CN113897590B - Method for growing graphene film on surface of copper powder - Google Patents
Method for growing graphene film on surface of copper powder Download PDFInfo
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- CN113897590B CN113897590B CN202010573258.6A CN202010573258A CN113897590B CN 113897590 B CN113897590 B CN 113897590B CN 202010573258 A CN202010573258 A CN 202010573258A CN 113897590 B CN113897590 B CN 113897590B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 144
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 67
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 44
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 28
- 239000012298 atmosphere Substances 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 230000001681 protective effect Effects 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000012300 argon atmosphere Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000006911 nucleation Effects 0.000 abstract description 5
- 238000010899 nucleation Methods 0.000 abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000010949 copper Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000001237 Raman spectrum Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0209—Pretreatment of the material to be coated by heating
- C23C16/0218—Pretreatment of the material to be coated by heating in a reactive atmosphere
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
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Abstract
A method for growing a graphene film on the surface of copper powder comprises the following steps: s1: after the copper powder or the copper powder mixture is initially heated to an oxidation temperature in a chemical vapor deposition furnace, performing pre-oxidation treatment on the copper powder; s2: after the pre-oxidation treatment is finished, continuously heating the chemical vapor deposition furnace to a growth temperature, and simultaneously carrying out reduction of the copper powder surface and growth operation of graphene; s3: and after the growth is finished, cooling the growth product. According to the method for growing the graphene film on the surface of the copper powder, disclosed by the invention, the growth process of the graphene film on the surface of the copper powder is simplified, and the overall process efficiency is improved. In addition, the pre-oxidation treatment is matched with the reduction and growth operation in the later period, so that nucleation points on the surface of the copper powder are reduced, the grain size of a graphene film formed by growing on the surface of the copper powder is larger, the grain boundary and defects of the graphene can be reduced, and the quality of the graphene is greatly improved.
Description
Technical Field
The invention relates to the technical field of graphene material preparation, in particular to a method for growing a graphene film on the surface of copper powder.
Background
Graphene is a two-dimensional crystal formed by stacking carbon atoms in an sp 2 hybridized connection mode, has good mechanical properties and electrical properties, can endow a composite material with more excellent properties by utilizing the excellent properties of the graphene through the composition with other materials, is an important part in the research of the graphene nanocomposite, and particularly is one of the hot spots in the current material research field.
It is known from the existing research reports and practical processes that the current method for growing the graphene film on the surface of the copper powder is mainly a chemical vapor deposition method. The chemical vapor deposition method is to put copper powder or copper powder mixed with an anti-sintering agent into a proper container, grow graphene in a chemical vapor deposition furnace, firstly raise the temperature from room temperature to the temperature required by growth in a protective atmosphere within a certain time, then anneal in a certain reducing atmosphere and protective atmosphere, then introduce the atmosphere required by growth to grow graphene, and naturally cool in the protective atmosphere after the growth is finished. The growth method comprises four stages of heating, annealing, growing and cooling, and the whole time consumption is long; in addition, although the graphene film with good coating property can be obtained on the surface of the copper powder by the method, the grain size of the grown graphene film is smaller and is generally only 1-2 microns, so that the grain boundary and defects of the graphene are relatively large, the quality of the graphene film is adversely affected, and the excellent performance of the graphene is prevented from being exerted.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method capable of effectively improving the overall process efficiency of the growth of a graphene film on the surface of copper powder and improving the quality of graphene.
In order to achieve the above purpose, the invention adopts the following technical scheme: the method for growing the graphene film on the surface of the copper powder is characterized by comprising the following steps of:
s1: after the copper powder or the copper powder mixture is initially heated to an oxidation temperature in a chemical vapor deposition furnace, performing pre-oxidation treatment on the copper powder;
S2: after the pre-oxidation treatment is finished, continuously heating the chemical vapor deposition furnace to a growth temperature, and simultaneously carrying out reduction of the copper powder surface and growth operation of graphene;
S3: and after the growth is finished, cooling the growth product.
Preferably, the specific operation of S1 is: heating copper powder or copper powder mixture from room temperature to oxidation temperature of 100-300 ℃ under protective atmosphere, wherein the protective atmosphere is nitrogen atmosphere or argon atmosphere; after the temperature in the chemical vapor deposition furnace reaches the oxidation temperature, oxidizing gas is introduced into the chemical vapor deposition furnace, and the surface of the copper powder is oxidized to form copper oxide, so that pre-oxidation treatment is realized.
Preferably, the oxidizing gas is oxygen or air, the flow rate of the oxidizing gas is 1 sccm-200 sccm, and the oxidation time of the pre-oxidation treatment is 10-60 min.
Preferably, the copper powder is spherical, dendritic or flaky, and the particle size of the copper powder is 100-15000 meshes.
Preferably, the copper powder mixture is mixed powder of copper powder and an anti-sintering agent, and the anti-sintering agent is one or more of polyvinyl alcohol, sodium chloride, magnesium oxide, graphite powder and potassium carbonate.
Preferably, the copper powder or the copper powder mixture in the step S1 is placed in a growth vessel, and the growth vessel is one of a quartz boat, a graphite boat or a ceramic boat.
Preferably, the specific operation of S2 is: raising the temperature in the chemical vapor deposition furnace to the growth temperature of 950-1050 ℃ under a protective atmosphere, wherein the protective atmosphere is nitrogen atmosphere or argon atmosphere; after the temperature in the chemical vapor deposition furnace reaches the growth temperature, introducing growth gas into the chemical vapor deposition furnace, and simultaneously realizing reduction of the copper powder surface and growth of graphene.
Preferably, the growth gas is a mixed gas formed by methane, hydrogen and a protective gas, the mixed gas is one of argon and nitrogen, the flow of the methane is 5-50 sccm, the flow of the hydrogen is 10-200 sccm, the flow of the protective gas is 40-300 sccm, and the graphene growth time is 30-120 min.
Preferably, the S3 cooling treatment is a natural cooling in a protective atmosphere, and the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
Preferably, the method for growing the graphene film on the surface of the copper powder further comprises the following steps:
s4: the product after the cooling treatment is cleaned by pure water, ethanol or acid solution to remove impurities.
According to the method for growing the graphene film on the surface of the copper powder, a section of pre-oxidation process of the copper powder is inserted in an initial temperature rising stage, so that the copper powder surface is oxidized to form copper oxide, and the reduction treatment of the copper powder and the growth process of the graphene are carried out simultaneously in a later stage, so that an annealing step in a traditional process is abandoned, the growth process of the graphene film on the surface of the copper powder is simplified, the overall process efficiency is improved, and the quality of the graphene is also improved.
The principle is that a copper powder pre-oxidation process is inserted in an initial temperature rising stage, but a reduction treatment in a later stage and a graphene growth process are carried out simultaneously, so that the process steps are increased, an annealing step in the traditional process is abandoned, and in the growth stage, the decomposition potential barrier of methane can be reduced due to the existence of oxygen atoms at a high temperature, so that the methane is easier to decompose, the growth rate of the graphene can be accelerated, the growth time is shortened to a certain extent, the whole time consumption is shortened by about 20% -30%, and the process efficiency is improved. Meanwhile, as the oxidation treatment on the surface of the copper powder is matched with the reduction and growth operation in the later period, nucleation points are reduced, so that the grain size of the graphene film obtained by growth is larger and can reach 5-10 microns generally, compared with the prior art, the grain boundary and defects are reduced, and the quality of the graphene is greatly improved.
Drawings
FIG. 1 is an SEM test chart of the internal cross-section of a sample three-dimensional copper/graphene in example 1 of the present invention;
Fig. 2 is an enlarged view of graphene grains grown on the surface of copper powder in the conventional process;
fig. 3 is an enlarged view of graphene grains grown on the surface of copper powder in the conventional process;
FIG. 4 is a graph of the graphene Raman spectrum of the sample in example 1 of the present invention;
FIG. 5 is a Raman spectrum of graphene formed by copper powder surface growth in the conventional process;
Fig. 6 is an SEM test chart of the sample copper powder of example 2 of the present invention with graphene grown on the surface.
Detailed Description
Specific embodiments of the method for growing graphene film on the surface of copper powder according to the present invention are further described below with reference to examples. The method of growing a graphene film on the surface of copper powder according to the present invention is not limited to the description of the following examples.
Embodiment one:
the embodiment provides a method for growing a graphene film on the surface of copper powder, which sequentially comprises the following steps:
S1: weighing 200g of 100-mesh copper powder, placing the copper powder into a ceramic boat, and uniformly spreading the copper powder, wherein the copper powder can be any one of spherical, dendritic or flaky copper powder; pushing a ceramic boat filled with copper powder to the center of a constant temperature area of a chemical vapor deposition furnace, introducing 300sccm of argon gas to enable the copper powder to be in an argon atmosphere, and raising the furnace temperature from room temperature to 300 ℃ in the argon atmosphere; closing argon, introducing 1sccm of oxygen to perform pre-oxidation treatment on the surface of the copper powder, and preserving the heat for 10min.
In the embodiment, a section of copper powder is inserted in the preliminary oxidation process of the copper powder in the initial temperature rising stage of the process, namely, when the temperature rises to a lower temperature, the copper powder is oxidized at the temperature, so that the oxidation degree of the copper powder can be better controlled, oxide skin is only on the outer surface layer of the copper powder, the copper powder cannot be oxidized seriously, the oxidized part of the copper powder can be reduced to the copper surface easily after the later hydrogen is introduced, and the conductivity of the sample copper graphene formed later cannot be influenced.
In addition, the surface of the copper powder is oxidized by the pre-oxidation treatment, so that impurities and defects on the surface of the copper powder can be reduced, nucleation points on the surface of the copper powder are reduced, the nucleation density of graphene is reduced, the growth of a graphene film with a larger-size crystal domain is facilitated, the grain boundary and defects of the graphene are reduced, and the quality of the graphene is improved.
S2: and (3) after the heat preservation is carried out for 10min, closing oxygen, and recovering the introduction of 300sccm argon again, continuously raising the furnace temperature to 1050 ℃ in the argon atmosphere, and then introducing mixed gas of methane, hydrogen and argon into the furnace, wherein the flow of methane is 50sccm, the flow of hydrogen is 200sccm, the flow of argon is 300sccm, in the atmosphere of the mixed gas, reducing the surface of copper powder, simultaneously starting to grow a graphene film on the surface of copper powder, and the growth time is 30min, thus obtaining a growth product.
In the step, methane, hydrogen and shielding gas argon are simultaneously introduced, so that the reduction of the copper powder surface and the growth of the graphene film are simultaneously carried out, and the whole time consumption of the process is saved. In addition, after S1 pre-oxidation treatment, copper oxide is formed on the surface of the copper powder by oxidation, and oxygen elements can reduce the decomposition potential barrier of methane, so that methane is easier to decompose, carbon atoms split from the methane are more rapid, and correspondingly, the growth rate of graphene is faster.
Meanwhile, the hydrogen is introduced to reduce the oxidized copper formed by oxidizing the copper powder surface, and under the environment of high growth temperature, the reduced copper powder surface is subjected to single crystallization reconstruction, so that more crystal faces suitable for the growth of graphene are formed on the copper powder surface, the copper powder surface becomes smooth, carbon atoms can migrate more smoothly on the copper surface, and the nucleation and growth rate is faster, so that the process efficiency of the growth of graphene is further improved.
The copper oxide formed by oxidizing the surface of the copper powder can slow down the sintering degree of the copper powder, the pure copper powder can be melted and sintered at high temperature, the copper powder surface after S1 pre-oxidation treatment forms an oxide layer, and the existence of the oxide layer can slow down the sintering degree of the copper powder, so that the structure of the 3D network through holes is reserved to the maximum extent, the interior of the 3D copper structure is promoted to be full of graphene, and the guarantee is provided for the successful preparation of the 3D copper/graphene composite material.
S3: and after the growth is finished, closing methane and hydrogen, and naturally cooling a growth product in an argon atmosphere formed by 300sccm of argon to form a sample.
The sample formed by the method is tested by means of Raman spectrum, a scanning electron microscope and the like, and the copper powder is sintered to form a three-dimensional network structure, as shown in figure 1, the graphene uniformly grows inside and outside the three-dimensional structure, the coating rate of the graphene on the copper surface is about 99%, the grain size of the graphene is larger and is about 8-10 microns, and the grain size of the graphene is far larger than that of the graphene formed by the growth on the copper powder surface in the traditional process.
Fig. 4 is a graphene raman spectrum of a sample of the embodiment, and fig. 5 is a graphene raman spectrum of a product prepared by a conventional process, as shown in fig. 4 and 5, a D peak in fig. 4 is significantly lower than a D peak in fig. 5, so that the sample prepared by the embodiment has low structural defect and more complete graphite crystallites.
According to calculation, compared with the traditional copper powder surface graphene growth method, the overall time of the method is shortened by 30%.
Example two
The embodiment provides a method for growing a graphene film on the surface of copper powder, which sequentially comprises the following steps:
S1: the mixed powder of the copper powder and the anti-sintering agent is placed in a quartz boat and uniformly spread, the anti-sintering agent can be one or more of polyvinyl alcohol, sodium chloride, magnesium oxide, graphite powder and potassium carbonate, the anti-sintering agent can be decomposed at high temperature to reduce the sintering degree of the copper powder, and the anti-sintering agent which is not decomposed at high temperature can be removed in pure water, ethanol or acid solution after the preparation of the sample is finished, so that the quality of a final sample is not affected. In the embodiment, 200g of copper powder with 15000 meshes and 40g of superfine sodium chloride powder are weighed, the copper powder and the sodium chloride powder are uniformly mixed by a powder mixer, the mixture is placed in a quartz boat and uniformly spread, the quartz boat filled with the mixed powder is pushed to the center of a constant temperature area of a chemical vapor deposition furnace, 200sccm of argon is introduced, the mixed powder is in an argon atmosphere, and the furnace temperature is raised from room temperature to 100 ℃ in the argon atmosphere; and closing argon, introducing 200sccm of oxygen to oxidize the surface of the copper powder, and preserving the heat for 60 minutes.
S2: and (3) after heat preservation for 60min, closing oxygen, recovering the introduction of 200sccm argon again, continuously raising the furnace temperature to 950 ℃ in the argon atmosphere, and then introducing mixed gas of methane, hydrogen and argon into the furnace, wherein the flow of methane is 5sccm, the flow of hydrogen is 10sccm, the flow of argon is 40sccm, reducing the surface of copper powder in the mixed gas atmosphere, and simultaneously starting to grow a graphene film on the surface of copper powder, wherein the growth time is 60min, so that a growth product is obtained.
S3: and after the growth is finished, closing methane and hydrogen, and naturally cooling the growth product in an argon atmosphere formed by 200sccm of argon.
S4: and cleaning the cooled product by pure water to remove the undegraded sodium chloride in the product to form a sample.
The copper powder in the sample formed by the method is tested by means of Raman spectrum, a scanning electron microscope and the like, and the copper powder is not sintered together, as shown in fig. 6, the graphene uniformly grows on the surface of the copper powder, the coating rate of the graphene on the surface of the copper is about 95%, the grain size of the graphene is larger, and the grain size of the graphene is about 5-8 microns.
According to calculation, compared with the traditional copper powder surface graphene growth method, the overall time of the method is shortened by 20%.
Example III
The embodiment provides a method for growing a graphene film on the surface of copper powder, which sequentially comprises the following steps:
S1: 200g of 200-mesh copper powder is weighed and placed in a ceramic boat and uniformly spread, wherein the copper powder can be any one of spherical, dendritic or flaky; pushing a ceramic boat filled with copper powder to the center of a constant temperature area of a chemical vapor deposition furnace, introducing 100sccm of nitrogen, enabling the copper powder to be in an argon atmosphere, and raising the furnace temperature from room temperature to 250 ℃ in the nitrogen atmosphere; and closing nitrogen, introducing oxygen of 2sccm to oxidize the surface of the copper powder, and preserving the heat for 10min.
S2: and (3) after the heat preservation is carried out for 10 minutes, closing oxygen, recovering the introduction of 100sccm nitrogen again, continuously increasing the furnace temperature to 1020 ℃ in an argon atmosphere, and then introducing mixed gas of methane, hydrogen and nitrogen into the furnace, wherein the flow of the methane is 10sccm, the flow of the hydrogen is 50sccm, the flow of the nitrogen is 100sccm, reducing the surface of copper powder in the atmosphere of the mixed gas, and simultaneously starting to grow a graphene film on the surface of copper powder, wherein the growth time is 120 minutes, so that a growth product is obtained.
S3: and after the growth is finished, closing methane and hydrogen, and naturally cooling the growth product in a nitrogen atmosphere formed by 100sccm of nitrogen to form a sample.
After the samples formed by the method are tested by means of Raman spectrum, a scanning electron microscope and the like, the copper powder is sintered to form a three-dimensional network structure, the graphene uniformly grows inside and outside the three-dimensional structure, the coating rate of the graphene on the copper surface is about 98%, the grain size of the graphene is larger, and the grain size of the graphene is about 7-9 microns.
According to calculation, compared with the traditional copper powder surface graphene growth method, the overall time of the method is shortened by 20%.
Example IV
The embodiment provides a method for growing a graphene film on the surface of copper powder, which sequentially comprises the following steps:
S1: placing mixed powder of copper powder and an anti-sintering agent in a quartz boat, uniformly spreading, wherein the anti-sintering agent can be one or more of polyvinyl alcohol, sodium chloride, magnesium oxide, graphite powder and potassium carbonate; and closing argon, introducing 100sccm of air to oxidize the surface of the copper powder, and preserving the heat for 30min.
S2: and (3) after heat preservation for 30min, closing air, recovering the introduction of 200sccm argon again, continuously raising the furnace temperature to 1000 ℃ in the argon atmosphere, and then introducing mixed gas of methane, hydrogen and argon into the furnace, wherein the flow of the methane is 20sccm, the flow of the hydrogen is 100sccm, the flow of the argon is 240sccm, reducing the surface of copper powder in the mixed gas atmosphere, and simultaneously starting to grow a graphene film on the surface of copper powder, wherein the growth time is 90min, so that a growth product is obtained.
S3: and after the growth is finished, closing methane and hydrogen, and naturally cooling the growth product in an argon atmosphere formed by 200sccm of argon.
S4: the cooled product is washed by sulfuric acid aqueous solution with the mass fraction of 1.5 percent so as to remove the non-decomposed magnesium oxide in the product and form a sample.
The copper powder in the sample formed by the method is tested by means of Raman spectrum, a scanning electron microscope and the like, and the copper powder is not sintered together, the graphene uniformly grows on the surface of the copper powder, the coating rate of the graphene on the surface of the copper is about 98%, the grain size of the graphene is larger, and the grain size of the graphene is about 7-10 microns.
According to calculation, compared with the traditional copper powder surface graphene growth method, the overall time of the method is shortened by 20%.
According to the first to fourth embodiments, compared with the whole time consumption of the traditional process, the method for growing the graphene film on the copper powder surface shortens 20% -30%, improves the processing efficiency of the graphene film, and greatly reduces the grain boundary and defects of the graphene film, and greatly improves the quality of the graphene.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (9)
1. The method for growing the graphene film on the surface of the copper powder is characterized by comprising the following steps of:
s1: after the copper powder is initially heated to an oxidation temperature in a chemical vapor deposition furnace, performing pre-oxidation treatment on the copper powder, wherein the specific operation of S1 is as follows: heating copper powder to an oxidation temperature of 100-300 ℃ from room temperature in a protective atmosphere to realize preliminary heating, introducing oxidizing gas into a chemical vapor deposition furnace after the temperature in the chemical vapor deposition furnace reaches the oxidation temperature, and oxidizing the surface of the copper powder to form copper oxide to realize pre-oxidation treatment; the flow of the oxidizing gas is 1 sccm-2 sccm, and the oxidation time of the pre-oxidation treatment is 10-60 min;
S2: after the pre-oxidation treatment is finished, continuously heating the chemical vapor deposition furnace to a growth temperature, and simultaneously carrying out reduction of the copper powder surface and growth operation of graphene; sintering copper powder into a three-dimensional network structure;
S3: and after the growth is finished, cooling the growth product.
2. The method for growing a graphene film on a copper powder surface according to claim 1, wherein the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
3. The method for growing a graphene film on the surface of copper powder according to claim 2, wherein the oxidizing gas is oxygen or air.
4. The method for growing a graphene film on the surface of copper powder according to claim 1, wherein the copper powder is spherical, dendritic or flaky, and the particle size of the copper powder is 100-15000 meshes.
5. The method for growing a graphene film on the surface of copper powder according to claim 1, wherein the copper powder in S1 is placed in a growth vessel, and the growth vessel is one of a quartz boat, a graphite boat or a ceramic boat.
6. The method for growing a graphene film on the surface of copper powder according to claim 1, wherein the specific operation of S2 is as follows: raising the temperature in the chemical vapor deposition furnace to the growth temperature of 950-1050 ℃ under a protective atmosphere, wherein the protective atmosphere is nitrogen atmosphere or argon atmosphere; after the temperature in the chemical vapor deposition furnace reaches the growth temperature, introducing growth gas into the chemical vapor deposition furnace, and simultaneously realizing reduction of the copper powder surface and growth of graphene.
7. The method for growing a graphene film on the surface of copper powder according to claim 6, wherein the growth gas is a mixed gas formed by methane, hydrogen and a protective gas, the protective gas is one of argon and nitrogen, the flow rate of the methane is 5-50 sccm, the flow rate of the hydrogen is 10-200 sccm, the flow rate of the protective gas is 40-300 sccm, and the graphene growth time is 30-120 min.
8. The method for growing a graphene film on the surface of copper powder according to claim 1, wherein the S3 cooling treatment is natural cooling in a protective atmosphere, and the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
9. The method for growing a graphene film on a copper powder surface according to claim 1, wherein the method for growing a graphene film on a copper powder surface further comprises:
s4: the product after the cooling treatment is cleaned by pure water, ethanol or acid solution to remove impurities.
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