CN113151935B - Graphene material with high strength and high toughness and preparation method thereof - Google Patents
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- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
- D01F11/121—Halogen, halogenic acids or their salts
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Mechanical Engineering (AREA)
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Abstract
The invention discloses a graphene material with high strength and high toughness and a preparation method thereof, wherein the graphene material has a set of high strength and high toughness, and the method comprises the following steps: when the graphene fiber is subjected to wet spinning, a fluid liquid crystal zoning device is added before spinning solution fluid is sprayed out, so that the graphene liquid crystal spinning solution is divided into countless small microfibrillated unit structures, graphene oxide fibers with microfibrillated structures are obtained after liquid gel fibers are solidified, and then the graphene fibers with high strength and high toughness are obtained after reduction treatment. The invention relates to a graphene material with high strength and high toughness and a preparation method thereof.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a graphene material with high strength and high toughness and a preparation method thereof.
Background
Strength and toughness are generally two properties that are difficult to combine in a material. High-strength materials are brittle, and tough materials are generally low in strength. Taking carbon fiber as an example, carbon fiber is mainly obtained by pyrolyzing several kinds of organic polymer fiber at high temperature at present, typically polyacrylonitrile carbon fiber and pitch-based carbon fiber, and through the pyrolysis process, organic matter forms an inorganic disordered-layer carbon network structure, so that the strength of the carbon fiber is very high, but the elongation at break is only less than 2%.
The 2011 university super topic group of Zhejiang university invents a macroscopic graphene fiber taking single-layer graphene as an assembly unit, and develops a new path for preparing a carbonaceous fiber by taking natural graphite as a raw material. At present, pure graphene fiber shows excellent characteristics in strength, electric conduction and heat conduction performance, but the toughness of the pure graphene fiber is very low and is generally less than 1% consistent with that of the traditional carbon fiber. The method has the advantages that the high strength of the graphene fiber is kept, the toughness of the graphene fiber is improved, and the graphene fiber with both high strength and high toughness is obtained, so that the method becomes a difficult problem.
The biological material is generally a tough and integrated sighting rod material, for example, a shell structure is composed of an inorganic layer and an organic layer which are alternately distributed (brick dust structure), and the shell has the characteristics of high strength and high toughness due to the interface action of the inorganic layer and the organic layer; spider silks are composed of multilevel microstructures including the precise arrangement of 7 amino acids on the nanometer scale, the formation of beta-sheet nanocrystals, the combination of nanocrystals with amorphous regions in space, and microfibrillated structures on the submicron scale, the combination of these hierarchical microstructures with each other and the optimized interactions between microfibrils, ensuring the optimization of mechanical properties. However, inorganic fibers such as carbonaceous fibers generally have a uniform structure, and it is difficult to design the structure, and therefore they generally exhibit only brittleness.
At present, the existing method for preparing graphene fiber is mainly based on liquid crystal wet spinning, and the obtained graphene oxide fiber structure is also single, so the existing graphene fiber is also a typical brittle material. Conventional carbon fibers are also typically brittle fractures due to the formation of a uniform turbostratic carbon network after pyrolysis of the organic polymeric precursor. In view of the advantage of the toughness and integration of biological materials, the distribution of the carbon fiber microphase texture is regulated, and the introduction of a weak interface between the microfibers can be one of effective methods for realizing the high toughness of the fibers. However, for pure inorganic materials, on the one hand, the structural micro-partition design lacks an effective means; on the other hand, soft substances such as heterogeneous molecules cannot be avoided by introducing a weak interface, and the soft substances are difficult to retain in the heat treatment process, so that the toughness and integration performance of the inorganic carbonaceous fibers cannot be realized.
Graphene is a typical two-dimensional molecular structure, in-plane is composed of covalent bonds, in-plane is attracted to each other by weak van der waals forces, and graphene fibers are directly assembled from individual graphene oxide units. A shunt grid is introduced in the wet spinning process of the graphene fiber, so that a microfibrillated structure in the graphene fiber is expected to be realized. The reason for this is that: the graphene oxide is a macromolecule, the dynamic stability of liquid crystal is good, and the microfibrillated structure of the graphene oxide after passing through the shunt grating can be maintained; the structure of the one-dimensional chain-shaped polymer after passing through the shunt grating is loosened quickly, and the chain entanglement structure makes the structure uniform, so that a weak interface cannot be provided by the chain entanglement structure. Therefore, the micro-regionalization regulation and control of the shunt grating is an effective method for regulating the structure of the two-dimensional macromolecules, and has no effect on the one-dimensional macromolecules.
Disclosure of Invention
In order to overcome the above-mentioned prior art short plate, the present invention provides a graphene/graphene oxide material having a microfibrillated structure and a method for preparing the same. The microfibrillated graphene oxide material is reduced to obtain a graphene material, and the related species mainly include fibers and films, but are not limited to these. The microfibrillated structure can increase crack propagation paths when the graphene/graphene oxide material is fractured, and increase energy consumed during fracture, so that the graphene/graphene oxide material has the performance of both high strength and high toughness.
The application carries out structural design to this kind of two-dimensional plane macromolecule of oxidation graphite alkene. The huge width-thickness ratio of the compound makes the compound have good lyotropic liquid crystal phenomenon, and the huge molecules make the dynamic stability of the liquid crystal good, so that the microfibrillated structure can be maintained. The graphene material with the microfibrillated structure has the performance of high strength and high toughness.
The invention also provides a method for preparing the microfibrillated graphene material, and the microfibrillated graphene material is obtained by arranging the partitioned flow channels. Cutting the graphene oxide spinning solution with the liquid crystal state into a plurality of microfibrillated structures by a shunt grid at the front end of a spinning pipe, and keeping the microfibrillated structures in the spinning pipe; the graphene material with a microfibrillated structure can be further obtained by reduction by one skilled in the art.
Specifically, the invention adopts the following technical scheme:
the graphene oxide material with high strength and high toughness has a microfibrillated structure and consists of side-by-side graphene oxide microfibers, and the graphene oxide microfibers are bonded through van der Waals acting force among graphene oxide sheets.
A graphene material with high strength and high toughness has a microfibrillated structure and consists of side-by-side graphene microfibers, and the graphene microfibers are combined through van der Waals acting force between graphene sheets.
Further, the material is a fiber or a film; the smaller the diameter of the microfibers, the greater the number of microfibers contained in the material, and the greater its strength and toughness.
The preparation method of the graphene material comprises the following steps:
(1) Extruding the graphene oxide spinning solution into a partitioned flow channel, wherein the partitioned flow channel comprises a spinning pipe and a flow distribution grid vertically arranged at the front section of the spinning pipe; cutting the graphene oxide spinning solution with the liquid crystal state into a plurality of microfibrillated structures by a shunt grid at the front end of the spinning tube, and keeping the microfibrillated structures in the rear section of the spinning tube;
(2) And extruding the graphene oxide liquid crystal with the microfibrillated structure into a coagulating bath to obtain the microfibrillated graphene oxide fiber.
The preparation method of the graphene material is characterized by comprising the following steps: the graphene oxide material prepared by the method is subjected to chemical reduction and heat treatment in sequence to obtain the graphene material with high strength and high toughness.
Further, the spinning tube shape is round, square or various complex irregular shapes.
Further, a circular spinning tube is used to prepare a fiber having both high strength and high tenacity, and a square spinning tube is used to prepare a film having both high strength and high tenacity.
Further, the spinning solution is an aqueous dispersion of graphene oxide, a DMF phase dispersion, a DMAc phase dispersion, and a DMSO phase dispersion, and the coagulation bath is ethyl acetate, dichloromethane, acetic acid, ethanol, water, isopropanol, chloroform, acetone, or a mixed coagulation bath thereof.
Further, the grid shape of the shunt grating includes, but is not limited to, circular, square, triangular, hexagonal, and various complex shapes.
Furthermore, reagents adopted by the chemical reduction are hydroiodic acid, hydrazine hydrate, sodium ascorbate, stannous chloride and the like, and the heat treatment temperature is 25-2800 ℃.
The invention has the beneficial effects that: according to the invention, the liquid crystal shunt grid device is additionally arranged in front of the spinning flow channel, the graphene oxide liquid crystal spinning solution is divided into a plurality of microfiber units, the microfibrillated structure is retained after solidification and drying by the coagulating bath, and meanwhile, the structural characteristics of microfibrillation cannot be changed in the heat treatment process. The microfibrillated structure increases the path of crack propagation when the graphene fiber is broken, so that the toughness of the graphene fiber is improved while the high strength of the graphene fiber is kept.
Drawings
Fig. 1 shows graphene oxide liquid crystal with microfibrillated structure characteristics after passing through a partitioned flow channel.
Fig. 2 shows the microfibrillated structure characteristics of the graphene oxide liquid crystal after lyophilization.
Fig. 3 is a microfibrillated SEM image of an axial cross section of a graphene fiber. (is a microfibrillated structure characterization plot of the axial cross-section of the fiber after drying in example 1).
Fig. 4 is a TEM microfiber texture of microfibrillated graphene fibers.
FIG. 5 is a typical mechanical curve for two graphene fibers, as-spun GF for an unpeelized fiber; micro-fibrillated GF is microfibrillated graphene fiber.
Fig. 6 is a mechanical curve of graphene fibers of different microfiber sizes.
Fig. 7 is a polarization picture of a microfibrillated graphene oxide gel film.
Detailed Description
Example 1
(1) Extruding a DMF (dimethyl formamide) phase graphene oxide liquid crystal spinning solution with the concentration of 8mg/g into a circular spinning pipe with the diameter of 100 micrometers at the speed of 0.2mL/min, enabling the liquid crystal spinning solution to pass through a shunt grating device, enabling the grid shape of the shunt grating to be square and enabling the size of a single hole to be 6.5 micrometers, and cutting the graphene oxide liquid crystal into a plurality of microfibrillated structures by a zoning flow channel, wherein the microfibrillated structures are shown in figure 1;
(2) Continuously extruding the segmented graphene oxide liquid crystal spinning solution into a coagulating bath of ethyl acetate, and drying to obtain microfibrillated graphene oxide fibers;
(3) The graphene oxide fibers after drying were subjected to chemical reduction with hydroiodic acid and heat treatment at 1300 degrees, to obtain graphene fibers having both high strength and high toughness, and SEM images of the axial cross sections thereof are shown in fig. 3 and TEM image 4.
Through mechanical test, the strength of the microfibrillated graphene fiber reaches 5.5GPa, the modulus is 337GPa, and the toughness is 113MJ/m 3 The elongation at break was 3%, as shown in FIG. 5.
Comparative example 1
This comparative example is the same as example 1 except that: extruding into spinning tubes without compartmentalized flow channels
(1) Extruding the DMF phase graphene oxide liquid crystal spinning solution with the concentration of 8mg/g into a circular spinning pipe with the diameter of a flow channel of 100 mu m at the speed of 0.2mL/min, wherein the graphene oxide liquid crystal spinning solution is not extruded into a device of a flow distribution grid before being extruded into the spinning pipe, and the graphene oxide liquid crystal spinning solution is not cut into a plurality of microfibrillated structures by a partitioned flow channel;
(2) Continuously extruding the graphene oxide liquid crystal spinning solution into a coagulating bath of ethyl acetate, and drying to obtain graphene oxide fibers which are not microfibrillated;
(3) And carrying out chemical reduction of hydroiodic acid and heat treatment at 1300 ℃ on the dried graphene oxide fibers to obtain the graphene fibers without microfibrillation.
Through mechanical tests, the strength of the graphene fiber without microfibrillation is only 3GPa, the modulus is 300GPa, and the elongation at break is only 1%, as shown in figure 5.
Example 2
(1) Extruding an aqueous phase graphene oxide liquid crystal spinning solution with the concentration of 8mg/g into a circular spinning pipe with the diameter of 100 micrometers at the speed of 0.1mL/min, wherein the liquid crystal spinning solution passes through a shunt grating device before being extruded into the spinning pipe, the grid shape of the shunt grating is square, the size of a single hole is 36 micrometers, and at the moment, the graphene oxide liquid crystal is cut into a plurality of microfibrillated structures by a zoning flow channel, as shown in FIG. 2;
(2) Continuously extruding the partitioned graphene oxide liquid crystal spinning solution into a calcium chloride aqueous solution (5%) coagulating bath, and drying to obtain microfibrillated graphene oxide fibers;
(3) And carrying out chemical reduction of hydroiodic acid and heat treatment at 1300 ℃ on the dried graphene oxide fiber to obtain the graphene fiber with high strength and high toughness.
Through mechanical test, the strength of the microfibrillated graphene fiber reaches 3.2GPa, and the toughness is 50MJ/m 3 The elongation at break was 1.5%, as shown in FIG. 6.
Example 3
(1) Extruding a DMF (dimethyl formamide) phase graphene oxide liquid crystal spinning solution with the concentration of 10mg/g into a die with the opening width of 2cm and the height of 2mm at the speed of 0.3mL/min, wherein a flow distribution grid is arranged at the middle section of the spinning die, the grid shape of the flow distribution grid is circular, the size of a single hole is 50 microns, at the moment, the graphene oxide liquid crystal is cut into a plurality of microfibrillated structures by a partitioned flow channel, and an ejected sample is a microfibrillated graphene oxide gel film, as shown in FIG. 7;
(2) Continuously extruding the partitioned graphene oxide liquid crystal spinning solution into a coagulating bath of DMF and ethyl acetate (1);
(3) The graphene oxide film after drying was subjected to chemical reduction with hydroiodic acid and ethanol (1.
Through mechanical test, the strength of the microfibrillated graphene film reaches 1.5GPa, and the elongation at break is 4%.
Claims (7)
1. A preparation method of a graphene oxide material with high strength and high toughness, wherein the graphene oxide material has a microfibrillated structure and consists of side-by-side graphene oxide microfibrils, and the graphene oxide microfibrils are bonded through van der Waals acting force between graphene oxide sheets; the method is characterized by comprising the following processes:
(1) Extruding the graphene oxide spinning solution into a partitioned flow channel, wherein the partitioned flow channel comprises a spinning pipe and a flow distribution grid vertically arranged at the front section of the spinning pipe; cutting the graphene oxide spinning solution into a plurality of microfibrillated structures through a shunt grid, and keeping the microfibrillated structures at the rear section of the spinning pipe;
(2) And extruding the graphene oxide liquid crystal with the microfibrillated structure into a coagulating bath to obtain the microfibrillated graphene oxide fiber.
2. The method of claim 1, wherein the method comprises: and sequentially carrying out chemical reduction and heat treatment on the prepared graphene oxide material to obtain the graphene material with high strength and high toughness.
3. The preparation method of claim 2, wherein the chemical reduction is carried out by using hydroiodic acid, hydrazine hydrate, sodium ascorbate and stannous chloride as reagents, and the heat treatment temperature is 25-2800 ℃.
4. The method of claim 1 or 2, wherein the spinning tube shape is circular, square or various complex irregular shapes.
5. The method of claim 4, wherein the circular spinning tube is used to produce the fiber having both high strength and high tenacity, and the square spinning tube is used to produce the film having both high strength and high tenacity.
6. The preparation method according to claim 1 or 2, wherein the spinning solution is an aqueous dispersion of graphene oxide, a DMF phase dispersion, a DMAc phase dispersion, a DMSO phase dispersion, and the coagulation bath is ethyl acetate, dichloromethane, acetic acid, ethanol, water, isopropanol, chloroform, acetone, or a mixed coagulation bath thereof.
7. The method of claim 1 or 2, wherein the grid shape of the splitter grid is circular, square, triangular, hexagonal, and various complex shapes.
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