WO2021128257A1 - 含有单层石墨烯的固化物、单层石墨烯及其制备方法和含有单层石墨烯的制品 - Google Patents
含有单层石墨烯的固化物、单层石墨烯及其制备方法和含有单层石墨烯的制品 Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
Definitions
- the present disclosure relates to the technical field of graphene, in particular to a cured product containing a single-layer graphene, a single-layer graphene, a preparation method thereof, and a product containing a single-layer graphene.
- Graphene is a two-dimensional carbon nanomaterial with a hexagonal honeycomb lattice composed of carbon atoms and sp hybrid orbitals. It has excellent optical, electrical, and mechanical properties. It is used in materials science, micro-nano processing, and energy. , Biomedicine and drug delivery have important application prospects, and are considered to be a revolutionary material in the future.
- the graphene prepared by the existing method is mostly multi-layer graphene (also called graphene microsheet), it is difficult to prepare a single-layer graphene, and a large amount of pollutants will be generated during the preparation process, and The preparation scale is small and it is difficult to realize industrial scale production.
- the present disclosure is proposed to solve at least one of the above technical problems.
- the first object of the present disclosure is to provide a method for preparing a cured product containing a single-layer graphene, which can prepare a cured product containing a single-layer graphene without pollution during the preparation process, and is suitable for industrialization Scale production.
- the second object of the present disclosure is to provide a cured product containing a single layer of graphene, which is prepared by using the above-mentioned method for preparing a cured product containing a single layer of graphene.
- the third objective of the present disclosure is to provide a method for preparing single-layer graphene, which uses the above-mentioned cured product containing single-layer graphene to obtain single-layer graphene.
- the fourth objective of the present disclosure is to provide a single-layer graphene, which is prepared by the above-mentioned single-layer graphene preparation method.
- the fifth objective of the present disclosure is to provide a product containing single-layer graphene, which is prepared by using the above-mentioned cured product containing the single-layer graphene or the above-mentioned single-layer graphene.
- the method for preparing a cured product containing a single-layer graphene provided by the present disclosure includes the following steps:
- step (c) Replace the graphite and the solidified material in step (a) with the expanded particulate material, and repeat steps (a) and (b) several times to obtain a solidified product containing a single layer of graphene.
- the curing material includes any one of thermoplastic polymer, flour or rice flour;
- the thermoplastic polymer includes any one or a combination of at least two of resin, plastic, thermoplastic rubber, thermoplastic elastomer or hot melt adhesive;
- the resin includes any one or a combination of at least two of polyethylene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyvinyl chloride or polypropylene;
- the plastic includes any one or a combination of at least two of rigid thermoplastics, soft plastics or semi-rigid plastics;
- thermoplastic rubber includes any one or a combination of at least two of TPU, NBR, SBS, TPE or EPDM;
- thermoplastic elastomer includes any one or a combination of at least two of TPEE, PUR, TPV or TEEE;
- the particle size of the graphite is 20-12500 mesh
- the mass ratio of the graphite to the solidified material is (0.5-200): 100;
- the particle size of the shaped pellets is 0.2-10 mm.
- step (b) the heating temperature is 50-880°C, and the heating time is 5-60 min;
- the gas includes any one or a combination of at least two of air, oxygen, hydrogen, carbon dioxide or nitrogen;
- step (b) the pressurization pressure is 0.3-50.0 MPa, and the pressurization time is 5-70 min;
- step (b) the pressure is released to normal pressure, and the time for the pressure to be released to normal pressure is less than 1 min.
- the first solvent includes water
- the second solvent includes water and/or lubricant.
- the preparation method of the solidified product containing single-layer graphene includes the following steps:
- step (c) Replace the graphite and solidified material in step (a) with the expanded particulate material, and repeat steps (a) and (b) several times to obtain a solidified product containing a single layer of graphene;
- the method for preparing a cured product containing a single-layer graphene includes the following steps:
- step (c) Replace the graphite and the solidified material in step (a) with the expanded particulate material, and repeat steps (a) and (b) several times to obtain a solidified product containing a single layer of graphene.
- the present disclosure also provides a cured product containing a single-layer graphene, which is prepared by using the above-mentioned preparation method of a cured product containing a single-layer graphene;
- the mass fraction of the single-layer graphene in the cured product containing the single-layer graphene is 20-99%.
- the present disclosure also provides a method for preparing single-layer graphene, including the following steps:
- the solidified product containing the single-layer graphene is subjected to carbonization treatment, and the product obtained by the carbonization treatment is separated to obtain the single-layer graphene.
- the solidified product containing the single-layer graphene is carbonized, and then the product obtained by the carbonization treatment is separated according to the specific gravity to obtain the single-layer graphene;
- the temperature of the carbonization treatment is 200-500°C, and the time of the carbonization treatment is 0.08-3.0h;
- the separation medium used for separation according to specific gravity is water.
- the present disclosure also provides a single-layer graphene, which is prepared by using the above-mentioned preparation method of the single-layer graphene.
- the present disclosure also provides a product containing single-layer graphene, which is prepared by using the above-mentioned cured product containing the above-mentioned single-layer graphene or the above-mentioned single-layer graphene.
- the cured product containing single-layer graphene, single-layer graphene and preparation method thereof, and products containing single-layer graphene provided by the present disclosure have the following beneficial effects:
- the present disclosure provides a method for preparing a cured product containing a single layer of graphene.
- First, graphite, a cured material and optionally a first solvent are mixed and cured to shape, and the molded particles obtained by curing and molding and optionally
- the system formed by the second solvent is heated, and then gas is introduced for pressurization. Under a certain pressure, the gas exerts a certain force on the shaped particles, and penetrates into the inside of the shaped particles. When the pressure is suddenly released, it will produce instantaneous The pressure difference and the strong impact effect make the molded particles produce a large number of micropores and expand.
- the graphite in the molded particles can be forcibly peeled off, and the obtained expanded particles are repeatedly cycled through the above steps.
- the conversion of graphite to single-layer graphene in the shaped particles can be realized, thereby obtaining a cured product containing single-layer graphene;
- the preparation method utilizes the physical effect of gas on the shaped particles to realize the conversion of graphite to graphene in the shaped particles without any chemical reaction with graphite, thereby ensuring the high purity of the solidified material containing single-layer graphene, and No pollutants are generated during the whole preparation process, and it can be applied to large-scale industrial preparation.
- the present disclosure provides a cured product containing a single-layer graphene, which is prepared by the above-mentioned preparation method of a cured product containing a single-layer graphene, and the cured product containing a single-layer graphene can be directly used in industrial production.
- the present disclosure provides a method for preparing a single-layer graphene, by carbonizing a cured product containing a single-layer graphene, and then separating the product obtained by the carbonization treatment to obtain a single-layer graphene.
- the preparation method has stable process, simple operation, and is suitable for industrial large-scale production.
- the single-layer graphene prepared by the preparation method has high purity and excellent performance.
- the present disclosure provides a single-layer graphene, which is prepared by the above-mentioned preparation method of single-layer graphene.
- the single-layer graphene has high purity and excellent performance, and can be directly used in industrial production and processing.
- the present disclosure provides a product containing single-layer graphene.
- the product containing single-layer graphene using it as a raw material Has the same advantages.
- Figure 1 is a morphological diagram of the shaped pellets provided in Example 1 of the present disclosure.
- Figure 2 is a morphological diagram of the expanded granular material provided in Example 1 of the present disclosure
- Example 3 is a high-resolution transmission electron microscope scanning image of a single-layer graphene provided in Example 13 of the disclosure.
- a method for preparing a cured product containing a single layer of graphene including the following steps:
- step (c) Replace the graphite and the solidified material in step (a) with the expanded particulate material, and repeat steps (a) and (b) several times to obtain a solidified product containing a single layer of graphene.
- the cured material refers to a material capable of bonding graphite
- the graphite in the subsequent processing (step (b)), the graphite is peeled off by the bonding effect between the cured material and the graphite.
- the solidified material can be mixed with graphite and solidified to form.
- the role of solidified molding is to prepare shaped particles by mixing graphite with solidified material, so that the interface between graphite and solidified material has a close adhesion force, which is beneficial to the subsequent processing process.
- the graphite is exfoliated.
- the curing material is not specifically limited, and a typical but non-limiting curing material may be a thermoplastic polymer, flour, rice flour, or the like.
- Typical but non-limiting curing and molding methods include: extrusion molding, extrusion molding, sheet molding, or flow molding.
- the "optionally first solvent" mentioned in step (a) in the present disclosure means that the first solvent may or may not be added. Whether the first solvent is added needs to be determined according to the characteristics of the cured material. Generally speaking, when the curing material and graphite can form a viscous mixture during curing and molding, the first solvent does not need to be added; when the curing material and graphite cannot form a viscous mixture during curing and molding, it is necessary to add The first solvent.
- step (b) the molded particles obtained by curing and molding and optionally a second solvent are mixed to form a system, and the system is heated.
- the heating treatment can make the molded particles in a semi-melted state, and then pass into the system
- the gas is pressurized, and the pressure treatment makes the gas exert a certain force on the molding particles in the system, and penetrate into the softened molding particles.
- the pressure is suddenly released, the instantaneous pressure difference and strong impact are generated.
- the "optionally second solvent” in the present disclosure means that the second solvent may or may not be added. Whether to add the second solvent or not needs to be determined according to the characteristics of the shaped pellets. For the present disclosure, when the solidified material is puffable food such as flour or rice noodles, the second solvent does not need to be added, and in other cases, the second solvent needs to be added.
- the type of the second solvent in step (b) is not specifically limited, as long as it can isolate the molded particles to a certain degree so as not to cause adhesion.
- the purpose of injecting gas into the molding pellets and optionally the second solvent forming system is to maintain a certain pressure in the system.
- the type of gas to be added is not specifically limited. Typical but non-limiting can be conventional gas, such as air, oxygen, hydrogen, nitrogen, or carbon dioxide.
- the heating temperature and time and the pressurizing pressure and time need to be determined according to the characteristics of the molded pellets (for example, the softening temperature).
- Typical but non-limiting pressurized pressures are 0.2MPa, 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 5.0MPa, 10.0MPa, 15.0MPa, 20.0MPa, 25.0MPa, 30.0MPa, 35.0MPa, 40.0MPa, 45.0MPa, 50.0MPa, 55.0MPa or 60.0MPa.
- the pressurized pressure cannot be too low. When the pressurized pressure is lower than 0.2 MPa, it is difficult to realize the conversion of graphite to graphene.
- the pressurized pressure is too high, when it is higher than 60.0MPa, it will not further improve the conversion effect of graphite to graphene, but will consume more energy, which will increase the production cost.
- step (c) Since it is difficult to convert the graphite in the expanded particulate material into a single-layer graphene by only performing step (b) once, it is necessary to perform step (c), replacing the graphite and solidified material in step (a) with the expanded particulate material, and repeat the step ( After a) and (b) several times (for example, 10-60 times), a cured product containing single-layer graphene is obtained.
- step (a) and (b) the graphite and solidified material in step (a) need to be replaced with the expanded particulate material.
- the number of repeating steps (a) and (b) needs to be set according to the particle size of graphite in the expanded particulate material obtained in step (b) and the required single-layer graphene content.
- the larger the particle size of graphite the more times (a) and (b) need to be repeated.
- the smaller the particle size of graphite the more steps need to be repeated ( The fewer the number of a) and (b).
- the surface/volume resistivity tester can also be used to measure the resistance value of the expanded pellets.
- the repeat steps (a) and (b) can be terminated to obtain the content Cured product of single-layer graphene.
- the lower the electrical resistance of the cured product containing single-layer graphene the higher the mass fraction of graphite converted into single-layer graphene.
- the higher the electrical resistance of the cured product containing single-layer graphene the graphite will be converted into a single layer. The lower the mass fraction of graphene.
- the preparation method realizes the conversion of graphite to multilayer graphene and then to single-layer graphene in the formed particles by using the physical effect of gas on the formed particles, without any chemical reaction with graphite, thereby ensuring that the single-layer graphite is contained
- the purity of the cured product of olefin, and no pollutants will be generated during the whole preparation process, which is suitable for large-scale industrial preparation.
- the curing material includes any one of thermoplastic polymer, flour or rice flour;
- the thermoplastic polymer includes any one or a combination of at least two of resin, plastic, thermoplastic rubber, thermoplastic elastomer or hot melt adhesive;
- the resin includes any one or a combination of at least two of polyethylene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyvinyl chloride or polypropylene;
- the plastic includes any one or a combination of at least two of rigid thermoplastics, soft plastics or semi-rigid plastics;
- the thermoplastic rubber includes thermoplastic polyurethane elastomer rubber (TPU), Nitrile Butadiene Rubber (NBR), and styrene-butadiene block copolymer (styrene-butadiene block copolymer). copolymer, SBS), TPE or EPDM (Ethylene Propylene Diene Monomer, EPDM), or a combination of at least two;
- the thermoplastic elastomer includes thermoplastic polyester elastomer (TPEE), polyurethane (Polyurethane, PUR), thermoplastic vulcanizate (Thermoplastic Vulcanizate, TPV) or ether ester type thermoplastic elastomer Any one or a combination of at least two of the body (Thermoplastic Elastomer Ether-Ester, TEEE).
- TPEE thermoplastic polyester elastomer
- PUR polyurethane
- thermoplastic vulcanizate Thermoplastic Vulcanizate
- TEEE ether ester type thermoplastic elastomer Any one or a combination of at least two of the body
- the selection of the type of curing material can be determined according to actual production needs. For example, when a polyethylene material containing a single layer of graphene needs to be processed in actual production, then the cured material is selected as polyethylene.
- the graphite used in step (a) can be flake or powder, and the particle size of the graphite can be determined according to the application.
- the particle size of graphite is 20-12500 mesh; typical but non-limiting graphite particle size is 20 mesh, 30 mesh, 40 mesh, 50 mesh, 60 mesh , 80 mesh, 90 mesh, 100 mesh, 200 mesh, 400 mesh, 500 mesh, 800 mesh, 1000 mesh, 2000 mesh, 3000 mesh, 4000 mesh, 5000 mesh, 6000 mesh, 7000 mesh, 8000 mesh, 9000 mesh, 10000 Mesh, 11000 mesh, 12000 mesh, or 12500 mesh.
- the mass ratio of graphite to solidified material is (0.5-200): 100; a typical but non-limiting mass ratio of graphite to solidified material is 0.5: 100, 1:100, 5:100, 10:100, 20:100, 30:100, 40:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100, 120: 100, 150:100 or 200:100.
- the final product contains the solidified species of single-layer graphene and the content of single-layer graphene is appropriate, which is beneficial to its subsequent direct production and utilization.
- the first solvent includes water.
- the particle size of the shaped pellets is 0.2-10 mm.
- the typical but non-limiting particle size of the shaped pellets is 0.2mm, 1mm, 2mm, 4mm, 5mm, 6mm, 8mm or 10mm.
- the heating temperature is 50-880° C.
- the heating time is 5-60 min.
- Typical but non-limiting heating temperature is 50°C, 60°C, 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650 °C, 700°C, 750°C, 800°C, 850°C or 880°C.
- Typical but non-limiting heating time is 5min, 6min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min.
- the heating time can be set according to the softening temperature of different molding particles (or curing materials).
- the heating time of the molded particles is 10-50min; when the curing material is a thermoplastic elastomer, the heating time of the molded particles is 5-30min. ; When the solidified material is rice noodles, the heating time of the shaped pellets is 5-20min.
- the gas in step (b), includes any one or a combination of at least two of air, oxygen, hydrogen, carbon dioxide, or nitrogen.
- step (b) gas is introduced into the system for pressurization, and the pressurization pressure and time can be determined according to the softening temperature of different shaped particles.
- step (b) the pressurizing pressure is 0.3-50.0 MPa, and the pressurizing time is 5-70 min.
- Typical but non-limiting pressurized pressures are 0.3MPa, 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 5.0MPa, 10.0MPa, 15.0MPa, 20.0MPa, 25.0MPa, 30.0MPa, 35.0MPa, 40.0MPa, 45.0MPa or 50.0MPa; typical but non-limiting pressurization time is 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min or 70min.
- the gas can exert a certain force on the molded pellets.
- the pressure is suddenly released, it is beneficial to the formation of micropores in the molded pellets. Contribute to the conversion of graphite to single-layer graphene.
- step (b) the pressure is relieved to normal pressure, and the time for the pressure to be relieved to normal pressure is less than 1 min.
- the pressure relief time can be determined according to the different molding granules. Generally speaking, the shorter the pressure relief time, the better.
- normal pressure refers to one atmosphere.
- the rapid pressure release in a short time can make the gas have a stronger exfoliation effect on the graphite in the shaped particles, which is more conducive to the conversion of graphite to single-layer graphene.
- the second solvent in step (b), includes water and/or lubricant.
- “and/or” means that the second solvent includes only water, or only lubricant, or both water and lubricant.
- the lubricant in step (b), includes any one or a combination of at least two of paraffin wax, polyethylene wax, or calcium stearate.
- lubricant can prevent the adhesion of expanded granules and expanded granules.
- the method for preparing a cured product containing a single layer of graphene includes the following steps:
- step (c) Replace the graphite and solidified material in step (a) with the expanded particulate material, and repeat steps (a) and (b) several times to obtain a solidified product containing a single layer of graphene;
- the method for preparing a cured product containing a single-layer graphene includes the following steps:
- step (c) Replace the graphite and the solidified material in step (a) with the expanded particulate material, and repeat steps (a) and (b) several times to obtain a solidified product containing a single layer of graphene.
- the content of the single-layer graphene in the prepared cured product containing the single-layer graphene is higher.
- a cured product containing a single-layer graphene which is prepared by the above-mentioned method for preparing a cured product containing a single-layer graphene.
- the single-layer graphene in the cured product containing single-layer graphene imparts corresponding characteristics to the cured product, and the cured product containing single-layer graphene does not require further treatment and can be directly applied to industrial production, for example, it can be directly prepared to contain Plastic products of single-layer graphene, etc.
- the mass fraction of the single-layer graphene in the cured product containing the single-layer graphene is 20-99%.
- the typical but non-limiting mass fraction of single-layer graphene is, for example, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%. %, 65%, 70%, 75%, 80%, 85%, 90%, 92%, 95% or 99%.
- the solidified product containing the single-layer graphene is subjected to carbonization treatment, and the product obtained by the carbonization treatment is separated to obtain the single-layer graphene.
- the actual components in the solidified material containing single-layer graphene include the solidified material and single-layer graphene; and when the graphite in the solidified material is not completely converted into graphene, it contains The actual components in the solidified single-layer graphene include solidified materials, graphite, and single-layer graphene.
- Carbonization treatment is actually a high-temperature heating treatment on the cured product containing single-layer graphene. The carbonization treatment will carbonize the cured material (including graphite) in the cured product containing single-layer graphene into carbon materials. Single-layer graphene causes the impact. After the carbonization treatment, the carbon material is separated from the single-layer graphene to obtain the single-layer graphene.
- thermoplastic polymer when the curing material is a thermoplastic polymer, the type and molecular weight of the thermoplastic polymer directly affect the temperature and time of the carbonization treatment. Generally speaking, under the premise of the same type of thermoplastic polymer, if you want to keep the performance parameters of single-layer graphene basically the same, the larger the molecular weight of the thermoplastic polymer, the higher the carbonization temperature or the longer the carbonization time. .
- the preparation method has stable technology, simple operation, and is suitable for industrial large-scale production.
- the single-layer graphene prepared by the preparation method has high purity and excellent performance, and can be directly used in industrial production.
- the carbon material obtained after the carbonization treatment can also be graphitized, and the product after the graphitization treatment is mixed with the solidified material and optionally the first solvent.
- a cured product containing single-layer graphene is prepared.
- the cured product containing single-layer graphene is subjected to carbonization treatment, and then the products obtained by the carbonization treatment are separated according to specific gravity to obtain single-layer graphene.
- the temperature of the carbonization treatment is 200-500°C
- the time of the carbonization treatment is 0.5-3h
- typical but non-limiting carbonization temperatures are 200°C, 220°C, 240°C, 250°C , 260°C, 280°C, 300°C, 320°C, 340°C, 350°C, 380°C, 400°C, 420°C, 440°C, 450°C, 480°C or 500°C
- the typical but non-restrictive carbonization time is 0.5 h, 1h, 1.3h, 1.6h, 2.0h, 2.3h, 2.6h or 3.0h.
- the separation medium used for separation according to specific gravity is water. Since the specific gravity of the carbon material in the product obtained by the carbonization treatment is different from that of the single-layer graphene in water, water can be used to separate them. According to the different specific gravity of the carbon material in the product obtained by the carbonization treatment, aqueous solutions of different specific gravity can be prepared in the water to achieve the purpose of separation.
- the single-layer graphene By limiting the carbonization temperature, time, and the separation medium used in the specific gravity separation, the single-layer graphene can be sufficiently separated from the carbonized product, thereby improving the yield and purity of the single-layer graphene.
- a single-layer graphene which is prepared by the above-mentioned single-layer graphene preparation method.
- the single-layer graphene is prepared by using the above-mentioned single-layer graphene preparation method, which has high purity and excellent performance, and can be directly used in industrial production.
- a product containing single-layer graphene which is prepared by using the above-mentioned cured product containing the single-layer graphene or the above-mentioned single-layer graphene.
- This embodiment provides a method for preparing a cured product containing a single layer of graphene, which includes the following steps:
- step (c) Replace the graphite and polypropylene cured materials in step (a) with the expanded particles, and repeat steps (a) and (b) 28 times to obtain a cured product containing a single layer of graphene.
- This embodiment provides a method for preparing a cured product containing a single layer of graphene, which includes the following steps:
- step (c) Replace the graphite and polypropylene cured materials in step (a) with the expanded particulate material, and after repeating steps (a) and (b) 18 times, a cured product containing a single layer of graphene is obtained.
- This embodiment provides a method for preparing a cured product containing a single layer of graphene, which includes the following steps:
- step (c) Replace the graphite and polypropylene cured materials in step (a) with the expanded particles, and repeat steps (a) and (b) 28 times to obtain a cured product containing a single layer of graphene.
- This embodiment provides a method for preparing a cured product containing a single layer of graphene, which includes the following steps:
- step (c) Replace the graphite and polyurethane cured materials in step (a) with the expanded particles, and repeat steps (a) and (b) 22 times to obtain a cured product containing a single layer of graphene.
- This embodiment provides a method for preparing a cured product containing a single layer of graphene, which includes the following steps:
- step (c) Replace the graphite and polycarbonate cured materials in step (a) with the expanded particulate material, and after repeating steps (a) and (b) 14 times, a cured product containing a single layer of graphene is obtained.
- This embodiment provides a method for preparing a cured product containing a single layer of graphene, which includes the following steps:
- step (c) Replace the graphite and hot melt adhesive curing material in step (a) with the expanded particulate material, and repeat steps (a) and (b) 10 times to obtain a cured product containing a single layer of graphene.
- This embodiment provides a method for preparing a cured product containing a single layer of graphene, which includes the following steps:
- This embodiment provides a method for preparing a cured product containing a single layer of graphene.
- step (a) the flour is replaced with rice noodles, and the remaining steps and process parameters are the same as in Example 7.
- This embodiment provides a method for preparing a cured product containing a single layer of graphene.
- step (a) the mass ratio of graphite and polypropylene cured material is 50:100, and the remaining steps and process parameters are the same as in Example 1.
- This embodiment provides a method for preparing a cured product containing a single-layer graphene.
- the pressurizing pressure in step (b) is 60 MPa, and the remaining steps and process parameters are the same as those in the first embodiment.
- This embodiment provides a method for preparing a cured product containing a single layer of graphene.
- the pressurizing pressure is 20 MPa, and the remaining steps and process parameters are the same as those in the first embodiment.
- This embodiment provides a method for preparing a cured product containing a single layer of graphene, which includes the following steps:
- step (c) Replace the graphite and EPDM in step (a) with the expanded particles, and repeat steps (a) and (b) 15 times to obtain a cured product containing a single layer of graphene.
- This embodiment provides a method for preparing single-layer graphene.
- the solidified product containing single-layer graphene provided in Example 1 is used as a raw material for preparation, including the following steps:
- the solidified product containing single-layer graphene is subjected to carbonization treatment at a temperature of 350° C. and a carbonization treatment time of 30 min. Then, water is used to separate the carbonized product according to specific gravity to obtain a single-layer graphene.
- This embodiment provides a method for preparing single-layer graphene.
- the cured product containing single-layer graphene provided in Example 2 is used as a raw material for preparation.
- the specific preparation method is the same as that in Example 13.
- This embodiment provides a method for preparing single-layer graphene.
- the cured product containing single-layer graphene provided in Example 3 is used as a raw material for preparation.
- the specific preparation method is the same as that in Example 13.
- This embodiment provides a method for preparing single-layer graphene.
- the cured product containing single-layer graphene provided in Example 4 is used as a raw material for preparation.
- the specific preparation method is the same as that in Example 13.
- This embodiment provides a method for preparing a single-layer graphene, including the following steps:
- the solidified product containing single-layer graphene provided in Example 5 was subjected to carbonization treatment, the temperature of the carbonization treatment was 500°C, and the time of the carbonization treatment was 180 minutes, and then water was used to separate the carbonized product according to the specific gravity to obtain a single layer Graphene.
- This embodiment provides a method for preparing a single-layer graphene, including the following steps:
- the solidified product containing single-layer graphene provided in Example 6 was subjected to carbonization treatment, the temperature of the carbonization treatment was 260°C, and the time of the carbonization treatment was 45 minutes, and then water was used to separate the carbonized product according to the specific gravity to obtain a single layer Graphene.
- This embodiment provides a method for preparing a single-layer graphene, including the following steps:
- the solidified product containing single-layer graphene provided in Example 7 was subjected to carbonization treatment, the temperature of the carbonization treatment was 200°C, and the time of the carbonization treatment was 25 minutes, and then water was used to separate the carbonized product according to the specific gravity to obtain a single layer Graphene.
- This embodiment provides a method for preparing a single-layer graphene, including the following steps:
- Example 8 The solidified product containing single-layer graphene provided in Example 8 was subjected to carbonization treatment at a temperature of 180° C. and a carbonization treatment time of 18 minutes. Then, the carbonized product was separated according to specific gravity with water to obtain single-layer graphene.
- This embodiment provides a method for preparing single-layer graphene.
- the cured product containing single-layer graphene provided in Example 9 is used as a raw material for preparation.
- the specific preparation method is the same as that in Example 13.
- This embodiment provides a method for preparing single-layer graphene.
- the cured product containing single-layer graphene provided in Example 10 is used as a raw material for preparation.
- the specific preparation method is the same as that in Example 13.
- This embodiment provides a method for preparing single-layer graphene.
- the cured product containing single-layer graphene provided in Example 11 is used as a raw material for preparation.
- the specific preparation method is the same as that in Example 13.
- This embodiment provides a method for preparing single-layer graphene.
- the cured product containing single-layer graphene provided in Example 12 is used as a raw material for preparation.
- the specific preparation method is the same as that in Example 13.
- This comparative example provides a method for preparing a cured product containing graphene.
- the heating treatment is not performed in step (b), and the remaining steps and process parameters are the same as in Example 1.
- This comparative example provides a method for preparing a cured product containing graphene, which includes the following steps:
- This comparative example provides a method for preparing a cured product containing graphene.
- the pressurizing pressure in step (b) is 0.15 MPa, and the remaining steps and process parameters are the same as in Example 1.
- This comparative example provides a method for preparing graphene.
- the cured product containing graphene provided in Comparative Example 1 is used as a raw material for preparation.
- the specific preparation method is the same as that of Example 13.
- This comparative example provides a method for preparing graphene.
- the cured product containing graphene provided in comparative example 2 is used as a raw material for preparation.
- the specific preparation method is the same as that of Example 13.
- This comparative example provides a method for preparing graphene.
- the cured product containing graphene provided in Comparative Example 3 is used as a raw material for preparation.
- the specific preparation method is the same as that of Example 13.
- Example 13 a high-resolution transmission electron microscope (HRTEM) was used to scan the single-layer graphene provided in Example 13, as shown in FIG. 3. It can be seen from Figure 3 that the morphology of the single-layer graphene is clearer, and its cross-sectional structure is not an ideal straight line, and its thickness is about 0.18 nm.
- HRTEM transmission electron microscope
- thermoplastic polymer such as resin or hot melt adhesive is used as a curing material, mixed with graphite, pelletized by an extruder, and expanded and separated to obtain a cured product containing a single layer of graphene, and will contain a single layer of graphene After the solidified product is carbonized, the yield of the obtained single-layer graphene is very high.
- flour or rice flour as the curing material, after expansion and separation, the content of single-layer graphene in the cured product containing single-layer graphene is less.
- the cured product containing single-layer graphene is carbonized. Single-layer graphene can be obtained, but the purity of single-layer graphene is low.
- thermoplastic polymer is preferred.
- the method for preparing a cured product containing a single-layer graphene does not generate pollutants during the entire preparation process, and ensures the high purity of the cured product containing a single-layer graphene.
- the cured product containing single-layer graphene can be directly applied to industrial production, and can also be subjected to carbonization treatment and separation to obtain single-layer graphene.
- the preparation method has stable process, simple operation, and is suitable for industrial large-scale production.
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Abstract
提供一种含有单层石墨烯的固化物、单层石墨烯及其制备方法和含有单层石墨烯的制品。该含有单层石墨烯的固化物的制备方法包括,(a)将石墨和固化材料以及可选的第一溶剂混合,固化成型,得到成型颗粒料;(b)对成型颗粒料和可选的第二溶剂形成的体系进行加热,再通入气体进行加压,然后泄压,得到膨胀颗粒料;(c)已膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次,得到含有单层石墨烯的固化物。将含有单层石墨烯的固化物进行碳化处理,分离,得到单层石墨烯。该含有单层石墨烯的制品含有单层石墨烯的固化物或单层石墨烯。该石墨烯纯度高、性能优异,可直接用于工业化生产加工。
Description
本公开涉及石墨烯技术领域,尤其是涉及一种含有单层石墨烯的固化物、单层石墨烯及其制备方法和含有单层石墨烯的制品。
石墨烯(Graphene)是一种由碳原子以sp杂化轨道组成六角形呈蜂巢晶格的二维碳纳米材料,其具有优异的光学、电学、力学特性,在材料学、微纳加工、能源、生物医学和药物传递等方面具有重要的应用前景,被认为是一种未来革命性的材料。
石墨烯的制备方法有很多。但是通过现有方法所制备出来的石墨烯多为多层石墨烯(也可称为石墨烯微片),很难制备出单层的石墨烯,且制备过程中会产生大量的污染物,且制备规模较小,很难实现工业化规模生产。
有鉴于此,特提出本公开以解决上述技术问题中的至少一个。
公开内容
本公开的第一个目的在于提供一种含有单层石墨烯的固化物的制备方法,该制备方法可制备得到含有单层石墨烯的固化物,且制备过程中不会产生污染,适合于工业化规模生产。
本公开的第二个目的在于提供一种含有单层石墨烯的固化物,采用上述含有单层石墨烯的固化物的制备方法制得。
本公开的第三个目的在于提供一种单层石墨烯的制备方法,采用上述含有单层石墨烯的固化物制备得到单层石墨烯。
本公开的第四个目的在于提供一种单层石墨烯,采用上述单层石墨烯的制备方法制得。
本公开的第五个目的在于提供一种含有单层石墨烯的制品,采用上述含有单层石墨烯的固化物或上述单层石墨烯制得。
本公开提供的一种含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和固化材料以及可选地第一溶剂混合,使其固化成型,得到成型颗粒料;
(b)对成型颗粒料以及可选地第二溶剂形成的体系进行加热,再向体系中通入气体进行加压,加压的压力为0.2-60.0MPa,然后泄压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次后,得到含有单层石墨烯的固化物。
进一步的,在上述技术方案的基础之上,步骤(a)中,所述固化材料包括热塑性聚合物、面粉或米粉中的任意一种;
优选地,步骤(a)中,所述热塑性聚合物包括树脂、塑料、热塑性橡胶、热塑性弹性体或热熔胶中的任意一种或至少两种的组合;
优选地,步骤(a)中,所述树脂包括聚乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚碳酸酯、聚氯乙烯或聚丙烯中的任意一种或者至少两种的组合;
优选地,步骤(a)中,所述塑料包括硬质热塑性塑料、软质塑料或半硬质塑料中的任意一种或至少两种的组合;
优选地,步骤(a)中,所述热塑性橡胶包括TPU、NBR、SBS、TPE或EPDM中的任意一种或至少两种的组合;
优选地,步骤(a)中,所述热塑性弹性体包括TPEE、PUR、TPV或TEEE中的任意一种或至少两种的组合;
优选地,步骤(a)中,所述石墨的粒度为20-12500目;
优选地,步骤(a)中,所述石墨与固化材料的质量比为(0.5-200):100;
优选地,步骤(a)中,所述成型颗粒料的粒径为0.2-10mm。
进一步的,在上述技术方案的基础之上,步骤(b)中,加热的温度为50-880℃,加热的时间为5-60min;
优选地,步骤(b)中,所述气体包括空气、氧气、氢气、二氧化碳或氮气中的任意一种或至少两种的组合;
优选地,步骤(b)中,加压的压力为0.3-50.0MPa,加压的时间为5-70min;
优选地,步骤(b)中,泄压至常压,泄压至常压的时间小于1min。
进一步的,在上述技术方案的基础之上,步骤(a)中,所述第一溶剂包括水;
优选地,步骤(b)中,所述第二溶剂包括水和/或润滑剂。
进一步的,在上述技术方案的基础之上,所述含有单层石墨烯的固化物的制备方法包括以下步骤:
(a)将石墨和固化材料混合,使其挤出成型,得到成型颗粒料;其中,所述固化材料包括热塑性聚合物;
(b)将成型颗粒料和水形成的体系置于密闭的反应装置中进行加热,加热的温度为50-880℃,加热时间为5-60min,再向反应装置中通入气体进行加压,加压的压力为0.2-60.0MPa,加压的时间为5-50min,然后于1min内泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次后,得到含有单层石墨烯的固化物;
或,所述含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和固化材料以及水混合,使其固化成型,干燥,得到成型颗粒料;其中,所述固化材料包括面粉或米粉;
(b)将成型颗粒料中置于密闭的反应装置中进行加热,加热的温度为60-200℃,加热时间为5-60min,再向反应装置中通入气体进行加压,加压的压力为0.2-60.0MPa,加压的时间为5-50min,然后于1min内泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次后,得到含有单层石墨烯的固化物。
本公开还提供了一种含有单层石墨烯的固化物,采用上述含有单层石墨烯的固化物的制备方法制得;
优选地,所述含有单层石墨烯的固化物中单层石墨烯的质量分数为20-99%。
本公开还提供了一种单层石墨烯的制备方法,包括以下步骤:
将上述含有单层石墨烯的固化物进行碳化处理,对碳化处理得到的产物分离,得到单层石墨烯。
进一步的,在上述技术方案的基础之上,将含有单层石墨烯的固化物进行碳化处理,然后将碳化处理得到的产物按照比重进行分离,得到单层石墨烯;
优选地,所述碳化处理的温度为200-500℃,碳化处理的时间为0.08-3.0h;
优选地,按照比重进行分离时所采用的分离介质为水。
本公开还提供了一种单层石墨烯,采用上述单层石墨烯的制备方法制得。
本公开还提供了一种含有单层石墨烯的制品,采用上述含有单层石墨烯的固化物或上述单层石墨烯制得。
本公开提供的含有单层石墨烯的固化物、单层石墨烯及其制备方法和含有单层石墨烯的制品具有以下有益效果:
(1)本公开提供了一种含有单层石墨烯的固化物的制备方法,先将石墨和固化材料以及可选地第一溶剂混合固化成型,对固化成型得到的成型颗粒料和可选地第二溶剂形成的体系进行加热,再通入气体进行加压,在特定的压力下气体对成型颗粒料产生一定的作用力,并渗入到成型颗粒料内部,当突然泄压时,会产生瞬时的压差和强烈的冲击作用使得成型颗粒料产生大量的微孔并发生膨胀,在微孔形成过程中能够对成型颗粒料中的石墨进行强制剥离,将得到的膨胀颗粒料反复循环上述步骤若干次,就可实现成型颗粒料中石墨到单层石墨烯的转变,从而得到含有单层石墨烯的固化物;
该制备方法利用气体对于成型颗粒料的物理作用实现成型颗粒料中石墨到石墨烯的转变,而不会与石墨产生任何化学反应,从而保证了含有单层石墨烯的固化物的高纯度,且整个制备过程中不会产生污染物,可适用于工业上大规模制备。
(2)本公开提供了一种含有单层石墨烯的固化物,采用上述含有单层石墨烯的固化物的制备方法制得,该含有单层石墨烯的固化物可直接用于工业生产。
(3)本公开提供了一种单层石墨烯的制备方法,通过将含有单层石墨烯的固化物进行碳化处理,然后对碳化处理得到的产物再进行分离,得到 单层石墨烯。该制备方法工艺稳定,操作简单,且适合于工业上规模化生产,通过该制备方法制得的单层石墨烯的纯度高,性能优异。
(4)本公开提供了一种单层石墨烯,采用上述单层石墨烯的制备方法制得,该单层石墨烯纯度高,性能优异,可直接用于工业生产加工。
(5)本公开提供了一种含有单层石墨烯的制品,鉴于上述含有单层石墨烯的固化物或单层石墨烯所具有的优势,使得以其作为原料的含有单层石墨烯的制品具有同样的优势。
为了更清楚地说明本公开具体实施方式或现有技术中的技术方案,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本公开的一些实施方式,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本公开实施例1提供的成型颗粒料的形态图;
图2为本公开实施例1提供的膨胀颗粒料的形态图;
图3为本公开实施例13提供的单层石墨烯的高分辨透射电子显微镜扫描图。
下面将结合实施例对本公开的技术方案进行清楚、完整地描述,显然,所描述的实施例是本公开一部分实施例,而不是全部的实施例。基于本公开中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本公开保护的范围。
根据本公开的第一个方面,提供了一种含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和固化材料以及可选地第一溶剂混合,使其固化成型,得到成型颗粒料;
(b)对成型颗粒料以及可选地第二溶剂形成的体系进行加热,再向体系中通入气体进行加压,加压的压力为0.2-60.0MPa,然后泄压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次后,得到含有单层石墨烯的固化物。
步骤(a)中,固化材料是指能够粘合石墨,并在后续处理过程中(步骤(b))利用固化材料与石墨之间的粘合作用对石墨进行剥离的材料。该固化材料可以与石墨混合并固化成型,固化成型的作用是通过将石墨与固化材料混合制得成型颗粒料,使得石墨与固化材料界面之间具有紧密的粘合力,从而有利于后续处理过程中(步骤(b))对石墨进行剥离。
在本公开中,固化材料不作具体限定,典型但非限制性的固化材料可以为热塑性聚合物、面粉或米粉等。
典型但非限制性的固化成型的方式包括:挤出成型、挤压成型、压片成型或流压成型等。
需要说明的是,本公开中步骤(a)中所述“可选地第一溶剂”是指第一溶剂可以加入,也可以不加入。第一溶剂是否加入需要根据固化材料的特性进行确定。一般而言,当固化材料与石墨在固化成型时能够形成粘性的混合料时,则不需要加入第一溶剂;当固化材料与石墨在固化成型时不能够形成粘性的混合料时,则需要加入第一溶剂。
步骤(b)中,将固化成型得到的成型颗粒料和可选地第二溶剂混合形成体系,对体系进行加热处理,加热处理可以使得成型颗粒料处于半融化状态,然后再向体系中通入气体进行加压,加压处理使得气体对体系中的成型颗粒料产生一定的作用力,并渗入到软化的成型颗粒料内部,当突然泄压时,所产生瞬时的压力差和强烈的冲击作用使得成型颗粒料发生膨胀并产生大量的微孔。由于成型颗粒料中的固化材料与石墨界面之间具有一定的粘合力,故成型颗粒料中的固化材料在形成的微孔过程中会对成型颗粒料中的石墨进行强制剥离,从而得到膨胀颗粒料。
需要说明的是,本公开中所述“可选地第二溶剂”是指第二溶剂可以加入,也可以不加入。第二溶剂是否加入需要根据成型颗粒料的特性进行确定。对于本公开,当固化材料为面粉或米粉等可膨化食物时,则不需要加入第二溶剂,其余情况则需要加入第二溶剂。步骤(b)中第二溶剂的种类不作具体限定,只要能够对成型颗粒料之间进行一定的隔离,使其不会产生粘连即可。
向成型颗粒料和可选地第二溶剂形成体系通入气体的目的是使得体系保持一定的压力。所加入的气体的种类不作具体限定,典型但非限制性可以为常规气体,例如空气、氧气、氢气、氮气或二氧化碳等。
加热的温度和时间以及加压的压力和时间,需要根据成型颗粒料的特性(例如软化温度)进行确定。典型但非限制性的加压的压力为0.2MPa、0.5MPa、1.0MPa、1.5MPa、2.0MPa、5.0MPa、10.0MPa、15.0MPa、20.0MPa、25.0MPa、30.0MPa、35.0MPa、40.0MPa、45.0MPa、50.0MPa、55.0MPa或60.0MPa。加压的压力不能过低,当加压的压力低于0.2MPa,则很难实现石墨向石墨烯的转变。加压的压力过高,当高于60.0MPa时,不会进一步提升石墨向石墨烯的转化效果,反而会耗费更多的能源,从而使得生产成本增加。
由于只进行一次步骤(b)很难实现膨胀颗粒料中石墨转化为单层石墨烯,故需要进行步骤(c),将膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次(例如10-60次)后,得到含有单层石墨烯的固化物。
需要说明的是,在首次得到膨胀颗粒料之后,以后每次重复步骤(a)和(b)时,均需要将步骤(a)中的石墨和固化材料替换为膨胀颗粒料。重复步骤(a)和(b)的次数,需要根据步骤(b)得到的膨胀颗粒料中石墨的粒度以及所需单层石墨烯的含量设定。当膨胀颗粒料中单层石墨烯的含量固定时,石墨的粒度越大,所需要重复步骤(a)和(b)的次数越多,相反,石墨的粒度越小,则所需要重复步骤(a)和(b)的次数越少。
对膨胀颗粒料中石墨烯或石墨的含量进行检测,当膨胀颗粒料中石墨转化为单层石墨烯的质量分数达到10-90%(例如当质量分数为10%,即有10%的石墨转化为单层石墨烯;例如当质量分数为90%,即有90%的石墨转化为单层石墨烯),即可终止重复步骤(a)和(b),从而得到含有单层石墨烯的固化物。
也可以采用表面/体积电阻率测试仪来测定膨胀颗粒料的电阻值,当循环前后膨胀颗粒料的电阻值基本不再发生变化时,即可终止重复步骤(a)和(b),得到含有单层石墨烯的固化物。一般说来,含有单层石墨烯的固化物的电阻越低,石墨转化为单层石墨烯的质量分数越高,反之含有单层石墨烯的固化物的电阻越高,则石墨转化为单层石墨烯的质量分数越低。
该制备方法通过利用气体对成型颗粒料的物理作用实现成型颗粒料中石墨到多层石墨烯进而到单层石墨烯的转变,而不会与石墨产生任何化学反应,从而保证了含有单层石墨烯的固化物的纯度,且整个制备过程中不会产生污染物,适用于工业上大规模制备。
作为本公开的一种可选实施方式,步骤(a)中,固化材料包括热塑性聚合物、面粉或米粉中的任意一种;
优选地,步骤(a)中,热塑性聚合物包括树脂、塑料、热塑性橡胶、热塑性弹性体或热熔胶中的任意一种或至少两种的组合;
优选地,步骤(a)中,树脂包括聚乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚碳酸酯、聚氯乙烯或聚丙烯中的任意一种或者至少两种的组合;
优选地,步骤(a)中,塑料包括硬质热塑性塑料、软质塑料或半硬质塑料中的任意一种或至少两种的组合;
优选地,步骤(a)中,热塑性橡胶包括热塑性聚氨酯弹性体橡胶(Thermoplastic polyurethanes,TPU)、丁腈橡胶(Nitrile Butadiene Rubber,NBR)、苯乙烯-丁二烯嵌段共聚物(styrene-butadiene block copolymer,SBS)、TPE或三元乙丙橡胶(Ethylene Propylene Diene Monomer,EPDM)中的任意一种或至少两种的组合;
优选地,步骤(a)中,所述热塑性弹性体包括热塑性聚酯弹性体(Thermoplastic polyester elastomer,TPEE)、聚氨酯(Polyurethane,PUR)、热塑性硫化橡胶(Thermoplastic Vulcanizate,TPV)或醚酯型热塑弹性体(Thermoplastic Elastomer Ether-Ester,TEEE)中的任意一种或至少两种的组合。
通过对固化材料具体种类的限定,使得其与石墨能够达到良好的固化效果。且固化材料种类的选定,可根据实际生产需要进行确定。例如,当实际生产中需要对含有单层石墨烯的聚乙烯材料进行加工时,此时固化材料就选为聚乙烯。
步骤(a)中所采用的石墨可以为鳞片状或粉状,石墨的粒度大小可以根据用途而定。作为本公开的一种可选实施方式,步骤(a)中,石墨的粒度为20-12500目;典型但非限制性的石墨的粒度为20目、30目、40目、50目、60目、80目、90目、100目、200目、400目、500目、800目、1000 目、2000目、3000目、4000目、5000目、6000目、7000目、8000目、9000目、10000目、11000目、12000目或12500目。
通过对石墨的粒度的进一步限定,使得石墨与固化材料可以达到良好的混合。
作为本公开的一种可选实施方式,步骤(a)中,石墨与固化材料的质量比为(0.5-200):100;石墨与固化材料典型但非限制性的质量比为0.5:100、1:100、5:100、10:100、20:100、30:100、40:100、50:100、60:100、70:100、80:100、90:100、100:100、120:100、150:100或200:100。
通过对石墨与固化材料的质量比的具体限定,使得最终产品含有单层石墨烯的固化物种单层石墨烯的含量适宜,有利于其后续直接生产利用。
作为本公开的一种可选实施方式,步骤(a)中,第一溶剂包括水。
作为本公开的一种可选实施方式,步骤(a)中,成型颗粒料的粒径为0.2-10mm。
成型颗粒料典型但非限制性的粒径为0.2mm、1mm、2mm、4mm、5mm、6mm、8mm或10mm。
作为本公开的一种可选实施方式,步骤(b)中,加热的温度为50-880℃,加热的时间为5-60min。
典型但非限制性的加热的温度为50℃、60℃、100℃、150℃、200℃、250℃、300℃、350℃、400℃、450℃、500℃、550℃、600℃、650℃、700℃、750℃、800℃、850℃或880℃。典型但非限制性的加热的时间为5min、6min、10min、15min、20min、25min、30min、35min、40min、45min、50min、55min或60min。
加热的时间可根据不同成型颗粒料(或固化材料)的软化温度进行设定。典型但非限制性的例如,当固化材料为聚乙烯时,此时成型颗粒料的加热时间为10-50min;当固化材料为热塑性弹性体的时候,此时成型颗粒的加热时间为5-30min;当固化材料为米粉时,此时成型颗粒料的加热时间为5-20min。
作为本公开的一种可选实施方式,步骤(b)中,气体包括空气、氧气、氢气、二氧化碳或氮气中的任意一种或至少两种的组合。
需要说明的是,在选用不同种类的气体混合时,需保证混合气体中各气体含量处于安全用量范围内,以确保不会产生潜在安全风险。
通过对气体种类的具体限定,使得其不会与石墨产生任何反应,保证了含有单层石墨烯的固化物的纯度。
步骤(b)中,向体系中通入气体进行加压,加压的压力以及时间可根据不同成型颗粒料的软化温度来确定。
作为本公开的一种可选实施方式,步骤(b)中,加压的压力为0.3-50.0MPa,加压的时间为5-70min。
典型但非限制性的加压的压力为0.3MPa、0.5MPa、1.0MPa、1.5MPa、2.0MPa、5.0MPa、10.0MPa、15.0MPa、20.0MPa、25.0MPa、30.0MPa、35.0MPa、40.0MPa、45.0MPa或50.0MPa;典型但非限制性的加压的时间为5min、10min、15min、20min、25min、30min、35min、40min、45min、50min、55min、60min、65min或70min。
通过对加热的温度和时间以及加压的压力和时间的限定,使得气体可对成型颗粒料产生一定的作用力,当突然泄压后,有利于在成型颗粒料中微孔的形成,从而有助于石墨向单层石墨烯的转化。
作为本公开的一种可选实施方式,步骤(b)中,泄压至常压,泄压至常压的时间小于1min。
可根据成型颗粒料的不同来确定泄压时间。一般而言,泄压时间越短越好。
需要说明的是,常压是指一个大气压。短时间内快速泄压,可使得气体对于成型颗粒料中石墨的剥离作用更强,更有利于石墨向单层石墨烯的转化。
作为本公开的一种可选实施方式,步骤(b)中,第二溶剂包括水和/或润滑剂。此处的“和/或”是指第二溶剂只包括水,或者只包括润滑剂,或者同时包括水和润滑剂。
作为本公开的一种可选实施方式,步骤(b)中,润滑剂包括石蜡、聚乙烯蜡或硬脂酸钙中的任意一种或至少两种的组合。
润滑剂的加入,可防止膨胀颗粒料与膨胀颗粒料的粘连。
作为本公开的一种可选实施方式,含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和固化材料混合,使其挤出成型,得到成型颗粒料;其中,固化材料包括热塑性聚合物;
(b)将成型颗粒料和水形成的体系置于密闭的反应装置中进行加热,加热的温度为50-880℃,加热时间为5-60min,再向反应装置中通入气体进行加压,加压的压力为0.2-60.0MPa,加压的时间为5-50min,然后于1min内泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次后,得到含有单层石墨烯的固化物;
或,所述含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和固化材料以及水混合,使其固化成型,干燥,得到成型颗粒料;其中,所述固化材料包括面粉或米粉;
(b)将成型颗粒料中置于密闭的反应装置中进行加热,加热的温度为60-200℃,加热时间为5-60min,再向反应装置中通入气体进行加压,加压的压力为0.2-60.0MPa,加压的时间为5-50min,然后于1min内泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次后,得到含有单层石墨烯的固化物。
通过对含有单层石墨烯的固化物的制备方法的进一步限定,使所制得的含有单层石墨烯的固化物中单层石墨烯的含量较高。
根据本公开的第二个方面,还提供了一种含有单层石墨烯的固化物,采用上述含有单层石墨烯的固化物的制备方法制得。
该含有单层石墨烯的固化物中的单层石墨烯赋予该固化物相应的特性,且该含有单层石墨烯的固化物无需进一步处理,可直接应用于工业生产,例如可直接制备成含有单层石墨烯的塑料制品等。
作为本公开的一种可选实施方式,含有单层石墨烯的固化物中单层石墨烯的质量分数为20-99%。
在含有单层石墨烯的固化物中,单层石墨烯典型但非限制性的质量分数例如为20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、80%、85%、90%、92%、95%或99%。
根据本公开的第三个方面,还提供了一种单层石墨烯的制备方法,包括以下步骤:
将上述含有单层石墨烯的固化物进行碳化处理,对碳化处理得到的产物分离,得到单层石墨烯。
当固化材料中的石墨完全转化为石墨烯时,含有单层石墨烯的固化物中的实际成分包括固化材料和单层石墨烯;而当固化材料中的石墨没有完全转化为石墨烯时,含有单层石墨烯的固化物中的实际成分包括固化材料、石墨和单层石墨烯。碳化处理,实际上就是对含有单层石墨烯的固化物进行高温加热处理,碳化处理会将含有单层石墨烯的固化物中的固化材料(包括石墨)碳化变为碳材料,而不会对单层石墨烯造成影响。碳化处理后,再将碳材料与单层石墨烯进行分离,即可得到单层石墨烯。
需要说明的是,当固化材料为热塑性聚合物时,热塑性聚合物的种类以及分子量的大小直接影响着碳化处理的温度以及时间。一般而言,在相同的热塑性聚合物种类的前提下,若想使得单层石墨烯的性能参数基本保持一致,热塑性聚合物的分子量越大,所需要的碳化处理温度越高或碳化时间越长。
该制备方法工艺稳定,操作简单,且适合于工业上规模化生产,通过该制备方法制得的单层石墨烯的纯度高,性能优异,可直接用于工业生产使用。
碳化处理后得到的碳材料还可进行石墨化处理,石墨化处理后的产物再与固化材料与可选地第一溶剂混合,根据本公开提供的含有单层石墨烯的固化物的制备方法,制备含有单层石墨烯的固化物。
作为本公开的一种可选实施方式,将含有单层石墨烯的固化物进行碳化处理,然后将碳化处理得到的产物按照比重进行分离,得到单层石墨烯。
作为本公开的一种可选实施方式,碳化处理的温度为200-500℃,碳化处理的时间为0.5-3h;典型但非限制性的碳化温度为200℃、220℃、240℃、250℃、260℃、280℃、300℃、320℃、340℃、350℃、380℃、400℃、420℃、440℃、450℃、480℃或500℃,典型但非限制性的碳化时间为0.5h、1h、1.3h、1.6h、2.0h、2.3h、2.6h或3.0h。
优选地,按照比重进行分离时所采用的分离介质为水。由于碳化处理得到的产物中碳材料与单层石墨烯在水中的比重有差别,故可采用水对其进行分离。根据碳化处理得到的产物中碳材料的比重不同,可以在水中配制不同比重的水溶液,从而达到分离的目的。
通过对碳化温度、时间以及采用比重分离时所采用的分离介质的限定,使得单层石墨烯可以从碳化后的产物中较为充分的分离出来,从而提高单层石墨烯的收率以及纯度。
根据本公开的第四个方面,还提供了一种单层石墨烯,采用上述单层石墨烯的制备方法制得。
采用上述单层石墨烯的制备方法制得,该单层石墨烯纯度高,性能优异,可直接用于工业生产。
根据本公开的第五个方面,还提供了一种含有单层石墨烯的制品,采用上述含有单层石墨烯的固化物或上述单层石墨烯制得。
含有单层石墨烯的制品有很多,例如为含有单层石墨烯的医用聚乙烯制品、含有单层石墨烯的ABS复合材料等。
鉴于上述含有单层石墨烯的固化物或单层石墨烯所具有的优势,其可赋予以其作为原料的含有单层石墨烯的制品具有同样的优势。
为了说明本公开所能达到的技术效果,特设以下实施例和对比例。
需要说明的是,实施例和对比例中所用到的原料来源如下:石墨均购自青岛金涛石墨有限公司(型号:80目);聚丙烯购自台塑工业(宁波)有限公司(型号:PP1120);聚碳酸酯购自科思创聚合物(中国)有限公司(型号:PC1703);热熔胶购自无锡莱恩科技有限公司(型号:LE-211)。
实施例1
本实施例提供一种含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和聚丙烯固化材料混合后,置于挤出机中进行挤出成型,得到直径为3mm且长度为3mm的成型颗粒料,具体如图1所示;其中,石墨和聚丙烯固化材料的质量比为30:100,石墨的平均粒度为100目,聚丙烯固化材料的重均分子量为1500;
(b)将成型颗粒料加入至反应釜中,然后加入水(成型颗粒料与水的质量比为100:60)并对反应釜进行加热,加热的温度为85℃,加热的时间为20min,然后通入空气进行加压,加压的压力为1.4MPa,加压的时间为15min,然后保压10min,于1s内快速泄压至常压,得到膨胀颗粒料,具体如图2所示;
(c)将膨胀颗粒料替换步骤(a)中的石墨和聚丙烯固化材料,重复步骤(a)和(b)28次后,得到含有单层石墨烯的固化物。
实施例2
本实施例提供一种含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和聚丙烯固化材料混合后,置于挤出机中进行挤出成型,得到直径为3mm且长度为3mm成型颗粒料;其中,石墨和聚丙烯固化材料的质量比为50:100,石墨的平均粒度为1500目,聚丙烯的重均分子量为8000;
(b)将成型颗粒料加入至反应釜中,然后加入水(成型颗粒料与水的质量比为100:60)并对反应釜进行加热,加热的温度为125℃,加热的时间为10min,然后通入空气进行加压,加压的压力为4MPa,加压的时间为25min,然后保压20min,于1s内快速泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和聚丙烯固化材料,重复步骤(a)和(b)18次后,得到含有单层石墨烯的固化物。
实施例3
本实施例提供一种含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和聚丙烯固化材料混合后,置于挤出机中进行挤出成型,得到直径为3mm且长度为3mm成型颗粒料;其中,石墨和聚丙烯固化材料的质量比为50:100,石墨的平均粒度为1500目,聚丙烯的重均分子量为10000;
(b)将成型颗粒料加入至反应釜中,然后加入水(成型颗粒料与水的质量比为100:60)并对反应釜进行加热,加热的温度为125℃,加热的时间为20min,然后通入空气进行加压,加压的压力为12MPa,加压的时间为20min,然后保压10min,于1s内快速泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和聚丙烯固化材料,重复步骤(a)和(b)28次后,得到含有单层石墨烯的固化物。
实施例4
本实施例提供一种含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和聚氨酯固化材料混合后,置于挤出机中进行挤出成型,得到直径为3mm且长度为3mm成型颗粒料;其中,石墨和聚氨酯固化材料的质量比为60:100,石墨的平均粒度为1500目,聚氨酯的重均分子量为10000;
(b)将成型颗粒料加入至反应釜中,然后加入水(成型颗粒料与水的质量比为100:60)并对反应釜进行加热,加热的温度为65℃,加热的时间为12min,然后通入空气进行加压,加压的压力为3MPa,加压的时间为11min,然后保压8min,于1s内快速泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和聚氨酯固化材料,重复步骤(a)和(b)22次后,得到含有单层石墨烯的固化物。
实施例5
本实施例提供一种含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和聚碳酸酯固化材料混合后,置于挤出机中进行挤出成型,得到直径为3mm且长度为3mm的成型颗粒料;其中,石墨和聚碳酸酯固化材料的质量比为50:100,石墨的平均粒度为2500目,聚碳酸酯固化材料的重均分子量为20000;
(b)将成型颗粒料加入至反应釜中,然后加入水(成型颗粒料与水的质量比为100:60)并对反应釜进行加热,加热的温度为150℃,加热的时间为65min,然后通入空气进行加压,加压的压力为57MPa,加压的时间为70min,然后保压70min,于2s快速泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和聚碳酸酯固化材料,重复步骤(a)和(b)14次后,得到含有单层石墨烯的固化物。
实施例6
本实施例提供一种含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和热熔胶固化材料混合后,置于挤出机中进行挤出成型,得到直径为5mm且长度为5mm的成型颗粒料;其中,石墨和热熔胶固化材料的质量比为40:100,石墨的平均粒度为5000目,热熔胶的重均分子量为100000;
(b)将成型颗粒料加入至反应釜中,然后加入水(成型颗粒料与水的质量比为100:60)并对反应釜进行加热,加热的温度为70℃,加热的时间为8min,然后通入空气进行加压,加压的压力为1.2MPa,加压的时间为7min,然后保压4min,于1s内快速泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和热熔胶固化材料,重复步骤(a)和(b)10次后,得到含有单层石墨烯的固化物。
实施例7
本实施例提供一种含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨、面粉和水混合后,置于面条机中进行拉条切粒,然后干燥,得到成型颗粒料;其中,石墨、面粉和水的质量比为30:100:35,石墨的平均粒度为4000目;
(b)将成型颗粒料加入至反应釜中,并对反应釜进行加热,加热的温度为100℃,加热的时间为10min,然后通入空气进行加压,加压的压力为1.5MPa,加压的时间为3min,然后保压5min,于0.5s内快速泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和面粉,重复步骤(a)和(b)14次后,得到含有单层石墨烯的固化物。
实施例8
本实施例提供一种含有单层石墨烯的固化物的制备方法,步骤(a)中将面粉替换为米粉,其余步骤以及工艺参数与实施例7相同。
实施例9
本实施例提供一种含有单层石墨烯的固化物的制备方法,步骤(a)石墨和聚丙烯固化材料的质量比为50:100,其余步骤以及工艺参数与实施例1相同。
实施例10
本实施例提供一种含有单层石墨烯的固化物的制备方法,步骤(b)加压的压力为60MPa,其余步骤以及工艺参数与实施例1相同。
实施例11
本实施例提供一种含有单层石墨烯的固化物的制备方法,步骤(b)加压的压力为20MPa,其余步骤以及工艺参数与实施例1相同。
实施例12
本实施例提供一种含有单层石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和三元乙丙橡胶固化材料混合后,置于挤出机中进行挤出成型,得到直径为5mm且长度为5mm的成型颗粒料;其中,石墨和三元乙丙橡胶固化材料的质量比为40:100,石墨的平均粒度为5000目,三元乙丙橡胶的门尼粘度为45N·m;
(b)将成型颗粒料加入至反应釜中,然后加入水(成型颗粒料与水的质量比为100:60)并对反应釜进行加热,加热的温度为95℃,加热的时间为8min,然后通入空气进行加压,加压的压力为1.6MPa,加压的时间为15min,然后保压4min,于0.5min内快速泄压至常压,得到膨胀颗粒料;
(c)将膨胀颗粒料替换步骤(a)中的石墨和三元乙丙橡胶固化材料,重复步骤(a)和(b)15次后,得到含有单层石墨烯的固化物。
实施例13
本实施例提供了一种单层石墨烯的制备方法,采用实施例1提供的含有单层石墨烯的固化物为原料进行制备,包括以下步骤:
将含有单层石墨烯的固化物进行碳化处理,碳化处理温度为350℃,碳化处理时间为30min,然后采用水将碳化处理后的产物按照比重进行分离,得到单层石墨烯。
实施例14
本实施例提供了一种单层石墨烯的制备方法,采用实施例2提供的含有单层石墨烯的固化物为原料进行制备,具体制备方法与实施例13相同。
实施例15
本实施例提供了一种单层石墨烯的制备方法,采用实施例3提供的含有单层石墨烯的固化物为原料进行制备,具体制备方法与实施例13相同。
实施例16
本实施例提供了一种单层石墨烯的制备方法,采用实施例4提供的含有单层石墨烯的固化物为原料进行制备,具体制备方法与实施例13相同。
实施例17
本实施例提供了一种单层石墨烯的制备方法,包括以下步骤:
将实施例5提供的含有单层石墨烯的固化物进行碳化处理,碳化处理的温度为500℃,碳化处理的时间为180min,然后采用水将碳化处理后的产物按照比重进行分离,得到单层石墨烯。
实施例18
本实施例提供了一种单层石墨烯的制备方法,包括以下步骤:
将实施例6提供的含有单层石墨烯的固化物进行碳化处理,碳化处理的温度为260℃,碳化处理的时间为45min,然后采用水将碳化处理后的产物按照比重进行分离,得到单层石墨烯。
实施例19
本实施例提供了一种单层石墨烯的制备方法,包括以下步骤:
将实施例7提供的含有单层石墨烯的固化物进行碳化处理,碳化处理的温度为200℃,碳化处理的时间为25min,然后采用水将碳化处理后的产物按照比重进行分离,得到单层石墨烯。
实施例20
本实施例提供了一种单层石墨烯的制备方法,包括以下步骤:
将实施例8提供的含有单层石墨烯的固化物进行碳化处理,碳化处理温度为180℃,碳化处理时间为18min,然后采用水将碳化后的产物按照比重进行分离,得到单层石墨烯。
实施例21
本实施例提供了一种单层石墨烯的制备方法,采用实施例9提供的含有单层石墨烯的固化物为原料进行制备,具体制备方法与实施例13相同。
实施例22
本实施例提供了一种单层石墨烯的制备方法,采用实施例10提供的含有单层石墨烯的固化物为原料进行制备,具体制备方法与实施例13相同。
实施例23
本实施例提供了一种单层石墨烯的制备方法,采用实施例11提供的含有单层石墨烯的固化物为原料进行制备,具体制备方法与实施例13相同。
实施例24
本实施例提供了一种单层石墨烯的制备方法,采用实施例12提供的含有单层石墨烯的固化物为原料进行制备,具体制备方法与实施例13相同。
对比例1
本对比例提供了一种含有石墨烯的固化物的制备方法,步骤(b)中未进行加热处理,其余步骤以及工艺参数与实施例1相同。
对比例2
本对比例提供了一种含有石墨烯的固化物的制备方法,包括以下步骤:
(a)将石墨和聚丙烯固化材料混合,使其成为成型浆料;其中,聚丙烯固化材料的,石墨和聚丙烯固化材料的质量比为30:100,石墨的平均粒度为100目,聚丙烯固化材料的重均分子量为1500;
(b)将成型浆料加入至反应釜中,其余步骤以及工艺参数与实施例1相同。
对比例3
本对比例提供了一种含有石墨烯的固化物的制备方法,步骤(b)加压的压力为0.15MPa,其余步骤以及工艺参数与实施例1相同。
对比例4
本对比例提供一种石墨烯的制备方法,采用对比例1提供的含有石墨烯的固化物为原料进行制备,具体制备方法与实施例13相同。
对比例5
本对比例提供一种石墨烯的制备方法,采用对比例2提供的含有石墨烯的固化物为原料进行制备,具体制备方法与实施例13相同。
对比例6
本对比例提供一种石墨烯的制备方法,采用对比例3提供的含有石墨烯的固化物为原料进行制备,具体制备方法与实施例13相同。
为验证上述各实施例和对比例的技术效果,特设以下实验例。
实验例1
以实施例13为例,采用高分辨透射电子显微镜(HRTEM)对实施例13提供的单层石墨烯对其进行扫描,具体如图3所示。从图3中可以看出单层石墨烯形貌较清晰,其剖面结构并不是理想的笔直直线,其厚度约为0.18nm左右。
对各实施例13-24和对比例4-6提供的单层石墨烯或石墨烯的平均厚度、透光率、收率和纯度进行检测,具体如表1所示。
表1
实验组别 | 平均厚度 | 透光率(%) | 收率(%) | 纯度(%) |
实施例13 | 0.18nm | 97.5 | 85 | 96 |
实施例14 | 0.19nm | 95.5 | 84 | 94 |
实施例15 | 0.21nm | 93.0 | 81 | 91 |
实施例16 | 0.19nm | 97.0 | 82 | 95 |
实施例17 | 0.18nm | 96.5 | 82 | 96 |
实施例18 | 0.18nm | 97.5 | 79 | 97 |
实施例19 | 0.18nm | 96.5 | 81 | 91 |
实施例20 | 0.18nm | 96.5 | 82 | 92 |
实施例21 | 0.18nm | 97.5 | 79 | 87 |
实施例22 | 0.18nm | 97.5 | 87 | 98 |
实施例23 | 0.18nm | 97.5 | 86 | 97 |
实施例24 | 0.18nm | 97.5 | 85 | 96 |
对比例4 | 150μm | 10 | 0 | 0 |
对比例5 | 9μm | 25 | 0 | 0 |
对比例6 | 150μm | 10 | 0 | 0 |
从表1中数据可以看出,本公开各实施例提供的单层石墨烯的制备方法整体要优于对比例。
具体的,以树脂或热熔胶等热塑性聚合物作为固化材料,与石墨混合后经过挤出机造粒,经过膨胀分离,能得到含有单层石墨烯的固化物,且将含有单层石墨烯的固化物进行碳化处理后,所得到的单层石墨烯的收率非常高。而以面粉或米粉作为固化材料,经过膨胀分离,所得到含有单层石墨烯的固化物中单层石墨烯的含量较少,相应的将含有单层石墨烯的固化物进行碳化处理后,虽然能获得单层石墨烯,但单层石墨烯的纯度较低。这主要是由于热塑性聚合物与石墨通过挤出机挤压造粒后,两者之间粘合力较高,而面粉或者米粉达不到挤出机造粒造成的粘合力。故在选择固化材料时,优选为热塑性聚合物。
最后应说明的是:以上各实施例仅用以说明本公开的技术方案,而非对其限制;尽管参照前述各实施例对本公开进行了详细的说明,本领域的 普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本公开各实施例技术方案的范围。
本公开提供的含有单层石墨烯的固化物的制备方法,整个制备过程中不会产生污染物,保证了含有单层石墨烯的固化物的高纯度。且该含有单层石墨烯的固化物可直接应用于工业生产,也可进行碳化处理,分离,得到单层石墨烯。该制备方法工艺稳定,操作简单,且适合于工业上规模化生产。
Claims (10)
- 一种含有单层石墨烯的固化物的制备方法,其特征在于,包括以下步骤:(a)将石墨和固化材料以及可选地第一溶剂混合,使其固化成型,得到成型颗粒料;(b)对成型颗粒料以及可选地第二溶剂形成的体系进行加热,再向体系中通入气体进行加压,加压的压力为0.2-60.0MPa,然后泄压,得到膨胀颗粒料;(c)将膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次后,得到含有单层石墨烯的固化物。
- 根据权利要求1所述的含有单层石墨烯的固化物的制备方法,其特征在于,步骤(a)中,所述固化材料包括热塑性聚合物、面粉或米粉中的任意一种;优选地,步骤(a)中,所述热塑性聚合物包括树脂、塑料、热塑性橡胶、热塑性弹性体或热熔胶中的任意一种或至少两种的组合;优选地,步骤(a)中,所述树脂包括聚乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚碳酸酯、聚氯乙烯或聚丙烯中的任意一种或者至少两种的组合;优选地,步骤(a)中,所述塑料包括硬质热塑性塑料、软质塑料或半硬质塑料中的任意一种或至少两种的组合;优选地,步骤(a)中,所述热塑性橡胶包括TPU、NBR、SBS、TPE或EPDM中的任意一种或至少两种的组合;优选地,步骤(a)中,所述热塑性弹性体包括TPEE、PUR、TPV或TEEE中的任意一种或至少两种的组合;优选地,步骤(a)中,所述石墨的粒度为20-12500目;优选地,步骤(a)中,所述石墨与固化材料的质量比为(0.5-200):100;优选地,步骤(a)中,所述成型颗粒料的粒径为0.2-10mm。
- 根据权利要求1所述的含有单层石墨烯的固化物的制备方法,其特征在于,步骤(b)中,加热的温度为50-880℃,加热的时间为5-60min;优选地,步骤(b)中,所述气体包括空气、氧气、氢气、二氧化碳或氮气中的任意一种或至少两种的组合;优选地,步骤(b)中,加压的压力为0.3-50.0MPa,加压的时间为5-70min;优选地,步骤(b)中,泄压至常压,泄压至常压的时间小于1min。
- 根据权利要求1-3任意一项所述的含有单层石墨烯的固化物的制备方法,其特征在于,步骤(a)中,所述第一溶剂包括水;优选地,步骤(b)中,所述第二溶剂包括水和/或润滑剂。
- 根据权利要求1-3任意一项所述的含有单层石墨烯的固化物的制备方法,其特征在于,包括以下步骤:(a)将石墨和固化材料混合,使其挤出成型,得到成型颗粒料;其中,所述固化材料包括热塑性聚合物;(b)将成型颗粒料和水形成的体系置于密闭的反应装置中进行加热,加热的温度为50-880℃,加热时间为5-60min,再向反应装置中通入气体进行加压,加压的压力为0.2-60.0MPa,加压的时间为5-50min,然后于1min内泄压至常压,得到膨胀颗粒料;(c)将膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次后,得到含有单层石墨烯的固化物;或,所述含有单层石墨烯的固化物的制备方法,包括以下步骤:(a)将石墨和固化材料以及水混合,使其固化成型,干燥,得到成型颗粒料;其中,所述固化材料包括面粉或米粉;(b)将成型颗粒料中置于密闭的反应装置中进行加热,加热的温度为60-200℃,加热时间为5-60min,再向反应装置中通入气体进行加压,加压的压力为0.2-60.0MPa,加压的时间为5-50min,然后于1min内泄压至常压,得到膨胀颗粒料;(c)将膨胀颗粒料替换步骤(a)中的石墨和固化材料,重复步骤(a)和(b)若干次后,得到含有单层石墨烯的固化物。
- 一种含有单层石墨烯的固化物,其特征在于,采用权利要求1-5任意一项所述的含有单层石墨烯的固化物的制备方法制得;优选地,所述含有单层石墨烯的固化物中单层石墨烯的质量分数为20-99%。
- 一种单层石墨烯的制备方法,其特征在于,包括以下步骤:将权利要求6所述的含有单层石墨烯的固化物进行碳化处理,对碳化处理得到的产物分离,得到单层石墨烯。
- 根据权利要求7所述的单层石墨烯的制备方法,其特征在于,将含有单层石墨烯的固化物进行碳化处理,然后将碳化处理得到的产物按照比重进行分离,得到单层石墨烯;优选地,所述碳化处理的温度为200-500℃,碳化处理的时间为0.08-3.0h;优选地,按照比重进行分离时所采用的分离介质为水。
- 一种单层石墨烯,其特征在于,采用权利要求7或8所述的单层石墨烯的制备方法制得。
- 一种含有单层石墨烯的制品,其特征在于,采用权利要求6所述的含有单层石墨烯的固化物或权利要求9所述的单层石墨烯制得。
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