CN108163848B - Graphene particles, preparation method and equipment thereof - Google Patents
Graphene particles, preparation method and equipment thereof Download PDFInfo
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Abstract
The invention provides graphene particles, a preparation method and equipment thereof, wherein the graphene particlesThe preparation method of (2) comprises the following steps: uniformly mixing graphene powder and a polar solvent containing an adhesive; and the resulting mixture was screened and dried. The invention also provides a preparation method of the graphene sheet and equipment for preparing graphene particles, comprising the following steps: the kettle comprises a kettle body, a stirring device, a powder injection device and a liquid atomization device, wherein the stirring device, the powder injection device and the liquid atomization device are arranged on the kettle body and are in airtight connection with the kettle body. The graphene particles prepared by the method disclosed by the invention have uniform structure and density of about 1-2.0 g/cm 3 。
Description
Technical Field
The invention belongs to the technical field of new materials. In particular to a graphene particle and a preparation method thereof, a graphene sheet prepared from the graphene particle and a preparation method thereof, and equipment for preparing the graphene particle.
Background
Graphene (Graphene) is a known two-dimensional material with the lightest thinnest, highest strength, large specific surface area and good physical and chemical stability, and has excellent conductive, flame retardant and reinforcing and toughening properties. However, the large specific surface area also results in graphene products with a generally small tap density (at 0.1g/cm 3 The following) under the same volume condition, the mass is smaller, and when the graphene powder with low density is added into the system, the graphene powder is easy to float out, so that dust pollution and waste of graphene are caused. The graphene powder is added into a solvent for processing, but the graphene powder can cause adsorption overlapping of graphene sheets, reduce the specific surface area of the graphene sheets, and change the chemical energy of the surface of the graphene sheets, so that the performance of the graphene sheets is affected. Currently, studies for preparing graphene particles having a large density have been reported, CN104010965B introduces a hydrocarbon precursor material into a heating zone, heats the hydrocarbon precursor material in the heating zone to form grapheme carbon particles from the hydrocarbon precursor material, andcollecting graphene carbon particles, and preparing the graphene material with specific surface area BET of about 50m 2 And/g, poor quality and low yield. CN102515152B disperses graphene in water or alcohol, and obtains spherical graphene by ultrasonic treatment, or ball milling, granulating and drying; or stirring and dispersing the graphene powder in water, carrying out dispersion treatment, granulating and drying to obtain spherical graphene. The BET of the stack of sheets of graphene after washing can be significantly reduced, thereby affecting the performance. CN102120573a adopts a method of reaction under microwave radiation to obtain graphene nanospheres attached with graphite, and then the graphene nanospheres are prepared by dispersion and centrifugation. The graphene spheres are not easy to disperse into monomer graphene, so that the excellent properties of the graphene sheets are weakened, and the application range of the graphene sheets is limited; and the prepared graphene has small density and large volume, occupies a large space in the transportation process, and causes waste of resources.
The matters in the background section are only those known to the inventors and do not, of course, represent prior art in the field.
Disclosure of Invention
In view of one or more of the deficiencies of the prior art, one aspect of the present invention provides a method of preparing graphene particles;
another aspect of the present invention provides a graphene particle and a method of preparing a graphene sheet using the obtained graphene particle;
in yet another aspect of the present invention, there is also provided an apparatus for preparing graphene particles.
The invention is realized by the following technical scheme:
in one aspect of the present invention, there is provided a method of preparing graphene particles, comprising:
uniformly mixing graphene powder and a polar solvent containing an adhesive; and
the resulting mixture was sieved and dried.
According to one aspect of the present invention, the method of uniformly mixing graphene powder and a polar solvent containing a binder includes:
setting graphene powder into a stable suspension system; and
spraying atomized polar solvent containing binder into the suspension system of graphene powder.
According to one aspect of the present invention, the binder content in the binder-containing polar solvent is 1 to 5vol%, preferably 1.2 to 4.5vol%.
According to one aspect of the present invention, the polar solvent of the polar solvent containing the binder is selected from at least one of ethanol, water, methanol, n-butanol, NMP, DMF, or acetone.
According to one aspect of the present invention, the binder in the polar solvent containing binder is at least one selected from epoxy-based binders, polyurethane-based binders, silicone-based binders, polyacrylate-based binders, polymethacrylate-based binders, or PVP.
According to one aspect of the invention, the graphene is conductive graphene.
According to one aspect of the invention, the specific surface area BET of the graphene is more than or equal to 450m 2 /g。
According to one aspect of the invention, the particle size D50 of the graphene is less than or equal to 27 mu m.
According to one aspect of the invention, the oxygen content Owt% of the graphene is less than or equal to 1wt%, wherein the oxygen content of the graphene refers to the mass fraction of oxygen atoms in the graphene.
According to one aspect of the invention, the amount of the graphene powder and the polar solvent containing the binder is in a mass ratio of 1:1000-1:10, preferably 1:700-1:50.
According to one aspect of the invention, the density of the suspension system of the graphene powder is 1g/m 3 ～100g/m 3 Preferably 1.5g/m 3 ～50g/m 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the pressure of the suspension system of the graphene powder is 0.0-0.3 MPa, preferably 0.03-0.2 MPa.
According to one aspect of the present invention, in the spraying of the atomized polar solvent containing the binder into the graphene powder suspension, the atomized polar solvent containing the binder is sprayed into the graphene powder suspension at 1 to 10ml/min.
According to one aspect of the invention, in the step of spraying the atomized polar solvent containing the adhesive into the suspension system of the graphene powder, spraying is performed from at least one of the upper part, the middle part or the lower part of the suspension system of the graphene powder, and the total spraying speed of the atomized polar solvent containing the adhesive entering the suspension system is 1-10 ml/min.
According to one aspect of the invention, the setting of the graphene powder into a stable suspension system is completed by stirring through a vacuum sealed space, preferably, the stirring speed is 100-3000 r/min, preferably 200-2500 r/min; the purpose of stirring is to form a stable and dispersed graphene suspension system more easily, so that the subsequent graphene powder and the polar solvent containing the adhesive can be fully contacted, and the formed graphene particles are not oversized.
According to one aspect of the invention, the vacuum-tight space is formed by a reaction kettle device.
According to one aspect of the invention, the temperature of the system is kept at 30-100 ℃, preferably 35-80 ℃ in the process of setting the graphene powder into a stable suspension system; in the process of spraying atomized polar solvent containing adhesive into the suspension system of graphene powder, the temperature of the system is kept at 30-100 ℃, preferably 35-80 ℃; the method is favorable for forming a hot air flow circulation at a certain temperature, is favorable for forming a stable graphene suspension system, and can also reduce the viscosity of the adhesive, so that the graphene powder is fully contacted with a solvent containing the adhesive.
According to one aspect of the invention, the system is stirred during the spraying of the atomized polar solvent containing binder into the suspension of graphene powder, said stirring speed being comprised between 100 and 3000r/min, preferably between 200 and 2500r/min.
According to one aspect of the invention, the resulting mixture is screened dry by a 20-50 mesh screen;
and/or drying at 70-90 ℃.
In one aspect of the present invention, there is provided a graphene particle comprising: graphene and a binder.
According to one aspect of the invention, the mass ratio of the graphene to the binder is 1:1-1:0.1;
and/or the particle size of the graphene particles is 30-50 meshes and/or the density is 1-2.0 g/cm 3 ；
And/or, the specific surface area BET of the graphene is more than or equal to 450m 2 /g；
And/or the particle size D50 of the graphene is less than or equal to 27 mu m;
and/or the oxygen content of the graphene is Owt percent or less than or equal to 1 weight percent.
According to an aspect of the present invention, the graphene particles are prepared by the method described above.
In another aspect of the present invention, there is provided a method for preparing graphene sheets, comprising:
and extruding the graphene particles from screw extrusion equipment.
According to one aspect of the invention, the extrusion speed of the screw extrusion device is 60-120 r/min, and the extrusion temperature is 180-240 ℃; preferably, the extrusion speed is 80-100 r/min, and the extrusion temperature is 185-230 ℃.
In yet another aspect of the present invention, there is provided an apparatus for preparing graphene particles, comprising: the stirring device, the powder injection device and the liquid atomization device are arranged on the kettle body and are in airtight connection with the kettle body; wherein,
The powder spraying device is used for spraying graphene powder into the cavity of the kettle;
the liquid atomization device is used for spraying a polar solvent containing an adhesive into the cavity of the kettle;
the stirring device is used for stirring materials in the cavity of the kettle.
According to one aspect of the invention, the stirring device comprises a motor arranged outside the kettle body, a rotating shaft connected with the motor and extending into the cavity of the kettle, and stirring paddles arranged on the rotating shaft.
According to one aspect of the invention, the nozzle of the liquid atomization device extends into the cavity of the kettle body from the top of the kettle body, and preferably, the kettle body is provided with at least one nozzle of the liquid atomization device.
According to one aspect of the invention, the nozzle of the powder spraying device extends into the cavity of the kettle body from the upper position of the kettle body, and the kettle body is provided with at least one nozzle of the powder spraying device.
According to one aspect of the invention, the nozzle of the liquid atomizing device is at least one of a conical solid nozzle or a conical hollow nozzle.
According to one aspect of the invention, the apparatus further comprises a temperature control device for controlling the temperature of the material within the tank body cavity. The temperature control device comprises a temperature measuring instrument and a steam heating wall, wherein the temperature measuring instrument is used for measuring the temperature of a cavity of the kettle body; the steam heating wall is arranged outside the kettle body and wraps the surface of the kettle body, and comprises a steam inlet, a condensate outlet and a channel which can be communicated with the steam inlet and the condensate outlet; preferably, the steam inlet is arranged at the upper part of the steam heating wall, and the condensed water outlet is arranged at the bottom of the steam heating wall.
According to one aspect of the invention, the bottom of the kettle body is provided with an air flow valve and a discharge hole, and the air flow valve is used for regulating and controlling the air pressure in the cavity of the kettle and/or forming an air flow circulation.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a schematic diagram of a graphene particle production apparatus according to one embodiment of the present invention;
FIG. 2 is a schematic top view of a graphene particle production apparatus according to one embodiment of the present invention;
FIG. 3 is a schematic top view of a graphene particle production apparatus according to one embodiment of the present invention;
fig. 4 is a morphology diagram of graphene particles prepared according to one embodiment of the present invention.
Detailed Description
Hereinafter, only certain exemplary embodiments are briefly described. As will be recognized by those of skill in the pertinent art, the described embodiments may be modified in various different ways without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature and not as restrictive.
In the description of the present invention, it should be understood that the directions or positional relationships indicated by the terms "upper", "lower", "top", "bottom", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, in the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, integrally connected, mechanically connected, electrically connected, or communicable with each other; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is less level than the second feature.
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not themselves indicate the relationship between the various embodiments and/or arrangements discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art will recognize the application of other processes and/or the use of other materials.
In one embodiment of the present invention, there is provided a method for preparing graphene particles, including:
uniformly mixing graphene powder and a polar solvent containing an adhesive; and
the resulting mixture was sieved and dried.
According to a preferred embodiment of the present invention, the method of uniformly mixing graphene powder and a polar solvent containing a binder includes:
setting graphene powder into a stable suspension system; and
spraying atomized polar solvent containing binder into the suspension system of graphene powder.
According to a preferred embodiment of the present invention, the binder content in the binder-containing polar solvent is 1 to 5vol%, for example: 1vol%, 1.5vol%, 2vol%, 2.5vol%, 3vol%, 3.5vol%, 4vol%, 4.5vol%, 5vol%, etc.; preferably 1.2 to 4.5vol%, for example: 1.2vol%, 1.5vol%, 2vol%, 2.5vol%, 3vol%, 3.5vol%, 4vol%, 4.5vol%, etc.
According to a preferred embodiment of the present invention, the polar solvent of the polar solvent containing the binder is selected from at least one of ethanol, water, methanol, n-butanol, NMP, DMF or acetone.
According to a preferred embodiment of the present invention, the binder in the polar solvent containing binder is at least one selected from epoxy-based binder, polyurethane-based binder, silicone-based binder, polyacrylate-based binder, polymethacrylate-based binder or PVP.
According to a preferred embodiment of the present invention, the graphene is conductive graphene.
According to a preferred embodiment of the invention, the specific surface area BET of the graphene is more than or equal to 450m 2 /g, for example: 450m 2 /g、460m 2 /g、470m 2 /g、480m 2 /g、490m 2 /g、500m 2 /g、510m 2 /g、520m 2 /g、530m 2 /g, etc.
According to a preferred embodiment of the present invention, the graphene has a particle size D50 less than or equal to 27 μm, for example: 27 μm, 24 μm, 21 μm, 18 μm, 15 μm, 12 μm, 9 μm, 8 μm, etc.
According to a preferred embodiment of the invention, the graphene has an oxygen content Owt% by weight or less than 1% by weight, for example: 1wt%, 0.9wt%, 0.8wt%, 0.7wt%, 0.6wt%, 0.5wt%, 0.4wt%, 0.3wt%, 0.2wt%, 0.1wt%, etc.; wherein the oxygen content of the graphene refers to the mass fraction of oxygen atoms in the graphene.
According to a preferred embodiment of the present invention, the amount of the graphene powder and the polar solvent containing the binder is in a mass ratio of 1:1000 to 1:10, for example: 1:1000, 1:900, 1:800, 1:700, 1:600, 1:500, 1:400, 1:300, 1:200, 1:100, 1:50, 1:10, etc.; preferably 1:700 to 1:50, for example: 1:700, 1:600, 1:500, 1:400, 1:300, 1:200, 1:100, 1:50, etc.
According to a preferred embodiment of the invention, the density of the suspension system of the graphene powder is 1g/m 3 ～100g/m 3 Preferably 1.5g/m 3 ～50g/m 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or, theThe pressure of the suspension system of the graphene powder is 0.0-0.3 MPa, preferably 0.03-0.2 MPa.
According to a preferred embodiment of the present invention, in the step of spraying the atomized polar solvent containing the binder into the suspension system of graphene powder, the atomized polar solvent containing the binder is sprayed into the suspension system of graphene powder at a speed of 1 to 10ml/min, for example, 1ml/min, 2ml/min, 3ml/min, 4ml/min, 5ml/min, 6ml/min, 7ml/min, 8ml/min, 9ml/min, 10ml/min, etc.
According to a preferred embodiment of the present invention, in the step of spraying the atomized binder-containing polar solvent into the suspension of graphene powder, spraying is performed from at least one of the upper, middle or lower parts of the suspension of graphene powder, and the total spraying speed of the atomized binder-containing polar solvent into the suspension is 1 to 10ml/min, for example: 1ml/min, 2ml/min, 3ml/min, 4ml/min, 5ml/min, 6ml/min, 7ml/min, 8ml/min, 9ml/min, 10ml/min, etc.
According to a preferred embodiment of the present invention, the setting of the graphene powder into a stable suspension system is completed by stirring in a vacuum-tight space, preferably, the stirring speed is 100-3000 r/min, for example: 100r/min, 500r/min, 1000r/min, 1500r/min, 2000r/min, 2500r/min, 3000r/min, etc.; preferably 200 to 2500r/min, for example: 200r/min, 500r/min, 1000r/min, 1500r/min, 2000r/min, 2500r/min, etc.; the purpose of stirring is to form a stable and dispersed graphene suspension system more easily, so that the subsequent graphene powder and the polar solvent containing the adhesive can be fully contacted, and the formed graphene particles are not oversized.
According to a preferred embodiment of the invention, the vacuum-tight space is formed by a reactor device.
According to a preferred embodiment of the present invention, the system temperature is maintained at 30 to 100 ℃ during the process of setting the graphene powder into a stable suspension system, for example: 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, etc.; preferably 35 to 80 ℃, for example: 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, etc. In performing the spray-atomizing of the polar solvent containing the binder into the suspension of graphene powder, the temperature of the system is maintained at 30 to 100 ℃, for example: 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, etc.; preferably 35 to 80 ℃, for example: 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, etc. The inventor of the application researches find that when the system of the graphene powder is favorable for forming a hot air flow circulation at the temperature of 30-100 ℃, the stable graphene suspension system is more favorable for forming, and the viscosity of the solution containing the adhesive can be reduced, so that the sedimentation speed of spraying in the system is reduced, and the graphene powder is more fully contacted with the solvent containing the adhesive.
According to a preferred embodiment of the present invention, in performing spraying of the atomized polar solvent containing the binder into the suspension system of graphene powder, the system is stirred at a stirring speed of 100 to 3000r/min, for example: 100r/min, 500r/min, 1000r/min, 1500r/min, 2000r/min, 2500r/min, 3000r/min, etc.; preferably 200 to 2500r/min, for example: 200r/min, 500r/min, 1000r/min, 1500r/min, 2000r/min, 2500r/min, etc. The graphene suspension system is characterized in that the graphene powder with extremely light mass is in a relatively closed reaction kettle under the condition of very active movement, so that higher requirements are put on stirring of the graphene powder, the graphene can be in a suspension state, the movement of the graphene is not too active, and the safety of the reaction kettle is ensured. The invention combines the technological conditions of graphene powder injection under the stirring rotation speed of 100-3000 r/min, and can meet the requirements. More preferably 200 to 2500 r/min.
According to a preferred embodiment of the invention, the resulting mixture is screened dry using a 20-50 mesh screen, such as a 20 mesh, 30 mesh, 40 mesh, 50 mesh, etc. screen.
According to a preferred embodiment of the invention, the mixture obtained is dried by sieving at a temperature of 70-90 c, for example at 70 c, 75 c, 80 c, 85 c, 90 c, etc.
In one embodiment of the present invention, there is provided a graphene particle including: graphene and a binder.
According to a preferred embodiment of the present invention, the mass ratio of the graphene to the binder is 1:1 to 1:0.1, for example: 1:1, 1:0.9, 1:0.8, 1:0.7, 1:0.6, 1:0.5, 1:0.4, 1:0.3, 1:0.2, 1:0.1, etc.
According to a preferred embodiment of the present invention, the particle size of the graphene particles is 30 to 50 mesh, for example: 30 mesh, 40 mesh, 50 mesh, etc.; and/or a density of 1 to 2.0g/cm 3 For example: 1.0g/cm 3 、1.2g/cm 3 、1.4g/cm 3 、1.6g/cm 3 、1.8g/cm 3 、2.0g/cm 3 And the like.
According to a preferred embodiment of the invention, the specific surface area BET of the graphene is more than or equal to 450m 2 /g, for example: 450m 2 /g、460m 2 /g、470m 2 /g、480m 2 /g、490m 2 /g、500m 2 /g、510m 2 /g、520m 2 /g、530m 2 /g, etc.
According to a preferred embodiment of the present invention, the graphene has a particle size D50 less than or equal to 27 μm, for example: 27 μm, 24 μm, 21 μm, 18 μm, 15 μm, 12 μm, 9 μm, 8 μm, etc.
According to a preferred embodiment of the invention, the graphene has an oxygen content Owt% by weight or less than 1% by weight, for example: 1wt%, 0.9wt%, 0.8wt%, 0.7wt%, 0.6wt%, 0.5wt%, 0.4wt%, 0.3wt%, 0.2wt%, 0.1wt%, etc.
According to a preferred embodiment of the present invention, the graphene particles are prepared by the method described above.
In one embodiment of the present invention, there is provided a method for preparing graphene sheets, including:
and extruding the graphene particles from screw extrusion equipment.
According to a preferred embodiment of the present invention, the extrusion speed of the screw extrusion apparatus is 60 to 120r/min, for example: 60r/min, 70r/min, 80r/min, 90r/min, 100r/min, 110r/min, 120r/min, etc.; the extrusion temperature is 180 to 240 ℃, for example: 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, etc. Preferably, the extrusion speed is 80 to 100r/min, for example: 80r/min, 85r/min, 90r/min, 95r/min, 100r/min, etc.; the extrusion temperature is 185 to 230 ℃, for example: 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, etc.
In another embodiment of the present invention, there is provided an apparatus for preparing graphene particles, as shown in fig. 1, an apparatus 1 for preparing graphene particles including: the kettle comprises a kettle body 2, a stirring device 3, a powder injection device 5 and a liquid atomization device 4, wherein the stirring device 3, the powder injection device 5 and the liquid atomization device 4 are arranged on the kettle body 2 and are in airtight connection with the kettle body 2. The powder spraying device 5 is used for spraying graphene powder into the cavity of the kettle body 2; the liquid atomization device 4 is used for spraying a polar solvent containing adhesive into the cavity of the kettle body 2; the stirring device 3 is used for stirring materials in the cavity of the kettle body 2. It will be appreciated by those skilled in the art that it is within the scope of the present invention to have the liquid atomizing device 4 attached to various portions of the tank 2, such as the liquid atomizing device 4 at the top, middle, upper middle, etc. portions of the tank 2. The powder spraying device 5 is connected to a plurality of different parts of the kettle body 2, for example, the powder spraying device 5 is arranged at the middle position, the upper middle position and other parts of the kettle body 2, and the powder spraying device is within the protection scope of the invention. According to a preferred embodiment of the present invention, the stirring device 3 includes a motor 31 disposed outside the kettle body, a rotating shaft 32 connected to the motor 31 and extending into the cavity of the kettle body 2, and a stirring paddle 33 disposed on the rotating shaft 32. It will be appreciated by those skilled in the art, based on the present disclosure, that the paddles 33 may also be other types of paddles, such as: anchor, frame, paddle, turbine, blade, combination, and the like are all within the scope of the present invention.
To be more suitable for the formation and maintenance of graphene suspension systems, so that the reaction is sufficient in the suspension system. According to a preferred embodiment of the present invention, the stirring paddle 33 includes a middle paddle 331, a lower paddle 332 and an end paddle 333, wherein the middle paddle 332 is located at the axial middle of the cavity of the kettle body 2, the end paddle 333 is disposed at the end of the rotating shaft 32 extending into the cavity and is located at the bottom of the cavity of the kettle body 2, and the lower paddle 332 is located between the middle paddle 331 and the end paddle 333 and is connected to the end paddle 333.
According to a preferred embodiment of the invention, the nozzle 41 of the liquid atomizing device 4 extends into the cavity of the kettle body 2 from the top of the kettle body 2. It will be appreciated by those skilled in the art that a plurality of nozzles 41 may be connected to the liquid atomizing device 4. For example, 3 to 5 nozzles 41 are uniformly distributed around the top of the tank 2, and the 3 to 5 nozzles 41 can spray the polar solvent containing the binder in the liquid atomizing device 4 into the tank 2, and 4 nozzles 41 are uniformly distributed around the top of the tank 2 as shown in fig. 2. The arrangement of the plurality of nozzles 41 enables the operation to be more flexible, all the nozzles 41 can be opened simultaneously, the plurality of nozzles 41 can be opened intermittently and can spray towards the kettle body 2, and the plurality of nozzle wheels can spray towards the kettle body 2.
According to a preferred embodiment of the invention, the nozzle 51 of the powder spraying device 5 protrudes into the cavity of the kettle 2 from an upper position of the kettle. It will be appreciated by those skilled in the art that the powder injection device 5 may have a plurality of nozzles 51 connected thereto. For example, at the upper part but below the height of the nozzles 41 of the liquid atomizing device 4, 3 to 5 or more nozzles 51 are uniformly distributed around the circumference of the tank 2, and these 3 to 5 nozzles 51 may spray the graphene powder in the powder spraying device 5 into the tank 2, and 4 nozzles 51 are uniformly distributed around the circumference of the tank 2 as shown in fig. 3. The arrangement of the plurality of nozzles 51 enables the operation to be more flexible, all the nozzles 51 can be opened simultaneously, the plurality of nozzles 51 can spray to the kettle body 2 simultaneously, or the plurality of nozzles 51 can be opened intermittently, and the plurality of nozzles 51 spray to the kettle body 2 in a wheel-flow manner.
According to a preferred embodiment of the present invention, the nozzle 41 of the liquid atomizing device 4 may be of the type of a screw nozzle, a fan nozzle, a clip nozzle, a rectangular nozzle, a fine atomizing nozzle, a high pressure nozzle, a steam atomizing nozzle, a square nozzle, or the like, which is within the scope of the present invention.
The nozzle 41 of the liquid atomizing device 4 in this embodiment is preferably at least one of a conical solid nozzle or a conical hollow nozzle. The solid conical nozzle is more suitable for the requirements of reaction kettle equipment requiring a regular round spraying surface through the solid conical nozzle of gas atomization, and is easier to generate uniform droplet distribution; the hollow conical nozzle not only can greatly increase the surface area of mist droplets, but also has narrower droplet size distribution and better mass transfer effect; a circular water curtain can be formed in a rotary flow mode, so that the graphene powder is more beneficial to contact, and the special wide inner diameter in the cavity is involved, so that blockage can be effectively prevented.
According to a preferred embodiment of the invention, the apparatus further comprises temperature control means for controlling the temperature of the material in the chamber of the tank 2. As shown in fig. 1, the temperature control device includes a thermometer 6 and a steam heating wall 7. Wherein the temperature measuring instrument 6 is used for measuring the temperature of the cavity of the kettle body 2; the steam heating wall 7 is arranged outside the kettle body 2 and wraps the surface of the kettle body 2. The heating mode of the steam heating wall 7 can be selected from electric heating, conduction oil circulation heating, far infrared heating, external (internal) coil heating, water heating and other heating modes. The preferred water heating of this embodiment, specific structural design is: the steam heating wall 7 is provided with a steam inlet 71, a condensate outlet 72, and a passage that communicates the steam inlet 71 and the condensate outlet 72. Preferably, the steam inlet 71 is provided at an upper portion of the steam heating wall 7, and the condensed water outlet 72 is provided at a bottom portion of the steam heating wall.
According to a preferred embodiment of the invention, an air flow valve 8 and a discharge hole 9 are arranged on the bottom of the kettle body 2, and the air flow valve 8 is used for regulating and controlling the air pressure in the cavity of the kettle body 2 and/or forming an air flow circulation.
High-quality graphene powder is large in specific surface area and small in density, occupies a large space in the transportation and storage processes, increases transportation cost, and is difficult to realize addition of graphene by utilizing traditional processing equipment, so that dust pollution is very easy to cause. In the research field of graphene particles, the method disclosed by the invention firstly mentions the concept of combining graphene and an adhesive in a suspension system, and by adopting the device disclosed by the invention, the existing chemical reaction kettle is modified so as to be suitable for the principle of combining graphene and an adhesive, and a powder spraying device and a liquid spraying device are respectively arranged at different positions of a kettle body, so that the graphene and the adhesive can be fully and comprehensively contacted in the suspension system. The method has exquisite conception, achieves the effect beyond the expectations of the technicians in the field, has high utilization value and plays an pioneering role in downstream application of the graphene. According to the preparation method, the graphene powder is sprayed into the reaction kettle by using the powder spraying device to form a stable graphene suspension system, then the polar solvent atomized liquid beads for dissolving the adhesive are sprayed into the graphene suspension system at a constant speed by using the liquid atomization spraying device, so that the polar solvent atomized liquid beads are fully contacted with the graphene powder, and the adhesive is used as a core, so that the graphene coats the surface of the adhesive under the stirring effect, and the prepared graphene has uniform particle structure, high density and stable performance. Referring specifically to fig. 4, a graphene particle prepared according to the method disclosed by the invention is shown. And the graphene polypropylene plastic particles prepared by the graphene particles prepared by the method are basically consistent with the graphene polypropylene plastic particles prepared by directly utilizing the graphene powder in terms of mechanical and conductive properties (see table 1), but the graphene particles are more convenient to add, and the phenomena of powder pollution and waste of graphene caused by the drifting-out of the graphene powder are avoided.
Table 1: the performance of the graphene polypropylene plastic particles prepared by the graphene particles is compared with that of the graphene polypropylene plastic particles prepared by the graphene powder
| 3wt% graphene particles | 3wt% graphene powder | |
| Tensile strength MPa | 34.4 | 35.2 |
| Elongation at break% | 16.4 | 15.9 |
| Flexural Strength MPa | 44.9 | 45.6 |
| Unnotched impact strength MPa | 38.2 | 36.1 |
| Surface resistivity Ω | 10 6 | 10 6 |
According to the invention, graphene and an adhesive are combined in a suspension system, a liquid atomization spraying device and a powder spraying device are utilized to fully contact polar solvent atomization liquid beads containing the adhesive with graphene powder, and the graphene particles with high density are prepared after sieving and drying. The particle size of the formed graphene particles is about 30-50 meshes, and the density is about 1-2.0 g/cm 3 Can be dispersed into graphene sheets under the conditions of strong shearing and high-temperature processing, and has excellent reservationThe original graphene has excellent properties, the problems of performance reduction and the like caused by BET reduction of graphene powder after liquid phase washing are avoided, and meanwhile, the graphene powder is convenient to transport, store and apply in processing.
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
Example 1:
an apparatus for preparing graphene particles, as shown in fig. 1, an apparatus 1 for preparing graphene particles includes: the kettle comprises a kettle body 2, a stirring device 3, a powder spraying device 5, a liquid atomizing device 4 and a temperature control device, wherein the stirring device 3, the powder spraying device 5, the liquid atomizing device 4 and the temperature control device are all arranged on the kettle body 2 and are in airtight connection with the kettle body 2. The powder spraying device 5 is used for spraying graphene powder into the cavity of the kettle body 2; the liquid atomization device 4 is used for spraying a polar solvent containing adhesive into the cavity of the kettle body 2; the stirring device 3 is used for stirring materials in the cavity of the kettle body 2; the temperature control device is used for controlling the temperature of materials in the cavity of the kettle body 2.
The stirring device 3 comprises a motor 31 arranged outside the kettle body, a rotating shaft 32 connected with the motor 31 and extending into the cavity of the kettle body 2, and stirring paddles 33 arranged on the rotating shaft 32. It will be appreciated by those skilled in the art, based on the present disclosure, that the paddles 33 may also be other types of paddles, such as: anchor, frame, paddle, turbine, blade, combination, and the like are all within the scope of the present invention. To be more suitable for the formation and maintenance of graphene suspension systems, so that the reaction is sufficient in the suspension system. In this embodiment, the stirring paddle 33 includes a middle paddle 331, a lower paddle 332, and an end paddle 333, where the middle paddle 332 is located in the axial middle of the cavity of the kettle body 2, and the end paddle 333 is disposed at the end of the rotating shaft 32 extending into one end of the cavity and is located at the bottom of the cavity of the kettle body 2, and the lower paddle 332 is located between the middle paddle 331 and the end paddle 333 and is connected to the end paddle 333.
The nozzle 41 of the liquid atomizing device 4 extends into the cavity of the kettle body 2 from the top of the kettle body 2. It will be appreciated by those skilled in the art that a plurality of nozzles 41 may be connected to the liquid atomizing device 4. For example, 3 to 5 nozzles 41 are uniformly distributed around the top of the tank 2, and the 3 to 5 nozzles 41 can spray the polar solvent containing the binder in the liquid atomizing device 4 into the tank 2, and 4 nozzles 41 are uniformly distributed around the top of the tank 2 as shown in fig. 2. The arrangement of the plurality of nozzles 41 enables the operation to be more flexible, all the nozzles 41 can be opened simultaneously, the plurality of nozzles 41 can be opened intermittently and can spray to the kettle body 2 simultaneously, and the plurality of nozzles 41 can spray to the kettle body 2 in a wheel-flow manner.
The nozzle 51 of the powder spraying device 5 extends into the cavity of the kettle body 2 from the upper position of the kettle body. Those skilled in the art will appreciate that a plurality of nozzles 51 may be connected. For example, at the upper part but below the height of the nozzles 41 of the liquid atomizing device 4, 3 to 5 or more nozzles 51 are uniformly distributed around the circumference of the tank 2, and these 3 to 5 nozzles 51 may spray the graphene powder in the powder spraying device 5 into the tank 2, and 4 nozzles 51 are uniformly distributed around the circumference of the tank 2 as shown in fig. 3. The arrangement of the plurality of nozzles 51 enables the operation to be more flexible, all the nozzles 51 can be opened simultaneously, the plurality of nozzles 51 can spray to the kettle body 2 simultaneously, or the plurality of nozzles 51 can be opened intermittently, and the plurality of nozzles 51 spray to the kettle body 2 in a wheel-flow manner.
The temperature control device comprises a thermometer 6 and a steam heating wall 7. Wherein the temperature measuring instrument 6 is used for measuring the temperature of the cavity of the kettle body 2; the steam heating wall 7 is arranged outside the kettle body 2 and wraps the surface of the kettle body 2. The heating mode of the steam heating wall 7 can be selected from electric heating, conduction oil circulation heating, far infrared heating, external (internal) coil heating, water heating and other heating modes. The preferred water heating of this embodiment, specific structural design is: the steam heating wall 7 is provided with a steam inlet 71, a condensate outlet 72, and a passage that communicates the steam inlet 71 and the condensate outlet 72. Preferably, the steam inlet 71 is provided at an upper portion of the steam heating wall, and the condensed water outlet 72 is provided at a bottom portion of the steam heating wall.
Example 2:
preparation of graphene particles:
graphene (BET: 450 m) 2 /g, D50:15 μm) powder is sprayed into a high-pressure reaction kettle through a powder spraying device, and is uniformly stirred and dispersed, wherein the temperature in the kettle is controlled at 30 ℃, and the stirring rotation speed is 100r/min; atomizing an adhesive epoxy ethanol solution containing 1vol% (the mass ratio of graphene powder to the adhesive epoxy ethanol solution is 1:10) by a liquid atomization spraying device, spraying the atomized adhesive epoxy ethanol solution into a graphene dispersion system at a speed of 1.0ml/min, fully contacting and mixing adhesive epoxy ethanol atomized liquid beads and graphene powder, settling, sieving and drying to obtain particles with uniform size and a density of about 1.0g/cm 3 Graphene particles with stable performance.
Example 3:
preparation of graphene particles:
graphene (BET: 502 m) 2 /g, D50:8 μm) powder is sprayed into a high-pressure reaction kettle through a powder spraying device, and is uniformly stirred and dispersed, wherein the temperature in the kettle is controlled at 80 ℃ and the stirring rotating speed is 350r/min; atomizing an ethanol solution containing 4.0vol% of binder PVP (the mass ratio of graphene powder to binder PVP ethanol solution is 1:700) by a liquid atomization spraying device, spraying the atomized ethanol solution into a graphene dispersion system at 3ml/min, fully contacting and mixing ethanol atomized liquid beads containing binder PVP with graphene powder, settling, sieving and drying to obtain a uniform particle size and a density of about 1.6g/cm 3 Graphene particles with stable performance.
Example 4:
preparation of graphene particles:
graphene (BET: 485m 2 /g, D50:27 μm) powder is sprayed into a high-pressure reaction kettle through a powder spraying device, and is uniformly stirred and dispersed, wherein the temperature in the kettle is controlled at 100 ℃, and the stirring rotating speed is 550r/min; atomizing an ethanol solution containing 5.0vol% of adhesive polypropylene (the mass ratio of graphene powder to the adhesive polypropylene ethanol solution is 1:1000) by a liquid atomization spraying device, spraying the atomized solution into a graphene dispersion system at 10ml/min, fully contacting and mixing adhesive polypropylene ethanol atomized liquid beads and graphene powder, settling, sieving and drying to obtain particles with uniform size and density of about 2.0g /cm 3 Graphene particles with stable performance.
Example 5:
preparation of graphene particles:
graphene (BET: 502 m) 2 /g, D50:8 μm) powder is sprayed into a high-pressure reaction kettle through a powder spraying device, and is uniformly stirred and dispersed, wherein the temperature in the kettle is controlled at 35 ℃, and the stirring rotating speed is 3000r/min; atomizing an ethanol solution containing 4.5vol% of binder PVP (the mass ratio of graphene powder to binder PVP ethanol solution is 1:200) by a liquid atomization spraying device, spraying the atomized ethanol solution into a graphene dispersion system at 5ml/min, fully contacting and mixing ethanol atomized liquid beads containing binder PVP with graphene powder, settling, sieving and drying to obtain a uniform particle size and a density of about 1.3g/cm 3 Graphene particles with stable performance.
Example 6:
preparation of graphene particles:
graphene (BET: 502 m) 2 /g, D50:8 μm) powder is sprayed into a high-pressure reaction kettle through a powder spraying device, and is uniformly stirred and dispersed, wherein the temperature in the kettle is controlled at 50 ℃, and the stirring rotation speed is 2500r/min; atomizing an ethanol solution containing 1.2vol% of binder PVP (the mass ratio of graphene powder to binder PVP ethanol solution is 1:50) by a liquid atomization spraying device, spraying the atomized ethanol solution into a graphene dispersion system at 7ml/min, fully contacting and mixing ethanol atomized liquid beads containing binder PVP with graphene powder, settling, sieving and drying to obtain a uniform particle size and a density of about 1.1g/cm 3 Graphene particles with stable performance.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (40)
1. A method of preparing graphene particles, comprising:
uniformly mixing graphene powder and a polar solvent containing an adhesive; and
sieving and drying the obtained mixture;
the method for uniformly mixing the graphene powder and the polar solvent containing the adhesive comprises the following steps:
setting graphene powder into a stable suspension system; and
spraying atomized polar solvent containing adhesive into the suspension system of graphene powder, taking the adhesive as a core, and coating the surface of the adhesive with graphene under the stirring effect.
2. The method of preparing graphene particles according to claim 1, wherein the binder content in the polar solvent containing the binder is 1 to 5vol%.
3. The method of preparing graphene particles according to claim 2, wherein the binder content in the polar solvent containing the binder is 1.2 to 4.5vol%.
4. The method of preparing graphene particles according to claim 1, wherein the polar solvent of the polar solvent containing the binder is at least one selected from ethanol, water, methanol, n-butanol, NMP, DMF, or acetone.
5. The method of preparing graphene particles according to claim 1, wherein the binder in the polar solvent containing the binder is at least one selected from epoxy-based binders, polyurethane-based binders, silicone-based binders, polyacrylate-based binders, polymethacrylate-based binders, and PVP.
6. The method for preparing graphene particles according to claim 1, wherein the graphene is conductive graphene.
7. The method for preparing graphene particles according to claim 1, wherein the specific surface area BET of the graphene is not less than 450m 2 /g。
8. The method for preparing graphene particles according to claim 1, wherein the particle diameter d50 of the graphene is less than or equal to 27 μm.
9. The method for preparing graphene particles according to claim 1, wherein the oxygen content of the graphene is Owt% or less than 1% by weight.
10. The method for preparing graphene particles according to claim 1, wherein the amount of the graphene powder and the polar solvent containing the binder is 1:1000 to 1:10 by mass.
11. The method for preparing graphene particles according to claim 10, wherein the amount of the graphene powder and the polar solvent containing the binder is 1:700 to 1:50 by mass.
12. The method for preparing graphene particles according to claim 1, wherein the density of the suspension system of the graphene powder is 1g/m 3 ～100g/m 3 。
13. The method for preparing graphene particles according to claim 12, wherein the density of the suspension system of the graphene powder is 1.5g/m 3 ～50g/m 3 。
14. The method for preparing graphene particles according to claim 1, wherein the pressure of the suspension system of the graphene powder is 0.0MPa to 0.3MPa.
15. The method for preparing graphene particles according to claim 14, wherein the pressure of the suspension system of the graphene powder is 0.03MPa to 0.2MPa.
16. The method of preparing graphene particles according to claim 1, wherein in the spraying of the atomized binder-containing polar solvent into the graphene powder suspension, the atomized binder-containing polar solvent is sprayed into the graphene powder suspension at 1 to 10 ml/min.
17. The method according to claim 1, wherein the spraying of the atomized polar solvent containing the binder into the suspension of the graphene powder is performed from at least one of the upper, middle or lower portions of the suspension of the graphene powder.
18. The method for preparing graphene particles according to claim 1, wherein the setting of graphene powder into a stable suspension system is accomplished by stirring in a vacuum-tight space.
19. The method for preparing graphene particles according to claim 18, wherein the stirring rotation speed of the stirring is 100-3000 r/min.
20. The method for preparing graphene particles according to claim 19, wherein the stirring rotation speed of the stirring is 200 to 2500r/min.
21. The method for preparing graphene particles according to claim 18, wherein the vacuum-tight space is formed using a reaction kettle device.
22. The method for preparing graphene particles according to claim 1, wherein the system temperature is maintained at 30 to 100 ℃ during the process of setting the graphene powder into a stable suspension system.
23. The method of preparing graphene particles according to claim 22, wherein the system temperature is maintained at 35 to 80 ℃ during the process of setting the graphene powder into a stable suspension system.
24. The method of preparing graphene particles according to claim 1, wherein the temperature of the system is maintained at 30 to 100 ℃ during the spraying of the atomized polar solvent containing the binder into the suspension system of the graphene powder.
25. The method of preparing graphene particles according to claim 24, wherein the temperature of the system is maintained at 35 to 80 ℃ during the spraying of the atomized polar solvent containing the binder into the suspension system of the graphene powder.
26. The method for preparing graphene particles according to claim 1, wherein the system is stirred during spraying of the atomized polar solvent containing the binder into the suspension system of the graphene powder, and the stirring speed is 100-3000 r/min.
27. The method of preparing graphene particles according to claim 26, wherein the system is stirred during spraying of the atomized polar solvent containing the binder into the suspension system of graphene powder, and the stirring speed is 200-2500 r/min.
28. The method for preparing graphene particles according to claim 1, wherein the obtained mixture is screened and dried by using a 20-50 mesh screen.
29. The method for preparing graphene particles according to claim 1, wherein the mixture obtained is dried by sieving at 70-90 ℃.
30. A graphene particle prepared according to the preparation method of any one of claims 1 to 29, comprising: and the graphene and the adhesive are mixed according to a mass ratio of 1:1-1:0.1.
31. The graphene particles of claim 30, wherein the graphene particles have a particle size of 30 to 50 mesh and/or a density of 1 to 2.0g/cm 3 。
32. The graphene particles of claim 30, wherein the specific surface area BET of the graphene is greater than or equal to 450m 2 /g。
33. The graphene particles of claim 30, wherein the graphene has a particle size d50+.27 μιη.
34. The graphene particles of claim 30, wherein the graphene has an oxygen content of Owt% to 1wt%.
35. An apparatus for preparing graphene particles according to the preparation method of any one of claims 1 to 29, comprising: the stirring device, the powder injection device and the liquid atomization device are arranged on the kettle body and are in airtight connection with the kettle body; wherein,
the powder spraying device is used for spraying graphene powder into the cavity of the kettle;
the liquid atomization device is used for spraying a polar solvent containing an adhesive into the cavity of the kettle, and a nozzle of the liquid atomization device extends into the cavity of the kettle from the top of the kettle;
the stirring device is used for stirring materials in the cavity of the kettle and comprises a motor arranged outside the kettle body, a rotating shaft connected with the motor and extending into the cavity of the kettle, and stirring paddles arranged on the rotating shaft;
the method comprises the steps of spraying graphene powder into a kettle cavity by using a powder spraying device to form a stable graphene suspension system, spraying polar solvent atomized liquid beads for dissolving an adhesive into the graphene suspension system at a constant speed by using a liquid atomization spraying device, enabling the polar solvent atomized liquid beads to fully contact with the graphene powder, taking the adhesive as a core, and enabling the graphene to cover the surface of the adhesive under the stirring effect.
36. The apparatus for preparing graphene particles according to claim 35, wherein the tank body is provided with at least one nozzle of a liquid atomizing device.
37. The apparatus for preparing graphene particles according to claim 35, wherein the nozzle of the powder spraying device protrudes into the cavity of the kettle body from an upper position of the kettle body, and the kettle body is provided with at least one nozzle of the powder spraying device.
38. The apparatus for preparing graphene particles according to claim 35, wherein the nozzle of the liquid atomizing device is at least one of a conical solid nozzle or a conical hollow nozzle.
39. The apparatus for preparing graphene particles according to claim 35, further comprising a temperature control device comprising a thermo detector and a steam heating wall, wherein,
the temperature measuring instrument is used for measuring the temperature of the cavity of the kettle body;
the steam heating wall is arranged outside the kettle body and wraps the surface of the kettle body, and comprises a steam inlet, a condensate outlet and a channel which can be communicated with the steam inlet and the condensate outlet.
40. The apparatus for preparing graphene particles according to claim 35, wherein an air flow valve and a discharge port are arranged on the bottom of the kettle body, and the air flow valve is used for regulating air pressure in the cavity of the kettle and/or forming an air flow circulation.
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