CN110846743A - Method for preparing three-dimensional graphene powder - Google Patents
Method for preparing three-dimensional graphene powder Download PDFInfo
- Publication number
- CN110846743A CN110846743A CN201911151011.9A CN201911151011A CN110846743A CN 110846743 A CN110846743 A CN 110846743A CN 201911151011 A CN201911151011 A CN 201911151011A CN 110846743 A CN110846743 A CN 110846743A
- Authority
- CN
- China
- Prior art keywords
- preparing
- graphene powder
- dimensional graphene
- temperature
- spinning
- 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.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
Abstract
The invention relates to a method for preparing three-dimensional graphene powder, which comprises the following operation steps: (1) manufacturing a protofilament; (2) preparing a spinning solution; (3) spinning; (4) pre-oxidizing; (5) drying; (6) and (6) carbonizing. The method for preparing the three-dimensional graphene powder adopts the thought of preoxidation and high-temperature pyrolysis carbonization of a polymer precursor containing polyacrylonitrile, avoids the process of catalytic carbonization of common polymers, does not need expensive catalysts, simplifies the product purification process, and has complete aromatization of the generated three-dimensional graphene powder; high carbon yield, easy process amplification, low production cost and strong controllability of product quality.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a method for preparing three-dimensional graphene powder.
Background
The three-dimensional graphene powder serving as an additive with excellent performance can be widely used, for example, the three-dimensional graphene powder can be added into polymer composite materials, battery materials, lubricating oil, cutting fluid, paint, road asphalt and the like, and can greatly improve the performance of the composite materials in the aspects of electric conduction, heat conduction, electromagnetic induction, mechanical strength, weather aging resistance and the like.
Different from the two-dimensional structure of common graphene, the three-dimensional graphene powder has a three-dimensional structure formed by the mutual connection of graphene sheets with different orientations. The three-dimensional structure well overcomes the defect that the common graphene is easy to stack to form graphite microcrystals and loses the characteristics of the graphene. The existing method for preparing the three-dimensional graphene powder is generally a catalytic cracking method of a high molecular polymer. Commonly used polymeric precursors are typically particles of crosslinked polymers or copolymers of styrene or acrylic monomers. A large amount of metal catalyst is adsorbed by a porous polymer precursor, and three-dimensional graphene powder is formed through high-temperature carbonization. The obtained product needs to be washed by strong acid to remove metal, and then is neutralized by weak base, filtered, dried and the like.
It can be seen that, in addition to the need for very expensive catalysts, the carbon yield is low, the work-up and purification of the product is rather cumbersome, and the number of graphene layers obtained and the control of defects are also not ideal. Meanwhile, the production cost of the methods is high, and the process is difficult to scale up and produce in large quantities.
Disclosure of Invention
In view of the above problems, the present invention adopts the following technical solutions: a method for preparing three-dimensional graphene powder comprises the following operation steps: (1) manufacturing a protofilament; (2) preparing a spinning solution; (3) spinning; (4) pre-oxidizing; (5) drying; (6) and (6) carbonizing.
Preferably, the specific steps in step (1) are: the spinning solution after demonomerization and deaeration passes through a spinneret plate and then directly enters a coagulating bath to be coagulated into nascent fiber, and then the nascent fiber is subjected to hot water drafting, water washing, drying densification, heat setting, high-temperature and high-pressure steam drafting, heat setting and other processes to obtain the final protofilament.
Preferably, the demonomerization and the debubbling in the step (1) adopt a vacuumizing mode.
Preferably, the whole production process of step (3) needs to be carried out in a clean environment, so as to avoid introducing impurities, and a dry-jet wet spinning mode is used.
Preferably, a pre-oxidation furnace is used in the step (4), the pre-oxidation temperature is set to be between 180 ℃ and 400 ℃, the temperature gradually increases from low to high, and the residence time of the process step is 60-120 min.
Preferably, the pre-oxidation furnace in the step (4) adopts a multi-layer operation mode, and the temperature of the furnace body shell cannot exceed 45 ℃.
Preferably, the step (6) is divided into two parts of low temperature carbonization and high temperature carbonization, wherein the former temperature is-300-.
The invention has the following beneficial effects: the idea of preoxidation and high-temperature pyrolysis carbonization of the polyacrylonitrile-containing polymer precursor is adopted, the process of catalytic carbonization of common polymers is avoided, an expensive catalyst is not needed, the product purification process is simplified, and the aromatization of the generated three-dimensional graphene powder is complete; high carbon yield, easy process amplification, low production cost and strong controllability of product quality.
Detailed Description
The following examples may assist those skilled in the art in a more complete understanding of the present invention, but are not intended to limit the invention in any way.
The invention provides a technical scheme that: a method for preparing three-dimensional graphene powder comprises the following operation steps: (1) manufacturing a protofilament; (2) preparing a spinning solution; (3) spinning; (4) pre-oxidizing; (5) drying; (6) carbonizing;
the specific steps in the step (1) are as follows: the spinning solution after demonomerization and deaeration passes through a spinneret plate and then directly enters a coagulating bath to be coagulated into nascent fiber, and then the nascent fiber is subjected to hot water drafting, water washing, drying densification, heat setting, high-temperature and high-pressure steam drafting, heat setting and other processes to obtain final protofilament;
in the step (1), a vacuumizing mode is adopted for demonomerization and defoaming;
the whole production flow of the step (3) needs to be carried out in a clean environment, so that impurities are prevented from being introduced, and a dry-jet wet spinning mode is used;
in the step (4), a pre-oxidation furnace is utilized, the pre-oxidation temperature is set to be between 180 ℃ and 400 ℃, the temperature is gradually increased from low to high, and the retention time of the process step is 60-120 min; in the step (4), the pre-oxidation furnace adopts a multilayer operation mode, and the temperature of the furnace body shell cannot exceed 45 ℃;
after the fibers are pre-oxidized in the step (5), a large amount of oxygen-containing hydrophilic groups are contained in the fibers, the pre-oxidized fibers are discharged from a pre-oxidation furnace or absorb water vapor in air, and in a subsequent carbonization furnace, moisture is subjected to oxidation reaction to cause the performance reduction of the carbon fibers, so that a drying device needs to be added between the pre-oxidation furnace and the carbonization furnace to take out the moisture contained in the fibers as much as possible;
the step (6) is divided into two parts of low-temperature carbonization and high-temperature carbonization, wherein the temperature of the former is-generally 300-1600 ℃, and the temperature of the latter is 1100-1600 ℃.
The method provided by the invention uses the copolymer containing the polyacrylonitrile block, does not need a catalyst, adopts a pre-oxidation process and a pyrolysis process to directly obtain the three-dimensional graphene powder, has high carbon yield, omits a post-treatment process, shortens a preparation path, simplifies a preparation process, reduces the production cost of the three-dimensional graphene powder, and provides a technical basis for large-scale production of graphene films.
The technical solutions provided by the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the descriptions of the embodiments are only used to help understanding the principles of the embodiments of the present invention; meanwhile, for a person skilled in the art, according to the embodiments of the present invention, there may be variations in the specific implementation manners and application ranges, and in summary, the content of the present description should not be construed as a limitation to the present invention.
Claims (7)
1. A method for preparing three-dimensional graphene powder is characterized by comprising the following operation steps:
(1) manufacturing a protofilament; (2) preparing a spinning solution; (3) spinning; (4) pre-oxidizing; (5) drying; (6) and (6) carbonizing.
2. The method for preparing three-dimensional graphene powder according to claim 1, wherein the specific steps in the step (1) are as follows: the spinning solution after demonomerization and deaeration passes through a spinneret plate and then directly enters a coagulating bath to be coagulated into nascent fiber, and then the nascent fiber is subjected to hot water drafting, water washing, drying densification, heat setting, high-temperature and high-pressure steam drafting, heat setting and other processes to obtain the final protofilament.
3. The method for preparing three-dimensional graphene powder according to claim 2, wherein the demonomerization and debubbling in the step (1) are performed by vacuum pumping.
4. The method for preparing three-dimensional graphene powder according to claim 1, wherein the whole production process of step (3) is performed in a clean environment, so as to avoid introducing impurities, and a dry-jet wet spinning method is used.
5. The method as claimed in claim 1, wherein a pre-oxidation furnace is used in the step (4), the pre-oxidation temperature is set to be 180-400 ℃, the temperature gradually increases from low to high, and the residence time in the process step is 60-120 min.
6. The method for preparing three-dimensional graphene powder according to claim 1, wherein the pre-oxidation furnace in the step (4) adopts a multilayer operation mode, and the temperature of the outer shell of the furnace body cannot exceed 45 ℃.
7. The method as claimed in claim 1, wherein the step (6) comprises low temperature carbonization and high temperature carbonization, the former is typically 300-1000 ℃ and the latter is 1100-1600 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911151011.9A CN110846743A (en) | 2019-11-21 | 2019-11-21 | Method for preparing three-dimensional graphene powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911151011.9A CN110846743A (en) | 2019-11-21 | 2019-11-21 | Method for preparing three-dimensional graphene powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110846743A true CN110846743A (en) | 2020-02-28 |
Family
ID=69603367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911151011.9A Pending CN110846743A (en) | 2019-11-21 | 2019-11-21 | Method for preparing three-dimensional graphene powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110846743A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500153A (en) * | 2020-05-26 | 2020-08-07 | 江苏金天辰新材料有限公司 | Three-dimensional graphene water-based heat-conducting anticorrosive paint and preparation method thereof |
| CN111534194A (en) * | 2020-05-26 | 2020-08-14 | 江苏金天辰新材料有限公司 | Application of three-dimensional graphene water-based heat-conducting anticorrosive paint |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534870A (en) * | 2011-12-29 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method of grapheme-modified acrylonitrile base carbon fiber |
| CN106012110A (en) * | 2016-06-30 | 2016-10-12 | 东华大学 | Flexible carbon fiber and preparation method thereof |
| CN107988660A (en) * | 2017-11-14 | 2018-05-04 | 哈尔滨工业大学深圳研究生院 | A kind of thermal chemical vapor deposition prepares the method and its application of three-dimensional grapheme fiber |
| CN109355735A (en) * | 2018-08-30 | 2019-02-19 | 北京化工大学 | Graphene carbon fiber and preparation method thereof |
| CN109881280A (en) * | 2019-02-18 | 2019-06-14 | 北京化工大学 | A kind of preparation method of polyacrylonitrile fibre, preparation method and its carbon fiber |
-
2019
- 2019-11-21 CN CN201911151011.9A patent/CN110846743A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534870A (en) * | 2011-12-29 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Preparation method of grapheme-modified acrylonitrile base carbon fiber |
| CN106012110A (en) * | 2016-06-30 | 2016-10-12 | 东华大学 | Flexible carbon fiber and preparation method thereof |
| CN107988660A (en) * | 2017-11-14 | 2018-05-04 | 哈尔滨工业大学深圳研究生院 | A kind of thermal chemical vapor deposition prepares the method and its application of three-dimensional grapheme fiber |
| CN109355735A (en) * | 2018-08-30 | 2019-02-19 | 北京化工大学 | Graphene carbon fiber and preparation method thereof |
| CN109881280A (en) * | 2019-02-18 | 2019-06-14 | 北京化工大学 | A kind of preparation method of polyacrylonitrile fibre, preparation method and its carbon fiber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500153A (en) * | 2020-05-26 | 2020-08-07 | 江苏金天辰新材料有限公司 | Three-dimensional graphene water-based heat-conducting anticorrosive paint and preparation method thereof |
| CN111534194A (en) * | 2020-05-26 | 2020-08-14 | 江苏金天辰新材料有限公司 | Application of three-dimensional graphene water-based heat-conducting anticorrosive paint |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101724922B (en) | Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber | |
| KR101170816B1 (en) | Manufacturing method for polyimide-based carbon nanofiber electrode and carbon nanotube composite electrode and CDI apparatus using the same | |
| CN110846743A (en) | Method for preparing three-dimensional graphene powder | |
| CN106629661A (en) | Process for preparing carbon nanospheres from bagasse | |
| CN111139554B (en) | High-permeability polyacrylonitrile-based carbon fiber and preparation method thereof | |
| CN110723734B (en) | Method for preparing activated carbon composite material by using corncob acid hydrolysis residues | |
| CN109205622B (en) | Preparation method of biomass tar derived porous carbon material | |
| CN110938897A (en) | Technology for rapidly preparing fibrous porous material | |
| CN114984777B (en) | Preparation method and application of phenolic resin carbon film | |
| CN109629227B (en) | Preparation method of fiber-based carbon nanotube conductive material | |
| CN116427101A (en) | Preparation method and equipment of high-purity hardly graphitized viscose-based carbon fiber felt | |
| KR101425305B1 (en) | Manufacturing method of carbon fiber paper using PAN fibrid | |
| CN106549151A (en) | A kind of preparation method of copper vanadate/polyacrylonitrile-radical carbon nano-fiber composite material | |
| JP5072668B2 (en) | Precursor fiber, and method for producing precursor fiber, flame-resistant fiber and carbon fiber | |
| CN105525388A (en) | Method for preparing carbon fiber precursor by employing sodium thiocyanate through dry and wet spinning process | |
| CN113862812B (en) | Polyacrylonitrile-based carbon fiber precursor special for carbon paper and preparation method thereof | |
| CN111187381A (en) | Preparation method of PAN (polyacrylonitrile) polymer for carbon hollow nano-fiber | |
| CN107999052A (en) | A kind of preparation method of photocatalytic degradation composite material | |
| KR100351131B1 (en) | High dense activated carbon fiber disk for capacitor's electrode of ultra high capacity and its production method | |
| CN101694059B (en) | Process for preparing PVDF insulation dielectric layer material for sulfuric dielectric capacitor | |
| CN113388921B (en) | Dry-method carbon fiber precursor and preparation method thereof | |
| KR101405481B1 (en) | Method for manufacturing activated carbon fiber and activated carbon fiber manufactured by the same | |
| CN107604481A (en) | The preparation method of high-performance inorganic carbonaceous fabric | |
| CN108866821B (en) | Preparation method of high-ortho-position cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane | |
| CN115948821B (en) | Hollow, porous and multi-layer polyacrylonitrile-based carbon fiber and preparation method thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200228 |