CN107500273B - Preparation method of graphene/copper composite powder material - Google Patents
Preparation method of graphene/copper composite powder material Download PDFInfo
- Publication number
- CN107500273B CN107500273B CN201710876842.7A CN201710876842A CN107500273B CN 107500273 B CN107500273 B CN 107500273B CN 201710876842 A CN201710876842 A CN 201710876842A CN 107500273 B CN107500273 B CN 107500273B
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphene oxide
- stirring
- copper
- copper acetate
- 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
-
- 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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention relates to a preparation method of a graphene/copper composite powder material. The method comprises the following steps: adding copper acetate monohydrate into a graphene oxide aqueous solution, and simultaneously carrying out high-speed shearing stirring on the mixed solution in the adding process; after the addition is finished, continuously shearing and stirring the mixed solution at a high speed, and simultaneously continuously extracting the mixed solution by using a spray dryer for spray drying to obtain precursor graphene oxide/copper acetate powder; and heating the obtained precursor powder to 350-700 ℃ in a reducing atmosphere, and preserving the heat for 15-30 min to obtain the graphene/copper composite powder material. The existing reduced graphene oxide preparation equipment is utilized, the method is simple and efficient, the cost is low, and the wide industrial application and popularization can be met.
Description
Technical Field
The invention relates to the field of graphene/metal composite materials, in particular to a preparation method of a graphene/copper powder composite powder material.
Background
Graphene is a two-dimensional crystalline ultrathin material composed of sp2 hybridized carbon atoms connected to each other to a thickness of only one atomic layer, and can exist stably at room temperature. The research on the application of carbon nanotube, graphene and carbon material as a reinforcing phase in metal matrix composite materials from traditional graphite to carbon fiber is always a focus of attention. The graphite and carbon fiber reinforced metal matrix composite material, particularly the copper-based material, has wide application in the fields of delivery vehicles, special equipment, aerospace and the like due to good wear resistance and lubricating property, higher specific strength, higher specific elastic modulus and damping property. The low density, high mechanical property, high thermal conductivity and low thermal expansion of graphene are considered to be a very promising reinforcement. At present, a plurality of methods are used for preparing graphene/copper powder composite materials, but the performance of the prepared graphene/copper composite materials is not ideal. In the preparation of the material, the method is not simple mixing, but the method which is adopted in the preparation of the precursor to enhance the combination is a commonly adopted method at present, but the prior molecular mixing technology needs to add a surfactant, such as a method adopted by JaewonHwang, Taeshik Yoon, Sung Hwan Jin, Jinsu Lee, Taek-Soo Kim, Soon great Hong and Seokwoo Jeon (Enhanced mechanical properties of graphene/covalent compositions using a molecular-level mixprocess [ J ] Adv. Mater,2013,25:6724 and 6729), and sodium hydroxide is used as the surfactant, which can bring about the influence of sodium ions which are difficult to completely remove on the final performance.
Disclosure of Invention
The invention aims to solve the problems of nonuniform mixing, easy agglomeration, poor interface combination, high cost and the like of the graphene and the copper, or the defects of the need of additionally adding a surfactant and the like. The spray drying is carried out while the shearing and stirring are carried out, so that the problem of uneven components caused by different precipitation speeds of solutes in the solution is solved while the uniform mixing is ensured. The preparation method can utilize the existing reduced graphene oxide preparation equipment, is simple and efficient, has low cost, and can meet the requirements of wide industrial application and popularization.
The invention adopts the following technical scheme:
a preparation method of a graphene/copper composite powder material comprises the following steps:
(1) preparation of graphene oxide/copper acetate mixed solution
Adding copper acetate monohydrate into a graphene oxide aqueous solution for dissolving, wherein the mixed solution is subjected to high-speed shearing stirring in the adding process; the rotating speed of shearing and stirring is 1000-20000rpm, and the concentration of the graphene oxide aqueous solution is 0.04-2 mg/mL; the mass ratio of graphene oxide: 1-copper acetate monohydrate: 40-2042; moreover, the upper limit of the addition amount of the copper acetate monohydrate in each 100mL of the graphene oxide aqueous solution is 8 g;
(2) preparation of graphene oxide/copper acetate precursor powder
After the copper acetate monohydrate is added, continuously shearing and stirring the mixed solution obtained in the step (1) at a high speed, and simultaneously continuously extracting the mixed solution by using a spray dryer for spray drying, wherein the extraction amount is 6-20mL/min, the air inlet temperature is 200-; obtaining precursor graphene oxide/copper acetate powder;
wherein, when the high-speed shearing stirring is carried out in the step (1) and the step (2), the temperature of the solution is kept between 30 and 35 ℃, and when the temperature of the solution reaches 35 ℃, the shearing stirring is stopped; when the temperature of the solution is reduced to 30 ℃, the high-speed shearing and stirring are resumed;
(3) preparation of graphene/copper composite powder
Heating the precursor powder obtained in the step (2) at a speed of 10-200 ℃/min in a reducing atmosphere, and preserving heat for 15-30 min after the temperature reaches 350-700 ℃ to obtain a graphene/copper composite powder material;
the reducing atmosphere is specifically hydrogen.
The invention has the beneficial effects that:
1. the prepared powder material has the advantages of uniform reinforced phase dispersion, strong interface combination with a matrix and stable structure of graphene.
2. The preparation process does not add a surfactant, and then the surfactant does not need to be removed in the subsequent process, and the surfactant generally contains sodium ions, potassium ions and the like, so that the surfactant cannot be thoroughly removed. The spray drying is carried out while the shearing and stirring are carried out, so that the problem of uneven components caused by different precipitation speeds of solutes in the solution is solved while the uniform mixing is ensured.
3. The production process is directly combined with the graphene preparation process, the existing graphene production equipment can be utilized to directly produce the powder material precursor after the equipment is simply modified, and mass production can be realized quickly.
Drawings
FIG. 1 is a scanning electron microscope image of a precursor graphene oxide/copper acetate composite powder, wherein FIG. 1a is a scanning electron microscope image of pure copper acetate particles subjected to spray drying; fig. 1b shows that the mass ratio of graphene to copper obtained in example 3 is 3: scanning electron microscope image of 1000 precursor graphene oxide/copper acetate composite powder, fig. 1c is a graph showing that the mass ratio of graphene to copper obtained in example 1 is 3: scanning electron microscope images of 100 precursor graphene oxide/copper acetate composite powder; FIG. 1d scanning electron micrograph of spray dried pure graphene oxide powder.
FIG. 2 is an infrared spectrum of a precursor graphene oxide/copper acetate composite powder;
fig. 3 shows that the mass ratio of graphene to copper in example 1 is 3: 100 graphene/copper composite powder scanning electron microscope image
FIG. 4 Raman spectra of graphene/copper composite powder with different graphene to copper mass ratios
Detailed Description
Example 1.
1800mL of graphene oxide (65% carbon) aqueous solution with the concentration of 1.2mg/mL is taken and stirred in a high-speed shear stirrer at the rotating speed of 1500rpm, and then 120 g of monohydrate copper acetate (the copper content is 38.2g) is added in the stirring process. After the mixing is finished, continuing to perform high-speed shearing stirring at the same speed, simultaneously drying the mixed solution by using a Spray dryer (a small Spray dryer H-Spray Mini, Beijing Hols Biotechnology Co., Ltd.), wherein the extraction amount is 6mL/min, the air inlet temperature is 220 ℃, the air outlet temperature is 120 ℃ (the drying gas flow is 800L/H, the same is applied to the following embodiment), the high-speed shearing stirring can adopt an intermittent mode in the Spray drying process, the shearing rotation speed is 1500rpm, wherein the temperature of the solution is kept between 30 and 35 ℃ during the high-speed shearing stirring, and the shearing stirring is stopped when the temperature of the solution reaches 35 ℃; when the temperature of the solution is reduced to 30 ℃, the high-speed shearing stirring is resumed. Spray drying to obtain precursor powder, heating at 10 deg.C/min in hydrogen atmosphere to 350 deg.C, maintaining for 30min, and reducing the mixed powder. Obtaining the graphene and copper mass ratio of 3: 100 of graphene/copper composite powder.
Example 2.
1800mL of graphene oxide aqueous solution with the concentration of 0.12mg/mL is taken, wherein the carbon content of the graphene oxide is 65%, and the graphene oxide aqueous solution is stirred in a high-speed shear stirrer at the rotating speed of 2000rpm, and then 120 g of monohydrate copper acetate is added during stirring, wherein the copper content is 38.2 g. After the mixing, the mixed solution was dried using a Spray dryer (small Spray dryer H-Spray Mini, Beijing Hols Biotech Co., Ltd.) with a draw-out volume of 12mL/min, an inlet air temperature of 220 ℃ and an outlet air temperature of 120 ℃, the high-speed shearing and stirring were performed intermittently during the Spray drying process at a shearing speed of 2000rpm to ensure that the mixed solution did not exceed 35 ℃ in the whole process, i.e., if the temperature would exceed 35 ℃, the high-speed shearing and stirring were immediately stopped, and the same speed of shearing and stirring were resumed after the temperature dropped to 30 ℃. Spray drying to obtain precursor powder, heating at 200 deg.C/min in hydrogen atmosphere, maintaining the temperature at 350 deg.C for 30min, and reducing the mixed powder. Obtaining the graphene and copper mass ratio of 1: 1000 of graphene/copper composite powder.
Example 3.
1800mL of graphene oxide aqueous solution with the concentration of 0.04mg/mL is taken, wherein the carbon content of the graphene oxide is 65%, and the graphene oxide aqueous solution is stirred in a high-speed shear stirrer at the rotating speed of 2000rpm, and then 120 g of copper acetate monohydrate is slowly added during stirring, wherein the copper content is 38.2 g. After mixing, drying the mixed solution by using a Spray dryer (small Spray dryer H-Spray Mini, Beijing Hols Biotechnology Co., Ltd.), with the extraction amount of 6mL/min, the air inlet temperature of 220 ℃ and the air outlet temperature of 120 ℃, adopting an intermittent mode for high-speed shearing and stirring in the Spray drying process, ensuring that the mixed solution does not exceed 35 ℃ in the whole process, immediately stopping the high-speed shearing and stirring if the mixed solution is about to exceed the shearing speed of 1500rpm, and recovering the shearing and stirring at the same speed again after the temperature is reduced to 30 ℃. Spray drying to obtain precursor powder, heating at 10 deg.C/min in hydrogen atmosphere to 350 deg.C, maintaining for 30min, and reducing the mixed powder. Obtaining the graphene and copper mass ratio of 3: 1000 of graphene/copper composite powder.
From fig. 1a, it can be seen that the copper acetate is shriveled into shriveled particles after spray drying, and the pure graphene powder after spray drying is turned into a corrugated sheet structure from fig. 1d, while fig. 1b and fig. 1c are graphene/copper composite powders of examples 3 and 1 with different contents, after the parameters of the examples are adopted, after the surfactant-free molecular-level mixing and spray drying, firstly the copper acetate is completely coated on the graphene oxide, and the graphene oxide becomes a 'supporting framework' of the copper acetate, and the shape of the composite particles is approximately based on the shape of the graphene oxide; and the second indicates that no free graphene oxide exists. This is further verified in fig. 2, and in both of the infrared spectra of examples 1 and 3, only the characteristic peak of copper acetate is present, and the characteristic peak of graphene oxide is absent. Fig. 1 and fig. 2 are compared to show that, in the preparation of the precursor, the graphene oxide and the copper acetate are uniformly mixed and firmly combined with each other, so that a good precursor is provided for further reduction. It can be seen from fig. 3 that the reduced graphene and copper are uniformly mixed, no agglomeration occurs, and the interface bonding is relatively firm. Fig. 4 shows that the graphene reduction degree is better by the method, and the structural stability of the graphene is maintained. Fig. 3 is compared with fig. 4, and the existence of graphene in the composite powder is firstly proved, so that the existence of graphene oxide in the precursor is proved, and it is important that the result is in line with the expectation of realizing the uniform dispersion of the reinforced phase graphene in the copper matrix, forming strong interface bonding and maintaining the stable structure of the graphene.
The invention is not the best known technology.
Claims (1)
1. A preparation method of a graphene/copper composite powder material is characterized by comprising the following steps:
(1) preparation of graphene oxide/copper acetate mixed solution
Adding copper acetate monohydrate into a graphene oxide aqueous solution for dissolving, wherein the mixed solution is subjected to high-speed shearing stirring in the adding process; the rotating speed of shearing and stirring is 1000-20000rpm, and the concentration of the graphene oxide aqueous solution is 0.04-2 mg/mL; the mass ratio of graphene oxide: 1-copper acetate monohydrate: 40-2042;
(2) preparation of graphene oxide/copper acetate precursor powder
After the copper acetate monohydrate is added, continuously shearing and stirring the mixed solution obtained in the step (1) at a high speed, and simultaneously continuously extracting the mixed solution by using a spray dryer for spray drying, wherein the extraction amount is 6-20mL/min, the air inlet temperature is 200-; obtaining precursor graphene oxide/copper acetate powder;
wherein, when the high-speed shearing stirring is carried out in the step (1) and the step (2), the temperature of the solution is kept between 30 and 35 ℃, and when the temperature of the solution reaches 35 ℃, the shearing stirring is stopped; when the temperature of the solution is reduced to 30 ℃, the high-speed shearing and stirring are resumed;
(3) preparation of graphene/copper composite powder
Heating the precursor powder obtained in the step (2) at a speed of 10-200 ℃/min in a reducing atmosphere, and preserving heat for 15-30 min after the temperature reaches 350-700 ℃ to obtain a graphene/copper composite powder material;
the reducing atmosphere is specifically hydrogen;
in the step (1), the upper limit of the addition amount of the copper acetate monohydrate in each 100mL of the graphene oxide aqueous solution is 8 g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710876842.7A CN107500273B (en) | 2017-09-25 | 2017-09-25 | Preparation method of graphene/copper composite powder material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710876842.7A CN107500273B (en) | 2017-09-25 | 2017-09-25 | Preparation method of graphene/copper composite powder material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107500273A CN107500273A (en) | 2017-12-22 |
| CN107500273B true CN107500273B (en) | 2020-05-26 |
Family
ID=60698712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710876842.7A Active CN107500273B (en) | 2017-09-25 | 2017-09-25 | Preparation method of graphene/copper composite powder material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107500273B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108889943A (en) * | 2018-09-05 | 2018-11-27 | 河北工业大学 | A kind of preparation of copper iron compound powder body material and its forming method |
| CN109095457A (en) * | 2018-09-12 | 2018-12-28 | 芦露华 | A method of quickly preparing reduced graphene and its composite material |
| CN109778105A (en) * | 2019-03-07 | 2019-05-21 | 上海海洋大学 | A kind of amorphous composite coating and preparation method thereof |
| CN110280244A (en) * | 2019-07-17 | 2019-09-27 | 肇庆市华师大光电产业研究院 | A kind of carbon dioxide electrochemical reduction catalyst and preparation method thereof |
| CN111515403B (en) * | 2020-05-18 | 2023-05-09 | 山东省科学院新材料研究所 | Method for preparing graphene reinforced aluminum matrix composite powder in short process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437494A (en) * | 2014-12-08 | 2015-03-25 | 华东理工大学 | Fenton-like catalyst of graphene coated ferriferrous oxide (Fe3O4) micro-spheres as well as preparation method and application thereof |
| CN104962185A (en) * | 2015-06-03 | 2015-10-07 | 陕西科技大学 | Graphene-loaded nanometer Fe3O4/aqueous polyurethane composite magnetic conductive wave absorbing coating material and preparation method thereof |
| CN106513694A (en) * | 2016-12-14 | 2017-03-22 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of graphene/ metal composite powder |
-
2017
- 2017-09-25 CN CN201710876842.7A patent/CN107500273B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437494A (en) * | 2014-12-08 | 2015-03-25 | 华东理工大学 | Fenton-like catalyst of graphene coated ferriferrous oxide (Fe3O4) micro-spheres as well as preparation method and application thereof |
| CN104962185A (en) * | 2015-06-03 | 2015-10-07 | 陕西科技大学 | Graphene-loaded nanometer Fe3O4/aqueous polyurethane composite magnetic conductive wave absorbing coating material and preparation method thereof |
| CN106513694A (en) * | 2016-12-14 | 2017-03-22 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of graphene/ metal composite powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107500273A (en) | 2017-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107500273B (en) | Preparation method of graphene/copper composite powder material | |
| JP6490253B2 (en) | Method for preparing graphene / silver composite material | |
| CN105525124B (en) | Fabricated in situ three-dimensional grapheme strengthens Cu-base composites preparation method | |
| CN101920336B (en) | Preparation method of rare-earth modified Co-cladded wolfram carbide hard alloy composite powder | |
| CN112758950B (en) | Boron alkene nanosheets and preparation method thereof | |
| CN108889959B (en) | rGO/Cu composite material and preparation method thereof | |
| CN104084578A (en) | Carbon nano tube enhanced copper-based composite material and preparation method thereof | |
| Eftekhari et al. | Flower-like bundles of ZnO nanosheets as an intermediate between hollow nanosphere and nanoparticles | |
| CN103433037A (en) | Preparation method of graphene foam and precious metal nano-particle composite material | |
| CN105543598A (en) | Preparation method of reinforced magnesium matrix composite | |
| CN104846228A (en) | Method for reinforcing metallic material by graphene | |
| CN108722198A (en) | A kind of preparation method and products thereof of full carbon composite membrane | |
| CN103449427A (en) | Preparation method of porous graphene-ferric oxide composite material | |
| CN108941547B (en) | Preparation method of copper-doped graphene reinforced aluminum-based composite material | |
| CN112920001A (en) | Method for preparing nano aluminum/porous copper oxide nano thermite by self-assembly of P4VP | |
| CN101069928A (en) | Method for preparing copper-base composite particles of internal carbon-inlaid nano pipe | |
| CN101161338B (en) | Oxidized graphite of loading Cu2O particle and its preparing method | |
| CN103252506B (en) | Preparation method of nanometer molybdenum powder containing homodisperse carbon nano tubes | |
| CN107815170A (en) | A kind of graphene coating masterbatch and preparation method | |
| CN108889326B (en) | Preparation method of three-dimensional network frame of molybdenum disulfide and graphite phase carbon nitride | |
| CN108640107B (en) | Intercalation agent for rapidly stripping graphite for mass production of high-quality graphene | |
| CN102560455A (en) | Preparation method of ultra-thin tungsten film-coated diamond | |
| CN107460021B (en) | Preparation method of low-temperature graphene-based nano borate composite material | |
| CN103482617A (en) | Method for preparing tin dioxide/graphene composite material | |
| CN105502357A (en) | Stripping agent special for preparing graphene through mechanical stripping and preparation method |
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 |