CN112573510A - Graphene slurry and preparation method and application thereof - Google Patents
Graphene slurry and preparation method and application thereof Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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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 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 monoatomic 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 epitaxial growth methods, chemical vapor deposition methods, redox methods, mechanical exfoliation methods, 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 film by using plasma enhanced chemical vapor deposition. The technology reduces the deposition rate of graphene by mixing a large amount of hydrogen gas and inert gas into carbon gas and increasing the pressure of the reaction in a reaction device to 1-10 Torr. Under the conditions of higher growth temperature (850-.
CN107032337A discloses a method for producing industrial graphene by using redox method. The method for producing graphene by the oxidation-reduction method comprises the following steps: (1) pretreatment of raw materials: mixing concentrated sulfuric acid and natural crystalline flake graphite, and heating for reaction to obtain an acidic mixed material; (2) and (3) oxidation: 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) washing with water: 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 oxidation-reduction method has the advantages of simple operation, short production period, high yield and the like, in the production process, strong oxidants of concentrated sulfuric acid, concentrated nitric acid, potassium permanganate and the like are firstly used for oxidizing graphite into graphite oxide, single-layer or multi-layer graphene oxide is formed after ultrasonic treatment, and then strong reducing agents of 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, easy 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 mills, sand mills, ball mills, or sonicators can provide limited shear capability, and therefore yield lower yields of single and few layer graphene. 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 through 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, has mild process conditions, and is 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 the 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 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 being used in a conductive agent.
The TPR particles of the present invention are prepared by blending and granulating styrene-butadiene-styrene copolymer (SBS).
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
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 content of the graphite particles in the mixed solution is 1 to 20% by mass, and may be, for example, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, or the like.
As a preferable technical scheme of the invention, the particle size of the grinding aid is 50-500 nm, for example, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm and the like.
According to the invention, the grinding aid with the particle size of 50-500 nm is adopted, strong intermolecular force is generated between the grinding aid and a graphite sheet layer, the grinding aid has proper elastic coefficient and toughness, and the grinding aid and the graphite sheet layer can increase the friction force and the adhesion force between a grinding tool bit and the graphite sheet layer through collision and friction effects in the grinding process, so that the shearing force on the graphite sheet 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 preferred embodiment of the present invention, the mixed solution further includes 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.
Preferably, the content of the filler in the mixed solution is 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 preferred 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%, or 1%.
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 of the polishing is 10to 40 ℃, for example, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃.
Preferably, the grinding time is 1-24 h, for example, 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24 h.
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 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 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:
according to the invention, 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, and 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 of the graphene 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.
The sources of some of the components 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 rong guang chemical limited, 0234;
acetyl triethyl citrate: shandong Run Biotech limited, 2202;
acetyl trihexyl citrate: wuhanxinwei light chemical limited, ATHC-99;
TPR particles: ningbo Orco Polymer New materials Co., Ltd, AK 6180;
polyvinyl alcohol: shanghai Hu industry Co., Ltd., PVA1799 (100-27);
polyvinylpyrrolidone: hubei Xin Rundchemical 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, sconzhou carbofeng graphene technologies ltd;
carbon black: tianjin Yihui Hui Huan Industrial science, Inc., N220;
nano carbon powder: suzhou carbofeng graphene technologies, TF-71001;
polycarboxylate salt: guangzhou Guangdong beautification industries, Inc., AMS-5040.
Example 1
The embodiment provides a 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 acetyl triethyl citrate 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 200 nm;
the triethyl acetylcitrate 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 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: 1.
The preparation method of the graphene slurry comprises the following steps:
and grinding the mixed solution containing the graphite particles, the acetyl triethyl citrate modified TPR particles, the polyvinyl alcohol, the carbon fibers, the xanthan gum and the ethanol at 25 ℃ for 12 hours to obtain the graphene slurry.
Example 2
The embodiment provides a 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 50 nm;
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: 1.
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 100 nm.
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 mu m, the grinding aid consists of unmodified TPR particles and acetyl trihexyl citrate modified TPR particles according to the mass ratio of 1:1, and the particle size of the grinding aid is 500 nm;
the acetyl trihexyl 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 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: 1.
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 a 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 phthalic acid diethylene glycol diacrylate and 92% of N-methylpyrrolidone; the particle size of the graphite is 100 mu m, and the particle size of the acetylcitric acid trihexyl ester modified TPR particles is 300 nm;
the acetyl trihexyl 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 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: 1.
The preparation method of the graphene slurry comprises the following steps:
and grinding the mixed solution containing graphite particles, the acetylcitric acid trihexyl ester modified TPR particles, phthalic acid diethylene glycol diacrylate and N-methyl pyrrolidone for 24 hours at 35 ℃ 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, in the graphene slurry, the mass percentage of the triethyl acetylcitrate-modified TPR particles 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 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 particle size of the triethyl acetylcitrate-modified TPR particles is 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 particle size of the triethyl acetylcitrate-modified TPR particles is 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 the other conditions are the same as example 1.
Comparative example 2
This comparative example provides a graphene paste and a method for preparing the same, which are different from example 1 only in that the triethyl acetylcitrate-modified TPR particles are not contained in the graphene paste, and the other conditions are the same as example 1.
The graphene slurries provided in the above examples and comparative examples were tested for their 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 area test material thickness values of the sample by adopting an atomic force microscope (model: Bruker FASTSCANBIO), 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 10 MPa.
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 graphene is 0.45-13.7 mu m, 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 stripping effect on graphite particles is poor, the average particle size and the average thickness of graphene are large, and the prepared graphene slurry is 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 18.1 mV; 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, i.e. it is not meant that the present invention must rely on the above detailed process flow to be implemented. 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 (10)
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.
2. The production method according to claim 1, wherein the graphite particles have a particle diameter of 0.5 to 100 μm;
preferably, the mass percentage of the graphite particles in the mixed solution is 1-20%.
3. The preparation method of claim 1 or 2, wherein the particle size of the grinding aid is 50-500 nm;
preferably, the mass percentage content of the grinding aid in the mixed solution is 0.3-2%;
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.
4. The preparation method according to any one of claims 1 to 3, wherein 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 or sodium dodecylbenzenesulfonate;
preferably, the mass percentage of the dispersing agent in the mixed solution is 0.05-1%.
5. The production method according to any one of claims 1 to 4, wherein the mixed solution further comprises a filler;
preferably, the filler is selected from any one or a combination of at least two of carbon fiber, carbon nanotube, carbon black or nano carbon powder;
preferably, the mass percentage of the filler in the mixed solution is 0.1-1%.
6. The production method according to any one of claims 1 to 5, wherein the mixed solution further comprises a suspending agent;
preferably, the suspending agent is selected from any one or a combination of at least two of xanthan gum, pectin, hydroxymethyl cellulose or polycarboxylate;
preferably, the mass percentage of the suspending agent in the mixed solution is 0.1-1%.
7. The production method according to any one of claims 1 to 6, wherein the solvent of the mixed solution is selected from ethanol and/or N-methylpyrrolidone;
preferably, the grinding temperature is 10-40 ℃;
preferably, the grinding time is 1-24 h;
preferably, the number of graphene layers in the graphene slurry is 1-10.
8. The method according to any one of claims 1 to 7, comprising in particular 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 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-methyl pyrrolidone.
9. Graphene slurry, wherein the graphene slurry is prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the graphene paste according to claim 9 in a conductive agent.
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| 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 |
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