CN117457260B - Novel conductive carbon black-modified graphene composite slurry and preparation method thereof - Google Patents
Novel conductive carbon black-modified graphene composite slurry and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention provides a novel conductive carbon black-modified graphene composite slurry and a preparation method thereof, belongs to the field of conductive material manufacturing, solves the problem that the surface of a non-metal material is difficult to realize electric connection, and comprises the following components in percentage by weight: conductive carbon black, modified graphene, carboxyl modified ternary vinyl chloride-acetate resin, an anti-settling agent, a powder orientation agent, a leveling agent, a powder wetting dispersant, an antioxidant and a crosslinking agent. The preparation steps of the composite slurry are as follows: s1, carrying out ultrasonic dispersion on a graphene raw material; s2, washing and drying; s3, modified graphene oxide treatment; s4, pre-dispersing treatment; s5, dissolving resin; s6, forming the slurry. The composite slurry has good comprehensive performance in electric conduction, heat conduction and electromagnetic wave shielding. In the preparation method of the composite slurry, the precise proportion of various components ensures the consistency and quality of the final product, and can greatly improve the performance of the final product.
Description
Technical Field
The invention belongs to the field of conductive material manufacturing, and relates to a slurry for enhancing the conductive performance of a non-metal surface, in particular to a novel conductive carbon black-modified graphene composite slurry and a preparation method thereof.
Background
In various army and civil industrial fields such as electronics, electrical appliances, aviation, chemical industry and the like, different parts are usually required to be connected to realize current conduction, and metal conductors are usually used as connecting materials, but in some special links, nonmetallic materials such as glass fibers, polyimide films, polycarbonate, epoxy resins, polytetrafluoroethylene and the like are also widely used due to the characteristics of light weight, flexibility and the like, and electric connection is required to be performed on nonmetallic surfaces to realize circuit integrity and normal work, however, nonmetallic materials are often poor in electric conduction and heat conduction performance, and in addition, the nonmetallic materials are difficult to absorb, conduct and attenuate electromagnetic waves like metals, so that the problem of electromagnetic wave interference cannot be effectively solved in the use of nonmetallic materials for a long time.
The problem is solved by spraying or brushing the slurry on the surface of the nonmetallic material, but the slurry on the market has not ideal comprehensive effect of electric conduction, heat conduction and shielding performance, has insufficient environmental stability and durability problems in long-term use, and especially has extreme working environment such as high temperature, high humidity or chemical corrosive environment; such as conductive silver paste, generally perform in electromagnetic shielding; carbon black slurry, which takes carbon black as a conductive agent, is low in price, but has lower conductivity and stability than metal conductive slurry, and has limited heat conduction performance and shielding effect; nickel-based conductive pastes are cheaper than silver pastes and have some conductivity, but are less conductive in high performance applications, environmental stability and durability.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides novel conductive carbon black-modified graphene composite slurry and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme: the novel conductive carbon black-modified graphene composite slurry comprises the following components in parts by weight: 27.0 to 33.0 percent of conductive carbon black, 1.0 to 5.0 percent of modified graphene, 54 to 70.5 percent of carboxyl modified ternary chlorine-containing resin, 0.1 to 1.0 percent of anti-settling agent, 0.1 to 2.0 percent of powder orientation agent, 0.5 to 2.0 percent of flatting agent, 0.2 to 0.5 percent of powder wetting dispersant, 0.1 to 0.5 percent of antioxidant and 0.5 to 2.0 percent of cross-linking agent.
The specific surface area of the conductive carbon black is 1300-1600 m/g, the oil absorption value of the conductive carbon black is 3-3.50ml/g, the tinting strength of the conductive carbon black is 110-140%, the particle size D50 of the conductive carbon black is 15-20nm, the ash content of the conductive carbon black is 0.8-1%, the density of the conductive carbon black is 130-155g/l, the anti-settling agent is a modified urea solution, the modified urea solution is BYK-410, the powder directing agent is ethylene-vinyl acetate copolymer wax dispersion, the leveling agent is polyether modified polydimethylsiloxane, the powder wetting dispersant is at least one of styrene-acrylic acid copolymer, methyl methacrylate-acrylic acid copolymer and butene-acrylic acid copolymer, and the antioxidant is beta-3, 5-di-tert-butyl-4-hydroxyphenylpropionate tetramer; the cross-linking agent is hexamethylene diisocyanate.
The preparation method of the novel conductive carbon black-modified graphene composite slurry comprises the following steps:
s1 graphene raw material treatment:
placing absolute ethyl alcohol into a constant-temperature water bath device, and adding graphene raw materials; ultrasonic dispersion is carried out by utilizing ultrasonic equipment, the working power of the ultrasonic equipment is 200-500 watts, and the working time of the ultrasonic equipment is 30-60 minutes, so that uniform graphene raw material dispersion liquid is obtained; the absolute ethyl alcohol is used as a solvent for dispersing the graphene raw material, and is beneficial to dispersing graphene raw material particles due to low polarity, so that agglomeration is reduced; the ultrasonic wave helps to break up graphene raw material particles, so that the particles are more uniformly dispersed in absolute ethyl alcohol, and the effective dispersion is ensured without damaging the structure of the graphene raw material by selecting power and time;
adding a first acetic acid solution into the graphene raw material dispersion liquid, continuously monitoring by a pH meter until the pH value is 3-4, ending adding the first acetic acid solution, then adding a silane coupling agent in a dropwise adding mode, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 60-80 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 22-26 hours, so as to obtain a modified graphene oxide mixed solution; the first acetic acid solution is used for adjusting the pH value to promote the reaction of the silane coupling agent and the graphene, and the pH adjustment is important to ensure the smooth progress of the reaction; the set temperature range is beneficial to optimizing the reaction rate and efficiency of the silane coupling agent and the graphene; the stirring speed and time of the mechanical stirring are chosen to ensure adequate mixing of the mixture while avoiding excessive shear forces damaging the graphene structure;
S2, washing and drying:
separating the modified graphene oxide mixed solution by adopting a centrifugal machine to obtain modified graphene oxide; washing the modified graphene oxide by using a washing solution with the mass ratio of absolute ethyl alcohol to deionized water being 1:1 for 15-30 minutes, wherein after washing, the modified graphene oxide has no color change, detecting the pH value of the last washing solution to be neutral by using a pH meter, and ending the washing; placing the modified graphene oxide into an oven for baking; the washing and drying steps are used to ensure removal of by-products and unreacted chemicals generated during the modification process;
s3, modified graphene oxide treatment:
placing the acetic acid solution II into a constant-temperature water bath device, adding modified graphene oxide, performing ultrasonic dispersion by using ultrasonic equipment with the working power of 200-500 watts, and performing ultrasonic dispersion for 30-60 minutes to obtain modified graphene oxide dispersion liquid; adding a hydroiodic acid solution to the modified graphene oxide dispersion liquid, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 45-55 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 12-24 hours, so as to obtain a modified graphene mixed solution; the hydroiodic acid plays a role of a reducing agent in the process and is used for reducing the modified graphene oxide into the modified graphene, and the hydroiodic acid is a strong reducing agent and can effectively remove oxygen functional groups in the graphene oxide, so that the conductivity of the graphene is recovered. In addition, the hydroiodic acid can perform reduction reaction at a relatively low temperature compared with other reducing agents, thereby reducing thermal damage to the graphene structure; similar to the step S1, the temperature and stirring parameters are selected to optimize the reaction conditions and improve the reaction efficiency and the product quality;
Separating the modified graphene mixed solution by adopting a centrifugal machine to obtain modified graphene;
and (3) cleaning the modified graphene by using a cleaning solution with the mass ratio of absolute ethyl alcohol to deionized water being 1:1 for 15-30 minutes, wherein after cleaning, the modified graphene has no color change, and detecting the pH value of the last cleaning solution to be neutral by using a pH meter, and finishing cleaning.
Drying the modified graphene in a vacuum drying oven for 4-6 hours, wherein the drying temperature is set to be 70-90 ℃;
s4, pre-dispersion treatment:
mixing conductive carbon black, modified graphene and N-methylpyrrolidone, and performing pre-dispersion treatment to obtain a pre-dispersion mixture, wherein the purity of the N-methylpyrrolidone is more than 99.5%, the ratio of the sum of the weight of the conductive carbon black and the weight of the modified graphene to the weight of the N-methylpyrrolidone is 1:2-1:3, and the N-methylpyrrolidone is taken as a non-reactive diluent and does not account for the components of the composite slurry; after the composite sizing agent is successfully prepared, N-methyl pyrrolidone with different weights can be added for dilution to meet the requirements of the processing technology;
s5, dissolving resin:
placing carboxyl modified ternary vinyl chloride-acetate resin into a stirring tank, adding cyclohexanone, stirring and dissolving at a stirring speed of 500-1000 rpm for 30-60 minutes; obtaining a resin mixture; carboxyl modified ternary vinyl chloride-acetate copolymer, as an adhesive of the composite slurry, cyclohexanone is used as a solvent for dissolving carboxyl modified ternary vinyl chloride-acetate copolymer to form a uniform resin substrate; the parameters of the stirring speed and the stirring time are selected to ensure that the resin is completely dissolved to form a uniform mixture, thereby providing a good basis for the next mixing step;
S6, forming slurry:
adding the pre-dispersed mixture into a resin mixture, stirring for 10-20 minutes by adopting a dispersing machine at a rotating speed of 1000-1200R/P, wherein high-speed stirring is beneficial to fully mixing all components to form uniform slurry, and the rotating speed and the stirring time are selected to ensure uniform distribution of the components and good dispersibility and avoid particle aggregation; then adding an anti-settling agent, a leveling agent, a powder wetting dispersant and an antioxidant in sequence, and stirring for 10-15 minutes at a rotating speed of 1000-1200R/P; finally adding a cross-linking agent, stirring for 5-8 minutes, and taking out to obtain a mixture of the composite slurry and the N-methylpyrrolidone, wherein the rotation speed and the stirring time are selected to further ensure that the added anti-settling agent, the flatting agent, the powder wetting dispersant, the antioxidant and the cross-linking agent are uniformly distributed in the slurry, thereby being beneficial to realizing uniform distribution and function maximization of the additives;
action of anti-settling agent: during the preparation of the slurry, an anti-settling agent is used to prevent settling of the solid components. The method helps to keep uniform dispersion of solid particles such as conductive carbon black and modified graphene in the slurry, prevents aggregation and sedimentation of the particles, and is important to ensure consistency and performance stability of the slurry during storage and use;
Leveling agent function: the leveling agent is used for improving the fluidity and surface smoothness of the slurry, and reduces the surface tension of the slurry during coating or application, thereby promoting more uniform coating formation, reducing bubbles and brush marks, and improving the surface finish and the aesthetic property of the final product;
action of powder wetting dispersant: the main function of the powder wetting dispersant is to promote wetting and dispersing of solid powder in a liquid medium, reduce aggregation tendency among powder particles, improve stability and uniformity of slurry, and is important to maintain high-quality coating and material performance;
antioxidant effect: the function of the antioxidant in the slurry is to prevent the material from deteriorating due to oxidation reaction, which may cause deterioration of organic components in the slurry, affecting the physical and chemical properties thereof, and the addition of the antioxidant helps to prolong the service life of the slurry and keep the properties thereof stable;
the function of the cross-linking agent: the crosslinking agent is added to enhance the mechanical strength and the thermal stability of the slurry, and the crosslinking agent forms a network structure in the slurry, so that the structural integrity and the durability of the slurry are improved;
the selection and the proportion of the additives can ensure that the composite slurry has excellent processing performance, stable storage characteristic and good application effect to the critical weight, and can obviously improve the quality and the performance of the final product.
In step S1, the silane coupling agent is KH560; the mass ratio of the silane coupling agent to the graphene raw material is 0.5:100-1:100; the mass ratio of the graphene raw material to the absolute ethyl alcohol is 1:400-1:600; the concentration of the first acetic acid solution is 1% -5%; the specific surface area of the graphene raw material is 10-280 m/g, the particle size D50 of the graphene raw material is less than 10um, the tap density of the graphene raw material is less than 0.10 g/cm, the carbon content of the graphene raw material is more than or equal to 97%, and KH560 and the surface of the graphene are subjected to chemical reaction to form a stable chemical bond. The modification not only improves the dispersibility of the graphene in the resin matrix, but also enhances the overall mechanical property of the composite material, and in addition, the use of KH560 is beneficial to improving the conductivity and durability of the final product;
in the step S2, the baking time of the baking oven is 2-4 hours, and the baking temperature of the baking oven is set to be 100-120 ℃;
in step S3, the concentration of the hydroiodic acid solution is 10% -30%; the concentration of the acetic acid solution II is 1% -5%; the mass ratio of the acetic acid contained in the second acetic acid solution to the modified graphene oxide is 1:5-1:10; the mass ratio of the hydroiodic acid contained in the hydroiodic acid solution to the acetic acid contained in the acetic acid solution II is 1:10-1:20; the concentration of the hydroiodic acid solution directly affects the efficiency of the reduction reaction and the quality of the product; the concentration of 10% -30% is selected for balancing the efficiency and safety of the reaction, too high concentration can cause reaction overstress to damage the structure of graphene, and too low concentration can cause incomplete reduction to influence the conductive performance of the product. Therefore, by selecting a suitable concentration, an efficient and safe reduction process can be ensured;
In step S4, the pre-dispersion processing steps are as follows: firstly, treating by using a dispersing machine, wherein the rotating speed of the dispersing machine is set to be 800-1000R/P, and the continuous working time of the dispersing machine is 40-50 minutes; then using ultrasonic equipment to perform secondary dispersion, wherein the power is 200-500 watts, the continuous working time of the ultrasonic equipment is 40-50 minutes, and finally using a sand mill to perform sand milling treatment, and the sand milling treatment time is 10-12 hours, so as to obtain a pre-dispersion mixture;
the rotating speed of the dispersing machine is set to 800-1000R/P, so that the shearing force caused by high-speed stirring is avoided to be overlarge while the effective dispersion is kept, and the structural integrity of the modified graphene and the conductive carbon black is kept; the continuous working time of the dispersing machine is 40-50 minutes, so that the purpose is to ensure sufficient mechanical dispersion, so that the components in the slurry are uniformly dispersed, and a good foundation is provided for the subsequent ultrasonic and sand grinding treatment.
The ultrasonic equipment performs secondary dispersion, the power is 200-500 watts, and the purpose is to further refine particle dispersion and improve the uniformity and stability of slurry through the mechanical action and micro vortex effect of ultrasonic waves; the ultrasonic apparatus is operated for a duration of 40 to 50 minutes to ensure sufficient time for effective ultrasonic treatment to further improve the dispersion state of the slurry.
Finally, sand milling is carried out by using a sand mill for 10-12 hours, so that the size of particles is further reduced by mechanical grinding, the surface activity is increased, the uniformity and fineness of slurry are improved, and the subsequent slurry application is facilitated.
In the step S5, the mass ratio of the carboxyl modified ternary vinyl chloride-acetate copolymer to the cyclohexanone is 1:4-1:6; the proportion is selected to balance the properties of the carboxyl modified ternary vinyl chloride-acetate resin and cyclohexanone to obtain proper fluidity, viscosity and hardening characteristics; the combination within this ratio provides optimal performance and application characteristics, making the slurry easier to handle during construction or coating, and achieving the desired physical properties after curing.
Compared with the prior art, the preparation method and application of the conductive silver paste have the following beneficial effects:
1. self-made modified graphene: according to the method, the uniformity and the dispersibility of graphene raw materials are effectively improved by adopting a composite process of ultrasonic dispersion and chemical modification, and fine regulation and control of graphene are realized by adding an acetic acid solution and a silane coupling agent, so that a highly modified graphene oxide mixed solution is obtained, secondary treatment steps including ultrasonic dispersion and acid treatment and cleaning and drying links are introduced in the preparation process, the purity and the stability of modified graphene are ensured, and compared with other manufacturing methods, the method fully considers fine control of the quality and the performance of graphene in the preparation process, so that a final product has more excellent conductivity, dispersibility and stability.
2. Improving the conductivity: by combining the modified graphene and the conductive carbon black, the slurry is excellent in improving the conductivity, and the addition of the modified graphene not only improves the overall conductivity, but also enhances the conductivity stability of the material due to the unique two-dimensional structure.
3. Optimizing thermal management capabilities: the components and proportions of the slurry are designed to provide good thermal conductivity and facilitate effective heat management in electronic and electrical devices, particularly under high load or high temperature conditions.
4. Enhancing mechanical stability: by using a carboxyl group-modified ternary vinyl chloride-acetate resin and suitable additives such as an antioxidant and a crosslinking agent, the slurry is excellent in mechanical stability and durability, and is particularly suitable for use in extreme environments.
5. The environmental adaptability is improved: the leveling agent and the powder wetting and dispersing agent added in the slurry are beneficial to improving the coating performance and the surface uniformity of the material, so that good performance is maintained under different environmental conditions.
6. Electromagnetic interference is reduced: due to the high conductivity of graphene and conductive carbon black, the slurry can effectively shield electromagnetic waves and reduce electromagnetic interference, which is particularly important for high-frequency electronic equipment.
7. The applicability is wide: due to its excellent electrical, thermal and mechanical properties, the paste is suitable for a variety of industrial applications, including electronics, electrical, aviation and chemical industry, meeting the market demand for high performance joining materials.
8. Reliability of the preparation method: by combining the conductive carbon black and the modified graphene, the composite slurry maintains good physical stability while providing excellent conductivity; the precise proportion of various components in the preparation method ensures the consistency and quality of the final product, and can greatly improve the performance of the final product.
In summary, the invention not only provides a composite paste with better conductivity, better thermal stability, good shielding effect and better environmental adaptability, but also provides a more effective and reliable material selection for the fields of electronics, electric appliances and other related industries.
Drawings
Fig. 1 is a 3D microscope image of a cured film according to a first embodiment of the present invention.
Fig. 2 is a 3D microscope image of a cured film according to a second embodiment of the present invention.
Fig. 3 is a 3D microscope image of a cured film of a third embodiment of the present invention.
Fig. 4 is a 3D microscope image of a cured film according to a fourth embodiment of the present invention.
Fig. 5 is a 3D microscope image of a cured film of a fifth embodiment of the present invention.
Fig. 6 is an infrared spectrum of modified graphene oxide in a third embodiment of the present invention.
FIG. 7 is an XRD spectrum of modified graphene oxide in a third embodiment of the invention.
Detailed Description
The following are specific embodiments of the present invention and the technical solutions of the present invention will be further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
First embodiment:
the novel conductive carbon black-modified graphene composite slurry comprises the following components in parts by weight: 27% of conductive carbon black, 1% of modified graphene, 70.5% of carboxyl modified ternary vinyl chloride-acetate copolymer, 0.1% of anti-settling agent, 0.1% of powder orientation agent, 0.5% of leveling agent and 0.2% of powder wetting dispersant; 0.1% of antioxidant and 0.5% of cross-linking agent.
The specific surface area of the conductive carbon black is 1300-1600 m/g, the oil absorption value of the conductive carbon black is 3-3.50ml/g, the tinting strength of the conductive carbon black is 110-140%, the particle diameter D50 of the conductive carbon black is 15-20nm, the ash content of the conductive carbon black is 0.8-1%, the density of the conductive carbon black is 130-155g/l, the anti-settling agent is a modified urea solution, the modified urea solution is BYK-410, the powder orientation agent is ethylene-vinyl acetate copolymer wax dispersoid, the leveling agent is polyether modified polydimethylsiloxane, the powder wetting dispersant is styrene-acrylic copolymer, and the antioxidant is beta-3, 5-di-tert-butyl-4-hydroxyphenylpropionic acid pentaerythritol ester tetramer; the cross-linking agent is hexamethylene diisocyanate.
Preferably, the preparation method of the novel conductive carbon black-modified graphene composite slurry comprises the following steps:
s1, ultrasonic dispersion of graphene raw materials:
preferably, absolute ethyl alcohol is put into a constant-temperature water bath device, and graphene raw materials are added; ultrasonic dispersion is carried out by utilizing ultrasonic equipment, the working power of the ultrasonic equipment is 400 watts, and the working time of the ultrasonic equipment is 45 minutes, so that uniform graphene raw material dispersion liquid is obtained;
adding a first acetic acid solution into the graphene raw material dispersion liquid, continuously monitoring by a pH meter until the pH is 3-4, ending adding the first acetic acid solution, then adding a silane coupling agent in a dropwise manner, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 70 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 24 hours, so as to obtain a modified graphene oxide mixed solution;
s2, washing and drying:
separating the modified graphene oxide mixed solution by adopting a centrifugal machine to obtain modified graphene oxide; the mass ratio of the absolute ethyl alcohol to the deionized water is 1:1, cleaning the modified graphene oxide for 5 times by using a cleaning solution, wherein the cleaning lasts for 30 minutes, the modified graphene oxide has no color change after cleaning, and a pH meter is used for detecting that the pH value of the last cleaning solution is neutral, and the cleaning is finished; placing the modified graphene oxide into an oven for baking;
S3, modified graphene oxide treatment:
placing the acetic acid solution II into a constant-temperature water bath device, adding modified graphene oxide, performing ultrasonic dispersion by using ultrasonic equipment, wherein the working power of the ultrasonic equipment is 450 watts, and performing ultrasonic dispersion for 40 minutes to obtain modified graphene oxide dispersion liquid;
adding a hydroiodic acid solution to the modified graphene oxide dispersion liquid, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 50 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 16 hours, so as to obtain a modified graphene mixed solution;
separating the modified graphene mixed solution by adopting a centrifugal machine to obtain modified graphene;
washing the modified graphene for 3-5 times by using a washing solution with the mass ratio of absolute ethyl alcohol to deionized water being 1:1, wherein the washing lasts for 15-30 minutes, after washing, the modified graphene has no color change, and a pH meter is used for detecting that the pH value of the last washing solution is neutral, and the washing is finished;
drying the modified graphene in a vacuum drying oven for 5 hours, wherein the drying temperature is set to 80 ℃;
s4, pre-dispersion treatment:
mixing conductive carbon black, modified graphene and N-methylpyrrolidone, and performing pre-dispersion treatment to obtain a pre-dispersion mixture, wherein the purity of the N-methylpyrrolidone is more than 99.5%; the ratio of the sum of the weights of the conductive carbon black and the modified graphene to N-methyl pyrrolidone is 1:2;
S5, dissolving resin:
placing carboxyl modified ternary vinyl chloride-acetate resin into a stirring tank, adding cyclohexanone, stirring and dissolving at a stirring speed of 500-1000 rpm for 45 minutes; obtaining a resin mixture;
s6, forming slurry:
adding the pre-dispersion mixture into the resin mixture, stirring for 15 minutes at the rotating speed of 1000-1200R/P by adopting a dispersing machine, then sequentially adding an anti-settling agent, a flatting agent, a powder wetting dispersant and an antioxidant, and stirring for 15 minutes at the rotating speed of 1000-1200R/P again; and finally adding the cross-linking agent, stirring for 5-8 minutes, and taking out to obtain a mixture of the composite slurry and the N-methylpyrrolidone.
Preferably, in step S1, the silane coupling agent is KH560; the mass ratio of the silane coupling agent to the graphene raw material is 0.7:100; the mass ratio of the graphene raw material to the absolute ethyl alcohol is 1:500; the concentration of the acetic acid solution I is 3%; the specific surface area of the graphene raw material is 10-280 m/g, the particle size D50 of the graphene raw material is less than 10um, the tap density of the graphene raw material is less than 0.10 g/cm, and the carbon content of the graphene raw material is more than or equal to 97%.
Preferably, in step S2, the oven drying time is 3 hours and the oven drying temperature is set to 110 ℃.
Preferably, in step S3, the concentration of the hydroiodic acid solution is 20%; concentration of acetic acid solution number two is 4%; the mass ratio of the acetic acid contained in the second acetic acid solution to the modified graphene oxide is 1:7; the mass ratio of the hydroiodic acid contained in the hydroiodic acid solution to the acetic acid contained in the acetic acid solution II is 1:15.
Preferably, in step S4, the pre-dispersion processing steps are as follows: firstly, treating by using a dispersing machine, wherein the rotating speed of the dispersing machine is set to 800-1000R/P, and the continuous working time of the dispersing machine is 50 minutes; and then performing secondary dispersion by using ultrasonic equipment, wherein the power of the ultrasonic equipment is 300 watts, the continuous working time of the ultrasonic equipment is 40 minutes, and finally, performing sanding treatment by using a sand mill for 11 hours to obtain a pre-dispersion mixture.
Preferably, in step S5, the mass ratio of the carboxyl modified ternary vinyl chloride-acetate resin to the cyclohexanone is 1:4.
Specific embodiment II:
the novel conductive carbon black-modified graphene composite slurry comprises the following components in parts by weight: 33% of conductive carbon black, 5% of modified graphene, 54% of carboxyl modified ternary vinyl chloride-acetate copolymer, 1% of anti-settling agent, 2% of powder orientation agent, 2% of leveling agent and 0.5% of powder wetting dispersant; 0.5% of antioxidant and 2% of cross-linking agent.
The specific surface area of the conductive carbon black is 1300-1600 m/g, the oil absorption value of the conductive carbon black is 3-3.50ml/g, the tinting strength of the conductive carbon black is 110-140%, the particle diameter D50 of the conductive carbon black is 15-20nm, the ash content of the conductive carbon black is 0.8-1%, the density of the conductive carbon black is 130-155g/l, the anti-settling agent is a modified urea solution, the modified urea solution is BYK-410, the powder orientation agent is ethylene-vinyl acetate copolymer wax dispersoid, the leveling agent is polyether modified polydimethylsiloxane, the powder wetting dispersant is styrene-acrylic copolymer, and the antioxidant is beta-3, 5-di-tert-butyl-4-hydroxyphenylpropionic acid pentaerythritol ester tetramer; the cross-linking agent is hexamethylene diisocyanate.
Preferably, the preparation method of the novel conductive carbon black-modified graphene composite slurry comprises the following steps:
s1, ultrasonic dispersion of graphene raw materials:
preferably, absolute ethyl alcohol is put into a constant-temperature water bath device, and graphene raw materials are added; ultrasonic dispersion is carried out by utilizing ultrasonic equipment, the working power of the ultrasonic equipment is 400 watts, and the working time of the ultrasonic equipment is 45 minutes, so that uniform graphene raw material dispersion liquid is obtained;
adding a first acetic acid solution into the graphene raw material dispersion liquid, continuously monitoring by a pH meter until the pH is 3-4, ending adding the first acetic acid solution, then adding a silane coupling agent in a dropwise manner, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 70 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 24 hours, so as to obtain a modified graphene oxide mixed solution;
s2, washing and drying:
separating the modified graphene oxide mixed solution by adopting a centrifugal machine to obtain modified graphene oxide; the mass ratio of the absolute ethyl alcohol to the deionized water is 1:1, cleaning the modified graphene oxide for 5 times by using a cleaning solution, wherein the cleaning lasts for 30 minutes, the modified graphene oxide has no color change after cleaning, and a pH meter is used for detecting that the pH value of the last cleaning solution is neutral, and the cleaning is finished; placing the modified graphene oxide into an oven for baking;
S3, modified graphene oxide treatment:
placing the acetic acid solution II into a constant-temperature water bath device, adding modified graphene oxide, performing ultrasonic dispersion by using ultrasonic equipment, wherein the working power of the ultrasonic equipment is 450 watts, and performing ultrasonic dispersion for 40 minutes to obtain modified graphene oxide dispersion liquid;
adding a hydroiodic acid solution to the modified graphene oxide dispersion liquid, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 50 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 16 hours, so as to obtain a modified graphene mixed solution;
separating the modified graphene mixed solution by adopting a centrifugal machine to obtain modified graphene;
washing the modified graphene for 3-5 times by using a washing solution with the mass ratio of absolute ethyl alcohol to deionized water being 1:1, wherein the washing lasts for 15-30 minutes, after washing, the modified graphene has no color change, and a pH meter is used for detecting that the pH value of the last washing solution is neutral, and the washing is finished;
drying the modified graphene in a vacuum drying oven for 5 hours, wherein the drying temperature is set to 80 ℃;
s4, pre-dispersion treatment:
mixing conductive carbon black, modified graphene and N-methylpyrrolidone, and performing pre-dispersion treatment to obtain a pre-dispersion mixture, wherein the purity of the N-methylpyrrolidone is more than 99.5%; the ratio of the sum of the weights of the conductive carbon black and the modified graphene to N-methyl pyrrolidone is 1:2;
S5, dissolving resin:
placing carboxyl modified ternary vinyl chloride-acetate resin into a stirring tank, adding cyclohexanone, stirring and dissolving at a stirring speed of 500-1000 rpm for 45 minutes; obtaining a resin mixture;
s6, forming slurry:
adding the pre-dispersion mixture into the resin mixture, stirring for 15 minutes at the rotating speed of 1000-1200R/P by adopting a dispersing machine, then sequentially adding an anti-settling agent, a flatting agent, a powder wetting dispersant and an antioxidant, and stirring for 15 minutes at the rotating speed of 1000-1200R/P again; and finally adding the cross-linking agent, stirring for 5-8 minutes, and taking out to obtain a mixture of the composite slurry and the N-methylpyrrolidone.
Preferably, in step S1, the silane coupling agent is KH560; the mass ratio of the silane coupling agent to the graphene raw material is 0.7:100; the mass ratio of the graphene raw material to the absolute ethyl alcohol is 1:500; the concentration of the acetic acid solution I is 3%; the specific surface area of the graphene raw material is 10-280 m/g, the particle size D50 of the graphene raw material is less than 10um, the tap density of the graphene raw material is less than 0.10 g/cm, and the carbon content of the graphene raw material is more than or equal to 97%.
Preferably, in step S2, the oven drying time is 3 hours and the oven drying temperature is set to 110 ℃.
Preferably, in step S3, the concentration of the hydroiodic acid solution is 20%; concentration of acetic acid solution number two is 4%; the mass ratio of the acetic acid contained in the second acetic acid solution to the modified graphene oxide is 1:7; the mass ratio of the hydroiodic acid contained in the hydroiodic acid solution to the acetic acid contained in the acetic acid solution II is 1:15.
Preferably, in step S4, the pre-dispersion processing steps are as follows: firstly, treating by using a dispersing machine, wherein the rotating speed of the dispersing machine is set to 800-1000R/P, and the continuous working time of the dispersing machine is 50 minutes; and then performing secondary dispersion by using ultrasonic equipment, wherein the power of the ultrasonic equipment is 300 watts, the continuous working time of the ultrasonic equipment is 40 minutes, and finally, performing sanding treatment by using a sand mill for 11 hours to obtain a pre-dispersion mixture.
Preferably, in step S5, the mass ratio of the carboxyl modified ternary vinyl chloride-acetate resin to the cyclohexanone is 1:4.
Third embodiment:
the novel conductive carbon black-modified graphene composite slurry comprises the following components in parts by weight: 30% of conductive carbon black, 3% of modified graphene, 64.3% of carboxyl modified ternary vinyl chloride-acetate resin, 0.1% of anti-settling agent, 0.1% of powder orientation agent, 1% of leveling agent and 0.5% of powder wetting dispersant; 0.5% of antioxidant and 0.5% of cross-linking agent.
The specific surface area of the conductive carbon black is 1300-1600 m/g, the oil absorption value of the conductive carbon black is 3-3.50ml/g, the tinting strength of the conductive carbon black is 110-140%, the particle diameter D50 of the conductive carbon black is 15-20nm, the ash content of the conductive carbon black is 0.8-1%, the density of the conductive carbon black is 130-155g/l, the anti-settling agent is a modified urea solution, the modified urea solution is BYK-410, the powder orientation agent is ethylene-vinyl acetate copolymer wax dispersoid, the leveling agent is polyether modified polydimethylsiloxane, the powder wetting dispersant is styrene-acrylic copolymer, and the antioxidant is beta-3, 5-di-tert-butyl-4-hydroxyphenylpropionic acid pentaerythritol ester tetramer; the cross-linking agent is hexamethylene diisocyanate.
Preferably, the preparation method of the novel conductive carbon black-modified graphene composite slurry comprises the following steps:
s1, ultrasonic dispersion of graphene raw materials:
preferably, absolute ethyl alcohol is put into a constant-temperature water bath device, and graphene raw materials are added; ultrasonic dispersion is carried out by utilizing ultrasonic equipment, the working power of the ultrasonic equipment is 400 watts, and the working time of the ultrasonic equipment is 45 minutes, so that uniform graphene raw material dispersion liquid is obtained;
adding a first acetic acid solution into the graphene raw material dispersion liquid, continuously monitoring by a pH meter until the pH is 3-4, ending adding the first acetic acid solution, then adding a silane coupling agent in a dropwise manner, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 70 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 24 hours, so as to obtain a modified graphene oxide mixed solution;
s2, washing and drying:
separating the modified graphene oxide mixed solution by adopting a centrifugal machine to obtain modified graphene oxide; the mass ratio of the absolute ethyl alcohol to the deionized water is 1:1, cleaning the modified graphene oxide for 5 times by using a cleaning solution, wherein the cleaning lasts for 30 minutes, the modified graphene oxide has no color change after cleaning, and a pH meter is used for detecting that the pH value of the last cleaning solution is neutral, and the cleaning is finished; placing the modified graphene oxide into an oven for baking;
S3, modified graphene oxide treatment:
placing the acetic acid solution II into a constant-temperature water bath device, adding modified graphene oxide, performing ultrasonic dispersion by using ultrasonic equipment, wherein the working power of the ultrasonic equipment is 450 watts, and performing ultrasonic dispersion for 40 minutes to obtain modified graphene oxide dispersion liquid;
adding a hydroiodic acid solution to the modified graphene oxide dispersion liquid, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 50 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 16 hours, so as to obtain a modified graphene mixed solution;
separating the modified graphene mixed solution by adopting a centrifugal machine to obtain modified graphene;
washing the modified graphene for 3-5 times by using a washing solution with the mass ratio of absolute ethyl alcohol to deionized water being 1:1, wherein the washing lasts for 15-30 minutes, after washing, the modified graphene has no color change, and a pH meter is used for detecting that the pH value of the last washing solution is neutral, and the washing is finished;
drying the modified graphene in a vacuum drying oven for 5 hours, wherein the drying temperature is set to 80 ℃;
s4, pre-dispersion treatment:
mixing conductive carbon black, modified graphene and N-methylpyrrolidone, and performing pre-dispersion treatment to obtain a pre-dispersion mixture, wherein the purity of the N-methylpyrrolidone is more than 99.5%; the ratio of the sum of the weights of the conductive carbon black and the modified graphene to N-methyl pyrrolidone is 1:2;
S5, dissolving resin:
placing carboxyl modified ternary vinyl chloride-acetate resin into a stirring tank, adding cyclohexanone, stirring and dissolving at a stirring speed of 500-1000 rpm for 45 minutes; obtaining a resin mixture;
s6, forming slurry:
adding the pre-dispersion mixture into the resin mixture, stirring for 15 minutes at the rotating speed of 1000-1200R/P by adopting a dispersing machine, then sequentially adding an anti-settling agent, a flatting agent, a powder wetting dispersant and an antioxidant, and stirring for 15 minutes at the rotating speed of 1000-1200R/P again; and finally adding the cross-linking agent, stirring for 5-8 minutes, and taking out to obtain a mixture of the composite slurry and the N-methylpyrrolidone.
Preferably, in step S1, the silane coupling agent is KH560; the mass ratio of the silane coupling agent to the graphene raw material is 0.7:100; the mass ratio of the graphene raw material to the absolute ethyl alcohol is 1:500; the concentration of the acetic acid solution I is 3%; the specific surface area of the graphene raw material is 10-280 m/g, the particle size D50 of the graphene raw material is less than 10um, the tap density of the graphene raw material is less than 0.10 g/cm, and the carbon content of the graphene raw material is more than or equal to 97%.
Preferably, in step S2, the oven drying time is 3 hours and the oven drying temperature is set to 110 ℃.
Preferably, in step S3, the concentration of the hydroiodic acid solution is 20%; concentration of acetic acid solution number two is 4%; the mass ratio of the acetic acid contained in the second acetic acid solution to the modified graphene oxide is 1:7; the mass ratio of the hydroiodic acid contained in the hydroiodic acid solution to the acetic acid contained in the acetic acid solution II is 1:15.
Preferably, in step S4, the pre-dispersion processing steps are as follows: firstly, treating by using a dispersing machine, wherein the rotating speed of the dispersing machine is set to 800-1000R/P, and the continuous working time of the dispersing machine is 50 minutes; and then performing secondary dispersion by using ultrasonic equipment, wherein the power of the ultrasonic equipment is 300 watts, the continuous working time of the ultrasonic equipment is 40 minutes, and finally, performing sanding treatment by using a sand mill for 11 hours to obtain a pre-dispersion mixture.
Preferably, in step S5, the mass ratio of the carboxyl modified ternary vinyl chloride-acetate resin to the cyclohexanone is 1:4.
Fourth embodiment:
the novel conductive carbon black-modified graphene composite slurry comprises the following components in parts by weight: 31% of conductive carbon black, 3% of modified graphene, 61% of carboxyl modified ternary vinyl chloride-acetate resin, 0.7% of anti-settling agent, 0.5% of powder orientation agent, 0.5% of leveling agent and 0.5% of powder wetting dispersant; 0.2% of antioxidant and 2% of cross-linking agent.
The specific surface area of the conductive carbon black is 1300-1600 m/g, the oil absorption value of the conductive carbon black is 3-3.50ml/g, the tinting strength of the conductive carbon black is 110-140%, the particle diameter D50 of the conductive carbon black is 15-20nm, the ash content of the conductive carbon black is 0.8-1%, the density of the conductive carbon black is 130-155g/l, the anti-settling agent is a modified urea solution, the modified urea solution is BYK-410, the powder orientation agent is ethylene-vinyl acetate copolymer wax dispersoid, the leveling agent is polyether modified polydimethylsiloxane, the powder wetting dispersant is styrene-acrylic copolymer, and the antioxidant is beta-3, 5-di-tert-butyl-4-hydroxyphenylpropionic acid pentaerythritol ester tetramer; the cross-linking agent is hexamethylene diisocyanate.
Preferably, the preparation method of the novel conductive carbon black-modified graphene composite slurry comprises the following steps:
s1, ultrasonic dispersion of graphene raw materials:
preferably, absolute ethyl alcohol is put into a constant-temperature water bath device, and graphene raw materials are added; ultrasonic dispersion is carried out by utilizing ultrasonic equipment, the working power of the ultrasonic equipment is 400 watts, and the working time of the ultrasonic equipment is 45 minutes, so that uniform graphene raw material dispersion liquid is obtained;
adding a first acetic acid solution into the graphene raw material dispersion liquid, continuously monitoring by a pH meter until the pH is 3-4, ending adding the first acetic acid solution, then adding a silane coupling agent in a dropwise manner, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 70 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 24 hours, so as to obtain a modified graphene oxide mixed solution;
s2, washing and drying:
separating the modified graphene oxide mixed solution by adopting a centrifugal machine to obtain modified graphene oxide; the mass ratio of the absolute ethyl alcohol to the deionized water is 1:1, cleaning the modified graphene oxide for 5 times by using a cleaning solution, wherein the cleaning lasts for 30 minutes, the modified graphene oxide has no color change after cleaning, and a pH meter is used for detecting that the pH value of the last cleaning solution is neutral, and the cleaning is finished; placing the modified graphene oxide into an oven for baking;
S3, modified graphene oxide treatment:
placing the acetic acid solution II into a constant-temperature water bath device, adding modified graphene oxide, performing ultrasonic dispersion by using ultrasonic equipment, wherein the working power of the ultrasonic equipment is 450 watts, and performing ultrasonic dispersion for 40 minutes to obtain modified graphene oxide dispersion liquid;
adding a hydroiodic acid solution to the modified graphene oxide dispersion liquid, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 50 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 16 hours, so as to obtain a modified graphene mixed solution;
separating the modified graphene mixed solution by adopting a centrifugal machine to obtain modified graphene;
washing the modified graphene for 3-5 times by using a washing solution with the mass ratio of absolute ethyl alcohol to deionized water being 1:1, wherein the washing lasts for 15-30 minutes, after washing, the modified graphene has no color change, and a pH meter is used for detecting that the pH value of the last washing solution is neutral, and the washing is finished;
drying the modified graphene in a vacuum drying oven for 5 hours, wherein the drying temperature is set to 80 ℃;
s4, pre-dispersion treatment:
mixing conductive carbon black, modified graphene and N-methylpyrrolidone, and performing pre-dispersion treatment to obtain a pre-dispersion mixture, wherein the purity of the N-methylpyrrolidone is more than 99.5%; the ratio of the sum of the weights of the conductive carbon black and the modified graphene to N-methyl pyrrolidone is 1:2;
S5, dissolving resin:
placing carboxyl modified ternary vinyl chloride-acetate resin into a stirring tank, adding cyclohexanone, stirring and dissolving at a stirring speed of 500-1000 rpm for 45 minutes; obtaining a resin mixture;
s6, forming slurry:
adding the pre-dispersion mixture into the resin mixture, stirring for 15 minutes at the rotating speed of 1000-1200R/P by adopting a dispersing machine, then sequentially adding an anti-settling agent, a flatting agent, a powder wetting dispersant and an antioxidant, and stirring for 15 minutes at the rotating speed of 1000-1200R/P again; and finally adding the cross-linking agent, stirring for 5-8 minutes, and taking out to obtain a mixture of the composite slurry and the N-methylpyrrolidone.
Preferably, in step S1, the silane coupling agent is KH560; the mass ratio of the silane coupling agent to the graphene raw material is 0.7:100; the mass ratio of the graphene raw material to the absolute ethyl alcohol is 1:500; the concentration of the acetic acid solution I is 3%; the specific surface area of the graphene raw material is 10-280 m/g, the particle size D50 of the graphene raw material is less than 10um, the tap density of the graphene raw material is less than 0.10 g/cm, and the carbon content of the graphene raw material is more than or equal to 97%.
Preferably, in step S2, the oven drying time is 3 hours and the oven drying temperature is set to 110 ℃.
Preferably, in step S3, the concentration of the hydroiodic acid solution is 20%; concentration of acetic acid solution number two is 4%; the mass ratio of the acetic acid contained in the second acetic acid solution to the modified graphene oxide is 1:7; the mass ratio of the hydroiodic acid contained in the hydroiodic acid solution to the acetic acid contained in the acetic acid solution II is 1:15.
Preferably, in step S4, the pre-dispersion processing steps are as follows: firstly, treating by using a dispersing machine, wherein the rotating speed of the dispersing machine is set to 800-1000R/P, and the continuous working time of the dispersing machine is 50 minutes; and then performing secondary dispersion by using ultrasonic equipment, wherein the power of the ultrasonic equipment is 300 watts, the continuous working time of the ultrasonic equipment is 40 minutes, and finally, performing sanding treatment by using a sand mill for 11 hours to obtain a pre-dispersion mixture.
Preferably, in step S5, the mass ratio of the carboxyl modified ternary vinyl chloride-acetate resin to the cyclohexanone is 1:4.
Fifth embodiment:
the novel conductive carbon black-modified graphene composite slurry comprises the following components in parts by weight: 32% of conductive carbon black, 4% of modified graphene, 59.2% of carboxyl modified ternary chlorine-vinegar resin, 0.5% of anti-settling agent, 0.5% of powder orientation agent, 1.5% of leveling agent and 0.3% of powder wetting dispersant; 0.5% of antioxidant and 1.5% of cross-linking agent.
The specific surface area of the conductive carbon black is 1300-1600 m/g, the oil absorption value of the conductive carbon black is 3-3.50ml/g, the tinting strength of the conductive carbon black is 110-140%, the particle diameter D50 of the conductive carbon black is 15-20nm, the ash content of the conductive carbon black is 0.8-1%, the density of the conductive carbon black is 130-155g/l, the anti-settling agent is a modified urea solution, the modified urea solution is BYK-410, the powder orientation agent is ethylene-vinyl acetate copolymer wax dispersoid, the leveling agent is polyether modified polydimethylsiloxane, the powder wetting dispersant is styrene-acrylic copolymer, and the antioxidant is beta-3, 5-di-tert-butyl-4-hydroxyphenylpropionic acid pentaerythritol ester tetramer; the cross-linking agent is hexamethylene diisocyanate.
Preferably, the preparation method of the novel conductive carbon black-modified graphene composite slurry comprises the following steps:
s1, ultrasonic dispersion of graphene raw materials:
preferably, absolute ethyl alcohol is put into a constant-temperature water bath device, and graphene raw materials are added; ultrasonic dispersion is carried out by utilizing ultrasonic equipment, the working power of the ultrasonic equipment is 400 watts, and the working time of the ultrasonic equipment is 45 minutes, so that uniform graphene raw material dispersion liquid is obtained;
adding a first acetic acid solution into the graphene raw material dispersion liquid, continuously monitoring by a pH meter until the pH is 3-4, ending adding the first acetic acid solution, then adding a silane coupling agent in a dropwise manner, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 70 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 24 hours, so as to obtain a modified graphene oxide mixed solution;
s2, washing and drying:
separating the modified graphene oxide mixed solution by adopting a centrifugal machine to obtain modified graphene oxide; the mass ratio of the absolute ethyl alcohol to the deionized water is 1:1, cleaning the modified graphene oxide for 5 times by using a cleaning solution, wherein the cleaning lasts for 30 minutes, the modified graphene oxide has no color change after cleaning, and a pH meter is used for detecting that the pH value of the last cleaning solution is neutral, and the cleaning is finished; placing the modified graphene oxide into an oven for baking;
S3, modified graphene oxide treatment:
placing the acetic acid solution II into a constant-temperature water bath device, adding modified graphene oxide, performing ultrasonic dispersion by using ultrasonic equipment, wherein the working power of the ultrasonic equipment is 450 watts, and performing ultrasonic dispersion for 40 minutes to obtain modified graphene oxide dispersion liquid;
adding a hydroiodic acid solution to the modified graphene oxide dispersion liquid, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 50 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 16 hours, so as to obtain a modified graphene mixed solution;
separating the modified graphene mixed solution by adopting a centrifugal machine to obtain modified graphene;
washing the modified graphene for 3-5 times by using a washing solution with the mass ratio of absolute ethyl alcohol to deionized water being 1:1, wherein the washing lasts for 15-30 minutes, after washing, the modified graphene has no color change, and a pH meter is used for detecting that the pH value of the last washing solution is neutral, and the washing is finished;
drying the modified graphene in a vacuum drying oven for 5 hours, wherein the drying temperature is set to 80 ℃;
s4, pre-dispersion treatment:
mixing conductive carbon black, modified graphene and N-methylpyrrolidone, and performing pre-dispersion treatment to obtain a pre-dispersion mixture, wherein the purity of the N-methylpyrrolidone is more than 99.5%; the ratio of the sum of the weights of the conductive carbon black and the modified graphene to N-methyl pyrrolidone is 1:2;
S5, dissolving resin:
placing carboxyl modified ternary vinyl chloride-acetate resin into a stirring tank, adding cyclohexanone, stirring and dissolving at a stirring speed of 500-1000 rpm for 45 minutes; obtaining a resin mixture;
s6, forming slurry:
adding the pre-dispersion mixture into the resin mixture, stirring for 15 minutes at the rotating speed of 1000-1200R/P by adopting a dispersing machine, then sequentially adding an anti-settling agent, a flatting agent, a powder wetting dispersant and an antioxidant, and stirring for 15 minutes at the rotating speed of 1000-1200R/P again; and finally adding the cross-linking agent, stirring for 5-8 minutes, and taking out to obtain a mixture of the composite slurry and the N-methylpyrrolidone.
Preferably, in step S1, the silane coupling agent is KH560; the mass ratio of the silane coupling agent to the graphene raw material is 0.7:100; the mass ratio of the graphene raw material to the absolute ethyl alcohol is 1:500; the concentration of the acetic acid solution I is 3%; the specific surface area of the graphene raw material is 10-280 m/g, the particle size D50 of the graphene raw material is less than 10um, the tap density of the graphene raw material is less than 0.10 g/cm, and the carbon content of the graphene raw material is more than or equal to 97%.
Preferably, in step S2, the oven drying time is 3 hours and the oven drying temperature is set to 110 ℃.
Preferably, in step S3, the concentration of the hydroiodic acid solution is 20%; concentration of acetic acid solution number two is 4%; the mass ratio of the acetic acid contained in the second acetic acid solution to the modified graphene oxide is 1:7; the mass ratio of the hydroiodic acid contained in the hydroiodic acid solution to the acetic acid contained in the acetic acid solution II is 1:15.
Preferably, in step S4, the pre-dispersion processing steps are as follows: firstly, treating by using a dispersing machine, wherein the rotating speed of the dispersing machine is set to 800-1000R/P, and the continuous working time of the dispersing machine is 50 minutes; and then performing secondary dispersion by using ultrasonic equipment, wherein the power of the ultrasonic equipment is 300 watts, the continuous working time of the ultrasonic equipment is 40 minutes, and finally, performing sanding treatment by using a sand mill for 11 hours to obtain a pre-dispersion mixture.
Preferably, in step S5, the mass ratio of the carboxyl modified ternary vinyl chloride-acetate resin to the cyclohexanone is 1:4.
In the third embodiment, as shown in FIGS. 6 and 7, after the modification treatment, the surface of 692cm -1 The diffraction peak generated by vibration of Si-0-C group is newly appeared, and furthermore, at 769cm -1 Appearance of the placeThe Si-H and NH,2 oscillation peaks also confirm successful covalent grafting of the silane to the GO surface.
As shown in FIGS. 1 to 5, the composite slurries prepared in the above examples one, two, three, four and five were coated into paint films, and the cured thickness was 13 to 15. Mu.m, and the properties of the paint films were tested.
Table 1 example test data
| Sample of | Square resistance R (Ω/≡) | Tensile strength MPa | Adhesive force (3M adhesive tape, 90 ℃ pulling) | Shielding effectiveness (dB, 10 GHz) | Coefficient of thermal conductivity (W/m.K) |
| Example 1 | 543 | 62 | No falling off | 62 | 2.31 |
| Example two | 332 | 51 | Small part is fallen off | 66 | 2.53 |
| Example III | 335 | 63 | No falling off | 65 | 2.54 |
| Example IV | 344 | 54 | No falling off | 61 | 2..51 |
| Example five | 337 | 52 | Small part is fallen off | 60 | 2.49 |
The following results were obtained by analyzing the test data of table 1:
the composite slurry of the invention has excellent conductive properties: the slurries of the present invention exhibited lower sheet resistance (Ω/≡), particularly in examples 2 and 3, a range of 332 to 335 Ω/≡. The conductivity is superior to conventional carbon black pastes and nickel-based conductive pastes, approaching or even exceeding that of certain silver pastes.
The composite slurry of the present invention has high tensile strength: the tensile strength in the test is excellent, and in particular, the tensile strength of examples 1 and 3 is as high as 62-63MPa, indicating that the slurry-coated paint film of the present invention has good mechanical strength and durability, which is hardly comparable to the conventional carbon black slurry and nickel-based conductive slurry.
The composite slurry has good adhesive force: the paint film in most examples does not fall off or falls off in small parts when tested using 3M tape at high temperature 90 ℃, which indicates excellent adhesion and environmental stability, which is particularly important for application scenarios requiring long-term stability.
The composite slurry has excellent shielding effectiveness: the shielding effectiveness measured at 10GHz is very high, especially the shielding effectiveness of examples 2 and 3 reaches 65-66dB, which is comparable to silver paste, and this high electromagnetic shielding performance makes the paste very advantageous in applications where protection against electromagnetic interference is required.
The composite slurry has good heat conductivity coefficient: tests have shown that the inventive paste has a relatively high thermal conductivity, exceeding 2.3W/(m·k) in all examples, and that the inventive paste performs better in terms of thermal conductivity than typical carbon black pastes and nickel-based conductive pastes, which is a significant advantage for applications requiring efficient heat dissipation.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (6)
1. The preparation method of the novel conductive carbon black-modified graphene composite slurry comprises the following components in percentage by weight: 27.0 to 33.0 percent of conductive carbon black, 1.0 to 5.0 percent of modified graphene, 54 to 70.5 percent of carboxyl modified ternary vinyl chloride-acetate resin, 0.1 to 1.0 percent of anti-settling agent, 0.1 to 2.0 percent of powder orientation agent, 0.5 to 2.0 percent of leveling agent, 0.2 to 0.5 percent of powder wetting dispersant, 0.1 to 0.5 percent of antioxidant and 0.5 to 2.0 percent of cross-linking agent, wherein the specific surface area of the conductive carbon black is 1300 to 1600m 2 The oil absorption value of the conductive carbon black is 3-3.50ml/g, the tinting strength of the conductive carbon black is 110-140%, the particle size D50 of the conductive carbon black is 15-20nm, the ash content of the conductive carbon black is 0.8-1%, the density of the conductive carbon black is 130-155g/l, the anti-settling agent is a modified urea solution, the powder orientation agent is an ethylene-vinyl acetate copolymer wax dispersion, the leveling agent is polyether modified polydimethylsiloxane, the powder wetting dispersant is at least one of a styrene-acrylic copolymer, a methyl methacrylate-acrylic copolymer and a butene-acrylic copolymer, and the antioxidant is beta-3, 5-di-tert-butyl-4-hydroxyphenylpropionic acid pentaerythritol tetramer; the cross-linking agent is hexamethylene diisocyanate, and is characterized in that the preparation method comprises the following steps:
s1, ultrasonic dispersion of graphene raw materials:
placing absolute ethyl alcohol into a constant-temperature water bath device, and adding graphene raw materials; ultrasonic dispersion is carried out by utilizing ultrasonic equipment, the working power of the ultrasonic equipment is 200-500 watts, and the working time of the ultrasonic equipment is 30-60 minutes, so that uniform graphene raw material dispersion liquid is obtained;
adding a first acetic acid solution into the graphene raw material dispersion liquid, continuously monitoring by a pH meter until the pH value is 3-4, ending adding the first acetic acid solution, then adding a silane coupling agent in a dropwise adding mode, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 60-80 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 22-26 hours, so as to obtain a modified graphene oxide mixed solution;
S2, washing and drying:
separating the modified graphene oxide mixed solution by adopting a centrifugal machine to obtain modified graphene oxide; washing the modified graphene oxide by using a washing solution with the mass ratio of absolute ethyl alcohol to deionized water being 1:1 for 15-30 minutes, wherein after washing, the modified graphene oxide has no color change, detecting the pH value of the last washing solution to be neutral by using a pH meter, and ending the washing; placing the modified graphene oxide into an oven for baking;
s3, modified graphene oxide treatment:
placing the acetic acid solution II into a constant-temperature water bath device, adding modified graphene oxide, performing ultrasonic dispersion by using ultrasonic equipment with the working power of 200-500 watts, and performing ultrasonic dispersion for 30-60 minutes to obtain modified graphene oxide dispersion liquid;
adding a hydroiodic acid solution to the modified graphene oxide dispersion liquid, and starting a constant-temperature water bath device, wherein the temperature of the constant-temperature water bath device is set to be 45-55 ℃; stirring at a constant speed by adopting mechanical stirring equipment, wherein the stirring speed is 1000-2000 rpm, and the stirring time is 12-24 hours, so as to obtain a modified graphene mixed solution;
separating the modified graphene mixed solution by adopting a centrifugal machine to obtain modified graphene;
Washing the modified graphene by using a washing solution with the mass ratio of absolute ethyl alcohol to deionized water being 1:1 for 15-30 minutes, wherein after washing, the modified graphene has no color change, detecting the pH value of the last washing solution to be neutral by using a pH meter, and ending washing;
drying the modified graphene in a vacuum drying oven for 4-6 hours, wherein the drying temperature is set to be 70-90 ℃;
s4, pre-dispersion treatment:
mixing conductive carbon black, modified graphene and N-methylpyrrolidone, and performing pre-dispersion treatment to obtain a pre-dispersion mixture, wherein the purity of the N-methylpyrrolidone is more than 99.5%; according to the weight ratio, the ratio of the sum of the weights of the conductive carbon black and the modified graphene to the N-methyl pyrrolidone is 1:2-1:3, and the N-methyl pyrrolidone is taken as a non-reactive diluent and does not account for the components of the composite slurry;
s5, dissolving resin:
placing carboxyl modified ternary vinyl chloride-acetate resin into a stirring tank, adding cyclohexanone, stirring and dissolving at a stirring speed of 500-1000 rpm for 30-60 minutes; obtaining a resin mixture;
s6, forming slurry:
adding the pre-dispersion mixture into a resin mixture, stirring for 10-20 minutes at a rotating speed of 1000-1200R/P by adopting a dispersing machine, then sequentially adding an anti-settling agent, a flatting agent, a powder wetting dispersing agent and an antioxidant, and stirring for 10-15 minutes at a rotating speed of 1000-1200R/P again; and finally adding the cross-linking agent, and stirring for 5-8 minutes to obtain a mixture of the composite slurry and the N-methylpyrrolidone.
2. The method for preparing a novel conductive carbon black-modified graphene composite paste according to claim 1, wherein in step S1, the silane coupling agent is KH560; the mass ratio of the silane coupling agent to the graphene raw material is 0.5:100-1:100; the mass ratio of the graphene raw material to the absolute ethyl alcohol is 1:400-1:600; the concentration of the first acetic acid solution is 1% -5%; the specific surface area of the graphene raw material is 10-280m 2 Per gram, the particle diameter D50 of the graphene raw material is less than 10um, and the tap density of the graphene raw material is less than 0.10g/cm 3 The carbon content of the graphene raw material is more than or equal to 97%.
3. The method for preparing a novel conductive carbon black-modified graphene composite paste according to claim 1, wherein in the step S2, the oven drying time is 2-4 hours, and the oven drying temperature is set to 100-120 ℃.
4. The method for preparing a novel conductive carbon black-modified graphene composite slurry according to claim 1, wherein in step S3, the concentration of the hydroiodic acid solution is 10% -30%; the concentration of the acetic acid solution II is 1% -5%; the mass ratio of the acetic acid contained in the second acetic acid solution to the modified graphene oxide is 1:5-1:10; the mass ratio of the hydroiodic acid contained in the hydroiodic acid solution to the acetic acid contained in the acetic acid solution II is 1:10-1:20.
5. The method for preparing a novel conductive carbon black-modified graphene composite paste according to claim 1, wherein in step S4, the pre-dispersion treatment step is as follows: firstly, treating by using a dispersing machine, wherein the rotating speed of the dispersing machine is set to be 800-1000R/P, and the continuous working time of the dispersing machine is 40-50 minutes; and then using ultrasonic equipment to carry out secondary dispersion, wherein the power of the ultrasonic equipment is 200-500 watts, the continuous working time of the ultrasonic equipment is 40-50 minutes, and finally using a sand mill to carry out sand milling treatment, and the sand milling treatment time is 10-12 hours to obtain a pre-dispersed mixture.
6. The method for preparing a novel conductive carbon black-modified graphene composite paste according to claim 1, wherein in step S5, the mass ratio of the carboxyl modified ternary vinyl chloride-acetate resin to the cyclohexanone is 1:4-1:6.
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