CN116536641A - High-conductivity copper graphene composite material and continuous preparation method thereof - Google Patents
High-conductivity copper graphene composite material and continuous preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 285
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 225
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 136
- 239000010949 copper Substances 0.000 title claims abstract description 136
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title description 15
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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
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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
- C23C16/44—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
-
- 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
- C23C16/52—Controlling or regulating the coating process
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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
- C23C16/44—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
- C23C16/54—Apparatus specially adapted for continuous coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a high-conductivity copper graphene composite material, which comprises a copper substrate and a graphene layer, wherein the graphene layer comprises a graphene bottom layer and a plurality of graphene units, the graphene bottom layer is covered on the surface of the copper substrate, the plurality of graphene units are continuously or intermittently distributed on the surface of the graphene bottom layer, each graphene unit comprises a plurality of graphene unit layers which are sequentially stacked from bottom to top and have the same area or sequentially reduced, the graphene coverage rate of the surface of the copper substrate is more than or equal to 96%, the characteristic peak of a graphene Raman spectrum comprises a D peak and a G peak, and the intensity ratio I of the D peak to the G peak D /I G 0 to 0.55. The invention can obtain a high-quality graphene layer, provide a continuous transmission path for electrons, reduce the scattering of electrons,and the copper base material is prevented from being oxidized or corroded, the conductivity and the conductivity stability of the copper graphene composite material are improved, the conductivity of the high-conductivity copper graphene composite material is not lower than 103% IACS, and the performance requirement of the related technical field on the high conductivity is met.
Description
Technical Field
The invention belongs to the technical field of copper-based composite materials, and particularly relates to a high-conductivity copper graphene composite material and a continuous preparation method thereof.
Background
Copper has good conductivity, is determined as one of main materials of wires, and is widely applied to the application fields with high conductive performance requirements, such as cable wires, automobile wire harnesses, 3C power wires, sound wires, PCBs, electronic packages, electromagnetic shielding and the like. With the technical improvement of the industry market, the requirements on the conductivity of copper are higher and higher, and particularly in the future high-speed transmission of 112G or more. Currently, the more conventional methods for improving the conductivity of copper are purification and single crystallization, but purification and single crystallization have approached the physical limit of copper.
Graphene is a research hotspot in the current industry, and has been found to be a material that can be changed in the future. Researches show that if graphene and copper can be combined to prepare a novel composite material, the advantages of the graphene and copper are complemented, and electrons can run more quickly. In the research and development of the graphene reinforced copper-based composite material conductivity at present, a powder metallurgy method, an electrodeposition method, a molecular level mixing method and a Chemical Vapor Deposition (CVD) method are mainly adopted, wherein the three methods can improve the dispersibility and the interfacial bonding strength of the graphene to a certain extent, but the quality and the distribution of the graphene in the copper-based material are poor, and the conductivity of the reinforced copper-based composite material is limited.
The structural integrity and uniform and ordered distribution of graphene are beneficial to exerting the high performance of the reinforcement and the copper matrix, and are also important factors affecting the conductivity of the composite material. The high performance of graphene can be maintained while the graphene and copper interface in the composite material prepared by CVD are well combined, and the CVD is expected to realize the copper graphene composite material with higher conductivity than pure copper, but still has the problems of low industrial production difficulty, low repeatability, poor stability and the like.
In view of the above, the excellent performance of graphene as a reinforcement in a copper matrix has not been fully developed. How to solve the complex problems, so as to prepare graphene-reinforced copper-based composite materials with continuous, high-quality and orderly distribution, and realize industrial production, and the preparation method is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a high-conductivity copper graphene composite material.
The technical scheme adopted by the invention for solving the first technical problem is as follows: the utility model provides a high-conductivity copper graphene composite, this high-conductivity copper graphene composite includes copper substrate and graphene layer, the graphene layer include graphene bottom and a plurality of graphene unit, the graphene bottom cover be in the surface of copper substrate, a plurality of graphene unit continuous or interval distribution be in the surface of graphene bottom, every graphene unit include from bottom to top stacks gradually and a plurality of graphene unit layers that the area is the same or reduces in proper order, the graphene coverage rate of copper substrate surface be greater than or equal to 96%, include D peak and G peak in the graphene raman spectrum characteristic peak, D peak and G peak's intensity ratio I D /I G 0 to 0.55.
According to the high-conductivity copper graphene composite material, the graphene coverage rate of the surface of the copper substrate is more than or equal to 96%, and the graphene layer provides a continuous transmission path for electrons on one hand, so that the scattering of the electrons is reduced; on the other hand, the high-coverage graphene can prevent the copper base material from being oxidized or corroded, and the conductivity stability of the copper graphene composite material are improved.
In raman spectroscopy, graphene has three characteristic peaks: d peak, G peak and 2D peak. Graphene at 1580cm -1 (G peak) and 2700cm -1 The two positions (2D peak) have more obvious absorption peaks. G peak (1580 cm) -1 ) Representing brillouin zone scattering E 2g Double degeneracy of vibrational modes revealing sp of carbon atoms 2 The bond structure reflects the degree of crystallization and symmetry within the sample. Generally, the higher the G peak, the sharper the peak form, the higher the graphene purity of the resulting sample; 2D peak (2700 cm) -1 ) The secondary Raman scattering from boundary phonons of the Brillouin zone is the most remarkable characteristic of graphene, and the position and the shape of the secondary Raman scattering are related to the formation and the layer number of the graphene; the D peak (1350 cm) sometimes appears -1 ) It represents a structural defect of graphene, and the lower the D peak, the more complete the structure of graphene. If the D peak is large and the peak shape is wide, the defects in the graphene layer are more. In other words, the graphene layer with higher quality may even have no D peak or very small D peak. Intensity ratio of D peak to G peak I D /I G Representing the degree of crystallization of the carbon material or the content of amorphous carbon, the lattice defects of the graphene layer can be quantitatively analyzed. Intensity ratio I D /I G The larger the specification, the greater the degree of lattice defect: the smaller the ratio, the higher the quality of the graphene layer.
The invention specifically limits the intensity ratio I of D peak to G peak of the characteristic peak of the graphene Raman spectrum in the graphene layer D /I G And the content of the graphene is 0 to 0.55, so that few defects and high quality of graphene in the graphene layer can be ensured. The high-quality graphene layer plays an important role in improving the conductivity of the copper graphene composite material, because the high-quality graphene layer has small defect density and complete crystal structure, and can reduce electron scattering, so that the conductivity of the copper graphene composite material is improved.
In the process of depositing graphene on the surface of the copper substrate, carbon atoms generated by pyrolysis can only be adsorbed on the surface of the copper substrate and migrate on the surface of the copper substrate, and then the graphene layer is obtained by nucleation and growth. The graphene follows a surface catalysis mechanism on the surface of the copper substrate, the deposition of a first layer of graphene (namely a graphene bottom layer) is preferentially completed on the surface of the copper substrate, when the first layer of graphene covers the surface of the copper substrate, the copper substrate is difficult to continuously catalyze and crack a carbon source, the speed and the area of each graphene unit layer which continuously grows subsequently are gradually and greatly reduced, and even the crystallinity of the subsequently deposited graphene is degraded. But at some active nucleation sites, deposition of multiple layers of graphene may be performed simultaneously, while deposition of the first layer of graphene is still preferentially accomplished. Therefore, the composition of the graphene layer on the surface of the copper substrate of the present invention is expressed as follows: the graphene unit layer comprises a graphene bottom layer directly attached to and covered on the surface of a copper substrate, and a plurality of graphene units based on the graphene bottom layer and distributed on the graphene bottom layer continuously or at intervals, wherein each graphene unit comprises a plurality of graphene unit layers which are stacked from bottom to top in sequence and have the same area or are reduced in sequence.
Preferably, the number of graphene unit layers of each graphene unit is 0 to 9. We find that when the number of graphene unit layers is higher than 9, the D peak intensity value of the graphene Raman spectrum in the graphene layer is obviously higher, which indicates that the crystal defects of the graphene layer are increased, and further the improvement of the conductivity of the copper substrate and the stability of the conductivity of the graphene are affected.
Preferably, the coverage area of the graphene bottom layer on the surface of the copper base material is marked as A, and the orthographic projection area of all graphene units with the number of layers being more than 5 on the surface of the copper base material is marked as B, so that the ratio B/A of B to A is less than or equal to 50%. According to a great amount of experimental researches, the conductivity of the copper graphene composite material is increased and then reduced along with the increase of the number of graphene layers on the surface of the copper substrate, namely, when the orthographic projection area ratio of all graphene units with the number of layers being more than 5 is increased, the conductivity of the copper graphene composite material is in a decreasing trend. The main reason is that after the orthographic projection area ratio of all graphene units with the number of layers being more than 5 is increased, on one hand, the crystal defects of the graphene layers are increased, and even a small amount of amorphous carbon is generated; on the other hand, the uniformity of the number of graphene layers is reduced, the probability of electron scattering is increased, and the conductivity of the copper graphene composite material is further affected.
Through detection, the conductivity of the high-conductivity copper graphene composite material is not lower than 103% IACS.
The second technical problem to be solved by the invention is to provide a continuous preparation method of a high-conductivity copper graphene composite material.
The invention solves the second technical problem by adopting the technical proposal that: a continuous preparation method of a high-conductivity copper graphene composite material comprises the following preparation steps:
(1) Providing a copper substrate as a substrate for depositing graphene;
(2) Depositing graphene on the surface of a copper substrate by utilizing chemical vapor deposition to form a graphene bottom layer, and forming a plurality of graphene units which are distributed continuously or at intervals on the surface of the graphene bottom layer, wherein each graphene unit comprises a plurality of graphene unit layers which are sequentially stacked from bottom to top and have the same or sequentially reduced areas, the graphene coverage rate of the surface of the copper substrate is controlled to be more than or equal to 96%, the characteristic peaks of the Raman spectrum of the graphene comprise a D peak and a G peak, and the intensity ratio I of the D peak to the G peak D /I G And 0 to 0.55 to obtain the copper graphene composite material.
Preferably, the chemical vapor deposition in the step (2) is performed twice, that is, after the first deposition to obtain the copper graphene composite material, the second deposition is performed to repair and improve the deposition quality of the graphene. Specifically, the deposition temperature of the first deposition is 600-1035 ℃, and the heat preservation time is 10-60 min; the deposition temperature of the second deposition is 650-1050 ℃, the heat preservation time is 1-60 min, the deposition temperature of the second deposition is 1-100 ℃ higher than the deposition temperature of the first deposition, and the temperature rising process of the second deposition keeps a reducing atmosphere. As the surface of the copper substrate is covered by the graphene bottom layer along with the extension of the graphene deposition time, the catalysis effect of the copper substrate is reduced, so that the subsequent graphene deposition speed is slowed down, the deposition of a plurality of graphene unit layers is difficult to complete or even increase the graphene deposition defect, and the uniformity of the number of graphene layers is reduced; on the other hand, through the secondary deposition and the increase of the deposition temperature, the deposition quality, the deposition efficiency and the coverage rate of the graphene can be improved, and the deposition of the multilayer uniform graphene can be realized.
Preferably, the chemical vapor deposition in the step (2) includes high temperature chemical vapor deposition and low temperature plasma chemical vapor deposition, wherein the deposition temperature of the high temperature chemical vapor deposition is 900 to 1050 ℃, and the deposition temperature of the low temperature plasma chemical vapor deposition is 600 to 900 ℃. Because copper wires with the wire diameter smaller than 100 μm are easy to break at high temperature, and continuous preparation is difficult to realize, low-temperature plasma chemical vapor deposition can be adopted to ensure that continuous preparation of the small-wire-diameter high-conductivity copper graphene composite material is realized. The radio frequency power of the low-temperature plasma chemical vapor deposition is 40-200W, and particularly, the proper radio frequency power can be selected according to the type of the carbon source and the air flow. The high radio frequency power can increase the number of active groups, and among the high number of active groups, one part of active groups promote the growth of graphene, and one part of active groups slow down the growth rate. On the other hand, high radio frequency power means enhanced surface bombardment, which may be detrimental to the growth of high quality graphene, increase electron scattering of copper graphene composites, and decrease conductivity; the low radio frequency power means that the bombardment effect is weakened, the complete cracking of the carbon source is not facilitated, and the deposition quality of graphene is reduced.
Preferably, the gases required for the chemical vapor deposition process in the step (2) include a carrier gas, a reducing gas and a carbon source gas, and the flow ratio of the reducing gas to the carbon source gas is 0 to 30. The carrier gas comprising Ar or N 2 Mainly functioning as carrier gas and maintaining an inert atmosphere. The reducing gas comprising H 2 On one hand, the reducing gas plays roles of assisting in cracking of a carbon source, promoting growth of crystal grains and etching graphene in the graphene deposition process; on the other hand, the method can play a role in eliminating trace oxygen and impurities in the furnace in the heating, cooling and graphene deposition processes, improve the surface quality of the copper substrate, reduce nucleation sites for graphene deposition and improve the deposition quality of graphene. Carbon source gas CH 4 、C 2 H 2 、C 2 H 4 One of the above, the carbon source gas is under deposition conditionsAnd (3) performing downward pyrolysis to generate H free radicals, wherein the H free radicals and the reducing gas are combined to complete pyrolysis of the carbon source, the cracked carbon atoms are adsorbed to the surface of the copper substrate to form graphene combined with copper, and when the deposition of the graphene can be completed by the H free radicals generated by the pyrolysis of the carbon source, no reducing gas is required to be introduced in the deposition process. Therefore, in the chemical vapor deposition process, the flow ratio of the reducing gas to the carbon source gas is controlled to be 0-30. If the flow rate of the reducing gas is too high, the graphene is severely etched, the deposition speed of the graphene is reduced, the preparation efficiency is reduced, and even high coverage rate deposition of the graphene is difficult to finish.
Preferably, the copper base material used in the step (1) comprises a copper wire having a wire diameter of 10 to 500 μm or a copper foil having a thickness of 4.5 to 500. Mu.m, and the surface roughness Ra of the copper wire or the copper foil is not more than 0.1. Mu.m. According to the invention, the chemical vapor deposition is adopted to continuously deposit graphene on the surface of the copper wire or the copper foil, so that the graphene is continuously distributed along the axial direction of the surface of the copper wire or the copper foil, and a continuous transmission path is provided for electrons. The surface roughness of the copper substrate is reduced through pretreatment, nucleation points in the graphene deposition process can be reduced, the non-uniformity of the number of graphene layers is further reduced, and the quality of the graphene layers is improved. The pretreatment of the copper substrate comprises surface polishing and annealing treatment, wherein the polishing adopts an electropolishing mode to reduce the surface roughness of the copper substrate, and a hydrochloric acid solution is adopted as a polishing solution for electropolishing, the constant voltage is 1-5V, and the polishing time is 1-60 s; the annealing adopts a reducing atmosphere, the annealing temperature is 400-1000 ℃, the annealing time is 15-180 min, and impurities on the surface of the copper substrate are removed at high temperature through annealing, so that the surface roughness of the copper substrate can be reduced, and nucleation sites in the graphene deposition process are reduced.
The invention adopts a roll-to-roll continuous preparation method in the chemical vapor deposition of graphene. In the preparation process, the winding speed of the reel-to-reel is 1-500 mm/min, the faster the speed is, the shorter the graphene deposition time is, and the specific winding speed is selected according to the deposition time. However, if the winding speed is too slow, the production efficiency is reduced, and if the winding speed is too fast, the copper substrate is in a softened state when the graphene is deposited at a high temperature, and the copper substrate is easily broken due to excessive tension, so that continuous production cannot be completed. The rolling swing range of the reel-to-reel is 1-100 mm, and if the swing range is too small, the amount of the windable copper graphene composite material is too small, so that the efficiency is low; if the swing range is too large, the requirement on the size of equipment is high, and the production cost is increased.
The deposition air pressure adopted in the chemical vapor deposition process of the graphene is 50-500 Pa, and the deposition layer number of the graphene can be controlled by adjusting the deposition air pressure. If the deposition air pressure is too low, the graphene deposition speed is too low, and the preparation efficiency is low; if the deposition air pressure is too high, the number of the deposited graphene layers is large, the quality is poor, and the conductivity of the copper graphene composite material is improved.
After the high-conductivity copper graphene composite material is continuously prepared by the method, the high-conductivity copper graphene composite material can be further processed, and the processing treatment comprises twisting, rolling and the like.
Compared with the prior art, the invention has the beneficial effects that: according to the high-conductivity copper graphene composite material, a graphene bottom layer is covered on the surface of a copper substrate, a plurality of graphene units are continuously or intermittently distributed on the surface of the graphene bottom layer, and the graphene coverage rate of the surface of the copper substrate and the intensity ratio I of a D peak to a G peak in a graphene Raman spectrum characteristic peak are controlled D /I G The high-quality graphene layer can be obtained, a continuous transmission path is provided for electrons, scattering of the electrons is reduced, oxidation or corrosion of a copper base material is prevented, the conductivity and the conductivity stability of the copper graphene composite material are improved, and the conductivity of the high-conductivity copper graphene composite material which is not lower than 103% IACS is realized. The high-conductivity copper graphene composite material meets the performance requirements of the related technical field on high conductivity, can be further processed into products such as large-size rods, wires, plates and strips, realizes industrial production, and is applied to different fields.
Drawings
FIG. 1 is a schematic flow chart of a continuous preparation method of a copper graphene composite material in embodiment 4 of the present invention;
FIG. 2 is a schematic cross-sectional structure of a copper graphene composite strip of the present invention;
FIG. 3 is a schematic cross-sectional structure of a copper graphene composite wire of the present invention;
FIG. 4 is a graph I of a copper graphene composite of example 7 D /I G A value;
fig. 5 is a schematic diagram of a local graphene layer structure of a copper graphene composite material in embodiment 4 of the present invention;
wherein the reference numerals are as follows:
10-copper-based material copper foil;
a 20-graphene layer;
30-copper-based copper wire;
a 40-graphene underlayer;
50-graphene unit layer.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
The invention provides 20 examples and 4 comparative examples, and examples 1-10 and examples 11-20 respectively adopt the continuous preparation method of the invention to prepare copper graphene composite wires and strips. The inventive examples and comparative examples used wires and foils with a length > 600mm as substrates. The specific examples and comparative examples are:
example 1
Copper wires with the wire diameter of 0.01mm are used as base materials to prepare copper graphene composite wires. The method comprises the following specific steps:
depositing graphene on the surface of a copper wire substrate: in C 2 H 2 Under the condition of low pressure, the gas is used as a carbon source, and the graphene is continuously deposited on the surface of the copper wire in situ by adopting a plasma chemical vapor deposition method, wherein the specific process comprises the following steps: first deposition: placing the copper wire into a paying-off bin at normal temperature, pulling one end of the copper wire to a winding bin to finish sample placement, and sealing the furnace tube; the residual air in the furnace is pumped out by using a vacuum pump, then the vacuum pump is closed, inert gas is introduced to atmospheric pressure, the furnace tube is repeatedly cleaned for three times, finally the furnace tube is kept in a vacuumizing state, and reducing gas H is introduced 2 And a carrier gas Ar, wherein Ar flow is 200sccm, H 2 The flow is 10sccm, winding is started, and the winding speed is 40mm/min; starting at room temperatureHeating to 600 ℃ at 10 ℃/min, then introducing a carbon source, and introducing a carbon source C 2 H 2 The flow is 10sccm, ar flow is kept unchanged, H 2 Changing flow rate to 50sccm, regulating air pressure to 400Pa, switching on radio frequency to 200W, maintaining for 15min, closing carbon source and radio frequency, and regulating H 2 Changing the flow rate into 5sccm, cooling to room temperature, taking out the sample, placing into a paying-off bin for secondary graphene deposition, cleaning the furnace tube for three times, and introducing 200sccm Ar and 10sccm H in a vacuumizing state 2 Raising the temperature from room temperature to 650 ℃ at a winding speed of 120mm/min and a heating speed of 10 ℃/min, and then introducing 6sccm of C 2 H 2 And 2sccm of H 2 And regulating the air pressure to 100Pa, then opening the radio frequency to 120W, keeping the temperature for 5min, closing the carbon source and the radio frequency, and finally cooling to room temperature to obtain the copper graphene composite wire with the wire length of 600 mm.
Example 2
Copper wires with the wire diameter of 0.08mm are used as base materials to prepare copper graphene composite wires. The method comprises the following specific steps:
copper wire substrate surface polishing: preparing polishing solution: adding proper amount of alcohol, isopropanol and urea into hydrochloric acid solution, mixing and stirring. Immersing the copper wire into a container containing electrochemical polishing solution to serve as an anode, immersing the copper wire into the container with the electrochemical polishing solution to serve as a cathode, providing constant voltage/current by a 1V direct current source for 60 seconds, flushing the copper wire with deionized water and alcohol to remove the surface polishing solution, and drying the copper wire by argon gas to obtain the copper wire with polished surfaces.
Depositing graphene on the surface of a copper wire substrate: the copper wire with the polished surface is deposited with graphene, the specific steps are as described in example 1, and the process parameters are shown in table 1.
Example 3
Copper wires with the wire diameter of 0.1mm are used as base materials to prepare copper graphene composite wires. The method comprises the following specific steps:
annealing the copper wire base material: copper wire was placed in a furnace tube before depositing graphene and annealed at 700 ℃ under a reducing atmosphere for 30min.
Depositing graphene on the surface of a copper wire substrate: the copper wire subjected to the annealing treatment is subjected to graphene deposition, the specific steps are as described in example 1, and the process parameters are shown in table 1.
Example 4
Copper wires with the wire diameter of 0.15mm are used as base materials to prepare copper graphene composite wires. The method comprises the following specific steps:
copper wire substrate surface polishing: the specific polishing process is as described in example 2.
Annealing the copper wire base material: the specific annealing process was as described in example 3.
Depositing graphene on the surface of a copper wire substrate: the copper wire subjected to the polishing and annealing treatment is used for depositing graphene, the specific steps are as described in example 1, and the process parameters are shown in table 1.
Examples 5 to 10 respectively use copper wires with wire diameters of 0.2mm, 0.26mm, 0.31mm, 0.35mm, 0.45mm and 0.5mm as base materials, and the specific process for preparing copper graphene wires is different from example 4 in that: the graphene deposition process parameters are different, and specific process parameters are shown in table 1.
Example 11
Copper foil with the thickness of 0.0045mm is used as a base material to prepare the copper graphene composite strip. The method comprises the following specific steps:
depositing graphene on the surface of the copper foil substrate: by CH 4 Under the condition of low pressure, the gas is used as a carbon source, and the chemical vapor deposition method is adopted to continuously grow graphene on the surface of the copper foil in situ, and the specific process is as follows: first deposition: placing the copper foil into a paying-off bin at normal temperature, pulling one end of the copper foil to a winding bin to finish sample placement, and sealing the furnace tube; the residual air in the furnace is pumped out by using a vacuum pump, then the vacuum pump is closed, inert gas is introduced to atmospheric pressure, the furnace tube is repeatedly cleaned for three times, finally the furnace tube is kept in a vacuumizing state, and reducing gas H of 10sccm is introduced 2 And Ar with current-carrying gas of 200sccm, and opening and winding, wherein the winding speed is 20mm/min; then the temperature is increased from room temperature to 950 ℃ at a heating rate of 10 ℃/min, and then a carbon source CH of 10sccm is introduced 4 Ar gas flow is kept unchanged, H 2 Changing air flow to 100sccm, regulating air pressure to 150Pa, maintaining the temperature for 30min, closing carbon source, and collecting H 2 The flow rate was changed to 5sccm, the temperature was lowered to room temperature and the sample was taken out, and thenPlacing the furnace tube into a paying-off bin for secondary graphene deposition, cleaning the furnace tube for three times, and introducing 200sccm Ar and 10sccm H in a vacuumizing state 2 Heating from room temperature to 1000 ℃ at a heating rate of 10 ℃/min at a winding speed of 24mm/min, and introducing 20sccm of carbon source CH 4 And 100sccm of H 2 And regulating the air pressure to 160Pa, keeping the temperature for 25min, closing the carbon source, and finally cooling to room temperature to obtain the copper graphene composite strip with the length of 600 mm.
Example 12
And preparing the copper graphene composite strip by taking a copper foil with the thickness of 0.03mm as a base material. The method comprises the following specific steps:
annealing the copper foil base material: copper foil was placed in a furnace tube before graphene growth and annealed at 800 ℃ under a reducing atmosphere for 30min.
Depositing graphene on the surface of the copper foil substrate: the specific steps of depositing graphene on the surface of the copper foil after the annealing treatment are as described in example 11, and specific process parameters are shown in table 1.
Examples 13 to 20 used copper foils with thicknesses of 0.1mm, 0.15mm, 0.2mm, 0.25mm, 0.3mm, 0.35mm, 0.4mm, and 0.5mm as the base materials, respectively, and the process for preparing the copper graphene composite strip was different from that of example 12 in that: the graphene deposition process parameters, specific process parameters are shown in table 1.
Comparative examples 1, 2 of the present invention differ from example 3 in that: in comparative example 1, no carbon source is introduced in the graphene deposition process, and a wire blank sample without graphene deposition is used; comparative example 2 only does not introduce a carbon source when graphene is deposited for the second time, and no second time graphene repairs the deposited wire comparative sample. Comparative examples 3, 4 differ from example 17 in that: comparative example 3 no carbon source was introduced during the graphene deposition process, no copper foil blank for graphene deposition; comparative example 4 no carbon source was introduced only when graphene was deposited a second time, and no second time graphene repaired the deposited copper foil control.
The characteristics and properties of the obtained examples and comparative examples were measured, and the measurement results are shown in Table 2.
(1) Conductivity of: the conductivity was measured using the bridge method. The length of a test sample wire/strip is more than or equal to 200mm, the test is repeated for three times of resistance through a bridge method, the average value is calculated to be used as the resistance of the sample, then the wire diameter/strip thickness is measured by adopting a ten-thousandth ruler, the size of 5 different positions of each sample is measured, the average value is calculated to be the wire diameter/strip thickness of the sample, and the conductivity is calculated according to the wire diameter/strip thickness of a copper wire, the resistance and the tested length;
(2) Number of graphene layers: graphene deposited on the copper-based surface was subjected to surface scanning by raman spectroscopy, and the intensity ratio (I 2D /I G ) Estimating the number of graphene layers and the layer number ratio by the range or the half-width of the 2D peak;
(3) Coverage rate of graphene: observing the graphene coverage rate of the copper-based surface by adopting a scanning electron microscope, heating a sample on a heating table at 150 ℃ for 30 seconds before observation, wherein the copper-based surface covered by graphene is not oxidized at high temperature, the uncovered copper-based surface is oxidized at high temperature and has a darkened color, and the sample can be obviously observed by the scanning electron microscope and the graphene coverage rate is calculated;
(4) Graphene characteristics: graphene deposited on the copper-based surface was subjected to surface scanning by raman spectroscopy, and the intensity ratio of D to G peaks (I D /I G ) Range.
(5) Roughness: roughness measurement is carried out according to GB/T1031-2016 (product geometry specification (GPS) surface structure contour method), and the surface roughness is assessed by adopting a central line system (contour method), and the specific detection method is as follows: and (3) slowly sliding the diamond stylus of the roughness measuring instrument along the axial direction of the surface of the strip, directly obtaining the Ra value of one measuring stroke from the indicating instrument, and measuring for three times to obtain the average value.
TABLE 1 key process for graphene deposition on copper wire/foil surface
TABLE 2 characteristics and Properties of copper graphene composite materials
| Group of | Roughness Ra (mum) | Graphene coverage rate | B/A | Number of graphene unit layer layers | I D /I G | Conductivity (% IACS) |
| Example 1 | 0.09 | ≥98％ | 9％ | 0 to 6 layers | 0.03～0.3 | 110 |
| Example 2 | 0.07 | ≥98％ | 13％ | 0 to 6 layers | 0.06～0.4 | 112 |
| Example 3 | 0.08 | ≥97％ | 7％ | 0 to 6 layers | 0.05～0.2 | 109 |
| Example 4 | 0.05 | ≥96％ | 5％ | 0 to 6 layers | 0.01～0.1 | 106 |
| Example 5 | 0.04 | ≥98％ | 11％ | 0 to 6 layers | 0.03～0.1 | 104 |
| Example 6 | 0.05 | ≥98％ | 6％ | 0 to 6 layers | 0.06～0.3 | 104 |
| Example 7 | 0.06 | ≥99％ | 40％ | 1 to 8 layers | 0.07～0.55 | 103 |
| Example 8 | 0.05 | ≥98％ | 11％ | 0 to 6 layers | 0.05～0.2 | 104 |
| Example 9 | 0.04 | ≥99％ | 13％ | 1 to 6 layers | 0.03～0.4 | 103 |
| Example 10 | 0.05 | ≥97％ | 13％ | 0 to 6 layers | 0.02～0.4 | 104 |
| Example 11 | 0.07 | ≥99％ | 0 | 0 to 3 layers | 0～0.2 | 103 |
| Example 12 | 0.06 | ≥98％ | 0 | 0 to 4 layers | 0.05～0.21 | 103 |
| Example 13 | 0.05 | ≥97％ | 0 | 0 to 4 layers | 0.02～0.25 | 103 |
| Example 14 | 0.06 | ≥98％ | 0 | 0 to 3 layers | 0.03～0.22 | 106 |
| Example 15 | 0.06 | ≥98％ | 0 | 0 to 3 layers | 0～0.1 | 104 |
| Example 16 | 0.05 | ≥99％ | 0 | 0 to 3 layers | 0.01～0.1 | 103 |
| Example 17 | 0.06 | ≥99％ | 0 | 0 to 3 layers | 0.05～0.3 | 103 |
| Example 18 | 0.05 | ≥98％ | 0 | 0 to 4 layers | 0～0.16 | 105 |
| Example 19 | 0.05 | ≥99％ | 0 | 0 to 3 layers | 0.04～0.25 | 103 |
| Example 20 | 0.05 | ≥98％ | 0 | 0 to 4 layers | 0.06～0.2 | 103 |
| Comparative example 1 | 0.08 | - | - | - | - | 99 |
| Comparative example 2 | 0.08 | ≥90％ | 0 | 0 to 5 layers | 0.4～1.0 | 101 |
| Comparative example 3 | 0.06 | - | - | - | - | 100 |
| Comparative example 4 | 0.06 | ≥92％ | 0 | 0 to 4 layers | 0.1～0.6 | 101 |
Claims (10)
1. The high-conductivity copper graphene composite material is characterized by comprising a copper base material and a graphene layer, wherein the graphene layer comprises a graphene bottom layer and a plurality of graphene units, and the graphene comprises a copper base material and a graphene layerThe graphene bottom layer covers the surface of the copper substrate, a plurality of graphene units are continuously or alternately distributed on the surface of the graphene bottom layer, each graphene unit comprises a plurality of graphene unit layers which are sequentially stacked from bottom to top and have the same area or sequentially reduced, the graphene coverage rate of the surface of the copper substrate is more than or equal to 96%, the characteristic peak of the graphene Raman spectrum comprises a D peak and a G peak, and the intensity ratio I of the D peak to the G peak D /I G 0 to 0.55.
2. The high-conductivity copper graphene composite material according to claim 1, wherein the number of graphene unit layers of each graphene unit is 0-9.
3. The high-conductivity copper graphene composite material according to claim 1, wherein the coverage area of a graphene bottom layer on the surface of a copper substrate is denoted as A, and the orthographic projection area of all graphene units with the number of layers being more than 5 on the surface of the copper substrate is denoted as B, so that the ratio B/A of B to A is less than or equal to 50%.
4. The high conductivity copper graphene composite material according to any one of claims 1 to 3, wherein the high conductivity copper graphene composite material has a conductivity of not less than 103% iacs.
5. The continuous production method of a high-conductivity copper graphene composite material according to any one of claims 1 to 4, comprising the following production steps:
(1) Providing a copper substrate as a substrate for depositing graphene;
(2) Depositing graphene on the surface of a copper substrate by utilizing chemical vapor deposition to form a graphene bottom layer, and forming a plurality of graphene units which are distributed continuously or at intervals on the surface of the graphene bottom layer, wherein each graphene unit comprises a plurality of graphene unit layers which are sequentially stacked from bottom to top and have the same or sequentially reduced areas, the graphene coverage rate of the surface of the copper substrate is controlled to be more than or equal to 96%, the characteristic peaks of the Raman spectrum of the graphene comprise a D peak and a G peak, and the intensity ratio I of the D peak to the G peak D /I G And 0 to 0.55 to obtain the copper graphene composite material.
6. The continuous production method according to claim 5, wherein the chemical vapor deposition in the step (2) is performed twice, that is, after the first deposition to obtain the copper graphene composite material, the second deposition is performed to repair and improve the deposition quality of the graphene.
7. The continuous production method according to claim 6, wherein the deposition temperature for the first deposition is 600 to 1035 ℃ and the holding time is 10 to 60 minutes; the deposition temperature of the second deposition is 650-1050 ℃, the heat preservation time is 1-60 min, the deposition temperature of the second deposition is 1-100 ℃ higher than the deposition temperature of the first deposition, and the temperature rising process of the second deposition keeps a reducing atmosphere.
8. The continuous production method according to any one of claims 5 to 7, wherein the chemical vapor deposition in the step (2) comprises high temperature chemical vapor deposition and low temperature plasma chemical vapor deposition, wherein the deposition temperature of the high temperature chemical vapor deposition is 900 to 1050 ℃, the deposition temperature of the low temperature plasma chemical vapor deposition is 600 to 900 ℃, and the radio frequency power of the low temperature plasma chemical vapor deposition is 40 to 200W.
9. The continuous production method according to claim 5, wherein the gases required for the chemical vapor deposition process in step (2) include a carrier gas, a reducing gas and a carbon source gas, the flow ratio of the reducing gas to the carbon source gas being 0 to 30, and the deposition gas pressure being 50 to 500Pa.
10. The continuous production method according to claim 5, wherein the copper substrate used in the step (1) comprises a copper wire having a wire diameter of 10 to 500 μm or a copper foil having a thickness of 4.5 to 500 μm, and the surface roughness Ra of the copper wire or the copper foil is not more than 0.1. Mu.m.
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