CN113429808A - Isolation dispersant for preventing graphene agglomeration, preparation method and application method - Google Patents
Isolation dispersant for preventing graphene agglomeration, preparation method and application method Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical additives, and provides a graphene agglomeration preventing isolation dispersant, a preparation method and an application method thereof. The isolating dispersant is prepared by mixing micronized fluorine-containing resin, polyethylene glycol and microcrystalline paraffin at a high speed, uniformly stirring, and then grinding with a micronized compound in a dry state; the micronized fluororesin is obtained by dry grinding the fluororesin; the micronized compound is obtained by dry grinding sulfonated melamine formaldehyde resin and sodium tripolyphosphate. The specific application method is to mix the isolation dispersant and the graphene, disperse the mixture uniformly at a high speed at 50-60 ℃, and naturally cool and store the mixture. The isolation dispersant provided by the invention has the functions of dispersing and isolating graphene powder, can better inhibit the aggregation of graphene in a powder state when being applied, and ensures that the graphene has good dispersibility when being stored and used.
Description
Technical Field
The invention relates to the technical field of chemical additives, in particular to a graphene agglomeration preventing isolation dispersant, a preparation method and an application method thereof.
Background
Graphene (Graphene) is a new material with sp hybridized connected carbon atoms tightly packed into a single-layer two-dimensional honeycomb lattice structure. Due to the special structure, the graphene shows excellent performance in various aspects, has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future.
In 2004, the physicists andrelim and consanguin norworth schloff, manchester university, uk, succeeded in separating graphene from graphite by micromechanical exfoliation, thus collectively awarding the nobel prize for physics in 2010. Then, various methods for preparing graphene are continuously proposed, and the common methods for producing graphene powder are a mechanical stripping method, an oxidation-reduction method, a SiC epitaxial growth method, and the like. However, the graphene prepared by any method is fluffy, mainly has a sheet structure and a high specific surface area, and is particularly less-layer or even single-layer graphene prepared by an oxidation-reduction method, so that the graphene is fluffy and is easy to agglomerate.
At present, graphene is applied in a complex dispersion manner, for example, graphene is dispersed in a polymer when used for reinforcing rubber polymers, conductive polymers and heat dissipation polymers; used in conductive coatings, anticorrosive coatings, and the like, need to be dispersed in a liquid-phase coating system. The difficulty in dispersing graphene is the greatest obstacle to the suppression of the application and performance of graphene.
Graphene is more prone to agglomeration and more difficult to disperse when stored and used in a powder state. In order to solve the dispersion problem of graphene, graphene is usually dispersed in a liquid phase and exists in a liquid state, so that the graphene dispersion liquid plays a good role in preventing graphene agglomeration. However, the liquid-phase dispersed graphene is very inconvenient to transport and store and has poor use adaptability. For example, liquid-phase dispersed graphene cannot be added directly to a polymer, and a dispersion solvent system cannot be adapted to a coating system even when used for a coating material because of its different dispersion system. A typical example of an application is: graphene is used for lithium batteries, and needs to be dispersed in an NMP system in a positive electrode and needs to be dispersed in a water system in a negative electrode.
Therefore, if the dispersibility of graphene in a powder state is improved, the storage and use of graphene will be greatly facilitated. Simple dispersant modification is difficult to enable the dispersibility of graphene to be well treated, and the research on novel graphene dispersants is generally regarded as important.
The Chinese patent application No. 201410020760.9 discloses a preparation method of graphene powder, which comprises the following steps: (1) reacting graphite oxide with a dispersant to obtain an intermediate product, wherein the dispersant comprises ammonium salt; (2) and carrying out heat treatment on the intermediate product to obtain graphene powder. The Chinese patent application No. 201711075572.6 discloses a graphene modification method, which comprises the following steps: (1) dissolving graphene in water to obtain a graphene solution, adding a dispersing agent, and mixing and stirring to obtain a graphene dispersion liquid; (2) adding an acrylamide monomer and a cross-linking agent into the graphene dispersion liquid, mixing and stirring, and pre-cooling to obtain a pre-cooling solution; (3) adding an initiator and a coagulant into the pre-cooling solution, mixing and stirring, and then transferring the mixed solution into a mould for sealing; (4) and cooling the mold, then unfreezing, taking out the crystal glue, cleaning and drying to obtain the modified graphene composite material. The above method improves the dispersibility of graphene to some extent, but the effect is not ideal.
In order to effectively improve the dispersibility of graphene powder and prevent agglomeration, a novel dispersant for graphene is needed to be provided, so that the powdery graphene has good dispersibility during storage and use, and the excellent performance of the graphene is fully exerted.
Disclosure of Invention
Aiming at the problems that the existing graphene powder is poor in dispersibility, easy to agglomerate during storage and use and has influence on the performance of graphene, the invention provides the isolation dispersant for preventing graphene agglomeration, and the preparation method and the application method thereof, so that graphene is well dispersed in a powder state, agglomeration is effectively prevented, and the powder graphene is promoted to be well dispersed during storage and use.
In order to achieve the purpose, the invention adopts the following technical scheme:
an isolation dispersant for preventing graphene agglomeration is prepared by mixing micronized fluorine-containing resin, polyethylene glycol and microcrystalline paraffin at a high speed, uniformly stirring, and then grinding with a micronized compound in a dry state; the micronized fluororesin is obtained by dry grinding the fluororesin; the micronized compound is obtained by dry grinding sulfonated melamine formaldehyde resin and sodium tripolyphosphate; the fluorine-containing resin is one or the combination of more than two of polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer and polyvinylidene fluoride; the number average molecular weight of the polyethylene glycol is 1500-.
The invention also provides a preparation method of the isolating dispersant for preventing graphene agglomeration, which comprises the following specific steps:
(1) adding sulfonated melamine formaldehyde resin and sodium tripolyphosphate into a ball mill, taking spherical zirconia as a grinding medium, and then grinding uniformly in a dry state to obtain a micronized compound;
(2) adding fluorine-containing resin into a ball mill, taking spherical zirconia as a grinding medium, and then carrying out dry grinding treatment to obtain micronized fluorine-containing resin;
(3) adding the micronized fluorine-containing resin, polyethylene glycol and microcrystalline wax into a high-speed stirrer, controlling the temperature at 50-60 ℃, uniformly stirring at a high speed, naturally cooling to room temperature, and uniformly grinding with the obtained micronized compound in a ball mill in a dry state to obtain the isolating dispersant for preventing graphene agglomeration.
Preferably, the rotation speed of the dry grinding in the step (1) is controlled to be 50-80rpm, and the grinding time is 30-60 min.
Preferably, the particle diameter of D50 in the finely divided fluorine-containing resin in the step (2) is less than 1 μm.
Preferably, the rotation speed of the high-speed stirring in the step (3) is controlled at 800-.
Preferably, in the preparation of the isolation dispersant, the mass ratio of the sulfonated melamine formaldehyde resin to the sodium tripolyphosphate to the fluorine-containing resin to the polyethylene glycol to the microcrystalline wax is 15-20: 5-10: 25-30: 5-10: 3-5.
The invention also provides an application method of the isolating dispersant for preventing graphene agglomeration, which comprises the following specific application methods: and mixing the isolation dispersant with the graphene, wherein the mass ratio of the graphene to the isolation dispersant is 30-60:1-2, the rotating speed is controlled at 1100-1300rpm, the temperature is controlled at 50-60 ℃, the dispersion is carried out for 10-20min, and the purpose of preventing the graphene from agglomerating can be realized through natural cooling storage.
Graphene is known to be attracting attention as a novel material having excellent properties. However, since the graphene powder has a small particle size and a large specific surface area, the graphene is more easily agglomerated and more difficult to disperse when stored and used in a powder state. In order to solve the dispersion problem of graphene, graphene is usually dispersed in a liquid phase and exists in a liquid state, so that the graphene dispersion liquid plays a good role in preventing graphene agglomeration. However, the liquid-phase dispersed graphene is very inconvenient to transport and store and has poor use adaptability. The effect of the current commonly used dispersing agent is not ideal. The isolation dispersant capable of preventing graphene from dispersing is prepared by creatively taking sulfonated melamine formaldehyde resin, sodium tripolyphosphate, fluorine-containing resin, polyethylene glycol and microcrystalline wax as raw materials through grinding and mixing, and the problems are effectively solved.
The invention firstly mixes the sulfonated melamine formaldehyde resin and the sodium tripolyphosphate and ball-mills by a dry method to prepare the micronized compound. The sulfonated melamine-formaldehyde resin is an anionic surfactant, and is a macromolecule formed by forming hydroxymethyl melamine by melamine and formaldehyde, generating melamine sulfonate under the action of a sulfonating agent and performing polycondensation; due to-SO in the sulfonated melamine formaldehyde resin molecule3And (4) the occurrence of groups, which have good surface activity, can effectively improve the surface activity of the graphene and improve the dispersibility. The sodium tripolyphosphate is amorphous water-soluble linear polyphosphate, has the effects of chelation, suspension, dispersion, peptization, emulsification, pH buffering and the like, and has a good dispersion effect on graphene. The micronized compound obtained by adding the sulfonated melamine formaldehyde resin and the sodium tripolyphosphate into the dispersing agent through dry ball milling has the suspension effect when the slurry is used for preparing graphene slurryThe floating dispersion effect can effectively prevent the agglomeration of the graphene.
Furthermore, the fluorine-containing resin is ground and refined, the excellent non-adhesiveness and the low friction coefficient of the micronized fluorine-containing resin are utilized, the adhesion can be effectively prevented, the interlayer stacking and aggregation of the graphene powder can be prevented by utilizing the isolation effect of the fluorine-containing resin, and the isolation dispersant can be ensured to effectively play a dispersing role in the graphene.
Furthermore, the micronized fluorine-containing resin, polyethylene glycol and microcrystalline wax are mixed and ground at a high speed, and finally, the micronized compound is added for dry grinding to prepare the isolating dispersant for preventing graphene agglomeration. Polyethylene glycol is an adhesive with excellent lubricity, moisture retention, dispersibility and viscosity; the polyethylene glycol is used as a dispersing agent and can be solidified at normal temperature, the temperature can be raised to 50-60 ℃ to be mixed with microcrystalline wax in a stirring manner, after the graphene powder is added, when the graphene powder is stored, the microcrystalline wax and the polyethylene glycol are solidified and fix and isolate the graphene powder, so that fine nano-particles can be prevented from agglomerating, when the graphene powder is used, the graphene can be dispersed in a solvent or other solid mixtures, and when the graphene powder is heated to 50-60 ℃, the microcrystalline wax and the polyethylene glycol are melted to release the fixed graphene, so that the graphene dispersion is promoted.
The existing graphene is poor in dispersibility and easy to agglomerate when stored and used in a powder state, so that the application of the graphene is limited. In view of the above, the invention provides an isolation dispersant for preventing graphene agglomeration, a preparation method and an application method thereof, wherein sulfonated melamine formaldehyde resin and sodium tripolyphosphate are added into a ball mill, spherical zirconia is used as a grinding medium, and dry grinding is carried out to obtain a micronized compound; adding the tetrafluoroethylene-hexafluoropropylene copolymer into a ball mill, and grinding by taking spherical zirconia as a grinding medium to obtain micronized fluorine-containing resin; adding the micronized fluorine-containing resin, polyethylene glycol and microcrystalline wax into a high-speed stirrer, stirring at a high speed, naturally cooling to room temperature, and grinding the micronized composite in a ball mill in a dry state to obtain the isolating dispersant layer for preventing graphene agglomeration. When the graphene isolation dispersant is specifically applied, the isolation dispersant and graphene are mixed, heated, stirred and naturally cooled for storage. The isolating and dispersing agent can ensure that the graphene is well dispersed in a powder state, prevent agglomeration and promote the powdery graphene to have good dispersion in storage and use.
The invention provides an isolation dispersant for preventing graphene from agglomerating, and a preparation method and an application method thereof, and compared with the prior art, the isolation dispersant has the outstanding characteristics and excellent effects that:
1. the isolation dispersant prepared by the invention has the functions of dispersing and isolating graphene powder, can better inhibit the aggregation of graphene in a powder state when applied, and ensures that the graphene has good dispersibility when stored and used.
2. The sulfonated melamine formaldehyde resin and the sodium tripolyphosphate in the isolation dispersant have good dispersion effect on the graphene, and are used for suspension dispersion when the graphene is used for preparing slurry.
3. The polyethylene glycol in the isolation dispersant is used as a dispersant, is solidified at normal temperature, is matched with microcrystalline paraffin, prevents fine nanoparticles from agglomerating when graphene powder is stored, can disperse graphene in a solvent when the graphene powder is used, and releases fixed graphene after heating, so that graphene slurry is formed.
4. The micronized fluorine-containing resin in the separation dispersant can effectively prevent adhesion, and is applied to graphene as a graphene separation agent to prevent stacking and aggregation between graphene layers.
Drawings
FIG. 1: the spacer dispersant dispersed graphene of example 1 was formulated into a sedimentation pattern of a slurry.
FIG. 2: the segregation dispersant dispersed graphene of comparative example 1 was formulated into a settling pattern of a slurry.
FIG. 3: the segregation dispersant dispersed graphene of comparative example 2 was formulated into a sedimentation pattern of a slurry.
FIG. 4: and preparing the graphene without the isolating dispersant into a settlement map of slurry.
FIG. 5: electron microscopy images of the spacer dispersant dispersed graphene of example 1 formulated into slurries.
FIG. 6: electron microscopy images of isolated dispersant dispersed graphene of comparative example 1 formulated into slurries.
FIG. 7: electron microscopy images of the isolated dispersant dispersed graphene of comparative example 2 formulated into a slurry.
FIG. 8: electron microscopy images of slurries formulated with graphene without spacer dispersant added.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
The preparation method comprises the following steps:
(1) adding 17.5kg of sulfonated melamine formaldehyde resin and 7.5kg of sodium tripolyphosphate into a ball mill, taking spherical zirconia as a grinding medium, then grinding uniformly in a dry state, controlling the rotating speed at 50rpm, and grinding for 45min to obtain a micronized compound;
(2) adding 27.5kg of tetrafluoroethylene-hexafluoropropylene copolymer into a ball mill, taking spherical zirconia as a grinding medium, and then carrying out dry grinding treatment to obtain the micronized tetrafluoroethylene-hexafluoropropylene copolymer with the D50 particle size of 0.5 mu m;
(3) adding the micronized tetrafluoroethylene-hexafluoropropylene copolymer, 7.5kg of polyethylene glycol PEG1500 and 4kg of microcrystalline paraffin into a high-speed stirrer, uniformly stirring at a high speed, controlling the rotating speed at 1000rpm and the temperature at 55 ℃, stirring at a high speed for 15min, naturally cooling to room temperature, and uniformly grinding the micronized compound and the obtained micronized compound in a ball mill in a dry state to obtain the isolating dispersant for preventing graphene agglomeration.
The specific application method is as follows:
1.5kg of isolation dispersant and 45kg of graphene are mixed, then the obtained mixture is heated and dispersed uniformly at high speed, the rotating speed is controlled at 1200rpm, the temperature is controlled at 55 ℃, the dispersion is carried out for 15min, and the aim of preventing the graphene from agglomerating can be achieved by natural cooling and storage.
Example 2
The preparation method comprises the following steps:
(1) adding 16kg of sulfonated melamine formaldehyde resin and 6kg of sodium tripolyphosphate into a ball mill, taking spherical zirconia as a grinding medium, then grinding uniformly in a dry state, controlling the rotating speed at 60rpm, and grinding for 50min to obtain a micronized compound;
(2) adding 29kg of polytetrafluoroethylene into a ball mill, taking spherical zirconia as a grinding medium, and then carrying out dry grinding treatment to obtain the micronized polytetrafluoroethylene with the D50 particle size of 0.3 mu m;
(3) adding micronized polytetrafluoroethylene, 6kg of polyethylene glycol PEG1500 and 3.5kg of microcrystalline paraffin into a high-speed stirrer, uniformly stirring at a high speed, controlling the rotating speed at 900rpm and the temperature at 52 ℃, stirring at a high speed for 18min, naturally cooling to room temperature, and uniformly grinding the micronized polytetrafluoroethylene and the obtained micronized compound in a ball mill in a dry state to obtain the isolating dispersant for preventing graphene agglomeration.
The specific application method is as follows:
1.2kg of isolation dispersant and 50kg of graphene are mixed, then the obtained mixture is heated and dispersed uniformly at a high speed, the rotating speed is controlled at 1150rpm, the temperature is controlled at 52 ℃, the mixture is dispersed for 18min, and the aim of preventing the graphene from agglomerating can be achieved through natural cooling and storage.
Example 3
The preparation method comprises the following steps:
(1) adding 19kg of sulfonated melamine formaldehyde resin and 9kg of sodium tripolyphosphate into a ball mill, taking spherical zirconia as a grinding medium, then grinding uniformly in a dry state, controlling the rotating speed at 50rpm, and grinding for 40min to obtain a micronized compound;
(2) adding 26kg of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer into a ball mill, taking spherical zirconia as a grinding medium, and then carrying out dry grinding treatment to obtain the micronized tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer with the D50 particle size of 0.8 mu m;
(3) adding the micronized tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, 9kg of polyethylene glycol PEG1500 and 4.5kg of microcrystalline paraffin into a high-speed stirrer, uniformly stirring at a high speed, controlling the rotating speed at 1100rpm and the temperature at 58 ℃, stirring at a high speed for 12min, naturally cooling to room temperature, and uniformly grinding the micronized compound and the obtained micronized compound in a ball mill in a dry state to obtain the isolating dispersant for preventing graphene agglomeration.
The specific application method is as follows:
1.8kg of isolation dispersant and 40kg of graphene are mixed, then the obtained mixture is heated and dispersed uniformly at a high speed, the rotating speed is controlled at 1250rpm, the temperature is controlled at 58 ℃, the dispersion is carried out for 12min, and the aim of preventing the graphene from agglomerating can be achieved through natural cooling storage.
Example 4
The preparation method comprises the following steps:
(1) adding 15kg of sulfonated melamine formaldehyde resin and 5kg of sodium tripolyphosphate into a ball mill, taking spherical zirconia as a grinding medium, then grinding uniformly in a dry state, controlling the rotating speed at 50rpm, and grinding for 60min to obtain a micronized compound;
(2) adding 30kg of polyvinylidene fluoride into a ball mill, taking spherical zirconia as a grinding medium, and then carrying out dry grinding treatment to obtain micronized polyvinylidene fluoride with the D50 particle size of 0.1 mu m;
(3) adding micronized polyvinylidene fluoride, 5kg of polyethylene glycol (PEG) 1500 and 3kg of microcrystalline paraffin into a high-speed stirrer, uniformly stirring at a high speed, controlling the rotating speed at 800rpm and the temperature at 50 ℃, stirring at a high speed for 20min, naturally cooling to room temperature, and uniformly grinding with the obtained micronized compound in a ball mill in a dry state to obtain the isolating dispersant for preventing graphene agglomeration.
The specific application method is as follows:
1kg of isolation dispersant and 60kg of graphene are mixed, then the obtained mixture is heated and dispersed uniformly at high speed, the rotating speed is controlled at 1100rpm, the temperature is controlled at 50 ℃, the dispersion is carried out for 20min, and the aim of preventing the graphene from agglomerating can be achieved through natural cooling storage.
Example 5
The preparation method comprises the following steps:
(1) adding 20kg of sulfonated melamine formaldehyde resin and 10kg of sodium tripolyphosphate into a ball mill, taking spherical zirconia as a grinding medium, then grinding uniformly in a dry state, controlling the rotating speed at 80rpm, and grinding for 30min to obtain a micronized compound;
(2) adding 25kg of tetrafluoroethylene-hexafluoropropylene copolymer into a ball mill, taking spherical zirconia as a grinding medium, and then carrying out dry grinding treatment to obtain a micronized tetrafluoroethylene-hexafluoropropylene copolymer with a D50 particle size of 0.6 mu m;
(3) adding micronized tetrafluoroethylene-hexafluoropropylene copolymer, 10kg of polyethylene glycol PEG1500 and 5kg of microcrystalline paraffin into a high-speed stirrer, uniformly stirring at high speed, controlling the rotating speed at 1200rpm and the temperature at 60 ℃, stirring at high speed for 10min, naturally cooling to room temperature, and uniformly grinding with the obtained micronized compound in a ball mill in a dry state to obtain the isolating dispersant for preventing graphene agglomeration.
The specific application method is as follows:
2kg of isolation dispersant and 30kg of graphene are mixed, then the obtained mixture is heated and dispersed uniformly at high speed, the rotating speed is controlled at 1300rpm, the temperature is controlled at 60 ℃, the dispersion is carried out for 10min, and the aim of preventing the graphene from agglomerating can be achieved through natural cooling storage.
Comparative example 1
The preparation method comprises the following steps:
(1) adding 17.5kg of sulfonated melamine formaldehyde resin and 7.5kg of sodium tripolyphosphate into a ball mill, taking spherical zirconia as a grinding medium, then grinding uniformly in a dry state, controlling the rotating speed at 50rpm, and grinding for 45min to obtain a micronized compound;
(2) adding 27.5kg of tetrafluoroethylene-hexafluoropropylene copolymer into a ball mill, taking spherical zirconia as a grinding medium, and then carrying out dry grinding treatment to obtain the micronized tetrafluoroethylene-hexafluoropropylene copolymer with the D50 particle size of 0.5 mu m;
(3) and uniformly grinding the micronized tetrafluoroethylene-hexafluoropropylene copolymer and the micronized compound in a ball mill in a dry state to obtain the isolating dispersant for preventing graphene agglomeration.
The specific application method is as follows:
1.5kg of isolation dispersant and 45kg of graphene are mixed, then the obtained mixture is heated and dispersed uniformly at high speed, the rotating speed is controlled at 1200rpm, the temperature is controlled at 55 ℃, the dispersion is carried out for 15min, and the aim of preventing the graphene from agglomerating can be achieved by natural cooling and storage.
Comparative example 1 compared with example 1, no polyethylene glycol and microcrystalline paraffin were added, and the rest was completely identical to example 1.
Comparative example 2
The preparation method comprises the following steps:
(1) adding 17.5kg of sulfonated melamine formaldehyde resin and 7.5kg of sodium tripolyphosphate into a ball mill, taking spherical zirconia as a grinding medium, then grinding uniformly in a dry state, controlling the rotating speed at 650rpm, and grinding for 45min to obtain a micronized compound;
(2) adding 7.5kg of polyethylene glycol (PEG) 1500 and 4kg of microcrystalline paraffin into a high-speed stirrer, uniformly stirring at a high speed, controlling the rotating speed at 1000rpm and the temperature at 55 ℃, stirring at a high speed for 15min, naturally cooling to room temperature, and uniformly grinding with the obtained micronized compound in a ball mill in a dry state to obtain the isolating dispersant for preventing graphene agglomeration.
The specific application method is as follows:
1.5kg of isolation dispersant and 45kg of graphene are mixed, then the obtained mixture is heated and dispersed uniformly at high speed, the rotating speed is controlled at 1200rpm, the temperature is controlled at 55 ℃, the dispersion is carried out for 15min, and the aim of preventing the graphene from agglomerating can be achieved by natural cooling and storage.
Comparative example 2 compared to example 1, no fluororesin was added, and the rest was completely the same as example 1.
The test method comprises the following steps:
and (3) testing the dispersibility: the isolation dispersant obtained in examples 1 to 5 and comparative examples 1 to 2 of the present invention was mixed with graphene (HGP-10 graphene provided by Qingdao rock-ocean carbon materials Co., Ltd.) having a particle size of 10 μm at a mass ratio of 1:30, dispersed at 1200rpm at 60 ℃ for 10min, and cooled for storage. (blank samples without spacer dispersant). Storing the sample for 1 month, adding graphene into water (the mass ratio of graphene to water is 1: 20), heating and stirring in a water bath at 60 ℃, standing to observe the sedimentation phenomenon, and simultaneously sampling to observe whether large agglomerated particles exist under an electron microscope. The test results are shown in table 1.
Table 1:
fig. 1 is a settlement plot of the release dispersant dispersed graphene of example 1 formulated into a slurry; fig. 2 is a settlement plot of a slurry formulated with the release dispersant dispersed graphene of comparative example 1; FIG. 3 is a settlement plot of a slurry formulated with the release dispersant dispersed graphene of comparative example 2; FIG. 4 is a settlement diagram of slurry prepared from graphene without an isolation dispersant; FIG. 5 is an electron microscope image of the release dispersant dispersed graphene of example 1 formulated into a slurry; fig. 6 is an electron microscope image of a slurry prepared from the release dispersant dispersed graphene of comparative example 1; fig. 7 is an electron microscope image of a slurry prepared from the release dispersant dispersed graphene of comparative example 2; fig. 8 is an electron microscope image of a slurry formulated with graphene without a spacer dispersant.
Through the tests, as can be seen from table 1 and the accompanying drawings, the isolation dispersant obtained in the embodiment of the invention satisfies the dispersion of graphene in a powder state, and the dispersed graphene is easy to disperse to prepare slurry without obvious aggregation of large particles. In contrast, in comparative example 1, polyethylene glycol and microcrystalline paraffin are not added to the isolation dispersant, so that the isolation dispersant lacks solidification and fixation, and graphene is easy to agglomerate. Comparative example 2 no fluorine-containing resin was added to the barrier dispersant, and graphene was easily layered and aggregated due to lack of barrier effect of the fluorine-containing resin. And no isolation dispersant is added into the blank sample, so that agglomeration is easy to occur.
Claims (7)
1. The isolating dispersant for preventing graphene agglomeration is characterized in that the isolating dispersant is prepared by mixing micronized fluorine-containing resin, polyethylene glycol and microcrystalline paraffin at a high speed, uniformly stirring, and then grinding with a micronized compound in a dry state; the micronized fluororesin is obtained by dry grinding the fluororesin; the micronized compound is obtained by dry grinding sulfonated melamine formaldehyde resin and sodium tripolyphosphate; the fluorine-containing resin is one or the combination of more than two of polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer and polyvinylidene fluoride; the number average molecular weight of the polyethylene glycol is 1500-.
2. The preparation method of the isolating dispersant for preventing graphene from agglomerating as claimed in claim 1, which is characterized by comprising the following steps:
(1) adding sulfonated melamine formaldehyde resin and sodium tripolyphosphate into a ball mill, taking spherical zirconia as a grinding medium, and then grinding uniformly in a dry state to obtain a micronized compound;
(2) adding fluorine-containing resin into a ball mill, taking spherical zirconia as a grinding medium, and then carrying out dry grinding treatment to obtain micronized fluorine-containing resin;
(3) adding the micronized fluorine-containing resin, polyethylene glycol and microcrystalline wax into a high-speed stirrer, controlling the temperature at 50-60 ℃, uniformly stirring at a high speed, naturally cooling to room temperature, and uniformly grinding with the obtained micronized compound in a ball mill in a dry state to obtain the isolating dispersant for preventing graphene agglomeration.
3. The preparation method of the isolating dispersant for preventing graphene from agglomerating as claimed in claim 2, wherein the dry grinding speed in step (1) is controlled at 50-80rpm for 30-60 min.
4. The method for preparing the isolating dispersant for preventing graphene from agglomerating as claimed in claim 2, wherein the D50 particle size of the micronized fluorine-containing resin in the step (2) is less than 1 μm.
5. The method for preparing the isolating dispersant for preventing graphene from agglomerating as claimed in claim 2, wherein the high-speed stirring speed in step (3) is controlled at 800-1200rpm and is stirred at a high speed for 10-20 min.
6. The preparation method of the isolation dispersant for preventing graphene from agglomerating as claimed in claim 2, wherein in the preparation of the isolation dispersant, the mass ratio of the sulfonated melamine formaldehyde resin, the sodium tripolyphosphate, the fluorine-containing resin, the polyethylene glycol and the microcrystalline paraffin is 15-20: 5-10: 25-30: 5-10: 3-5.
7. The application method of the isolating dispersant for preventing graphene from agglomerating as claimed in claim 1, is characterized in that the specific application method is as follows: and mixing the isolation dispersant with the graphene, wherein the mass ratio of the graphene to the isolation dispersant is 30-60:1-2, the rotating speed is controlled at 1100-1300rpm, the temperature is controlled at 50-60 ℃, the dispersion is carried out for 10-20min, and the purpose of preventing the graphene from agglomerating can be realized through natural cooling storage.
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