CN112573510B - Graphene slurry and preparation method and application thereof - Google Patents
Graphene slurry and preparation method and application thereof Download PDFInfo
- Publication number
- CN112573510B CN112573510B CN202011613255.7A CN202011613255A CN112573510B CN 112573510 B CN112573510 B CN 112573510B CN 202011613255 A CN202011613255 A CN 202011613255A CN 112573510 B CN112573510 B CN 112573510B
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- mixed solution
- particles
- graphene slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention provides graphene slurry and a preparation method and application thereof. The preparation method comprises the following steps: grinding a mixed solution containing graphite particles, a grinding aid and a dispersing agent to obtain the graphene slurry; the grinding aid is selected from modified TPR particles and/or unmodified TPR particles. The invention adopts the specific grinding aid, which not only can enhance the stripping effect of graphite particles, but also can improve the grinding efficiency, thereby improving the stripping efficiency; the preparation method provided by the invention is simple and easy to operate, the process conditions are mild, and the prepared graphene slurry has excellent uniformity, stability and good conductivity and is suitable for being used in a conductive agent.
Description
Technical Field
The invention belongs to the technical field of graphene, and particularly relates to graphene slurry and a preparation method and application thereof.
Background
Since 2004, geom et al, university of manchester, uk, started the research hot tide of graphene materials after single-layer graphene was first prepared and observed using a simple method of adhering an adhesive tape to a piece of graphite and then tearing it off. The graphene material has an ideal single-atomic-layer two-dimensional crystal structure and consists of hexagonal lattices, and the special structure endows the graphene with excellent thermal, mechanical and electrical properties. At present, the preparation methods of graphene materials mainly include an epitaxial growth method, a chemical vapor deposition method, a redox method, a mechanical lift-off method, and the like.
The epitaxial growth method is a method in which a SiC single crystal is heated at a high temperature to evaporate Si atoms on the SiC surface and separate the Si atoms from the surface, and the remaining C atoms are reconstructed in a self-assembled form to obtain graphene based on a SiC substrate. The method has the advantages of high energy consumption, small yield, high cost of the obtained graphene and incapability of meeting the requirement of large-scale production. Although the chemical vapor deposition method can meet the requirement of large-scale preparation of high-quality graphene, the prepared graphene has nonuniform thickness, high cost and complex process. CN110228806A discloses a method for preparing graphene thin films by plasma enhanced chemical vapor deposition. According to the technology, a large amount of hydrogen and inert gas are mixed into carbon gas, and the pressure of the reaction in a reaction device is increased to 1-10Torr, so that the deposition rate of graphene is reduced. Under the conditions of higher growth temperature (850-1000 ℃) and lower deposition rate, the technology improves the carrier mobility of the graphene film on the insulating substrate material, and prepares the graphene film with higher quality, but the energy consumption of the technical method is higher, and the cost is higher.
CN107032337A discloses a method for producing industrial graphene by using a redox method. The method for producing graphene by the oxidation-reduction method comprises the following steps: raw material pretreatment: mixing concentrated sulfuric acid and natural crystalline flake graphite, and heating for reaction to obtain an acidic mixed material; (2) oxidizing: cooling the acidic mixed material, sequentially adding potassium permanganate and water for reaction, and adding hydrogen peroxide after the reaction is finished to obtain a graphite oxide solution; (3) water washing: centrifuging and washing the graphite oxide solution to be neutral; (4) ultrasonic: preparing the solution obtained in the step (3) into a suspension, and performing ultrasonic treatment to obtain a graphene oxide solution; (5) reduction: and heating the graphene oxide solution, adding hydrazine hydrate for reaction, drying and crushing to obtain graphene solid powder. Although the graphene material prepared by the redox method has the advantages of simple operation, short production period, high yield and the like, in the production process, strong oxidant concentrated sulfuric acid, concentrated nitric acid, potassium permanganate and the like are used for oxidizing graphite into graphite oxide, single-layer or multi-layer graphene oxide is formed by ultrasonic treatment, and then strong reducing agent hydrazine hydrate, sodium borohydride and the like are used for reducing the graphene oxide into graphene. The method brings great environmental pollution, and crystal structure defects of the graphene are easily caused in the oxidation-reduction process, so that the conductivity of the graphene is influenced.
The mechanical stripping method not only can prepare high-quality graphene on a large scale, but also has the advantages of low cost, easiness in operation, no pollution and the like. The mechanical stripping method comprises a medium grinding stripping method and an ultrasonic stripping method, wherein the medium grinding stripping method is used for stripping graphene from the surface of a graphite sheet layer by layer under the auxiliary action of a medium through grinding. Typical stripping equipment such as grinders, sand mills, ball mills, or sonicators can provide limited shear capability, and thus yield of single and few layer graphene is low. For example, CN106927456A discloses a production apparatus and method for preparing graphene by using a mechanical stripping method. The method comprises the following steps: putting a graphite raw material with the purity of more than 98% and the particle size of 2 mu m-1 cm into a high-pressure water flow crushing device, starting a high-pressure pump, adjusting the pressure, and filtering and drying the graphite flake mixed liquid in a collecting tank; adding graphite flakes, a dispersing agent and a solvent into a graphite expansion heating device, and obtaining a uniformly dispersed suspension by ultrasonic vibration; discharging the heated suspension into a high shear device for shearing; conveying the graphene suspension into a centrifuge to obtain a filter cake; washing the obtained filter cake with a proper amount of distilled water for 3 times, transferring the filter cake into a freeze-drying machine, and freeze-drying for 3 hours to obtain the graphene product. Although the method for preparing the graphene product by the technology has the advantages of no pollution and simple operation, a special high shear device is required to improve the yield of the graphene.
Therefore, how to develop a preparation method of graphene with simple steps, mild process conditions, high yield and no environmental pollution becomes a problem of great concern, and how to provide a graphene slurry with better uniformity and stability becomes a problem to be solved urgently at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide graphene slurry and a preparation method and application thereof. The graphene slurry provided by the invention has excellent uniformity, stability and conductivity, and the preparation method is simple, mild in process conditions and suitable for large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing graphene slurry, including the following steps:
grinding a mixed solution containing graphite particles, a grinding aid and a dispersing agent to obtain graphene slurry;
the grinding aid is selected from modified TPR particles and/or unmodified TPR particles.
According to the preparation method provided by the invention, the modified TPR particles and/or TPR particles are/is used as the grinding aid, and the introduction of the specific grinding aid not only enhances the stripping effect of the graphene particles, but also improves the stripping efficiency, so that the graphene with smaller average particle size and smaller average thickness is prepared. Meanwhile, the preparation method of the graphene slurry provided by the invention is simple in steps, mild in process conditions, free of pollution to the environment and suitable for industrial production, and the obtained graphene slurry has good uniformity, stability and conductivity and is suitable for a conductive agent.
The TPR particles of the present invention are obtained by blending and granulating styrene-butadiene-styrene copolymer (SBS).
The following are preferred embodiments of the present invention, but not limiting the technical solutions provided by the present invention, and the objects and advantages of the present invention can be better achieved and achieved by the following preferred embodiments.
In a preferred embodiment of the present invention, the graphite particles have a particle size of 0.5 to 100. Mu.m, for example, 0.5. Mu.m, 1. Mu.m, 2. Mu.m, 5. Mu.m, 10. Mu.m, 15. Mu.m, 20. Mu.m, 25. Mu.m, 30. Mu.m, 40. Mu.m, 50. Mu.m, 60. Mu.m, 70. Mu.m, 80. Mu.m, 90. Mu.m, or 100. Mu.m.
Preferably, the graphite particles in the mixed solution are contained in an amount of 1 to 20% by mass, for example, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, or the like.
As a preferable embodiment of the invention, the particle size of the grinding aid is 50 to 500nm, and may be, for example, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm.
According to the invention, the grinding aid with the particle size of 50-500 nm is adopted, strong intermolecular acting force is generated between the grinding aid and a graphite flake layer, the grinding aid has proper elasticity coefficient and toughness, and the grinding aid and the graphite flake layer can increase the friction force and adhesion force between a grinding tool bit and the graphite flake through collision and friction effects in the grinding process, so that the shearing force on the graphite flake layer is improved, and the better stripping efficiency is achieved.
Preferably, the content of the grinding aid in the mixed solution is 0.3 to 2% by mass, and may be, for example, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, or the like.
Preferably, the modified TPR particles include any one or a combination of at least two of acetyl tri-n-butyl citrate modified TPR particles, acetyl triethyl citrate modified TPR particles, or acetyl trihexyl citrate modified TPR particles.
As a preferred embodiment of the present invention, the dispersant is selected from any one or a combination of at least two of polyvinyl alcohol, polyvinylpyrrolidone, sodium polystyrene sulfonate, diethylene glycol diacrylate phthalate, and sodium dodecylbenzenesulfonate.
The content of the dispersant in the mixed solution is preferably 0.05 to 1% by mass, and may be, for example, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.
As a preferable technical scheme of the invention, the mixed solution also comprises a filler.
Preferably, the filler is selected from any one of carbon fiber, carbon nanotube, carbon black or nano carbon powder or a combination of at least two of the same.
The content of the filler in the mixed solution is preferably 0.1 to 1% by mass, and may be, for example, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, or 1%.
As a preferable technical solution of the present invention, the mixed solution further comprises a suspending agent.
Preferably, the suspending agent is selected from any one of xanthan gum, pectin, hydroxymethyl cellulose or polycarboxylate, or a combination of at least two thereof.
Preferably, the content of the suspending agent in the mixed solution is 0.1 to 1% by mass, and may be, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or the like.
In a preferred embodiment of the present invention, the solvent of the mixed solution is selected from ethanol and/or N-methylpyrrolidone.
Preferably, the temperature for the polishing is 10to 40 ℃, for example, 10 ℃,15 ℃, 20 ℃,25 ℃, 30 ℃, 35 ℃ or 40 ℃.
Preferably, the grinding time is 1 to 24 hours, and may be, for example, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, or the like.
Preferably, the number of graphene layers in the graphene slurry is 1 to 10, and may be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:
grinding the mixed solution containing graphite particles, a grinding aid, a dispersing agent, an optional filler and an optional suspending agent at 10-40 ℃ for 1-24 h to obtain the graphene slurry; in the mixed solution, the particle size of graphite particles is 0.5-100 mu m, the mass percentage content is 1-20%, the particle size of grinding aid is 50-500 nm, the mass percentage content is 0.3-2%, the mass percentage content of dispersing agent is 0.05-1%, the mass percentage content of filler is 0.1-1%, the mass percentage content of suspending agent is 0.1-1%, and the solvent of the mixed solution is selected from ethanol and/or N-methyl pyrrolidone.
In a second aspect, the present invention provides a graphene paste prepared by the preparation method according to the first aspect.
In a third aspect, the present invention provides a use of the graphene paste according to the second aspect in a conductive agent.
Compared with the prior art, the invention has the following beneficial effects:
the modified TPR particles and/or TPR particles are used as grinding aids, and the content of the grinding aids in the graphene slurry is controlled within a specific range, the particle size of the grinding aids is controlled within a specific range, so that the uniform, stable and good-conductivity graphene slurry is prepared, and the graphene slurry is suitable for a conductive agent, and has the viscosity of 81.0-2792.8 mPa & S, the Zeta potential of 29.0-40.7 mV and the powder conductivity of 420-864S/cm; the average particle size of graphene in the prepared graphene slurry is 0.45-13.7 mu m, and the average thickness is 1.3-4.4 nm. The preparation method of the graphene slurry provided by the invention has the advantages of simple steps, mild process conditions, high yield and no pollution to the environment, and is suitable for industrial production.
Detailed Description
The following examples further illustrate the technical solutions of the present invention. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Some of the component sources in the examples and comparative examples are as follows:
graphite particles: 1000-98 of Qingdao Dongkai graphite, inc.;
acetyl tri-n-butyl citrate: ji nan grong guan chemical limited, 0234;
acetyl triethyl citrate: shandong-Run Biotech limited, 2202;
acetyl trihexyl citrate: wuhan Xin Wei is related to chemical industry Co., ltd., ATHC-99;
TPR particles: ningbo Orco Polymer New materials Co., ltd, AK6180;
polyvinyl alcohol: shanghai Hu industry Co., ltd., PVA1799 (100-27);
polyvinylpyrrolidone: hubeixin Rundy chemical Co., ltd., 25655-41-8;
sodium polystyrene sulfonate: hubei Xin Rundchemical Co., ltd, 152-89-54;
carbon fiber: shenzhen Tuling evolution science and technology Limited, 400 mesh;
carbon nanotube: CNTs-002, scozhou carbofeng graphene technologies ltd;
carbon black: tianjin Yihui Hui chemical technology Co., ltd., N220;
nano carbon powder: suzhou carbofeng graphene technologies, TF-71001;
polycarboxylate salt: guangzhou Guangdong beautification industries, inc., AMS-5040.
Example 1
The embodiment provides graphene slurry and a preparation method thereof, wherein the graphene slurry comprises the following components in percentage by mass: 10% of graphite particles, 1% of triethyl acetylcitrate modified TPR particles, 0.5% of polyvinyl alcohol, 0.5% of carbon fibers, 0.5% of xanthan gum and 87.5% of ethanol; the particle size of the graphite is 50 microns, and the particle size of the triethyl acetylcitrate modified TPR particles is 200nm;
the triethyl acetylcitrate modified TPR particle is prepared by adopting the following method:
adding TPR plastic particles into a plastic refining machine (Xihua detection instrument, inc. of Dongguan city, model number is Xihua XH-421), heating to 250 ℃, adding acetyl triethyl citrate into the plastic refining machine, mixing for 30min, granulating by using a rubber granulator (the model number is DLS-160, available from Changzhou Qibao drying equipment, inc.), and then crushing by using a rubber powder high-shear crusher (the model number is GM-2000, available from Shanghai Si Jie Co., ltd.) at 25 ℃ for 60min to obtain the acetyl triethyl citrate modified TPR particles; the mass ratio of the TPR particles to the acetyl triethyl citrate is 100.
The preparation method of the graphene slurry comprises the following steps:
grinding a mixed solution containing graphite particles, triethyl acetylcitrate modified TPR particles, polyvinyl alcohol, carbon fibers, xanthan gum and ethanol at 25 ℃ for 12 hours to obtain the graphene slurry.
Example 2
The embodiment provides graphene slurry and a preparation method thereof, wherein the graphene slurry comprises the following components in percentage by mass: 15% of graphite particles, 0.4% of acetyl tributyl citrate modified TPR particles, 0.1% of polyvinylpyrrolidone, 1% of carbon nano tubes, 0.7% of pectin and 82.8% of ethanol; the particle size of the graphite is 0.5 mu m, and the particle size of the acetyl tributyl citrate modified TPR particles is 50nm;
the acetyl tri-n-butyl citrate modified TPR particles are prepared by the following method:
adding TPR plastic particles into a plastic refining machine (Xihua detection instrument, inc., of Dongguan city, model number is Xihua XH-421), heating to 250 ℃, adding acetyl tributyl citrate into the plastic refining machine, mixing for 30min, granulating by using a rubber granulator (DLS-160, model number, available from Changzhou Qibao drying equipment, inc., and then crushing for 60min by using a rubber powder high-shear crusher (GM-2000, model number, available from Shanghai Si Jian mechanical equipment, inc.) at 25 ℃ to obtain the acetyl tributyl citrate modified TPR particles; the mass ratio of the TPR particles to the acetyl tributyl citrate is 100.
The preparation method of the graphene slurry comprises the following steps:
grinding a mixed solution containing graphite particles, acetyl tributyl citrate modified TPR particles, polyvinylpyrrolidone, carbon nanotubes, pectin and ethanol at 15 ℃ for 1h to obtain the graphene slurry.
Example 3
The embodiment provides a graphene slurry and a preparation method thereof, wherein the graphene slurry comprises the following components in percentage by mass: 20% of graphite particles, 0.3% of TPR particles, 0.05% of sodium polystyrene sulfonate, 0.1% of carbon black, 1% of hydroxymethyl cellulose and 78.55% of N-methylpyrrolidone; the particle size of the graphite is 20 mu m, and the particle size of the grinding aid is 100nm.
The preparation method of the graphene slurry comprises the following steps:
and grinding the mixed solution containing graphite particles, TPR particles, sodium polystyrene sulfonate, carbon black, hydroxymethyl cellulose and N-methyl pyrrolidone at 10 ℃ for 16 hours to obtain the graphene slurry.
Example 4
The embodiment provides a graphene slurry and a preparation method thereof, wherein the graphene slurry comprises the following components in percentage by mass: 1% of graphite particles, 1.5% of grinding aid, 0.6% of sodium dodecyl benzene sulfonate, 0.4% of nano carbon powder, 0.1% of polycarboxylate and 96.4% of ethanol; the particle size of the graphite is 70 microns, the grinding aid consists of unmodified TPR particles and acetyl trihexyl citrate modified TPR particles according to a mass ratio of 1;
the acetyl trihexyl citrate modified TPR particle is prepared by adopting the following method:
adding TPR plastic particles into a plastic refining machine (Xihua detection instrument, inc., of Dongguan city, model number is Xihua XH-421), heating to 250 ℃, adding acetyl trihexyl citrate into the plastic refining machine, mixing for 30min, granulating by using a rubber granulator (DLS-160, model number, qibao drying equipment, inc., of Changzhou), and crushing for 60min by using a rubber powder high-shear crusher (GM-2000, model number, of Shanghai Si Jiang mechanical equipment, inc.) at 25 ℃ to obtain the acetyl trihexyl citrate modified TPR particles; the mass ratio of the TPR particles to the acetyl trihexyl citrate is 100.
The preparation method of the graphene slurry comprises the following steps:
and grinding the mixed solution containing graphite particles, a grinding aid, sodium dodecyl benzene sulfonate, nano carbon powder, polycarboxylate and ethanol at 40 ℃ for 6 hours to obtain the graphene slurry.
Example 5
The embodiment provides graphene slurry and a preparation method thereof, wherein the graphene slurry comprises the following components in percentage by mass: 5% of graphite particles, 2% of acetylcitric acid trihexyl ester modified TPR particles, 1% of diethylene glycol diacrylate phthalate and 92% of N-methylpyrrolidone; the particle size of the graphite is 100 mu m, and the particle size of the acetyl trihexyl citrate modified TPR particles is 300nm;
the acetyl trihexyl citrate modified TPR particle is prepared by adopting the following method:
adding TPR plastic particles into a plastic refining machine (Xihua detection instrument, inc., of Dongguan city, model number is Xihua XH-421), heating to 250 ℃, adding acetyl trihexyl citrate into the plastic refining machine, mixing for 30min, granulating by using a rubber granulator (DLS-160, model number, qibao drying equipment, inc., of Changzhou), and crushing for 60min by using a rubber powder high-shear crusher (GM-2000, model number, of Shanghai Si Jiang mechanical equipment, inc.) at 25 ℃ to obtain the acetyl trihexyl citrate modified TPR particles; the mass ratio of the TPR particles to the acetyl trihexyl citrate is 100.
The preparation method of the graphene slurry comprises the following steps:
grinding a mixed solution containing graphite particles, acetylcitric acid trihexyl ester modified TPR particles, diethylene glycol diacrylate phthalate and N-methylpyrrolidone at 35 ℃ for 24 hours to obtain the graphene slurry.
Example 6
The embodiment provides graphene slurry and a preparation method thereof, and the difference from the embodiment 1 is only that the mass percentage content of the triethyl acetylcitrate-modified TPR particles in the graphene slurry is 0.3%, and other conditions are the same as those in the embodiment 1.
Example 7
The embodiment provides graphene slurry and a preparation method thereof, and the difference from the embodiment 1 is only that the mass percentage content of the triethyl acetylcitrate-modified TPR particles in the graphene slurry is 2%, and other conditions are the same as those in the embodiment 1.
Example 8
The embodiment provides graphene slurry and a preparation method thereof, and the difference from the embodiment 1 is only that the mass percentage content of the triethyl acetylcitrate-modified TPR particles in the graphene slurry is 0.2%, and other conditions are the same as those in the embodiment 1.
Example 9
The embodiment provides graphene slurry and a preparation method thereof, and the difference from the embodiment 1 is only that the mass percentage content of the triethyl acetylcitrate-modified TPR particles in the graphene slurry is 2.5%, and other conditions are the same as those in the embodiment 1.
Example 10
This example provides a graphene slurry and a method for preparing the same, which are different from example 1 only in that the triethyl acetylcitrate-modified TPR particles have a particle size of 50nm, and other conditions are the same as example 1.
Example 11
This example provides a graphene slurry and a method for preparing the same, which are different from example 1 only in that the triethyl acetylcitrate-modified TPR particles have a particle size of 50nm, and other conditions are the same as example 1.
Example 12
This example provides a graphene slurry and a method for preparing the same, which are different from example 1 only in that the particle size of the triethyl acetylcitrate-modified TPR particles is 40nm, and other conditions are the same as example 1.
Example 13
This example provides a graphene slurry and a method for preparing the same, which are different from example 1 only in that the particle size of the triethyl acetylcitrate-modified TPR particles is 600nm, and other conditions are the same as example 1.
Comparative example 1
This comparative example provides a graphene slurry and a method for preparing the same, which are different from example 1 only in that triethyl acetylcitrate-modified TPR particles are replaced with carbon black, and other conditions are the same as example 1.
Comparative example 2
The present comparative example provides a graphene slurry and a preparation method thereof, which are different from example 1 only in that the graphene slurry does not contain the triethyl acetylcitrate-modified TPR particles, and other conditions are the same as example 1.
The graphene slurry provided by the above examples and comparative examples was tested for performance according to the following test criteria:
average particle size: testing the granularity of the graphene slurry by using a Malvern 3000 laser granularity meter;
average thickness: selecting 10 regions of the sample by using an atomic force microscope (model: bruker FASTSCANBIO) to test the thickness value of the material, and calculating the average value to be the average thickness of the graphene;
viscosity: the test was carried out at 25 ℃ using a viscometer (model Brookfield DV-II);
zeta potential: the Zeta potential of the graphene oxide electroplating solution was measured using a Nanotrac wave type II Zeta potential tester from Microtrac.
Powder conductivity: and (3) adopting a four-probe powder resistivity tester (model number is FT-7200A) to carry out conductivity test on the slurry after freeze drying, wherein the freeze drying temperature is-50 ℃, the pressure is 10Pa, the freeze drying time is 24h, and the resistivity test pressure is 10MPa.
TABLE 1
As can be seen from Table 1, the modified TPR particles and/or TPR particles are used as the grinding aid, and the content of the grinding aid in the graphene slurry and the particle size of the graphene slurry are controlled within a specific range, so that the uniform, stable and good-conductivity graphene slurry is prepared, the viscosity of the graphene slurry is 81.0-2792.8 mPa & S, the Zeta potential is 29.0-40.7 mV, and the powder conductivity is 420-864S/cm; in the graphene slurry prepared at the same time, the average particle size of the graphene is 0.45-13.7 μm, and the average thickness is 1.3-4.4 nm.
Compared with example 1, if the content of the grinding aid in the graphene slurry is low (example 8), the graphene slurry has a poor stripping effect on graphite particles, the average particle size of graphene in the graphene slurry is larger than 13.9 μm, the average thickness of graphene in the graphene slurry is larger than 4.5nm, and the prepared graphene slurry has low powder conductivity of 213S/cm and poor conductivity; if the content of the grinding aid in the graphene slurry is high (example 9), although the average particle size of the prepared graphene is smaller than 4.8 μm and the average thickness is smaller than 1.2nm, the powder conductivity of the graphene slurry is lower than 167S/cm. Therefore, when the content of the grinding aid in the graphene slurry is not in a specific range, the prepared graphene slurry has low powder conductivity, is not suitable for being used in a conductive agent, and may cause the average particle size and the average thickness of graphene to be large and the stripping effect of graphite particles to be poor.
Compared with example 1, if the particle size of the grinding aid is smaller (example 12), although the average particle size of the prepared graphene is smaller than 3.7 μm and the average thickness is smaller than 1.3nm, the powder conductivity of the graphene slurry is lower than 196S/cm, and the conductivity is poor; if the particle size of the grinding aid is larger (example 13), the stripping effect on graphite particles is poor, the average particle size of the prepared graphene is larger than 15.3 μm, the average thickness of the prepared graphene is larger than 4.9nm, and the powder conductivity of the graphene slurry is lower than 196S/cm. Therefore, when the particle size of the grinding aid is not in a specific range, the graphite particles are relatively poor in stripping effect, so that the average particle size and the average thickness of graphene are relatively large, and the prepared graphene slurry is relatively poor in conductivity.
Compared with the example 1, if the grinding aid is replaced by other grinding aids (comparative example 1), the average particle size of the prepared graphene is larger than 10.4 μm, the average thickness of the prepared graphene is larger than 37nm, the stripping effect on graphite particles is poor, the conductivity of graphene slurry is poor, the powder conductivity is lower than 11.6S/cm, the stability of the graphene slurry is poor, and the Zeta potential is 18.1mV; if no grinding aid is used, the average particle size of the prepared graphene is larger than 11.7 mu m, the average thickness of the prepared graphene is larger than 50nm, the powder conductivity of the graphene slurry is lower than 14.9S/cm, the Zeta potential is lower than 16.8mV, and the prepared graphene slurry is uniform and poor in stability. Therefore, the specific grinding aid is adopted, the stripping effect of graphite particles can be improved, the graphene with smaller average particle size and average thickness is prepared, and the prepared graphene slurry has better uniformity, stability and excellent conductivity.
In conclusion, the modified TPR particles and/or TPR particles are used as the grinding aid, the content of the grinding aid in the graphene slurry and the particle size of the grinding aid are further controlled within a specific range, the stripping effect of the graphite particles is improved, and the uniform, stable and good-conductivity graphene slurry is prepared. Meanwhile, the preparation method of the graphene slurry provided by the invention is simple in steps, mild in process conditions, high in yield, free of pollution to the environment and suitable for industrial production.
The applicant states that the process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, which means that the present invention must not be implemented by the above detailed process flow. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (19)
1. A preparation method of graphene slurry is characterized by comprising the following steps:
grinding a mixed solution containing graphite particles, a grinding aid and a dispersing agent to obtain the graphene slurry;
the grinding aid is selected from modified TPR particles and/or unmodified TPR particles;
the modified TPR particles comprise any one or the combination of at least two of acetyl tri-n-butyl citrate modified TPR particles, acetyl triethyl citrate modified TPR particles or acetyl trihexyl citrate modified TPR particles;
the particle size of the grinding aid is 50-500 nm.
2. The production method according to claim 1, wherein the graphite particles have a particle diameter of 0.5 to 100 μm.
3. The method according to claim 1, wherein the graphite particles are contained in the mixed solution in an amount of 1 to 20% by mass.
4. The preparation method of claim 1, wherein the mass percentage of the grinding aid in the mixed solution is 0.3-2%.
5. The method for preparing the emulsion according to claim 1, wherein the dispersant is selected from any one of or a combination of at least two of polyvinyl alcohol, polyvinylpyrrolidone, sodium polystyrene sulfonate, diethylene glycol diacrylate phthalate or sodium dodecyl benzene sulfonate.
6. The preparation method according to claim 1, wherein the mass percentage of the dispersant in the mixed solution is 0.05 to 1%.
7. The method according to claim 1, wherein a filler is further included in the mixed solution.
8. The method for preparing a carbon fiber composite material according to claim 7, wherein the filler is selected from any one of carbon fiber, carbon nanotube, carbon black or nano carbon powder or a combination of at least two of the carbon fiber, the carbon nanotube and the carbon black.
9. The preparation method according to claim 7, wherein the mass percentage of the filler in the mixed solution is 0.1 to 1%.
10. The method according to claim 1, wherein a suspending agent is further included in the mixed solution.
11. The method of claim 10, wherein the suspending agent is selected from any one of xanthan gum, pectin, hydroxymethyl cellulose or polycarboxylate, or a combination of at least two thereof.
12. The preparation method according to claim 10, wherein the content of the suspending agent in the mixed solution is 0.1 to 1% by mass.
13. The method according to claim 1, wherein the solvent of the mixed solution is selected from ethanol and/or N-methylpyrrolidone.
14. The method according to claim 1, wherein the temperature of the grinding is 10to 40 ℃.
15. The method according to claim 1, wherein the grinding time is 1 to 24 hours.
16. The preparation method according to claim 1, wherein the number of graphene layers in the graphene slurry is 1 to 10.
17. The preparation method according to claim 1, characterized in that the preparation method specifically comprises the steps of:
grinding a mixed solution containing graphite particles, a grinding aid, a dispersing agent, an optional filler and an optional suspending agent at 10-40 ℃ for 1-24 h to obtain the graphene slurry; in the mixed solution, the particle size of graphite particles is 0.5-100 mu m, the mass percentage content is 1-20%, the particle size of grinding aid is 50-500 nm, the mass percentage content is 0.3-3%, the mass percentage content of dispersing agent is 0.05-1%, the mass percentage content of filler is 0.1-1%, the mass percentage content of suspending agent is 0.1-1%, and the solvent of the mixed solution is selected from ethanol and/or N-methylpyrrolidone.
18. Graphene slurry, characterized in that it is prepared by the preparation method according to any one of claims 1 to 17.
19. Use of the graphene paste according to claim 18 in a conductive agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011613255.7A CN112573510B (en) | 2020-12-30 | 2020-12-30 | Graphene slurry and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011613255.7A CN112573510B (en) | 2020-12-30 | 2020-12-30 | Graphene slurry and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112573510A CN112573510A (en) | 2021-03-30 |
| CN112573510B true CN112573510B (en) | 2022-11-29 |
Family
ID=75145092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011613255.7A Active CN112573510B (en) | 2020-12-30 | 2020-12-30 | Graphene slurry and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112573510B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116936161A (en) * | 2023-08-02 | 2023-10-24 | 四川永星电子有限公司 | Preparation method and application of composite carbon material conductive agent for carbon-based resistor film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712339A (en) * | 2014-12-01 | 2016-06-29 | 江阴碳谷科技有限公司 | Physical stripping production method of graphene |
| CN106698386A (en) * | 2015-08-18 | 2017-05-24 | 中国科学院上海微***与信息技术研究所 | Method for preparing graphene from graphite through HPLC (high performance liquid chromatography) stripping |
| US10081550B2 (en) * | 2016-06-26 | 2018-09-25 | Nanotek Instruments, Inc. | Direct ultrasonication production of graphene sheets from coke or coal |
| CN106744870B (en) * | 2016-10-25 | 2019-01-04 | 成都新柯力化工科技有限公司 | A kind of abrasive media grinding removing graphene for slurry |
| CN107827102A (en) * | 2017-11-27 | 2018-03-23 | 内蒙古碳烯石墨新材料有限公司 | A kind of method for preparing graphene |
| CN111326274B (en) * | 2018-12-13 | 2022-01-28 | 山东欧铂新材料有限公司 | Modified graphene composite slurry with high dispersion stability and preparation method thereof |
| CN109455707A (en) * | 2018-12-27 | 2019-03-12 | 宁波杉元石墨烯科技有限公司 | A kind of graphene slurry and preparation method thereof of the grinding aid containing dispersion |
-
2020
- 2020-12-30 CN CN202011613255.7A patent/CN112573510B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112573510A (en) | 2021-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Structure-controlled Co-Al layered double hydroxides/reduced graphene oxide nanomaterials based on solid-phase exfoliation technique for supercapacitors | |
| Xu et al. | Surface modification of multi-walled carbon nanotubes by O2 plasma | |
| CN101935036B (en) | Stable dispersions of single and multiple graphene layers in solution | |
| US10472243B2 (en) | Industrial method for preparing large-sized graphene | |
| KR101818703B1 (en) | Method for preparation of graphene by using pre-high speed homogenization and high pressure homogenization | |
| Mao et al. | Use of in-situ polymerization in the preparation of graphene/polymer nanocomposites | |
| KR20150076093A (en) | Preparation method of graphene and dispersed composition of graphene | |
| CN105110318A (en) | Graphene aqueous slurry, and preparation method thereof | |
| Ramachandran et al. | Synthesis of cobalt sulfide–graphene (CoS/G) nanocomposites for supercapacitor applications | |
| CN112542577B (en) | Nano bismuth/nitrogen-doped carbon foam nanosheet two-dimensional composite material and preparation method and application thereof | |
| CN106976870B (en) | The efficiently method that removing graphite powder prepares big size graphene | |
| JP2017502900A (en) | Method for producing graphene | |
| CN102815043B (en) | Preparation method of grapheme and polyaniline composite paper, and products thereof | |
| CN105271170B (en) | Preparation method of nano carbon and composite material of nano carbon | |
| CN104163417B (en) | A kind of method for peeling off preparing graphite alkene | |
| CN110157931B (en) | Nano carbon reinforced metal matrix composite material with three-dimensional network structure and preparation method thereof | |
| CN112573510B (en) | Graphene slurry and preparation method and application thereof | |
| Qiang et al. | Ultrasound-enhanced preparation and photocatalytic properties of graphene-ZnO nanorod composite | |
| Nam et al. | Green, fast, and scalable production of reduced graphene oxide via Taylor vortex flow | |
| CN111559743B (en) | Preparation method and application of graphene powder | |
| WO2015099378A1 (en) | Graphene production method, and graphene dispersion composition | |
| Guo et al. | Preparation of graphene via liquid-phase exfoliation with high gravity technology from edge-oxidized graphite | |
| CN104891485A (en) | Method for preparing nano graphite sheet | |
| Ma et al. | Functionalized graphene materials: Definition, classification, and preparation strategies | |
| Shen et al. | Preparation of high quality graphene using high gravity technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |