CN105937066A - Preparation method of highly oriented graphene oxide fiber - Google Patents
Preparation method of highly oriented graphene oxide fiber Download PDFInfo
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- CN105937066A CN105937066A CN201510993611.5A CN201510993611A CN105937066A CN 105937066 A CN105937066 A CN 105937066A CN 201510993611 A CN201510993611 A CN 201510993611A CN 105937066 A CN105937066 A CN 105937066A
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- graphene oxide
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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
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- 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
Abstract
The invention belongs to the technical field of graphene fiber material preparation, and in particular to a preparation method of highly oriented graphene oxide fiber. The method comprises the following steps: preparing a large-layer graphene oxide solution by using a large-layer expandable natural flake graphite as a base material, concentrating to obtain a graphene oxide spinning solution, and preparing a solidified liquid from a long-chain monoamine reagent; first preparing a native gel graphene oxide fiber by a wet spinning method, then drawing the virgin fibers at a certain temperature, forming a large displacement of the graphene oxide layer in the tensile process by using the entanglement effect between the long chains at the end of the solidified liquid molecules, so as to endow the fiber with higher orientation and mechanical strength; and further drying to obtain the highly oriented graphite oxide fiber. The invention has the advantages of simple operation, low cost, good orientation results, and effective improvement on the mechanical properties of fibers. The graphene oxide fiber has significantly enhanced tensile strength compared with the native graphene oxide fiber.
Description
Technical field
The present invention relates to the preparation method of a kind of highly oriented graphene oxide fiber, belong to graphene fiber technical field of material.
Background technology
Graphene since within 2004, being found, has just obtained the extensive concern of people as a kind of novel two-dimensional material.The single or multiple lift Graphene prepared by CVD or epitaxial growth method has the mechanics of excellence, electricity, thermal property so that it all will have extremely wide application in fields such as structural material, energy storage device, electronic device, induction apparatuss.
Along with epoch development, various fibrous materials have become requisite element in the productive life of people, how graphene sheet layer are assembled into the one dimension fibre material of macroscopic view, it is achieved Graphene application in practice, is that present stage people need facing challenges.Based on this, the research work of the fibrous material of Graphene launches in succession.As, CNT (CNT) fiber based on graphene sheet layer prepared by CVD or wet spinning process and carbon fiber have mechanical performance and the electric property of superelevation.And both prepares the experiment condition the most more harshness of fiber.Wet spinning process is used to prepare the fibrous material based on Graphene that graphene sheet layer axially arranges, compared with the preparation process of first two fiber, experiment condition wants gentle many, and its preparation method is easily enlarged production, it is simple to prepare substantial amounts of macroscopic view one dimension fibre material.
In order to improve fibre property further, many is studied the degree of orientation of raising fiber as a kind of approach, as, spinning process rotates solidification liquid, make fiber by the stretching action of solution in forming process thus fiber is played certain drawing effect, or use one step hydro thermal method to utilize template to prepare highly oriented GO fiber, but level of stretch all ratios are relatively limited, it is difficult to reach bigger orientation, limits the breakthrough of its mechanical performance.
Summary of the invention
Therefore, invent the degree of orientation that technical problem to be solved is to overcome prior art to be difficult to be effectively improved graphene oxide fiber, thus improve the mechanical performance of fiber and realize more actual application.
To this end, the present invention provides the preparation method of a kind of effective highly oriented graphene oxide fiber, comprise the following steps:
With the inflatable natural flake graphite of big lamella as raw material, prepare graphene oxide by sufficient intercalation oxidation, and prepare graphene oxide spinning liquid；
Preparation solidification liquid, utilizes wet spinning process to prepare primary gel oxidizing graphene fiber；
The arrangement of primary gel oxidizing graphene fiber being fixed on stretching device, stretch fiber at a certain temperature, drying obtains high-mechanical property orientation graphene oxide fiber.
In the preparation method of above-mentioned highly oriented graphene oxide fiber, the size of described expansible graphite is 300 μm～500 μm.
In the preparation method of above-mentioned highly oriented graphene oxide fiber, graphene oxide is prepared in described intercalation oxidation, can directly concentrate prepared graphene oxide solution and prepare spinning liquid, graphene oxide lyophilizing also can be obtained solid oxidation Graphene, again solid oxidation Graphene is dissolved in a solvent, form graphene oxide spinning liquid.
In the preparation method of above-mentioned highly oriented graphene oxide fiber, described spinning liquid thickening temperature is 40 DEG C-55 DEG C.
In the preparation method of above-mentioned highly oriented graphene oxide fiber, described solvent be in polar organic solvent, aqueous solution any one or two kinds with the mixed liquor of arbitrary proportion mixed preparing.
In the preparation method of above-mentioned highly oriented graphene oxide fiber, described polar organic solvent is any one in methanol, propanol, butanol, DMF, acetonitrile.
In the preparation method of above-mentioned highly oriented graphene oxide fiber, described graphene oxide concentration of dope is 5mg/ml-15mg/ml.
In the preparation method of above-mentioned highly oriented graphene oxide fiber, described solidification liquid can be long-chain fat race monoamine or the aqueous solution of long-Chain aromatic race monoamine or alcoholic solution.
In the preparation method of above-mentioned highly oriented graphene oxide fiber, the speed of described wet spinning is 0.3ml/min-0.8ml/min, and selected spinning syringe needle internal diameter is 0.25mm-1mm；
In the preparation method of above-mentioned highly oriented graphene oxide fiber, described draft temperature is 40 DEG C--60 DEG C, drying time is 5-48h.
The preparation method of a kind of highly oriented graphene oxide fiber of the present invention has the advantage that
1. the preparation method of a kind of highly oriented graphene oxide fiber of the present invention, by selecting the inflatable natural scale graphite of big lamella to prepare graphene oxide as spinning liquid, improve graphene oxide lamella size, make lamella realize more effectively stacking in spinning process, improve the mechanical performance of fiber.
2. the preparation method of a kind of highly oriented graphene oxide fiber of the present invention, select long-chain fat race monoamine or the aqueous solution of long-Chain aromatic race monoamine or polar organic solvent as solidification liquid, primary gel oxidizing graphene fiber is prepared first with wet spinning process, again prepared primary gel oxidizing graphene fiber arrangement is fixed on stretching device, and at a certain temperature fiber is done stretch processing, utilize the mutual entanglement between solidification liquid strand, make GO lamella can reach larger displacement, thus obtain higher orientation and improve the mechanical performance of fiber.Stretching is carried out at a certain temperature, can the effect of further reinforced sheet interlayer, select amine can also promote on coagulator and graphene oxide lamella the reaction between group as coagulator, improve the adhesion of sheet interlayer.Therefore, the preparation method of the highly oriented graphene oxide fiber that the present invention provides, the graphene oxide fibre orientation prepared is good, mechanical performance is high and preparation method simple, can be widely applied to graphene fiber technical field of material.
Accompanying drawing explanation
Fig. 1 is fiber stretch orientation schematic diagram.
Fig. 2 is the protofibre (a) in embodiment 1, and the electronic fiber scarnning mirror figure of orientation fiber (b).
Fig. 3 is the mechanical performance figure of the fiber in embodiment 1.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme is clearly and completely described, it is clear that described invention is a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
Embodiment 1
The preparation of big lamella graphene oxide: weigh 5g, the inflatable natural flake graphite of 300 μm, add 200mL concentrated sulphuric acid and 50mL fuming nitric aicd, after stirring 24h, mixture is poured slowly in 2L deionized water at normal temperatures, use a diameter of 90mm, aperture is the cellulose membrane sucking filtration of 0.2um and is washed with deionized twice, dries 24h after washing at 60 DEG C.Dried graphite is expanded under 1000 DEG C of high temperature 30s, obtains expanded graphite.Adding 200mL concentrated sulphuric acid, 13.2g K2S2O8 and 16.2gP2O5 stirs 5h at 80 DEG C of constant temperature, is poured into by mixed liquor in 2L deionized water, to be cooled to room temperature, using a diameter of 90mm, aperture is the cellulose membrane sucking filtration of 0.2um and is washed with deionized twice, puts drying 48h at room temperature.It is added into after drying in 200mL concentrated sulphuric acid, is slowly added to 15g potassium permanganate under ice bath, is sufficiently stirred for, 5h is reacted at 35 DEG C, mixed liquor is poured slowly in 2L deionized water, waits solution to be cooled to 50 DEG C of hydrogenperoxide steam generators adding 20mL 30%, become pale yellow solution to solution.Stand 1 day, pour out supernatant liquid, with deionized water centrifuge washing 2 times, 1mol/L dilute hydrochloric acid solution centrifuge washing 2 times, then with deionized water centrifuge washing until GO aqueous solution is neutrality, i.e. prepare big lamella graphene oxide solution；
The preparation of spinning liquid: take prepared big lamella graphene oxide solution 200ml, is placed in stirring concentration at 50 DEG C in oil bath pan, obtains the big lamella graphene oxide spinning liquid that concentration is 8mg/ml；
The preparation of aniline solidification liquid: the hexylamine alcoholic solution of preparation mass fraction 5% is as solidification liquid；
Prepared by primary graphene oxide fiber: utilize mechanical syringe pump, the spinning syringe needle selecting internal diameter to be 0.43mm, pushes syringe by syringe pump and is injected in solidification liquid with the speed of 0.3ml/min by spinning liquid, forms primary gel oxidizing graphene fiber；
The preparation of orientation graphene oxide fiber: prepared primary graphene oxide fiber is vertically arranged and is fixed on stretching device, under infrared lamp auxiliary baking, wherein baking temperature controls at about 60 DEG C, slow stretching fiber, then fiber is put be dried at room temperature 5h obtain be orientated graphene oxide fiber.
The flow chart of the present embodiment is as shown in Figure 1, and prepared primary graphene oxide fiber, orientation graphene oxide fiber are carried out SEM electron microscope scanning analysis respectively, its result is respectively as shown in Fig. 2 (a) and Fig. 2 (b), knowable to Fig. 2 compares, the fold of primary graphene oxide fiber axial graphene oxide sheet layer is more apparent, the degree of orientation is the highest, and the fiber oxidation graphene sheet layer of stretched process is axially presenting more perfect orientations；Fig. 3 is the mechanical performance comparison diagram of fiber before and after stretching, it can be clearly seen that, the mechanical performance of stretched process fiber substantially increases than protofibre.
Embodiment 2
The preparation of graphene oxide: different from embodiment 1 be: the inflatable natural flake graphite selecting lamella size to be 500 μm prepares graphene oxide as raw material.
Preparing of spinning liquid: take prepared big lamella graphene oxide solution 200ml, is placed in stirring concentration at 50 DEG C in oil bath pan, obtains the big lamella graphene oxide spinning liquid that concentration is 10mg/ml；
The preparation of solidification liquid: the octylame aqueous solution of preparation mass fraction 5% is as solidification liquid；
Prepared by primary graphene oxide fiber: with embodiment 1；
The preparation of orientation graphene oxide fiber: prepared primary graphene oxide fiber is vertically arranged and is fixed on stretching device, under infrared lamp auxiliary baking, wherein baking temperature controls at about 65 DEG C, slow stretching fiber, is then placed in fiber in vacuum drying oven dry 12h and obtains being orientated graphene oxide fiber.
Embodiment 3
The preparation of graphene oxide: with embodiment 2.
Preparing of spinning liquid: with embodiment 2.
The preparation of solidification liquid: the ODA alcoholic solution of preparation mass fraction 5% is as solidification liquid；
Prepared by primary graphene oxide fiber: utilize mechanical syringe pump, the spinning syringe needle selecting internal diameter to be 0.5mm, pushes syringe by syringe pump and is injected in solidification liquid with the speed of 0.5ml/min by spinning liquid, forms primary gel oxidizing graphene fiber；
The preparation of orientation graphene oxide fiber: prepared primary gel oxidizing graphene fiber is vertically arranged and is fixed on stretching device, under infrared lamp auxiliary baking, wherein baking temperature controls at about 65 DEG C, slow stretching fiber, is then placed in fiber in vacuum drying oven dry 24h and obtains being orientated graphene oxide fiber.
Embodiment 4
The preparation of graphene oxide: with embodiment 1；
Preparing of spinning liquid: take prepared big lamella graphene oxide solution 200ml, is placed in stirring concentration at 55 DEG C in oil bath pan, obtains the big lamella graphene oxide spinning liquid that concentration is 12mg/ml；
The preparation of solidification liquid: preparation mass fraction is that the octylame aqueous solution of 4% is as solidification liquid.
Prepared by primary graphene oxide fiber: utilize mechanical syringe pump, the spinning syringe needle selecting internal diameter to be 0.34mm, pushes syringe by syringe pump and is injected in solidification liquid with the speed of 0.2ml/min by spinning liquid, forms primary gel oxidizing graphene fiber；
The preparation of orientation graphene oxide fiber: prepared primary gel oxidizing graphene fiber is vertically arranged and is fixed on stretching device, under infrared lamp auxiliary baking, wherein baking temperature controls at about 70 DEG C, slow stretching fiber, is then placed in fiber in vacuum drying oven dry 36h and obtains being orientated graphene oxide fiber.
Claims (10)
1. a preparation method for highly oriented graphene oxide fiber, comprises the following steps:
With the inflatable natural flake graphite of big lamella as raw material, prepare graphene oxide by sufficient intercalation oxidation, and configure graphene oxide spinning liquid；
Preparation solidification liquid, utilizes wet spinning process to prepare primary gel oxidizing graphene fiber；
The arrangement of primary gel oxidizing graphene fiber being fixed on stretching device, stretch fiber at a certain temperature, drying obtains high-mechanical property orientation graphene oxide fiber.
The preparation method of highly oriented graphene oxide fiber the most according to claim 1, it is characterised in that: the size of described inflatable crystalline flake graphite is 300 μm～500 μm.
The preparation method of highly oriented graphene oxide fiber the most according to claim 1 and 2, it is characterised in that: the concentration of described graphene oxide spinning liquid is 5～20mg/ml.
4. according to the preparation method of the preparation method of the arbitrary described highly oriented graphene oxide fiber of claim 1-3, it is characterized in that: graphene oxide is prepared in described intercalation oxidation, can directly concentrate prepared graphene oxide solution and prepare spinning liquid, graphene oxide lyophilizing also can be obtained solid oxidation Graphene, again solid oxidation Graphene is dissolved in a solvent, form graphene oxide spinning liquid.
The preparation method of highly oriented graphene oxide fiber the most according to claim 4, it is characterised in that: thickening temperature is 40 DEG C-55 DEG C.
The preparation method of highly oriented graphene oxide fiber the most according to claim 4, it is characterised in that: described solvent be in polar organic solvent, aqueous solution any one or two kinds with the mixed liquor of arbitrary proportion mixed preparing.
7. according to the preparation method of the highly oriented graphene oxide fiber described in claim 1-6, it is characterised in that: described polar organic solvent is any one in methanol, propanol, butanol, DMF, acetonitrile.
8. according to the preparation method of the arbitrary described highly oriented graphene oxide fiber of claim 1-7, it is characterised in that: described solidification liquid can be long-chain fat race monoamine or the aqueous solution of long-Chain aromatic race monoamine or alcoholic solution.
9. according to the preparation method of the arbitrary described highly oriented graphene oxide fiber of claim 1-8, it is characterised in that: the speed of described wet spinning is 0.3ml/min-0.8ml/min, and selected spinning syringe needle internal diameter is 0.25mm-1mm.
10. according to the preparation method of the arbitrary described highly oriented graphene oxide fiber of claim 1-9, it is characterised in that: described draft temperature is 40 DEG C--60 DEG C, drying time is 5-48h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110629325A (en) * | 2019-09-30 | 2019-12-31 | 华中科技大学 | Multi-element doped graphene fiber, and preparation and application thereof |
| CN111003703A (en) * | 2019-11-29 | 2020-04-14 | 杭州高烯科技有限公司 | Structure function integrated graphene material and preparation method thereof |
| CN114250529A (en) * | 2021-12-14 | 2022-03-29 | 浙江大学 | Aerogel fiber with specific section morphological characteristics and preparation method and device thereof |
| CN115341307A (en) * | 2022-09-23 | 2022-11-15 | 内蒙古大学 | High-orientation-degree graphene oxide fiber and preparation method thereof |
| WO2022265586A1 (en) * | 2021-06-19 | 2022-12-22 | National Science And Technology Development Agency | A method for preparing graphene oxide fibers by wet spinning |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050205847A1 (en) * | 2004-03-17 | 2005-09-22 | Anne Dailly | Methods for purifying carbon materials |
| 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 |
| CN103741264A (en) * | 2013-11-14 | 2014-04-23 | 南京新月材料科技有限公司 | Method for preparing graphene fibers through self-assembly of large lamellar graphene oxide |
-
2015
- 2015-12-27 CN CN201510993611.5A patent/CN105937066A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050205847A1 (en) * | 2004-03-17 | 2005-09-22 | Anne Dailly | Methods for purifying carbon materials |
| CN103741264A (en) * | 2013-11-14 | 2014-04-23 | 南京新月材料科技有限公司 | Method for preparing graphene fibers through self-assembly of large lamellar graphene oxide |
| 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110629325A (en) * | 2019-09-30 | 2019-12-31 | 华中科技大学 | Multi-element doped graphene fiber, and preparation and application thereof |
| CN111003703A (en) * | 2019-11-29 | 2020-04-14 | 杭州高烯科技有限公司 | Structure function integrated graphene material and preparation method thereof |
| WO2022265586A1 (en) * | 2021-06-19 | 2022-12-22 | National Science And Technology Development Agency | A method for preparing graphene oxide fibers by wet spinning |
| CN114250529A (en) * | 2021-12-14 | 2022-03-29 | 浙江大学 | Aerogel fiber with specific section morphological characteristics and preparation method and device thereof |
| CN114250529B (en) * | 2021-12-14 | 2023-08-22 | 浙江大学 | Aerogel fiber with specific cross-sectional morphological characteristics and preparation method and device thereof |
| CN115341307A (en) * | 2022-09-23 | 2022-11-15 | 内蒙古大学 | High-orientation-degree graphene oxide fiber and preparation method thereof |
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Application publication date: 20160914 |