CN113277864B - Preparation method of carbonaceous aerogel and aerogel - Google Patents
Preparation method of carbonaceous aerogel and aerogel Download PDFInfo
- Publication number
- CN113277864B CN113277864B CN202010104187.5A CN202010104187A CN113277864B CN 113277864 B CN113277864 B CN 113277864B CN 202010104187 A CN202010104187 A CN 202010104187A CN 113277864 B CN113277864 B CN 113277864B
- Authority
- CN
- China
- Prior art keywords
- carbon
- carbonaceous
- aerogel
- composite material
- isolation structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/522—Graphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
- C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a carbonaceous aerogel and the aerogel, wherein the preparation method comprises the steps of carbonizing a high polymer composite material with an isolation structure, so that carbon left by pyrolysis of a high polymer component and the component forming the isolation structure form a three-dimensional network together, and graphitizing the three-dimensional network to obtain the carbonaceous aerogel. The preparation method of the invention takes the composite material with the isolation structure as the raw material, the composite material takes the carbonaceous material as the network of the isolation structure, takes the high molecular component as the support body, removes the high molecular component in the carbon material by the heat treatment way of high-temperature carbonization, leads the left carbonaceous material to form a three-dimensional network, and obtains the aerogel with high porosity and excellent compression strength by graphitization.
Description
Technical Field
The invention belongs to the technical field of aerogel, and particularly relates to a preparation method of carbonaceous aerogel and aerogel.
Background
The carbon aerogel is a three-dimensional graphene material with a porous structure, realizes the conversion from a two-dimensional material to a three-dimensional material, not only retains the excellent physical and chemical properties, good electrical conductivity, thermal conductivity and excellent mechanical properties of the original carbon material, but also endows the two-dimensional material with structural characteristics of low density, large specific surface area, high porosity and the like which are not possessed by the two-dimensional material, further widens the application range of the material, and can meet the application requirements of the fields of advanced functional materials such as adsorbents, catalyst carriers, biosensors, battery and supercapacitor electrode materials.
Currently, common ways of preparing carbonaceous aerogels can be summarized as self-assembly, templating, and 3D printing. For example, the invention patent with publication number CN109824037A discloses a preparation method of a graphene aerogel electrode material, in which a graphene hydrogel is generated by a one-step hydrothermal method through a reductive ionic liquid compound and graphene oxide, and the graphene aerogel electrode material is obtained after freeze-drying. The patent publication No. CN110127675A discloses a method for producing graphene aerogel, in which a polymer foam is immersed in a graphene oxide solution to obtain a graphene oxide-coated polymer foam, and then the graphene aerogel is obtained by heat treatment. The invention patent with publication number CN108584937A discloses a preparation method of a novel compressible and resilient graphene aerogel, which comprises the steps of preparing a graphene inkjet precursor and a carbon nanotube inkjet precursor, printing a three-dimensional graphene block by adopting a 3D printing platform, performing hydrothermal reaction to obtain a three-dimensional graphene hydrogel, and performing freeze drying to obtain the graphene aerogel. Although the aerogel with the three-dimensional graphene structure can be prepared in the prior art, graphene oxide is used as a raw material, and therefore a reducing agent and the like need to be added in the preparation process, and the preparation process is complex and is not environment-friendly.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a preparation method of the carbonaceous aerogel, wherein a carbonaceous material which is not subjected to oxidation treatment is mixed with a high molecular polymer and then is subjected to thermoforming to prepare a composite material with an isolation structure; and removing the high molecular phase by taking the composite material as a raw material through high-temperature carbonization and graphitization, thereby obtaining the aerogel with the carbonaceous three-dimensional network.
In order to solve the technical problems, the invention adopts the technical scheme that:
the invention provides a preparation method of a carbonaceous aerogel, which comprises the steps of carbonizing a high polymer composite material with an isolation structure, enabling carbon left by pyrolysis of a high polymer component and the component forming the isolation structure to jointly form a three-dimensional network, and graphitizing the three-dimensional network to obtain the carbonaceous aerogel.
In the above scheme, the polymer composite material with an isolation structure means that carbon-based materials are selectively distributed in a composite system, the carbon-based materials are distributed on the surface of polymer particles, and then an effective network structure is formed in the composite system through a certain forming process. Unlike the prior art in which graphene oxide is used as a raw material, and a reducing agent is added to prepare the aerogel through freeze drying, the method adopts graphene raw sheets which are not subjected to redox treatment as the raw material, and adopts a thermal forming mode without applying extra pressure or a freeze drying process.
According to the preparation method, the formation of the carbonaceous aerogel is in negative correlation with the melt index of the composite powder in the polymer composite material with the isolation structure, namely the composite powder with low melt index is more beneficial to forming the carbonaceous aerogel; by adjusting the content of the carbon material and the melt fluidity of the high molecular component, the isolation network structure in the composite material is completely reserved after carbonization, and further the carbon aerogel with a designable structure can be obtained after graphitization.
In the above scheme, the thermoforming of the polymer component refers to a process of raising the temperature above the melting point of the polymer, entangling molecular chains of the polymer melt with each other, and finally cooling and crystallizing. In the composite material system, the addition of the carbon-based material can hinder the entanglement among polymer chains, and the hindering effect is more and more obvious along with the increase of the content of the carbon-based material. The content of the carbon-based material is reduced, the blocking effect of mutual entanglement among polymer chains is reduced, the appearance of the composite material is flat and compact, the porosity is low or zero, volatile substances generated by thermal degradation of polymer components in the carbonization process do not have an escaping channel, and the impact force of the volatile substances can damage an isolation structure to cause collapse of a network. Therefore, the content of the carbon-based material is properly increased, and the composite material is rough and loose in appearance and has high porosity due to the obstruction of entanglement among polymer chains, so that volatile substances generated by thermal degradation of polymer components in the carbonization process can be smoothly discharged out of the system, and the integrity of an isolation network structure is reserved. Further, the present inventors have discovered that in situations where aerogel design requirements are met, such as where the amount of carbon-based material added needs to be reduced, to ensure structural integrity of the aerogel, a high molecular weight polymer with low melt flow (lower melt index) can be used. In the thermal forming process, the polymer powder with poor melt flowability basically does not flow, the melt is poor in mutual adhesion, the macro morphology of the prepared composite material is rough and loose, and pores exist in the macro morphology, so that volatile substances generated by thermal degradation of polymers in the carbonization process can escape from channels formed by the pores, and the original three-dimensional network structure is reserved.
According to the preparation method, the polymer composite material with the isolation structure is prepared by the following steps: adding a carbon-based material into water to disperse to prepare slurry with the solid content of 1-4 wt%, mechanically mixing the slurry with a high polymer component, drying to obtain composite powder, paving the composite powder in a mold, heating the material in the mold to 180-330 ℃, preserving heat for 10-60 min, and cooling to obtain the high polymer composite material, wherein the isolation structure is made of the carbon-based material.
In the scheme, the carbon-based material and water are prepared into uniformly dispersed slurry, and the slurry and the high molecular component are mechanically mixed to prepare the composite material with the isolation structure. The isolating network structure is well preserved because the pressure of hot press molding is not applied in the preparation process, and compared with the traditional extrusion and injection molding modes, the isolating structure in the composite material is not deformed in the molding process, so that the isolating network structure is not damaged by any external force fundamentally, and the aerogel prepared subsequently has structural integrity and better structural strength.
According to the preparation method, the dispersion of the carbon-based material in water refers to that a mixture of the carbon-based material and water is placed in a colloid mill to be ground for 5-60 min, then ultrasonic waves with the power of 165-430W are applied to the ground mixture, and the ultrasonic waves are dispersed for 5-60 min to prepare uniformly dispersed slurry.
In the above scheme, the related workers of the present invention find that different types of carbon-based materials are selected, and the dispersion effects in water are different, and if only a single dispersion means is used, it is difficult to achieve uniform distribution of the carbon-based materials in the slurry, and the non-uniform slurry affects uniform adhesion to the surface of the polymer particles in subsequent mixing with the polymer component, and also affects formation of a continuous isolation structure. And the carbon-series material can be effectively dispersed in water by adopting a colloid mill and an ultrasonic dispersion mode in sequence, so that the slurry prepared by dispersion in the mode is more beneficial to preparing a continuous isolation structure.
According to the preparation method, the mechanical mixing comprises the step of mixing the slurry and the high molecular components by using a high-speed mixer, wherein the mixing speed is 5000-25000 rpm, and the mixing time is 1-5 min.
In the scheme, the mixing speed of the mechanical mixing of the slurry and the high molecular components can ensure that the carbon-based material in the slurry is coated on the surfaces of the high molecular particles on the premise of not damaging the completeness of the particle size of the high molecular components.
According to the preparation method, the carbonization termination temperature in the carbonization process is 600-1800 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time of each heating stage is 30-180 min.
According to the above production method, the graphitization process includes: the termination temperature of the graphitization treatment is 2000-3200 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time of each heating stage is 30-180 min.
According to the preparation method, the polymer composite material comprises the following components in parts by weight: 80-99.5 parts of high molecular component and 0.5-20 parts of carbon material; the melt index of the high molecular component is 0.1-10 g/10 min. Preferably, when the content of the carbon-based material in the polymer composite material is less than or equal to 3 wt%, the melt index of a polymer component used for preparing the isolation structure composite material is not more than 2g/10min, and the preferred melt index is 0.1-2 g/10 min; when the content of the carbon-based material in the polymer composite material is more than 3 wt%, the melt index of a polymer component used for preparing the isolation structure composite material is 2-10 g/10 min;
preferably, when the polymeric component comprises a plurality of polymers having different melt indices, the melt index is measured after the plurality of polymers are mixed.
According to the preparation method, the high molecular component comprises one or more of powdery polymers with the melt index of 0.1-10 g/10min, and the powdery polymers are selected from one or more of polyethylene, polypropylene, polycarbonate, ethylene-octene copolymer, ethylene-butene copolymer and polylactic acid; the carbon-based material is selected from one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon fibers, graphite and graphene, and is preferably graphene.
According to the preparation method, the composite powder is spread on a die and subjected to tapping, the tapping vibration frequency is 30-40 Hz, the amplitude is 0.8-1.2 cm, the applied excitation force is 1000-1500N, and the tapping time is 0.5-2 min.
In the scheme, the mixture is processed by a subsequent compaction process, so that the polymer powder is more compact, gaps among particles are eliminated as much as possible, the carbon materials are further more closely contacted, and the isolation network structure prepared by thermoforming is more compact.
According to the above preparation method, the preparation method further comprises the steps of immersing the carbonized product in a solvent after the carbonization treatment, and then drying the carbonized product; the solvent is selected from water and a mixed solution of water and alcohol, and the water content in the mixed solution is not less than 70 wt%; the soaking time is 1-10 min; the drying treatment comprises drying for 10-40 min at 80-100 ℃ in a vacuum environment.
In the scheme, the polymer composite material with the isolation structure is used as a substrate, the polymer components in the polymer composite material are removed in a heat treatment mode, the carbon remained by pyrolysis of the polymer components is infiltrated by a solvent, gaps between the carbon and a carbon material are reduced, the strength of the aerogel is further enhanced, and the carbon aerogel with high porosity and excellent strength can be obtained through subsequent graphitization treatment.
The preparation method specifically comprises the following steps:
(1) adding a carbon material into deionized water to prepare a mixture, placing the mixture into a colloid mill to grind for 5-60 min, and then carrying out ultrasonic dispersion with the power of 165-430W for 5-60 min to obtain slurry with the solid content of 1-4 wt%; mixing the slurry and the high molecular component in a high-speed mixer at the speed of 5000-25000 rpm for 1-5 min, and drying at the temperature of 60-90 ℃ for 0.5-8 h to prepare composite powder with a certain carbon material content;
(2) spreading the composite powder prepared in the step (1) in a mold, heating the material in the mold to 180-330 ℃, preserving heat for 10-60 min, and cooling to obtain a polymer composite material with an isolation structure;
(3) carbonizing the polymer composite material prepared in the step (2) under the protection of inert atmosphere, and then cooling to room temperature, wherein the carbonization termination temperature is 600-1800 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time of each heating stage is 30-180 min;
(4) and (3) graphitizing the sample in the step (3) in an inert atmosphere, and then cooling to room temperature to obtain the carbonaceous aerogel, wherein the termination temperature of graphitization is 2000-3200 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time of each heating stage is 30-180 min.
Preferably, the step (2) further comprises the step of compacting the material paved in the die, wherein the vibration frequency of the compaction is 30-40 Hz, the amplitude is 0.8-1.2 cm, the applied exciting force is 1000-1500N, and the compacting time is 0.5-2 min.
Preferably, the step (3) further comprises the steps of soaking the carbonized sample in a solvent for 1-10 min, and then transferring the carbonized sample to a vacuum oven to dry the carbonized sample at the temperature of 80-100 ℃ for 10-40 min, wherein the solvent is selected from water or a mixed solution of water and alcohol, and the water content in the mixed solution is not less than 70 wt%.
The invention also provides the carbonaceous aerogel prepared by the preparation method of the carbonaceous aerogel, and the carbonaceous aerogel has a three-dimensional reticular porous structure.
After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. in the preparation method of the carbonaceous aerogel, the unique isolated dispersion network of the carbon-based material in the polymer composite material with the isolated structure provides a three-dimensional network framework for the aerogel;
2. in the preparation method of the carbonaceous aerogel, the content of the carbon-based material and the melt fluidity of the high molecular component are adjusted, so that the isolation network structure in the composite material is completely reserved after carbonization, and the carbonaceous aerogel with a designable structure can be further obtained after graphitization;
3. in the preparation method of the carbonaceous aerogel, the carbonized sample is soaked by the solvent, the gap between the residual carbon after pyrolysis of the high polymer and the carbonaceous material of the isolation structure can be filled and soaked by the solvent liquid, and after the carbonaceous material is quickly dried in a vacuum environment, the gap between the residual carbon after pyrolysis of the high polymer and the carbonaceous network of the isolation structure is closed along with the evaporation of solvent molecules, so that the residual carbon and the carbonaceous network of the isolation structure are firmly adhered, and the structural strength of the carbonized sample is enhanced.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention to the right. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
FIG. 1 is an SEM image of a carbonaceous aerogel prepared in example 1 of the present invention;
fig. 2 is an enlarged SEM image of the aerogel structure of the black box portion of fig. 1.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
In this example, the carbonaceous aerogel was prepared by the following method:
(1) adding graphene into deionized water to prepare a mixture, placing the mixture in a colloid mill for grinding for 5min, and then performing ultrasonic dispersion with power of 430W and time of 5min to obtain slurry with solid content of 1 wt%; mixing the slurry with linear low density polyethylene with the melt index of 3.5g/10min in a high-speed mixer at the speed of 5000rpm for 1min, and drying at the temperature of 90 ℃ for 6h to prepare composite powder with the graphene content of 6 wt%;
(2) spreading the composite powder prepared in the step (1) in a mould, heating the material in the mould to 310 ℃, preserving heat for 10min, and cooling to obtain a polymer composite material;
(3) carbonizing the polymer composite material prepared in the step (2) under the protection of inert atmosphere, and then cooling to room temperature, wherein the carbonization process comprises the following steps: the temperature rise rate in the stage of room temperature to 350 ℃ is 10 ℃/min; the temperature rise rate at the stage of 350-600 ℃ is 1 ℃/min, and the temperature is kept for 120 min;
(4) graphitizing the sample obtained in the step (3) under the protection of inert atmosphere, and then cooling to room temperature to obtain graphene aerogel, wherein the graphitizing process comprises the following steps: the temperature rise rate in the room temperature-1000 ℃ stage is 10 ℃/min, and the temperature is kept for 180 min; the temperature rise rate at the stage of 1000-2000 ℃ is 3 ℃/min, and the temperature is kept for 180 min.
Example 2
In this example, the carbonaceous aerogel was prepared by the following method:
(1) adding carbon nano tubes into deionized water to prepare a mixture, grinding the mixture in a colloid mill for 30min, and then performing ultrasonic dispersion with the power of 165W and the time of 40min to obtain slurry with the solid content of 2.5 wt%; mixing the slurry with polypropylene with melt index of 10g/10min in a high-speed mixer at 15000rpm for 3min, and drying at 60 deg.C for 8h to obtain composite powder with carbon nanotube content of 20 wt%;
(2) spreading the composite powder prepared in the step (1) in a mould, heating the material in the mould to 180 ℃, preserving heat for 60min, and cooling to obtain a polymer composite material;
(3) carbonizing the polymer composite material prepared in the step (2) under the protection of inert atmosphere, and then cooling to room temperature, wherein the carbonization process comprises the following steps: the temperature rise rate in the stage of room temperature to 350 ℃ is 5 ℃/min; the temperature rise rate at the stage of 350-600 ℃ is 1 ℃/min, and the temperature is kept for 30 min; the temperature rise rate at the stage of 600-900 ℃ is 5 ℃/min, and the temperature is kept for 30 min; soaking the carbonized sample in water-alcohol solution for 1min, wherein the water content is 80 wt%, and transferring to a vacuum oven to dry at 90 ℃ for 25 min;
(4) graphitizing the sample dried in the step (3) under the protection of inert atmosphere, and cooling to room temperature to obtain the carbon nanotube aerogel, wherein the graphitizing process comprises the following steps: the temperature rise rate in the room temperature-1000 ℃ stage is 10 ℃/min, and the temperature is kept for 30 min; the temperature rise rate at the stage of 1000-2000 ℃ is 1 ℃/min, and the temperature is kept for 60 min; the temperature rise rate in the 2000-2300 ℃ stage is 1 ℃/min, and the temperature is kept for 60 min.
Example 3
In this example, the carbonaceous aerogel was prepared by the following method:
(1) adding graphene into deionized water to prepare a mixture, placing the mixture in a colloid mill, grinding for 40min, and then performing ultrasonic dispersion with the power of 324W and the time of 30min to obtain slurry with the solid content of 2.5 wt%; mixing the slurry with a mixture of ultra-high molecular weight polyethylene with a melt index of 0.1g/10min and linear low density polyethylene with a melt index of 2g/10min (the melt index of the ultra-high molecular weight polyethylene and the linear low density polyethylene after mixing is 0.5g/10min and is in the range of 0.1-2 g/10 min) in a high-speed mixer at the speed of 24000rpm for 2min, and drying at the temperature of 80 ℃ for 7h to prepare composite powder with the graphene content of 2.5 wt%;
(2) flatly paving the composite powder prepared in the step (1) in a mould and carrying out tap treatment, wherein the tap vibration frequency is 35Hz, the amplitude is 1.0cm, the applied exciting force is 1100N, the tap time is 1.5min, then heating the material in the mould to 310 ℃, carrying out heat preservation for 30min, and then cooling to obtain the polymer composite material;
(3) carbonizing the polymer composite material prepared in the step (2) under the protection of inert atmosphere, and then cooling to room temperature, wherein the carbonization process comprises the following steps: the temperature rise rate in the stage of room temperature to 350 ℃ is 7 ℃/min; the temperature rise rate at the stage of 350-600 ℃ is 1 ℃/min, and the temperature is kept for 60 min; the temperature rise rate at the stage of 600-800 ℃ is 1 ℃/min, and the temperature is kept for 60 min; the temperature rise rate at the stage of 800-1600 ℃ is 1 ℃/min, and the temperature is kept for 60 min;
(4) graphitizing the sample obtained in the step (3) under the protection of inert atmosphere, and cooling to room temperature to obtain graphene aerogel, wherein the graphitizing process is as follows: the temperature rise rate in the stage of room temperature to 1000 ℃ is 10 ℃/min; preserving the heat for 60 min; the temperature rise rate at the stage of 1000-2000 ℃ is 5 ℃/min, and the temperature is kept for 60 min; the temperature rise rate at the stage of 2000-2800 ℃ is 5 ℃/min, and the temperature is kept for 60 min.
Example 4
In this example, the carbonaceous aerogel was prepared by the following method:
(1) adding carbon fibers into deionized water to prepare a mixture, placing the mixture in a colloid mill for grinding for 60min, and then performing ultrasonic dispersion with the power of 324W and the time of 60min to obtain slurry with the solid content of 4 wt%; mixing the slurry with ultra-high molecular weight polyethylene with a melt index of 0.1g/10min and polypropylene with a melt index of 4g/10min (the melt index of the mixed ultra-high molecular weight polyethylene and polypropylene is 1.0g/10min and is in the range of 0.1-2 g/10 min) in a high-speed mixer at the speed of 25000rpm for 5min, and drying at the temperature of 75 ℃ for 4h to prepare composite powder with the carbon fiber content of 1 wt%;
(2) spreading the composite powder prepared in the step (1) in a mould, heating the material in the mould to 330 ℃, preserving heat for 40min, and cooling to obtain a polymer composite material;
(3) carbonizing the polymer composite material prepared in the step (2) under the protection of inert atmosphere, and then cooling to room temperature, wherein the carbonization process comprises the following steps: the temperature rise rate in the stage of room temperature to 350 ℃ is 8 ℃/min; the temperature rise rate at the stage of 350-600 ℃ is 3 ℃/min, and the temperature is kept for 60 min; the temperature rise rate at the stage of 600-800 ℃ is 3 ℃/min, and the temperature is kept for 60 min; the temperature rise rate at the stage of 800-1400 ℃ is 3 ℃/min, and the temperature is kept for 60 min; the temperature rise rate at the stage of 1400-1800 ℃ is 3 ℃/min, and the temperature is kept for 60 min;
(4) graphitizing the sample obtained in the step (3) under the protection of inert atmosphere, and then cooling to room temperature to obtain the carbon fiber aerogel, wherein the graphitizing process comprises the following steps: the temperature rise rate in the stage of room temperature to 1000 ℃ is 5 ℃/min; preserving the heat for 120 min; the temperature rise rate at the stage of 1000-2000 ℃ is 2 ℃/min, and the temperature is kept for 120 min; the temperature rise rate in the 2000-3200 ℃ stage is 2 ℃/min, and the temperature is kept for 120 min.
Example 5
In this example, the carbonaceous aerogel was prepared by the following method:
(1) adding graphene and carbon nanotubes into deionized water to prepare a mixture, placing the mixture into a colloid mill for grinding for 30min, and then performing ultrasonic dispersion with power of 430W and time of 40min to obtain slurry with solid content of 3 wt%; mixing the slurry with polycarbonate with a melt index of 5g/10min in a high-speed mixer at a speed of 5000rpm for 1min, and drying at the temperature of 90 ℃ for 8h to prepare composite powder with the content of 10 wt% of graphene and carbon nano tubes;
(2) flatly paving the composite powder prepared in the step (1) in a mould and carrying out tap treatment, wherein the tap vibration frequency is 30Hz, the amplitude is 1.2cm, the applied exciting force is 1000N, the tap time is 2min, then heating the material in the mould to 310 ℃, carrying out heat preservation for 30min, and then cooling to obtain the polymer composite material;
(3) carbonizing the polymer composite material prepared in the step (2) under the protection of inert atmosphere, and then cooling to room temperature, wherein the carbonization process comprises the following steps: the temperature rise rate in the stage of room temperature to 350 ℃ is 10 ℃/min; the temperature rise rate at the stage of 350-600 ℃ is 1 ℃/min, and the temperature is kept for 120 min; the temperature rise rate at the stage of 600-1500 ℃ is 5 ℃/min, and the temperature is kept for 120 min; soaking the carbonized sample in water for 10min, and transferring to a vacuum oven to dry at 80 deg.C for 40 min;
(4) graphitizing the sample obtained in the step (3) under the protection of inert atmosphere, and cooling to room temperature to obtain the graphene-carbon nanotube aerogel, wherein the graphitizing process comprises the following steps: the temperature rise rate in the stage of room temperature to 1000 ℃ is 5 ℃/min; preserving the temperature for 180 min; the temperature rise rate in the stage of 1000-2000 ℃ is 3 ℃/min, the temperature is kept for 180min, the temperature rise rate in the stage of 2000-2600 ℃ is 3 ℃/min, and the temperature is kept for 180 min.
Example 6
This embodiment is different from embodiment 3 in that: in this example, the carbon-based materials selected in step (1) are carbon nanotubes and carbon fibers, the content of the carbon nanotubes and the carbon fibers in the composite material of the barrier structure is 2 wt%, and other embodiments of this example are the same as example 3.
Example 7
In this example, the carbonaceous aerogel was prepared by the following method:
(1) adding graphene and carbon fibers into deionized water to prepare a mixture, placing the mixture in a colloid mill, grinding for 60min, and then performing ultrasonic dispersion with power of 350W and time of 30min to obtain slurry with solid content of 2.5 wt%; mixing the slurry with a mixture of polylactic acid with a melt index of 7g/10min and polyethylene with a melt index of 4g/10min (the melt index of the mixed polylactic acid and polyethylene is 6g/10min and is within the range of 2-10 g/10 min) in a high-speed mixer at the speed of 5000rpm for 1min, and drying at the temperature of 90 ℃ for 8h to prepare composite powder with the content of graphene and carbon fiber of 15 wt%;
(2) flatly paving the composite powder prepared in the step (1) in a mould and carrying out tap treatment, wherein the tap vibration frequency is 40Hz, the amplitude is 0.8cm, the applied exciting force is 1500N, the tap time is 0.5min, then heating the material in the mould to 310 ℃, carrying out heat preservation for 40min, and then cooling to obtain the polymer composite material;
(3) carbonizing the polymer composite material prepared in the step (2) under the protection of inert atmosphere, and then cooling to room temperature, wherein the carbonization process comprises the following steps: the temperature rise rate in the stage of room temperature to 350 ℃ is 10 ℃/min; the temperature rise rate at the stage of 350-600 ℃ is 1 ℃/min, and the temperature is kept for 120 min; the temperature rise rate at the stage of 600-800 ℃ is 5 ℃/min, and the temperature is kept for 120 min; the temperature rise rate at the stage of 800-1200 ℃ is 3 ℃/min, and the temperature is kept for 120 min; soaking the carbonized sample in water-alcohol solution for 3min, wherein the water content is 70 wt%, and transferring to a vacuum oven to dry at 100 deg.C for 10 min;
(4) graphitizing the sample obtained in the step (3) under the protection of inert atmosphere, and cooling to room temperature to obtain the graphene-carbon fiber aerogel, wherein the graphitizing process is as follows: the temperature rise rate in the stage of room temperature to 1000 ℃ is 5 ℃/min; preserving the temperature for 180 min; the temperature rise rate in the stage of 1000-2000 ℃ is 3 ℃/min, the heat preservation time is 180min, the temperature rise rate in the stage of 2000-3000 ℃ is 3 ℃/min, and the heat preservation time is 180 min.
Example 8
This example differs from example 7 in that: in the present example, the carbon-based material selected in step (1) is graphene, carbon nanotubes, or carbon fibers, and other embodiments of the present example are the same as example 7.
Comparative example 1
In comparative example 1, the amount of the carbon-based material added to the composite material for an insulation structure in step (1) was adjusted to 3.5 wt% based on example 3, and the other embodiments of the comparative example were the same as example 3.
Comparative example 2
In comparative example 2, the amount of the carbon-based material added to the composite material for an insulation structure in step (1) was adjusted to 2.5 wt% based on example 1, and the other embodiments of the comparative example were the same as example 1.
Experimental example 1
In this experimental example, the carbonaceous aerogels prepared in examples 1 to 8 and comparative examples 1 to 2 were subjected to performance tests, and the results are shown in the following table:
| density (mg/cm)3) | Pores ofPercentage (%) | Compressive Strength (MPa) | |
| Example 1 | 116.5 | 94.71 | 0.431 |
| Example 2 | 167.8 | 92.37 | 0.794 |
| Example 3 | 119.8 | 94.55 | 0.451 |
| Example 4 | 142.4 | 93.53 | 0.735 |
| Example 5 | 136.7 | 93.79 | 0.948 |
| Example 6 | 110.9 | 94.96 | 0.806 |
| Example 7 | 148.5 | 93.25 | 0.659 |
| Example 8 | 120.6 | 94.52 | 0.473 |
| Comparative example 1 | 356.9 | 83.77 | 0.376 |
| Comparative example 2 | 376.2 | 82.90 | 0.282 |
As can be seen from the above table, the aerogels prepared in embodiments 1 to 8 of the present invention all adopt composite materials with isolation structures, which are subjected to component adjustment, and the isolation network structures in the composite materials are completely retained after carbonization by adjusting the content of the carbon-based material and the melt flowability of the polymer components, so as to obtain the carbonaceous aerogel with high porosity and certain mechanical strength. In comparative examples 1 and 2, on the basis of examples 3 and 1, the addition amount of the carbonaceous material is adjusted, so that the melt index of the composite powder with the isolation structure is influenced, the network structure of the carbonaceous aerogel is further influenced, and the mechanical property and the porosity of the obtained aerogel product are reduced.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention.
Claims (9)
1. The preparation method of the carbonaceous aerogel is characterized by comprising the steps of carbonizing a high polymer composite material with an isolation structure to enable carbon left by pyrolysis of a high polymer component and the component forming the isolation structure to jointly form a three-dimensional network, and graphitizing the three-dimensional network to obtain the carbonaceous aerogel;
the polymer composite material comprises 80-99.5 parts by weight of polymer component and 0.5-20 parts by weight of carbon material;
the high molecular component comprises one or more of powdery polymers with the melt index of 0.1-10 g/10min, and the powdery polymers are selected from one or more of polyethylene, polypropylene, polycarbonate, ethylene-octene copolymer, ethylene-butene copolymer and polylactic acid; the carbon-based material is selected from one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon fibers, graphite and graphene;
the polymer composite material with the isolation structure is prepared by the following method: adding a carbon-based material into water for dispersion to prepare a slurry with a solid content of 1-4 wt%, mechanically mixing the slurry with a high polymer component, drying to obtain composite powder, spreading the composite powder in a mold, heating the material in the mold to 180-330 ℃, preserving heat for 10-60 min, and cooling to obtain the high polymer composite material, wherein the isolation structure is made of the carbon-based material.
2. The method for preparing the carbonaceous aerogel according to claim 1, wherein the step of adding the carbon-based material into water for dispersion is to grind a mixture of the carbon-based material and water in a colloid mill for 5-60 min, and then apply ultrasonic dispersion to the ground mixture at a power of 165-430W for 5-60 min to obtain a uniformly dispersed slurry.
3. The method for preparing the carbonaceous aerogel according to claim 1, wherein the mechanical mixing comprises mixing the slurry and the polymer component by a high-speed mixer, wherein the mixing speed is 5000-25000 rpm, and the mixing time is 1-5 min.
4. The method for producing the carbonaceous aerogel according to claim 1, wherein the carbonization termination temperature in the carbonization step is 600 to 1800 ℃, the temperature rise rate is 1 to 10 ℃/min, and the holding time in each temperature rise stage is 30 to 180 min.
5. The method for producing a carbonaceous aerogel according to claim 1, wherein the termination temperature of the graphitization treatment is 2000 to 3200 ℃, the temperature increase rate is 1 to 10 ℃/min, and the heat preservation time in each temperature increase stage is 30 to 180 min.
6. The method for preparing a carbonaceous aerogel according to claim 1, wherein when the content of the carbon-based material is 3 wt% or less, the melt index of the composite powder used for preparing the composite material for the insulation structure is not more than 2g/10 min;
when the content of the carbon-based material is more than 3 wt%, the melt index of composite powder used for preparing the isolation structure composite material is 2-10 g/10 min;
when the polymeric component is composed of a plurality of polymers having different melt indices, the melt index is a melt index measured after the plurality of polymers are mixed.
7. The method for preparing a carbonaceous aerogel according to claim 1, wherein when the content of the carbon-based material is 3 wt% or less, the melt index of the composite powder used for preparing the composite material having the insulation structure is 0.1 to 2g/10 min.
8. The method for preparing the carbonaceous aerogel according to claim 1, further comprising compacting the composite powder after spreading the composite powder in a mold, wherein the compacting has a vibration frequency of 30 to 40Hz, an amplitude of 0.8 to 1.2cm, an applied excitation force of 1000 to 1500N, and a compacting time of 0.5 to 2 min.
9. The method for producing a carbonaceous aerogel according to claim 1, further comprising immersing the carbonized product in a solvent after the carbonization treatment, followed by drying treatment; the solvent is selected from water and a mixed solution of water and alcohol, and the water content in the mixed solution is not less than 70 wt%; the soaking time is 1-10 min; the drying treatment comprises drying for 10-40 min at 80-100 ℃ in a vacuum environment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010104187.5A CN113277864B (en) | 2020-02-20 | 2020-02-20 | Preparation method of carbonaceous aerogel and aerogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010104187.5A CN113277864B (en) | 2020-02-20 | 2020-02-20 | Preparation method of carbonaceous aerogel and aerogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113277864A CN113277864A (en) | 2021-08-20 |
| CN113277864B true CN113277864B (en) | 2022-05-31 |
Family
ID=77274994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010104187.5A Active CN113277864B (en) | 2020-02-20 | 2020-02-20 | Preparation method of carbonaceous aerogel and aerogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113277864B (en) |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002003211A (en) * | 2000-06-20 | 2002-01-09 | Asahi Glass Co Ltd | Method for producing carbon material and activated carbon |
| CN103073891B (en) * | 2013-01-15 | 2015-07-15 | 华东理工大学 | Preparation method of high-conductivity flexible conductive composite material |
| CN105161312B (en) * | 2015-09-24 | 2017-11-17 | 复旦大学 | A kind of carbon nano-fiber graphene composite aerogel and its collaboration process for assembly preparing |
| WO2017217832A1 (en) * | 2016-06-17 | 2017-12-21 | 한국기계연구원 | Method for producing carbon aerogel precursor, and carbon aerogel precursor and carbon aerogel produced thereby |
| CN106365142B (en) * | 2016-09-13 | 2019-01-25 | 同济大学 | A kind of preparation method of the compound carbon aerogels of high-specific surface area High conductivity graphene based on chemical crosslinking |
| CN106634859B (en) * | 2017-01-16 | 2019-08-13 | 西南科技大学 | A kind of preparation method of the graphene conductive fixed phase change heat material with isolation structure |
| CN106809822B (en) * | 2017-01-22 | 2018-06-22 | 戴天元 | A kind of preparation method of super-elasticity graphene aerogel |
| CN108862234A (en) * | 2017-05-11 | 2018-11-23 | 北京化工大学 | A kind of preparation method of fibre reinforced carbon aerogel composite material |
| US11707721B2 (en) * | 2017-10-11 | 2023-07-25 | University Of Utah Research Foundation | Methods of making permeable aerogels |
| CN109904451A (en) * | 2017-12-11 | 2019-06-18 | 中国科学院化学研究所 | A kind of graphene composite material and its preparation method and application |
| CN108250728B (en) * | 2018-03-09 | 2020-11-03 | 四川大学 | Polymer/graphene aerogel composite foam material and preparation method thereof |
| CN110127675B (en) * | 2019-06-27 | 2021-01-26 | 中素新科技有限公司 | Method for producing graphene aerogel |
-
2020
- 2020-02-20 CN CN202010104187.5A patent/CN113277864B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113277864A (en) | 2021-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106832774B (en) | A kind of 3D graphene/epoxy resin composite material and its preparation method and application of aramid fiber enhancing | |
| Allahbakhsh et al. | Self-assembled and pyrolyzed carbon aerogels: an overview of their preparation mechanisms, properties and applications | |
| CN107946086B (en) | supercapacitor flexible self-supporting all-carbon electrode taking graphene as binder and preparation method thereof | |
| CN108504096B (en) | Preparation method of carbon nano tube/polymer composite material | |
| CN112174670B (en) | Preparation method for densification modification of graphite material, densified graphite material obtained by preparation method and application of densified graphite material | |
| CN108039465B (en) | Composite electrode material, preparation method and application thereof | |
| CN113617301B (en) | Fluororubber modified carbon aerogel and preparation method thereof | |
| CN110040724B (en) | Preparation method of folded graphene and electromagnetic shielding material thereof | |
| CN101049928B (en) | Method for manufacturing high heat conducting foam material of graphite with even apertures | |
| Wilson et al. | Low-density microcellular carbon foams from sucrose by NaCl particle templating using glycerol as a plasticizing additive | |
| CN103342574A (en) | Enhanced block carbon nanofiber (CNF)/carbon composite material and preparation method thereof | |
| US20240128455A1 (en) | Fibrillar carbon-silicon composite materials and methods of manufacture thereof | |
| CN113277864B (en) | Preparation method of carbonaceous aerogel and aerogel | |
| CN112225201A (en) | Method for preparing thick graphene heat dissipation film by utilizing silk screen | |
| CN113161161B (en) | Nano carbon material composite resin hard carbon electrode material and preparation method and application thereof | |
| CN113150360B (en) | Method for promoting dispersion of nano filler by using stretching action of pore wall of polymer foaming material | |
| CN114685177A (en) | High-strength carbon graphite material and preparation method and application thereof | |
| CN110416544B (en) | Method for preparing high-capacity artificial graphite cathode material by block semi-closed pore catalytic graphitization | |
| CN106683909A (en) | In-situ preparation method for cubic copper oxide/graphene aerogel composite material | |
| CN115746498A (en) | Preparation method of high-thermal-conductivity graphene phenolic moulding plastic | |
| CN113278218B (en) | Conductive composite material with isolation structure and preparation method thereof | |
| CN115010119B (en) | Graphene thick film and preparation method thereof | |
| CN111484002A (en) | Preparation method and application of porous graphene membrane | |
| CN116675221B (en) | Graphene film with high electrical conductivity and high thermal conductivity as well as preparation method and application thereof | |
| CN117263164A (en) | Preparation method of large-block carbon electrode with controllable micro-channel size and morphology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |