CN112429722A - Nano metal particle doped graphene film and preparation method thereof - Google Patents
Nano metal particle doped graphene film and preparation method thereof Download PDFInfo
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- 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
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- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- 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
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- 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
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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- 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
- C01B32/194—After-treatment
Abstract
The invention relates to a nano metal particle doped graphene film and a preparation method thereof, wherein the method comprises the following steps: 1. mixing metal salt, graphene oxide/graphite oxide and water/organic solvent, and uniformly stirring to prepare graphene oxide suspension or slurry mixed with the metal salt; the metal salt is a metal salt capable of being pyrolyzed or chemically reduced to form metal oxides or metal particles; 2. preparing the suspension or slurry into a graphene oxide/metal salt mixed precursor film, and drying the graphene oxide/metal salt mixed precursor film to uniformly dope the metal salt into the graphene oxide film; 3. and (3) carrying out pyrolysis or chemical reduction on the metal salt in the mixed precursor film to obtain metal nano particles, and simultaneously reducing the graphene oxide to obtain the nano metal particle doped composite film. The method can improve the weak out-of-plane heat-conducting property of the graphene film, obtain the graphene film uniformly doped with the metal nanoparticles, and keep the excellent in-plane heat-conducting property of the graphene film.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a nano metal particle doped graphene film and a preparation method thereof.
Background
Graphene has excellent thermal conductivity, but in the practical application process, a nano graphene material needs to be assembled into a macroscopic graphene film. Although the macroscopic graphene thin film has excellent thermal conductivity, it has a significant anisotropic structure. In the graphene film plane, carbon atoms pass through sp2Hybridized and combined by covalent bonds to form a six-membered ring honeycomb structure, and the thermal conductivity of the graphene film in the plane direction can reach 2000W.m at most-1.K-1However, the interlayer of the graphene thin film is stacked by pi-pi bonds, and the interlayer spacing is about 0.34nm by van der waals force, and thus, the thermal conductivity in the out-of-plane direction of the graphene thin film is extremely low, generally less than 5w.m-1.K-1. In order to improve the out-of-plane heat conduction performance of the graphene film, a metal heat conduction channel can be constructed between layers. However, researchers usually mix nano metal particles with a graphene oxide suspension, and then prepare a film by suction filtration, and this method is limited by the density difference between the metal particles and the graphene oxide, and it is difficult to obtain a uniformly doped graphene film; in addition, researchers (ACS appl. mater. interfaces 2019,11, 21795-. The metal-doped graphene film prepared by the patent (application number: 201911033820.X) can improve the graphene film to a certain extent by intercalating metal salt to the edge of a graphene sheet layer through vacuum low pressureThe out-of-plane thermal conductivity can only form metal particles at the edge of the graphene sheet layer, the distribution of the metal particles in the thin film is not uniform, and the performance is difficult to meet the requirement.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nano metal particle doped graphene film and a preparation method thereof.
The technical scheme for solving the technical problems is as follows:
the method for doping the graphene film with the nano metal particles comprises the following steps:
step 1: mixing metal salt, graphene oxide and pure water or an organic solvent to prepare graphene oxide suspension or slurry mixed with the metal salt, and uniformly stirring.
Further, the metal salt is preferably one or more of Ag-based, Cu-based, Ni-based, Co-based, Zn-based, Ti-based, W-based, and the like metal salts capable of forming metal oxides or metal particles by pyrolysis, such as AgNO3，Cu(NO3)2、Ni(COOH)2And ammonium metatungstate, and the like;
further, the graphene oxide can also be replaced by graphite oxide;
further, the concentration of the graphene oxide in the suspension is controlled to be 0.01mg/ml to 5mg/ml, the concentration of the graphene oxide in the slurry is controlled to be 5mg/ml to 50mg/ml, and the concentration of the metal salt is controlled to be 0.01mg/ml to 50 mg/ml;
furthermore, the stirring process can be realized by ultrasonic-assisted stirring, magneton stirring, manual stirring, homogenizer stirring and other processes.
Further, the suspension or the slurry is made into a film, the film is a graphene oxide/metal salt mixed precursor film, and the mixed precursor film is dried at a certain temperature, so that the metal salt is uniformly doped in the graphene oxide film.
Further, the step 2 can be realized by vacuum filtration, blade coating, spin coating, hydrothermal evaporation and other methods, wherein the temperature of warm water during hydrothermal evaporation is controlled between 30 ℃ and 99 ℃;
furthermore, the drying temperature is between 30 ℃ and 99 ℃, the drying time is between 2min and 48h, and the thickness of the dried precursor film is between 100nm and 1 mm.
And step 3: and (3) carrying out pyrolysis or chemical reduction on the metal salt in the mixed precursor film to obtain metal nano particles, wherein in the process, the graphene oxide is gradually reduced, and finally the nano metal particle doped composite film is obtained.
Pyrolysis of Metal salt in step 3 the mixed precursor film is heated to above the pyrolysis temperature of the Metal salt for a period of time, e.g., AgNO, depending on the pyrolysis temperature of the different metals3The pyrolysis temperature of (a) is about 440 ℃, so that the pyrolysis of the metal salt requires heating the mixed precursor film above the pyrolysis temperature.
Furthermore, the heat preservation time above the pyrolysis temperature is between 5min and 12 h.
The reduction of the metal salt in the step 3 can also be realized by chemical reduction, by selecting a chemical reducing agent which does not react with the doped metal and setting a relevant reduction environment, for example, the reduction of the metal salt can be realized by reducing a mixed precursor film by ascorbic acid, mixing 0.1mol/ml ascorbic acid with ultrapure water and ethanol, and placing the mixture in an environment at 80 ℃.
Further, the reducing agent may preferably be sodium borohydride, sodium hypophosphite, sodium ascorbate (sodium), ethylenediamine, or the like.
And 4, step 4: and performing high-temperature reduction treatment and rolling treatment on the composite film to finally obtain the graphene film uniformly doped with the nano metal particles.
Further, the high-temperature reduction treatment of the composite film doped with the nano metal particles can be selectively carried out, the high-temperature reduction temperature range is 600-3000 ℃, the heat preservation time is 10 min-12 h, and the high-temperature reduction treatment needs to be carried out under the protective atmosphere or the high-vacuum environment;
further, the protective atmosphere includes nitrogen, argon, or a reducing gas such as hydrogen, etc.;
further, the rolling treatment of the composite film can be selectively carried out, and the rolling pressure range is between 0.1MPa and 300 MPa.
The nano metal particle doped graphene film is prepared by the method.
The invention has the beneficial effects that: the method can improve the weak out-of-plane heat-conducting property of the graphene film, obtain the graphene film uniformly doped with the metal nanoparticles, and keep the excellent in-plane heat-conducting property of the graphene film.
Drawings
FIG. 1 is a flow chart of a composite film precursor prepared by a doctor blade coating method;
FIG. 2 is a macroscopic view of the Ag nanoparticle-doped graphene film;
fig. 3 is an XRD spectrum of the Ag nanoparticle-doped graphene thin film;
FIG. 4 is a scanning electron microscope image of a cross section of the Ag nanoparticle-doped graphene thin film;
FIG. 5 is a distribution diagram of surface elements of the Ag nanoparticle-doped graphene film;
FIG. 6 is a flow chart of a process for preparing a composite film by a hydrothermal evaporation method;
FIG. 7 is a macroscopic view of a Cu nanoparticle-doped graphene thin film;
fig. 8 is an XRD spectrum of the Cu nanoparticle-doped graphene thin film;
FIG. 9 is a distribution diagram of elements in a section of a Cu nanoparticle-doped graphene thin film;
FIG. 10 is a flow chart of the preparation of a composite film by a vacuum filtration method;
FIG. 11 is a scanning electron microscope image of the surface of a Ni nanoparticle-doped graphene thin film;
fig. 12 is a distribution chart of surface elements of the Ni nanoparticle-doped graphene thin film;
fig. 13 is a scanning electron microscope image of a cross section of the Ni nanoparticle-doped graphene thin film after peeling.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
In this example, AgNO was first introduced3The mass ratio of the metal salt to the graphene oxide is 1:5Mixing the graphene oxide slurry with ultrapure water in a quantitative ratio to prepare graphene oxide slurry mixed with metal salt, wherein the concentration of the graphene oxide slurry is 20mg/ml, and then uniformly stirring the graphene oxide slurry by a homogenizer; then, a mixed precursor film is prepared by blade coating with a scraper, and the precursor film is dried in an oven at 60 ℃ for 24h to obtain a composite precursor film with the thickness of about 40 μm, as shown in fig. 1. And then, carrying out pyrolysis reduction on the composite precursor film in an environment of 900 ℃, carrying out the process under the nitrogen protection atmosphere, keeping the temperature for 1h, and taking out to obtain the graphene film uniformly doped with the nano Ag particles. And finally, placing the obtained graphene film at 2800 ℃ under an argon protection environment, carrying out high-temperature annealing treatment for 30min, wherein the obtained final sample is shown in fig. 2, and an XRD (X-ray diffraction) spectrum of the sample shows that the graphene oxide is completely reduced (fig. 3) and a large amount of Ag element exists inside the graphene oxide. The scanning electron micrograph (fig. 4) of the cross section of the sample shows that the Ag nanoparticles are uniformly doped in the graphene film. The element distribution spectrum (fig. 5) of the sample indicates that the nanoparticles in the graphene film are Ag particles. The Ag nano particles uniformly distributed can provide a heat flow channel between layers of the graphene, and the out-of-plane heat conduction performance of the graphene film can be effectively improved.
Example 2
In this example, first, Cu (NO) is added3)2Mixing metal salt and graphene oxide with ultrapure water according to the mass ratio of 1:10 to prepare a graphene oxide suspension mixed with the metal salt, wherein the concentration of the graphene oxide suspension is 2mg/ml, and then uniformly stirring by using a homogenizer; then, a mixed precursor film was prepared by hydrothermal evaporation, which was carried out in a water bath at 80 ℃ to obtain a composite precursor film having a thickness of about 20 μm, as shown in fig. 6. And then, preparing the graphene film uniformly doped with the nano Cu particles by using the composite precursor film through chemical reduction, wherein the chemical reducing agent is ascorbic acid, the concentration of the ascorbic acid is 0.1mol/ml, the solvent is a mixed solution of ultrapure water and absolute ethyl alcohol in a ratio of 1:1, the chemical reduction is carried out in a water bath environment, the water bath temperature is 80 ℃, and the reduction time is 4 hours. Finally, placing the obtained graphene film at 2500 ℃ in an argon gas protection environment, and performing high-temperature annealingAfter fire treatment and the holding time is 1h, the obtained final sample is shown in fig. 7, and the XRD pattern (fig. 8) of the sample shows that the graphene oxide is completely reduced (fig. 3) and a large amount of Cu element exists inside. The element distribution spectrum (fig. 9) of the sample indicates that the nanoparticles in the graphene film are Cu particles. The Cu nanoparticles distributed uniformly can provide a heat flow channel for the interlayer of the graphene, and the out-of-plane heat conduction performance of the graphene film can be effectively improved.
Example 3
In this embodiment, first, NiSO is added4Mixing metal salt and graphene oxide with ultrapure water according to the mass ratio of 2:5 to prepare a graphene oxide suspension mixed with the metal salt, wherein the concentration of the graphene oxide suspension is 1mg/ml, and then uniformly stirring by ultrasonic waves; then, a mixed precursor film (as shown in fig. 10) is prepared by vacuum filtration, and the precursor film is dried in an oven at 70 ℃ for 48h to obtain a composite precursor film with the thickness of about 20 μm. And then, carrying out pyrolysis reduction on the composite precursor film in an environment of 1000 ℃, carrying out the process under the protection atmosphere of argon, keeping the temperature for 30min, and taking out to obtain the graphene film uniformly doped with the nano Ni particles. Finally, the obtained graphene film is placed at 2600 ℃ and the vacuum degree is 10-2And (5) carrying out high-temperature annealing treatment in a Pa environment for 1h to obtain a final sample. The scanning electron microscope image of the surface of the sample shows (fig. 11), a large amount of uniformly distributed Ni nanoparticles are formed and distributed on the surface of the graphene film. The element distribution spectrum of the sample surface (fig. 12) indicates that the nanoparticles in the graphene film are Ni particles. The graphene film was peeled off with a tape, and the peeled cross section was observed (fig. 13), and nano Ni particles uniformly distributed between the cross-sectional layers of the graphene film were observed. The uniformly distributed Ni nanoparticles can provide a heat flow channel for the interlayer of the graphene, and can effectively improve the out-of-plane heat conduction performance of the graphene film.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the nano metal particle doped graphene film is characterized by comprising the following steps:
step 1: mixing metal salt, graphene oxide/graphite oxide and water/organic solvent, and uniformly stirring to prepare graphene oxide suspension or slurry mixed with the metal salt; the metal salt is a metal salt capable of pyrolytically forming metal oxides or metal particles;
step 2: preparing the suspension or the slurry into a film, wherein the film is a graphene oxide/metal salt mixed precursor film, and drying the mixed precursor film to uniformly dope the metal salt in the graphene oxide film;
and step 3: and (3) carrying out pyrolysis or chemical reduction on the metal salt in the mixed precursor film to obtain metal nano particles, and simultaneously reducing the graphene oxide to finally obtain the nano metal particle doped composite film.
2. The method of preparing a nano-metal particle-doped graphene thin film according to claim 1, wherein the metal salt in the step 1 comprises any one or more of Ag-based metal salt, Cu-based metal salt, Ni-based metal salt, Co-based metal salt, Zn-based metal salt, Ti-based metal salt, and W-based metal salt.
3. The method for preparing the nano-metal particle doped graphene film according to claim 1, wherein the film preparation method in the step 2 is any one of blade coating, hydrothermal evaporation, vacuum filtration and spin coating.
4. The method for preparing the nano-metal particle doped graphene film according to claim 1, wherein the drying temperature in the step 2 is 30-99 ℃, the drying time is 2 min-48 h, and the thickness of the dried precursor film is 100 nm-1 mm.
5. The method for preparing a nano-metal particle doped graphene film according to claim 1, wherein when a physical reduction method is adopted in the step 3, the mixed precursor film is heated to a temperature higher than the pyrolysis temperature of all metal salts in the step 1 and is kept warm for 5min to 24 h.
6. The method for preparing a nano-metal particle doped graphene film according to claim 1, wherein when a chemical reduction method is adopted in the step 3, the method is realized by selecting a chemical reducing agent which does not react with the doped metal salt and setting a corresponding reduction environment.
7. The method for preparing a nano-metal particle doped graphene film according to claim 5, wherein when a chemical reduction method is adopted, any one of sodium borohydride, sodium hypophosphite, sodium ascorbate and ethylenediamine is adopted as a reducing agent.
8. The method for preparing the nano-metal particle doped graphene film according to claim 1, wherein the step 3 is followed by a step of performing high-temperature reduction treatment on the nano-metal particle doped composite film, wherein the high-temperature reduction is performed in a protective atmosphere or a high-vacuum environment, the temperature range is 600 ℃ to 3000 ℃, and the heat preservation time is 10min to 12 h.
9. The method for preparing a nano-metal particle doped graphene film according to claim 1, wherein the step 3 is followed by a step of performing a rolling process on the nano-metal particle doped composite film, wherein the rolling pressure is in a range of 0.1MPa to 300 MPa.
10. The nano metal particle doped graphene film is characterized by being prepared by the method of any one of claims 1 to 8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113088124A (en) * | 2021-04-02 | 2021-07-09 | 宁波龙圣新材料科技有限公司 | Preparation process and method of graphene heating film |
| CN113593769A (en) * | 2021-07-07 | 2021-11-02 | 宁波石墨烯创新中心有限公司 | Graphene composite film and preparation method thereof |
| CN114853004A (en) * | 2022-04-25 | 2022-08-05 | 蜂巢能源科技股份有限公司 | Negative electrode material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466607A (en) * | 2013-09-09 | 2013-12-25 | 东南大学 | Graphene-metallic oxide nano-particle three-dimensional porous composite material |
| CN103579632A (en) * | 2012-07-24 | 2014-02-12 | 海洋王照明科技股份有限公司 | Graphene composite negative current collector, preparation method thereof and lithium ion battery |
| CN103787328A (en) * | 2014-03-11 | 2014-05-14 | 华南师范大学 | Modified grapheme preparation method |
| CN104200873A (en) * | 2014-09-09 | 2014-12-10 | 郑州轻工业学院 | Large-sized graphene-metal fine particle composite film and preparation method and applications thereof |
| CN106531975A (en) * | 2015-09-10 | 2017-03-22 | 中国科学院宁波材料技术与工程研究所 | Graphene composite material, and preparation methods and application thereof |
| CN106698402A (en) * | 2017-01-05 | 2017-05-24 | 东南大学 | Production method of metal nano-particle doped flexible self-supporting graphene film |
| CN106835082A (en) * | 2017-01-11 | 2017-06-13 | 东南大学 | The preparation method of the flexible self-supporting graphene film of metal nanoparticle doping |
-
2020
- 2020-12-01 CN CN202011389039.9A patent/CN112429722A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579632A (en) * | 2012-07-24 | 2014-02-12 | 海洋王照明科技股份有限公司 | Graphene composite negative current collector, preparation method thereof and lithium ion battery |
| CN103466607A (en) * | 2013-09-09 | 2013-12-25 | 东南大学 | Graphene-metallic oxide nano-particle three-dimensional porous composite material |
| CN103787328A (en) * | 2014-03-11 | 2014-05-14 | 华南师范大学 | Modified grapheme preparation method |
| CN104200873A (en) * | 2014-09-09 | 2014-12-10 | 郑州轻工业学院 | Large-sized graphene-metal fine particle composite film and preparation method and applications thereof |
| CN106531975A (en) * | 2015-09-10 | 2017-03-22 | 中国科学院宁波材料技术与工程研究所 | Graphene composite material, and preparation methods and application thereof |
| CN106698402A (en) * | 2017-01-05 | 2017-05-24 | 东南大学 | Production method of metal nano-particle doped flexible self-supporting graphene film |
| CN106835082A (en) * | 2017-01-11 | 2017-06-13 | 东南大学 | The preparation method of the flexible self-supporting graphene film of metal nanoparticle doping |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113088124A (en) * | 2021-04-02 | 2021-07-09 | 宁波龙圣新材料科技有限公司 | Preparation process and method of graphene heating film |
| CN113593769A (en) * | 2021-07-07 | 2021-11-02 | 宁波石墨烯创新中心有限公司 | Graphene composite film and preparation method thereof |
| CN114853004A (en) * | 2022-04-25 | 2022-08-05 | 蜂巢能源科技股份有限公司 | Negative electrode material and preparation method and application thereof |
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Inventor after: Fu Huaqiang Inventor after: Xiao Yong Inventor after: Li Lun Inventor before: He Daping Inventor before: Fu Huaqiang Inventor before: Xiao Yong Inventor before: Li Lun |