CN115519840A - Metal graphene composite material, preparation method and application thereof, and electronic component - Google Patents
Metal graphene composite material, preparation method and application thereof, and electronic component Download PDFInfo
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- CN115519840A CN115519840A CN202211156816.4A CN202211156816A CN115519840A CN 115519840 A CN115519840 A CN 115519840A CN 202211156816 A CN202211156816 A CN 202211156816A CN 115519840 A CN115519840 A CN 115519840A
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Abstract
The application relates to the technical field of composite materials, in particular to a metal graphene material, a preparation method and application thereof, and an electronic component. The method is used for solving the problem that the traditional heating process in the related art cannot meet the requirements of high strength and high compactness of the metal graphene composite material. A preparation method of a metal graphene composite material comprises the following steps: s1), growing graphene on the surface of a metal substrate to prepare a metal graphene composite layer; s2), overlapping at least two metal graphene composite layers along the thickness direction of the metal graphene composite layers, enabling metal substrates on two adjacent metal graphene composite layers to be opposite, and preparing a metal graphene composite material through hot-pressing sintering; wherein in S1), the metal substrate is subjected to surface heat treatment by applying a pulse current to the metal substrate. The application is used for preparing the metal graphene composite material.
Description
Technical Field
The application relates to the technical field of composite materials, in particular to a metal graphene material, a preparation method and application thereof, and an electronic component.
Background
Metal materials have been widely studied and used for their high specific strength, high specific modulus, high corrosion resistance, excellent electric heating properties, and excellent processability. However, with the rapid development of scientific technology, especially in some special environments, metal materials have not been able to meet the application requirements. Graphene draws attention to people because of its characteristics such as high thermal conductivity, excellent mechanical properties, low thermal expansion coefficient, and good chemical stability. By combining the metal and the graphene, the excellent performance of the graphene can be maintained, and the finally formed metal graphene composite material can show better performance than the single graphene and metal material by utilizing the synergistic effect of the metal and the graphene.
In the related art, when graphene is deposited on a metal surface to obtain a metal graphene composite material, an adopted heat treatment process is a chemical fuel combustion heating process, and although the heating process can meet the mass production of large-size products, the heating process is not suitable for preparing products with microstructures.
Particularly, for the metal graphene composite material with a plurality of metal graphene composite layers, the metal graphene composite material with higher strength and higher compactness needs to be obtained by prolonging the time of hot-pressing sintering and improving the reaction conditions of the hot-pressing sintering, so that on one hand, the preparation time of the whole metal graphene composite material is prolonged, and the efficiency is further reduced, on the other hand, the improvement method is limited, the metal graphene composite material with higher strength and higher compactness is difficult to obtain, and the preparation efficiency and the quality of the product with the microstructure are not improved.
Disclosure of Invention
Based on the above, the application provides a metal graphene material, and a preparation method, an application and an electronic component thereof, so as to solve the problem that the traditional heating process in the related art cannot meet the requirements of high strength and high compactness of the metal graphene composite material.
In a first aspect of the present application, a method for preparing a metal graphene composite material is provided, including:
s1), growing graphene on the surface of a metal substrate to prepare a metal graphene composite layer;
s2), overlapping at least two metal graphene composite layers along the thickness direction of the metal graphene composite layers, enabling metal substrates on two adjacent metal graphene composite layers to be opposite, and preparing a metal graphene composite material through hot-pressing sintering;
wherein, in S1), the metal substrate is subjected to surface heat treatment by applying a pulse current to the metal substrate.
In a possible implementation manner of the first aspect, in S1), the surface heat treatment includes a multi-stage heat treatment process, and according to that the heating temperatures of the metal substrate in different heat treatment stages are the same, the ranges of the pulse current densities applied to the metal substrate in different stages are controlled to be the same, according to that the heating temperatures of the metal substrate in different heat treatment stages are different, the ranges of the pulse current densities applied to the metal substrate in different stages are controlled to be different, and the power supply frequency and the duty ratio of the pulse current applied to the metal substrate in different stages are controlled to be the same.
In a possible embodiment of the first aspect, in S1), the surface heat treatment of the metal substrate by applying a pulse current to the metal substrate includes:
in the pretreatment stage of the metal substrate, applying a first pulse current to the metal substrate, heating the metal substrate to a first temperature, and continuing for a first preset time;
in the graphene deposition stage, applying a second pulse current to the metal substrate, heating the metal substrate to a second temperature, and continuing for a second preset time;
in the graphene growth stage, applying a third pulse current to the metal substrate, heating the metal substrate to the first temperature, and continuing for a third preset time;
wherein, the first temperature is the recovery and recrystallization temperature of the metal substrate, and the second temperature is the phase transition temperature of the metal substrate; the value ranges of the pulse current densities of the first pulse current and the third pulse current are the same, and the value ranges of the pulse current densities of the first pulse current and the second pulse current are different; the value ranges of the power supply frequency and the duty ratio of the first pulse current, the second pulse current and the third pulse current are the same.
In a possible embodiment of the first aspect, a lower limit value of a range of values of the pulse current density of the first pulse current is greater than an upper limit value of a range of values of the pulse current density of the second pulse current.
In one possible embodiment of the first aspect, the metal substrate is copper;
the value ranges of the pulse current densities of the first pulse current and the third pulse current are both 2000A/mm 2 ～2500A/mm 2 ；
The value range of the pulse current density of the second pulse current is 1200A/mm 2 ～1800A/mm 2 。
In one possible embodiment of the first aspect, the metal substrate is nickel;
the value ranges of the pulse current densities of the first pulse current and the third pulse current are both 1000A/mm 2 ～1500A/mm 2 ；
The value range of the pulse current density of the second pulse current is 500A/mm 2 ～800A/mm 2 。
In a possible implementation manner of the first aspect, the power supply frequency of the first pulse current, the second pulse current, and the third pulse current ranges from 100Hz to 1000Hz.
In a possible implementation manner of the first aspect, the duty ratios of the first pulse current, the second pulse current, and the third pulse current are all in a range of 0.1 to 0.5.
In a possible implementation manner of the first aspect, the first preset time and the third preset time have the same value range, and are both 5min to 10min;
the value range of the second preset time is different from the value range of the first preset time, and the upper limit value of the value range of the second preset time is smaller than or equal to the lower limit value of the value range of the first preset time.
In a possible implementation manner of the first aspect, the second preset time ranges from 1min to 5min.
In one possible embodiment of the first aspect, at the stage of pre-treatment of the metal substrate, the method further comprises: and introducing hydrogen into the reaction cavity, wherein the gas volume flow of the hydrogen is 10-20 sccm.
In a second aspect of the present application, there is provided a metal graphene composite material prepared by the method according to the first aspect.
In one possible embodiment of the second aspect, the metal graphene composite material comprises 3 to 5 layers of the metal graphene composite layer.
In a possible embodiment of the second aspect, in the metal graphene composite material, the metal substrates included in the metal graphene composite layers of different layers are the same or different.
In a possible embodiment of the second aspect, the metal substrates of the different layers are each independently selected from a simple metal or an alloy of multiple metals of iron, cobalt, nickel, magnesium, copper, titanium.
In a third aspect of the present application, an application of the metal graphene composite material as described in the second aspect in the preparation of an electronic component is provided.
In a fourth aspect of the present application, there is provided an electronic component, including:
the metal graphene composite material according to the second aspect.
In one possible embodiment of the fourth aspect, the electronic component is a printed circuit board, a lithium battery or a transformer.
In the preparation method of the metal graphene composite material, the metal substrate is subjected to surface heat treatment by adopting a mode of applying pulse current to the metal substrate, the Joule heat effect and the electro-plastic effect can be utilized, the microstructure of the metal substrate is well regulated, the morphology, the evolution rate and the like of the microstructure on the surface of the metal substrate are effectively controlled at different heat treatment stages, so that a more favorable microcosmic environment can be provided for the nucleation and growth of graphene, the nucleation and growth speed of graphene is improved, the preparation efficiency of the metal graphene composite material can be improved, and the problems that the heat loss caused by the traditional heating mode is large, the heating time is long, the preparation efficiency is low and the environmental pollution is possibly caused are solved. Meanwhile, a more favorable surface microcosmic environment is provided for nucleation and growth of graphene, and a microstructure with less annealing twin crystals, lower dislocation density and fine grains can be obtained, so that the metal graphene composite material with higher strength and compactness can be obtained. In addition, tests show that the obtained metal graphene composite material has better mechanical property and is not easy to wrinkle or bend. And the metal graphene composite material is sintered in a laminated manner, so that the industrial requirement and batch and large-scale production of the product with the microstructure can be realized, and the production efficiency can be improved.
Drawings
Fig. 1 is a microstructure diagram of a metal substrate of a metal graphene composite layer provided in example 1;
fig. 2 is a microstructure and topography of a metal substrate of the metal graphene composite layer provided in example 4;
FIG. 3 is a microstructure and morphology diagram of a metal substrate of the metal graphene composite layer provided in comparative example 1;
FIG. 4 is a microstructure and topography of a metal substrate of the metal graphene composite layer provided in comparative example 2;
FIG. 5 shows a metal substrate made of AZ31 magnesium alloyThe pulse current density of gold is 20A/mm 2 A lower microstructure topography;
FIG. 6 shows the pulse current density of 40A/mm when the metal substrate is AZ31 magnesium alloy 2 A lower microstructure topography;
FIG. 7 shows the pulse current density of 80A/mm when the metal substrate is AZ31 magnesium alloy 2 A lower microstructure topography;
FIG. 8 shows the pulse current density of 1200A/mm when the metal substrate is made of copper alloy 2 A lower microstructure topography;
FIG. 9 shows a pulse current density of 2200A/mm when the metal substrate is copper alloy 2 A lower microstructure topography;
FIG. 10 shows a copper alloy as the metal substrate at a pulse current density of 3000A/mm 2 A lower microstructure topography;
FIG. 11 shows the pulse current density of 0A/mm when the metal substrate is made of titanium alloy 2 A lower microstructure topography;
FIG. 12 shows the pulse current density of 100A/mm when the metal substrate is made of titanium alloy 2 A lower microstructure topography;
FIG. 13 shows a titanium alloy substrate at a pulse current density of 140A/mm 2 A lower microstructure topography;
FIG. 14 shows the pulse current density of 0A/mm when the metal substrate is made of rare earth magnesium alloy 2 A lower microstructure topography;
FIG. 15 shows the pulse current density of 15A/mm when the metal substrate is made of rare earth magnesium alloy 2 A lower microstructure topography;
FIG. 16 shows the pulse current density of 40A/mm when the metal substrate is made of rare earth magnesium alloy 2 And (3) a microstructure topography.
Detailed Description
To facilitate an understanding of the present application, the present application will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present application are given in the accompanying drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the present application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In order to solve the problem that the conventional heating process in the related art cannot meet the requirements of high strength and high degree of densification of the metal graphene composite material, the applicant has sought a new and effective heat treatment process for solving the above problems, and the specific embodiments are described as follows:
some embodiments of the present disclosure provide a metal graphene composite material preparation method, including:
s1), growing graphene on the surface of a metal substrate to prepare a metal graphene composite layer;
s2), overlapping at least two metal graphene composite layers along the thickness direction of the metal graphene composite layers, enabling metal substrates on two adjacent metal graphene composite layers to be opposite, and preparing a metal graphene composite material through hot-pressing sintering;
wherein in S1), the metal substrate is subjected to surface heat treatment by applying a pulse current to the metal substrate.
The pulse is the waveform of voltage or current, like the waveform of pulse beat on electrocardiogram, and the pulse current is the current with instantaneous and sudden change and extremely short action time. It may be periodically repeated or aperiodic.
The waveform of the pulse current includes a square wave, a triangular wave, a sawtooth wave, a step wave, and the like as required, and is not particularly limited herein.
Compared with the traditional heating process, on one hand, the pulse current can intensively transmit heat to the metal substrate, so that the metal substrate can be rapidly heated in a very short time to generate a joule heat effect, and the heat loss caused by the traditional heating process is effectively avoided, so that the heating time can be shortened, the heating efficiency can be improved, the production efficiency of the metal graphene composite material can be improved, and the energy consumption can be reduced. On the other hand, compared with the traditional heating process, the pulse current is more suitable for heating a product with a microstructure, so that the heating heat can be concentrated on the surface of the microstructure product, the heat utilization efficiency is improved, and the heat overflow is reduced. On the other hand, compared with the traditional heating process which may generate a large amount of pollution, the electric heating process can also reduce the emission of waste gas, and has the advantages of energy conservation and environmental protection.
In addition, compared with the condition that only current or voltage can be supplied and adjusted by direct current, the pulse current has three independent parameters of pulse current density, pulse on-time and pulse off-time, and is more beneficial to adjusting the heating temperature and the microstructure of the surface of the metal substrate.
Specifically, by applying a pulse current to the metal substrate, the microstructure of the metal substrate can be well adjusted by the joule heating effect and the electro-plasticity effect.
The microstructure of the metal substrate during heating is changed as follows:
after the metal substrate is plastically deformed, the metal substrate is in a thermodynamically unstable high free energy state due to the increase of the density of structural defects such as vacancies, dislocations and the like and the increase of distortion energy (energy stored by crystal defects), and has a tendency of spontaneously returning to a low free energy state before deformation. But at room temperature, the atom mobility is small, the recovery is slow, once heated, when the temperature is high, the atom diffusion capability is improved, and a series of changes can occur in the organization and the performance. This variation can be represented in three stages with increasing heating temperature: recovery stage, recrystallization stage and grain growth stage.
In the recovery stage, cold plastically deformed metals, when heated, produce some substructure and property changes before the optical microstructure changes (i.e., before recrystallized grains form). At this stage, the strength and hardness of the metal substrate change little, and the internal stress and resistance are significantly reduced.
In the recrystallization stage, a new nucleus of distortion-free grains is first generated in the area with large distortion degree, and then the surrounding deformation matrix is gradually consumed to grow until the deformation structure is completely reformed into new, distortion-free, fine equiaxed grains. At this stage, the strength and hardness of the metal substrate are significantly reduced, plasticity is increased, density is sharply increased, work hardening is eliminated, and properties are restored to the extent before deformation.
In the crystal grain growth stage, new crystal grains are swallowed mutually to grow under the drive of the surface energy of the crystal boundary, and finally, crystal grains with more stable sizes are obtained. At this stage, the strength and hardness of the metal substrate continue to decrease, the plasticity continues to increase, and coarsening declines when severe.
Here, it should be noted that the size of crystal grains after recrystallization annealing mainly depends on the degree of preliminary deformation and the annealing temperature. The larger the degree of deformation, the finer the crystal grains after annealing, and conversely, the coarser the crystal grains. In addition, annealing twin crystals appear after recrystallization annealing after some face-centered cubic metals and alloys such as copper and copper alloys, nickel and nickel alloys, austenitic stainless steel and the like are cold-deformed, because the metal layer fault energy is low and the energy condition for twin crystal growth is met.
Based on the microstructure change process of the metal substrate in the heating process, the pulse current is applied to the metal substrate, so that the microstructure of the metal substrate can be well regulated by utilizing the joule heating effect and the electro-plastic effect, the appearance, the evolution rate and the like of the microstructure on the surface of the metal substrate can be effectively controlled at different heat treatment stages, a more favorable microcosmic environment can be provided for the nucleation and growth of graphene, and the nucleation and growth speed of the graphene can be improved. Meanwhile, a more favorable surface microcosmic environment is provided for nucleation and growth of graphene, and a microstructure with less annealing twin crystals, lower dislocation density and fine grains can be obtained, so that the metal graphene composite material with higher strength and compactness can be obtained, which cannot be achieved in the related technology. In addition, tests show that the obtained metal graphene composite material has better mechanical property and is not easy to wrinkle or bend. And the metal graphene composite material is sintered in a laminated manner, so that the industrial requirement can be met.
In the preparation process of the metal graphene composite material, pulse currents with different parameters can be applied to the metal substrate according to requirements according to different microstructures of the metal substrate in different heat treatment stages.
In some embodiments, in S1), the surface heat treatment includes a multi-stage heat treatment process, and the ranges of the pulse current densities applied to the metal substrate in different stages are controlled to be the same according to the same heating temperature of the metal substrate in different heat treatment stages, the ranges of the pulse current densities applied to the metal substrate in different stages are controlled to be different according to the different heating temperatures of the metal substrate in different heat treatment stages, and the ranges of the power frequency and the duty ratio of the pulse current applied to the metal substrate in different stages are controlled to be the same.
In a pulse period, because the current is conducted only in part of time and the other time is zero, the current density is divided by the average current density and the peak current density, the peak current density is also the pulse current density, the pulse current density cannot be vertically increased from zero to the peak value, a certain ' climbing slope ' is needed, and the current density ' climbs to the peak value, namely the pulse current density is obtained. The power frequency refers to the number of times per second that is done from one peak to another. Duty cycle refers to the percentage of the pulse on time in a pulse cycle that is the total pulse cycle time.
In the embodiments, the heating temperatures in different heat treatment stages are the same, the value ranges of the pulse current density applied to the metal substrate are the same, and the value ranges of the power frequency and the duty ratio of the pulse current applied to the metal substrate in different stages are controlled to be the same, so that the parameters of the power supply of the pulse current in different stages can be effectively controlled, and the control complexity of the power supply is reduced. And according to different heating temperatures of different heat treatment stages, the value ranges of the pulse current densities applied to the metal substrate in different stages are controlled to be different, and the metal substrate can be heated to corresponding temperatures in a certain time range by combining the pulse current densities with parameters such as power supply frequency, duty ratio and the like, and corresponding microstructures of the metal substrate in different heat treatment stages are obtained.
In S1), the parameter settings of the pulse current applied in different heat treatment stages are not particularly limited, as long as the conditions that the ranges of the pulse current density applied to the metal substrate are the same according to the same heating temperature of the metal substrate in different heat treatment stages, the ranges of the pulse current density applied to the metal substrate are different according to the different heating temperatures of the metal substrate in different heat treatment stages, and the ranges of the power frequency and the duty ratio applied to the metal substrate in different stages are controlled to be the same are satisfied.
In some embodiments, in S1), the metal substrate is subjected to surface heat treatment by applying a pulse current to the metal substrate, including:
in the pretreatment stage of the metal substrate, applying a first pulse current to the metal substrate, heating the metal substrate to a first temperature, and continuing for a first preset time;
in the graphene deposition stage, applying a second pulse current to the metal substrate, heating the metal substrate to a second temperature, and continuing for a second preset time;
in the graphene growth stage, applying a third pulse current to the metal substrate, heating the metal substrate to the first temperature, and continuing for a third preset time;
the first temperature is the recovery and recrystallization temperature of the metal substrate, the second temperature is the phase transition temperature of the metal substrate, the value ranges of the pulse current densities of the first pulse current and the third pulse current are the same, and the value ranges of the pulse current densities of the first pulse current and the second pulse current are different; the value ranges of the power supply frequency and the duty ratio of the first pulse current, the second pulse current and the third pulse current are the same.
In the embodiment of the application, in the pretreatment stage of the metal substrate, the first pulse current is applied to the metal substrate, so that the plasticity of the metal substrate can be greatly improved, the forming force is reduced, the forming limit of a material is improved, the surface quality of the metal substrate is improved, and compared with the traditional heating process, the method is more favorable for realizing high-efficiency heating and can save energy. In addition, the first pulse current can enable the internal crystal grain orientation of the metal substrate to be consistent, and the effect of refining the crystal grains can be achieved by enhancing the mobility of vacancies and dislocation and the migration of atoms, so that the quality of the graphene grown by subsequent deposition is higher, and the nucleation of the graphene is promoted. In the deposition stage of the graphene, the second pulse current is applied to the metal substrate, so that the graphene can be deposited under the action of the pulse current, and the graphene deposition device has the characteristics of high efficiency and energy conservation. On the other hand, the joule heat and the electro-plasticity effect generated by applying the second pulse current promote dislocation slippage, climbing and annihilation, and improve the evolution rate of the microstructure, so that the recovery and recrystallization processes of the metal are accelerated, the microstructure with less annealing twin crystals, lower dislocation density and fine crystal grains is obtained, and the metal substrate has better mechanical property. In the graphene growth stage, the third pulse current is applied to the metal substrate, so that the problem that the forming performance is gradually reduced along with the reduction of the thickness of the composite material due to the deposition of the graphene, and the cracking failure caused by uneven deformation is easy to occur in the forming process can be solved.
In the whole treatment process, in the pretreatment stage and the graphene growth stage of the metal substrate, the first pulse current and the third pulse current are applied to the metal substrate, so that the metal substrate can be rapidly heated through the joule heating effect, the recovery rate and the recrystallization rate of the metal substrate are improved when the pulse current is applied, and the graphene deposition efficiency can be accelerated. In the graphene deposition stage, the second pulse current is applied to the metal substrate, so that the metal substrate can be rapidly heated and rapidly cooled through the joule heating effect, and an instantaneous thermal stress is generated in the process, so that the metal substrate on which the graphene is deposited under the influence of the thermal stress, and the forming is completed. In the process, by controlling the value range of the pulse current density of the first pulse current to be different from the value range of the pulse current density of the second pulse current, for example, the higher pulse current density can be adopted to ensure that the formation rate of crystal nuclei is far greater than the growth rate of original crystals, so that fine crystal grains can be formed, the crystals are fine and have high density, and the composite material with the graphene deposited on the surface can obtain better mechanical properties.
In some embodiments, a lower limit value of the range of the pulse current density of the first pulse current is larger than an upper limit value of the range of the pulse current density of the second pulse current.
Specific value ranges of parameters such as the pulse current density, the power supply frequency, the duty ratio and the like of the first pulse current, the second pulse current and the third pulse current are not particularly limited as long as the processing conditions are satisfied.
In some embodiments, the metal substrate is copper; the value ranges of the pulse current densities of the first pulse current and the third pulse current are both 2000A/mm 2 ～2500A/mm 2 (ii) a The value range of the pulse current density of the second pulse current is 1200A/mm 2 ～1800A/mm 2 。
In these embodiments, the pulse current density of the first pulse current and the third pulse current may be 2000A/mm 2 ～2500A/mm 2 Can be arbitrarily selected within the range of (1), and the pulse current density of the second pulse current can be 1200A/mm 2 ～1800A/mm 2 Any value is taken within the range of (1). The difficulty in selecting other parameters of the pulse current can be reduced under the condition that the processing conditions are met.
In some embodiments, the first pulsed current may have a pulse current density of 2000A/mm 2 、2100A/mm 2 、2200A/mm 2 、2300A/mm 2 、2400A/mm 2 And 2500A/mm 2 The pulse current density of the second pulse current can be 1200A/mm 2 、1300A/mm 2 、1400A/mm 2 、1500A/mm 2 、1600A/mm 2 、1700A/mm 2 And 1800A/mm 2 The pulse current density of the third pulse current can be 2000A/mm 2 、2100A/mm 2 、2200A/mm 2 、2300A/mm 2 、2400A/mm 2 And 2500A/mm 2 Any value of (a).
In other embodiments, the metal substrate is nickel; the value ranges of the pulse current densities of the first pulse current and the third pulse current are both 1000A/mm 2 ～1500A/mm 2 (ii) a The value range of the pulse current density of the second pulse current is 500A/mm 2 ～800A/mm 2 。
In these embodiments, the pulse current density of the first pulse current and the third pulse current may be 1000A/mm 2 ～1500A/mm 2 And the pulse current density of the second pulse current may be 500A/mm 2 ～800A/mm 2 Any value is taken within the range of (1). The difficulty in selecting other parameters of the pulse current can be reduced under the condition that the processing conditions are met.
In some embodiments, the pulse current density of the first pulse current may be 1000A/mm 2 、1100A/mm 2 、1200A/mm 2 、1300A/mm 2 、1400A/mm 2 And 1500A/mm 2 The pulse current density of the second pulse current may be 500A/mm 2 、600A/mm 2 、700A/mm 2 、800A/mm 2 The pulse current density of the third pulse current can be 1000A/mm 2 、1100A/mm 2 、1200A/mm 2 、1300A/mm 2 、1400A/mm 2 And 1500A/mm 2 Any value of (1).
In some embodiments, the power supply frequency of the first pulse current, the second pulse current and the third pulse current ranges from 100Hz to 1000Hz.
In the embodiments, the power supply frequencies of the first pulse current, the second pulse current and the third pulse current are all valued in the same value range, so that the control complexity of the pulse power supply can be reduced. Meanwhile, the value range of the power supply frequency is within the range of 100Hz to 1000Hz, and the method is easy to realize.
In some embodiments, the pulse duty ratio of each of the first pulse current, the second pulse current and the third pulse current is 0.1 to 0.5. In the embodiments, the duty ratios of the first pulse current, the second pulse current and the third pulse current are all valued in the same value range, so that the control complexity of the pulse power supply can be reduced. Meanwhile, the duty ratio is adopted within the range of 0.1-0.5, and the method is easy to realize. In some embodiments, the first preset time and the third preset time have the same value range, which is 5min to 10min; the value range of the second preset time is different from the value range of the first preset time, and the upper limit value of the value range of the second preset time is smaller than or equal to the lower limit value of the value range of the first preset time.
In the embodiments, the metal graphene composite material with high quality can be obtained by keeping the same value range of the first preset time and the third preset time, and the whole graphene deposition time can be shortened to the greatest extent, so that the efficiency is improved. Meanwhile, the quality of the metal graphene composite material can be effectively controlled by controlling the upper limit value of the value range of the second preset time to be less than or equal to the lower limit value of the value range of the first preset time, the preparation time of the metal graphene composite material can be reduced to the greatest extent, and the efficiency is further improved.
In some embodiments, it is found through experiments that the second predetermined time is in a range of 1min to 5min.
In some embodiments, the method further comprises, during a pre-treatment stage of the metal substrate: and introducing hydrogen into the reaction cavity, wherein the gas volume flow of the hydrogen is 10-20 sccm.
In these embodiments, the hydrogen gas functions to inhibit the dissolution of carbon into the metal substrate, facilitating the deposition of carbon atoms on the surface of the metal substrate. By applying the first pulse current to the metal substrate and heating the metal substrate, the recovery and recrystallization rate of the metal substrate can be improved, and the pretreatment time of the metal substrate is shortened.
In some embodiments, during the graphene deposition phase, the method further comprises: and introducing a protective gas, an auxiliary gas and a carbon source into the reaction cavity, wherein the gas volume flow of the protective gas is 100-120 sccm, and the gas volume flow of the auxiliary gas is 20-100 sccm.
In these embodiments, similarly to the above-mentioned introduction of hydrogen into the reaction chamber, the second pulse current is applied to the metal substrate to heat the metal substrate, so that the deposition rate of graphene can be increased, and the deposition time can be shortened. Meanwhile, the carbon source deposition is facilitated, so that the carbon source can be saved, and the utilization efficiency of the carbon source can be improved.
The carbon source may be a gaseous carbon source, a liquid carbon source, or a solid carbon source, and is not particularly limited herein.
In some embodiments, the carbon source can be a gaseous carbon source such as methane, ethylene, and the like. In this case, the gas volume flow rate of the carbon source may be 5sccm.
In some embodiments, the shielding gas may be argon, nitrogen, helium, or the like. The assist gas may be hydrogen.
The material of the metal base is not particularly limited. The metal substrate can be any metal simple substance or alloy with higher conductivity.
In some embodiments, the metal substrate may be independently selected from one metal element or an alloy of multiple metals of iron, cobalt, nickel, magnesium, copper and titanium.
In the hot-pressing sintering process, the metal substrates included in the at least two metal graphene composite layers may be the same or different.
In some embodiments, after preparing the metal graphene composite layers and before sintering at least two metal graphene composite layers, the method further includes: and cutting the metal graphene composite layer into a rectangle with a certain size requirement, and sequentially placing the metal graphene composite layer in acetic acid, deionized water and ethanol solution for ultrasonic cleaning for 5min. Some embodiments of the present application provide a metal graphene composite material prepared by the method as described above. The metal graphene composite material comprises at least two metal graphene composite layers.
In some embodiments, the metal graphene composite material comprises 3 to 5 metal graphene composite layers.
In the at least two metal graphene composite layers, the metal substrates included in the metal graphene composite layers of different layers may be the same or different, and are not specifically limited herein.
In some embodiments, the metal graphene composite layers of different layers comprise different metal substrates.
For example, in the case that the metal graphene composite material includes 3 metal graphene composite layers, the metal substrate included in the metal graphene composite layers arranged in sequence from bottom to top may be copper, cobalt, and nickel, respectively.
Some embodiments of the present application provide an application of the metal graphene composite material as described above in the preparation of electronic components.
In some embodiments, the electronic component may be a circuit board, a super capacitor, or the like.
The metal graphene composite material can be used as a conducting layer in a circuit board and a super capacitor, and has higher strength and better electrothermal property than the single metal and graphene.
Some embodiments of the present application provide an electronic component, comprising: the metal graphene composite material as described above.
In some embodiments, the electronic component may be a printed circuit board, a lithium battery, a transformer, or the like.
In the case where the electronic component includes a printed circuit board, the metal graphene composite may be a conductive layer in the printed circuit board, in the case where the electronic component includes a lithium battery, the metal graphene composite may be an electrode in the lithium battery, and in the case where the electronic component includes a transformer, the metal graphene composite may be a capacitor plate in the transformer.
The embodiments of the present application are introduced above, and in order to objectively explain the technical effects produced by the present application, next, description will be made by the following examples and comparative examples.
In the following examples and comparative examples, all the raw materials were commercially available, and in order to maintain the reliability of the experiment, the raw materials used in the following examples and comparative examples all had the same physical and chemical parameters or were subjected to the same treatment.
Example 1
Preparing a metal graphene composite material:
step 1), pretreating a metal substrate: selecting a copper foil as a growth substrate of graphene, pretreating the copper foil, introducing 10sccm hydrogen, regulating and controlling a pulse power supply to enable the pulse current density to reach 2000A/mm 2 Regulating the frequency of a pulse power supply to be 100Hz, regulating the duty ratio of the pulse to be 0.1, and continuously introducing current for 5min when the temperature of the copper foil reaches 800 ℃ in the environment to complete the surface recrystallization of the copper foil so as to remove impurity elements.
Step 2), graphene deposition: continuously introducing 100sccm argon gas, 100sccm hydrogen gas and 5sccm methane gas to the surface of the copper foil, and regulating the pulse power supply to make the pulse current density reach 1200A/mm 2 And regulating the frequency of a pulse power supply to be 100Hz and the duty ratio of the pulse to be 0.1, wherein the temperature of the copper foil reaches 300 ℃ in the environment, and continuously introducing current for 1min to finish the deposition of the graphene on the surface of the copper foil.
Step 3), graphene growth: carrying out post-treatment on the copper foil with the surface deposited with the graphene, continuously introducing 100sccm argon, regulating and controlling a pulse power supply to enable the pulse current density to reach 2000A/mm 2 Regulating and controlling the frequency of a pulse power supply to be 100Hz and the duty ratio of the pulse to be 0.1, keeping the temperature of the copper foil to be 800 ℃ in the environment, continuously introducing current for 5min, and then, the copper foil deposited with the graphene film deforms under the action of hot-pressing stress to finish the growth of graphene, thereby finishing the preparation of the copper-graphene composite film material.
And 4) sintering the prepared copper graphene composite film material by 3 laminated layers, and carrying out contact molding on the copper graphene composite film material of two adjacent layers under a vacuum condition to prepare the metal graphene composite material, wherein the sintering time is 2h.
Example 2
The preparation method of example 2 is substantially the same as that of example 1 except that: in the step 1), the gas volume flow of the hydrogen is adjusted to be 12sccm, and the pulse current density is adjusted to be 2500A/mm 2 The frequency of the pulse power supply is regulated to be 500Hz, the duty ratio of the pulse is regulated to be 0.5, the temperature of the copper foil is 1000-1083 ℃, and the time for continuously introducing the pulse current is 10min. In the step 2), the volume flow of the gas introduced with argon is adjusted to be 200sccm, the volume flow of the gas introduced with hydrogen is 20sccm, the volume flow of the gas introduced with methane is 30sccm, the density of the regulated pulse current is 1800A/mm < 2 >, the frequency of the regulated pulse power supply is 500Hz, the regulated pulse duty ratio is 0.5, the temperature of the copper foil is 500 ℃, and the time for continuously introducing the pulse current is 5min. In the step 3), the volume flow of the gas introduced with the argon is adjusted to be 200sccm, and the pulse power supply is regulated and controlled to ensure that the pulse current density reaches 2500A/mm 2 The frequency of a pulse power supply is regulated and controlled to be 100Hz, the duty ratio of the pulse is regulated and controlled to be 0.1, the temperature of the copper foil is 1000-1083 ℃, and the time for continuously introducing pulse current is 10min. And in the step 4), 5-layer-by-layer sintering is carried out on the prepared copper graphene composite film material, wherein the sintering time is 2 hours.
Example 3
The preparation method of example 3 is substantially the same as that of example 1 except that: in the step 1), the gas volume flow of the hydrogen is adjusted to be 11sccm, and the pulse current density is adjusted to be 2300A/mm 2 Regulating the frequency of a pulse power supply to be 1000Hz, regulating the duty ratio of the pulse to be 0.3, regulating the temperature of the copper foil to be 1000-1083 ℃, and continuously introducing pulse current for 10min. In the step 2), the volume flow of the argon gas is adjusted to be 150sccm, the volume flow of the hydrogen gas is adjusted to be 50sccm, the volume flow of the methane gas is adjusted to be 30sccm, and the pulse current density is adjusted to be 1500A/mm 2 Regulating the frequency of a pulse power supply to 1000Hz, regulating the duty ratio of the pulse to 0.3, controlling the temperature of the copper foil to be 500 ℃, and continuously introducing pulse powerThe flow time was 3min. In the step 3), the volume flow of the gas introduced with the argon is adjusted to be 150sccm, and the pulse power supply is regulated and controlled to ensure that the pulse current density reaches 2300A/mm 2 Regulating the frequency of a pulse power supply to be 200Hz, regulating the duty ratio of the pulse to be 0.2, controlling the temperature of the copper foil to be 1000-1083 ℃, and controlling the time of continuously introducing pulse current to be 8min. In the step 4), the prepared copper graphene composite film material is subjected to 4-layer-stacked sintering, wherein the sintering time is 2 hours.
Example 4
The preparation method of example 4 is substantially the same as that of example 1 except that: in the step 1), nickel is adopted as a growth substrate of graphene, and the pulse current density is adjusted to 1200A/mm 2 The temperature of the nickel is 1400-1453 ℃, and the time of continuously introducing the pulse current is 5min. In the step 2), the pulse current density is regulated and controlled to be 800A/mm 2 The temperature of the nickel is 800 ℃, and the time of continuously introducing the pulse current is 1min. In the step 3), the pulse power supply is regulated and controlled to enable the pulse current density to reach 1200A/mm 2 The temperature of the nickel is 1400-1453 ℃. In the step 4), 10 laminated layers of the prepared copper graphene composite film material are sintered for 2 hours.
Example 5
The production method of example 5 is substantially the same as that of example 4 except that: in the step 1), the pulse current density is adjusted to 1000A/mm 2 The temperature of the nickel is 1400-1453 ℃, and the continuous pulse current is introduced for 8min. In the step 2), the pulse current density is regulated and controlled to be 600A/mm 2 The temperature of the nickel is 800 ℃, and the time of continuously introducing the pulse current is 5min. In step 3), regulating and controlling a pulse power supply to enable the pulse current density to reach 1000A/mm 2 The temperature of the nickel is 1400-1453 ℃. And in the step 4), sintering the prepared copper graphene composite film material for 10 laminated layers for 2 hours.
Example 6
The preparation method of example 6 is substantially the same as that of example 4 except that: in the step 1), the pulse current density is adjusted to be 1500A/mm 2 The temperature of the nickel is 1400-1453 DEG CThe time for continuously supplying the pulse current is 10min. In the step 2), the pulse current density is regulated and controlled to be 900A/mm 2 The temperature of the nickel is 800 ℃, and the time of continuously introducing the pulse current is 2min. In step 3), regulating and controlling a pulse power supply to enable the pulse current density to reach 1500A/mm 2 The temperature of the nickel is 1400-1453 ℃. In the step 4), 10 laminated layers of the prepared copper graphene composite film material are sintered for 2 hours.
Comparative example 1
The production method of comparative example 1 is substantially the same as that of example 1 except that: the metal substrate is subjected to heat treatment by means of fuel combustion, and the time for sintering the laminated layers is 2h.
Comparative example 2
The production method of comparative example 1 is substantially the same as that of example 4 except that: the metal substrate is subjected to heat treatment by means of fuel combustion, and the time for sintering the laminated layers is 2h.
The metal substrate micro-topography of the metal graphene composite layer obtained by the preparation method of the embodiment 1 is shown in fig. 1, the metal substrate micro-topography of the metal graphene composite layer obtained by the preparation method of the embodiment 4 is shown in fig. 2, the metal substrate micro-topography of the metal graphene composite layer obtained by the preparation method of the comparative example 1 is shown in fig. 3, and the metal substrate micro-topography of the metal graphene composite layer obtained by the preparation method of the comparative example 2 is shown in fig. 4.
As can be seen from fig. 1 and 3, in example 1, the grains of the metal substrate are finer and the texture is denser than in comparative example 1.
As can be seen from fig. 2 and 4, in example 2, the grains of the metal substrate are finer and the texture is denser than in comparative example 2.
Here, in the same metal, in a certain pulse current density range, the crystal grains of the metal base become finer and the texture becomes denser as the pulse current density becomes higher.
As shown in FIGS. 5, 6 and 7, in the case where the metal substrate is an AZ31 magnesium alloy, the metal substrate was subjected to a pulse current density of 20A/mm 2 、40A/mm 2 、80A/mm 2 And (4) a microstructure topography. As can be seen from fig. 5, 6 and 7, the densification of the metal substrate of the AZ31 magnesium alloy tends to increase as the pulse current density increases.
As shown in FIGS. 8, 9 and 10, in the case where the metal substrate is a copper alloy, the metal substrate has a pulse current density of 1200A/mm 2 、2200A/mm 2 、3000A/mm 2 And (4) a microstructure topography. As can be seen from fig. 8, 9 and 10, the densification of the metal base of the copper alloy tends to increase as the pulse current density increases.
As shown in FIGS. 11, 12 and 13, in the case where the metal substrate is a titanium alloy, the metal substrate is subjected to a pulse current density of 0A/mm 2 、100A/mm 2 、140A/mm 2 Microstructure topography. As can be seen from fig. 11, 12 and 13, the densification of the metal substrate of the titanium alloy tends to increase with the increase of the pulse current density.
As shown in FIGS. 14, 15 and 16, in the case where the metal substrate is a rare earth magnesium alloy, the metal substrate has a pulse current density of 0A/mm 2 、15A/mm 2 、40A/mm 2 Microstructure topography. As can be seen from fig. 14, 15 and 16, the densification of the metal substrate of the rare earth magnesium alloy tends to increase as the pulse current density increases.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, and these are all within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (18)
1. A preparation method of a metal graphene composite material is characterized by comprising the following steps:
s1), growing graphene on the surface of a metal substrate to prepare a metal graphene composite layer;
s2), overlapping at least two metal graphene composite layers along the thickness direction of the metal graphene composite layers, enabling metal substrates on two adjacent metal graphene composite layers to be opposite, and preparing the metal graphene composite material through hot-pressing sintering;
wherein, in S1), the metal substrate is subjected to surface heat treatment in a manner of applying a pulse current to the metal substrate.
2. The method of claim 1,
in S1), the surface heat treatment includes a multi-stage heat treatment process, and the ranges of the pulse current densities applied to the metal substrate in different stages are controlled to be the same according to the same heating temperature of the metal substrate in different heat treatment stages, the ranges of the pulse current densities applied to the metal substrate in different stages are controlled to be different according to the different heating temperatures of the metal substrate in different heat treatment stages, and the ranges of the power frequency and the duty ratio of the pulse current applied to the metal substrate in different stages are controlled to be the same.
3. The method according to claim 2, wherein in S1), the metal substrate is subjected to surface heat treatment by applying a pulse current to the metal substrate, including:
in the pretreatment stage of the metal substrate, applying a first pulse current to the metal substrate, heating the metal substrate to a first temperature, and keeping the temperature for a first preset time;
in the graphene deposition stage, applying a second pulse current to the metal substrate, heating the metal substrate to a second temperature, and continuing for a second preset time;
in the graphene growth stage, applying a third pulse current to the metal substrate, heating the metal substrate to the first temperature, and continuing for a third preset time;
wherein the first temperature is the recovery and recrystallization temperature of the metal substrate, and the second temperature is the phase transition temperature of the metal substrate; the value ranges of the pulse current densities of the first pulse current and the third pulse current are the same, and the value ranges of the pulse current densities of the first pulse current and the second pulse current are different; the value ranges of the power supply frequency and the duty ratio of the first pulse current, the second pulse current and the third pulse current are the same.
4. The method of claim 3,
the lower limit value of the range of the pulse current density of the first pulse current is larger than the upper limit value of the range of the pulse current density of the second pulse current.
5. The method of claim 3 or 4, wherein the metal substrate is copper;
the value ranges of the pulse current densities of the first pulse current and the third pulse current are both 2000A/mm 2 ～2500A/mm 2 ；
The value range of the pulse current density of the second pulse current is 1200A/mm 2 ～1800A/mm 2 。
6. The method of claim 3 or 4, wherein the metal substrate is nickel;
the value ranges of the pulse current densities of the first pulse current and the third pulse current are both 1000A/mm 2 ～1500A/mm 2 ；
The value range of the pulse current density of the second pulse current is 500A/mm 2 ～800A/mm 2 。
7. The method of claim 3,
the value ranges of the power supply frequencies of the first pulse current, the second pulse current and the third pulse current are all 100 Hz-1000 Hz.
8. The method of claim 3,
the duty ratio of the first pulse current, the second pulse current and the third pulse current ranges from 0.1 to 0.5.
9. The method of claim 3,
the value ranges of the first preset time and the third preset time are the same and are both 5 min-10 min;
the value range of the second preset time is different from the value range of the first preset time, and the upper limit value of the value range of the second preset time is smaller than or equal to the lower limit value of the value range of the first preset time.
10. The method of claim 9,
the value range of the second preset time is 1-5 min.
11. The method of claim 3,
in a pre-treatment stage of the metal substrate, the method further comprises: and introducing hydrogen into the reaction cavity, wherein the gas volume flow of the hydrogen is 10-20 sccm.
12. A metal graphene composite material, characterized by being prepared by the method of any one of claims 1 to 11.
13. The metal graphene composite material according to claim 12,
the metal graphene composite material comprises 3-5 layers of the metal graphene composite layer.
14. The metal graphene composite material according to claim 12,
in the metal graphene composite material, the metal substrates contained in the metal graphene composite layers of different layers are the same or different.
15. The metal graphene composite material according to claim 14,
the metal substrates of different layers are respectively and independently selected from one metal simple substance or an alloy consisting of a plurality of metals of iron, cobalt, nickel, magnesium, copper and titanium.
16. Use of the metal graphene composite material according to any one of claims 12 to 15 in the preparation of electronic components.
17. An electronic component, comprising:
the metal graphene composite material according to any one of claims 12 to 15.
18. The electronic component as claimed in claim 17,
the electronic component is a printed circuit board, a lithium battery or a transformer.
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