CN109267181B - Preparation process of graphene fiber with hollow structure - Google Patents
Preparation process of graphene fiber with hollow structure Download PDFInfo
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- CN109267181B CN109267181B CN201811122048.4A CN201811122048A CN109267181B CN 109267181 B CN109267181 B CN 109267181B CN 201811122048 A CN201811122048 A CN 201811122048A CN 109267181 B CN109267181 B CN 109267181B
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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
- 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
Abstract
The invention discloses a preparation process of graphene fibers with hollow structures, which comprises the following steps: (1) preparing graphene oxide water dispersion liquid to a set mass ratio concentration; (2) and (3) wet spinning: wet spinning by using a 19-26G coaxial needle; the coaxial needle comprises an inner tube and an outer tube, wherein liquid in the inner tube is core solution, and the core solution is acetic acid; the liquid between the inner pipe and the outer pipe is a skin solution, and the skin solution is the graphene oxide aqueous dispersion prepared in the step (1); (3) and (3) solidification: the coagulation bath used was the same as the core solution; (4) drying; (5) reducing to obtain graphene fiber filaments with hollow structures; (6) drying: and cleaning the residual reducing solution by using a cleaning agent, and drying. The preparation process of the graphene fiber with the hollow structure can overcome the defect that the hollow graphene fiber filament cannot be continuously prepared in the prior art, so that the graphene fiber filament can be produced in a connected mode.
Description
Technical Field
The invention relates to the technical field of fiber preparation, in particular to a preparation process of graphene fibers with hollow structures.
Background
The single-layer sheet graphene composed of carbon atoms has high mechanical strength, elasticity, thermal conductivity and electron mobility. The graphene can be used for field effect transistors, high-frequency devices, super microprocessors, single-molecule detectors and the like. The three-dimensional structure material formed by taking graphene as a basic unit, such as a film and a block material, can be applied to the fields of functional materials, such as controllable air-permeable membranes, anisotropic ion conductors, super capacitors, lithium ion batteries, energy catalysis and the like.
One of the main problems in the research and application of graphene is the effective assembly of the graphene macrostructure, and the current successful assembly is to obtain a three-dimensional structural film and a block. In the aspect of assembling the graphene with a macrostructure being a one-dimensional structure. The graphene hollow fiber constructed by the graphene has good flexibility and higher surface area on the basis of keeping the inherent characteristics of the graphene. Therefore, the material has potential application value in the fields of electrode materials, energy storage materials, catalytic materials and the like and is highly concerned by people.
Although graphene fibers have been prepared at present, it is difficult to prepare graphene hollow fibers due to low solubility and poor viscosity of graphene itself. In the existing preparation method of graphene hollow fibers, a document of a triptolide and the like reports that a graphene oxide solution is injected into a capillary tube with a copper wire inside, the graphene/copper wire fibers are hydrothermally synthesized, and the copper wire is removed after cooling to obtain the hollow graphene micro-nano tube. The graphene micro-nano tube prepared by the method reported by the documents such as the troxerite and the like has certain flexibility, but the method cannot be used for continuous production, only can be used for obtaining the graphene micro-nano tube, and cannot be used for obtaining the graphene oxide hollow fiber, and the subsequent treatment and impurity removal operation in the method are long in time, so that a new method needs to be improved or developed.
The chinese patent application No. 201611121245.5 discloses that a composite one-dimensional material template is formed by combining an intelligent material that can reversibly change in volume when environmental conditions change with a one-dimensional material template to prepare a graphene-based hollow fiber, that is, a graphene-based material is coated on the surface of the intelligent material when the intelligent material is in volume expansion, then the composite one-dimensional material and the graphene-based material layer coated by the intelligent material are separated when the intelligent material is in volume contraction, and then the graphene-based hollow fiber can be obtained by taking away the composite one-dimensional material template or taking out the graphene-based hollow fiber. The method has the same defects as the method for preparing the graphene hollow fiber by adopting the graphene/copper wire, and the continuous graphene hollow fiber cannot be prepared.
Disclosure of Invention
The invention aims to provide a preparation process of graphene fibers with hollow structures, which can realize continuous manufacturing of graphene hollow fibers.
In order to solve the technical problem, the invention aims to realize that:
the invention relates to a preparation process of graphene fibers with hollow structures, which comprises the following steps:
(1) preparing graphene oxide water dispersion liquid to a set mass ratio concentration;
(2) and (3) wet spinning: wet spinning by using a 19-26G coaxial needle; the coaxial needle comprises an inner tube and an outer tube, wherein liquid in the inner tube is core solution, and the core solution is acetic acid; the liquid between the inner pipe and the outer pipe is a skin solution, and the skin solution is the graphene oxide water dispersion liquid prepared in the step (1); the core solution and the sheath solution have the same or different advancing speeds;
(3) and (3) solidification: the coagulation bath used is the same as the core solution;
(4) and (3) drying: drying the solidified graphene oxide fiber filament with the hollow structure obtained in the step (3);
(5) reduction: reducing the graphene oxide fiber filament with the hollow structure after drying in the step (4) by using a reducing solution to obtain a graphene fiber filament with the hollow structure;
(6) drying: and (3) cleaning the residual reducing solution in the graphene fiber filament with the hollow structure by using a cleaning agent, and drying.
As a further illustration of the above scheme, in the step (1), the graphene oxide aqueous dispersion solution is prepared by a Hummer method.
As a further explanation of the above scheme, in the coaxial needle used in step (2), the inner diameter of the inner tube is 0.24mm, the outer diameter of the inner tube is 0.45mm, the inner diameter of the outer tube is 0.7mm, and the outer diameter of the outer tube is 1.06 mm.
As a further explanation of the above scheme, in the step (2), the advancing speed of the sheath solution in the wet spinning is 10ml/h, and the advancing speed of the core solution is 8-12 ml/h.
As a further explanation of the above embodiment, in the step (3), the coagulation time is 10 to 30 seconds.
As a further illustration of the scheme, in the step (5), the graphene oxide fiber filament with the hollow structure is placed in a hydrogen iodine solution at the temperature of 80-90 ℃ for reduction treatment for 8 hours.
As a further explanation of the above scheme, the drying in step (4) and step (6) is infrared drying.
As a further explanation of the above scheme, a specific method for preparing a graphene oxide aqueous dispersion by using Hummer is as follows: according to the following proportion, 250mL of concentrated sulfuric acid is placed in a 1000mL flask, 5g of graphene powder is added into the beaker, 5g of sodium nitrate is added, 18g of potassium permanganate is added in a small amount for multiple times within 20min of stirring in an ice water bath, the mixture is continuously stirred for 20-30min after the potassium permanganate is added, and the mixture is taken out of the ice water bath and stirred for 12 hours at normal temperature; then 15mL of 30% hydrogen peroxide is added dropwise; performing suction filtration by using a funnel, washing by using hydrochloric acid and deionized water in sequence after the suction filtration, wherein a product obtained after the suction filtration is graphene oxide, and performing freeze drying on the graphene oxide; and adding the dried graphene oxide into deionized water, and uniformly dispersing the graphene oxide in the water by using ultrasonic waves to reach the set solid content.
The beneficial effects of the invention are: the preparation process of the graphene fiber with the hollow structure can overcome the defect that the hollow graphene fiber filament cannot be continuously prepared in the prior art, so that the graphene fiber filament can be produced in a connected mode. And the graphene oxide fiber filament with the hollow structure is reduced to obtain the graphene fiber filament with the hollow structure in the production process, so that subsequent impurities do not need to be clear, and the graphene fiber filament with the hollow structure can be obtained continuously in a large quantity.
Drawings
FIG. 1-a is a scanning electron micrograph of a comparative example;
FIG. 1-b is a scanning electron micrograph of the first embodiment;
FIG. 1-c is a scanning electron micrograph of example II;
FIG. 1-d is a scanning electron micrograph of the third embodiment;
FIG. 1-e is a scanning electron micrograph of example four;
FIG. 1-f is a scanning electron micrograph of example five;
FIG. 2 is the tensile strength curves of example one, example two, example three, example four, example five and the comparative example;
FIG. 3 is a graph of the relationship between the rate of change in resistance and the tensile elongation for the first, second, third, fourth, fifth and comparative examples;
FIG. 4 is a graph of the creep of the weight for the rates of change of resistance of the first, second, third, fourth, fifth and comparative examples;
FIG. 5 is a graph showing changes in piezoresistance of the first, second, third, fourth, fifth and comparative examples;
FIG. 6 shows all the devices for testing piezoresistance of the first, second, third, fourth, fifth and comparative examples.
The symbols in the figure illustrate the following: 1-a wire; 2-a pressure head; 3-graphene fiber filaments; 4-fixing the plate.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
The invention relates to a preparation process of graphene fibers with hollow structures, which comprises the following steps:
(1) preparing graphene oxide aqueous dispersion. The mass ratio concentration of the graphene oxide aqueous dispersion is 1.93%. In the step, the graphene oxide aqueous dispersion solution is prepared by a Hummer method, and the method comprises the following specific steps: according to the following proportion, 250mL of concentrated sulfuric acid is placed in a 1000mL flask, 5g of graphene powder is added into the beaker, 5g of sodium nitrate is added, a small amount of 18g of potassium permanganate is added for multiple times within 20min of stirring in an ice water bath, the mixture is continuously stirred for 20-30min after the potassium permanganate is added, and the mixture is taken out of the ice water bath and stirred for 12 hours at normal temperature; then 15mL of 30% hydrogen peroxide is added dropwise; performing suction filtration by using a funnel, washing by using hydrochloric acid and deionized water in sequence after the suction filtration, wherein a product obtained after the suction filtration is graphene oxide, and performing freeze drying on the graphene oxide; and adding the dried graphene oxide into deionized water, and uniformly dispersing the graphene oxide in the water by using ultrasonic waves to reach the set solid content.
(2) And (4) wet spinning. Wet spinning with 19-26G coaxial needle. The coaxial needle includes an inner tube and an outer tube. The inner diameter of the inner tube of the coaxial needle used in the step is 0.24mm, the outer diameter of the inner tube is 0.45mm, the inner diameter of the outer tube is 0.7mm, and the outer diameter of the outer tube is 1.06 mm.
The liquid in the inner tube is core solution which is acetic acid; and (2) taking the liquid between the inner pipe and the outer pipe as a skin solution, wherein the skin solution is the graphene oxide aqueous dispersion prepared in the step (1).
The specific spinning process parameters in the wet spinning are as follows: the advancing speed of the sheath solution is 10ml/h, and the advancing speed of the core solution is 8-12 ml/h. The inner tube and the outer tube of the coaxial needle are both connected with injection pumps, and the core solution and the skin core solution are respectively injected into the inner tube and the outer tube. Due to the difference of the diameters of the inner tube and the outer tube, when the core solution and the sheath solution are sprayed out of the coaxial needle head, the speed of the core solution is different from that of the sheath solution. In the invention, because the diameters of the inner tube and the outer tube are different greatly, and the propelling amounts of the core solution and the sheath solution per hour are not different greatly, the speed of the core solution is higher than that of the sheath solution, so that the core solution can drive the sheath solution in contact with the core solution, and the prepared graphene oxide fiber with a hollow structure can be more uniform in evenness.
(3) And (5) solidifying. And (3) placing the skin solution and the core sink ejected from the coaxial needle head into a coagulation bath, wherein the coagulation time is 10-30s, so that the graphene oxide in the graphene oxide aqueous dispersion is coagulated. The coagulation bath used was the same as the core solution. Pure acetic acid is used for both the coagulating bath and the core solution, so that other impurities cannot be introduced during production, and subsequent treatment of the graphene oxide filament with the hollow structure is facilitated.
(4) And (5) drying. And (4) drying the solidified graphene oxide fiber filament with the hollow structure obtained in the step (3) by using infrared rays.
(5) And (4) reduction. And (4) reducing the dried graphene oxide hollow filaments obtained in the step (4) by using a reducing solution to obtain the graphene fiber filaments with hollow structures. The reduction treatment is to put the graphene oxide fiber filament with a hollow structure into a hydroiodic acid solution at the temperature of 80-90 ℃ for reduction treatment for 8 hours. The concentration of hydroiodic acid used is between 25 and 30% by weight.
(6) And (3) drying: and (3) cleaning the residual reducing solution in the graphene fiber filament with the hollow structure by using a cleaning agent, and drying by infrared. The cleaning agent used in this step is deionized water.
Example one
In the preparation process of the graphene fiber with the hollow structure according to the embodiment, the graphene oxide aqueous dispersion solution is prepared by a Hummer method in the embodiment, and the specific steps are as follows: according to the following proportion, 250mL of concentrated sulfuric acid is placed in a 1000mL flask, 5g of graphene powder is added into the beaker, 5g of sodium nitrate is added, a small amount of 18g of potassium permanganate is added for multiple times within 20min of stirring in an ice water bath, the mixture is continuously stirred for 20-30min after the potassium permanganate is added, and the mixture is taken out of the ice water bath and stirred for 12 hours at normal temperature; then 15mL of 30% hydrogen peroxide is added dropwise; performing suction filtration by using a funnel, washing by using hydrochloric acid and deionized water in sequence after the suction filtration, wherein a product obtained after the suction filtration is graphene oxide, and performing freeze drying on the graphene oxide; adding the dried graphene oxide into deionized water, and uniformly dispersing the graphene oxide in the water by using ultrasonic waves to form a graphene oxide water dispersion solution with the mass ratio of 1.93%.
And injecting the graphene oxide aqueous dispersion serving as a sheath solution and an acetic acid core solution into a coaxial needle head by an injection pump for wet spinning, wherein the advancing speed of the sheath solution in the spinning process is 10ml/h, the advancing speed of the core solution is 8ml/h, solidifying in an acetic acid coagulation bath for 10-30s, and performing infrared drying to prepare the graphene oxide fiber filament with the hollow structure. And then placing the graphene oxide fiber filament with the hollow structure into 30 wt% of hydroiodic acid solution at the temperature of 80 ℃, reducing for 8 hours, washing redundant hydrogen iodine solution with deionized water, and performing infrared drying to finally obtain the graphene fiber filament with the hollow structure. Then the short fiber is formed by drafting and cutting.
Example two
In the preparation process of the graphene fiber with a hollow structure according to this embodiment, the preparation of the graphene oxide aqueous dispersion solution is the same as that in the first embodiment, and the mass ratio concentration of the prepared graphene oxide aqueous dispersion solution is also the same. One of the differences from the first example is that the advancing speed of the sheath solution during spinning is 10ml/h and the advancing speed of the core solution is 9 ml/h. Another difference is that the graphene oxide fiber filaments with hollow structure were put into 28% wt hydriodic acid solution at 85 ℃.
EXAMPLE III
In the preparation process of the graphene fiber with a hollow structure according to this embodiment, the preparation of the graphene oxide aqueous dispersion solution is the same as that in the first embodiment, and the mass ratio concentration of the prepared graphene oxide aqueous dispersion solution is also the same. One difference from the first example is that the advancing speed of the sheath solution during spinning is 10ml/h and the advancing speed of the core solution is 10 ml/h. Another difference is that the graphene oxide fiber filaments with hollow structures were put into a 25% wt hydriodic acid solution at 90 ℃.
Example four
In the preparation process of the graphene fiber with the hollow structure according to this embodiment, the preparation of the graphene oxide aqueous dispersion solution is the same as that in the first embodiment, and the mass ratio concentration of the prepared graphene oxide aqueous dispersion solution is also the same. One of the differences from the first example is that the advancing speed of the sheath solution during spinning is 10ml/h and the advancing speed of the core solution is 11 ml/h. Another difference is that the graphene oxide fiber filaments with hollow structure were put into 28% wt hydriodic acid solution at 85 ℃.
EXAMPLE five
In the preparation process of the graphene fiber with a hollow structure according to this embodiment, the preparation of the graphene oxide aqueous dispersion solution is the same as that in the first embodiment, and the mass ratio concentration of the prepared graphene oxide aqueous dispersion solution is also the same. One difference from the first example is that the advancing speed of the sheath solution during spinning was 10ml/h and the advancing speed of the core solution was 12 ml/h. Another difference is that the graphene oxide fiber filaments with hollow structure were put into 28% wt hydriodic acid solution at 85 ℃.
Comparative example
In the preparation process of the graphene fiber according to this embodiment, the preparation of the graphene oxide aqueous dispersion solution is the same as that in the first embodiment, and the mass ratio concentration of the prepared graphene oxide aqueous dispersion solution is also the same. One difference from the first embodiment is that the needle used in the spinning process has no inner tube, the inner diameter of the needle is 0.6mm, and the spun yarn is solid graphene fiber filament. The solution advancing speed during spinning was 10 ml/h.
The following table shows the test results of the graphene fiber filaments prepared in examples one to five and comparative example.
As can be seen from the table, the thickness of the skin structure of the graphene fiber decreases as the advancing speed of the core solution increases.
Fig. 2 shows the strength tensile curves of the first, second, third, fourth, fifth and comparative examples. It can be seen that the slopes of the tensile curves are, in order from large to small, example five, example four, comparative example, example three, example two, and example one. It can be seen that the graphene fiber filaments obtained in the third, second and first embodiments have high hollowness and small modulus.
Fig. 3 shows a graph of the relationship between the rate of change in resistance and the tensile elongation for the first, second, third, fourth, fifth and comparative examples. As can be seen from the figures, the resistance change rates of the graphene fiber filaments obtained in the fourth and fifth examples were stable and almost unchanged before the stretch breaking. The tensile resistance strain of the graphene fiber filaments obtained in the first, second and third examples is greater than the change in tensile resistance strain of the graphene fiber filaments obtained in the fourth, fifth and comparative examples. Particularly, before the strain is less than 2%, the tensile resistance sensitivity of the graphene fiber filaments obtained in the fourth example, the fifth example and the comparative example is about 0 and is almost unchanged. The hollowness is suitable for small strain sensitivity test.
Fig. 4 is a graph showing the creep rates of the weight of the graphene fiber filaments obtained in the first, second, third, fourth, fifth and comparative examples.
Fig. 5 shows piezoresistive variation diagrams of the first embodiment, the second embodiment, the third embodiment, the fourth embodiment, the fifth embodiment and a comparative example. The piezoresistive change diagram was tested by the apparatus shown in fig. 6, in which the lead wire 1 was fixed to the fixing plates 4, the distance between the two fixing plates 4 was 5cm, and the graphene fiber filament 3 was fixedly connected to the lead wire 1 in a state where it was straightened and did not elongate. During the test, with pressure head 2 in the intermediate position of graphite alkene fibre long filament 3, press the distance of settlement with graphite alkene fibre long filament 3 to one side, in this test, the distance of oppressing is 1mm, 3mm, 5mm, 7mm and 9 mm. The tested structure is shown in fig. 5. After the graphene fiber filaments prepared in the comparative examples are subjected to a certain pressure, the minimum resistance is larger than the initial resistance value, and the minimum resistance is far smaller than the initial resistance value after the graphene fiber filaments prepared in the first embodiment, the second embodiment, the third embodiment, the fourth embodiment and the fifth embodiment are subjected to a certain pressure. The graphene fiber filament with the hollow structure is proved that when the graphene fiber filament is subjected to an acting force perpendicular to the axial direction, the internal interaction force is smaller, so that the graphene fiber filament is not easily damaged by the internal stress of the graphene fiber filament, and the strength is higher.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (5)
1. A preparation process of graphene fibers with hollow structures is characterized by comprising the following steps:
(1) preparing graphene oxide water dispersion liquid to a set mass ratio concentration;
(2) and (3) wet spinning: wet spinning by using a 19-26G coaxial needle; the coaxial needle head comprises an inner tube and an outer tube, wherein liquid in the inner tube is core solution, and the core solution is acetic acid; the liquid between the inner pipe and the outer pipe is a skin solution, and the skin solution is the graphene oxide water dispersion liquid prepared in the step (1); the core solution and the skin solution have the same or different propulsion speeds;
(3) and (3) solidifying: the coagulation bath used is the same as the core solution;
(4) and (3) drying: drying the solidified graphene oxide fiber filament with the hollow structure obtained in the step (3);
(5) reduction: reducing the graphene oxide fiber filaments with the hollow structures after drying in the step (4) by using a reducing solution to obtain graphene fiber filaments with hollow structures;
(6) and (3) drying: cleaning residual reducing solution in the graphene fiber filament with the hollow structure by using a cleaning agent, and drying;
the inner diameter of the inner tube of the coaxial needle used in the step (2) is 0.24mm, the outer diameter of the inner tube is 0.45mm, the inner diameter of the outer tube is 0.7mm, and the outer diameter of the outer tube is 1.06 mm;
in the step (2), the advancing speed of the sheath solution in wet spinning is 10ml/h, and the advancing speed of the core solution is 8-12 ml/h;
in the step (3), the solidification time is 10-30 s.
2. The process for preparing graphene fibers with hollow structures according to claim 1, wherein in the step (1), the graphene oxide aqueous dispersion solution is prepared by a Hummer method.
3. The process for preparing graphene fiber with hollow structure according to claim 1, wherein the step (5) is that the graphene oxide fiber filament with hollow structure is placed in a hydroiodic acid solution at 80-90 ℃ for reduction treatment for 8 h.
4. The process for preparing graphene fibers with a hollow structure according to claim 1, wherein the drying in the steps (4) and (6) is infrared drying.
5. The preparation process of the graphene fiber with the hollow structure according to claim 2, wherein the specific method for preparing the graphene oxide aqueous dispersion by using Hummer is as follows: according to the following proportion, 250mL of concentrated sulfuric acid is placed in a 1000mL flask, 5g of graphene powder is added into the beaker, 5g of sodium nitrate is added, 18g of potassium permanganate is added in a small amount for multiple times within 20min of stirring in an ice water bath, the mixture is continuously stirred for 20-30min after the potassium permanganate is added, and the mixture is taken out of the ice water bath and stirred for 12 hours at normal temperature; then 15mL of 30% hydrogen peroxide is added dropwise; performing suction filtration by using a funnel, washing by using hydrochloric acid and deionized water in sequence after the suction filtration, wherein a product obtained after the suction filtration is graphene oxide, and performing freeze drying on the graphene oxide; and adding the dried graphene oxide into deionized water, and uniformly dispersing the graphene oxide in the water by using ultrasonic waves to reach the set solid content.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031618A (en) * | 2012-12-26 | 2013-04-10 | 北京理工大学 | Preparation method of graphene oxide hollow fiber and graphene hollow fiber |
| CN103603088A (en) * | 2013-10-22 | 2014-02-26 | 浙江大学 | Conductive fiber with scabbard type structure and preparation method thereof |
| CN103726133A (en) * | 2014-01-02 | 2014-04-16 | 东华大学 | High-strength, compact and ordered porous graphene fiber and continuous preparation method thereof |
| CN106012086A (en) * | 2016-07-02 | 2016-10-12 | 苏州大学 | Graphene/polyaniline composite fiber and preparation method thereof |
| CN106120025A (en) * | 2016-07-02 | 2016-11-16 | 苏州大学 | A kind of graphene fiber and preparation method thereof |
| WO2017084622A1 (en) * | 2015-11-20 | 2017-05-26 | 济南圣泉集团股份有限公司 | Modified fiber and preparation method therefor |
| CN106835353A (en) * | 2016-12-31 | 2017-06-13 | 南京新月材料科技有限公司 | A kind of preparation method of Graphene doughnut |
| CN107022810A (en) * | 2017-05-05 | 2017-08-08 | 嘉兴学院 | A kind of amine based polymer composite graphite alkene height leads fiber and preparation method thereof |
| CN108520830A (en) * | 2018-03-13 | 2018-09-11 | 东华大学 | A kind of preparation method of core-skin type porous graphene fiber and ultracapacitor |
-
2018
- 2018-09-26 CN CN201811122048.4A patent/CN109267181B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031618A (en) * | 2012-12-26 | 2013-04-10 | 北京理工大学 | Preparation method of graphene oxide hollow fiber and graphene hollow fiber |
| CN103603088A (en) * | 2013-10-22 | 2014-02-26 | 浙江大学 | Conductive fiber with scabbard type structure and preparation method thereof |
| CN103726133A (en) * | 2014-01-02 | 2014-04-16 | 东华大学 | High-strength, compact and ordered porous graphene fiber and continuous preparation method thereof |
| WO2017084622A1 (en) * | 2015-11-20 | 2017-05-26 | 济南圣泉集团股份有限公司 | Modified fiber and preparation method therefor |
| CN106012086A (en) * | 2016-07-02 | 2016-10-12 | 苏州大学 | Graphene/polyaniline composite fiber and preparation method thereof |
| CN106120025A (en) * | 2016-07-02 | 2016-11-16 | 苏州大学 | A kind of graphene fiber and preparation method thereof |
| CN106835353A (en) * | 2016-12-31 | 2017-06-13 | 南京新月材料科技有限公司 | A kind of preparation method of Graphene doughnut |
| CN107022810A (en) * | 2017-05-05 | 2017-08-08 | 嘉兴学院 | A kind of amine based polymer composite graphite alkene height leads fiber and preparation method thereof |
| CN108520830A (en) * | 2018-03-13 | 2018-09-11 | 东华大学 | A kind of preparation method of core-skin type porous graphene fiber and ultracapacitor |
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