CN107151835A - A kind of Flexible graphene fiber and its continuous preparation method - Google Patents
A kind of Flexible graphene fiber and its continuous preparation method Download PDFInfo
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- CN107151835A CN107151835A CN201710360799.9A CN201710360799A CN107151835A CN 107151835 A CN107151835 A CN 107151835A CN 201710360799 A CN201710360799 A CN 201710360799A CN 107151835 A CN107151835 A CN 107151835A
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- 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
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses a kind of Flexible graphene fiber and its continuous preparation method, this method is that (elongation at break is 20 50% by the graphene oxide band with both macro and micro fold, intensity is 20 200MPa) continuous flexible graphene oxide fiber is obtained through twisting, further obtain Flexible graphene fiber through reduction；It has good mechanical strength and excellent flexibility concurrently, while having good electric conductivity and heat conductivility；Its elongation at break is 10 100%, and intensity is 30 150MPa, and conductance is 2 × 104‑5×105S/m, thermal conductivity is 200 1000W/ (MK).This Flexible graphene fiber can be used for preparing graphene fabric, and advantage is taken with good.At apparel industry (electric heating clothes etc.), the multiple fields such as lightweight wire have important application.
Description
Technical field
The present invention relates to field of nano material preparation, particularly a kind of Flexible graphene fiber and its serialization preparation side
Method.
Background technology
Graphene is the two dimensional crystal material being made up of monoatomic layer, and it has excellent electric property, and (electronics is moved at room temperature
Shifting rate is up to 2 × 105cm2/ Vs), prominent heat conductivility 5000W/ (MK), extraordinary specific surface area (2630M2/ g), its poplar
Family name's modulus (1100GPa) and fracture strength (125GPa) etc. so that its application prospect is very wide.Stone is reported first within 2011
Since the preparation of black alkene fiber (Nat.Commun.2011,2,571), the preparation of graphene fiber and its functionalization turn into be worked as
Preceding study hotspot.Although the graphene fiber that has prepared at present, the graphene fiber of report it is flexible poor,
The graphene fiber (Adv.Mater.2016,28,6449) that intensity most reaches by force 2.2GPa is reported within 2016, but its stretching is disconnected
Elongation is split less than 1%, it is shown that excessively poor flexibility, it is virtually impossible to meet the requirement of fibrage.
Contrasted with the pure graphene fiber of the twisting of existing report, patent (application number：201510000105.1) main
If being based on CVD high temperature load graphene film under copper foil catalysis, graphene fiber is obtained through separating twisting；Patent (Shen
Please number：201510000113.6) mainly cut graphene oxide film, twist into graphene fiber；Patent
(201610049453.2,201610049310.1) are mainly based upon the graphene film winding reduced and obtain graphene fibre
Dimension.
Graphene film is a macroscopical application form of graphene.However, current Flexible graphene film is all based on drawing greatly
The contraction for the polymer-based end stretched controls the macroscopic view lying fold of graphene film or the surface texture based on substrate to prepare
The graphene film of corresponding construction.It is not that macroscopical graphene film, this fold are assembled by controlling the state of graphene monolithic
It is not spontaneous generation.In twisting process, the effect of stretching distortion can be produced, due to microcosmic monolithic during this film twisting processing
It is flexible poor, it is easy to produce defect, cause the overall intensity of fiber to decline serious.Importantly, tradition prepares graphite
The polymer-based bottom material of the method choice of alkene film fold, is pre-stretched or is surface-treated to polymer-based end due to needing,
It has suffered from very big limitation in application aspect.
The present invention is from the angle of two-dimentional macromolecular, based on poor solvent processing so that graphene oxide sheet is collapsed fold, piece
Mutually overlapped between piece, form physical crosslinking, occurred gelation, the graphene oxide gel band of self-supporting is obtained, through drying
The continuous oxidation graphene ribbon with abundant microcosmic and macrofold is obtained, it has fabulous flexibility, elongation at break 20
~50%；Flexible graphene oxide band obtains flexible stone through twisting into flexible graphene oxide fiber through reduction and post processing
Black alkene fiber.Therefore it is a kind of can high-efficiency and continuous prepare and have mechanical strength concurrently and flexible graphene fiber can more meet graphene
Fiber takes requirement, so as to more preferable large-scale application.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of Flexible graphene fiber and its serialization system
Preparation Method.
The purpose of the present invention is achieved through the following technical solutions：A kind of Flexible graphene fiber, the soft graphite
Alkene fiber, through twisting into flexible graphene oxide fiber, is further obtained after carrying out reduction by graphene oxide band；The oxidation stone
Black alkene band is mutually overlapped by the graphene oxide sheet of fold to be formed, and crystallinity is less than 60%.
A kind of continuous preparation method of Flexible graphene fiber, comprises the following steps：
(1) graphene oxide is dissolved in polar solvent, obtains graphene oxide liquid crystal solution, concentration is 1-30 mg/
mL。
(2) graphene oxide liquid crystal solution is extruded by the spinning die head of rectangle, and shape is solidified by poor solvent coagulating bath
Into the graphene oxide gel band of self-supporting.
(3) collect, dry through drying roll shaft, obtain continuous many fold graphene oxide bands.
(4) continuous oxidation graphene ribbon is twisted through twister, Flexible graphene fiber is obtained after reduction.
Further, in step 1, the polar solvent is selected from：DMF, water, 1-METHYLPYRROLIDONE,
One or more in dimethyl sulfoxide, DMA etc. are mixed by any proportioning.
Further, in step 2, poor solvent coagulating bath is selected from：Ethyl acetate, dichloromethane, alkanes, methanol, second
It is a kind of or many in alcohol, n-butanol, ethylene glycol, propane diols, glycerine, isobutanol, methyl acetate, butyl acetate, acetic acid etc.
Plant and mixed according to arbitrary proportion.
Further, can be by adjusting the gathering speed of roll shaft in step 3, it is 1 to obtain draw ratio:1 to 5:1, orientation
Graphene oxide band of the degree more than 50%, the intensity of highly oriented graphene oxide band is up to 200 MPa.
Further, in step 4, reduction mode is selected from electronation, thermal reduction, electroreduction etc..For example：By graphite oxide
Alkene fiber is immersed in hydriodic acid aqueous solution, in heating 5-24h at 70-100 DEG C.
Further, in addition to the Flexible graphene fiber obtained after reduction post-process, the post processing includes
Heat treatment, electroplating processes, starching is handled, and doping treatment etc. is one or more of to be handled simultaneously.
Further, the heat treatment is the processing such as heating, annealing；Electroplating processes mainly electroplate gold in fiber surface
Category, including gold, silver, copper etc.；Starching processing mainly coats polymeric coating layer in fiber surface；Doping treatment is mainly by logical
The elements such as the incorporation of overdoping technology K, Ca, Br, N, P, B, Li, Be, Na.For example：By graphene fiber through 3000 DEG C heat treatment
Obtain graphited graphene fiber.
Beneficial effects of the present invention：The present invention using good solvent and poor solvent interaction, construct with it is microcosmic,
The continuous graphite alkene band of macroscopical multistage fold, with fabulous flexibility, resistance to certain stretching and bending.And by this soft graphite
Alkene band twists into continuous flexible graphene oxide fiber, and Flexible graphene fiber is obtained through reduction and post processing.It has concurrently
Mechanical strength and elongation at break, while having excellent conduction and heat conductivility.After tested, its mechanical strength is up to 30-
150MPa, elongation at break is 10-100%, and conductance is 2X104-5X105S/m, thermal conductivity is 200-1000W/ (MK).It is this
Flexible graphene fiber can be used for preparing graphene fabric, in apparel industry (such as electric heating clothes), the multiple fields such as lightweight wire
With important application.
Brief description of the drawings
Fig. 1 flexibility continuous graphite alkene fibers prepare schematic diagram；
Flexible graphene oxide band SEM (A) and sectional view (B) that Fig. 2 is handled through poor solvent；
The outside drawing for the Flexible graphene fiber that Fig. 3 twisting is obtained；
The stress strain curve of Fig. 4 Flexible graphene fibers；
The I-V test charts of Fig. 5 Flexible graphene fibers；
Fig. 6 draw ratios are 1:2 flexible graphene oxide band；
Fig. 7 is the XRD of two kinds of fibers prepared by embodiment 4 and embodiment 5.
Embodiment
The present invention is raw material based on industrialized graphene oxide, using the gelling of poor solvent, continuous system
Standby to have microcosmic, macrofold Flexible graphene band, elongation at break 20-50%, intensity is 20-200MPa；Further plus
Sth. made by twisting obtains flexible graphene oxide fiber, obtains Flexible graphene fiber through reduction and post processing, after tested, its mechanical strength can
Up to 30-150MPa, elongation at break is 10-100%, and conductance is 2 × 104-5×105S/m, thermal conductivity is 200-1000W/
(MK).Which obviate precious metal high-temperature catalysis, it is to avoid the graphene fiber of film dividing twisting sufficient length difficult to realize
Shortcoming.The present invention can high-efficiency and continuous prepare and have mechanical strength concurrently and flexible graphene fiber can more meet graphene fiber
Requirement is taken, so as to more preferable large-scale application.
As shown in figure 1, the present invention extrudes graphene liquid crystal solution by rectangle spinning die head device, it is solidifying through poor solvent
Gu bath solidification, the good solvent of liquid GO films is replaced by poor solvent, causes graphene oxide sheet to shrink and cave in, GO pieces occur
Fold, mutually overlap joint, similar cross-linked polymer formation cross-linked network, so as to construct the GO bands of indefinite form (amorphous state), enter
One step is collected through drying roll shaft, dried, in the drying process, and poor solvent volatilization under capillarity, is sent out on macroscopic form
Raw fold again, so as to obtain continuous flexible graphene oxide band.This microcosmic and macroscopical multistage fold imparts graphene
Band has fabulous flexibility, resistance to certain stretching and bending.After tested, its crystallinity is less than 60%, even up to less than 30%,
Elongation at break 20~50%.Twisted by twister, reduction and post processing obtain Flexible graphene fiber.
Below in conjunction with the accompanying drawings and embodiment the invention will be further described, the present embodiment be served only for making the present invention into
The explanation of one step, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according in foregoing invention
Appearance makes some nonessential changes and adjustment, belongs to protection scope of the present invention.
Embodiment 1：
1st, concentration is placed in rectangle spinning die head device for 10mg/mL graphene oxide water solution and prepares continuous liquid
State graphene oxide band.
2nd, solidify to form graphene oxide gel band through ethyl acetate coagulating bath.
3rd, collected through dry roll shaft without drawing-off and obtain continuous flexible graphene oxide band (as shown in Figure 2).Wherein graphite
Alkene belt surface has very abundant pleated structure, while the bending fluctuation of sectional view also illustrate that graphene film is not regular accumulation
, it can thus be appreciated that graphene ribbon is comprehensive fold from inside to outside.The crystallinity of its band is 23%, and elongation at break is 18%,
Doubling repeatedly does not leave folding line more than 100,000 times.
4th, continuous graphene oxide band twists the graphene oxide fiber for obtaining flexibility (such as Fig. 3 institutes through twister
Show).
5th, graphene oxide fiber is washed drying, obtains graphene fiber through 80 DEG C of reduction 10h of hydriodic acid aqueous solution.
Its stress strain curve is as shown in figure 4, elongation at break about 85%, intensity about 60MPa.Its C-V curve is as shown in figure 5, conductance is
About 2.5 × 104S/m, thermal conductivity is 200W/ (MK).
Embodiment 2：
1st, concentration is placed in rectangle device for spinning for the 1-METHYLPYRROLIDONE solution of 5mg/mL graphene oxide and made
Standby continuous liquid oxidatively graphene ribbon.
2nd, graphene oxide gel band is formed through alcohol solidification bath solidification.
3rd, through drying roll shaft 1:2 drawing-offs are collected and obtain continuous graphene oxide band (as shown in Figure 6), the crystallinity of its film
For 40%, elongation at break is 18%, and doubling repeatedly does not leave folding line more than 100,000 times.
4th, continuous graphene oxide band twists obtained graphene oxide fiber through twister.
5th, graphene oxide fiber is washed drying, obtains graphene fiber through 85 DEG C of reduction 8h of hydriodic acid aqueous solution.
6th, after graphene fiber is handled via 3000 DEG C of high temperature graphitizations, its elongation at break about 40%, intensity is about
150MPa.Conductance is about 2 × 105S/m, thermal conductivity is 800W/ (MK).
Embodiment 3：
1st, the N,N-dimethylformamide solution by concentration for 15mg/mL graphene oxide is placed in rectangle device for spinning
Prepare continuous liquid oxidatively graphene fiber.
2nd, solidify to form graphene oxide gel band through n-butanol coagulating bath.
3rd, through drying roll shaft 1:1 drawing-off, which is collected, obtains continuous graphene oxide band, and its crystallinity is 21%, extension at break
Rate is 31%, and doubling repeatedly does not leave folding line more than 100,000 times.
4th, continuous graphene oxide band twists obtained graphene oxide fiber through twister.
5th, graphene oxide fiber is washed drying, obtains graphene fiber through 70 DEG C of reduction 15h of hydriodic acid aqueous solution.
6th, by graphene fiber via being wrapped up again through macromolecule (PS) coating after 3000 DEG C of high temperature graphitization processing, it is broken
Elongation about 100%, intensity about 110MPa.Conductance is about 1.5 × 105S/m, thermal conductivity is 600W/ (MK).
It can be seen that from above example 1-3 and prepare continuous graphene fiber through poor solvent gelation processing and have
Flexible well, elongation at break is up to 100%；Its intensity has also reached 150MPa simultaneously, can well meet and take volume
Knit requirement.
Embodiment 4：
1st, concentration is placed in rectangle spinning die head device for 15mg/mL graphene oxide DMF solution and prepares 20cm's
Liquid oxidatively graphene ribbon.
2nd, solidify to form graphene oxide gel band through ethyl acetate coagulating bath.
3rd, collected through dry roll shaft without drawing-off and obtain continuous flexible graphene oxide band, its crystallinity is 22%, mechanical
Elongation at break in tension test is 15%, and doubling repeatedly does not leave folding line more than 100,000 times.
4th, continuous graphene oxide band twists the graphene oxide fiber for obtaining flexibility through twister.
5th, graphene oxide fiber is washed drying, obtains Flexible graphene fine through 90 DEG C of reduction 10h of hydriodic acid aqueous solution
Dimension.Its elongation at break about 80%, intensity about 75MPa.
Embodiment 5：
1st, concentration is placed in preparation 20cm length in rectangle spinning die head device for 15mg/mL graphene oxide DMF solution
Liquid oxidatively graphene ribbon.
2nd, graphene oxide band is formed through direct 80 DEG C of dryings, its elongation at break is 2%, and crystallinity is 80%.
3rd, graphene oxide band obtains graphene oxide fiber through twister twisting.
4th, graphene oxide fiber is washed drying, obtains graphene fiber through 90 DEG C of reduction 10h of hydriodic acid aqueous solution.
Its elongation at break about 8%, intensity about 30MPa.
From embodiment 4 and embodiment 5 contrast as can be seen that via poor solvent gelation handle prepare have it is micro-
See, the graphene ribbon of macrofold has extraordinary flexible advantage, its corresponding graphene fiber obtained by twisting, reduction
Also good mechanical strength and flexibility are had concurrently.The elongation at break of another conventional graphene ribbon only has 2% or so, through twisting
Obtained graphene fiber is reduced also without flexible and mechanical strength well.Fig. 7 XRD diffraction comparison diagrams clearly illustrate
It is via the crystallinity of the graphene fiber of poor solvent immersion treatment very low.Because contraction of the graphene film in poor solvent
Fold and gel band are shunk in the drying process and can cause the macroshrinkage of graphene ribbon caused by solvent volatilization.And without
Poor solvent immersion treatment, which accumulates regular graphene fiber, has higher peak crystallization, similar to crystalline polymer.
Claims (8)
1. a kind of Flexible graphene fiber, it is characterised in that the Flexible graphene fiber is by graphene oxide band through twisting into
Flexible graphene oxide fiber, is further obtained after carrying out reduction；The graphene oxide band by fold graphene oxide sheet phase
Mutually overlap joint is formed, and crystallinity is less than 60%.
2. a kind of continuous preparation method of Flexible graphene fiber, it is characterised in that comprise the following steps：
(1) graphene oxide is dissolved in polar solvent, obtains graphene oxide liquid crystal solution, concentration is 1-30mg/mL.
(2) graphene oxide liquid crystal solution is extruded by the spinning die head of rectangle, solidifies to be formed certainly by poor solvent coagulating bath
The graphene oxide gel band of support.
(3) collect, dry through drying roll shaft, obtain continuous many fold graphene oxide bands.
(4) continuous oxidation graphene ribbon is twisted through twister, Flexible graphene fiber is obtained after reduction.
3. method as described in claim 2, it is characterised in that：In step 1, the polar solvent is selected from：N, N- dimethyl
One or more in formamide, water, 1-METHYLPYRROLIDONE, dimethyl sulfoxide, DMA etc. are by arbitrarily matching somebody with somebody
Than mixing.
4. method as described in claim 2, it is characterised in that：In step 2, poor solvent coagulating bath is selected from：Ethyl acetate,
Dichloromethane, alkanes, methanol, ethanol, n-butanol, ethylene glycol, propane diols, glycerine, isobutanol, methyl acetate, acetic acid fourth
One or more in ester, acetic acid etc. are mixed according to arbitrary proportion.
5. method as described in claim 2, it is characterised in that：In step 3, it can be obtained by adjusting the gathering speed of roll shaft
It is 1 to draw ratio:1 to 5:1, the degree of orientation is more than 50% graphene oxide band, and the intensity of highly oriented graphene oxide band can
Up to 200MPa.
6. method as described in claim 2, it is characterised in that：In step 4, reduction mode be selected from electronation, thermal reduction,
Electroreduction etc..For example：Graphene oxide fiber is immersed in hydriodic acid aqueous solution, in heating 5-24h at 70-100 DEG C.
7. method as claimed in claim 2, it is characterised in that also including being carried out to the Flexible graphene fiber obtained after reduction
Post processing, the post processing includes heat treatment, and electroplating processes, starching is handled, and doping treatment etc. is one or more of to be handled simultaneously.
8. method as claimed in claim 7, it is characterised in that：The heat treatment is the processing such as heating, annealing；Electroplating processes master
If electroplating metal, including gold, silver, copper etc. in fiber surface；Starching processing mainly coats polymeric coating layer in fiber surface；
Doping treatment is mainly by passing through the elements such as doping techniques incorporation K, Ca, Br, N, P, B, Li, Be, Na.For example：By graphite
Alkene fiber is thermally treated resulting in graphited graphene fiber through 3000 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710360799.9A CN107151835B (en) | 2017-05-19 | 2017-05-19 | A kind of Flexible graphene fiber and its continuous preparation method |
| PCT/CN2018/077328 WO2018210027A1 (en) | 2017-05-19 | 2018-02-27 | Flexible graphene fibers and continuous preparation method therefor |
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| CN107804839A (en) * | 2017-11-28 | 2018-03-16 | 航天特种材料及工艺技术研究所 | A kind of high resiliency graphene aerogel and preparation method thereof |
| CN108625161A (en) * | 2018-04-26 | 2018-10-09 | 五邑大学 | The method that graphene oxide is grafted fragrant fiber manufacture high temperature wire material |
| WO2018188420A1 (en) * | 2017-04-11 | 2018-10-18 | 杭州高烯科技有限公司 | Flexible graphene film and preparation method therefor |
| WO2018210027A1 (en) * | 2017-05-19 | 2018-11-22 | 杭州高烯科技有限公司 | Flexible graphene fibers and continuous preparation method therefor |
| CN109322009A (en) * | 2018-08-24 | 2019-02-12 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of graphene fiber and preparation method thereof of wet spinning preparation |
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| CN108625161A (en) * | 2018-04-26 | 2018-10-09 | 五邑大学 | The method that graphene oxide is grafted fragrant fiber manufacture high temperature wire material |
| CN109322009A (en) * | 2018-08-24 | 2019-02-12 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of graphene fiber and preparation method thereof of wet spinning preparation |
| CN110015659A (en) * | 2019-04-08 | 2019-07-16 | 杭州高烯科技有限公司 | A kind of continuous electric heating graphitization rolling equipment |
| CN111218732A (en) * | 2020-03-06 | 2020-06-02 | 杭州高烯科技有限公司 | Preparation method of graphene twisted fiber |
| CN112127030A (en) * | 2020-09-22 | 2020-12-25 | 杭州高烯科技有限公司 | Preparation method of twisted self-fused graphene fiber |
| CN112522796A (en) * | 2020-11-13 | 2021-03-19 | 浙江大学 | Nano fiber and preparation method thereof |
| CN112522796B (en) * | 2020-11-13 | 2021-09-28 | 浙江大学 | Nano fiber and preparation method thereof |
| CN115233338A (en) * | 2022-08-04 | 2022-10-25 | 浙江大学 | Preparation method of graphene material |
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| WO2018210027A1 (en) | 2018-11-22 |
| CN107151835B (en) | 2019-07-23 |
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