CN113148992B - Preparation method of small-size graphene - Google Patents
Preparation method of small-size graphene Download PDFInfo
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- CN113148992B CN113148992B CN202110349436.1A CN202110349436A CN113148992B CN 113148992 B CN113148992 B CN 113148992B CN 202110349436 A CN202110349436 A CN 202110349436A CN 113148992 B CN113148992 B CN 113148992B
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Abstract
A preparation method of small-size graphene. The invention belongs to the technical field of carbon nano material preparation. The invention provides a preparation method of small-size graphene. The preparation method comprises the following steps: step 1: plating copper on the aluminum film silicon dioxide thin plate by an electroplating method to manufacture a substrate; and 2, step: putting the substrate into a reaction chamber for preheating under the protection of inert gas; and step 3: introducing a mixture of inert gas and carbon-containing organic gaseous substances for carbonization treatment; and 4, step 4: and taking out the substrate, putting the substrate into mixed acid solution for treatment, then washing the substrate to be neutral, and filtering and drying the substrate to obtain the small-size graphene. The method can be used for preparing the small-size graphene with the advantages of high purity, small size, uniform distribution, good controllability and the like. And the method has the advantages of low energy consumption, environment-friendly raw materials and low cost. The small-size graphene is a transparent film in appearance, has a micro-morphology of small-size graphene, a transverse size of 50-200nm, and a carbon content of more than 92%.
Description
Technical Field
The invention belongs to the technical field of carbon nano-material preparation, and particularly relates to a preparation method of small-size graphene.
Background
Carbon is one of the most abundant elements in nature, and carbon atoms can form a complex cross-linked network structure which is crucial to the existence of organic chemistry and living bodies. Carbon materials are a special material that can exist in nature in zero-to three-dimensional forms. In addition, carbon allotropes have different physicochemical properties. Carbon allotropes play an important role from the superhard material diamond to the soft material graphite, from the insulating material diamond to the semiconductor material graphite to the conductive material graphene. Although the carbon allotropes have different structures and properties, the carbon allotrope, which has a magic two-dimensional structure, has a unique special position in the field of materials, namely graphene. Graphene is very specific in structure, and a two-dimensional graphene crystal is a honeycomb structure with a thickness of only one atomic layer, and the honeycomb structure is compounded by rings composed of 6 carbon atoms, so that graphene is an aromatic macrocyclic molecule with a planar structure, which makes it have many unique properties. Compared with other allotropes of carbon, such as carbon nanotubes and fullerene, graphene has great advantages in the fields of biosensors, lithium ion batteries, drug-loaded delivery materials and the like.
The preparation methods of graphene are classified into 3 types: the first is a top-down synthesis method; the second is a bottom-up synthesis method; and thirdly, other synthesis methods. The top-down synthesis method comprises the following steps: the method comprises the steps of mechanical stripping, oxidation-reduction, arc discharge synthesis, and large-scale preparation of graphene and the like by using natural graphite as a carbon source and stripping or cutting through a physical-chemical method. The synthesis method from bottom to top comprises the following steps: chemical vapor deposition methods, organic synthesis methods, preparation of single-layer or multi-layer graphene using small molecule carbon-containing compounds, and the like. Other synthesis methods such as epitaxial growth, etc.
Application publication No. CN 111285356A discloses a preparation method of small-size graphene, 1) weighing graphite and adding the graphite into deionized water. 2) An aqueous solution of graphite was sonicated and freeze dried. 3) The dried graphite is subjected to a heat treatment. 4) And irradiating the graphite subjected to the heat treatment. 5) Weighing and mixing concentrated sulfuric acid and concentrated phosphoric acid in proportion, weighing the irradiated graphite and potassium permanganate in proportion, adding the mixed acid, and heating for enough time to obtain graphite oxide. 6) And cleaning and carrying out ultrasonic treatment on the graphite oxide solution, and then drying to obtain a graphene oxide solid. 7) And taking out the N, N-dimethylformamide solution and the graphene oxide solid according to the proportion, mixing and carrying out ultrasonic treatment. 8) And placing the solution after ultrasonic treatment in a reaction kettle for heating for a certain time. 9) And filtering the black precipitate to obtain a brown suspension, namely obtaining the DMF solution of the small-size graphene quantum dots. Although the transverse dimension of the prepared small-size graphene is small, the method is complex in process, needs concentrated acid, has dangerousness and environmental pollution, is not suitable for large-scale production, is complex in impurity components of the product, is difficult to completely remove, and limits the large-scale application of the technology.
Application publication No. CN 112279241A discloses a rapid preparation method of low-layer-number and small-size graphene, which comprises the steps of taking nano-carbon or graphene with the thickness of less than 100nm as a raw material, dispersing the nano-carbon or graphene in a solvent in the presence of a dispersing agent to prepare a pre-dispersion liquid, then contacting the spray of the pre-dispersion liquid with a combustible gas, and burning to prepare the graphene. According to the invention, high-temperature and high-pressure shock waves generated by combustion of combustible gas are utilized to smash the fully dispersed nano-carbon or graphene so as to achieve the effect of refining the nano-carbon or graphene, so that the prepared graphene with smaller sheet diameter and low layer number is obtained. Although the method can be used for quickly preparing the small-size graphene, a dispersing agent is introduced and participates in the reaction in the process, no description is given to whether the material has secondary defects and impurities, and the manufacturing process adopts an explosion method, so that the manufacturing of the high-quality small-size graphene is limited, and the danger is existed, the size distribution is not uniform.
Application publication No. CN 110963488A discloses a preparation method of graphene oxide, which comprises the following steps: firstly, mixing purified microcrystalline graphite with mixed acid, adding an oxidant for reaction, and quenching to obtain a reaction system; the mixed acid comprises trifluoromethanesulfonic acid; and then heating the reaction system obtained in the step, keeping the temperature constant, cooling, and adding a reducing agent for reduction to obtain the graphene oxide. The acid used in the method contains concentrated sulfuric acid, and the oxidant comprises one or more of potassium permanganate, sodium permanganate, lithium permanganate, potassium manganate, potassium ferrate, sodium periodate, sodium dichromate, potassium perchlorate, potassium chlorate, sodium hypochlorite, potassium perborate, chromium trioxide and ammonium persulfate, so that serious environmental pollution and safety problems exist, the purification mode is high-temperature melting purification, the energy consumption is huge, and the popularization of large-scale production is limited.
Disclosure of Invention
The present invention provides a method for preparing small-sized graphene to solve the above technical problems.
The preparation method of the small-size graphene comprises the following steps:
step 1: adding the mixture of copper chloride and potassium salt and the compound additive into water to prepare plating solution, and then adding the plating solution into the plating solution at the pH value of 8.0 +/-0.5, the temperature of the plating solution of 40-50 ℃ and the current density of 2A/dm 2 ～5A/dm 2 Under the condition of constant-temperature oil bath with the ultrasonic power of 100-140W and the ultrasonic frequency of 40-50 KHz, copper plating is carried out by taking a copper bar as an anode and an aluminum film silicon dioxide thin plate as a cathode to obtain a substrate;
step 2: continuously introducing inert gas into the reaction chamber to exhaust air in the reaction chamber, then placing the substrate into the reaction chamber under the protection of the inert gas, heating the reaction chamber to 670-1100 ℃ from room temperature in a staged heating mode, and preserving heat for 10-30 min after the temperature is reached;
and 3, step 3: introducing a mixture of inert gas and carbon-containing organic gaseous substances into the reaction chamber after the step 2 for reaction for 10-30 min, stopping introducing the carbon-containing organic gaseous substances after the reaction is finished, continuously introducing the inert gas for 10-30 min, and cooling by adopting circulating cooling oil until the temperature of the reaction chamber is reduced to room temperature;
and 4, step 4: and taking out the substrate, putting the substrate into a mixed acid solution for treatment for 60-90 min, putting the filtered product into a sulfuric acid solution again for treatment for 120-200 min, washing the filtered product to be neutral, filtering and drying to obtain the small-size graphene.
Further limiting, in the step 1, the concentration of the copper chloride in the plating solution is 10 g/L-30 g/L, the concentration of the potassium salt mixture is 15 g/L-75 g/L, and the concentration of the compound additive is 5 g/L-30 g/L.
Further, the potassium salt mixture in step 1 is a mixture of any two of potassium citrate, potassium chloride, potassium hydroxide and boric acid in any ratio.
Further limiting, the compound additive in the step 1 is a hydrate of Mo.
Further defined, the main component of the hydrate of Mo is (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O。
Further limiting, in the step 1, the area ratio of the anode to the cathode is (2-3): 1.
further limiting, the copper plating time in the step 1 is 10 min-15 min.
Further limiting, the step 2 of raising the temperature in the stage comprises the following specific steps: the temperature is raised from the room temperature to 150-250 ℃ at the heating rate of 8-12 ℃/min, then is raised from 150-250 ℃ to 600-900 ℃ at the heating rate of 14-16 ℃/min, is kept at the temperature for 10-30 min, and is raised from 600-900 ℃ to 670-1100 ℃ at the heating rate of 4-6 ℃/min.
Further defining that the flow ratio of the inert gas and the carbon-containing organic gaseous substance in the mixture in the step 3 is 1: (3-4).
Further, in step 3, the inert gas is nitrogen, argon or helium, and the carbon-containing organic gaseous substance is a carbon-containing organic gas or a gasified organic liquid.
Further limited, the carbon-containing organic gas is methane, natural gas, ethane, ethylene, acetylene, propane and propylene, the gasified organic liquid is absolute methanol, absolute ethanol, benzene, toluene and xylene, and the gasification temperature is 120-300 ℃.
Further, the cooling by the circulating cooling oil in the step 3 is realized by forming a cooling oil pipeline network which is arranged outside the reaction chamber and fully covers the reaction chamber in a spiral mode.
Further limiting, the cooling rate of the cooling oil by adopting the circulating cooling oil in the step 3 is 30-50 ℃/min.
Further limiting, in the step 4, the mixed acid is a mixture of hydrochloric acid and nitric acid, wherein the volume ratio of the hydrochloric acid to the nitric acid is 3.
Further limiting, the concentration of the sulfuric acid solution in the step 4 is 8 mol/L-10 mol/L.
Further limiting, the transverse size of the small-size graphene obtained in the step 4 is 50-200nm, and the carbon content is more than or equal to 87%.
Compared with the prior art, the invention has the following advantages:
1) According to the invention, high-quality small-size graphene is prepared by a special preparation process, and can be used as a final product after further treatment, so that a good structure of the graphene is retained to the maximum extent, and performance is ensured. It can be used as conductive additive for various materials, and has soft and smooth and lubricating effects.
2) The method can be used for preparing the small-size graphene with the advantages of high purity, small size, uniform distribution, good controllability and the like. And the method has the advantages of low energy consumption, environment-friendly raw materials and low cost. The small-size graphene is a transparent film in appearance, has a micro-morphology of small-size graphene (different transparency conditions due to the fact that a small amount of impurities are contained), has a transverse size of 50-200nm, and has a carbon content of more than 92%.
3) Compared with the common graphene preparation method, the substrate preparation method disclosed by the invention has the advantages that the graphite layer structure is mechanically stripped and damaged by oxidation reduction in the precursor preparation process, the stability and the uniformity are obvious, waste gas and waste water are not generated, the energy consumption is obviously lower compared with an arc discharge method, the raw material requirement is simpler, the formed size is smaller, and compared with organic micromolecule synthesis and CO reduction, the method is more controllable, and the reaction process is quicker.
4) The temperature of the plating solution in the substrate preparation method of the invention has relatively important influence on the relative film weight, and a heavier product can be obtained on the premise that the temperature of the plating solution is relatively higher, because the diffusion rate of copper ions in the solution is increased along with the rise of the temperature of the plating solution in the substrate preparation process, which is beneficial to the mass transfer electroplating process, reduces the concentration polarization and improves the electroplating efficiency; however, the temperature of the plating solution is not too high, the water in the plating solution is evaporated due to the increase of the temperature, the concentration of salt ions in the plating solution cannot be continuously stabilized, the internal proportion of the plating solution is unbalanced, and the test cannot be continued.
5) The whole substrate preparation process is heated in an oil bath at constant temperature, the bearing box body is sealed, the internal unbalance of the plating solution caused by liquid loss due to overhigh temperature is avoided, meanwhile, the mixed solution is preheated when being prepared, the initialization values of all parameters of the mixed solution are ensured to be stable, and the stability of the experiment is further ensured.
6) In the preparation process of the substrate, the action mechanism of ultrasonic agitation is a special depolarization in essence, the vibration phenomenon and the cavitation phenomenon caused when the ultrasonic wave acts on the substrate preparation solution are equivalent to the extremely strong agitation action applied to the substrate solution, the agitation action greatly reduces the thickness of a diffusion layer near the cathode surface, effectively reduces concentration difference polarization, increases the mass concentration of copper ions in a liquid layer close to the cathode surface, reduces more copper ions on the cathode, and improves the relative film weight of the substrate. This experiment sets up ultrasonic equipment in constant temperature oil bath heating cabin, has both guaranteed the constant temperature and the leakproofness of bathing, can play the effect of carrying out the supersound stirring again.
7) The invention selects a high-temperature fixed bed, the temperature range is 800-1500 ℃, the required gas is a gas containing carbon-hydrogen bonds and a protective gas, wherein the gas containing carbon-hydrogen bonds can crack carbon and hydrogen, the former is a raw material gas required by carbonization reaction, the latter is a gas required by reduction of metal oxide, and the protective gas is N 2 Or Ar, the mixture of the two is directly communicated, the advantage lies in, can improve the carbon-hydrogen bond concentration in the reaction atmosphere, reduce the shielding gas influence, has guaranteed stability and continuity of the atmosphere, help purity promotion and continuity experiment of the product, the process adopts CVD method to prepare, different from traditional fixed bed, this experimental facilities add the cooling oil pipeline network of fast cooling on the original basis, this net locates at the outer end of the heating zone of main reaction with the spiral form, the purpose is to give the reaction substrate fast controllable cooling speed, the net outer tube docks the high low temperature all-in-one, guarantee the temperature is controllable and continuous.
Drawings
FIG. 1 is a topographic map of small-sized graphene obtained in example 1;
FIG. 2 is a morphology of small-sized graphene obtained in example 2;
FIG. 3 is a morphology of small-sized graphene obtained in example 3;
FIG. 4 is a morphology of small-sized graphene obtained in example 4;
FIG. 5 is a morphology of small-sized graphene obtained in example 5;
FIG. 6 is a graph showing the weight of a plated film on a substrate according to the temperature of the plated film obtained in step 1 of examples 1 and 6;
fig. 7 is a bar graph of the coating weights of the coating films on the substrates obtained in step 1 of examples 1 and 7 as a function of the stirring manner.
Detailed Description
Example 1: the preparation method of the small-size graphene of the embodiment includes the following steps:
step 1: adding copper chloride, potassium salt mixture and compound additive into water to prepare plating solution, and then adding the solution at pH value of 8.0 +/-0.5, plating solution temperature of 45 ℃ and current density of 3A/dm 2 Under the conditions that the ultrasonic power is 120W and the ultrasonic frequency is 45KHz, copper plating is carried out by taking a copper bar as an anode and an aluminum film silicon dioxide thin plate as a cathode to obtain a substrate; the concentration of copper chloride in the plating solution is 15g/L, the concentration of potassium salt mixture is 45g/L, and the concentration of compound additive is 10g/L; the potassium salt mixture is prepared from potassium citrate and boric acid according to a mass ratio of 1.5: 1; the compound additive is a hydrate of Mo, wherein (NH) in the hydrate of Mo 4 ) 6 Mo 7 O 24 ·4H 2 The mass fraction of O is 90 percent, and the balance is ammonium acetate; the area ratio of the anode to the cathode is 2.5:1; the copper plating time is 12min;
and 2, step: continuously introducing N into the reaction chamber 2 The air in the reaction chamber is exhausted and then is in the N 2 Under the protection of (2), putting the substrate into a reaction chamber, heating from room temperature to 200 ℃ at a heating rate of 10 ℃/min, then heating from 200 ℃ to 900 ℃ at a heating rate of 15 ℃/min, keeping the temperature for 20min, then heating from 900 ℃ to 940 ℃ at a heating rate of 5 ℃/min, and after the temperature is reachedPreserving the heat for 20min;
and 3, step 3: introducing N into the reaction chamber after the step 2 2 And CH 4 The mixture of (1) is reacted for 20min, wherein N 2 And CH 4 The flow ratio of (1): 3.5, after the reaction is finished, stopping introducing CH 4 ，N 2 Continuously introducing for 30min, and cooling the reaction chamber to room temperature at a cooling rate of 30 ℃/min by adopting circulating cooling oil; the cooling by adopting the circulating cooling oil is realized by forming a cooling oil pipeline network which is arranged outside the reaction chamber and fully covers the reaction chamber in a spiral mode;
and 4, step 4: taking out the substrate, placing the substrate into a mixed acid solution consisting of 20wt% hydrochloric acid and 35wt% nitric acid according to a volume ratio of 3 2 The carbon content is 93 percent, and the appearance is shown in figure 1.
Example 2: the preparation method of the small-size graphene of the embodiment includes the following steps:
step 1: adding the mixture of copper chloride and potassium salts and the compound additive into water to prepare a plating solution, and then adding the copper chloride, the potassium salt mixture and the compound additive into the plating solution at a pH value of 8.0 +/-0.5, a plating solution temperature of 45 ℃ and a current density of 3A/dm 2 Under the conditions that the ultrasonic power is 120W and the ultrasonic frequency is 45KHz, copper plating is carried out by taking a copper bar as an anode and an aluminum film silicon dioxide thin plate as a cathode to obtain a substrate; the concentration of copper chloride in the plating solution is 15g/L, the concentration of potassium salt mixture is 45g/L, and the concentration of compound additive is 10g/L; the potassium salt mixture is prepared from potassium citrate and boric acid according to a mass ratio of 1.5: 1; the compound additive is a Mo hydrate, wherein (NH) in the Mo hydrate 4 ) 6 Mo 7 O 24 ·4H 2 The mass fraction of O is 90 percent, and the balance is ammonium acetate; the area ratio of the anode to the cathode is 2.5:1; the copper plating time is 12min;
and 2, step: continuously introducing Ar into the reaction chamber to exhaust air in the reaction chamber, then placing the substrate into the reaction chamber under the protection of Ar, heating the substrate from room temperature to 200 ℃ at the heating rate of 10 ℃/min, then heating the substrate from 200 ℃ to 800 ℃ at the heating rate of 15 ℃/min, preserving heat at the temperature for 20min, heating the substrate from 800 ℃ to 850 ℃ at the heating rate of 5 ℃/min, and preserving heat for 20min after the substrate reaches the temperature;
and step 3: and (3) introducing a mixture of Ar and the gasified absolute ethyl alcohol at the temperature of 130 ℃ into the reaction chamber after the step 2 for reaction for 15min, wherein the flow ratio of Ar to the gasified absolute ethyl alcohol is 1:3, after the reaction is finished, stopping introducing the gasified absolute ethyl alcohol, continuously introducing Ar for 30min, and then cooling the reaction chamber to room temperature at the cooling rate of 35 ℃/min by adopting circulating cooling oil; the cooling by adopting the circulating cooling oil is realized by forming a cooling oil pipeline network which is arranged outside the reaction chamber and fully covers the reaction chamber in a spiral mode;
and 4, step 4: taking out the substrate, putting the substrate into a mixed acid solution consisting of 20wt% hydrochloric acid and 35wt% nitric acid according to a volume ratio of 3 2 The carbon content is 92.5 percent per gram, and the appearance is shown in figure 2.
Example 3: the preparation method of the small-size graphene of the embodiment includes the following steps:
step 1: adding copper chloride, potassium salt mixture and compound additive into water to prepare plating solution, and then adding the solution at pH value of 8.0 +/-0.5, plating solution temperature of 45 ℃ and current density of 3A/dm 2 Under the conditions that the ultrasonic power is 120W and the ultrasonic frequency is 45KHz, copper plating is carried out by taking a copper bar as an anode and an aluminum film silicon dioxide thin plate as a cathode to obtain a substrate; the concentration of copper chloride in the plating solution is 15g/L, the concentration of potassium salt mixture is 45g/L, and the concentration of the compound additive is 10g/L; the potassium salt mixture is prepared from potassium citrate and boric acid according to a mass ratio of 1.5: 1; the compound additive is a hydrate of Mo, wherein (NH) in the hydrate of Mo 4 ) 6 Mo 7 O 24 ·4H 2 The mass fraction of O is 90 percent, and the balance is ammonium acetate; the area ratio of the anode to the cathode is 2.5:1; the copper plating time is 12min;
and 2, step: continuously introducing Ar into the reaction chamber to exhaust air in the reaction chamber, then placing the substrate into the reaction chamber under the protection of Ar, heating the substrate from room temperature to 200 ℃ at the heating rate of 10 ℃/min, then heating the substrate from 200 ℃ to 700 ℃ at the heating rate of 15 ℃/min, preserving heat for 20min at the temperature, then heating the substrate from 700 ℃ to 760 ℃ at the heating rate of 5 ℃/min, and preserving heat for 20min after the substrate reaches the temperature;
and 3, step 3: introducing Ar and C into the reaction chamber after the step 2 2 H 4 Is reacted for 25min, wherein Ar and C 2 H 4 The flow ratio of (1) 2 H 4 Ar and the gas are continuously introduced for 30min, and then the reaction chamber is cooled to room temperature at the cooling rate of 40 ℃/min by adopting circulating cooling oil; the cooling by adopting the circulating cooling oil is realized by forming a cooling oil pipeline network which is arranged outside the reaction chamber and fully coats the reaction chamber in a spiral mode;
and 4, step 4: taking out the substrate, placing the substrate into a mixed acid solution consisting of 20wt% hydrochloric acid and 35wt% nitric acid according to a volume ratio of 3 2 The carbon content is 93.5 percent per gram, and the appearance is shown in figure 3.
Example 4: the preparation method of the small-size graphene of the embodiment includes the following steps:
step 1: adding the mixture of copper chloride and potassium salts and the compound additive into water to prepare a plating solution, and then adding the copper chloride, the potassium salt mixture and the compound additive into the plating solution at a pH value of 8.0 +/-0.5, a plating solution temperature of 45 ℃ and a current density of 3A/dm 2 Under the conditions that the ultrasonic power is 120W and the ultrasonic frequency is 45KHz, copper plating is carried out by taking a copper bar as an anode and an aluminum film silicon dioxide thin plate as a cathode to obtain a substrate; concentration of copper chloride in the plating solutionThe degree is 15g/L, the concentration of the sylvite mixture is 45g/L, and the concentration of the compound additive is 10g/L; the potassium salt mixture is prepared from potassium citrate and boric acid according to the mass ratio of 1.5: 1; the compound additive is a hydrate of Mo, wherein (NH) in the hydrate of Mo 4 ) 6 Mo 7 O 24 ·4H 2 The mass fraction of O is 90 percent, and the balance is ammonium acetate; the area ratio of the anode to the cathode is 2.5:1; the copper plating time is 12min;
step 2: continuously introducing Ar into the reaction chamber to exhaust air in the reaction chamber, then placing the substrate into the reaction chamber under the protection of Ar, heating the substrate from room temperature to 200 ℃ at the heating rate of 10 ℃/min, then heating the substrate from 200 ℃ to 700 ℃ at the heating rate of 15 ℃/min, preserving heat for 20min at the temperature, then heating the substrate from 700 ℃ to 720 ℃ at the heating rate of 5 ℃/min, and preserving heat for 20min after the substrate reaches the temperature;
and step 3: introducing Ar and C into the reaction chamber after the step 2 3 H 8 Is reacted for 20min, wherein Ar and C 3 H 8 The flow ratio of (1) to (3), and after the reaction was completed, the introduction of C was stopped 3 H 8 Continuously introducing Ar for 30min, and cooling the reaction chamber to room temperature at a cooling rate of 45 ℃/min by adopting circulating cooling oil; the cooling by adopting the circulating cooling oil is realized by forming a cooling oil pipeline network which is arranged outside the reaction chamber and fully covers the reaction chamber in a spiral mode;
and 4, step 4: taking out the substrate, putting the substrate into a mixed acid solution consisting of 20wt% hydrochloric acid and 35wt% nitric acid according to a volume ratio of 3 2 The carbon content is 91 percent per gram, and the appearance is shown in figure 4.
Example 5: the preparation method of the small-size graphene of the embodiment includes the following steps:
step 1: adding copper chloride, potassium salt mixture and compound additive into water to prepare plating solution, and then adding the plating solution into the plating solutionAt pH of 8.0 + -0.5, plating solution temperature of 45 deg.C, and current density of 3A/dm 2 Under the conditions that the ultrasonic power is 120W and the ultrasonic frequency is 45KHz, copper plating is carried out by taking a copper bar as an anode and an aluminum film silicon dioxide thin plate as a cathode to obtain a substrate; the concentration of copper chloride in the plating solution is 15g/L, the concentration of potassium salt mixture is 45g/L, and the concentration of the compound additive is 10g/L; the potassium salt mixture is prepared from potassium citrate and boric acid according to the mass ratio of 1.5: 1; the compound additive is a hydrate of Mo, wherein (NH) in the hydrate of Mo 4 ) 6 Mo 7 O 24 ·4H 2 The mass fraction of O is 90 percent, and the balance is ammonium acetate; the area ratio of the anode to the cathode is 2.5:1; the copper plating time is 12min;
and 2, step: continuously introducing Ar into the reaction chamber to exhaust air in the reaction chamber, then placing the substrate into the reaction chamber under the protection of Ar, heating the substrate from room temperature to 200 ℃ at the heating rate of 10 ℃/min, then heating the substrate from 200 ℃ to 600 ℃ at the heating rate of 15 ℃/min, preserving heat at the temperature for 20min, heating the substrate from 600 ℃ to 670 ℃ at the heating rate of 5 ℃/min, and preserving heat for 20min after the substrate reaches the temperature;
and step 3: introducing Ar and C into the reaction chamber after the step 2 3 H 6 Is reacted for 30min, wherein Ar and C 3 H 6 The flow ratio of (1) 3 H 6 Continuously introducing Ar for 30min, and cooling the reaction chamber to room temperature at a cooling rate of 50 ℃/min by adopting circulating cooling oil; the cooling by adopting the circulating cooling oil is realized by forming a cooling oil pipeline network which is arranged outside the reaction chamber and fully coats the reaction chamber in a spiral mode;
and 4, step 4: taking out the substrate, placing the substrate into a mixed acid solution consisting of 20wt% hydrochloric acid and 35wt% nitric acid according to a volume ratio of 3 2 The carbon content is 91 percent per gram, and the appearance is shown in figure 5.
Example 6, the difference of this example from example 1 is: in step 1, the temperature of the plating solution is 25 ℃, 30 ℃, 35 ℃, 40 ℃, 50 ℃, 55 ℃ and 60 ℃. The other steps and parameters were the same as in example 1.
Example 7, this example is different from example 1 in that: the stirring mode in the step 1 is magnetic stirring, and the magnetic stirring parameter is 150r/min. The other steps and parameters were the same as in example 1.
Example 8 visual evaluation of the appearance of the copper plating layer obtained in step 1 of examples 1 to 5 was carried out, and the appearance was rated a.
| Grade | Appearance of the product |
| A | The surface of the plating layer is bright and bright in color |
| B | The semi-bright color and luster of the surface of the plating layer are relatively bright |
| C | The surface of the plating layer has slight brightness and dark color |
| D | The surface of the plating layer has no brightness and dark color |
Example 9, the coatings on the substrates obtained in step 1 of examples 1 and 6 were examined, and a graph showing the change of the coating weight with the temperature of the coating solution as shown in fig. 6 was obtained.
Example 10, the coatings on the substrates obtained in step 1 of examples 1 and 7 were examined, and a bar graph showing the change of coating film weight depending on the stirring manner as shown in fig. 7 was obtained.
Claims (5)
1. A preparation method of small-size graphene is characterized by comprising the following steps:
step 1: adding the mixture of copper chloride and sylvite and compound additive into water to prepare plating solution, and then controlling the pH value to be 8.0 +/-0.5, the temperature of the plating solution to be 40-50 ℃ and the current density to be 2A/dm 2 ～5A/dm 2 Under the condition of constant-temperature oil bath with the ultrasonic power of 100W-140W and the ultrasonic frequency of 40 KHz-50 KHz, copper plating is carried out by taking a copper bar as an anode and an aluminum film silicon dioxide thin plate as a cathode to obtain a substrate; the concentration of copper chloride in the plating solution is 10-30 g/L, the concentration of potassium salt mixture is 15-75 g/L, the concentration of compound additive is 5-30 g/L, the potassium salt mixture is the mixture of any two of potassium citrate, potassium chloride, potassium hydroxide and boric acid, and the compound additive is a hydrate of Mo;
and 2, step: continuously introducing inert gas into the reaction chamber to exhaust air in the reaction chamber, then placing the substrate into the reaction chamber under the protection of the inert gas, heating the reaction chamber to 670-1100 ℃ from room temperature in a staged heating mode, and keeping the temperature for 10-30 min after the temperature is reached;
and 3, step 3: introducing a mixture of inert gas and carbon-containing organic gaseous substances into the reaction chamber after the step 2 for reaction for 10-30 min, stopping introducing the carbon-containing organic gaseous substances after the reaction is finished, continuously introducing the inert gas for 10-30 min, and cooling by adopting circulating cooling oil until the temperature of the reaction chamber is reduced to room temperature; the cooling by adopting the circulating cooling oil is realized by forming a cooling oil pipeline network which is arranged outside the reaction chamber and fully coats the reaction chamber in a spiral form, the cooling rate of the cooling by adopting the circulating cooling oil in the step 3 is 30-50 ℃/min, and the flow ratio of inert gas to carbon-containing organic gaseous substances in the mixture is 1: (3-4);
and 4, step 4: taking out the substrate, putting the substrate into a mixed acid solution for treatment for 60-90 min, putting the filtered product into a sulfuric acid solution again for treatment for 120-200 min, washing the filtered product to be neutral, filtering and drying to obtain the small-size graphene, wherein the transverse size of the obtained small-size graphene is 50-200nm, and the carbon content is more than or equal to 87%.
2. The method for preparing small-size graphene according to claim 1, wherein the area ratio of the anode to the cathode in step 1 is (2-3): 1, the copper plating time in the step 1 is 10-15 min.
3. The method for preparing small-size graphene according to claim 1, wherein the step 2 of raising the temperature in the stage comprises the following specific steps: the temperature is raised from the room temperature to 150-250 ℃ at the heating rate of 8-12 ℃/min, then is raised from 150-250 ℃ to 600-900 ℃ at the heating rate of 14-16 ℃/min, is kept at the temperature for 10-30 min, and is raised from 600-900 ℃ to 670-1100 ℃ at the heating rate of 4-6 ℃/min.
4. The method for preparing small-size graphene according to claim 1, wherein the inert gas in step 3 is nitrogen, argon or helium, the carbon-containing organic gaseous substance is a carbon-containing organic gas or a gasified organic liquid, the carbon-containing organic gas is methane, natural gas, ethane, ethylene, acetylene, propane or propylene, the gasified organic liquid is absolute methanol, absolute ethanol, benzene, toluene or xylene, and the gasification temperature is 120-300 ℃.
5. The method according to claim 1, wherein the mixed acid in the step 4 is a mixture of hydrochloric acid and nitric acid, wherein the volume ratio of hydrochloric acid to nitric acid is 3:1, the mass concentration of hydrochloric acid is 15-25%, the mass concentration of nitric acid is 30-40%, and the concentration of the sulfuric acid solution in the step 4 is 8-10 mol/L.
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