CN114057190B - Catalyst carrier carbon material for preparing carbon nano tube and preparation method and application thereof - Google Patents
Catalyst carrier carbon material for preparing carbon nano tube and preparation method and application thereof Download PDFInfo
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J35/51—
-
- B01J35/615—
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
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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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- 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
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a catalyst carrier carbon material for preparing carbon nanotubes, a preparation method and application thereof, wherein the preparation method of the carbon material comprises the following steps: providing a graphene oxide dispersion liquid with conducting particles intercalated; and granulating the graphene oxide dispersion liquid with the conductive particles intercalated, and removing the solvent to obtain the carbon material. The invention obtains the carbon material with excellent loading performance by using a simple and low-cost mode, and the carbon material has the excellent comprehensive performance of high specific surface area, difficult agglomeration and surface activity, can be used as a carrier for preparing the carbon nanotube catalyst, and can greatly promote the controllable preparation and wide application of the carbon nanotube.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a catalyst carrier carbon material for preparing carbon nanotubes, a preparation method and application thereof.
Background
The catalyst is one of the indispensable raw materials in the synthesis process of the carbon nano tube, and the type, chemical property, particle size, distribution and the like of the catalyst are important factors for controlling the morphology and structure of the carbon nano tube. For the same catalyst, the particle size of the catalyst is a key factor for controlling the diameter of the carbon nano tube. Hafner et al believe that when the catalyst size is less than 3nm, nucleation and growth of single-walled carbon nanotubes thereon is favored, and as the catalyst particle size increases, the catalyst surface may tend to coat the carbon causing the catalyst to "deactivate" or grow multi-walled carbon nanotubes, even carbon fibers.
On the one hand, the catalyst is seriously deactivated, so that the yield of the carbon nano tube is seriously reduced, and meanwhile, the carbon-coated catalyst is difficult to remove in the subsequent purification process and remains in the finished product of the carbon nano tube, so that the impurity content is high, and the practical application of the carbon nano tube is influenced, and the catalyst is particularly used as a conductive additive of a battery.
The use of different carriers to fix catalysts of uniform particle size distribution is a common idea for synthesizing high quality carbon nanotubes. For example, a high density carbon nanotube array (e.g., chinese patent applications CN102502589a, CN101077773 a) can be obtained by supporting uniform, nano-scale catalyst particles on a substrate. In addition, the porous carrier is an effective means for mass-preparing carbon nanotube powder, including carbon-based materials.
The use of carbon materials as catalyst carriers has been reported in related art both at home and abroad. The carbon material described herein relates to a single component or a composite of two components of porous carbon black, ketjen black, graphene and derivatives thereof, and further relates to a carbon material obtained after carbonization of a polymer. The above materials generally suffer from one or more of the following problems: (1) The preparation process is carried out at high temperature, the temperature is not equal to 500-2000 ℃, even exceeds 2000 ℃, and the preparation process is dangerous and has serious energy consumption (for example, chinese patent application CN105073260A, CN106876729B, CN 109935846A); (2) The polymer needs to undergo small molecular polymerization reaction in the early stage of carbonization, the synthesis steps are complicated, and a large amount of small molecular residues such as initiator, monomer and the like (for example, chinese patent application CN 106876729B); (3) The surface is inert in chemical reaction, low in activity, and the catalyst is supported mainly by defect sites distributed on the surface at random, the loading rate and the loading uniformity are uncontrollable, and other surface modifiers are generally needed (for example, chinese patent application CN 109935846A); (4) The carrier itself is agglomerated in the process of removing the solvent or synthesizing the carbon nano tube, so that the practical utilization surface is greatly reduced.
Therefore, the carbon material which is simple, efficient, high in specific surface, not easy to agglomerate and active on the surface is searched to be used as the carrier of the carbon nanotube catalyst, is very important for preparing high-quality carbon nanotubes in batches, and can greatly promote the controllable preparation and wide application of the carbon nanotubes. In addition, the method has reference significance for other catalytic fields such as fuel cells, industrial catalysis and the like.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art, and provides a catalyst carrier carbon material for preparing carbon nano tubes, a preparation method and application thereof, so as to solve the problems of complex preparation process, uncontrollable load rate and load uniformity, easy agglomeration and the like of the existing catalyst carbon carrier.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a first aspect of the present invention provides a method for producing a carbon material, comprising: providing a graphene oxide dispersion liquid with conducting particles intercalated; and granulating the graphene oxide dispersion liquid with the conductive particles intercalated, and removing the solvent to obtain the carbon material.
According to one embodiment of the present invention, the graphene oxide dispersion liquid in which the conductive particles are intercalated is obtained by the steps of: dispersing graphene oxide in a first solvent to obtain graphene oxide dispersion liquid; dispersing conductive particles in a second solvent to obtain a conductive particle dispersion; and fully mixing the graphene oxide dispersion liquid and the conductive particle dispersion liquid to obtain the graphene oxide dispersion liquid with the conductive particles intercalated.
According to one embodiment of the invention, the thorough mixing comprises mixing with a homogenizing treatment and/or grinding treatment, wherein the pressure of the homogenizing treatment is 1000 bar-1200 bar, the flow rate is 0.1 mL/s-5 mL/s, and the treatment time is 20 min-60 min.
According to one embodiment of the invention, the concentration of the graphene oxide dispersion liquid is 0.05 mg/mL-40 mg/mL, and the conductive particles account for 1% -30% of the total mass of the graphene oxide and the conductive particles; the conductive particles are selected from one or more of carbon black, ketjen black, onion carbon and fullerenes.
According to one embodiment of the present invention, the first solvent and the second solvent are each independently selected from one or more of water, an aromatic solvent, and a low molecular alcohol solvent having not more than 3 carbon atoms; the first solvent and/or the second solvent further comprises a surfactant, wherein the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, sodium lignin sulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane and gamma-aminopropyl triethoxysilane.
According to one embodiment of the invention, the dispersion is subjected to the granulating and desolventizing by spray drying, wherein the treatment pressure of the spray drying is 0.1-0.5 MPa, the treatment temperature is 120-200 ℃, and the treatment flow rate is 800-1500 mL/h.
The second aspect of the invention provides a carbon material, wherein the carbon material is in a sphere-like or spherical structure, and the sphere-like or spherical structure is formed by aggregating carbon sheets formed by intercalation of multiple layers of conductive particles and graphene oxide.
According to one embodiment of the invention, the interior of the sphere-like or spherical structure is provided with nano pore channels, and the specific surface area of the carbon material is 10m 2 /g～350m 2 The particle size of the carbon material is 0.1-100 mu m; the carbon sheet comprises1-10 layers of graphene oxide.
A third aspect of the present invention provides a catalyst support employing the aforementioned carbon material.
In a fourth aspect, the present invention provides the use of the foregoing catalyst support for the preparation of carbon nanotubes and composites thereof.
According to the technical scheme, the beneficial effects of the invention are as follows:
the invention provides a novel carbon material and a preparation method thereof, wherein a specific process is adopted to obtain conductive intercalated graphene oxide dispersion liquid, and the carbon material with excellent loading performance is obtained after granulating and desolvation. The method has simple process and low cost, and the prepared carbon material has excellent comprehensive properties of high specific surface area, difficult agglomeration and surface activity, can be used as a carrier for preparing the carbon nanotube catalyst, can greatly promote the controllable preparation of the carbon nanotubes and the composite materials thereof, and has good application prospect.
Drawings
The following drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain the invention, without limitation to the invention.
FIG. 1 is a flow chart of a process for preparing a carbon material according to one embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of the carbon material of example 1;
FIG. 3 is an X-ray diffraction pattern of the carbon material of example 1;
FIG. 4 is a Raman spectrum of the carbon material of example 1;
FIG. 5 is an X-ray photoelectron spectrum of the carbon material of example 1;
FIG. 6 is a scanning electron microscope image of the carbon material of comparative example 1;
FIG. 7 is a scanning electron microscope image of a grapheme carbon nanotube composite of application example 1;
FIGS. 8a and 8b are transmission electron micrographs of the grapheme carbon nanotube composite of application example 1, respectively;
FIG. 9 is a transmission electron microscope image of the catalyst nanoparticle formed in application example 1;
FIG. 10 is a statistical distribution diagram of particle diameters of the catalyst nanoparticles formed in application example 1.
Detailed Description
The following provides various embodiments or examples to enable those skilled in the art to practice the invention as described herein. These are, of course, merely examples and are not intended to limit the invention from that described. The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
A first aspect of the present invention provides a method for producing a carbon material, the method comprising: providing a graphene oxide dispersion liquid with conducting particles intercalated; and granulating the graphene oxide dispersion liquid with the conductive particles intercalated, and removing the solvent to obtain the carbon material.
Fig. 1 shows a process flow diagram of the preparation of a carbon material according to an embodiment of the present invention, and as shown in fig. 1, in this embodiment, the preparation method of the carbon material includes: dispersing graphene oxide in a first solvent to obtain graphene oxide dispersion liquid; dispersing conductive particles in a second solvent to obtain a conductive particle dispersion; fully mixing the graphene oxide dispersion liquid and the conductive particle dispersion liquid to obtain a conductive particle intercalated graphene oxide dispersion liquid; granulating the graphene oxide dispersion liquid with the conductive particles intercalated, and removing the solvent to obtain the carbon material.
According to the invention, in the synthesis process of the carbon nanotubes, the particle size of the catalyst is a key factor for controlling the diameter of the carbon nanotubes, and the use of different catalyst carriers for fixing the catalyst with uniform particle size distribution is a common thought for synthesizing high-quality carbon nanotubes, so that the selection of the catalyst carriers plays an important role in the quality of the synthesized carbon nanotubes. The catalyst carrier is usually made of carbon material, however, the existing catalyst carbon carrier is complex in preparation process and harsh in reaction condition; or the load rate and the load uniformity of the obtained carrier are uncontrollable; or is easy to agglomerate, so that the actual utilization surface is greatly reduced. The inventor of the invention discovers that the carbon composite material with a multistage assembly structure can be prepared by a simple low-cost process method, and the carbon material can effectively improve the efficiency and quality of catalyst loading.
Specifically, the preparation process of the carbon material disclosed by the invention comprises the steps of firstly preparing graphene oxide dispersion liquid with conductive particle intercalation, utilizing the high single-layer rate and high surface activity of graphene oxide, and simultaneously enabling the dispersion liquid to still maintain a higher specific surface after removing a solvent by the intercalation technology of the conductive particles, so that collapse and damage of a structure caused by agglomeration are avoided. The solvent is removed by continuous granulation on the basis, so that the dried material macroscopically forms a similar ball structure with folds while microscopically not agglomerating, and the active surface capable of being loaded by the catalyst is further exposed and fixed. In addition, due to low drying temperature, the preparation process has no high temperature, most of oxygen-containing groups are reserved, a large number of active sites are provided for capturing the catalyst, and the efficiency and quality of the catalyst loading are improved.
The method for producing the carbon material of the present invention is specifically described below with reference to fig. 1.
First, graphene Oxide (GO) is dispersed in a first solvent to obtain a graphene oxide dispersion liquid.
The graphene oxide may be a graphene oxide powder or a filter cake, or a graphene oxide pre-dispersion liquid that has been dispersed to some extent in advance. Dispersing the graphene oxide in a first solvent such as water, aromatic solvent, or a solvent having no more than 3 (n) C And.ltoreq.3) low molecular alcohol solvents, such as ethanol, propanol, etc. The concentration of the graphene oxide dispersion liquid is 0.05 mg/mL-40 mg/mL, for example, 0.05mg/mL, 0.1mg/mL, 1mg/mL, 10mg/mL, 15mg/mL, 20mg/mL, 30mg/mL, and the like. For better dispersion of graphene oxide, the first solvent may also be added with proper amount of surfactant including but not limited to sodium dodecyl benzene sulfonate, polyethyleneOne or more of allyl pyrrolidone, sodium lignin sulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane (KH-560) and gamma-aminopropyl triethoxysilane (KH-550).
Next, the conductive particles are dispersed in a second solvent to obtain a conductive particle dispersion liquid.
The conductive particles are selected from one or more of carbon black, ketjen black, onion carbon, and fullerenes. The conductive particle dispersion liquid can be obtained by mixing and dispersing it in a certain proportion and a soluble second solvent. Wherein the second solvent is selected from water, aromatic solvents, and solvents having no more than 3 (n) C And.ltoreq.3) low molecular alcohol solvents, such as ethanol, propanol, etc. The conductive particles account for 1% -30%, e.g., 1%, 5%, 10%, 15%, 20%, 30%, etc., of the total mass of graphene oxide and conductive particles. Likewise, suitable amounts of surfactants may also be added to the second solvent, including, but not limited to, one or more of sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and gamma-aminopropyl triethoxysilane (KH-550).
In some embodiments, the foregoing dispersion of graphene oxide and dispersion of conductive particles may be performed by a dispersing device such as ultrasonic dispersion, a high-speed dispersing disc, or an emulsifying machine.
Further, after the two dispersions were obtained, the two were thoroughly mixed. The mixing device may be a homogenizer, a centrifugal mill, or a combination thereof, to which the present invention is not limited. During the homogenization treatment, the pressure of the homogenization treatment is generally 1000bar to 1200bar, for example, 1000bar, 1100bar, 1150bar, 1180bar, 1200bar, etc., and the flow rate is 0.1mL/s to 5mL/s, for example, 0.1mL/s, 0.8mL/s, 1mL/s, 2mL/s, 2.5mL/s, 3mL/s, etc., and the treatment time is 20min to 60min, for example, 20min, 30min, 50min, 55min, 60min, etc. And mixing to obtain graphene oxide dispersion liquid with conducting particles intercalated, and granulating to remove the solvent to obtain the carbon material.
The graphene oxide dispersion liquid intercalated by the conductive particles can still maintain a higher specific surface area after solvent removal treatment, and is not easy to agglomerate. Preferably, the desolventizing is performed by a spray drying technique, which can macroscopically make the material take on a spheroid or sphere-like structure with folds while ensuring that the material is microscopically not agglomerated, and further exposes and fixes the active surface that the catalyst can support.
In some embodiments, the aforementioned spray drying process pressure is 0.1MPa to 0.5MPa, e.g., 0.1MPa, 0.3MPa, 0.4MPa, 0.5MPa, etc., the process flow rate is 800mL/h to 1500mL/h, e.g., 800mL/h, 900mL/h, 1000mL/h, 1200mL/h, 1500mL/h, etc., and the process temperature is 120 ℃ to 200 ℃, e.g., 120 ℃, 130 ℃, 150 ℃, 180 ℃, etc. Because the drying temperature is low, most oxygen-containing groups of the material are reserved, a large number of active sites are provided for capturing the catalyst, and the efficiency and the quality of the catalyst loading are further improved.
The carbon material prepared by the method is in a sphere-like or spherical structure, wherein the sphere-like or spherical structure is formed by gathering a plurality of layers of thin and flexible carbon sheets, the carbon sheets are composed of graphene oxide with conductive particles intercalated, and a large number of nano-pore channels are formed in the carbon sheets. The X-ray diffraction represents 002 diffraction peaks with graphite, each carbon sheet approximately comprises graphene oxide with the thickness of 1-10 layers, wherein the higher the oxidation degree is, the thinner the number of layers of the graphene oxide is, and oxygen-containing groups on the surface provide more active sites for adsorbing conductive particles, so that stacking of reduced graphene oxide sheets in the reduction process is inhibited, on the other hand, more load sites can be provided for the catalyst, and the carrier utilization efficiency is improved.
The X-ray photoelectron spectrum of the carbon material contains a large amount of oxygen-containing groups besides C, which shows that the carbon material has chemical activity. There are obvious defect peaks in the raman spectrum of the carbon material, which are beneficial to better dispersing the loaded substances on the surface of the material when the carbon material is used as a carrier.
In some embodiments, the specific surface area of the carbon material is 10m 2 /g～350m 2 /g, e.g. 10m 2 /g、50m 2 /g、100m 2 /g、230m 2 /g、290m 2 And/g, etc., the particle size of the carbon material is 0.1 μm to 100 μm, for example, 0.1 μm, 1 μm, 10 μm, 50 μm, 70 μm, 90 μm, 100 μm, etc. The high specific surface area of the material can ensure the higher loading rate of the carbon material.
In summary, the carbon material with excellent loading performance is obtained by using a simple and low-cost mode, has excellent comprehensive performance of simple preparation process, high specific surface area, difficult agglomeration and surface activity, can be used as a carrier for preparing the carbon nanotube catalyst, effectively solves the problems of deactivation and particle size distribution of the carbon nanotube catalyst, is crucial for preparing high-quality carbon nanotubes in batches, and can greatly promote controllable preparation and wide application of the carbon nanotubes. In addition, the method has reference significance for other catalytic fields such as fuel cells, industrial catalysis and the like.
The invention will be further illustrated by the following examples, but the invention is not limited thereby. The reagents, materials, etc. used in the present invention are commercially available unless otherwise specified.
Example 1
1) And taking 4g of graphene oxide and 500mL of deionized water, and uniformly blending the graphene oxide and the deionized water by a mechanical stirrer, wherein the rotating speed is 3000rpm, and the treatment time is 30min, so as to prepare 8mg/mL of graphene oxide coarse dispersion.
2) Taking 0.05g of Keqin black and 20ml of deionized water, and uniformly blending the Keqin black and the deionized water through magnetic stirring, wherein the rotating speed is 200rpm, and the treatment time is 30min, so as to prepare the coarse dispersion liquid of the conductive particles.
3) And adding the coarse dispersion liquid of the conductive particles into the coarse dispersion liquid of the graphene oxide, and treating the coarse dispersion liquid of the conductive particles by an ultracentrifuge grinder, wherein the rotating speed of the ultracentrifuge grinder is 15000rpm, and the treatment time is 20min, so as to prepare the graphene oxide mixed dispersion liquid with the conductive particles intercalated.
4) Granulating and desolventizing the graphene oxide mixed dispersion liquid with the conductive particle intercalation through spray drying equipment, wherein the treatment pressure of the spray drying equipment is 0.2MPa, the treatment flow rate is 1500ml/h, and the treatment temperature is 140 ℃, so that the carbon material is finally prepared.
Fig. 2 is a scanning electron microscope image of the carbon material of example 1, and it can be seen from fig. 2 that the carbon material has a spheroid-like structure with a particle diameter of about 5 μm. The specific surface area of the carbon material is 300m 2 /g。
Fig. 3 is an X-ray diffraction pattern (XRD) of the carbon material of example 1, having 002 diffraction peaks of graphite therein. FIG. 4 is a Raman spectrum of the carbon material of example 1, and as can be seen from FIG. 4, the Raman spectrum has a significant defect peak, I D /I G =1.02. Fig. 5 is an X-ray photoelectron spectrum (XPS) of the carbon material of example 1, and it can be seen from fig. 5 that the carbon material contains a large amount of oxygen-containing groups in addition to C, and has chemical activity.
Example 2
1) 6g of graphene oxide and 500mL of KH-550 are taken and are uniformly blended through magnetic stirring, the rotating speed is 500rpm, the treatment time is 60min, and the crude graphene oxide dispersion liquid with the concentration of 12mg/mL is prepared.
2) Taking 0.2g of onion carbon and 25ml of deionized water, and uniformly blending the onion carbon and the deionized water through magnetic stirring, wherein the rotating speed is 200rpm, and the treatment time is 30min, so as to prepare the coarse dispersion liquid of the conductive particles.
3) And adding the crude dispersion liquid of the conductive particles into the crude dispersion liquid of the graphene oxide, and treating the crude dispersion liquid of the conductive particles by a high-pressure homogenizer, wherein the treatment pressure is 1200bar, and the treatment is carried out for 15min under the condition of the flow rate of 0.5mL/s, so as to prepare the graphene oxide mixed dispersion liquid of the conductive particle intercalation.
4) Granulating and desolventizing the graphene oxide mixed dispersion liquid with the conductive particle intercalation through spray drying equipment, wherein the treatment pressure of the spray drying equipment is 0.3MPa, the treatment flow rate is 1200ml/h, and the treatment temperature is 160 ℃, so that the carbon material is finally prepared.
Example 3
1) And uniformly blending 10g of graphene oxide and 500mL of deionized water by a mechanical stirrer, wherein the rotating speed is 4000rpm, and the treatment time is 40min, so as to prepare 20mg/mL of graphene oxide coarse dispersion.
2) The crude dispersion of conductive particles was prepared by taking 0.5g of carbon black, 1g of sodium dodecylbenzenesulfonate and 30ml of deionized water, and uniformly blending them by magnetic stirring at 500rpm for 30 min.
3) And adding the coarse dispersion liquid of the conductive particles into the coarse dispersion liquid of the graphene oxide, and treating the coarse dispersion liquid of the conductive particles by a micro-jet homogenizer, wherein the treatment pressure is 1000bar, and the treatment is carried out for 30min under the condition of the flow rate of 0.5mL/s, so as to prepare the graphene oxide mixed dispersion liquid of the conductive particle intercalation.
4) Granulating and desolventizing the graphene oxide mixed dispersion liquid with the conductive particle intercalation through spray drying equipment, wherein the treatment pressure of the spray drying equipment is 0.4MPa, the treatment flow rate is 1000ml/h, and the treatment temperature is 150 ℃ to finally prepare the carbon material.
Comparative example 1
A carbon material was prepared by the method of example 1, except that no conductive particles were added, namely:
1) And taking 4g of graphene oxide and 500mL of deionized water, and uniformly blending the graphene oxide and the deionized water by a mechanical stirrer, wherein the rotating speed is 3000rpm, and the treatment time is 30min, so as to prepare 8mg/mL of graphene oxide coarse dispersion.
2) Granulating and desolventizing the graphene oxide mixed dispersion liquid through spray drying equipment, wherein the treatment pressure of the spray drying equipment is 0.2MPa, the treatment flow rate is 1500ml/h, and the treatment temperature is 140 ℃ to obtain the carbon material.
Characterization of this carbon material and comparison with example 1, FIG. 6 is a scanning electron microscope image of the carbon material of comparative example 1, showing that the spherical particles obtained from the scanning electron microscope image of FIG. 6 have a reduced uniformity in particle size and have partially non-spherical irregular carbon clusters, with individual particle sizes exceeding 10 μm; the corresponding specific surface area was measured to be 210m 2 And/g. From this, it is presumed that intercalation of the conductive particles contributes to suppression of stacking of the sheets of graphene oxide, improvement of uniformity of dispersion of the sheets, more regular and uniform spherical carbon particles, narrow particle size distribution, and corresponding increase in specific surface area. In addition, the conductive particles are not added,the powder yield of spray drying is only 38%, the addition of conductive particles is maintained at more than 90%, and the cost is greatly reduced.
Application example 1
The carbon materials of example 1 were used as catalyst carriers, respectively, to prepare carbon nanotube composites.
Specifically, a carbon material is filled into a quartz tube, hydrogen and argon are respectively and simultaneously introduced at a flow rate of 300sccm, and the carbon material is stably suspended in the quartz tube under the air flow. Heating the fluidized bed reaction chamber to 450 ℃, then introducing Ar gas of 100sccm as carrier gas, introducing supersaturated ferrocene ethanol solution at a constant temperature of 60 ℃ into the reaction chamber by a bubbling method, carrying ferrocene and ethanol, and then thermally cracking to form pre-carbonized iron (Fe) catalyst nano particles attached to the surface of a carbon material carrier, wherein the bubbling duration is 20 minutes. Then, the temperature of the fluidized bed reaction chamber was raised to 700 ℃, hydrogen and argon were simultaneously introduced at a flow rate of 300sccm, and then carbon monoxide was introduced as a carbon source at a flow rate of 100sccm, and after 30 minutes, the carbon monoxide gas was turned off. After stopping the reaction and waiting for the equipment to cool to room temperature, closing all gases to obtain the grapheme carbon nano tube composite material with the sea-urchin-like structure, wherein the grapheme carbon nano tube composite material comprises grapheme microspheres and a plurality of carbon nano tubes formed on the surfaces of the grapheme microspheres, the grapheme microspheres are formed by gathering a plurality of thin and flexible carbon sheets, the carbon sheets are formed by reducing graphene oxide in a plurality of layers, and nanometer pore channels are formed in the grapheme microspheres.
Fig. 7 is a scanning electron microscope image of a graphene carbon nanotube composite material of application example 1, wherein the graphene carbon nanotube composite material is sea-urchin-like, and carbon nanotubes with lengths of tens of micrometers are grown on the surface of graphene microspheres in a dispersed manner, and are lapped with carbon nanotubes on other graphene microspheres to form a continuous conductive network. Fig. 8a and 8b are respectively transmission electron microscope diagrams of graphene carbon nanotube composite materials of application example 1, and as can be seen from fig. 8a and 8b, the carbon nanotubes prepared under the conditions are single-walled carbon nanotubes, and the tube diameters are 1nm to 3nm.
Fig. 9 is a transmission electron microscope image of the catalyst nanoparticle formed in application example 1, and fig. 10 is a statistical distribution diagram of the particle diameter of the catalyst nanoparticle formed in application example 1. As can be seen from fig. 9 and 10, the catalyst nanoparticles on the surface of graphene oxide are uniformly distributed, the average particle diameter is 1.78nm, and more than 95% of the particles have a diameter less than 3nm, which is beneficial to preparing single-walled carbon nanotubes with relatively small tube diameters.
Therefore, the carbon material can be used as a catalyst carrier for growing the carbon nanotube composite material, and when the carbon material is used as the catalyst carrier, the particle size of the supported catalyst is proper and uniformly distributed, so that the quality of the grown carbon nanotubes can be effectively improved, and the controllable preparation and application of the carbon nanotubes are promoted. It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (6)
1. A method for producing a carbon material, comprising:
providing a graphene oxide dispersion liquid with conducting particles intercalated; a kind of electronic device with high-pressure air-conditioning system
Granulating the graphene oxide dispersion liquid with the conductive particles intercalated to remove the solvent to obtain the carbon material;
wherein, the graphene oxide dispersion liquid of the conductive particle intercalation is obtained by the following steps:
dispersing graphene oxide in a first solvent to obtain graphene oxide dispersion liquid;
dispersing conductive particles in a second solvent to obtain a conductive particle dispersion; a kind of electronic device with high-pressure air-conditioning system
Fully mixing the graphene oxide dispersion liquid and the conductive particle dispersion liquid to obtain a graphene oxide dispersion liquid with the conductive particles intercalated;
the full mixing comprises mixing by adopting homogenizing treatment and/or grinding treatment, wherein the pressure of the homogenizing treatment is 1000 bar-1200 bar, the flow rate is 0.1-5 mL/s, and the treatment time is 20-60 min;
the concentration of the graphene oxide dispersion liquid is 0.05 mg/mL-40 mg/mL, and the conductive particles account for 1% -30% of the total mass of the graphene oxide and the conductive particles; the conductive particles are selected from one or more of carbon black, ketjen black, onion carbon and fullerene;
the dispersion liquid adopts spray drying to carry out granulation and solvent removal, the treatment pressure of the spray drying is 0.1 MPa-0.5 MPa, the treatment temperature is 120-200 ℃, and the treatment flow rate is 800-1500 mL/h;
the first solvent and/or the second solvent further comprises a surfactant, wherein the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, sodium lignin sulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane and gamma-aminopropyl triethoxysilane.
2. The method according to claim 1, wherein the first solvent and the second solvent are each independently selected from one or more of water, an aromatic solvent, and a low molecular alcohol solvent having not more than 3 carbon atoms.
3. A carbon material prepared by the method of claim 1 or 2, wherein the carbon material has a spheroid or spherical structure formed by aggregation of carbon sheets of graphene oxide intercalated with multiple layers of conductive particles.
4. A carbon material according to claim 3, wherein the interior of the spheroid or spherical structure has nanochannels, the specific surface area of the carbon material being 10m 2 /g～350m 2 And/g, wherein the particle size of the carbon material is 0.1-100 μm; the carbon sheet comprises 1 to 10 layers of graphene oxide.
5. A catalyst support employing the carbon material of claim 3 or 4.
6. The use of the catalyst carrier according to claim 5 for preparing carbon nanotubes and composites thereof.
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