CN109734079B - Dendritic graphene and preparation method thereof - Google Patents
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Abstract
The invention discloses dendritic graphene and a preparation method thereof, and relates to the field of graphene material preparation. According to the invention, copper salt and a reducing agent react under an alkaline condition, and a dendritic three-dimensional copper substrate is formed by self-assembly; depositing graphene on a dendritic three-dimensional copper substrate by a chemical vapor deposition technology; and adding corrosive liquid to remove the copper substrate, thus obtaining the dendritic three-dimensional graphene. The dendritic three-dimensional graphene disclosed by the invention has a good dispersion type, and the problems of stacking, porosity, unstable configuration and the like are effectively prevented. The preparation method disclosed by the invention is simple in preparation process, mild in condition, wide in raw material source, suitable for batch production and wide in application prospect.
Description
Technical Field
The invention relates to the technical field of graphene materials, in particular to dendritic graphene and a preparation method thereof.
Background
In recent thirty years, carbon nanomaterials have been the leading field of scientific and technological innovation, and from fullerene in 1985 to carbon nanotube discovery in 1991, the carbon nanomaterials rapidly arouse wide attention and huge reverberation, and in 2004, England scientists Andeli, ham and Constantine, Nuowoshuloff firstly obtain graphene with a single atomic layer by a mechanical stripping method, and then add new members to the carbon nanofamily, and two scientists obtain Nobel prize in 2010 by virtue of the achievement.
Graphene is a two-dimensional lamellar nanomaterial composed of carbon six-membered rings, which can be warped to form zero-dimensional fullerene, can be curled into one-dimensional carbon nanotubes, and can also be stacked into three-dimensional graphite, however, few-lamellar graphene has many physicochemical properties superior to other carbon nanomaterials, such as high thermal conductivity (5300W/(m.K)), excellent Young modulus (1.0TPa) and mechanical properties (1060GPa), theoretical specific surface area (2600 m)2/g) large electron mobility (15000 cm)2V · s), and the like.
Due to a great amount of research investment, various preparation methods have been developed for graphene, and the application of graphene also relates to various fields, but in the application process, graphene is often used together with other materials due to the defect that graphene is easy to agglomerate, so that a relatively ideal effect can be exerted. Although modification techniques such as loading, intercalation, and the like have been developed to provide some anti-agglomeration effect, other properties of the graphene may be degraded due to the introduction of new components. For a long time, people are limited by a two-dimensional structure of graphene, and often neglect to regulate and control the appearance of the graphene. In fact, graphene materials with different morphologies, such as dendrites, can be obtained by chemical vapor deposition on substrate materials with different morphologies. So far, no report is found on the research of the graphene material with the dendritic structure.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the dendritic graphene with a novel structure and the preparation method thereof, so as to solve the technical problems of the prior art, such as the agglomeration phenomenon of the graphene.
In order to achieve the purpose, the invention provides the following technical scheme:
in one aspect, the present invention provides a dendritic graphene having a three-dimensional hollow dendritic structure.
Further, dendritic graphene includes trunk and branches, and the branches distribute in the trunk surface along trunk extending direction, the trunk diameter is 300 ~ 500nm, the branch diameter is 200 ~ 300nm, branch length is about 3 ~ 5 mu m, branch and trunk contained angle is 60. The included angle between the branch and the trunk is preferably 60 degrees (because the surface free energy of different crystal faces of the copper nanocrystal is different, the growth direction generally proceeds along the crystal face direction with high surface energy, and is more inclined to the direction close to the included angle of 60 degrees).
On the other hand, the invention also provides a preparation method of the dendritic graphene, which comprises the following specific steps:
1) slowly dripping alkali liquor into copper salt under the stirring state, adding a reducing agent after uniformly mixing, carrying out hydrothermal reaction, and cooling to room temperature to obtain dendritic nano copper;
2) putting the dendritic nano copper obtained in the step 1 into a CVD (chemical vapor deposition) tube furnace, introducing mixed atmosphere, heating, and introducing carbon source gas to obtain dendritic graphene growing on the surface of the copper substrate;
3) and (3) immersing the dendritic graphene growing on the surface of the copper substrate obtained in the step (2) into a corrosive liquid to obtain the dendritic graphene.
Further, the copper salt is one or a combination of copper sulfate, copper nitrate, copper acetate, copper chloride, copper bromide and copper fluoride, and preferably, the copper salt is one or a combination of copper sulfate, copper nitrate and copper chloride.
Further, the concentration of the copper salt is 0.01-1.0 mol/L, further, the concentration of the copper salt is 0.01-0.5 mol/L, and preferably, the concentration of the copper salt is 0.01-0.05 mol/L.
Further, the alkali may be ammonia, NaOH, KOH, Na2CO3、Na3PO4、Na3BO4、K2CO3The alkali can be one or a combination of ammonia water, NaOH and KOH, and preferably, the alkali is ammonia water.
Further, the alkali liquor is used for adjusting the pH value of the copper salt solution to 10' 12.
Further, in the step 1), after the alkali liquor is dripped, stirring is carried out for 5-30 min, and the stirring speed is controlled to be 300-500 r/min.
Further, the reducing agent can be one or more of hydrazine hydrate, sodium borohydride, sodium hypophosphite, potassium hypophosphite, sodium hypophosphite and red phosphorus, and preferably, the reducing agent is red phosphorus.
Further, the hydrothermal reaction is carried out at the temperature of 140-180 ℃ for 2-8 h. Preferably, the temperature of the invention is 140 ℃, 160 ℃ and 180 ℃; the heat preservation time is 1-5 hours, preferably, the time is 2, 4 or 8 hours. Further, after the product of the hydrothermal reaction is cooled to room temperature, the obtained product is washed with deionized water and absolute ethyl alcohol for three times in sequence and dried at 60 ℃.
Further, the preparation process of the dendritic nano copper is as follows: dissolving a copper salt in a solvent to obtain a copper salt solution, adding an alkali into the copper salt solution, adjusting the pH value, stirring, transferring the solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, adding a reducing agent, heating, preserving heat, cooling to room temperature after the reaction is finished to obtain a red product, washing the red product with deionized water and absolute ethyl alcohol for three times respectively to remove impurities, and drying to obtain the dendritic nano copper crystal.
Further, in the step 1), the red product is washed with deionized water and absolute ethyl alcohol for three times respectively to remove impurities, and the dendritic copper nanocrystals are obtained after drying. The drying temperature can be 10-100 ℃, further, the drying temperature is 40-100 ℃, and preferably, the drying temperature is 60 ℃.
Further, the mass ratio of the copper salt to the reducing agent is 0.5-5: 1, further the mass ratio of the copper salt to the reducing agent is 0.5-2: 1, and preferably the mass ratio of the copper salt to the reducing agent is 0.5:1, 1:1, 2: 1.
Further, in the step 2), the dendritic nano copper crystal is placed into a CVD tube furnace, a mixed atmosphere consisting of hydrogen and argon is introduced, heating and temperature rising are carried out, the hydrogen flow rate is adjusted after temperature rising is finished, a carbon source gas is introduced, heat preservation is carried out, the hydrogen and the carbon source gas are closed, and the temperature is reduced to the room temperature in the argon atmosphere, so that the reaction is finished.
Further, in the step 2), the mixed atmosphere consists of hydrogen and argon, the flow rate ratio of the hydrogen to the argon is 1-3: 20-200, the flow rate ratio of the hydrogen to the argon is 1-3: 20-100, and preferably, the flow rate ratio of the hydrogen to the argon is 1: 60,2:80,3:100.
Further, the carbon source gas is one or a combination of methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butene and butyne, further, the carbon source gas is one or a combination of methane, ethane, ethylene and acetylene, and preferably, the carbon source gas is one of methane, ethylene and acetylene.
Further, in step 2), the temperature rise process is as follows: heating to 800-1000 ℃ at a speed of 5 ℃/min, preferably, the heating process is as follows: the temperature is raised to 800 ℃, 900 ℃ and 1000 ℃ at the speed of 5 ℃/min.
Further, after the temperature rise is finished, the ratio of the hydrogen flow rate to the argon flow rate is adjusted to be 1-3: 5-100.
Further, the ratio of the flow rate of the carbon source gas to the flow rate of the argon gas is 1-5: 10-200.
Further, the heat preservation time is 10-30 min, preferably 10, 15 and 20 min.
Further, the corrosive liquid in the step 3) can be nitric acid, concentrated hydrochloric acid, dilute hydrochloric acid, hydrogen peroxide and ferric chloride, and the concentration of the corrosive liquid is 0.1-1.0 mol/L, and preferably, the reagent is ferric chloride, and the concentration of the ferric chloride is 0.1mol/L, 0.5mol/L and 1.0 mol/L.
Further, after the copper substrate is corroded and removed by the reagent in the step 3), centrifuging the liquid, washing the obtained black solid for a plurality of times by deionized water, and drying to obtain the dendritic graphene.
Further, the drying temperature in the step 3) is 50 ℃ to 200 ℃, further, the drying temperature is 50 ℃ to 100 ℃, preferably, the drying temperature is 50 ℃, 60 ℃, 80 ℃.
Further, the preparation method comprises the following specific steps:
1) slowly adding alkali into the copper salt solution under the stirring state, adjusting the pH value, stirring, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining for complete dissolution, adding a reducing agent, heating to a certain temperature, preserving heat for hydrothermal reaction, cooling after the reaction is finished, washing the obtained red product with deionized water and absolute ethyl alcohol for three times respectively, and drying to obtain the dendritic copper nanocrystal;
2) putting the dendritic copper nanocrystals obtained in the step 1) into a CVD (chemical vapor deposition) tubular furnace, heating the tubular furnace at a certain speed in a mixed atmosphere of hydrogen and argon, then adjusting the air flow rate, introducing carbon source gas, keeping the temperature, turning off the hydrogen and carbon source gas, cooling to room temperature in the atmosphere of argon, and taking out a sample to obtain dendritic graphene growing on the surface of the copper substrate;
3) immersing the material obtained in the step 2) into a corrosive liquid, standing for two days, centrifuging the liquid after the copper substrate is completely corroded and disappears, washing the liquid for several times by using deionized water, and drying the obtained black solid to obtain the dendritic graphene.
The basic principle of the invention is as follows: formation of Cu (NH) from copper salts in alkaline solutions, e.g. ammonia3)4 2+First Cu (NH)3)4 2+Is reduced into copper by red phosphorus to obtain a large number of crystal nuclei. The crystal nuclei randomly diffuse in the solution, collide with each other and gather; in order to reduce the energy of the whole system, the growth direction of the particles is adjusted according to the lowest energy. These nuclei grow in a certain direction into rods, constituting the "trunk". As the reaction proceeds, the newly formed copper particles are gathered on the rod into ribs parallel to the rod, protrusions are grown on the ribs, and the protrusions are grown to form side branches. The lateral branches are formed by small polyhedrons which are lapped in an oriented manner. This is because a large number of crystal nuclei are generated in a short time to form a supersaturated solution of copper, and the thermodynamic equilibrium of the system is broken, which is advantageous for the formation of dendrites. The crystal nucleus grows into the nano-crystal, the surface energy of the nano-crystal is higher, and the nano-crystal is in a thermodynamically unstable state in a system, so that the nano-crystal is gathered together to reduce the surface energy. In the process of adjusting the direction aggregation, the probability of mutual lapping of crystal faces with the highest surface energy is the largest, and the energy of a system after lapping is the lowest and the most stable, so that small crystal grains are lappedThe orientation is consistent, and dendritic copper nanocrystals are formed. The method of preparing graphene by CVD using copper as a substrate is prior art, and the principle thereof is not described herein again.
According to the invention, copper salt and a reducing agent react under an alkaline condition, and a dendritic three-dimensional copper substrate is formed by self-assembly; depositing graphene on the dendritic three-dimensional copper substrate by a chemical vapor deposition technology; and adding corrosive liquid to remove the copper substrate, thus obtaining the dendritic three-dimensional graphene. The dendritic three-dimensional graphene disclosed by the invention has a good dispersion type, and the problems of stacking, porosity, unstable configuration and the like are effectively prevented. The preparation method disclosed by the invention is simple in preparation process, mild in condition, wide in raw material source, suitable for batch production and wide in application prospect.
Advantageous effects
The dendritic copper substrate template for preparing graphene is prepared by a one-step hydrothermal method, the preparation process is simple, corrosion removal is easy, the used red phosphorus is a reducing agent and a structure regulator, and has double functions, and the red phosphorus has a relatively large long chain structure and is beneficial to the growth of a dendritic structure of copper in the reaction process.
The invention provides a novel structure of graphene, wherein due to the difference of surface energy of different crystal faces of copper nanocrystals, the included angle between a trunk and a branch of the prepared dendritic graphene is 60 degrees, the defect number is small, and due to the supporting effect of the structure, the agglomeration phenomenon of the graphene is overcome, so that the novel structure is endowed with an ultra-large specific surface area and ultra-high electric conductivity, and the problem of reduction of other performances of the graphene caused by the avoidance of agglomeration of a graphene modification technology in the prior art is effectively solved.
Drawings
FIG. 1 is a schematic diagram of a preparation process of dendritic three-dimensional graphene; a dendritic copper; b, copper-based loaded graphene; c dendritic graphene.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will be further described below with reference to specific embodiments.
Example 1
A preparation method of dendritic graphene comprises the following steps:
1) slowly dropwise adding ammonia water into a copper sulfate solution (60mL, 0.03mol/L) under a stirring state until the pH value of the solution is 12, stirring for 10min, then transferring the solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, adding 0.29g of red phosphorus, preserving heat for 4h at 160 ℃ for hydrothermal reaction, cooling to room temperature after the reaction is finished, washing the obtained red product with deionized water and absolute ethyl alcohol for three times respectively, and drying at 60 ℃ to obtain the dendritic copper nanocrystal;
2) putting the dendritic copper obtained in the step 1 into a CVD (chemical vapor deposition) tube furnace, heating the tube furnace to 1000 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen (the flow rate is 20sccm) and argon (the flow rate is 800sccm), then adjusting the flow rate of the hydrogen to 100sccm, introducing methane gas at the flow rate of 30sccm, keeping the temperature for 15min, turning off the hydrogen and the methane gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain dendritic graphene growing on the surface of the copper substrate;
3) and (3) immersing the material obtained in the step (2) into ferric chloride corrosive liquid (0.5mol/L), standing for two days, centrifuging the liquid after the copper substrate is completely corroded and disappears, washing for several times by using deionized water, and drying the obtained black solid at 60 ℃ to obtain the dendritic graphene.
Example 2
A preparation method of dendritic graphene comprises the following steps:
1) slowly dropwise adding ammonia water into a copper nitrate solution (60mL, 0.01mol/L) under a stirring state until the pH value of the solution is 10, stirring for 5min, then transferring the solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, adding 0.22g of red phosphorus, preserving heat for 8h at 140 ℃ for hydrothermal reaction, cooling to room temperature after the reaction is finished, washing the obtained red product with deionized water and absolute ethyl alcohol for three times respectively, and drying at 60 ℃ to obtain the dendritic copper nanocrystal;
2) putting the dendritic copper obtained in the step 1 into a CVD (chemical vapor deposition) tube furnace, heating the tube furnace to 800 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen (the flow rate is 10sccm) and argon (the flow rate is 600sccm), then adjusting the flow rate of the hydrogen to 80sccm, introducing ethylene gas at the flow rate of 10sccm, keeping the temperature for 20min, turning off the hydrogen and the ethylene gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain dendritic graphene growing on the surface of the copper substrate;
3) and (3) immersing the material obtained in the step (3) into ferric chloride corrosive liquid (0.1mol/L), standing for two days, centrifuging the liquid after the copper substrate is completely corroded and disappears, washing the liquid for several times by using deionized water, and drying the obtained black solid at 50 ℃ to obtain the dendritic graphene.
Example 3
A preparation method of dendritic graphene comprises the following steps:
1) slowly dropwise adding ammonia water into a copper chloride solution (60mL, 0.05mol/L) under a stirring state until the pH value of the solution is 11, stirring for 30min, then transferring the solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, adding 0.20g of red phosphorus, preserving heat for 2h at 180 ℃ for hydrothermal reaction, cooling to room temperature after the reaction is finished, washing the obtained red product with deionized water and absolute ethyl alcohol for three times respectively, and drying at 60 ℃ to obtain the dendritic copper nanocrystal;
2) putting the dendritic copper obtained in the step 1 into a CVD (chemical vapor deposition) tube furnace, heating the tube furnace to 900 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen (the flow rate is 30sccm) and argon (the flow rate is 1000sccm), then adjusting the flow rate of the hydrogen to 120sccm, introducing acetylene gas at the flow rate of 50sccm, keeping the temperature for 10min, turning off the hydrogen and the acetylene gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain dendritic graphene growing on the surface of the copper substrate;
3) and (3) immersing the material obtained in the step (3) into ferric chloride corrosive liquid (1mol/L), standing for two days, centrifuging the liquid after the copper substrate is completely corroded and disappears, washing the liquid with deionized water for several times, and drying the obtained black solid at the temperature of 80 ℃ to obtain the dendritic graphene.
Example 4
Specific surface area, electrical conductivity and thermal conductivity tests were performed on the conventional two-dimensional lamellar graphene prepared by the CVD method and the dendritic graphene prepared in example 1 of the present invention, respectively, and the obtained results are shown in table 1.
TABLE 1
| Group of | Example 1 | Tradition of |
| Material | Dendritic graphene | Two-dimensional lamellar graphene |
| Specific surface area (m)2·g-1) | 1230 | 467 |
| Electrical conductivity (S.m)-1) | 28855 | 21307 |
| Thermal conductivity (W.m)-1·K-1) | 1800 | 1350 |
The result shows that the specific surface area of the dendritic graphene is far larger than that of the two-dimensional sheet graphene, so that the specific surface area of the dendritic graphene is obviously improved, the agglomeration phenomenon is restrained, and meanwhile, the electric conduction and heat conduction performance of the dendritic graphene is greatly improved.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and scope of the invention, and these modifications and improvements are also considered to be included in the scope of the invention.
Claims (6)
1. A preparation method of dendritic graphene is characterized by comprising the following specific steps:
1) slowly dripping alkali liquor into copper salt under the stirring state, adding a reducing agent after uniformly mixing, carrying out hydrothermal reaction, and cooling to room temperature to obtain dendritic nano copper;
2) putting the dendritic nano copper crystal obtained in the step 1 into a CVD (chemical vapor deposition) tube furnace, introducing mixed atmosphere consisting of hydrogen and argon, heating, raising the temperature, adjusting the hydrogen flow rate after the temperature is raised, introducing carbon source gas, preserving the heat, closing the hydrogen and the carbon source gas, and cooling to room temperature in the argon atmosphere to complete the reaction to obtain dendritic graphene growing on the surface of the copper substrate;
3) immersing the dendritic graphene growing on the surface of the copper substrate obtained in the step 2 into a corrosive solution to obtain dendritic graphene;
the dendritic graphene has a three-dimensional hollow dendritic structure and comprises a main stem and branches, and the branches are distributed on the surface of the main stem along the extension direction of the main stem;
the diameter of the trunk is 300-500 nm, the diameter of the branches is 200-300 nm, the length of the branches is 3-5 mu m, and the included angle between the branches and the trunk is 60 degrees;
the reducing agent is red phosphorus;
in the step 2), the temperature rise process is as follows: heating to 800-1000 ℃ at the speed of 5 ℃/min;
after the temperature rise is finished, adjusting the ratio of the hydrogen flow rate to the argon flow rate to be 1-3: 5-100;
the ratio of the flow rate of the carbon source gas to the flow rate of the argon gas is 1-5: 10-200;
the heat preservation time is 10-30 min.
2. The preparation method of dendritic graphene according to claim 1, wherein the copper salt is one or a combination of copper sulfate, copper nitrate, copper acetate, copper chloride, copper bromide and copper fluoride;
the alkali liquor is ammonia water, NaOH, KOH, Na2CO3、Na3PO4、Na3BO4、K2CO3One or the combination of sodium methoxide, sodium ethoxide and potassium tert-butoxide.
3. The preparation method of dendritic graphene according to claim 1, wherein in the step 1), after the alkali liquor is added dropwise, stirring is carried out for 5-30 min, and the stirring speed is controlled to be 300-500 r/min;
the concentration of the copper salt is 0.01-1.0 mol/L;
the hydrothermal reaction is carried out at 140-180 ℃ for 2-8 h;
and cooling the product of the hydrothermal reaction to room temperature, washing the obtained product with deionized water and absolute ethyl alcohol for three times in sequence, and drying to obtain the dendritic copper nanocrystal.
4. The preparation method of the dendritic graphene according to claim 1, wherein in the step 1), the mass ratio of the copper salt to the reducing agent is 0.5-5: 1, and the alkali solution is used for adjusting the pH of the copper salt solution to 10-12.
5. The preparation method of dendritic graphene according to claim 1, wherein in the step 2), the mixed atmosphere consists of hydrogen and argon, and the flow rate ratio of hydrogen to argon is 1-3: 20-200;
the carbon source gas is one or the combination of methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylene and butyne.
6. The preparation method of dendritic graphene according to claim 1, wherein the corrosive solution in step 3) is nitric acid, concentrated hydrochloric acid, diluted hydrochloric acid and hydrogen peroxide, or ferric chloride, and the concentration of the corrosive solution is 0.1-1.0 mol/L;
after the copper substrate is removed through corrosion of the corrosive liquid, centrifuging the liquid, washing the obtained black solid for several times by using deionized water, and drying to obtain dendritic graphene;
the drying temperature is 50-200 ℃.
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| CN105417525A (en) * | 2015-12-09 | 2016-03-23 | 东南大学 | Dendritic three-dimensional graphene and preparation method thereof |
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| CN105417525A (en) * | 2015-12-09 | 2016-03-23 | 东南大学 | Dendritic three-dimensional graphene and preparation method thereof |
| CN107473208A (en) * | 2017-06-26 | 2017-12-15 | 南京航空航天大学 | The preparation method of selfreparing sensor based on woods shape graphene interleaving network |
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