CN114250529A - Aerogel fiber with specific section morphological characteristics and preparation method and device thereof - Google Patents
Aerogel fiber with specific section morphological characteristics and preparation method and device thereof Download PDFInfo
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Abstract
The invention discloses an aerogel fiber with specific section morphological characteristics and a preparation method and a device thereof, wherein the arrangement form of a section two-dimensional nanosheet of the aerogel fiber is adjustable, and the adjusting and controlling method comprises the following steps: and (2) adding a rotary flow field device before the spinning solution fluid is sprayed out during wet spinning, wherein the rotary flow field enables the two-dimensional nanosheets to form a specific lamellar arrangement form in the cross section direction of the gel fiber under the action of rotary shearing, and the gel fiber with the specific form cross section structure is prepared under the condition of freeze drying to obtain the graphene oxide aerogel fiber with the specific form structure (concentric circles and spiral lines). The hydrogel fiber with the concentric circle structure is dried, densified, stretched and reduced to obtain the graphene fiber with high modulus and high thermal conductivity, and compared with the existing graphene fiber, the thermal conductivity and the modulus of the graphene fiber are improved.
Description
Technical Field
The invention relates to the field of nano materials, in particular to aerogel fibers with specific section morphological characteristics and a preparation method and a preparation device thereof.
Background
Aerogel fiber is a new material combining the excellent characteristics of aerogel and fiber, and is a fiber variety which is obtained by subjecting gel fiber prepared by wet spinning to freeze drying or normal pressure drying and has light weight, high specific surface area and high porosity. The two-dimensional sheet-like molecule is a molecule having a large aspect ratio with a thickness of a single atomic layer, and has an extremely high tensile strength, young's modulus, high electrical conductivity, and highest thermal conductivity at room temperature, taking graphene as an example. The aerogel fiber prepared by taking two-dimensional flaky molecules as assembly units has more excellent mechanical-electrical-thermal properties besides the characteristics of high porosity and the like.
However, at present, research on the aerogel fiber assembled by two-dimensional nanosheets only stays at a starting point of successful preparation, and no method is provided for regulating and controlling the internal structure of the aerogel fiber, particularly for the two-dimensional anisotropy of the two-dimensional nanosheets in space, the two-dimensional anisotropy not only has axial orientation in the fiber, but also has a state that the two-dimensional nanosheets are arranged in the circumferential cross section direction of the fiber in a disordered manner. The disorder of two-position nanosheets arranged in the circumferential section direction of the aerogel fiber can lead to the reduction of the compression resistance of the aerogel fiber, so that the application of the aerogel fiber in the actual life is influenced, and meanwhile, the arrangement form of the two-dimensional nanosheets with high electric conductivity and high heat conductivity can also influence the effective transmission of electrons and phonons between the two-dimensional nanosheets and influence the conductivity of the aerogel fiber. Therefore, finding a strategy for effectively and accurately regulating and controlling the ordering of the two-dimensional sheet arrangement in the aerogel fiber becomes a great research direction. The aerogel fiber with specific section morphological characteristics can be prepared by accurately regulating and controlling the arrangement of the two-dimensional nanosheets in the aerogel fiber, so that the practical application of the aerogel fiber is promoted.
The 2011 super topic group of Zhejiang university invents a macroscopic graphene fiber taking single-layer graphene as an assembly unit, and creates a new path for preparing a carbon fiber by taking natural graphite as a raw material. At present, the pure graphene fiber shows excellent characteristics in the aspect of thermal conductivity, which are far higher than those of traditional carbon fibers, but the mechanical performance of the graphene fiber is flat, and although the monofilament mechanical strength of the graphene fiber can reach 3.4 GPa at present, the modulus of the graphene fiber does not break through 400 GPa, which is inconsistent with the rule that the modulus and the thermal conductivity of the traditional carbon fibers are improved at the same time, namely the thermal conductivity of the graphene fiber is far higher than that of the traditional carbon fibers, but the modulus of the graphene fiber is lower than that of the traditional carbon fibers.
High thermal conductivity and high modulus are two key indicators of simultaneous improvement in conventional carbon fibers, and are generally closely related to the degree of orientation and density of the fibers. At present, the orientation degree of the graphene fiber can reach more than 90%, however, the graphene fiber is directly assembled by single-layer graphene, the graphene is a typical two-dimensional macromolecular structure, and the density of the graphene fiber is finally determined by the order of the folding arrangement of the graphene, so that the order of the arrangement of two-dimensional graphene sheets in the graphene fiber is improved, the density of the graphene fiber is improved, and the high-modulus and high-thermal conductivity graphene fiber is prepared.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides aerogel fibers with specific section morphology characteristics, a preparation method and a device thereof, and high-modulus and high-thermal-conductivity graphene fibers are obtained.
Aiming at the two-dimensional plane nanosheet, the good lyotropic liquid crystal phenomenon is achieved based on the unique huge width-thickness ratio of the two-dimensional plane nanosheet; based on the specific macromolecules of the two-dimensional planar nanosheets, the dynamic stability of the liquid crystal is good, and the two-dimensional planar nanosheet liquid crystal spinning solution forms the hydrogel fiber with a specific structure after passing through a rotating flow field. The gel fiber is freeze-dried to obtain the aerogel fiber with a specific section shape. The hydrogel fiber is dried and densified to obtain nascent graphene oxide fiber, and the nascent graphene oxide fiber is subjected to plasticizing stretching, chemical reduction and heat treatment to obtain the high-modulus and high-heat-conductivity graphene fiber.
In one aspect, the aerogel fiber with specific section morphological characteristics is composed of two-dimensional nanosheets, and the fiber sections are arranged in concentric circle lamella or in radial spiral lamella.
The preparation method of the aerogel fiber comprises the following steps: extruding the dispersion liquid of the two-dimensional nanosheets into a coagulating bath, and fixing the structure after coagulation to obtain aerogel fibers with specific section morphological characteristics; the extrusion speed comprises an axial speed in the extrusion direction and a circumferential rotational speed perpendicular to the axial speed.
Further, the circumferential velocity is brought about by introducing a circumferential rotational shear force in the dispersion of the two-dimensional nanoplatelets.
Further, the two-dimensional nanosheets are nanosheets and various mixed two-dimensional nanosheets, wherein the nanosheets are graphene oxide, graphene, Mxene, molybdenum disulfide and montmorillonite with two-dimensional anisotropy.
Further, the concentration of the dispersion of the two-dimensional nanoplatelets is greater than 1 mg/g.
The invention also relates to a device for preparing aerogel fibers with specific section morphological characteristics, which at least comprises an extrusion device, a coagulating bath and a freeze-drying system; the extrusion device comprises a spinning tube, and circumferential rotating shearing force is arranged in the spinning tube.
Further, a rotor is arranged in the spinning pipe and is positioned at the axis of the spinning pipe.
Further, the rotor in the spinning tube rotates along its axis.
On the other hand, the invention also provides a high-modulus and high-thermal-conductivity graphene fiber which is composed of graphene two-dimensional nanosheets, the cross sections of the fibers are arranged in concentric wafer layers, and the graphene two-dimensional nanosheets are arranged along the axial direction; the graphene sheets form a plurality of graphite crystals with axial length of more than 200 nm and radial length of more than 100 nm; the density of the graphene fiber is more than or equal to 1.9 g/cm3。
The invention also relates to a preparation method of the graphene fiber, which comprises the following steps: extruding the dispersion liquid of the graphene oxide two-dimensional nanosheets into a coagulating bath, and drying to obtain nascent graphene oxide fibers; then sequentially carrying out plasticizing stretching, chemical reduction and heat treatment to obtain high-modulus and high-heat-conductivity graphene fibers; wherein the extrusion speed comprises an axial speed along the extrusion direction and a circumferential rotational speed perpendicular to the axial speed.
Further, the circumferential velocity is brought about by introducing a circumferential rotational shear force in the dispersion of the two-dimensional nanoplatelets.
Further, the dispersion liquid of the graphene oxide two-dimensional nanosheet is an aqueous dispersion liquid of graphene oxide, a DMF phase dispersion liquid, a DMAc phase dispersion liquid and a DMSO phase dispersion liquid, and the coagulating bath is a mixed coagulating bath of ethyl acetate, dichloromethane, acetic acid, ethanol, isopropanol, trichloromethane, acetone and the like or an aqueous solution coagulating bath of high-valent salt, wherein the high-valent salt is calcium chloride, ferrous chloride or ferric sulfate.
Further, the plastic stretching means: stretching the fibers by immersion in a plasticizer selected from the group consisting of: glycerol, propylene glycol, ethylene glycol, triethylene glycol, acetone, isopropanol, acetic acid, methanol, tetraethylene glycol, pentaethylene glycol, hydrochloric acid, dilute sulfuric acid, organic amine and the like or mixed plasticizers thereof.
Furthermore, reagents used for chemical reduction are hydriodic acid, hydrazine hydrate, sodium ascorbate, stannous chloride and the like, and the heat treatment temperature is 1300-3000 ℃.
Finally, the invention also provides the application of the fiber in sensing, phase change energy storage and catalytic energy.
The invention has the beneficial effects that:
1) through the arrangement of the two-dimensional nanosheets inside the aerogel fibers, the aerogel fibers with specific section morphological characteristics can be prepared, and the problem that the two-dimensional nanosheets inside the aerogel fibers cannot accurately regulate and control the arrangement of the lamella is solved, so that the mechanical property and the conductivity of the aerogel fibers are improved, and the practical application of the aerogel fibers is promoted.
2) According to the invention, the graphene fiber structure with a specific structure is constructed, so that the arrangement order of graphene sheets in the fiber is improved, the density of the finally heat-treated graphene fiber is improved, the crystallinity of graphene in the heat treatment process is obviously improved, the crystal size is obviously increased, and the heat conductivity and modulus of the graphene fiber are greatly improved.
Drawings
FIG. 1 is a schematic view of a homemade rotary extrusion spinning apparatus.
Fig. 2 shows a rotor structure in a rotary extrusion apparatus.
Fig. 3 is a cross-sectional shape of graphene oxide aerogel fibers prepared at different graphene liquid crystal spinning solution concentrations and different rotor speeds.
Fig. 4 is a cross-sectional morphology of a typical three graphene oxide aerogel fibers, including a being a disordered distribution cross-sectional structure; b is a section structure of concentric circles; c is the cross-sectional structure of the spiral line.
Fig. 5 is a mechanical curve of graphene fiber, in which the Concentric GF is the graphene fiber obtained by solidifying, drying and heat-treating gel fibers distributed concentrically; the Random GF is graphene fiber obtained by solidifying, drying and thermally treating gel fiber which is distributed in a disordered way.
Detailed Description
Comparative example 1
(1) Extruding the water-phase graphene oxide liquid crystal spinning solution with the concentration of 6mg/g into a circular spinning pipe with the diameter of 500 mu m at the speed of 0.2 mL/min, wherein the liquid crystal spinning solution passes through a device for rotating a rotor at the rotating speed of 0 rpm when being extruded into the spinning pipe, and the graphene oxide liquid crystal spinning solution does not undergo the shearing action of the rotation of the rotor;
(2) continuously extruding the graphene oxide liquid crystal spinning solution into a coagulating bath of 3wt% calcium chloride aqueous solution, coagulating to obtain graphene oxide gel fibers, soaking the gel fibers in deionized water for 3 times, and cleaning redundant free calcium ions;
(3) and (3) freezing the graphene oxide aerogel fiber in a refrigerator at the temperature of-80 ℃ for one hour, then putting the graphene oxide aerogel fiber into a freeze dryer for freeze drying, and drying to obtain the graphene oxide aerogel fiber.
The cross-sectional morphology of the prepared graphene oxide aerogel fiber is shown in fig. 4 a.
Example 1
(1) Extruding the water-phase graphene oxide liquid crystal spinning solution with the concentration of 6mg/g into a circular spinning pipe with the diameter of 500 mu m at the speed of 0.2 mL/min, wherein the liquid crystal spinning solution passes through a device for rotating a rotor at the rotating speed of 100 rpm when being extruded into the spinning pipe, and the graphene oxide liquid crystal spinning solution forms a concentric circle arrangement structure through the shearing action of the rotation of the rotor;
(2) continuously extruding the graphene oxide liquid crystal spinning solution arranged in concentric circles into a coagulating bath of 3wt% calcium chloride aqueous solution, coagulating to obtain graphene oxide gel fibers, soaking the gel fibers in deionized water for 3 times, and cleaning redundant free calcium ions;
(3) and (3) freezing the graphene oxide aerogel fiber in a refrigerator at the temperature of-80 ℃ for one hour, then putting the graphene oxide aerogel fiber into a freeze dryer for freeze drying, and drying to obtain the graphene oxide aerogel fiber.
The cross-sectional morphology of the prepared graphene oxide aerogel fiber is shown in fig. 4 b. The graphene oxide is a macromolecule, so that the stability of liquid crystal on dynamics is good, the specific structure of the liquid crystal can be maintained after the liquid crystal passes through a rotating flow field, and finally the arrangement structure of the graphene macromolecule after the liquid crystal passes through the rotating flow field can be continued to the graphene oxide aerogel fiber and the corresponding graphene aerogel fiber.
On the basis of this example 1, the concentration of graphene oxide and the rotor speed were controlled, and the results are shown in fig. 3. The cross section form of the aerogel fiber is mainly determined by the concentration of the graphene oxide liquid crystal spinning solution and the rotating speed of the rotor. The concentration of the graphene oxide solution determines whether the graphene oxide solution can form a liquid crystal, and as a general knowledge in the art, the concentration of the graphene oxide solution is 0.1wt% or more to form a liquid crystal. When the concentration is fixed, the rotating speed of the rotor is increased, the cross section of the graphene oxide aerogel fiber is of a concentric circle structure, and when the rotating speed is further increased, the cross section of the fiber is of a spiral line structure. The method for forming liquid crystal by regulating the concentration of graphene oxide is common knowledge in the field, and a person skilled in the art can regulate the cross-sectional morphology of the gel fiber according to the rotating speed rule.
Example 2
(1) Extruding the water-phase graphene oxide liquid crystal spinning solution with the concentration of 6mg/g into a circular spinning pipe with the diameter of 500 mu m at the speed of 0.2 mL/min, wherein the liquid crystal spinning solution passes through a device for rotating a rotor at the rotating speed of 500 rpm when being extruded into the spinning pipe, and the graphene oxide liquid crystal spinning solution forms an arrangement structure of a spiral line under the shearing action of the rotation of the rotor;
(2) continuously extruding the graphene oxide liquid crystal spinning solution in the spiral line arrangement into a coagulating bath of 3wt% calcium chloride water solution, coagulating to obtain graphene oxide gel fiber, soaking the gel fiber in deionized water for 3 times, and cleaning redundant free calcium ions;
(3) and (3) freezing the graphene oxide aerogel fiber in a refrigerator at the temperature of-80 ℃ for one hour, then putting the graphene oxide aerogel fiber into a freeze dryer for freeze drying, and drying to obtain the graphene oxide aerogel fiber.
The cross-sectional morphology of the prepared graphene oxide aerogel fiber is shown in fig. 4 c.
Example 3
(1) Extruding the water-phase graphene oxide liquid crystal spinning solution with the concentration of 8 mg/g into a circular spinning pipe with the diameter of 300 mu m at the speed of 0.2 mL/min, wherein the liquid crystal spinning solution passes through a device for rotating a rotor at the rotating speed of 50 rpm when being extruded into the spinning pipe, and the graphene oxide liquid crystal spinning solution forms a concentric circle arrangement structure through the shearing action of the rotation of the rotor;
(2) continuously extruding the graphene oxide liquid crystal spinning solution arranged in concentric circles into a coagulating bath of 3wt% ferrous chloride aqueous solution, coagulating to obtain graphene oxide gel fibers, soaking the gel fibers in deionized water for 3 times, and cleaning redundant free ferrous ions;
(3) soaking the cleaned graphene oxide gel fiber in a 1% sodium ascorbate aqueous solution, heating to 80 ℃, reducing for 12 hours to obtain a chemically reduced graphene gel fiber, and clearly replacing by deionized water;
(4) freezing the prepared graphene aerogel fiber in a liquid nitrogen environment at-120 ℃ for one hour, then putting the graphene aerogel fiber into a freeze dryer for freeze drying, and drying to obtain the graphene aerogel fiber.
(5) And (3) carrying out 2800 ℃ heat treatment on the dried graphene aerogel fibers with concentric circle arrangement in an argon environment to finally obtain the pure graphene aerogel fibers.
Through tests, the prepared graphene aerogel fiber after heat treatment has high thermal conductivity which reaches 15W/(m K), and in contrast, the thermal conductivity of the graphene aerogel fiber in disordered arrangement is only less than 10W/(m K), and the graphene aerogel fiber framework with high thermal conductivity can be used as a functional material with thermal, electrical and optical responses.
Example 4
(1) Extruding the Mxene spinning solution with the concentration of 6mg/g into a circular spinning pipe with the diameter of 500 mu m at the speed of 0.2 mL/min, wherein the spinning solution passes through a device for rotating a rotor at the rotating speed of 200 rpm when being extruded into the spinning pipe, and the spinning solution forms an arrangement structure of concentric circles under the shearing action of the rotation of the rotor;
(2) continuously extruding the Mxene spinning solution arranged in concentric circles into a coagulating bath of 6 wt% of ammonium chloride aqueous solution, coagulating to obtain Mxene gel fibers, soaking the gel fibers in deionized water to mix with a cleaning solution for 3 times, and cleaning redundant free ions;
(3) and (3) freezing the Mxene aerogel fiber in a refrigerator at the temperature of-80 ℃ for one hour, then putting the Mxene aerogel fiber into a freeze dryer for freeze drying, and drying to obtain the Mxene aerogel fiber.
Example 5
(1) Extruding the water-phase graphene oxide liquid crystal spinning solution with the concentration of 6mg/g into a circular spinning pipe with the diameter of 500 mu m at the speed of 0.2 mL/min, wherein the spinning pipe rotates under the action of external machinery when the water-phase graphene oxide liquid crystal spinning solution is extruded into the spinning pipe, so that the graphene oxide two-dimensional nanosheets undergo circumferential rotary shearing action under the rotation action of the spinning pipe to form a concentric circle arrangement structure;
(2) continuously extruding the graphene oxide liquid crystal spinning solution arranged in concentric circles into a coagulating bath of 3wt% calcium chloride aqueous solution, coagulating to obtain graphene oxide gel fibers, soaking the gel fibers in deionized water for 3 times, and cleaning redundant free calcium ions;
(3) and (3) freezing the graphene oxide aerogel fiber in a refrigerator at the temperature of-80 ℃ for one hour, then putting the graphene oxide aerogel fiber into a freeze dryer for freeze drying, and drying to obtain the graphene oxide aerogel fiber.
Example 6
(1) Extruding the graphene oxide and montmorillonite spinning solution with the concentration of 10mg/g into a circular spinning pipe with the diameter of 500 mu m at the speed of 0.2 mL/min, wherein the spinning solution passes through a device for rotating a rotor at the rotating speed of 400 rpm when being extruded into the spinning pipe, and the spinning solution forms an arrangement structure of a spiral line under the shearing action of the rotation of the rotor;
(2) continuously extruding the spinning solution in the spiral line arrangement into a coagulating bath of a 4 wt% calcium chloride water solution, coagulating to obtain mixed gel fibers of graphene oxide and montmorillonite, soaking the gel fibers in deionized water to mix with a cleaning solution for 3 times, and cleaning redundant free ions;
(3) freezing the mixed gel fiber of the graphene oxide and the montmorillonite for one hour in a liquid nitrogen environment, then putting the frozen gel fiber into a freeze dryer for freeze drying, and drying to obtain the mixed gel fiber of the graphene oxide and the montmorillonite.
Example 7
(1) Extruding a DMF (dimethyl formamide) phase graphene oxide liquid crystal spinning solution with the concentration of 6mg/g into a circular spinning pipe with the diameter of 100 mu m at the speed of 0.2 mL/min, wherein the liquid crystal spinning solution passes through a device for rotating a rotor at the rotating speed of 100 rpm before being extruded into the spinning pipe, and the graphene oxide liquid crystal is driven to be in a concentric circle structure by the rotation of the rotating rotor at the moment, as shown in figure 2;
(2) continuously extruding the graphene oxide liquid crystal spinning solution with the concentric circle structure into a coagulating bath of ethyl acetate, and drying to obtain nascent graphene oxide fibers;
(3) soaking the nascent graphene oxide fiber in acetic acid for plasticizing, plasticizing and stretching the plasticized graphene oxide fiber at a stretching rate of 30%, and then keeping the current length for drying;
(4) and carrying out chemical reduction of hydroiodic acid and heat treatment at 2700 ℃ on the dried graphene oxide fibers to obtain the high-modulus and high-thermal-conductivity graphene fibers.
Through mechanical tests, the strength of the graphene fiber prepared from the concentric round gel fiber reaches 3 GPa, the modulus is 833 GPa, and the thermal conductivity reaches 1590W/(m K). The mechanical curves are shown in fig. 5Concentric GF.
Comparative example 2
This comparative example differs from example 7 in that: extruding into spinning tubes without rotors
(1) Extruding the DMF phase graphene oxide liquid crystal spinning solution with the concentration of 6mg/g into a circular spinning pipe with the diameter of a flow channel of 100 mu m at the speed of 0.2 mL/min, wherein the spinning pipe is not provided with a rotor, and the graphene oxide liquid crystal is not driven into a concentric structure by a rotating flow field at the moment and is in a typical uncontrolled disordered distribution state;
(2) continuously extruding the graphene oxide liquid crystal spinning solution in disordered distribution into a coagulating bath of ethyl acetate, and drying to obtain nascent graphene oxide fibers;
(3) soaking the nascent graphene oxide fiber in acetic acid for plasticizing, plasticizing and stretching the plasticized graphene oxide fiber at a stretching rate of 30%, and then keeping the current length for drying;
(4) and carrying out chemical reduction of hydroiodic acid and heat treatment at 2700 ℃ on the dried graphene oxide fibers to obtain the graphene fibers prepared from the gel fibers in disordered distribution.
Through mechanical tests, the graphene fiber without microfibrillation has the strength of 3.1 GPa, the modulus of 343 GPa and the thermal conductivity of 1400W/(m K). The mechanical curves are shown in fig. 5Random GF.
Example 8
(1) Extruding the DMF phase graphene oxide liquid crystal spinning solution with the concentration of 8 mg/g into a circular spinning pipe with the diameter of 100 mu m at the speed of 0.2 mL/min, wherein the liquid crystal spinning solution passes through a device for rotating a rotor at the rotating speed of 50 rpm before being extruded into the spinning pipe, and the graphene oxide liquid crystal is driven to be in a concentric circle structure by the rotation of the rotating rotor;
(2) continuously extruding the graphene oxide liquid crystal spinning solution with the concentric circle structure into a coagulating bath of ethyl acetate, and drying to obtain nascent graphene oxide fibers;
(3) soaking the nascent graphene oxide fiber in ethanol for plasticizing, plasticizing and stretching the plasticized graphene oxide fiber at a stretching rate of 10%, and then keeping the current length for drying;
(4) and carrying out chemical reduction of hydroiodic acid and heat treatment at 2700 ℃ on the dried graphene oxide fibers to obtain the final graphene fibers.
Through mechanical tests, the strength of the graphene fiber prepared under the condition reaches 2 GPa, the modulus is 650 GPa, and the thermal conductivity reaches 1490W/(m K).
Example 9
This comparative example differs from example 8 in that: the rotor speed was 500 rpm, forming a helix.
(1) Extruding a DMF (dimethyl formamide) phase graphene oxide liquid crystal spinning solution with the concentration of 8 mg/g into a circular spinning pipe with the diameter of 100 mu m at the speed of 0.2 mL/min, wherein the liquid crystal spinning solution passes through a device for rotating a rotor at the rotating speed of 500 rpm before being extruded into the spinning pipe, and the graphene oxide liquid crystal is driven to be in a spiral line structure by the rotation of the rotating rotor;
(2) continuously extruding the graphene oxide liquid crystal spinning solution with the spiral line structure into a coagulating bath of ethyl acetate, and drying to obtain nascent graphene oxide fibers;
(3) soaking the nascent graphene oxide fiber in ethanol for plasticizing, plasticizing and stretching the plasticized graphene oxide fiber at a stretching rate of 10%, and then keeping the current length for drying;
(4) and carrying out chemical reduction of hydroiodic acid and heat treatment at 2700 ℃ on the dried graphene oxide fibers to obtain the final graphene fibers.
Through mechanical tests, the strength of the graphene fiber prepared under the condition reaches 1.8 GPa, the modulus is 500 GPa, and the thermal conductivity reaches 1360W/(m K).
Claims (15)
1. The aerogel fiber with the specific section morphological characteristics is characterized by being composed of two-dimensional nanosheets, and the fiber sections are arranged in concentric circle sheet layers or in radial spiral sheet layers.
2. The method of preparing aerogel fibers of claim 1, comprising: extruding the dispersion liquid of the two-dimensional nanosheets into a coagulating bath, and fixing the structure after coagulation to obtain aerogel fibers with specific section morphological characteristics; the extrusion speed comprises an axial speed in the extrusion direction and a circumferential rotational speed perpendicular to the axial speed.
3. The method of claim 2, wherein the circumferential velocity is imparted by introducing a circumferential rotational shear force in the dispersion of two-dimensional nanoplatelets.
4. The method of claim 2, wherein the two-dimensional nanoplatelets are graphene oxide, graphene, Mxene, molybdenum disulfide, nanoplatelets having two-dimensional anisotropy of montmorillonite, and a plurality of mixed two-dimensional nanoplatelets.
5. The method of claim 2, wherein the dispersion of two-dimensional nanoplatelets has a concentration greater than 1 mg/g.
6. An apparatus for preparing aerogel fibers having particular cross-sectional morphology features, comprising at least an extrusion device, a coagulation bath, and a freeze-drying system; the extrusion device comprises a spinning tube, and circumferential rotating shearing force is arranged in the spinning tube.
7. The apparatus of claim 6, wherein the spin tube has a rotor therein, the rotor being located at the axial center of the spin tube.
8. The apparatus of claim 6, wherein the rotor in the spinning tube rotates along its axis.
9. The high-modulus and high-heat-conductivity graphene fiber is characterized by being composed of graphene two-dimensional nanosheets, and the cross section of the fiber isThe concentric circular sheet layers are arranged, and the graphene two-dimensional nanosheets are arranged along the axial direction in an oriented manner; the graphene sheets form a plurality of graphite crystals with axial length of more than 200 nm and radial length of more than 100 nm; the density of the graphene fiber is more than or equal to 1.9 g/cm3。
10. The method for preparing a graphene fiber according to claim 9, wherein the dispersion of graphene oxide two-dimensional nanoplatelets is extruded into a coagulation bath and dried to obtain a nascent graphene oxide fiber; then sequentially carrying out plasticizing stretching, chemical reduction and heat treatment to obtain high-modulus and high-heat-conductivity graphene fibers; wherein the extrusion speed comprises an axial speed along the extrusion direction and a circumferential rotational speed perpendicular to the axial speed.
11. The method of claim 10, wherein the circumferential velocity is imparted by introducing a circumferential rotational shear force in the dispersion of two-dimensional nanoplatelets.
12. The method according to claim 10, wherein the dispersion of the graphene oxide two-dimensional nanoplatelets is an aqueous dispersion of graphene oxide, a DMF phase dispersion, a DMAc phase dispersion, a DMSO phase dispersion, and the coagulation bath is a coagulation bath of ethyl acetate, dichloromethane, acetic acid, ethanol, isopropanol, trichloromethane, acetone, and the like, and a mixture thereof, or an aqueous coagulation bath of a high-valent salt, and the high-valent salt is calcium chloride/ferrous chloride, ferric sulfate, and the like.
13. The method of claim 10, wherein the plastic stretching is: stretching the fibers by immersion in a plasticizer selected from the group consisting of: glycerol, propylene glycol, ethylene glycol, triethylene glycol, acetone, isopropanol, acetic acid, methanol, tetraethylene glycol, pentaethylene glycol, hydrochloric acid, dilute sulfuric acid, organic amine and the like or mixed plasticizers thereof.
14. The method as claimed in claim 10, wherein the chemical reduction is carried out using hydriodic acid, hydrazine hydrate, sodium ascorbate, stannous chloride, etc., and the heat treatment temperature is 1300-3000 ℃.
15. Use of the fiber of any one of claims 1 to 14 in sensing, phase change energy storage, catalytic energy, structural materials.
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| CN115490241A (en) * | 2022-09-27 | 2022-12-20 | 大连理工大学 | Preparation method and application of gas hydrate accelerant based on MXene-vermiculite composite aerogel |
| CN115490241B (en) * | 2022-09-27 | 2023-09-19 | 大连理工大学 | Preparation method and application of gas hydrate promoter based on MXene-vermiculite composite aerogel |
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