified in the prior art is overcome; the method for purifying the carbon nano tube is simple and has small operation difficulty, and the cost for treating the purified carbon nano tube is favorably reduced, so the purification treatment effect of the carbon nano tube is better.
In addition, in the pulping process, the carbon nano tube is easy to break along the structural defect generated by the purification, and the tube length of the carbon nano tube is shortened, so that the dispersibility of the carbon nano tube is improved, and therefore, the problem that the existing carbon nano tube is difficult to disperse is solved.
Preferably, the reaction temperature is 10-70 ℃, and the reaction time is 30-200 min.
Under the reaction conditions, the carbon nano tube can be effectively purified, the structural damage degree of the carbon nano tube is small, the carbon nano tube keeps good conductivity while having good purification effect, the purification reaction temperature of the carbon nano tube is low, the reaction time is short, the energy consumption of the purified carbon nano tube can be effectively reduced, and therefore, the energy is effectively saved, and the high economic value is achieved.
Preferably, said H+The concentration is 3.5-13.5 mol/L.
By oxidizing agent with a specific concentration of H+In combination, the carbon nanotube has a good oxidation degree, so that the transition metal impurities are not easy to remain after the carbon nanotube is purified, the carbon nanotube has a high purification degree, and the carbon nanotube has a low structural damage degree so that the electrical conductivity is not easy to decrease, and the carbon nanotube can obtain better dispersibility in the pulping process.
Preferably, the dilute acid is a non-oxidizing acid.
Non-oxidizing acids such as hydrochloric acid, carbonic acid, dilute sulfuric acid, silicic acid, meta-aluminate and the like, which are weak in oxidizing property, are synergistically matched with an oxidizing agent to achieve the effect of purifying the carbon nanotubes, and the carbon nanotubes are not easily excessively oxidized to reduce the conductivity of the carbon nanotubes.
Further, the non-oxidizing acid is dilute sulfuric acid. Compared with other non-oxidizing acids, the dilute sulfuric acid is not easy to generate toxic and harmful substances in the purification reaction process, and has small overall pollution and safe reaction environment.
Preferably, the oxidant is one or more of potassium permanganate, potassium perchlorate, potassium dichromate and hydrogen peroxide solution, and the mass fraction of the hydrogen peroxide is not lower than 20%.
The potassium permanganate, the hydrogen peroxide, the potassium perchlorate and the potassium dichromate have better oxidability, and the components can better control the oxidation degree of the carbon nano tube by matching with dilute sulfuric acid, so that the degree of surface damage of the carbon nano tube is reduced, the carbon nano tube obtains better purification effect and keeps better conductivity. Potassium perchlorate and potassium dichromate are easy to produce polluting chlorine or heavy metal chromium after the carbon nano tube purification reaction, and potassium permanganate and hydrogen peroxide are safe and are not easy to produce toxic and harmful substances, so potassium permanganate and hydrogen peroxide are further selected as oxidants in the method.
Preferably, the carbon nanotube is one or a combination of two of original multi-wall carbon nanotube, double-wall carbon nanotube and single-wall carbon nanotube.
The original multi-walled carbon nanotubes, single-walled carbon nanotubes, double-walled carbon nanotubes and mixtures thereof can be purified better under the above method, and better electrical conductivity can be maintained.
Preferably, the post-treatment is solid-liquid separation after the reaction is finished, and then the carbon nanotube is washed to be neutral, so that the purified carbon nanotube is obtained.
The post-treatment is simple, the operation is convenient, and the obtained purified carbon nano tube has high purity, small conductivity change rate and good dispersibility. Further, water is used as a liquid for washing the carbon nanotubes.
In a second aspect, the present application provides a carbon nanotube conductive paste, which adopts the following technical scheme:
the carbon nanotube slurry is prepared from the carbon nanotubes purified by the method, a dispersing agent and a solvent according to the mass ratio of 1: (0.2-1): (5-125).
The carbon nanotube slurry is prepared by mixing and uniformly dispersing the carbon nanotube purified by the method, a dispersing agent and a solvent according to the mass ratio.
The carbon nanotube slurry with high dispersibility and stability is obtained by uniformly dispersing the carbon nanotube purified by the method in a solvent, and the slurry can be further applied to battery products as a conductive slurry. The slurry is used as a raw material of the silicon negative electrode material slurry, and the dispersibility of the carbon nano tube purified by the method is improved, so that the viscosity of the silicon negative electrode material slurry and the resistivity of a silicon negative electrode plate are reduced, and the electrochemical performance of the battery is improved.
In summary, the present application has the following advantages:
1. the method and the device have the advantages that the diluted acid, the oxidant and the carbon nano tube are controlled to be matched in a specific proportion, the carbon nano tube is enabled to keep a good conductivity effect while the carbon nano tube is purified, the process of purifying the carbon nano tube is simple, implementation is convenient, and the economic value is high.
2. The method adopts the non-oxidizing acid and the oxidant to control the oxidation degree of the carbon nano tube in a specific ratio, so that the purification effect of the carbon nano tube is better, the damage to the surface structure is smaller, and the change of the conductivity of the carbon nano tube is smaller.
3. The carbon nanotube slurry prepared from the purified carbon nanotubes has the advantages of high purity, good conductivity and good dispersibility, and has high economic value.
Drawings
Fig. 1 is a process flow diagram of a method for purifying carbon nanotubes.
Fig. 2 is an SEM image of carbon nanotubes in the slurry prepared in application example 3.
Fig. 3 is an SEM image of carbon nanotubes in the slurry prepared in application comparative example 1.
Fig. 4 is an SEM image of the purified carbon nanotube slurry prepared in application example 3 in a silicon negative electrode slurry.
Fig. 5 is an SEM image of the purified carbon nanotube slurry prepared in application comparative example 1 in a silicon negative electrode slurry.
Fig. 6 is a Raman spectrum of the purified carbon nanotubes prepared in example 3 and comparative example 4.
Detailed Description
In the following examples, a process flow diagram of a method of purifying carbon nanotubes is shown in fig. 1.
Example 1
A method for purifying carbon nanotubes comprises the following steps:
step (1), 5g of single-walled carbon nanotube and 1g of potassium permanganate (6.3X 10)-3mol) is added into 150g of 9.38mol/L dilute sulphuric acid and reacted for 30min at 10 ℃.
And (2) after the reaction is finished, carrying out suction filtration for solid-liquid separation, and then washing the reacted single-walled carbon nanotube to be neutral by using deionized water to obtain the purified carbon nanotube.
Experiment 2
A method for purifying carbon nanotubes comprises the following steps:
step (1), 5g of single-walled carbon nanotube and 5g of potassium permanganate (31.6X 10)-3mol) is added into 600g of 0.94mol/L dilute sulphuric acid and reacted for 200min at 50 ℃.
And (2) after the reaction is finished, carrying out suction filtration for solid-liquid separation, and then washing the reacted single-walled carbon nanotube to be neutral by using deionized water to obtain the purified carbon nanotube.
Example 3
A method for purifying carbon nanotubes comprises the following steps:
step (1), 5g of single-walled carbon nanotube and 1.5 g of potassium permanganate (9.4X 10)-3mol) are added into 500g of dilute sulfuric acid of 6.57mol/L and reacted for 1h at 30 ℃.
And (2) after the reaction is finished, carrying out suction filtration for solid-liquid separation, and then washing the reacted single-walled carbon nanotube to be neutral by using deionized water to obtain the purified carbon nanotube.
Example 4
A method for purifying carbon nanotubes comprises the following steps:
step (1), 5g of single-walled carbon nanotube and 5g of potassium permanganate (31.6X 10)-3mol) is added into 500g of 1.87mol/L dilute sulphuric acid and reacted for 2h at 30 ℃.
And (2) after the reaction is finished, carrying out suction filtration for solid-liquid separation, and then washing the reacted single-walled carbon nanotube to be neutral by using deionized water to obtain the purified carbon nanotube.
Example 5
A method for purifying carbon nanotubes comprises the following steps:
step (1), 5g of single-walled carbon nanotubes and 2.5g of hydrogen peroxide (22.1X 10) with the mass fraction of 30 percent are taken-3mol) is added into 200g of 4.69mol/L dilute sulphuric acid and reacted for 2h at 30 ℃.
And (2) after the reaction is finished, carrying out suction filtration for solid-liquid separation, and then washing the reacted single-walled carbon nanotube to be neutral by using deionized water to obtain the purified carbon nanotube.
Example 6
A method for purifying carbon nanotubes comprises the following steps:
step (1), taking 5g of multi-wall carbon nano-tube and 3.5g of potassium permanganate (22.1 multiplied by 10)-3mol) is added into 200g of dilute sulphuric acid of 4.69mol/L and reacted for 1.5h at 30 ℃.
And (2) after the reaction is finished, carrying out suction filtration for solid-liquid separation, and then washing the multi-walled carbon nano tube after the reaction to be neutral by using deionized water to obtain the purified carbon nano tube.
Example 7
A method for purifying carbon nanotubes comprises the following steps:
step (1), 5g of multi-walled carbon nanotubes and 5g of 20 mass percent hydrogen peroxide (29.4X 10)-3mol) is added into 200g of 1.87mol/L, and the mixture reacts for 1.5h at the temperature of 30 ℃.
And (2) after the reaction is finished, carrying out suction filtration for solid-liquid separation, and then washing the multi-walled carbon nano tube after the reaction to be neutral by using deionized water to obtain the purified carbon nano tube.
Comparative example 1
5g of single-walled carbon nanotube is taken and put into a tube furnace for preoxidation treatment at 500 ℃ for 2h, then diluted hydrochloric acid of 1.63mol/L is used for acid cleaning, finally, solid-liquid separation is carried out by using a suction filtration method, and then deionized water is used for washing the reacted single-walled carbon nanotube to be neutral, thus obtaining the purified carbon nanotube.
Comparative example 2
5g of multi-walled carbon nano-tube is put into a tube furnace for pre-oxidation treatment at 400 ℃ for 2h, then diluted hydrochloric acid of 1.63mol/L is used for acid washing, finally, solid-liquid separation is carried out by using a suction filtration method, and then deionized water is used for washing the multi-walled carbon nano-tube after reaction to be neutral, thus obtaining the purified carbon nano-tube.
Comparative example 3
The difference from example 3 is that: in the step (1), 5g of single-walled carbon nanotubes are added into 500g of 6.57mol/L dilute sulfuric acid without adding potassium permanganate, and the mixture reacts for 30min at 10 ℃.
Comparative example 4
The difference from example 3 is that: in the step (1), 13.14mol/L concentrated sulfuric acid is used for equivalently replacing 6.57mol/L dilute sulfuric acid.
Application example 1
A carbon nanotube slurry is prepared by the following steps:
step a, 3.2g of sodium methyl cellulose is dissolved in 393.6g of water, and sanding is carried out for 10 minutes at the rotating speed of 4500r/min, so as to obtain the sodium methyl cellulose dispersion.
And b, adding 3.2g of the single-walled carbon nanotubes purified in the example 1 into the sodium methylcellulose dispersion, and sanding for 60 minutes at the rotating speed of 4500r/min to obtain carbon nanotube slurry.
Application examples 2 to 5
The difference from application example 1 is that: in the step b, the application examples 2 to 5 respectively adopt the single-walled carbon nanotubes purified in the examples 2 to 5 to equally replace the single-walled carbon nanotubes purified in the example 1.
Application example 6
A carbon nanotube slurry is prepared by the following steps:
step a, dissolving 15g of polyvinylpyrrolidone in 410g of water, and dispersing by sanding for 10 minutes at the rotating speed of 4500r/min to obtain polyvinylpyrrolidone dispersion liquid.
And b, adding 75g of the multi-walled carbon nanotubes purified in the embodiment 6 into the polyvinylpyrrolidone dispersion liquid, and performing sand grinding for 50 minutes at the rotating speed of 4500r/min to disperse the multi-walled carbon nanotubes to obtain carbon nanotube slurry.
Application example 7
The differences from application example 6 are: in step b, the multi-walled carbon nanotubes purified in example 7 were used in place of the multi-walled carbon nanotubes purified in example 6 in equal amounts in application example 7.
Blank sample 1
The difference from application example 3 is that: in the step b, the single-walled carbon nanotubes which are not purified are used for equally replacing the single-walled carbon nanotubes purified in the example 1.
Blank sample 2
The differences from application example 6 are: in step b, the multi-walled carbon nanotubes which are not purified are used for replacing the multi-walled carbon nanotubes purified in the example 6 in equal amount.
Application comparative example 1
The difference from application example 3 is that: in the step b, the single-walled carbon nanotube obtained in the comparative example 1 is used for replacing the single-walled carbon nanotube purified in the example 1 in an equal amount.
Comparative application example 2
The differences from application example 6 are: in step b, the multi-walled carbon nanotubes obtained in comparative example 2 were used in place of the multi-walled carbon nanotubes purified in example 6 in equal amounts.
Comparative application example 3
The difference from application example 3 is that: in step b, the single-walled carbon nanotubes obtained in the comparative example 3 are used for replacing the single-walled carbon nanotubes purified in the example 1 in equal amount.
Application comparative example 4
The difference from application example 3 is that: in step b, the single-walled carbon nanotubes obtained in the comparative example 4 are used for replacing the single-walled carbon nanotubes purified in the example 1 in equal amount.
Performance test
Experiment 1
The purity of the carbon nanotubes in each example was tested using a simultaneous thermogravimetric analyzer model TA Discovery SDT 650.
Experiment 2
The viscosity of the carbon nanotube slurry of each application example and the application comparative example was measured using an antopa RheolabQC model rheometer.
Experiment 3
Viscosity test and conductivity test of carbon nanotube slurry
Preparing cathode mixed slurry by using the carbon nano tube slurry, testing the viscosity of the cathode mixed slurry, coating the prepared cathode mixed slurry on a copper foil for drying, and testing the film resistivity by using a pole piece resistivity tester.
The cathode mixed slurry prepared by the carbon nanotube slurry of the application examples 1 to 5 and the carbon nanotube slurry of the application comparative examples 1, 3 and 4 comprises the following components in percentage by mass: 96.4% by mass of a silicon-graphite composite material (capacity of 500mAh/g), 3.5% by mass of sodium carboxymethylcellulose, and 0.1% by mass of carbon nanotube slurry prepared by applying the single-walled carbon nanotubes of comparative examples 1, 3 and 4.
The negative electrode mixed slurry prepared by the carbon nanotube slurry of the application examples 6 to 7 and the application comparative example 2 is composed of the following components in percentage by mass: 95.5% by mass of a silicon-graphite composite material (capacity of 500mAh/g), 3.5% by mass of sodium carboxymethylcellulose, 1% by mass of application examples 6 to 7, and carbon nanotube slurry prepared by applying the multi-walled carbon nanotube of comparative example 2.
The experimental data for experiments 1-3 are detailed in Table 1.
TABLE 1
The data of application examples 1-7 and blank samples 1-2 in table 1 can be used to obtain that, compared with the carbon nanotube which is not subjected to purification treatment, the purity of the single-walled carbon nanotube in examples 1-7 is greater than 99%, and the single-walled carbon nanotube in examples 1-7 is applied to the silicon negative electrode plate, and the measured resistivity change rate of the silicon negative electrode plate is smaller, so that the conductivity change of the single-walled carbon nanotube after purification is small, the structure damage degree of the single-walled carbon nanotube after purification treatment is smaller, and the viscosity test of the carbon nanotube slurry and the viscosity test of the silicon negative electrode slurry show that the single-walled carbon nanotube purification process is simple, the operation is convenient, and in summary, the single-walled carbon nanotube purification process has the advantages of good purification effect, small conductivity change and simple purification process. In addition, the viscosity of the carbon nanotube slurry in application examples 1 to 7 is reduced, and the carbon nanotubes are more easily dispersed in the solvent, so that the dispersibility and the stability of the carbon nanotubes are improved.
Compared with the data of the application example 3 and the application comparative example 1, and the data of the application example 6 and the application comparative example 2 in the table 1, compared with the traditional pre-oxidation treatment purification method, the effect of purifying the carbon nano tube and the conductivity of the purified carbon nano tube are close to those of the traditional pre-oxidation treatment purification method, but the method for purifying the carbon nano tube is very simple and convenient to operate, is beneficial to reducing the operation difficulty and energy consumption of the purified carbon nano tube, and has higher economic value. In addition, as can be seen from fig. 2 to 5, the carbon nanotubes purified in example 3 of the present application can be well dispersed in the solution system both in the slurry and in the silicon negative electrode slurry, while the carbon nanotubes in comparative example 1 can easily exist in the form of clusters both in the slurry and in the silicon negative electrode slurry, and have poor dispersibility, so that the carbon nanotubes purified in the present application have the advantage of better dispersibility than the carbon nanotubes purified in comparative example 1.
As can be seen from the comparison of the data of application example 3 and application comparative examples 3-4 in table 1, the results of application comparative example 3 show that the effect of purifying carbon nanotubes by using dilute sulfuric acid alone is poor without adding an oxidizing agent, and thus it is difficult to obtain high purity carbon nanotubes, and in order to obtain carbon nanotubes with good purity, one prefers to use an oxidizing acid or an oxidizing agent or a combination of both as a reagent for purifying carbon nanotubes at a high concentration, and the effect of purifying carbon nanotubes can be expected indeed if application comparative example 4 uses a concentrated acid with strong oxidizing property and an oxidizing agent as a reagent for the purification reaction. Referring to fig. 6, the IG/ID of the carbon nanotube in the raman spectrum of example 3 is 10.53, the IG/ID ratio of example 3 is larger, which indicates that the structure of the carbon nanotube after purification in example 3 is more complete and the electrical conductivity is good, while the IG/ID of the carbon nanotube after purification in comparative example 4 is 4.21, which is significantly smaller than that of example 3, which indicates that the surface of the carbon nanotube in comparative example 4 is more functional groups than the surface of the carbon nanotube in example 3, which leads to more severe surface damage of the carbon nanotube after purification in comparative example 4, because the surface structure of the carbon nanotube is more severely damaged after the concentrated sulfuric acid and the oxidant are matched in comparative example 4, which leads to the electrical conductivity of the carbon nanotube being reduced, thus seriously affecting the application of the carbon nanotube as the electrical conductive agent in the battery field, the dilute sulfuric acid adopted in example 3 of the present application is a non-oxidizing acid, after the dilute sulfuric acid is matched with the potassium permanganate, the purified carbon nano tube obtains better purity, and the resistivity of the prepared silicon negative electrode piece is not greatly changed, so that the degree of damage to the surface structure of the carbon nano tube is low after the dilute sulfuric acid is matched with the potassium permanganate, and the conductivity of the carbon nano tube is not greatly changed.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A method of purifying carbon nanotubes, comprising: mixing the carbon nano tube, an oxidant and dilute acid for reaction,adding every 1g of carbon nano-tube (6X 10)-3~32×10-3) Oxidant of mol and 150-600g H+Diluted acid with the concentration of 1.8-20mol/L is subjected to post-treatment after the reaction is finished to obtain the purified carbon nano tube.
2. The method of claim 1, wherein the step of purifying the carbon nanotubes comprises: the reaction temperature is 10-70 ℃, and the reaction time is 30-200 min.
3. The method of claim 2, wherein: said H+The concentration is 3.5-13.5 mol/L.
4. The method of claim 1, wherein the step of purifying the carbon nanotubes comprises: the dilute acid is a non-oxidizing acid.
5. The method of claim 4, wherein: the non-oxidizing acid is dilute sulfuric acid.
6. The method of claim 1, wherein the step of purifying the carbon nanotubes comprises: the oxidant is one or a combination of more of potassium permanganate, potassium perchlorate, potassium dichromate and hydrogen peroxide solution, and the mass fraction of the hydrogen peroxide is not less than 20%.
7. The method of claim 1, wherein the step of purifying the carbon nanotubes comprises: the carbon nano tube is one or the combination of two of original multi-wall carbon nano tube, double-wall carbon nano tube and single-wall carbon nano tube.
8. The method of claim 1, wherein the step of purifying the carbon nanotubes comprises: and the post-treatment is to perform solid-liquid separation after the reaction is finished, and wash the carbon nano tube to be neutral to obtain the purified carbon nano tube.
9. The method of claim 8, wherein the step of purifying the carbon nanotubes comprises: water is used as the liquid for washing the carbon nanotubes.
10. A carbon nanotube slurry, characterized in that: the carbon nano tube purified by the method, the dispersing agent and the solvent are mixed according to the mass ratio of 1: (0.2-1): (5-125).
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| CN116462187A (en) * | 2023-03-27 | 2023-07-21 | 南京齐超环保科技有限公司 | Batch purification method of carbon nano tube |
| CN117208896A (en) * | 2023-09-25 | 2023-12-12 | 福建中禾新材料有限公司 | Purification preparation method of crude carbon nano tube |
| CN117735535A (en) * | 2023-12-21 | 2024-03-22 | 湖南京舟股份有限公司 | A method for purifying carbon nanotubes |
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