Corrosion-resistant slurry based on carbon nanotubes and preparation method thereof

Abstract

The invention relates to the technical field of carbon nanotube materials, in particular to corrosion-resistant slurry based on carbon nanotubes and a preparation method of the corrosion-resistant slurry. Comprising the following steps: step 1, (1) mixing aluminum-doped carbon nanotubes, modified graphene, sodium dodecyl benzene sulfonate and toluene, filtering, and freeze-drying to obtain a composite filler; (2) adding the composite filler into an ethanol water solution, adding a sulfydryl silane coupling agent, hydrolyzing, adjusting the pH value to 4.5-5.5 by using acetic acid, and stirring; the preparation method comprises the following steps: adding a free radical initiator in a nitrogen atmosphere, and carrying out sulfydryl click, washing and drying to obtain a raw material A; step 2, adding the raw material A and polyethersulfone resin into a solvent, stirring and grinding; therefore, the corrosion-resistant slurry based on the carbon nanotubes is obtained.

Description

Technical Field

[0001] The invention relates to the technical field of carbon nanotube materials, in particular to a corrosion-resistant slurry based on carbon nanotubes and a preparation method thereof. Background Art

[0002] Carbon nanotubes, with their unique nanostructure, excellent electrical conductivity, and good chemical stability, have shown great potential for application in many fields, including corrosion-resistant slurries. Their unique nanotube structure gives them a large specific surface area, providing more channels for electron transport and further improving electrical conductivity.

[0003] As a two-dimensional carbon material, graphene also has excellent electrical conductivity and good chemical stability. It has a two-dimensional sheet structure and can form a barrier-like structure in the slurry, further preventing the intrusion of corrosive substances and improving corrosion resistance.

[0004] However, there are still many problems in the actual preparation of corrosion-resistant slurry: on the one hand, untreated carbon nanotubes and graphene have poor dispersion in the slurry and are prone to agglomeration, which makes it impossible to exert the excellent performance of carbon nanotubes; on the other hand, although the use of single carbon nanotubes in slurry preparation can improve the overall conductivity of the slurry, it cannot completely improve the corrosion resistance of the slurry, and it is difficult to meet actual use needs.

[0005] In order to improve the above problems, the following method is selected: aluminum doping technology is adopted to provide more electron transmission pathways and change the electronic structure of carbon nanotubes by doping aluminum elements into carbon nanotubes. However, in the existing technology, the research on the aluminum doping content has not been in-depth, and it is difficult to determine the optimal aluminum doping amount that satisfies both the influence of aluminum on the carbon nanotube structure and the complexation of aluminum elements with phenolic hydroxyl groups to improve corrosion resistance.

[0006] In summary, it is of great significance to solve the above problems and prepare a corrosion-resistant slurry based on carbon nanotubes. Summary of the Invention

[0007] The purpose of the present invention is to provide a corrosion-resistant slurry based on carbon nanotubes and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0008] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0009] A method for preparing a corrosion-resistant slurry based on carbon nanotubes comprises the following steps:

[0010] Step 1: (1) mixing aluminum-doped carbon nanotubes, modified graphene, sodium dodecylbenzenesulfonate, and toluene, filtering, and freeze-drying to obtain a composite filler; (2) adding the composite filler to an ethanol aqueous solution, adding a mercaptosilane coupling agent, hydrolyzing, adjusting the pH to 4.5-5.5 with acetic acid, and stirring; under a nitrogen atmosphere, adding a free radical initiator, clicking the mercapto group, washing, and drying to obtain raw material A;

[0011] Step 2: Add raw material A and polyethersulfone resin to the solvent, stir and grind to obtain a corrosion-resistant slurry.

[0012] In a further embodiment, the mercaptosilane coupling agent includes one or more of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethoxysilane.

[0013] In a further embodiment, the free radical initiator includes one or both of benzoyl peroxide and azobisisobutyronitrile.

[0014] In a further embodiment, the hydrolysis temperature is 50-60° C., the hydrolysis time is 3-4 h, the thiol click ligation temperature is 50-60° C., and the thiol click ligation time is 3-4 h.

[0015] More optimally, the raw materials of the corrosion-resistant slurry include the following components: 5 to 7 parts by mass of composite filler, 2 to 3 parts by mass of mercaptosilane coupling agent, 15 to 25 parts by mass of polyethersulfone resin, and 60 to 80 parts by mass of solvent;

[0016] The mass ratio of ethanol to deionized water in the ethanol aqueous solution is 2:2-2.5.

[0017] More optimally, the composite filler includes aluminum-doped carbon nanotubes and modified graphene in a mass ratio of 2-3:5-6.

[0018] More optimally, the preparation process of the aluminum-doped carbon nanotubes is as follows: under an argon atmosphere, aluminum chloride hexahydrate is added to deionized water and stirred, then anhydrous sodium carbonate and carbon nanotubes are added and stirred, reacted at 70-90° C. for 10-14 hours, and centrifuged to obtain aluminum-doped carbon nanotubes.

[0019] More optimally, the raw materials of the aluminum-doped carbon nanotubes include the following components: 2 to 3 parts by mass of aluminum chloride hexahydrate, 1 to 2 parts by mass of anhydrous sodium carbonate, and 2 to 4 parts by mass of carbon nanotubes.

[0020] More optimally, the preparation process of the modified graphene is: adding graphite to a pyridine-N,N-dimethylformamide mixed solvent for ultrasonic dispersion and mixing, adding sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde, refluxing at 140-150°C for 90-100h, filtering, washing, and drying to obtain modified graphene.

[0021] More optimally, the mass ratio of pyridine to N,N-dimethylformamide in the pyridine-N,N-dimethylformamide mixed solvent is 1:5-5.5;

[0022] In the raw materials of the modified graphene, the mass ratio of graphite, sarcosine, 3,4-dihydroxybenzaldehyde and 4-vinylbenzaldehyde is 1:4-6:3-4:1-2.

[0023] More optimally, the solvent includes one or more of butanone, toluene, and N-methyl nitrogen-containing heterocycloalkanone.

[0024] More optimally, in step 2, the process parameters are: the stirring temperature is 10-25°C, the stirring rate is 1000-1200 r / min, and the stirring time is 2-4 hours; the grinding rate is 4000-4800 r / min; and the grinding time is 3-5 hours.

[0025] In the scheme, modified graphene is combined with aluminum-doped carbon nanotubes to form a composite filler with a surface-line intercalation structure, and then added to polyethersulfone resin. The three work together to improve corrosion resistance and electrical conductivity.

[0026] Among them, the modified graphene introduces a large number of nitrogen-containing heterocycles, phenolic hydroxyl groups and other groups through 1,3-dipolar cycloaddition reaction, which has the following advantages: First, the introduction of nitrogen-containing heterocycles can further improve the conductivity of the slurry; second, the introduction of phenolic hydroxyl groups provides active sites for subsequent complexation with aluminum elements to form ligands; third, the introduction of vinyl groups improves the compatibility with silane coupling agents to prevent the occurrence of agglomeration, and improves the dispersibility of the composite filler itself and the dispersibility with polyethersulfone resin; fourth, the introduction of aromatic rings further improves the intercalation structure of the composite filler.

[0027] Among them, aluminum-doped carbon nanotubes prepared by controlling the specific amount of aluminum doping have the following advantages: on the one hand, under weakly acidic conditions, aluminum-doped carbon nanotubes can form ligands by complexing with the phenolic hydroxyl groups in modified graphene, improving compatibility and forming a complex layer, further protecting the slurry from attack by corrosive media and further improving corrosion resistance; on the other hand, aluminum doping provides more carrier transmission pathways, further improving conductivity. During the preparation process, it is necessary to control the aluminum doping content because: if the aluminum doping amount is too high, it will destroy the original structure of the carbon nanotubes, reduce stability and corrosion resistance; if the aluminum doping amount is too low, the complexation will be incomplete, and the corrosion resistance and conductivity will not be improved enough; at the same time, it is necessary to meet the optimal specific doping amount for complexation with the phenolic hydroxyl groups. The reason is that if the aluminum doping amount is too high, the complex layer formed is too thick, affecting intercalation, easily cracking, and corrosive media are easily penetrated, reducing corrosion resistance; if the aluminum doping amount is too low, the complexation sites with the phenolic hydroxyl groups are reduced, and a dense complex layer cannot be formed, which reduces corrosion resistance.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] This solution forms a composite filler with a surface-line intercalation structure by compounding modified graphene with aluminum-doped carbon nanotubes, and adds it to a polyethersulfone resin. By doping the carbon nanotubes with a specific amount of aluminum, a composite filler is formed that satisfies both the optimal conditions of aluminum element doping with the carbon nanotubes and the optimal conditions of complexation with phenolic hydroxyl groups, thereby synergistically improving corrosion resistance and electrical conductivity. DETAILED DESCRIPTION

[0030] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0031] It should be noted that the following parts are by mass, and all raw materials involved in the present invention are purchased from manufacturers without any special restrictions, and are exemplified as follows: in the following embodiments, the CAS number of 3-mercaptopropyltriethoxysilane is 14814-09-6; the molecular weight of the polyethersulfone resin is 50,000; the CAS number of aluminum chloride hexahydrate is 7784-13-6, and the product number is 15200; the CAS number of anhydrous sodium carbonate is 497-19-8; the carbon nanotubes are multi-walled carbon nanotubes with a diameter of 20 to 30 nm; the specification of graphite is 10 μm; the CAS number of sarcosine is 107-97-1; the CAS number of 3,4-dihydroxybenzaldehyde is 139-85-5; and the CAS number of 4-vinylbenzaldehyde is 1791-26-0.

[0032] The following examples are particularly described:

[0033] (1) The mass ratio of pyridine to N,N-dimethylformamide in the pyridine-N,N-dimethylformamide mixed solvent is 1:5.2;

[0034] (2) The mass ratio of ethanol to deionized water in the ethanol aqueous solution is 2:2.3.

[0035] Example 1: A method for preparing a corrosion-resistant slurry based on carbon nanotubes, comprising the following steps:

[0036] Step 1: Under an argon atmosphere, 2.5 parts of aluminum chloride hexahydrate were added to deionized water with stirring, followed by the addition of 1.5 parts of anhydrous sodium carbonate and 3 parts of carbon nanotubes with stirring. The mixture was reacted at 80°C for 12 hours and centrifuged to obtain aluminum-doped carbon nanotubes.

[0037] Step 2: adding graphite to a pyridine-N,N-dimethylformamide mixed solvent and ultrasonically dispersing and mixing, adding sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde, the mass ratio of graphite, sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde is 1:5:3.5:1.5, reflux at 145°C for 95h, filter, wash, and dry to obtain modified graphene;

[0038] Step 3: (1) According to the mass ratio of aluminum-doped carbon nanotubes to modified graphene of 2.5:5.5, aluminum-doped carbon nanotubes, modified graphene, sodium dodecylbenzenesulfonate and toluene are mixed, filtered and freeze-dried to obtain a composite filler; (2) 6 parts of the composite filler are added to an ethanol aqueous solution and 2.5 parts of 3-mercaptopropyltriethoxysilane are added, and the mixture is hydrolyzed at 55°C for 3.5 hours, and the pH is adjusted to 5.0 with acetic acid and stirred; under a nitrogen atmosphere, azobisisobutyronitrile is added, and the thiol group is click-catalyzed at 55°C for 3.5 hours, washed and dried to obtain raw material A;

[0039] Step 4: Add raw material A and 20 parts of polyethersulfone resin to 70 parts of toluene, stir at a rate of 1100 r / min at 15°C for 3 hours, and then grind at a rate of 4400 r / min for 4 hours to obtain a corrosion-resistant slurry.

[0040] Example 2: A method for preparing a corrosion-resistant slurry based on carbon nanotubes, comprising the following steps:

[0041] Step 1: Under an argon atmosphere, 2 parts of aluminum chloride hexahydrate were added to deionized water with stirring, followed by the addition of 1.5 parts of anhydrous sodium carbonate and 3 parts of carbon nanotubes with stirring, and the mixture was reacted at 80°C for 12 hours, and centrifuged to obtain aluminum-doped carbon nanotubes;

[0042] Step 2: adding graphite to a pyridine-N,N-dimethylformamide mixed solvent and ultrasonically dispersing and mixing, adding sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde, with a mass ratio of graphite, sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde being 1:4:3:1, reflux at 145°C for 95h, filtering, washing, and drying to obtain modified graphene;

[0043] Step 3: (1) According to the mass ratio of aluminum-doped carbon nanotubes to modified graphene of 2:5, aluminum-doped carbon nanotubes, modified graphene, sodium dodecylbenzenesulfonate and toluene are mixed, filtered and freeze-dried to obtain a composite filler; (2) 5 parts of the composite filler are added to an ethanol aqueous solution and 2 parts of 3-mercaptopropyltriethoxysilane are added, and the mixture is hydrolyzed at 55°C for 3.5 hours, and the pH is adjusted to 5.0 with acetic acid and stirred; under a nitrogen atmosphere, azobisisobutyronitrile is added, and the thiol group is click-catalyzed at 55°C for 3.5 hours, washed and dried to obtain raw material A;

[0044] Step 4: Add raw material A and 15 parts of polyethersulfone resin to 70 parts of toluene, stir at a rate of 1100 r / min at 15°C for 3 hours, and then grind at a rate of 4400 r / min for 4 hours to obtain a corrosion-resistant slurry.

[0045] Example 3: A method for preparing a corrosion-resistant slurry based on carbon nanotubes, comprising the following steps:

[0046] Step 1: Under an argon atmosphere, 3 parts of aluminum chloride hexahydrate were added to deionized water with stirring, followed by the addition of 1.5 parts of anhydrous sodium carbonate and 3 parts of carbon nanotubes with stirring, and the mixture was reacted at 80°C for 12 hours, and centrifuged to obtain aluminum-doped carbon nanotubes;

[0047] Step 2: adding graphite to a pyridine-N,N-dimethylformamide mixed solvent and ultrasonically dispersing and mixing, adding sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde, the mass ratio of graphite, sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde is 1:6:4:2, reflux at 145°C for 95h, filter, wash, and dry to obtain modified graphene;

[0048] Step 3: (1) According to the mass ratio of aluminum-doped carbon nanotubes to modified graphene of 3:6, aluminum-doped carbon nanotubes, modified graphene, sodium dodecylbenzenesulfonate and toluene are mixed, filtered and freeze-dried to obtain a composite filler; (2) 7 parts of the composite filler are added to an ethanol aqueous solution and 3 parts of 3-mercaptopropyltriethoxysilane are added, and the mixture is hydrolyzed at 55°C for 3.5 hours, and the pH is adjusted to 5.0 with acetic acid and stirred; under a nitrogen atmosphere, azobisisobutyronitrile is added, and the thiol group is click-catalyzed at 55°C for 3.5 hours, washed and dried to obtain raw material A;

[0049] Step 4: Add raw material A and 25 parts of polyethersulfone resin to 70 parts of toluene, stir at a rate of 1100 r / min at 15°C for 3 hours, and then grind at a rate of 4400 r / min for 4 hours to obtain a corrosion-resistant slurry.

[0050] Comparative Example 1: Based on Example 1, no mercaptosilane coupling agent was added, and the other processes remained unchanged, specifically:

[0051] Step 1: Under an argon atmosphere, 2.5 parts of aluminum chloride hexahydrate were added to deionized water with stirring, followed by the addition of 1.5 parts of anhydrous sodium carbonate and 3 parts of carbon nanotubes with stirring. The mixture was reacted at 80°C for 12 hours and centrifuged to obtain aluminum-doped carbon nanotubes.

[0052] Step 2: adding graphite to a pyridine-N,N-dimethylformamide mixed solvent and ultrasonically dispersing and mixing, adding sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde, the mass ratio of graphite, sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde is 1:5:3.5:1.5, reflux at 145°C for 95h, filter, wash, and dry to obtain modified graphene;

[0053] Step 3: (1) According to the mass ratio of aluminum-doped carbon nanotubes to modified graphene of 2.5:5.5, aluminum-doped carbon nanotubes, modified graphene, sodium dodecylbenzenesulfonate, and toluene are mixed, filtered, and freeze-dried to obtain a composite filler; (2) 6 parts of the composite filler are added to an ethanol aqueous solution, the pH is adjusted to 5.0 with acetic acid, and stirred; under a nitrogen atmosphere, azobisisobutyronitrile is added, and a thiol click reaction is carried out at 55°C for 3.5 hours, followed by washing and drying to obtain raw material A;

[0054] Step 4: Add raw material A and 20 parts of polyethersulfone resin to 70 parts of toluene, stir at a rate of 1100 r / min at 15°C for 3 hours, and then grind at a rate of 4400 r / min for 4 hours to obtain a corrosion-resistant slurry.

[0055] Comparative Example 2: Based on Example 1, the aluminum content in the aluminum-doped carbon nanotubes was adjusted, and the other processes remained unchanged, specifically:

[0056] Step 1: Under an argon atmosphere, 5 parts of aluminum chloride hexahydrate were added to deionized water with stirring, followed by the addition of 1.5 parts of anhydrous sodium carbonate and 3 parts of carbon nanotubes with stirring, and the mixture was reacted at 80°C for 12 hours, and centrifuged to obtain aluminum-doped carbon nanotubes;

[0057] Step 2: adding graphite to a pyridine-N,N-dimethylformamide mixed solvent and ultrasonically dispersing and mixing, adding sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde, the mass ratio of graphite, sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde is 1:5:3.5:1.5, reflux at 145°C for 95h, filter, wash, and dry to obtain modified graphene;

[0058] Step 3: (1) According to the mass ratio of aluminum-doped carbon nanotubes to modified graphene of 6:5.5, aluminum-doped carbon nanotubes, modified graphene, sodium dodecylbenzenesulfonate and toluene are mixed, filtered and freeze-dried to obtain a composite filler; (2) 6 parts of the composite filler are added to an ethanol aqueous solution and 2.5 parts of 3-mercaptopropyltriethoxysilane are added, and the mixture is hydrolyzed at 55°C for 3.5 hours, and the pH is adjusted to 5.0 with acetic acid and stirred; under a nitrogen atmosphere, azobisisobutyronitrile is added, and the thiol group is click-catalyzed at 55°C for 3.5 hours, washed and dried to obtain raw material A;

[0059] Step 4: Add raw material A and 20 parts of polyethersulfone resin to 70 parts of toluene, stir at a rate of 1100 r / min at 15°C for 3 hours, and then grind at a rate of 4400 r / min for 4 hours to obtain a corrosion-resistant slurry.

[0060] Comparative Example 3: Based on Example 1, the aluminum-doped carbon nanotubes were replaced with carbon nanotubes, and the other processes remained unchanged, specifically:

[0061] Step 1: adding graphite to a pyridine-N,N-dimethylformamide mixed solvent and ultrasonically dispersing and mixing, adding sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde, with a mass ratio of graphite, sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde being 1:5:3.5:1.5, reflux at 145°C for 95h, filtering, washing, and drying to obtain modified graphene;

[0062] Step 2: (1) according to the mass ratio of carbon nanotubes to modified graphene of 2.5:5.5, carbon nanotubes, modified graphene, sodium dodecylbenzenesulfonate and toluene were mixed, filtered and freeze-dried to obtain a composite filler; (2) 6 parts of the composite filler were added to an ethanol aqueous solution and 2.5 parts of 3-mercaptopropyltriethoxysilane were added, and the mixture was hydrolyzed at 55°C for 3.5 hours, and the pH was adjusted to 5.0 with acetic acid and stirred; under a nitrogen atmosphere, azobisisobutyronitrile was added, and the thiol group was click-catalyzed at 55°C for 3.5 hours, washed and dried to obtain raw material A;

[0063] Step 3: Add raw material A and 20 parts of polyethersulfone resin to 70 parts of toluene, stir at a rate of 1100 r / min at 15°C for 3 hours, and then grind at a rate of 4400 r / min for 4 hours to obtain a corrosion-resistant slurry.

[0064] Comparative Example 4: Based on Example 1, the modified graphene was adjusted to graphene, and the other processes remained unchanged, specifically:

[0065] Step 1: Under an argon atmosphere, 2.5 parts of aluminum chloride hexahydrate were added to deionized water with stirring, followed by the addition of 1.5 parts of anhydrous sodium carbonate and 3 parts of carbon nanotubes with stirring. The mixture was reacted at 80°C for 12 hours and centrifuged to obtain aluminum-doped carbon nanotubes.

[0066] Step 2: (1) According to the mass ratio of aluminum-doped carbon nanotubes to graphene of 2.5:5.5, aluminum-doped carbon nanotubes, graphene, sodium dodecylbenzenesulfonate and toluene are mixed, filtered and freeze-dried to obtain a composite filler; (2) 6 parts of the composite filler are added to an ethanol aqueous solution and 2.5 parts of 3-mercaptopropyltriethoxysilane are added, and the mixture is hydrolyzed at 55°C for 3.5 hours, the pH is adjusted to 5.0 with acetic acid, and stirred; under a nitrogen atmosphere, azobisisobutyronitrile is added, and the thiol group is click-catalyzed at 55°C for 3.5 hours, washed, and dried to obtain raw material A;

[0067] Step 3: Add raw material A and 20 parts of polyethersulfone resin to 70 parts of toluene, stir at a rate of 1100 r / min at 15°C for 3 hours, and then grind at a rate of 4400 r / min for 4 hours to obtain a corrosion-resistant slurry.

[0068] Detection experiment: The corrosion-resistant slurry based on carbon nanotubes prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was subjected to performance testing: (1) Corrosion resistance test: The corrosion amount of the corrosion-resistant slurry based on carbon nanotubes prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was tested. The lower the corrosion amount, the better the corrosion resistance. The test results are shown in Table 1. (2) Conductivity test: The corrosion-resistant slurry based on carbon nanotubes prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was coated on a carbon film and its conductivity was tested. The higher the conductivity value, the better the conductivity. The test results are shown in Table 1.

[0069]

[0070]

[0071] Table 1

[0072] Result analysis: According to the data analysis in Table 1, it can be seen that this solution improves the corrosion resistance and electrical conductivity of the slurry by introducing modified graphene, aluminum-doped carbon nanotubes and polyethersulfone resin in a synergistic manner. From the data of Comparative Example 1, it can be seen that without adding the mercaptosilane coupling agent, the dispersibility of the modified graphene with the aluminum-doped carbon nanotubes and the polyethersulfone resin is reduced, agglomeration is likely to occur, and it cannot play a significant role, and the corrosion resistance and conductivity are reduced; from the data of Comparative Example 2, it can be seen that adjusting the aluminum content in the aluminum-doped carbon nanotubes, if the aluminum doping amount is too high, on the one hand, will destroy the original structure of the carbon nanotubes, significantly reduce the corrosion resistance and conductivity; on the other hand, it will cause the complex layer formed by the aluminum element and the phenolic hydroxyl group to be too thick, affecting the intercalation result, easily generating cracks, corrosive media are easy to penetrate, and the corrosion resistance is reduced; from the data of Comparative Example 3, it can be seen that adjusting the aluminum-doped carbon nanotubes to carbon nanotubes without introducing the aluminum element, the carrier transmission channel is reduced, the ligand cannot be complexed to form a complex film, and the corrosion resistance and conductivity are greatly reduced; from the data of Comparative Example 4, it can be seen that adjusting the modified graphene to graphene lacks the introduction of a large number of nitrogen-containing heterocycles, phenolic hydroxyl groups and other groups, and the conductivity and corrosion resistance are significantly reduced.

[0073] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

Claims

1. A method for preparing a corrosion-resistant slurry based on carbon nanotubes, characterized in that: The following steps are involved: Step 1: (1) mixing aluminum-doped carbon nanotubes, modified graphene, sodium dodecylbenzenesulfonate, and toluene, filtering, and freeze-drying to obtain a composite filler; (2) adding the composite filler to an ethanol aqueous solution, adding a mercaptosilane coupling agent, hydrolyzing, adjusting the pH to 4.5-5.5 with acetic acid, and stirring; under a nitrogen atmosphere, adding a free radical initiator, clicking the mercapto group, washing, and drying to obtain raw material A; Step 2: Add raw material A and polyethersulfone resin to the solvent, stir and grind to obtain a corrosion-resistant slurry.

2. The method for preparing a corrosion-resistant slurry based on carbon nanotubes according to claim 1, characterized in that: The raw materials of the corrosion-resistant slurry include the following components: 5 to 7 parts by mass of composite filler, 2 to 3 parts by mass of mercaptosilane coupling agent, 15 to 25 parts by mass of polyethersulfone resin, and 60 to 80 parts by mass of solvent; The mass ratio of ethanol to deionized water in the ethanol aqueous solution is 2:2-2.

5.

3. The method for preparing a corrosion-resistant slurry based on carbon nanotubes according to claim 2, characterized in that: The composite filler comprises aluminum-doped carbon nanotubes and modified graphene in a mass ratio of 2-3:5-6.

4. The method for preparing a corrosion-resistant slurry based on carbon nanotubes according to claim 3, characterized in that: The preparation process of the aluminum-doped carbon nanotubes is as follows: under an argon atmosphere, aluminum chloride hexahydrate is added to deionized water and stirred, then anhydrous sodium carbonate and carbon nanotubes are added and stirred, reacted at 70-90° C. for 10-14 hours, and centrifuged and dried to obtain aluminum-doped carbon nanotubes.

5. The method for preparing a corrosion-resistant slurry based on carbon nanotubes according to claim 4, characterized in that: The raw materials of the aluminum-doped carbon nanotubes include the following components: 2 to 3 parts of aluminum chloride hexahydrate, 1 to 2 parts of anhydrous sodium carbonate, and 2 to 4 parts of carbon nanotubes, calculated by mass.

6. The method for preparing a corrosion-resistant slurry based on carbon nanotubes according to claim 3, characterized in that: The preparation process of the modified graphene is as follows: adding graphite to a pyridine-N,N-dimethylformamide mixed solvent for ultrasonic dispersion and mixing, adding sarcosine, 3,4-dihydroxybenzaldehyde, and 4-vinylbenzaldehyde, refluxing at 140-150° C. for 90-100 hours, filtering, washing, and drying to obtain the modified graphene.

7. The method for preparing a corrosion-resistant slurry based on carbon nanotubes according to claim 6, characterized in that: The mass ratio of pyridine to N,N-dimethylformamide in the pyridine-N,N-dimethylformamide mixed solvent is 1:5-5.5; In the raw materials of the modified graphene, the mass ratio of graphite, sarcosine, 3,4-dihydroxybenzaldehyde and 4-vinylbenzaldehyde is 1:4-6:3-4:1-2.

8. The method for preparing a corrosion-resistant slurry based on carbon nanotubes according to claim 1, characterized in that: The solvent includes one or more of butanone, toluene, and N-methyl nitrogen-containing heterocyclic alkanone.

9. The method for preparing a corrosion-resistant slurry based on carbon nanotubes according to claim 1, characterized in that: In step 2, the process parameters are: the stirring temperature is 10-25° C., the stirring rate is 1000-1200 r / min, and the stirring time is 2-4 h; the grinding rate is 4000-4800 r / min; and the grinding time is 3-5 h. 10 . A corrosion-resistant slurry prepared according to the method for preparing a corrosion-resistant slurry based on carbon nanotubes according to any one of claims 1 to 9 .

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