CN107151835B - 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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- CN107151835B CN107151835B CN201710360799.9A CN201710360799A CN107151835B CN 107151835 B CN107151835 B CN 107151835B CN 201710360799 A CN201710360799 A CN 201710360799A CN 107151835 B CN107151835 B CN 107151835B
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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
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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
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- 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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a kind of Flexible graphene fiber and its continuous preparation methods, this method is graphene oxide band (the elongation at break 20-50% that will have both macro and micro fold, intensity is 20-200MPa) continuous flexible graphene oxide fiber is obtained through twisting, further Flexible graphene fiber is obtained through reduction；It has both good mechanical strength and excellent flexibility, while having good electric conductivity and heating conduction；Its elongation at break is 10-100%, and intensity 30-150MPa, conductivity is 2 × 104‑5×105S/m, thermal conductivity are 200-1000W/ (MK).This Flexible graphene fiber can be used for preparing graphene fabric, take advantage 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, especially a kind of Flexible graphene fiber and its serialization preparation side
Method.
Background technique
Graphene is the two dimensional crystal material being made of monoatomic layer, and having excellent electric property, (electronics moves at room temperature
Shifting rate is up to 2 × 105cm2/ Vs), heating conduction 5000W/ (MK) outstanding, extraordinary specific surface area (2630M2/ g), poplar
Family name's modulus (1100GPa) and breaking strength (125GPa) etc., so that its application prospect is very wide.Stone is reported for the first time within 2011
Since the preparation of black alkene fiber (Nat.Commun.2011,2,571), the preparation of graphene fiber and its functionalization have become and work as
Preceding research hotspot.Although having the graphene fiber being prepared at present, the flexibility of the graphene fiber of report is poor,
The graphene fiber (Adv.Mater.2016,28,6449) that intensity most reaches by force 2.2GPa is reported within 2016, but it stretches and breaks
Elongation is split less than 1%, it is shown that excessively poor flexibility, it is virtually impossible to meet the requirement of fibrage.
Pure graphene fiber comparison made of twisting with existing report, patent (application number: 201510000105.1) main
If being based on CVD method high temperature load graphene film under copper foil catalysis, graphene fiber is obtained through separation twisting；Patent (Shen
Please number: 201510000113.6) mainly graphene oxide film is cut, twist at graphene fiber；Patent
(201610049453.2,201610049310.1) are mainly based upon the graphene film restored and wind to obtain graphene fibre
Dimension.
Graphene film is a macroscopical application form of graphene.However, current Flexible graphene film is all based on greatly drawing
The contraction of the polymer-based end stretched controls the macroscopic view lying fold of graphene film or prepared by the surface texture based on substrate
The graphene film of corresponding construction.It is not to assemble macroscopical graphene film, this fold by controlling the state of graphene monolithic
It is not spontaneous generation.In twisting process, the effect for stretching distortion can be generated, due to microcosmic monolithic when this film twisting is handled
Flexibility it is poor, it is easy to generate defect, cause fiber entirety intensity decline seriously.Importantly, tradition prepares graphite
The polymer-based bottom material of the method choice of alkene film fold, due to needing is pre-stretched polymer-based end or is surface-treated,
It has suffered from very big limitation in application aspect.
The present invention is handled, the fold so that graphene oxide sheet is collapsed, piece from the angle of two-dimentional macromolecular based on poor solvent
It is mutually overlapped between piece, forms physical crosslinking, gelation occurs, the graphene oxide gel band of self-supporting is obtained, through drying
It has obtained with the continuous oxidation graphene ribbon for enriching micro and macro fold, with fabulous flexibility, elongation at break 20
~50%；Graphene oxide band flexible is twisted into flexible graphene oxide fiber, is restored and post-processing obtains flexible stone
Black alkene fiber.Therefore one kind can high-efficiency and continuous preparation have both mechanical strength and graphene fiber flexible is more able to satisfy graphene
Fiber takes requirement, so as to better large-scale application.
Summary 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 what is be achieved through the following technical solutions: a kind of Flexible graphene fiber, the soft graphite
Alkene fiber is twisted into flexible graphene oxide fiber by graphene oxide band, is further obtained after carrying out reduction；The oxidation stone
Black alkene band is mutually formed by overlapping by the graphene oxide sheet of fold, and crystallinity is lower than 60%.
A kind of continuous preparation method of Flexible graphene fiber, comprising 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 squeezed out by the spinning die head of rectangle, solidifies shape by poor solvent coagulating bath
At the graphene oxide gel band of self-supporting.
(3) it is collected through dry roll shaft, is dry, obtaining continuous more 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: n,N-Dimethylformamide, water, N-Methyl pyrrolidone,
Dimethyl sulfoxide, one or more of n,N-dimethylacetamide etc. are mixed by any proportion.
Further, in step 2, poor solvent coagulating bath is selected from: ethyl acetate, methylene chloride, alkanes, methanol, second
Alcohol, n-butanol, ethylene glycol, propylene glycol, glycerine, isobutanol, methyl acetate, butyl acetate, one of acetic acid etc. or more
Kind is mixed according to arbitrary proportion.
Further, can be by the gathering speed of adjusting roll shaft in step 3, obtaining draw ratio is 1:1 to 5:1, orientation
Degree is greater than 50% graphene oxide band, and 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..Such as: by graphite oxide
Alkene fiber is immersed in hydriodic acid aqueous solution, heats 5-24h at 70-100 DEG C.
It further, further include being post-processed to the Flexible graphene fiber obtained after reduction, the post-processing includes
Heat treatment, electroplating processes, starching processing, the one or more such as doping treatment are handled simultaneously.
Further, the heat treatment is the processing such as heating, annealing；Electroplating processes are mainly in fiber surface electroplating gold
Belong to, including gold, silver, copper etc.；Starching processing mainly coats polymeric coating layer in fiber surface；Doping treatment mainly passes through logical
Overdoping technology mixes K, Ca, Br, N, P, B, Li, the elements such as Be, Na.Such as: by graphene fiber through 3000 DEG C be heat-treated
Obtain graphited graphene fiber.
Beneficial effects of the present invention: the present invention utilize good solvent and poor solvent interaction, construct with it is microcosmic,
The continuous graphite alkene band of macroscopical multistage fold, has fabulous flexibility, resistance to certain stretching and bending.And by this soft graphite
The twisting of alkene band is restored at continuous flexible graphene oxide fiber and post-processing obtains Flexible graphene fiber.It has both
Mechanical strength and elongation at break, while there is excellent conduction and heating conduction.After tested, mechanical strength is up to 30-
150MPa, elongation at break 10-100%, conductivity 2X104-5X105S/m, thermal conductivity are 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.
Detailed description of the invention
Fig. 1 flexibility continuous graphite alkene fiber prepares schematic diagram；
Flexible graphene oxide band SEM (A) and the sectional view (B) that Fig. 2 is handled through poor solvent；
The outside drawing for the Flexible graphene fiber that Fig. 3 is twisted；
The stress strain curve of Fig. 4 Flexible graphene fiber；
The I-V test chart of Fig. 5 Flexible graphene fiber；
Fig. 6 draw ratio is the flexible graphene oxide band of 1:2；
Fig. 7 is the XRD diagram of two kinds of fibers prepared by embodiment 4 and embodiment 5.
Specific embodiment
It is raw material the present invention is based on industrialized graphene oxide, it is continuous to make using the gelling of poor solvent
It is standby that there is microcosmic, macrofold Flexible graphene band, elongation at break 20-50%, intensity 20-200MPa；Further plus
Twirl obtains flexible graphene oxide fiber, is restored and post-processing obtains Flexible graphene fiber, after tested, mechanical strength can
Up to 30-150MPa, elongation at break 10-100%, conductivity is 2 × 104-5×105S/m, thermal conductivity 200-1000W/
(MK).Which obviate precious metal high-temperature catalysis, avoid film dividing and twist the graphene fiber for being difficult to realize sufficient length
Disadvantage.The present invention can high-efficiency and continuous preparation have both mechanical strength and graphene fiber flexible is more able to satisfy graphene fiber
Requirement is taken, so as to better large-scale application.
As shown in Figure 1, the present invention squeezes out 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 film are replaced by poor solvent, graphene oxide sheet is caused to shrink collapsing, GO piece occurs
Fold mutually overlaps, and similar cross-linked polymer forms cross-linked network, so that the GO band of indefinite form (amorphous state) is constructed, into
One step collects through dry roll shaft, is dry, and in the drying process, poor solvent volatilization under capillarity, is sent out on macroscopic form
Raw fold again, to obtain continuous flexible graphene oxide band.This micro and macro multistage fold imparts graphene
Band has fabulous flexibility, resistance to certain stretching and bending.After tested, crystallinity be lower than 60%, even up to 30% hereinafter,
Elongation at break 20~50%.It is twisted by twister, reduction and post-processing obtain Flexible graphene fiber.
The invention will be further described with reference to the accompanying drawings and embodiments, the present embodiment be served only for making the present invention into
The explanation of one step should not be understood as limiting the scope of the invention, and those skilled in the art is according in foregoing invention
Appearance makes some nonessential changes and adjustment, all belongs to the scope of protection of the present invention.
Embodiment 1:
1, the graphene oxide water solution that concentration is 10mg/mL is placed in rectangle spinning die head device and prepares continuous liquid
State graphene oxide band.
2, it solidifies to form graphene oxide gel band through ethyl acetate coagulating bath.
3, it collects to obtain continuous flexible graphene oxide band (as shown in Figure 2) without drawing-off through dry roll shaft.Wherein graphite
Alkene belt surface has pleated structure very abundant, while it is regular accumulation that the bending fluctuation of sectional view, which also illustrates graphene film not,
, it can thus be appreciated that graphene ribbon is comprehensive fold from inside to outside.The crystallinity of its band is 23%, elongation at break 18%,
Repeatedly folding line is not left doubling 100,000 times or more.
4, continuous graphene oxide band twists to obtain graphene oxide fiber flexible (such as Fig. 3 institute through twister
Show).
5, 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, conductivity is
About 2.5 × 104S/m, thermal conductivity are 200W/ (MK).
Embodiment 2:
1, the N-Methyl pyrrolidone solution for the graphene oxide that concentration is 5mg/mL is placed in rectangle device for spinning and is made
Standby continuous liquid oxidatively graphene ribbon.
2, graphene oxide gel band is formed through alcohol solidification bath solidification.
3, it collects to obtain continuous graphene oxide band (as shown in Figure 6), the crystallinity of film through dry roll shaft 1:2 drawing-off
It is 40%, elongation at break 18% does not leave folding line doubling 100,000 times or more repeatedly.
4, the graphene oxide fiber that continuous graphene oxide band is twisted through twister.
5, graphene oxide fiber is washed drying, obtains graphene fiber through 85 DEG C of reduction 8h of hydriodic acid aqueous solution.
6, after handling graphene fiber via 3000 DEG C of high temperature graphitizations, elongation at break about 40%, intensity is about
150MPa.Conductivity is about 2 × 105S/m, thermal conductivity are 800W/ (MK).
Embodiment 3:
1, the N,N-dimethylformamide solution for the graphene oxide that concentration is 15mg/mL is placed in rectangle device for spinning
Prepare continuous liquid oxidatively graphene fiber.
2, it solidifies to form graphene oxide gel band through n-butanol coagulating bath.
3, it collects to obtain continuous graphene oxide band, crystallinity 21%, extension at break through dry roll shaft 1:1 drawing-off
Rate is 31%, does not leave folding line doubling 100,000 times or more repeatedly.
4, the graphene oxide fiber that continuous graphene oxide band is twisted through twister.
5, graphene oxide fiber is washed drying, obtains graphene fiber through 70 DEG C of reduction 15h of hydriodic acid aqueous solution.
6, it is wrapped up again through macromolecule (PS) coating after handling graphene fiber via 3000 DEG C of high temperature graphitizations, fracture
Elongation about 100%, intensity about 110MPa.Conductivity is about 1.5 × 105S/m, thermal conductivity are 600W/ (MK).
It can be seen that from above embodiments 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 meet well and take volume
Knit requirement.
Embodiment 4:
1, the graphene oxide DMF solution that concentration is 15mg/mL is placed in rectangle spinning die head device and prepares 20cm's
Liquid oxidatively graphene ribbon.
2, it solidifies to form graphene oxide gel band through ethyl acetate coagulating bath.
3, it collects to obtain continuous flexible graphene oxide band without drawing-off through dry roll shaft, crystallinity 22% is mechanical
Elongation at break in tension test is 15%, does not leave folding line doubling 100,000 times or more repeatedly.
4, continuous graphene oxide band twists to obtain graphene oxide fiber flexible through twister.
5, graphene oxide fiber is washed into drying through 90 DEG C of reduction 10h of hydriodic acid aqueous solution, obtains Flexible graphene fibre
Dimension.Its elongation at break about 80%, intensity about 75MPa.
Embodiment 5:
1, the graphene oxide DMF solution that concentration is 15mg/mL is placed in preparation 20cm long in rectangle spinning die head device
Liquid oxidatively graphene ribbon.
2, graphene oxide band, elongation at break 2%, crystallinity 80% are formed through direct 80 DEG C of dryings.
3, graphene oxide band twists to obtain graphene oxide fiber through twister.
4, 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 comparison as can be seen that via poor solvent gelation processing be prepared have it is micro-
It sees, the graphene ribbon of macrofold has extraordinary flexible advantage, the corresponding graphene fiber obtained by twisting, reduction
Also good mechanical strength and flexibility are had both.The elongation at break of another conventional graphene ribbon only has 2% or so, through twisting
It restores obtained graphene fiber and does not also have flexible and mechanical strength well.The XRD diffraction comparison diagram of Fig. 7 clearly illustrates
It is via the crystallinity of the graphene fiber of poor solvent immersion treatment very low.Because of contraction of the graphene film in poor solvent
Fold and gel band shrink the macroshrinkage that will lead to graphene ribbon caused by solvent volatilization in the drying process.And without
Poor solvent immersion treatment accumulates regular graphene fiber peak crystallization with higher, is similar to crystalline polymer.
Claims (7)
1. a kind of continuous preparation method of Flexible graphene fiber, which comprises the following steps:
(1) graphene oxide is dissolved in polar solvent, obtains graphene oxide liquid crystal solution, concentration 1-30mg/mL；
(2) graphene oxide liquid crystal solution is squeezed out 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) it is collected through dry roll shaft, is dry, obtaining continuous more fold graphene oxide bands；
(4) continuous oxidation graphene ribbon is twisted through twister, Flexible graphene fiber is obtained after reduction.
2. method as described in claim 1, it is characterised in that: in step 1, the polar solvent is selected from: N, N- dimethyl
Formamide, water, N-Methyl pyrrolidone, dimethyl sulfoxide, one or more of n,N-dimethylacetamide press any proportion
It mixes.
3. method as described in claim 1, it is characterised in that: in step 2, poor solvent coagulating bath is selected from: ethyl acetate,
Methylene chloride, alkanes, methanol, ethyl alcohol, n-butanol, ethylene glycol, propylene glycol, glycerine, isobutanol, methyl acetate, acetic acid fourth
Ester, one or more of acetic acid are mixed according to arbitrary proportion.
4. method as described in claim 1, it is characterised in that: in step 3, can be obtained by the gathering speed of adjusting roll shaft
It is 1:1 to 5:1 to draw ratio, the degree of orientation is greater than 50% graphene oxide band, and the intensity of highly oriented graphene oxide band can
Up to 200MPa.
5. method as described in claim 1, it is characterised in that: in step 4, reduction mode be selected from electronation, thermal reduction,
Electroreduction.
6. the method as described in claim 1, which is characterized in that further include being carried out to the Flexible graphene fiber obtained after reduction
Post-processing, the post-processing include heat treatment, and the one or more of electroplating processes, starching processing, doping treatment are handled simultaneously.
7. method as claimed in claim 6, it is characterised in that: the heat treatment is heating, annealing；Electroplating processes be
Fiber surface plating metal, including gold, silver, copper；Starching processing is to coat polymeric coating layer in fiber surface；Doping treatment is logical
Overdoping technology mixes K, Ca, Br, N, P, B, Li, Be, Na element.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN201710360799.9A CN107151835B (en) | 2017-05-19 | 2017-05-19 | A kind of Flexible graphene fiber and its continuous preparation method |
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| CN107151835B true CN107151835B (en) | 2019-07-23 |
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| RU2742409C1 (en) * | 2017-04-11 | 2021-02-05 | Ханчжоу Гаоси Технолоджи Ко., Лтд. | Flexible graphene film and method for its production |
| CN107151835B (en) * | 2017-05-19 | 2019-07-23 | 杭州高烯科技有限公司 | A kind of Flexible graphene fiber and its continuous preparation method |
| CN107502995B (en) * | 2017-08-08 | 2019-08-16 | 杭州高烯科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
| CN107804839B (en) * | 2017-11-28 | 2019-12-10 | 航天特种材料及工艺技术研究所 | High-elasticity 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 |
| 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 |
| CN110015659B (en) * | 2019-04-08 | 2020-11-10 | 杭州高烯科技有限公司 | Continuous electric heating graphitization rolling equipment |
| KR102695190B1 (en) * | 2019-11-05 | 2024-08-13 | 한국전기연구원 | Method for producing conductive graphene fibers using high heat resistant graphene oxide and conductive graphene fibers prepared using the same |
| 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 |
| CN112522796B (en) * | 2020-11-13 | 2021-09-28 | 浙江大学 | Nano fiber and preparation method thereof |
| CN115233338B (en) * | 2022-08-04 | 2024-04-30 | 浙江大学 | Preparation method of graphene material |
| CN115748234A (en) * | 2022-11-21 | 2023-03-07 | 浙江大学 | Preparation method of high-strength graphene material |
| CN116281986B (en) * | 2023-04-17 | 2024-10-29 | 华能新能源股份有限公司 | Preparation method, drafting device and application of three-dimensional graphene |
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| US20140050920A1 (en) * | 2012-08-14 | 2014-02-20 | Nthdegree Technologies Worldwide Inc. | Graphene-Based Threads, Fibers or Yarns with Nth-Order Layers and Twisting and Methods of Fabricating Same |
| CN104219797B (en) * | 2014-09-10 | 2016-01-06 | 浙江碳谷上希材料科技有限公司 | A kind of Graphene Electric radiant Heating Film |
| CN105803602B (en) * | 2015-01-02 | 2018-03-09 | 中原工学院 | The method that the graphene film twisting method of forming prepares graphene fiber |
| CN105803587B (en) * | 2015-01-02 | 2017-11-07 | 中原工学院 | The method that the tape casting prepares graphene fiber |
| US10875986B2 (en) * | 2015-01-05 | 2020-12-29 | The Boeing Company | Graphene fiber for aerospace composites |
| CN105544016B (en) * | 2016-01-25 | 2018-02-09 | 浙江碳谷上希材料科技有限公司 | A kind of super stretchable highly conductive graphene fiber and preparation method thereof |
| CN105648579A (en) * | 2016-03-31 | 2016-06-08 | 浙江大学 | Superfine graphene fibers and method for preparing same |
| CN106702731B (en) * | 2016-12-26 | 2019-08-20 | 浙江大学 | A kind of graphene-silver composite fibre and preparation method thereof |
| CN107151835B (en) * | 2017-05-19 | 2019-07-23 | 杭州高烯科技有限公司 | A kind of Flexible graphene fiber and its continuous preparation method |
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| WO2018210027A1 (en) | 2018-11-22 |
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