CN113927041B - Graphene copper-based composite material and preparation method and application thereof - Google Patents
Graphene copper-based composite material and preparation method and application thereof Download PDFInfo
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Abstract
The application relates to the technical field of composite materials, and provides a graphene copper-based composite material as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: establishing a graphene copper-based composite material model by utilizing machine learning and high-throughput screening technologies; carrying out first mixing treatment on graphene, a complexing agent and an organic solvent to obtain a mixed product, carrying out separation treatment on the mixed product in different centrifugal rotating speed intervals, and then screening to obtain a graphene product modified by the complexing agent; according to the graphene copper-based composite material model, carrying out second mixing treatment on a soluble copper salt, a graphene product modified by a complexing agent and an organic solvent to obtain a graphene-complexing agent-copper complex dispersion liquid; and providing a reducing agent, and carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and the reducing agent to obtain the graphene copper-based composite material. The graphene is ensured to have good dispersion effect in the copper matrix and good interface composite effect, and the wide application of the composite material is facilitated.
Description
Technical Field
The application belongs to the technical field of composite materials, and particularly relates to a graphene copper-based composite material and a preparation method and application thereof.
Background
The railway is a national economy aorta, a key infrastructure and a great civil engineering, is a backbone of a comprehensive transportation system and one of main transportation modes, and is of great importance in the status and the function in the development of the national economy and society. At present, high-speed electrified railways in various countries of the world all adopt copper alloy material contact lines. In Japan, pure copper materials are adopted on a new trunk line with the speed of 210km per hour, the line is required to be changed after running for about two years due to poor wear resistance, and research and test determine to adopt copper-tin material contact lines with better wear resistance; in France, a copper-tin material contact line and a copper-magnesium material contact line are adopted on a high-speed railway with the speed per hour of 350km or more; the contact wire made of copper and silver materials is adopted in Germany and Spain at the speed of 250-300 km per hour, and the contact wire made of copper and magnesium materials is adopted at the speed of more than 300km per hour. Since 2003, the 'upward continuous extrusion cold-working forming technology' independently innovated in China is applied to the production of contact wires made of copper-silver alloy materials, has been popularized in electrified railways for more than 15000km and can be suitable for high-speed electrified railways with the speed per hour of 250-300 km; subsequently, copper-magnesium alloy contact wires are further developed, which have higher mechanical strength and higher conductivity and can be suitable for high-speed electrified railways with the speed per hour of 350 km. With the high-speed development of railway electrification, railway transportation is accelerated again and again, and the requirement on the performance of a contact line for the electrified railway is higher and higher. The copper alloy material is difficult to meet the requirements of the contact line for the new generation of high-speed rail with the speed of 400km per hour on the aspects of conductivity, mechanical strength, wear resistance, corrosion resistance and the like. Therefore, the development of new high-end copper-based composite materials is becoming a new focus of the research of new copper-based materials.
The copper-based composite material takes copper as a matrix, breaks through the limitation of a single metal or alloy matrix by adding a proper reinforcing phase, and has excellent thermal, electrical and mechanical properties, wear resistance and corrosion resistance. The surface of the graphene folds is beneficial to improving the bonding force and the contact area between the graphene folds and the matrix interface, and the unique two-dimensional structure can effectively block the dislocation migration and remarkably reduce the expansion of microcracks in the composite material through energy loss. Thus, graphene is considered to be an ideal reinforcing phase for copper-based composites.
The preparation method of the graphene copper-based composite material mainly adopts a traditional ball milling method at first, and mainly comprises the steps of mixing graphene and copper powder, adding a solvent, dispersing in an electromagnetic oscillation instrument, drying, and putting the mixture and grinding balls into a ball milling tank to grind and mix at a certain speed and time. Considering the non-wetting between copper and carbon, the traditional ball milling method is only limited to micro-nano mechanical mixing, so that the problems of low interface strength, poor comprehensive performance and the like are easily caused, and strong impact in the grinding process can cause the defects of graphene and reduce the inherent characteristics. On the basis, in order to realize uniform mixing of graphene and a copper matrix on a more microscopic scale, the graphene and copper matrix are subjected to a molecular level mixing method, an in-situ chemical vapor deposition method, an electrochemical deposition method and the like. The above method improves the problem of the decrease in strengthening efficiency due to poor wettability of copper and graphene through molecular bonding between carbon atoms and metal atoms. However, due to process limitations, the preparation cost is high, and the content of the obtained graphene is low, which is not beneficial to realizing excellent functional characteristics of the graphene in a uniform configuration. Although the research direction of graphene enhancement in copper matrix mainly focuses on the preparation of bulk composite materials, there are also a lot of research and development reports on applying graphene to coatings. The electrochemical technology is used for depositing the copper-based composite material coating, and the method is a reliable method for preparing the copper-based composite material. For graphene enhanced coatings, graphene is dispersed in an electroplating solution containing copper ions by ultrasonic waves, and then the graphene and copper particles are co-deposited on the surface of a cathode. However, the method is only suitable for preparing the foil composite material, and cannot be used for preparing the graphene reinforced copper-based bulk composite material, so that the wide application of the material is limited.
Disclosure of Invention
The application aims to provide a graphene copper-based composite material, and a preparation method and application thereof, and aims to solve the problem that graphene in the preparation method of the graphene copper-based composite material in the prior art is poor in copper matrix dispersibility, wettability and interface bonding property.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a graphene copper-based composite material, including the following steps:
establishing a graphene copper-based composite material model by utilizing machine learning and high-throughput screening technologies;
carrying out first mixing treatment on graphene, a complexing agent and an organic solvent to obtain a mixed product, carrying out separation treatment on the mixed product in different centrifugal rotation speed intervals, and then screening to obtain a graphene product modified by the complexing agent;
according to the graphene copper-based composite material model, carrying out second mixing treatment on a soluble copper salt, a graphene product modified by a complexing agent and an organic solvent to obtain a graphene-complexing agent-copper complex dispersion liquid;
and providing a reducing agent, and carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and the reducing agent to obtain the graphene copper-based composite material.
Further, the method for predicting the graphene copper-based composite material model by utilizing the machine learning and high-throughput screening technology comprises the following steps of:
constructing a copper crystal model through DFT theoretical calculation;
combining DFT theoretical calculation with machine learning, adding graphene on the surface of a copper crystal model, establishing graphene-copper crystal models under different scales, and performing model optimization processing on intrinsic structures, defects, forms and graphene-copper interfaces of the graphene;
based on the Sabatier principle, the graphene-copper crystal model is subjected to high-throughput screening by utilizing high-throughput DFT calculation, and a graphene copper-based composite material model is established.
Further, the mass ratio of the graphene to the complexing agent is 1:0.2 to 1.5.
Further, the complexing agent is selected from at least one of methylamine, ethylenediamine, isopropylamine, isobutylamine, cyclopropylamine, sec-butylamine, tert-butylamine, hexylamine, dodecylamine, hexadecylamine and octadecylamine.
Further, the first mixing treatment is any one selected from a ball milling treatment, a stirring treatment, a grinding treatment, a mechanical mixing treatment, and an ultrasonic treatment.
Further, in the step of separating the mixed product in different centrifugal rotation speed intervals, the different centrifugal rotation speed intervals are respectively selected from: 0-2000r/min;2000-6000r/min;6000-9000r/min;9000 to 13000r/min.
Further, after the mixed product is subjected to separation treatment in different centrifugal rotating speed intervals, the method also comprises the steps of sequentially carrying out sedimentation treatment, separation treatment and washing treatment.
Further, the mass ratio of the soluble copper salt to the complexing agent-modified graphene product is 0.01-3: 1.
further, the molar ratio of the soluble copper salt to the reducing agent is 1:0.5 to 3.
Further, the soluble copper salt is selected from at least one of copper sulfate, copper nitrate, copper acetate, copper chloride, copper isooctanoate and copper tartrate.
Further, the reducing agent is at least one selected from hydrazine hydrate, hydrogen, sodium borohydride, formaldehyde, acetaldehyde and propionaldehyde.
Further, in the step of performing a second mixing treatment on the soluble copper salt, the graphene product modified by the complexing agent and the organic solvent, mixing in a stirring manner, wherein the stirring speed is 200-1000 rpm, and the stirring time is 5-30 minutes.
Further, in the step of carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and the reducing agent, the temperature of the reduction reaction is 25-75 ℃, and the time of the reduction reaction is 5-30 minutes.
In a second aspect, the application provides a graphene copper-based composite material, which is prepared by a preparation method.
In a third aspect, the application provides a high-speed rail contact line, the high-speed rail contact line is selected from a graphene copper-based composite material, and the graphene copper-based composite material is a graphene copper-based composite material.
According to the preparation method of the graphene copper-based composite material, firstly, accurate prediction of a high-strength and high-conductivity graphene copper-based composite material model is achieved by utilizing machine learning and high-throughput screening technologies, the model is further used for knowing preparation of subsequent materials, then a complexing agent is provided to react with graphene to obtain a graphene product of a surface-modified complexing agent, the graphene product and a copper salt material are subjected to copper mirror reaction to accurately regulate and control deposition of copper atoms on the surface of the graphene, on one hand, the graphene can be uniformly dispersed into an organic system through the surface-modified complexing agent, on the other hand, the graphene surface complexing agent is subjected to complexing with copper ions to form a graphene-complexing agent-copper ion complex dispersion system, and the dispersibility of the graphene in a copper matrix is improved; furthermore, in the reduction process, the deposition process of copper atoms on the surface of graphene is accurately regulated and controlled by changing the type and the quantity of graphene surface complexing agents, and good interface recombination between graphene and copper is realized on the molecular atom level. On the basis, an interface cross-scale composite mechanism of graphene in the copper crystal crystallization process is further disclosed, a coupling process route of graphene to the copper crystal crystallization process is established, a large-scale stable preparation technology of the graphene copper-based composite material is provided, the technical problem of uniform implantation of the graphene copper-based composite material into an industrial preparation technology is solved, and the high-end development of the copper-based material industry is promoted.
According to the graphene copper-based composite material provided by the second aspect of the application, the graphene copper-based composite material is prepared by the preparation method, the preparation efficiency is high, the strength of the obtained graphene copper-based composite material is not lower than 600MPa, the conductivity is not lower than 110IACS, the elongation is not lower than 3.0%, the property is excellent, the dispersion effect is good, the interface bonding property is strong, and the wide market demand can be met.
According to the high-speed railway contact wire provided by the third aspect of the application, the high-speed railway contact wire is selected from graphene copper-based composite materials, the graphene copper-based composite materials are graphene copper-based composite materials, and based on the provided graphene copper-based composite materials, the obtained high-speed railway contact wire is high in strength, high in mechanical property and conductivity, superior to the level of foreign like products in quality, capable of occupying obvious advantages in the high-speed railway market and high in economic benefit.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the specification of the embodiments of the present application may not only refer to the specific content of each component, but also refer to the proportional relationship of the weight of each component, and therefore, the proportional enlargement or reduction of the content of the related components according to the specification of the embodiments of the present application is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be a mass unit known in the chemical field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiments of the present application provides a method for preparing a graphene copper-based composite material, including the following steps:
s01, establishing a graphene copper-based composite material model by utilizing machine learning and high-throughput screening technologies;
s02, carrying out first mixing treatment on graphene, a complexing agent and an organic solvent to obtain a mixed product, carrying out separation treatment on the mixed product in different centrifugal rotation speed intervals, and then screening to obtain a graphene product modified by the complexing agent;
s03, according to the graphene copper-based composite material model, carrying out second mixing treatment on a soluble copper salt, a graphene product modified by a complexing agent and an organic solvent to obtain a graphene-complexing agent-copper complex dispersion liquid;
s04, providing a reducing agent, and carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and the reducing agent to obtain the graphene copper-based composite material. Graphene-complexing agent-copper complex.
According to the preparation method of the graphene copper-based composite material, firstly, accurate prediction of a high-strength and high-conductivity graphene copper-based composite material model is achieved by utilizing machine learning and high-throughput screening technologies, the model is further used for knowing preparation of subsequent materials, then a complexing agent is provided to react with graphene to obtain a graphene product of a surface-modified complexing agent, the graphene product and a copper salt material are subjected to copper mirror reaction to accurately regulate and control deposition of copper atoms on the surface of the graphene, on one hand, the graphene can be uniformly dispersed into an organic system through the surface-modified complexing agent, on the other hand, the graphene surface complexing agent is subjected to complexing with copper ions to form a graphene-complexing agent-copper ion complex dispersion system, and the dispersibility of the graphene in a copper matrix is improved; furthermore, in the reduction process, the deposition process of copper atoms on the surface of graphene is accurately regulated and controlled by changing the type and the quantity of graphene surface complexing agents, and good interface recombination between graphene and copper is realized on the molecular atom level. On the basis, an interface cross-scale composite mechanism of graphene in the copper crystal crystallization process is further disclosed, a coupling process route of graphene to the copper crystal crystallization process is established, a large-scale stable preparation technology of the graphene copper-based composite material is provided, the technical problem of uniform implantation of the graphene copper-based composite material into an industrial preparation technology is solved, and the high-end development of the copper-based material industry is promoted.
In the step S01, a graphene copper-based composite material model is established by utilizing machine learning and high-throughput screening technologies, and a multi-factor coupling mechanism in the process of crystallizing a copper crystal material by utilizing machine learning multi-scale graphene can realize accurate prediction of the high-strength and high-conductivity graphene copper-based composite material model, so that theoretical guidance is provided for preparing the high-strength and high-conductivity graphene copper-based composite material in a laboratory.
In some embodiments, the method for modeling graphene copper-based composites using machine learning and high throughput screening techniques comprises the steps of:
s011, constructing a copper crystal model through DFT theoretical calculation;
s012, combining DFT theoretical calculation with machine learning, adding graphene on the surface of a copper crystal model, establishing graphene-copper crystal models under different scales, and performing model optimization processing on intrinsic structures, defects, forms and graphene-copper interfaces of the graphene;
s013, based on a Sabatier principle, high-flux screening is carried out on the graphene-copper crystal model by utilizing high-flux DFT calculation, and a graphene copper-based composite material model is established.
In step S011, a copper crystal model is constructed by DFT theoretical calculation.
In some embodiments, the built copper crystal model is controlled to have high conductivity, so that the obtained composite material has better conductive effect. The influence mechanisms of crystal orientation, different exposed crystal faces, crystal defect density and the like of the crystal model on the conductivity need to be fully considered for constructing the copper crystal model, and accurate prediction of the copper crystal model with ultrahigh conductivity is realized.
In step S012, DFT theoretical calculation and machine learning are combined, graphene is added on the surface of the copper crystal model, graphene-copper crystal models at different scales are established, and model optimization is performed by the intrinsic structure, defects, morphology of graphene, and the form of graphene-copper interface.
In some embodiments, the step of adding graphene on the surface of the copper crystal model and establishing the graphene-copper crystal model at different scales includes modeling the content, size, distribution, orientation and the like of the added graphene.
In some embodiments, model optimization is performed on the intrinsic structure, defects and morphology of graphene and the form of a graphene-copper interface, and through optimization processing of the model, the influence mechanism of graphene introduction on conductivity, strength, hardness, wear resistance and the like of the copper-based composite material is revealed, so as to guide subsequent screening.
In step S013, based on the Sabatier principle, high-throughput screening is performed on the graphene-copper crystal model by using high-throughput DFT calculation, and a graphene copper-based composite material model is established. In some embodiments, the screening is performed mainly according to the properties of the model, wherein the screening includes screening the model for high strength and high conductivity, and establishing the graphene copper-based composite material model.
In step S02, carrying out first mixing treatment on graphene, a complexing agent and an organic solvent to obtain a mixed product, carrying out separation treatment on the mixed product in different centrifugal rotation speed intervals, and then screening to obtain a graphene product modified by the complexing agent.
In some embodiments, the mass ratio of graphene to complexing agent is 1:0.2 to 1.5. The mass ratio of the graphene to the complexing agent is controlled, the number of the complexing agent on the surface of the graphene can be well regulated and controlled, and then the complexing agent can be complexed with copper ions to form a complex.
In some embodiments, the mass ratio of graphene to complexing agent is 1:0.2, 1:0.5, 1:1. 1:1.5.
in some embodiments, the graphene is selected from a crystalline flake graphene material, and providing a flake graphene material facilitates obtaining a particular size and a particular number of layers of graphene.
In some embodiments, the complexing agent is selected from at least one of methylamine, ethylenediamine, isopropylamine, isobutylamine, cyclopropylamine, sec-butylamine, tert-butylamine, hexylamine, dodecylamine, hexadecylamine, octadecylamine. The group of the provided complexing agent is modified on the surface of the graphene material, so that the graphene material is favorably combined with a copper base through the complexing agent to form a graphene-complexing agent-copper base complex, and the combining capacity of the graphene and the copper base is further improved. The organic amine with different C contents can regulate the types of organic amine on the surface of the graphene, so that composite materials with different properties are formed.
Further, an organic solvent is provided to dissolve the graphene and the complexing agent, and the provided organic solvent can dissolve various complexing agents and can have good wettability with the graphene, so that the wettability of the graphene and a copper-based material is improved. In some embodiments, the organic solvent is selected from any one of an alcoholic solvent, cyclohexane.
In some embodiments, the ratio of the added amount of graphene to the added amount of organic solvent is 1g: (10-15) mL, and the addition amount of the organic solvent is controlled to be moderate, so that the reactants can be better dissolved and mixed.
In some embodiments, the first mixing treatment is selected from any one of ball milling treatment, stirring treatment, grinding treatment, mechanical mixing treatment and ultrasonic treatment, and the mixing treatment is performed by the first mixing treatment, so that the complexing agent in the obtained mixed product can modify the graphene.
In some embodiments, the first mixing process is selected from a ball milling process with a rotational speed of 200 to 600r/min for a time of 1 to 10 hours. The rotation speed and time of ball milling treatment are controlled, so that thorough ball milling treatment can be ensured, and the surface structure of graphene in the obtained product is controlled to be kept, thereby being beneficial to subsequent use. If the rotation speed of the ball milling treatment is too low, the ball milling treatment is not thorough, the generation of products is not facilitated, and if the rotation speed of the ball milling treatment is too high, the surface structure of the graphene is damaged, and the preparation of the subsequent composite material is influenced. If the ball milling time is too short, the ball milling treatment is not thorough, and the yield of the product is influenced; if the ball milling treatment time is too long, graphene is oxidized, and the subsequent preparation of the composite material is influenced.
In some embodiments, the rotational speed of the ball milling process is selected from 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, 550r/min, 600r/min. The selection of the rotational speed for a particular ball milling process can be determined based on the amount of addition of a particular reactant.
In some embodiments, the ball milling is performed for a time selected from the group consisting of 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, and 10 hours.
Further, the mixed product is separated in different centrifugal rotation speed intervals, and graphene with different sizes and layers can be obtained through separation in different centrifugal rotation speed intervals, so that the preparation of the composite material with copper salt in the follow-up process is facilitated.
In some embodiments, in the step of subjecting the mixed product to the separation treatment in different centrifugation rotation speed intervals, the different centrifugation rotation speed intervals are respectively selected from: 0-2000r/min;2000-6000r/min;6000-9000r/min; 9000-13000 r/min. Through different centrifugal rotational speeds, can separate the graphite alkene of the different number of piles, mainly utilize its centrifugal force, at low-speed centrifugation scope, the great graphite alkene of the number of piles is because gravity or centrifugal force, the centrifuging tube bottom that preferentially subsides, along with centrifugal scope risees, the continuation that the number of piles is thin subsides, consequently can obtain the graphite alkene product of the different number of piles through regulation and control centrifugation scope.
In a specific embodiment, the separation at different centrifuge speed ranges results in the following numbers of layers within the corresponding centrifuge ranges: separating at a centrifugal rotating speed of 0-2000r/min to obtain 30-100 layers of graphene products; the graphene product obtained by separation at the centrifugal rotating speed of 2000-6000r/min is 10-30 layers; separating at a centrifugal rotating speed of 6000-9000r/min to obtain 3-10 layers of graphene products; the graphene product obtained by separation at the centrifugal rotating speed of 9000-13000 r/min is a single layer or within 3 layers, and the required number of layers of graphene products can be obtained by adjusting the range of the centrifugal rotating speed.
In some implementations, after the separation treatment is performed on the mixed product in different centrifugal rotation speed intervals, the settling treatment, the separation treatment and the washing treatment are sequentially performed. And respectively carrying out sedimentation treatment, separation treatment and washing treatment on the graphene products with different layers obtained in different centrifugal speed intervals to obtain the graphene product modified by the complexing agent with higher purity.
In some embodiments, a settling treatment is performed first, primarily to settle the product to the bottom to facilitate separation. And performing separation treatment, including centrifugal separation treatment, to separate precipitate from solution to the maximum extent. And finally, washing treatment is carried out, and the organic solvent or the redundant alcohol can be washed away by adopting water or ethanol or cyclohexane, so that the pollution caused by the washing is reduced.
And further, screening to obtain a graphene product modified by the complexing agent. And in the screening process, carrying out subsequent research on the graphene product modified by the complexing agent with the least layers obtained by adopting the maximum centrifugal rotating speed.
In the step S03, according to the graphene copper-based composite material model, mixing soluble copper salt, a graphene product modified by a complexing agent and an organic solvent to obtain a graphene-complexing agent-copper complex dispersion liquid; and determining the addition amount of each reactant according to the predicted excellent properties of the graphene copper-based composite material model to prepare the composite material.
In some embodiments, the mass ratio of the soluble copper salt to the complexing agent-modified graphene product is 0.01 to 3:1. the mass ratio of the soluble copper salt to the complexing agent modified graphene product is controlled, so that the conductive effect of the graphene can be fully exerted, and the conductivity and the strength of the composite material can be influenced if the amount of the graphene product is too much by being beneficial to good combination of the graphene and the soluble copper salt.
In some embodiments, the mass ratio of the soluble copper salt to the complexing agent-modified graphene product is 0.01: 1. 0.05: 1. 0.1: 1. 0.5: 1. 1:1. 1.5: 1. 2: 1. 2.5: 1. 3:1.
in some embodiments, the soluble copper salt is selected from at least one of copper sulfate, copper nitrate, copper acetate, copper chloride, copper isooctanoate, copper tartrate.
In some embodiments, the step of subjecting the soluble copper salt, the complexing agent modified graphene product, and the organic solvent to a second mixing treatment comprises: dispersing the graphene product modified by the complexing agent into an organic solvent to obtain graphene product dispersion liquid modified by the complexing agent, dispersing soluble copper salt into the organic solvent to obtain copper salt dispersion liquid, and mixing the graphene product dispersion liquid and the copper salt dispersion liquid. The soluble copper salt and the graphene product modified by the complexing agent are respectively dispersed to obtain dispersion liquid, and then the dispersion liquid is mixed, so that the reaction between the two reactants is more complete, and the effect is better. In the step of dispersing the soluble copper salt into the organic solvent to obtain the copper salt dispersion liquid, the molar concentration of the soluble copper salt in the organic solvent is controlled to be 0.01-2 mol/L, the amount of the soluble copper salt in the solution is controlled, and excessive soluble copper salt can cause over-saturation, influence the dissolution and be not beneficial to the experiment. In some embodiments, the molar concentration of the soluble copper salt in the alcoholic solvent is 0.01mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L.
In some embodiments, in the step of performing the second mixing treatment on the soluble copper salt, the graphene product modified by the complexing agent and the organic solvent, mixing is performed in a stirring manner, wherein the stirring speed is 200 to 1000rpm, and the stirring time is 5 to 30 minutes. The graphene-complexing agent-copper complex dispersion liquid with high uniformity and stability can be formed by complexing the complexing agent modified on the surface of the graphene with copper ions by adopting a stirring method and controlling the stirring speed and time.
In some implementations, the speed of agitation is selected from 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm; the stirring time is selected from 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes.
In step S04, a reducing agent is provided, and the graphene-complexing agent-copper complex dispersion liquid and the reducing agent are subjected to reduction reaction to obtain the graphene copper-based composite material.
In some embodiments, the reducing agent is selected from at least one of hydrazine hydrate, sodium borohydride, hydrogen, formaldehyde, acetaldehyde, propionaldehyde, the reducing agent being provided to ensure that reduction occurs.
In some embodiments, the molar ratio of soluble copper salt to reducing agent is 1:0.5 to 3. The molar ratio of the reducing agent to the soluble copper salt is controlled, so that the reduction reaction can be accurately controlled, and the graphene copper-based composite material can be obtained. In some embodiments, the molar ratio of soluble copper salt to reducing agent is selected from 1:0.5, 1:1. 1:1.5, 1:2. 1:2.5, 1:3.
in some embodiments, in the step of subjecting the graphene-complexing agent-copper complex dispersion to a reduction reaction with a reducing agent, the temperature of the reduction reaction is 25 to 75 ℃, and the time of the reduction reaction is 5 to 30 minutes. And carrying out reduction reaction to obtain the graphene copper-based composite material.
In some embodiments, in the reduction reaction process, the reduction reaction rate can be accurately regulated and controlled by changing the amount and the type of the organic amine on the surface of the graphene, and in specific embodiments, the reduction reaction rate can be effectively reduced by increasing the amount of the organic amine on the surface of the graphene or increasing the chain length of the organic amine.
In some embodiments, the product obtained by the reduction reaction further comprises: and (3) separation treatment and washing treatment are carried out, so that the obtained graphene copper-based composite material is high in purity and free of impurity doping.
The second aspect of the embodiments of the present application provides a graphene copper-based composite material, which is prepared by a preparation method.
According to the graphene copper-based composite material provided by the second aspect of the application, the graphene copper-based composite material is prepared by the preparation method, the preparation efficiency is high, the strength of the obtained graphene copper-based composite material is not lower than 600MPa, the conductivity is not lower than 110IACS, the elongation is not lower than 3.0%, the property is excellent, the dispersion effect is good, the interface bonding property is strong, and the wide market demand can be met.
In some embodiments, the obtained graphene copper-based composite material has the advantages of strength not lower than 600MPa, conductivity not lower than 110IACS, elongation not lower than 3.0% and excellent properties.
In a third aspect of the embodiments of the present application, a high-speed rail contact line is selected from a graphene copper-based composite material, and the graphene copper-based composite material is a graphene copper-based composite material.
According to the high-speed railway contact line provided by the third aspect of the application, the high-speed railway contact line is selected from graphene copper-based composite materials, the graphene copper-based composite materials are graphene copper-based composite materials, and based on the provided graphene copper-based composite materials, the obtained high-speed railway contact line is high in strength, high in mechanical property and conductivity, and capable of ensuring that the product quality is superior to the level of similar products abroad, ensuring that the high-speed railway contact line can occupy obvious advantages in the market of high-speed railways, and having great economic benefits.
In some embodiments, the graphene copper-based composite material is prepared by the provided preparation method and applied to a high-speed rail contact line, the provided preparation method is a pilot line of the high-speed rail copper contact line, and the annual capacity is greater than 1000 tons.
In some embodiments, the high-speed rail contact line provided is a contact line material for a high-speed rail meeting a speed of 400km per hour.
The following description is given with reference to specific examples.
Example 1
A graphene copper-based composite material is prepared by the following steps:
(1) Establishing a graphene copper-based composite material model by utilizing machine learning and high-throughput screening technologies;
constructing a copper crystal model through DFT theoretical calculation;
combining DFT theoretical calculation with machine learning, adding graphene on the surface of a copper crystal model, establishing graphene-copper crystal models under different scales, and performing model optimization processing on intrinsic structures, defects, forms and graphene-copper interfaces of the graphene;
based on the Sabatier principle, the graphene-copper crystal model is subjected to high-throughput screening by utilizing high-throughput DFT calculation, and a graphene copper-based composite material model is established.
(2) Carrying out first mixing treatment on graphene, a complexing agent and an organic solvent to obtain a mixed product, carrying out separation treatment on the mixed product in different centrifugal rotation speed intervals, and then screening to obtain a graphene product modified by the complexing agent;
weighing 1g of crystalline flake graphene, 200mg of dodecylamine and 10ml of sec-butyl alcohol, putting the crystalline flake graphene, 200mg of dodecylamine and 10ml of sec-butyl alcohol into a 100ml ball milling tank, carrying out ball milling for 10 hours at a rotating speed of 400r/min to obtain ball milling products, carrying out centrifugal separation treatment on the ball milling products in different centrifugal intervals (0-2000 r/min,2000-6000r/min,6000-9000r/min and 9000-13000 r/min) respectively to obtain graphene products in corresponding centrifugal intervals, then carrying out sedimentation, separation and washing on the centrifugal products in different intervals, circulating for 3 times, and re-dispersing the dodecylamine modified graphene products with the least layers obtained by centrifugal separation at the rotating speed of 9000-13000 r/min into sec-butyl alcohol for later use.
(3) According to the graphene copper-based composite material model, carrying out second mixing treatment on a soluble copper salt, a graphene product modified by a complexing agent and an organic solvent to obtain a graphene-complexing agent-copper complex dispersion liquid;
mixing Cu (CH) 3 COO) 2 ·H 2 Dissolution of O into sec-butanol to form Cu (CH) 3 COO) 2 ·H 2 O, wherein the molar concentration of the copper salt in the organic solvent is 0.05mol/L; and then adding graphene dispersion liquid with the surface modified by dodecylamine, wherein the mass ratio of graphene with the surface modified by dodecylamine to copper is 1: and 3, fully stirring for 10 minutes at the speed of 400-500 rpm to complex the dodecylamine modified on the surface of the graphene and copper ions to form the graphene-complexing agent-copper complex dispersion liquid with high uniformity and stability.
(4) And providing a reducing agent, and carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and the reducing agent to obtain the graphene copper-based composite material.
Providing acetaldehyde as an aldehyde reducing agent, wherein the molar ratio of acetaldehyde to copper salt is 0.5:1, carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and an aldehyde reducing agent at 25 ℃ for 10 minutes, and then carrying out impurity removal treatment to obtain the graphene copper-based composite material.
Example 2
A graphene copper-based composite material is prepared by the following steps:
(1) Establishing a graphene copper-based composite material model by utilizing machine learning and high-throughput screening technologies;
constructing a copper crystal model through DFT theoretical calculation;
combining DFT theoretical calculation with machine learning, adding graphene on the surface of a copper crystal model, establishing graphene-copper crystal models under different scales, and performing model optimization processing on intrinsic structures, defects, forms and graphene-copper interfaces of the graphene;
based on the Sabatier principle, high-throughput screening is carried out on the graphene-copper crystal model by utilizing high-throughput DFT calculation, and a graphene copper-based composite material model is established.
(2) Carrying out first mixing treatment on graphene, a complexing agent and an organic solvent to obtain a mixed product, carrying out separation treatment on the mixed product in different centrifugal rotation speed intervals, and then screening to obtain a graphene product modified by the complexing agent;
weighing 1g of graphene, 500mg of ethylenediamine and 10ml of ethanol, putting the graphene, the 500mg of ethylenediamine and the 10ml of ethanol into a 100ml ball milling tank, carrying out ball milling for 10 hours at a rotating speed of 200r/min to obtain ball milling products, carrying out centrifugal separation treatment on the ball milling products in different centrifugal intervals (0-2000 r/min,2000-6000r/min,6000-9000r/min and 9000-13000 r/min) respectively to obtain graphene products in corresponding centrifugal intervals, then carrying out sedimentation, separation and washing on the centrifugal products in different intervals, circulating for 3 times, and re-dispersing the ethylenediamine modified graphene product with the least layers obtained by carrying out centrifugal separation at the rotating speed of 9000-13000 r/min into ethanol for later use.
(3) According to the graphene copper-based composite material model, carrying out second mixing treatment on a soluble copper salt, a graphene product modified by a complexing agent and an organic solvent to obtain a graphene-complexing agent-copper complex dispersion liquid;
dissolving copper sulfate into ethanol to form an ethanol solution of copper sulfate, wherein the molar concentration of copper salt in an organic solvent is 1mol/L; and then adding graphene dispersion liquid of surface modified ethylenediamine, wherein the mass ratio of graphene to copper of the surface modified ethylenediamine is 1:0.5, fully stirring for 30 minutes at the speed of 200-300 rpm to complex the ethylenediamine modified on the surface of the graphene and copper ions to form highly uniform and stable graphene-complexing agent-copper complex dispersion liquid.
(4) And providing a reducing agent, and carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and the reducing agent to obtain the graphene copper-based composite material.
Providing formaldehyde as an aldehyde reducing agent, wherein the molar ratio of the formaldehyde to the copper salt is 2:1, carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and an aldehyde reducing agent at 40 ℃ for 10 minutes, and then carrying out impurity removal treatment to obtain the graphene copper-based composite material.
Example 3
A preparation method of a graphene copper-based composite material comprises the following steps:
(1) Establishing a graphene copper-based composite material model by utilizing machine learning and high-throughput screening technologies;
constructing a copper crystal model through DFT theoretical calculation;
combining DFT theoretical calculation with machine learning, adding graphene on the surface of a copper crystal model, establishing graphene-copper crystal models under different scales, and performing model optimization processing on intrinsic structures, defects, forms and graphene-copper interfaces of the graphene;
based on the Sabatier principle, high-throughput screening is carried out on the graphene-copper crystal model by utilizing high-throughput DFT calculation, and a graphene copper-based composite material model is established.
(2) Carrying out first mixing treatment on graphene, a complexing agent and an organic solvent to obtain a mixed product, carrying out separation treatment on the mixed product in different centrifugal rotation speed intervals, and then screening to obtain a graphene product modified by the complexing agent;
weighing 1g of graphene, 1g of cyclopropylamine and 10ml of butanol, putting the graphene, the cyclopropylamine and the butanol into a 100ml ball milling tank, ball milling for 10 hours at a rotating speed of 600r/min to obtain ball milling products, performing centrifugal separation treatment on the ball milling products in different centrifugal intervals (0-2000 r/min,2000-6000r/min,6000-9000r/min and 9000-13000 r/min) to obtain graphene products in corresponding centrifugal intervals, then performing sedimentation, separation and washing on the centrifugal products in different intervals, circulating for 3 times, and re-dispersing the cyclopropylamine-modified graphene product with the least layers obtained by centrifugal separation at the rotating speed of 9000-13000 r/min into the butanol for later use.
(3) According to the graphene copper-based composite material model, carrying out second mixing treatment on a soluble copper salt, a graphene product modified by a complexing agent and an organic solvent to obtain a graphene-complexing agent-copper complex dispersion liquid;
dissolving copper isooctanoate in butanol to form a butanol solution of copper isooctanoate, wherein the molar concentration of copper salt in an organic solvent is 1.5mol/L; and then, adding a graphene dispersion liquid with the surface modified by cyclopropylamine, wherein the mass ratio of graphene to copper of the surface modified by cyclopropylamine is 1:0.5, fully stirring for 15 minutes at the speed of 900-1000 rpm to complex the cyclopropylamine modified on the surface of the graphene with copper ions to form a highly uniform and stable graphene-complexing agent-copper complex dispersion liquid.
(4) And providing a reducing agent, and carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and the reducing agent to obtain the graphene copper-based composite material.
Propionaldehyde is provided as an aldehyde reducing agent, wherein the molar ratio of propionaldehyde to copper salt is 2:1, carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and an aldehyde reducing agent at 70 ℃ for 5 minutes, and then carrying out impurity removal treatment to obtain the graphene copper-based composite material.
Property measurement
The electrical conductivity, tensile strength and elongation of the graphene copper-based composite materials obtained in examples 1 to 3 were measured, respectively, by the following methods:
(1) Conductivity: the four-end method for double-arm bridge is adopted, the current is kept still at 20 +/-0.5 ℃ for 24h and 8A, and the average value of the positive and negative polarities of the switching power supply is used for measurement (IACS).
(2) Tensile strength: the size of a tensile sample is designed to be a cuboid with the gauge length of 10mm and the section of 2mm multiplied by 1.5mm, an RG2000-20 type stretcher is used for carrying out a tensile test, and the initial tensile speed is 1mm/min. Measuring and calculating resistance (MPa) of maximum uniform plastic deformation of material
(3) Elongation percentage: the size of a tensile sample is designed to be a cuboid with the gauge length of 10mm and the section of 2mm multiplied by 1.5mm, an RG2000-20 type stretcher is used for carrying out a tensile test, and the initial tensile speed is 1mm/min. After the sample was tensile broken, the percentage (%) of the ratio of the elongation of the original gauge length to the original gauge length was calculated.
Analysis of results
The electrical conductivity, tensile strength and elongation of the graphene copper-based composite materials obtained in the embodiments 1 to 3 are respectively measured, and the results are shown in the following table 1, which shows that the electrical conductivity, tensile strength and elongation of the graphene copper-based composite materials obtained in the embodiments 1 to 3 are not lower than 110IACS, not lower than 600MPa and not lower than 3.0%, and each index is superior to the level of foreign like products, and the graphene copper-based composite materials have obvious advantages in the high-speed railway market, and have great economic benefits.
TABLE 1
In summary, according to the preparation method of the graphene copper-based composite material, accurate prediction of a high-strength and high-conductivity graphene copper-based composite material model is achieved by utilizing machine learning and high-throughput screening technologies, so that preparation of subsequent materials is known, organic amine is provided to react with graphene to obtain a graphene product with a surface modified with organic amine, the graphene product is reacted with a copper salt material through a copper mirror to accurately regulate and control copper atoms, and then deposition on the surface of the graphene is performed, on one hand, the graphene can be uniformly dispersed into an organic system through the surface modified with organic amine, on the other hand, the organic amine on the surface of the graphene is complexed with copper ions to form a graphene-organic amine-copper ion complex dispersion system, and the dispersibility of the graphene in a copper matrix is improved; furthermore, in the aldehyde reduction process, the copper atoms are accurately regulated and controlled in the graphene surface deposition process by changing the type and the quantity of organic amine on the graphene surface, and good interface recombination between the graphene and the copper is realized on the molecular atom level. On the basis, an interface cross-scale composite mechanism of graphene in the copper crystal crystallization process is further disclosed, a coupling process route of graphene to the copper crystal crystallization process is established, a large-scale stable preparation technology of the graphene copper-based composite material is provided, the technical problem of uniform implantation of the graphene copper-based composite material into an industrial preparation technology is solved, and the high-end development of the copper-based material industry is promoted.
The graphene copper-based composite material prepared by the method is high in preparation efficiency, good in dispersion effect of graphene and the copper-based material and strong in interface bonding property, and can meet wide market demands. The conductive material has high mechanical property and conductivity, ensures that the product quality is superior to the level of foreign similar products, ensures that the conductive material can occupy obvious advantages in the high-speed railway market, and has great economic benefit.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (8)
1. The preparation method of the graphene copper-based composite material is characterized by comprising the following steps:
establishing a graphene copper-based composite material model by utilizing machine learning and high-throughput screening technologies; by utilizing a multi-factor coupling mechanism in the process of crystallizing a copper crystal material by machine learning of multi-scale graphene, accurate prediction of a graphene copper-based composite material model is realized, and theoretical guidance is improved for preparing the graphene copper-based composite material in a laboratory;
carrying out first mixing treatment on graphene, a complexing agent and an organic solvent to obtain a mixed product, carrying out separation treatment on the mixed product in different centrifugal rotation speed intervals, and then screening to obtain a graphene product modified by the complexing agent; wherein the complexing agent is selected from at least one of methylamine, ethylenediamine, isopropylamine, isobutylamine, cyclopropylamine, sec-butylamine, tert-butylamine, hexylamine, dodecylamine, hexadecylamine and octadecylamine; the mass ratio of the graphene to the complexing agent is 1:0.2 to 1.5;
according to the graphene copper-based composite material model, carrying out second mixing treatment on a soluble copper salt, the graphene product modified by the complexing agent and an organic solvent to obtain a graphene-complexing agent-copper complex dispersion liquid;
providing a reducing agent, and carrying out reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and the reducing agent to obtain a graphene copper-based composite material;
in the reduction process, the copper atom deposition process on the surface of the graphene is accurately regulated and controlled by changing the type and the quantity of the graphene surface complexing agents.
2. The method for preparing the graphene copper-based composite material according to claim 1, wherein the method for predicting the graphene copper-based composite material model by using machine learning and high-throughput screening technology comprises the following steps:
constructing a copper crystal model through DFT theoretical calculation;
combining DFT theoretical calculation with machine learning, adding graphene on the surface of the copper crystal model, establishing graphene-copper crystal models under different scales, and performing model optimization processing on the intrinsic structure, defects, morphology and graphene-copper interface form of the graphene;
based on the Sabatier principle, high-throughput screening is carried out on the graphene-copper crystal model by utilizing high-throughput DFT calculation, and a graphene copper-based composite material model is established.
3. The method for preparing the graphene copper-based composite material according to claim 1 or 2, wherein the first mixing treatment is any one selected from a ball milling treatment, a stirring treatment, a grinding treatment, a mechanical mixing treatment, and an ultrasonic treatment.
4. The preparation method of the graphene copper-based composite material according to claim 1 or 2, wherein in the step of separating the mixed product at different centrifugal rotation speed intervals, the different centrifugal rotation speed intervals are respectively selected from: 0-2000r/min;2000-6000r/min;6000-9000r/min;9000 to 13000 r/min; and/or the presence of a gas in the atmosphere,
and after the mixed product is separated in different centrifugal rotating speed intervals, the method also comprises the steps of settling treatment, separation treatment and washing treatment in sequence.
5. The preparation method of the graphene copper-based composite material according to claim 1 or 2, wherein the mass ratio of the soluble copper salt to the complexing agent-modified graphene product is 0.01 to 3:1; and/or the presence of a gas in the atmosphere,
the molar ratio of the soluble copper salt to the reducing agent is 1:0.5 to 3; and/or the presence of a gas in the gas,
the soluble copper salt is selected from at least one of copper sulfate, copper nitrate, copper acetate, copper chloride, copper isooctanoate and copper tartrate; and/or the presence of a gas in the gas,
the reducing agent is at least one selected from hydrazine hydrate, hydrogen, sodium borohydride, formaldehyde, acetaldehyde and propionaldehyde.
6. The preparation method of the graphene copper-based composite material according to claim 1 or 2, wherein in the step of performing second mixing treatment on the soluble copper salt, the graphene product modified by the complexing agent and the organic solvent, the graphene copper-based composite material is mixed in a stirring manner, wherein the stirring speed is 200 to 1000rpm, and the stirring time is 5 to 30 minutes.
7. The method for preparing the graphene copper-based composite material according to claim 1 or 2, wherein in the step of carrying out the reduction reaction on the graphene-complexing agent-copper complex dispersion liquid and the reducing agent, the temperature of the reduction reaction is 25 to 75 ℃, and the time of the reduction reaction is 5 to 30 minutes.
8. The preparation method of the graphene copper-based composite material according to claim 1 or 2, wherein the prepared graphene copper-based composite material is used for a high-speed rail contact line.
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