CN113278838B - Preparation method of multidimensional carbon material composite reinforced copper-based material - Google Patents
Preparation method of multidimensional carbon material composite reinforced copper-based material Download PDFInfo
- Publication number
- CN113278838B CN113278838B CN202110542727.2A CN202110542727A CN113278838B CN 113278838 B CN113278838 B CN 113278838B CN 202110542727 A CN202110542727 A CN 202110542727A CN 113278838 B CN113278838 B CN 113278838B
- Authority
- CN
- China
- Prior art keywords
- powder
- copper
- carbon
- sintering
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/176—Cutting
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The invention discloses a preparation method of a multidimensional carbon material composite reinforced copper-based material, which comprises the steps of uniformly mixing a carbon precursor with concentrated acid, heating, stirring and refluxing, neutralizing a product with an alkaline substance, dialyzing in ultrapure water, performing rotary evaporation, freeze-drying to obtain mixed powder of carbon nano tube-graphene quantum dots, performing ball milling on copper powder and the mixed powder, reducing to obtain copper and carbon nano tube-graphene quantum dot composite powder, and sintering to obtain a composite material; the method of the invention has simple operation and easy industrialized preparation, the obtained composite reinforcement is uniformly distributed, the relative proportion of the three dimensional reinforcements is controllable, and the method can play a remarkable role in multi-dimensional reinforcement on the base material.
Description
Technical Field
The invention relates to a method for preparing a multidimensional carbon material composite reinforced copper-based material, belonging to the field of composite material preparation and powder metallurgy.
Background
The graphene quantum dots are carbon-based zero-dimensional materials. The graphene quantum dots have the advantages of excellent optical properties, good water solubility, low toxicity, environmental friendliness, wide raw material source, low cost, good biocompatibility and the like. Carbon nanotubes, also known as buckytubes, are one-dimensional nanomaterials with special structures (radial dimension is nanometer magnitude, axial dimension is micrometer magnitude, both ends of the tube are substantially sealed). Carbon nanotubes are coaxial circular tubes consisting of several to tens of layers of carbon atoms arranged in a hexagonal pattern. The distance between layers is kept constant, about 0.34nm, the diameter is generally 2-50 nm, and the carbon hexagons can be divided into three types, namely a sawtooth shape, an armchair shape and a spiral shape according to different orientations of the carbon hexagons along the axial direction. The carbon nano tube is used as a one-dimensional nano material, has light weight, perfect connection of a hexagonal structure and a plurality of abnormal mechanical, electrical and chemical properties. Graphene is a basic structural unit constituting graphite; the carbon nanotube is a cylindrical structure formed by curling graphene, and the graphene is a planar structure formed by cracking the carbon nanotube. Structurally, carbon nanotubes are a one-dimensional crystal structure of carbon; and the graphene is only composed of a single carbon atom layer and is a two-dimensional crystal structure in the true sense. From the aspect of performance, graphene has characteristics comparable to or superior to those of carbon nanotubes, such as high electrical and thermal conductivity, high carrier mobility, free electron mobility space, high strength and rigidity, and the like. As representatives of zero-dimensional (0D), one-dimensional (1D), and two-dimensional (2D) nanomaterials, the graphene quantum dots, the carbon nanotubes, and the graphene have complementarity in structure and performance.
The carbon nano material is widely used as a reinforcement of metal, ceramic and polymer materials due to excellent mechanical, electrical and thermal properties, so that the mechanical property of the matrix can be increased, the performance of the matrix in the aspects of electrical, thermal, magnetic and optical functions can be improved, the application range of the composite material is widened, and the service cycle of related products is prolonged. Most of the existing researches are focused on the reinforcing effect of the carbon nanotube and the graphene in the aspect of composite materials, and the research on the reinforcing effect of the zero-dimensional graphene quantum dot on the composite materials is less, but theoretically, the combination of the three in three different dimensions can effectively increase the consistency of various performances of the composite materials in three-dimensional space, and in addition, the synergistic effect of the three is not negligible, for example, the excellent dispersibility of the graphene quantum dot is not possessed by the other two, the preparation cost of the graphene quantum dot is very low compared with that of the graphene and the carbon nanotube, but the mechanical strength of the graphene quantum dot in nanometer size is not similar to that of the graphene and the carbon nanotube, in addition, the performances of the graphene in a specific direction are not similar to that of the carbon nanotube, the carbon nanotube generally has the characteristics of directionality and difficult dispersion, and the like, and in conclusion, the combination of the three is not only mutually complementary in a simple space structure, more importantly, the advantages of the function are complementary.
Disclosure of Invention
Aiming at the problem that the strength of a copper-based composite material is difficult to be enhanced and the elongation and the electric conductivity are not lost due to the interface combination problem after copper is combined with various reinforcements, the invention quickly prepares the carbon nano tube-graphene quantum dot multidimensional composite enhanced powder by a one-pot method, is used for multifunctional enhanced copper-based materials, and simultaneously increases the strength, the elongation and the electric conductivity of copper, and aims to improve the comprehensive performance of the composite material.
The method comprises the steps of preparing the carbon nanotube-graphene quantum dot multidimensional composite reinforced powder (acid cracking, alkali neutralization, dialysis, rotary evaporation and freeze drying) and preparing the copper-carbon nanotube-graphene quantum dot composite material (ball milling, reduction and sintering).
The technical scheme of the invention is as follows:
a preparation method of a multidimensional carbon material composite reinforced copper-based material comprises the following specific steps:
(1) acid cracking: uniformly mixing the carbon precursor with concentrated acid, heating, stirring and refluxing the mixture;
(2) alkali neutralization: neutralizing and titrating a reaction product obtained in the step (1) to be neutral by using an alkaline substance;
(3) and (3) dialysis: dialyzing the neutralized dispersion liquid obtained in the step (2) in ultrapure water for 4-6 days;
(4) and (3) drying: performing rotary evaporation on the dispersion liquid dialyzed in the step (3), and performing freeze drying to obtain carbon nanotube-graphene quantum dot powder;
(5) preparing composite powder: ball-milling copper powder and the powder obtained in the step (4), and then reducing to obtain a carbon nanotube-graphene quantum dot-copper composite powder body;
(6) preparing a composite block: and (4) sintering the composite powder obtained in the step (5) to obtain the composite material.
The carbon precursor in the step (1) is a carbon nano tube, and comprises one or a mixture of more of an industrialized carbon nano tube, a doped carbon nano tube, a graphitized carbon nano tube, a carboxylated carbon nano tube, a hydroxylated carbon nano tube and the like (comprising carbon nano tubes of all other types) in any proportion; the concentrated acid is commercial concentrated nitric acid with the mass fraction of 68%, or the commercial concentrated nitric acid with the mass fraction of 68% is mixed with concentrated sulfuric acid with the mass fraction of 98% in any proportion.
The temperature of heating, stirring and refluxing in the step (1) is 100-160 ℃, and the time is 12-96 h; and after the reflux is started, replenishing the carbon precursor every 4-48h, wherein the replenished carbon precursor is 10-50% of the mass of the initially added carbon precursor, and the volume ratio of the mass of the initially added carbon precursor to the concentrated acid, namely mg: mL, is 0.2-4.0: 1.
The alkaline substance in the step (2) is alkali or alkaline solution, the alkali is sodium hydroxide, potassium hydroxide, sodium carbonate and the like, the alkaline solution is a solution with the pH value of more than 7, and the neutralization can be carried out in ice bath or water bath to absorb heat release.
In the step (3), a dialysis bag with the molecular weight of 500-.
And (4) continuously vacuumizing the rotary evaporation process at the rotary evaporation temperature of 60-90 ℃.
The mass ratio of the copper powder in the step (5) to the powder in the step (4) is 1000: 1-10; the ball milling process comprises the following steps: firstly, low-speed ball milling is carried out for 5-10 hours, then high-speed ball milling is carried out for 2-5 hours, the rotation speed of the low-speed ball milling is 50-200rpm, and the rotation speed of the high-speed ball milling is not less than 400 rpm; the reduction is carried out in a reducing atmosphere, the temperature is kept at 250-350 ℃ for 2-8h, and the reducing atmosphere is hydrogen or a mixed atmosphere of hydrogen and inert gas in any proportion.
The sintering mode in the step (6) is spark plasma sintering, cold pressing sintering or hot isostatic pressing sintering, the sintering temperature is 500-800 ℃, the sintering heat preservation time is 5-60min, the sintering pressure is 10-50MPa, and the sintering vacuum degree is less than 0.1 Pa.
The invention has the beneficial effects that:
(1) the multidimensional reinforcement carbon nanotube (one-dimensional) -graphene (two-dimensional) -graphene quantum dot (zero-dimensional) powder is prepared by a one-pot method, wherein graphene quantum dots grow on the surface and the edge of graphene, and after acid oxidation cutting, the surfaces of the carbon nanotube, the graphene and the graphene quantum dot are rich in oxygen-containing functional groups (carboxyl, carbonyl, hydroxyl and the like), so that the carbon nanotube-graphene quantum dot composite reinforcement is uniformly dispersed, and the interface bonding strength with copper is good.
(2) Compared with the traditional copper-based composite material, the carbon nanotube-graphene quantum dot multidimensional reinforcement reinforced copper-based material has the advantages that the strength and the elongation are obviously improved, and the electric conductivity is also improved to a certain degree.
Drawings
Fig. 1 is a sunlight irradiation picture (left), a red laser pen irradiation picture (middle) and a 365nm ultraviolet lamp irradiation picture (right) of the carbon nanotube-graphene quantum dot powder dispersed in ultrapure water of example 1;
fig. 2 is a transmission electron microscope image of the nitrogen-doped carbon nanotube-graphene quantum dot multi-dimensional reinforcement prepared in example 1;
fig. 3 is a stress-strain curve diagram of the nitrogen-doped carbon nanotube-graphene quantum dot-copper-based composite material prepared in example 1 and pure copper;
fig. 4 is a stress-strain curve diagram of the graphitized carbon nanotube-graphene quantum dot-copper-based composite material prepared in example 2 and pure copper.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description. The materials used in the examples of the present invention are all commercially available products unless otherwise specified, and the respective parameters of the carbon precursor materials used are as follows:
TABLE 1
Example 1
A preparation method of a multidimensional carbon material composite reinforced copper-based material comprises the following specific steps:
(1) acid cracking: uniformly mixing 500mg of nitrogen-doped carbon nanotubes and 250mL of concentrated nitric acid with the mass fraction of 68% in a 1L three-neck round-bottom flask, heating to 140 ℃, and stirring and refluxing for 48 hours;
(2) alkali neutralization: neutralizing the reflux liquid obtained in the step (1) to be neutral by using sodium hydroxide in an ice bath;
(3) and (3) dialysis: dialyzing the neutralized dispersion liquid in the step (2) in ultrapure water for 5 days by using a dialysis bag of 500 Da;
(4) and (3) drying: rotationally evaporating the dispersion liquid in the dialysis bag obtained in the step (3) at 60 ℃ until the volume is about 50mL, freezing and drying to obtain nitrogen-doped carbon nanotube-graphene quantum dot powder, and continuously vacuumizing in the rotary evaporation process to improve the rotary evaporation efficiency;
(5) preparing composite powder: and (3) ball-milling and mixing 10000mg of pure copper powder and 30mg of the powder obtained in the step (4), wherein the ball-milling process comprises the following steps: ball-milling at a low speed of 200rpm for 6h, then ball-milling at a high speed of 400rpm for 4h to ensure that copper powder is fully combined with nitrogen-doped carbon nanotube-graphene quantum dot powder, putting the ball-milled composite powder into a vacuum tube furnace, and reducing at 250 ℃ for 6h in a reducing atmosphere, thereby obtaining copper-nitrogen-doped carbon nanotube-graphene quantum dot composite powder, wherein the reducing atmosphere is hydrogen;
(6) preparing a composite block: and (3) sintering the copper-nitrogen doped carbon nanotube-graphene quantum dot composite powder obtained in the step (5) by using discharge plasma, wherein the sintering temperature is 800 ℃, the sintering heat preservation time is 5min, the sintering pressure is 50MPa, and the sintering vacuum degree is less than 0.1Pa, so that the nitrogen doped carbon nanotube-graphene quantum dot-copper base composite material is obtained.
The dispersion liquid of the carbon nanotube-graphene quantum dot powder prepared by the nitrogen-doped carbon nanotube in the ultrapure water is shown in fig. 1, and the pictures of the dispersion liquid under the sun illumination, the infrared laser pen illumination and the 365nm ultraviolet lamp illumination are sequentially arranged from left to right, the dispersion liquid shows brown under the sun illumination, the red laser pen illumination has an obvious tyndall effect to indicate that nanoparticles exist in the dispersion liquid, and the mixed dispersion liquid emits green light after the ultraviolet lamp illumination to indicate that the graphene quantum dot is successfully prepared.
Fig. 2 is a transmission electron microscope image of the nitrogen-doped carbon nanotube-graphene quantum dot powder prepared in this embodiment, the left image shows an obvious structure of the carbon nanotube, the middle image shows graphene quantum dots attached to the graphene, and the right image clearly shows lattice stripes of the graphene quantum dots.
Fig. 3 is a stress-strain curve diagram of the nitrogen-doped carbon nanotube-graphene quantum dot-copper-based composite material prepared in this embodiment and pure copper, and it can be seen from the graph that the yield strength and the tensile strength of the composite material are both significantly improved compared with pure copper, where the tensile strength is increased from 214MPa to 262MPa of pure copper and is increased by 22.4%, and the elongation of the copper-carbon nanotube-graphene quantum dot composite material is increased from 35% to 49% and is increased by 40% compared with pure copper.
Example 2
A preparation method of a multidimensional carbon material composite reinforced copper-based material comprises the following specific steps:
(1) acid cracking: uniformly mixing 250mg of graphitized carbon nanotube and 250mL of concentrated nitric acid with the mass fraction of 68% in a 1L three-neck round-bottom flask, heating to 140 ℃, and stirring and refluxing for 48 hours;
(2) alkali neutralization: neutralizing the reflux liquid obtained in the step (1) to be neutral by using potassium hydroxide in a water bath;
(3) and (3) dialysis: dialyzing the neutralized dispersion liquid in the step (2) in ultrapure water for 4 days by using a dialysis bag of 1000 Da;
(4) and (3) drying: performing rotary evaporation on the dispersion liquid in the dialysis bag obtained in the step (3) at 70 ℃ until the volume is about 50mL, performing freeze drying to obtain graphitized carbon nanotube-graphene quantum dot powder, and continuously performing vacuum pumping in the rotary evaporation process to improve the rotary evaporation efficiency;
(5) preparing composite powder: and (3) ball-milling and mixing 10000mg of pure copper powder and 20mg of the powder obtained in the step (4), wherein the ball-milling process comprises the following steps: ball-milling at a low speed of 200rpm for 5h, then ball-milling at a high speed of 400rpm for 4h to ensure that copper powder is fully combined with graphitized carbon nanotube-graphene quantum dot powder, putting the ball-milled composite powder into a vacuum tube furnace, and reducing at 280 ℃ for 5h in a reducing atmosphere to obtain copper-graphitized carbon nanotube-graphene quantum dot composite powder, wherein the reducing atmosphere is obtained by mixing hydrogen and argon in a volume ratio of 1: 1;
(6) preparing a composite block: and (3) sintering the copper-graphitized carbon nanotube-graphene quantum dot composite powder obtained in the step (5) by using discharge plasma (SPS), wherein the sintering temperature is 700 ℃, the sintering heat preservation time is 5min, the sintering pressure is 40MPa, and the sintering vacuum degree is less than 0.1Pa, so that the graphitized carbon nanotube-graphene quantum dot-copper base composite material is obtained.
Fig. 4 is a stress-strain curve diagram of the graphitized carbon nanotube-graphene quantum dot-copper-based composite material and pure copper in this embodiment, and it can be seen from the graph that the yield strength and the tensile strength of the composite material are both significantly improved compared with pure copper, and compared with pure copper, the tensile strength is increased from 214MPa to 259MPa, which is improved by 21%, and in addition, the elongation is increased from 35% to 60%, which is improved by 71%.
Example 3
A preparation method of a multidimensional carbon material composite reinforced copper-based material comprises the following specific steps:
(1) acid cracking: uniformly mixing 1000mg of industrial carbon nanotubes and 250mL of concentrated nitric acid with the mass fraction of 68% in a 1L three-neck round-bottom flask, heating the mixture to 100 ℃, and stirring and refluxing the mixture for 96 hours;
(2) alkali neutralization: neutralizing the reflux liquid obtained in the step (1) to be neutral by using a potassium hydroxide solution with the concentration of 5mol/L in an ice bath;
(3) and (3) dialysis: dialyzing the neutralized dispersion liquid in the step (2) in ultrapure water for 6 days by using a 3500Da dialysis bag;
(4) and (3) drying: rotationally evaporating the dispersion liquid in the dialysis bag obtained in the step (3) to about 50mL at 80 ℃, freeze-drying to obtain industrialized carbon nanotube-graphene quantum dot powder, and continuously vacuumizing in the process of rotational evaporation to improve the rotational evaporation efficiency;
(5) preparing composite powder: and (3) ball-milling and mixing 10000mg of pure copper powder and 10mg of the powder obtained in the step (4), wherein the ball-milling process comprises the following steps: performing low-speed ball milling for 10 hours at the rotating speed of 50rpm, then performing high-speed ball milling for 2 hours at the rotating speed of 500rpm, fully combining copper powder and the industrialized carbon nanotube-graphene quantum dot powder, putting the ball-milled composite powder into a vacuum tube furnace, and reducing for 4 hours at 300 ℃ in a reducing atmosphere, so as to obtain the copper-industrialized carbon nanotube-graphene quantum dot composite powder, wherein the reducing atmosphere is obtained by mixing hydrogen and argon in a volume ratio of 1: 2;
(6) preparing a composite block: and (5) sintering the copper-industrial carbon nanotube-graphene quantum dot composite powder obtained in the step (5) by hot pressing at the sintering temperature of 600 ℃, with the sintering heat preservation time of 60min, the sintering pressure of 50MPa and the sintering vacuum degree of less than 0.1Pa to obtain the industrial carbon nanotube-graphene quantum dot-copper base composite material.
Example 4
A preparation method of a multidimensional carbon material composite reinforced copper-based material comprises the following specific steps:
(1) acid cracking: 50mg of hydroxylated carbon nanotubes and 250mL of mixed acid (68% by mass of HNO) 3 98 percent of H by mass 2 SO 4 1:3, V/V) was mixed well in a 500mL three-necked round bottom flask, heated to 140 ℃ and stirred at reflux for 48 h;
(2) alkali neutralization: neutralizing the reflux liquid obtained in the step (1) to be neutral in an ice bath by using sodium carbonate;
(3) and (3) dialysis: dialyzing the neutralized dispersion liquid in the step (2) in ultrapure water for 5 days by using a dialysis bag of 1000 Da;
(4) and (3) drying: performing rotary evaporation on the dispersion liquid in the dialysis bag obtained in the step (3) at 90 ℃ until the volume is about 50mL, performing freeze drying to obtain hydroxylated carbon nanotube-graphene quantum dot powder, and continuously vacuumizing in the rotary evaporation process to improve the rotary evaporation efficiency;
(5) preparing composite powder: and (3) ball-milling and mixing 10000mg of pure copper powder and 50mg of the powder obtained in the step (4), wherein the ball-milling process comprises the following steps: performing low-speed ball milling for 10 hours at the rotating speed of 50rpm, then performing high-speed ball milling for 2 hours at the rotating speed of 400rpm, fully combining copper powder and the mixed powder of the hydroxylated carbon nanotube-graphene quantum dot, putting the ball-milled composite powder into a vacuum tube furnace, and reducing for 5 hours at 280 ℃ in a reducing atmosphere, so as to obtain copper-hydroxylated carbon nanotube-graphene quantum dot composite powder, wherein the reducing atmosphere is hydrogen;
(6) preparing a composite block: and (3) sintering the copper-hydroxylated carbon nanotube-graphene quantum dot composite powder obtained in the step (5) by cold pressing, wherein the sintering temperature is 600 ℃, the sintering heat preservation time is 15min, the sintering pressure is 30MPa, and the sintering vacuum degree is less than 0.1Pa, so that the hydroxylated carbon nanotube-graphene quantum dot-copper base composite material is obtained.
Example 5
A preparation method of a multidimensional carbon material composite reinforced copper-based material comprises the following specific steps:
(1) acid cracking: 50mg of carboxylated carbon nanotubes and 250mL of mixed acid (68% by mass of HNO) 3 98 percent of H by mass 2 SO 4 3:1, V/V) in a 500mL three-necked round-bottomed flask, heating it to 100 ℃ and refluxing with stirring for 96h, adding 5mg of hydroxylated carbon nanotubes every 12h, i.e. 12h, 24h, 48h, 60h, 72h, 84h, after the start of refluxing;
(2) alkali neutralization: neutralizing the reflux liquid obtained in the step (1) to be neutral by using a potassium hydroxide solution with the concentration of 5mol/L in an ice bath;
(3) and (3) dialysis: dialyzing the neutralized dispersion liquid in the step (2) in ultrapure water for 6 days by using a 3500Da dialysis bag;
(4) and (3) drying: performing rotary evaporation on the dispersion liquid in the dialysis bag obtained in the step (3) at 80 ℃ until the volume is about 50mL, performing freeze drying to obtain carboxylated carbon nanotube/hydroxylated carbon nanotube-graphene quantum dot powder, and continuously vacuumizing in the rotary evaporation process to improve the rotary evaporation efficiency;
(5) preparing composite powder: and (3) ball-milling and mixing 10000mg of pure copper powder and 40mg of the powder obtained in the step (4), wherein the ball-milling process comprises the following steps: performing low-speed ball milling for 10 hours at the rotating speed of 50rpm, then performing high-speed ball milling for 2 hours at the rotating speed of 500rpm, fully combining copper powder with the carboxylated carbon nanotube/hydroxylated carbon nanotube-graphene quantum dot powder, putting the ball-milled composite powder into a vacuum tube furnace, and reducing for 4 hours at 300 ℃ in a reducing atmosphere to obtain copper-carboxylated carbon nanotube/hydroxylated carbon nanotube-graphene quantum dot composite powder, wherein the reducing atmosphere is obtained by mixing hydrogen and argon in a volume ratio of 1: 2;
(6) preparing a composite block: and (4) sintering the copper-carboxylated carbon nanotube/hydroxylated carbon nanotube-graphene quantum dot composite powder obtained in the step (5) by using hot isostatic pressing, wherein the sintering temperature is 500 ℃, the sintering heat preservation time is 30min, the sintering pressure is 10MPa, and the sintering vacuum degree is less than 0.1Pa, so that the carboxylated carbon nanotube/hydroxylated carbon nanotube-graphene quantum dot-copper base composite material is obtained.
Example 6
A preparation method of a multidimensional carbon material composite reinforced copper-based material comprises the following specific steps:
(1) acid cracking: 50mg of carboxylated carbon nanotubes, 50mg of nitrogen-doped carbon nanotubes and 250mL of mixed acid (68% by mass of HNO) 3 98 percent of H by mass 2 SO 4 1:1, V/V) was mixed uniformly in a 500mL three-necked round-bottom flask, heated to 160 ℃ and stirred under reflux for 12 hours, and 6mg of carboxylated carbon nanotubes and 6mg of nitrogen-doped carbon nanotubes were added every 4 hours, i.e., 4 hours and 8 hours, after the start of reflux;
(2) alkali neutralization: neutralizing the reflux liquid obtained in the step (1) to be neutral in an ice bath by using sodium carbonate;
(3) and (3) dialysis: dialyzing the neutralized dispersion liquid obtained in the step (2) in ultrapure water for 5 days by using a 14000Da dialysis bag;
(4) and (3) drying: performing rotary evaporation on the dispersion liquid in the dialysis bag obtained in the step (3) at 80 ℃ until the volume is about 50mL, performing freeze drying to obtain carboxylated carbon nanotube/nitrogen-doped carbon nanotube-graphene quantum dot powder, and continuously vacuumizing in the rotary evaporation process to improve the rotary evaporation efficiency;
(5) preparing composite powder: and (3) ball-milling and mixing 10000mg of pure copper powder and 50mg of the powder obtained in the step (4), wherein the ball-milling process comprises the following steps: performing low-speed ball milling for 8 hours at the rotating speed of 150rpm, then performing high-speed ball milling for 3 hours at the rotating speed of 400rpm, fully combining copper powder with the carboxylated carbon nanotube/nitrogen-doped carbon nanotube-graphene quantum dot powder, putting the ball-milled composite powder into a vacuum tube furnace, and reducing for 2 hours at 350 ℃ in a reducing atmosphere to obtain copper-carboxylated carbon nanotube/nitrogen-doped carbon nanotube-graphene quantum dot composite powder, wherein the volume ratio of hydrogen to nitrogen is 1: 1;
(6) preparing a composite block: and (3) sintering the copper-carboxylated carbon nanotube/nitrogen-doped carbon nanotube-graphene quantum dot composite powder obtained in the step (5) by using discharge plasma, wherein the sintering temperature is 500 ℃, the sintering heat preservation time is 7min, the sintering pressure is 20MPa, and the sintering vacuum degree is less than 0.1Pa, so that the carboxylated carbon nanotube/nitrogen-doped carbon nanotube-graphene quantum dot-copper-based composite material is obtained.
Example 7
A preparation method of a multidimensional carbon material composite reinforced copper-based material comprises the following specific steps:
(1) acid cracking: uniformly mixing 500mg of nitrogen-doped carbon nanotubes and 250mL of concentrated nitric acid with the mass fraction of 68% in a 1L three-neck round-bottom flask, heating to 150 ℃, stirring and refluxing for 48 hours, and adding 250mg of graphitized carbon nanotubes every 24 hours after the reflux is started, namely at the time point of 24 hours;
(2) alkali neutralization: neutralizing the reflux liquid obtained in the step (1) to be neutral by using sodium hydroxide in an ice bath;
(3) and (3) dialysis: dialyzing the neutralized dispersion liquid in the step (2) in ultrapure water for 5 days by using a dialysis bag of 1000 Da;
(4) and (3) drying: performing rotary evaporation on the dispersion liquid in the dialysis bag obtained in the step (3) at 60 ℃ until the volume is about 50mL, performing freeze drying to obtain nitrogen-doped carbon nanotube/graphitized carbon nanotube-graphene quantum dot powder, and continuously vacuumizing in the rotary evaporation process to improve the rotary evaporation efficiency;
(5) preparing composite powder: and (3) ball-milling and mixing 10000mg of pure copper powder and 100mg of the powder obtained in the step (4), wherein the ball-milling process comprises the following steps: ball-milling at a low speed of 100rpm for 6h, then ball-milling at a high speed of 400rpm for 5h to ensure that copper powder is fully combined with the nitrogen-doped carbon nanotube/graphitized carbon nanotube-graphene quantum dot powder, putting the ball-milled composite powder into a vacuum tube furnace, and reducing at 280 ℃ for 6h in a reducing atmosphere to obtain the copper-nitrogen-doped carbon nanotube/graphitized carbon nanotube-graphene quantum dot composite powder, wherein the volume ratio of hydrogen to nitrogen is 1: 5;
(6) preparing a composite block: and (3) sintering the copper-nitrogen doped carbon nanotube/graphitized carbon nanotube-graphene quantum dot composite powder obtained in the step (5) by using discharge plasma, wherein the sintering temperature is 700 ℃, the sintering heat preservation time is 8min, the sintering pressure is 30MPa, and the sintering vacuum degree is less than 0.1Pa, so that the nitrogen doped carbon nanotube/graphitized carbon nanotube-graphene quantum dot-copper base composite material is obtained.
Example 8
A preparation method of a multidimensional carbon material composite reinforced copper-based material comprises the following specific steps:
(1) acid cracking: 100mg of nitrogen-doped carbon nanotubes, 100mg of graphitized carbon nanotubes, 200mg of industrial carbon nanotubes, 100mg of hydroxylated carbon nanotubes, 100mg of carboxylated carbon nanotubes and 250mL of mixed acid (68% by mass of HNO) 3 98 percent of H by mass 2 SO 4 1:1, V/V) in a 1L three-necked round-bottomed flask, heating the mixture to 140 ℃ and stirring and refluxing the mixture for 72 hours, and adding 10mg of nitrogen-doped carbon nanotube, 10mg of graphitized carbon nanotube, 20mg of industrial carbon nanotube, 10mg of hydroxylated carbon nanotube and 10mg of carboxylated carbon nanotube at 48 hours, i.e., 48 hours after the start of the reflux;
(2) alkali neutralization: neutralizing the reflux liquid obtained in the step (1) to be neutral by using a potassium hydroxide solution in an ice bath;
(3) and (3) dialysis: dialyzing the neutralized dispersion liquid in the step (2) in ultrapure water for 6 days by using a 3500Da dialysis bag;
(4) and (3) drying: rotationally evaporating the dispersion liquid in the dialysis bag obtained in the step (3) at 70 ℃ to about 50mL in volume, freezing and drying to obtain powder, and continuously vacuumizing in the process of the rotational evaporation to improve the rotational evaporation efficiency;
(5) preparing composite powder: and (3) ball-milling and mixing 10000mg of pure copper powder and 30mg of the powder obtained in the step (4), wherein the ball-milling process comprises the following steps: performing low-speed ball milling for 10 hours at the rotating speed of 50rpm, then performing high-speed ball milling for 2 hours at the rotating speed of 500rpm to ensure that copper powder is fully combined with powder, putting the ball-milled composite powder into a vacuum tube furnace, and reducing for 8 hours at the temperature of 250 ℃ in a reducing atmosphere to obtain composite powder, wherein the volume ratio of hydrogen to argon is 1: 2;
(6) preparing a composite block: and (3) sintering the composite powder obtained in the step (5) by using discharge plasma, wherein the sintering temperature is 700 ℃, the sintering heat preservation time is 10min, the sintering pressure is 50MPa, and the sintering vacuum degree is less than 0.1Pa, so that the multi-dimensional carbon material composite reinforced copper-based material is obtained.
Table 2 shows the compactness, conductivity and comparison between the copper-based composite materials prepared in examples 1 and 2 and pure copper, and it can be seen from table 2 that the compactness of the copper-based composite materials prepared in examples 1 and 2 is not much different from that of the pure copper, but the conductivity is higher than that of the pure copper.
TABLE 2
| Density (%) | Electrical conductivity (% IACS) | |
| Pure copper | 98.5％ | 93 |
| Example 1 | 98.3％ | 97 |
| Example 2 | 98.2％ | 96 |
Claims (6)
1. The preparation method of the multidimensional carbon material composite reinforced copper-based material is characterized by comprising the following specific steps:
(1) uniformly mixing the carbon precursor with concentrated acid, heating, stirring and refluxing; the carbon precursor is a carbon nano tube, and comprises one or a mixture of several of an industrialized carbon nano tube, a doped carbon nano tube, a graphitized carbon nano tube, a carboxylated carbon nano tube and a hydroxylated carbon nano tube in any proportion; the concentrated acid is commercial concentrated nitric acid with the mass fraction of 68%, or the commercial concentrated nitric acid with the mass fraction of 68% is mixed with concentrated sulfuric acid with the mass fraction of 98% in any proportion; the temperature of heating, stirring and refluxing is 100-160 ℃, and the time is 12-96 h; after the reflux is started, supplementing a carbon precursor every 4-48h, wherein the supplemented carbon precursor accounts for 10% -50% of the mass of the initially added carbon precursor, and the volume ratio of the mass of the initially added carbon precursor to the concentrated acid, namely mg: mL, is 0.2-4.0: 1;
(2) neutralizing and titrating the reflux product obtained in the step (1) to be neutral by using an alkaline substance;
(3) dialyzing the neutralized dispersion liquid obtained in the step (2) in ultrapure water for 4-6 days; a dialysis bag of 500-14000Da is adopted during dialysis;
(4) performing rotary evaporation on the dispersion liquid dialyzed in the step (3), and performing freeze drying to obtain carbon nanotube-graphene quantum dot powder;
(5) ball-milling copper powder and the product powder obtained in the step (4) and then reducing to obtain carbon nanotube-graphene quantum dot-copper composite powder;
(6) and (4) sintering the composite powder obtained in the step (5) to obtain the composite material.
2. The method for preparing the multi-dimensional carbon material composite reinforced copper-based material according to claim 1, wherein the temperature of the rotary evaporation in the step (4) is 60-90 ℃.
3. The method for preparing the multi-dimensional carbon material composite reinforced copper-based material as claimed in claim 1, wherein the mass ratio of the copper powder in the step (5) to the powder of the product in the step (4) is 1000:1-10.
4. The preparation method of the multidimensional carbon material composite reinforced copper-based material as claimed in claim 1, wherein the ball milling process in the step (5) is as follows: firstly carrying out low-speed ball milling for 5-10 hours, and then carrying out high-speed ball milling for 2-5 hours, wherein the rotation speed of the low-speed ball milling is 50-200rpm, and the rotation speed of the high-speed ball milling is not less than 400 rpm.
5. The method for preparing the multi-dimensional carbon material composite reinforced copper-based material as claimed in claim 1, wherein the reduction in the step (5) is performed in a reducing atmosphere, the temperature is maintained at 250-350 ℃ for 2-8h, and the reducing atmosphere is hydrogen or a mixed atmosphere of hydrogen and inert gas in any proportion.
6. The preparation method of the multi-dimensional carbon material composite reinforced copper-based material as claimed in claim 1, wherein the sintering manner in the step (6) is spark plasma sintering, hot pressing sintering, cold pressing sintering or hot isostatic pressing sintering, the sintering temperature is 500-800 ℃, the sintering heat preservation time is 5-60min, the sintering pressure is 10-50MPa, and the sintering vacuum degree is less than 0.1 Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110542727.2A CN113278838B (en) | 2021-05-18 | 2021-05-18 | Preparation method of multidimensional carbon material composite reinforced copper-based material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110542727.2A CN113278838B (en) | 2021-05-18 | 2021-05-18 | Preparation method of multidimensional carbon material composite reinforced copper-based material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113278838A CN113278838A (en) | 2021-08-20 |
| CN113278838B true CN113278838B (en) | 2022-08-12 |
Family
ID=77279697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110542727.2A Active CN113278838B (en) | 2021-05-18 | 2021-05-18 | Preparation method of multidimensional carbon material composite reinforced copper-based material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113278838B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114042928B (en) * | 2021-11-25 | 2022-11-11 | 西北有色金属研究院 | Preparation method of ruthenium-cobalt-nickel-iron-copper high-entropy alloy nanoparticles |
| CN115007852B (en) * | 2022-01-25 | 2024-07-26 | 昆明理工大学 | Method for preparing composite material by in-situ generation of carbon dots on surface of copper powder |
| CN114804878B (en) * | 2022-04-21 | 2023-05-19 | 哈尔滨工业大学 | Gao Jiangtan-based material for synthesizing graphene based on combustion and preparation method |
| CN114890408B (en) * | 2022-05-12 | 2023-08-22 | 湖南湘投轻材科技股份有限公司 | Preparation method of carbon nano tube with controllable size distribution and preparation method of carbon nano tube reinforced aluminum matrix composite material |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005012171A2 (en) * | 2003-07-28 | 2005-02-10 | William Marsh Rice University | Sidewall functionalization of carbon nanotubes with organosilanes for polymer composites |
| CN103738941A (en) * | 2013-11-14 | 2014-04-23 | 盐城增材科技有限公司 | Graphene quantum dot preparation method |
| CN104630526A (en) * | 2014-12-30 | 2015-05-20 | 昆明理工大学 | Method for preparing carbon nano-tube reinforced copper base composite material by using microwave sintering |
| CN104692357A (en) * | 2015-02-15 | 2015-06-10 | 清华大学 | Carbon nano-tube/carbon multilevel pore spherical composite and preparation method thereof |
| CN105502356A (en) * | 2015-12-18 | 2016-04-20 | 上海交通大学 | Method for preparing graphene quantum dots from sp<2>-hybridized carbon materials |
| CN105624445A (en) * | 2016-01-06 | 2016-06-01 | 昆明理工大学 | Preparation method of graphene-reinforced copper-based composite |
| CN107586981A (en) * | 2017-08-16 | 2018-01-16 | 昆明理工大学 | A kind of preparation method of carbon nanotube reinforced copper-base composite material |
| CN108760101A (en) * | 2018-04-26 | 2018-11-06 | 中国科学院兰州化学物理研究所 | A kind of three-dimensional grapheme/carbon nanotube elastomer and its application in flexible piezoresistive transducer |
| CN108975311A (en) * | 2018-10-26 | 2018-12-11 | 江苏德林环保技术有限公司 | A kind of preparation method of Water-soluble carbon quantum dot |
| CN111647766A (en) * | 2020-06-11 | 2020-09-11 | 昆明理工大学 | Preparation method of copper-based composite material |
| CN111977635A (en) * | 2020-09-04 | 2020-11-24 | 中南大学 | Carbon nano tube and preparation method thereof |
| CN112011705A (en) * | 2019-05-30 | 2020-12-01 | 哈尔滨工业大学 | Batch preparation method of nano-carbon reinforced copper-based composite material |
| WO2021077006A1 (en) * | 2019-10-18 | 2021-04-22 | The University Of North Carolina At Chapel Hill | Membrane-perovskite films, devices, and methods of preparation |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100669750B1 (en) * | 2004-11-04 | 2007-01-16 | 삼성에스디아이 주식회사 | Mesoporous carbon composite containing carbon nanotube |
| US10059595B1 (en) * | 2014-09-17 | 2018-08-28 | Neil Farbstein | Ultra high strength nanomaterials and methods of manufacture |
| CN109161709B (en) * | 2018-08-01 | 2020-07-31 | 昆明理工大学 | Preparation method of cracked carbon nanotube reinforced copper-based composite material |
-
2021
- 2021-05-18 CN CN202110542727.2A patent/CN113278838B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005012171A2 (en) * | 2003-07-28 | 2005-02-10 | William Marsh Rice University | Sidewall functionalization of carbon nanotubes with organosilanes for polymer composites |
| CN103738941A (en) * | 2013-11-14 | 2014-04-23 | 盐城增材科技有限公司 | Graphene quantum dot preparation method |
| CN104630526A (en) * | 2014-12-30 | 2015-05-20 | 昆明理工大学 | Method for preparing carbon nano-tube reinforced copper base composite material by using microwave sintering |
| CN104692357A (en) * | 2015-02-15 | 2015-06-10 | 清华大学 | Carbon nano-tube/carbon multilevel pore spherical composite and preparation method thereof |
| CN105502356A (en) * | 2015-12-18 | 2016-04-20 | 上海交通大学 | Method for preparing graphene quantum dots from sp<2>-hybridized carbon materials |
| CN105624445A (en) * | 2016-01-06 | 2016-06-01 | 昆明理工大学 | Preparation method of graphene-reinforced copper-based composite |
| CN107586981A (en) * | 2017-08-16 | 2018-01-16 | 昆明理工大学 | A kind of preparation method of carbon nanotube reinforced copper-base composite material |
| CN108760101A (en) * | 2018-04-26 | 2018-11-06 | 中国科学院兰州化学物理研究所 | A kind of three-dimensional grapheme/carbon nanotube elastomer and its application in flexible piezoresistive transducer |
| CN108975311A (en) * | 2018-10-26 | 2018-12-11 | 江苏德林环保技术有限公司 | A kind of preparation method of Water-soluble carbon quantum dot |
| CN112011705A (en) * | 2019-05-30 | 2020-12-01 | 哈尔滨工业大学 | Batch preparation method of nano-carbon reinforced copper-based composite material |
| WO2021077006A1 (en) * | 2019-10-18 | 2021-04-22 | The University Of North Carolina At Chapel Hill | Membrane-perovskite films, devices, and methods of preparation |
| CN111647766A (en) * | 2020-06-11 | 2020-09-11 | 昆明理工大学 | Preparation method of copper-based composite material |
| CN111977635A (en) * | 2020-09-04 | 2020-11-24 | 中南大学 | Carbon nano tube and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| High strength and electrical conductivity of copper matrix composites reinforced by carbon nanotube-graphene oxide hybrids with hierarchical structure and nanoscale twins;Xia Wei等;《Diamond & Related Materials》;20190905;第99卷;第1-10页 * |
| Multiscale graphene/carbon fiber reinforced copper matrix hybrid composites: Microstructure and properties;Xinjiang Zhang等;《Materials Science & Engineering A》;20181124;第743卷;第512-519页 * |
| 石墨烯复合材料的应用研究进展;巩金瑞等;《热加工工艺》;20170331(第06期);第31-35页 * |
| 碳纳米管的表面改性及在铜基复合材料中的应用;周泉竹等;《功能材料》;20190430;第4201-4206页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113278838A (en) | 2021-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113278838B (en) | Preparation method of multidimensional carbon material composite reinforced copper-based material | |
| He et al. | Porous carbon nanosheets: Synthetic strategies and electrochemical energy related applications | |
| Wang et al. | Preparation of polypyrrole/graphene nanosheets composites with enhanced thermoelectric properties | |
| Xu et al. | 3D hierarchical carbon-rich micro-/nanomaterials for energy storage and catalysis | |
| Lu et al. | Enhanced-performance PEDOT: PSS/Cu2Se-based composite films for wearable thermoelectric power generators | |
| Xu et al. | Convenient construction of poly (3, 4-ethylenedioxythiophene)–graphene pie-like structure with enhanced thermoelectric performance | |
| Ran et al. | Recent progress in carbon-based nanoarchitectures for advanced supercapacitors | |
| He et al. | Graphene-based transparent flexible electrodes for polymer solar cells | |
| US20130252499A1 (en) | Graphene derivative-carbon nanotube composite material and preparation methods thereof | |
| Wei et al. | Polyaniline nanotubes doped with sulfonated carbon nanotubes made via a self‐assembly process | |
| CN108517435B (en) | Nano-carbon reinforced copper-based composite material for maglev train and preparation method thereof | |
| Li et al. | Graphene emerges as a versatile template for materials preparation | |
| Wang et al. | An efficient thermoelectric material: Preparation of reduced graphene oxide/polyaniline hybrid composites by cryogenic grinding | |
| CN104084578B (en) | A kind of carbon nanotube reinforced copper-base composite material and preparation method thereof | |
| CN102719693A (en) | Graphene and carbon nanotube mixed enhanced metal-matrix composite material and preparation method thereof | |
| Adekoya et al. | Structure-property relationship and nascent applications of thermoelectric PEDOT: PSS/carbon composites: A review | |
| Wang et al. | One-step and green synthesis of nitrogen-doped carbon quantum dots for multifunctional electronics | |
| CN112011705A (en) | Batch preparation method of nano-carbon reinforced copper-based composite material | |
| Feng et al. | Improved electrical and optical properties of Poly (3, 4-ethylenedioxythiophene) via ordered microstructure | |
| CN113186417A (en) | Preparation method of graphene oxide-carbon quantum dot reinforced copper-based composite material | |
| CN115747551B (en) | Method for preparing carbon nano tube reinforced copper-based composite material by introducing tungsten carbide interface phase | |
| Miao et al. | Small-size graphene oxide (GO) as a hole injection layer for high-performance green phosphorescent organic light-emitting diodes | |
| CN111269014A (en) | Cu-S-based composite thermoelectric material and preparation method thereof | |
| CN111204741B (en) | Preparation method of three-dimensional graphene/carbon nanotube cross-linked composite material | |
| Ye et al. | Derivitization of pristine graphene for bulk heterojunction polymeric photovoltaic devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |