CN107502995B - Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof - Google Patents
Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof Download PDFInfo
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- CN107502995B CN107502995B CN201710670077.3A CN201710670077A CN107502995B CN 107502995 B CN107502995 B CN 107502995B CN 201710670077 A CN201710670077 A CN 201710670077A CN 107502995 B CN107502995 B CN 107502995B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 114
- 239000000835 fiber Substances 0.000 title claims abstract description 92
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000009987 spinning Methods 0.000 claims description 10
- 238000002166 wet spinning Methods 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 238000009825 accumulation Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 2
- 229930003268 Vitamin C Natural products 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 claims description 2
- 230000002950 deficient Effects 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 235000019154 vitamin C Nutrition 0.000 claims description 2
- 239000011718 vitamin C Substances 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 239000012279 sodium borohydride Substances 0.000 claims 1
- 229910000033 sodium borohydride Inorganic materials 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
- D01F11/16—Chemical after-treatment of artificial filaments or the like during manufacture of carbon by physicochemical methods
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Nonwoven Fabrics (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of graphene fiber with pleated structure and graphene fiber non-woven fabrics and preparation method thereof, contain the micro-structure of a large amount of folds in the graphene fiber surface, and it can be used for constituting more pleated structure graphene fiber non-woven fabrics, so that the specific surface area of non-woven fabrics is significantly increased, and graphene fiber and the connected network structure being made of fiber while electric conductivity with higher and flexibility, therefore can be used as flexible electrode material and be applied in wearable energy storage device.
Description
Technical field
The present invention relates to graphite made of graphene fiber and fabric more particularly to a kind of graphene film accumulation as fold
Alkene fiber and graphene fiber non-woven fabrics and preparation method thereof.
Background technique
Graphene fiber non-woven fabrics is a kind of novel non-woven fabrics fabric (Nature being made of graphene fiber
Communications, 2016,13684), due to realizing graphene fiber merging into each other in lap-joint, so that this nothing
Woven fabric material has the excellent performances such as conductive, thermally conductive, to fully demonstrate the good characteristic of graphene on a macroscopic scale
(Science,2004,306:666-669).Have benefited from the highly conductive network structure that graphene fiber non-woven fabrics is presented, it will
It has great application potential in the energy storage devices such as capacitor and battery field as textile electrode flexible.
Existing graphene fiber non-woven fabrics is flexible preferably, and electric conductivity is high, however forms the graphene fiber of non-woven fabrics
Surface micro-structure is less, when being used as the electrode material of supercapacitor since active surface area is smaller, significantly limits electricity
The specific capacitance value of container.If can be by special means in a large amount of micro-structure of graphene fiber surface construction, significantly to increase
Add the specific surface area of fiber, the electric double layer capacitance of graphene fiber non-woven fabrics electrode can be greatly promoted, obtain higher performance
Energy storage device.Currently, the graphene fiber non-woven fabrics with multilevel structure is not seen in report.
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 the graphene fiber and graphene fibre of a kind of fold
Tie up non-woven fabrics and preparation method thereof.
The invention is realized by the following technical scheme: a kind of graphene fiber of fold, is accumulated by the graphene film of fold
It forms, the pleated structure of the graphene film has defective graphene film and formed under capillary forces.
A kind of preparation method of graphene fiber, comprising the following steps:
(1) continuous wet spinning is carried out by spinning solution of graphene oxide dispersion.
(2) obtained graphene oxide fiber is being placed at room temperature for 12h or more, then not higher than 80 DEG C at a temperature of it is true
The dry 3h of sky.
(3) sufficiently dry graphene oxide fiber is immersed in the water heating kettle equipped with water and carries out hydro-thermal process, hydro-thermal
The temperature range of processing is 80-200 DEG C.
(4) graphene fiber as made of the graphene oxide sheet accumulation of fold is obtained after air drying.
Further, spinning solution is the aqueous solution or n,N-Dimethylformamide solution of graphene oxide.It is corresponding, it spins
The coagulating bath that silk process uses is calcium chloride/water/alcohol mixeding liquid or ethyl acetate.
A kind of High-performance graphene fabric nonwoven cloth, is mutually overlapped by graphene fiber and forms network, at grid node
Graphene fiber mutually merges.
A kind of preparation method of High-performance graphene fabric nonwoven cloth, (1) using graphene oxide dispersion as spinning solution into
The continuous wet spinning of row；(2) obtained graphene oxide fiber is placed at room temperature for 12h or more, is then not higher than 80 DEG C
At a temperature of be dried in vacuo 3h；(3) sufficiently dry graphene oxide fiber is immersed in the water heating kettle equipped with water and carries out hydro-thermal
Processing, the temperature range of hydro-thermal process are 80-200 DEG C；It (4) will be after hydro-thermal process in step 3 using high shear homomixer
Graphene fiber blends into the staple fiber that length is 1-7mm in aqueous solution, then after filter deposited thereon, air drying
To graphene fiber non-woven fabrics.
Further, the revolving speed of high shear agitation is 3000-8000rpm.
Further, this method further includes that the graphene fiber non-woven fabrics after drying further is restored.Reduction side
Method is that reduction or 100-3000 DEG C of thermal reduction are carried out using chemical reducing agents such as hydroiodic acid, hydrazine hydrate, Vitamin C, sodium borohydrides.
Compared with the prior art, the present invention has the following beneficial effects:
(1) graphene fiber is accumulated by the graphene film of fold, significantly increases specific surface area, has bigger work
Property surface, is conducive to its application in textile electrode.
(2) flexibility that graphene fiber non-woven fabrics is maintained while obtaining fiber surface multilevel structure, can wear in flexibility
Energy storage device field is worn to be with a wide range of applications.
(3) preparation method is simple, and the micro-structure of fiber surface can pass through fiber predrying temperature and hydro-thermal process temperature
Controllable adjustment is realized in variation.
Detailed description of the invention
Fig. 1 is electron scanning micrograph of the fold graphene fiber under different amplification.
Fig. 2 is the forming process schematic diagram (a) and the scanning electron microscope (SEM) photograph in each stage (b~e) of fold graphene fiber；
Fig. 3 is schematic diagram (b) at the schematic diagram (a) and fusion of fold graphene fiber non-woven fabrics.
Specific embodiment
The present invention takes full advantage of the hydrophily of graphene oxide, impregnates graphene oxide molten by absorbing water afterwards in water
Swollen effect assigns graphene sheet layer and is conducive to the formation of pleated structure with certain freedom degree, and uses the lower water of temperature
It is heat-treated the building that micro-structure is carried out to graphene fiber, low energy consumption, and method is simple.In hydro-thermal process by graphite oxide
The reduction (removing of oxygenated functional group) of alkene lamella introduces defect in graphene sheet layer, provides answering for pleated structure formation
Power centrostigma.Graphene fiber spontaneously dries in air after hydro-thermal process, and the volatilization of the aqueous solvent contained in fiber forms huge
Big capillary force forms micro-structure on graphene fiber surface and inside so that graphene sheet layer spontaneously produces fold,
Dramatically increase the specific surface area of graphene fiber.Detailed process is as shown in Figure 2.
Above-mentioned fiber is mutually fused into network structure, constitutes pure graphene non-woven fabrics, as shown in figure 3, guaranteeing non-woven fabrics
The specific surface area of graphene fiber non-woven fabrics has been obviously improved while high conductivity.Based on features above, multistage of the invention
Pleated structure graphene fiber and graphene fiber non-woven fabrics are being used as textile electrode Shi Keling energy storage device with high flexibility
Excellent chemical property is obtained simultaneously, is hopeful to be applied in wearable electronic devices field.
The present invention is specifically described below by embodiment, the present embodiment is served only for doing further the present invention
It is bright, it should not be understood as limiting the scope of the invention, those skilled in the art makes one according to the content of foregoing invention
A little nonessential changes and adjustment, all belong to the scope of protection of the present invention.
Embodiment 1:
(1) using concentration for 5mg/mL graphene oxide/aqueous solution as spinning solution, calcium chloride/water/alcohol mixeding liquid (matter
Amount is than 20:300:100) it is that coagulating bath carries out continuous wet spinning.
(2) obtained graphene oxide fiber is being placed at room temperature for 12h, then 80 DEG C at a temperature of be dried in vacuo 3h.
(3) sufficiently dry graphene oxide fiber is immersed in the water heating kettle equipped with water and carries out hydro-thermal process, handled
Condition is 200 DEG C, 12h.
(4) more fold graphene fibers are obtained after air drying.
By above step, obtained graphene fiber has apparent pleated structure, and fibre strength about 90MPa is conductive
Rate is 102S/m.
Embodiment 2:
(1) using concentration for 5mg/mL graphene oxide/n,N-Dimethylformamide solution as spinning solution, ethyl acetate is
Coagulating bath carries out continuous wet spinning.
(2) obtained graphene oxide fiber is placed at room temperature for 14h, 60 DEG C of vacuum drying 3h.
(3) sufficiently dry graphene oxide fiber is immersed in the water heating kettle equipped with water and carries out hydro-thermal process, handled
Condition is 150 DEG C, 12h.
(4) graphene fiber after hydro-thermal process is blended by growth with the revolving speed of 3000rpm using high shear homomixer
Degree is the staple fiber of 4mm, and obtains graphene fiber non-woven fabrics after filter deposited thereon, air drying.
By above step, obtained graphene fiber non-woven fabrics has multilevel structure, and graphene fiber rough surface contains
There is the micro-structure of a large amount of fold and protrusion, specific surface area reaches 190m2/ g, conductivity 80S/m, and the nonwoven cloth material is flexible
Preferably, tolerance repeatedly bends and keeps stable structure.
Embodiment 3:
(1) using concentration for 15mg/mL graphene oxide water solution as dispersion liquid, calcium chloride/water/alcohol mixeding liquid is solidifying
Gu bath carries out continuous wet spinning.
(2) obtained graphene oxide fiber is placed at room temperature for 15h, 100 DEG C of vacuum drying 3h.
(3) sufficiently dry graphene oxide fiber is immersed in the water heating kettle equipped with water and carries out hydro-thermal process, handled
Condition is 80 DEG C, 12h.
(4) graphene fiber after hydro-thermal process is blended into the revolving speed of 5000rpm using high shear homomixer short
Fiber, and the graphene fiber non-woven fabrics of multilevel structure is obtained after filter deposited thereon, air drying.
(5) further electronation is carried out using hydrazine hydrate to the graphene fiber non-woven fabrics after drying.
By above step, obtained graphene fiber non-woven fabrics has multistage pleated structure, but due to preheating in step 2
Drying temperature is excessively high, reduces the hydrophily of graphene fiber, so that final graphene fiber surface folding degree is not high, fiber
Surface micro-structure is mostly to be distributed loose strip ridge projections.The specific surface area of non-woven fabrics is 63m2/ g, conductivity 88S/m.
Embodiment 4:
Further reduction of the step 1-4 with embodiment 1, without step 5.Gained graphene fiber non-woven fabrics has multistage
Pleated structure, conductivity 1.2S/m.
Embodiment 5:
Step 1 are as follows: using concentration for 5mg/mL graphene oxide/n,N-Dimethylformamide solution as spinning solution, acetic acid
Ethyl ester is that coagulating bath carries out continuous wet spinning.
Step 2-5 is the same as embodiment 2.
Two pieces of equal areas (~0.8cm are taken after obtaining more fold graphene non-woven fabrics2) non-woven fabrics as super capacitor
The positive and negative electrode of device, using filter paper as diaphragm between two-stage, 1MH2SO4Solution is assembled into supercapacitor as electrolyte.Through surveying
Examination, the supercapacitor quality specific capacitance based on more fold graphene non-woven fabrics are up to 244F/g (current density 1A/g),
Area specific capacitance is up to 1060mF/cm2(current density 1mA/cm2), show higher electro-chemical activity.
Claims (7)
1. a kind of preparation method of graphene fiber, which comprises the following steps:
(1) continuous wet spinning is carried out by spinning solution of graphene oxide dispersion；
(2) obtained graphene oxide fiber is being placed at room temperature for 12 h or more, then in the at a temperature of vacuum not higher than 80 DEG C
Dry 3h；
(3) sufficiently dry graphene oxide fiber is immersed in the water heating kettle equipped with water and carries out hydro-thermal process, hydro-thermal process
Temperature range be 80-200 DEG C；
(4) graphene fiber as made of the graphene film accumulation of fold is obtained after air drying；
The graphene fiber is accumulated by the graphene film of fold, and the pleated structure of the graphene film is with defect
Graphene film under capillary forces formed.
2. the method according to claim 1, wherein spinning solution is the aqueous solution or N of graphene oxide, N- diformazan
Base formamide solution；The coagulating bath that spinning process uses is calcium chloride/water/alcohol mixeding liquid or ethyl acetate.
3. a kind of preparation method of High-performance graphene fabric nonwoven cloth, which is characterized in that
(1) continuous wet spinning is carried out by spinning solution of graphene oxide dispersion；
(2) obtained graphene oxide fiber is being placed at room temperature for 12 h or more, then in the at a temperature of vacuum not higher than 80 DEG C
Dry 3h；
(3) sufficiently dry graphene oxide fiber is immersed in the water heating kettle equipped with water and carries out hydro-thermal process, hydro-thermal process
Temperature range be 80-200 DEG C；
(4) graphene fiber after hydro-thermal process in step (3) is blended into growth in aqueous solution using high shear homomixer
Degree is the staple fiber of 1-7mm, then obtains graphene fiber non-woven fabrics after filter deposited thereon, air drying.
4. according to the method described in claim 3, it is characterized in that, the revolving speed of high shear agitation is 3000-8000 rpm.
5. according to the method described in claim 3, it is characterized in that, this method further includes the graphene fiber nonwoven after drying
Cloth is further restored；Restoring method is that chemical reducing agent carries out reduction or 100-3000 DEG C of thermal reduction.
6. according to the method described in claim 5, it is characterized in that, the chemical reducing agent is hydroiodic acid, hydrazine hydrate, vitamin
C, sodium borohydride.
7. a kind of High-performance graphene fabric nonwoven cloth that preparation method as claimed in claim 4 obtains, which is characterized in that described
Graphene fiber is accumulated by the graphene film of fold, and the pleated structure of the graphene film is the defective graphene film of tool
It is formed under capillary forces, the graphene fiber mutually overlaps and forms network, the graphene fiber phase at grid node
Mutually fusion.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710670077.3A CN107502995B (en) | 2017-08-08 | 2017-08-08 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
| PCT/CN2018/084334 WO2019029191A1 (en) | 2017-08-08 | 2018-04-25 | Draped graphene fiber and graphene fiber non-woven fabric and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710670077.3A CN107502995B (en) | 2017-08-08 | 2017-08-08 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
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| Publication Number | Publication Date |
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| CN107502995A CN107502995A (en) | 2017-12-22 |
| CN107502995B true CN107502995B (en) | 2019-08-16 |
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| WO (1) | WO2019029191A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN108708076A (en) * | 2018-04-09 | 2018-10-26 | 南京捷纳思新材料有限公司 | The method that wet spinning prepares core/shell polyurethane-carbon nanotube conducting non-woven fabrics |
| CN108707998A (en) * | 2018-04-11 | 2018-10-26 | 杭州牛墨科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
| CN108914251B (en) * | 2018-07-09 | 2020-10-30 | 杭州高烯科技有限公司 | Nitrogen-doped graphite fiber and preparation method thereof |
| CN109281224A (en) * | 2018-09-21 | 2019-01-29 | 杭州高烯科技有限公司 | A kind of porous graphene fabric nonwoven cloth and preparation method thereof |
| CN109267416A (en) * | 2018-09-21 | 2019-01-25 | 杭州高烯科技有限公司 | A kind of reduced graphene fibrous paper and preparation method thereof from fusion |
| CN109295796A (en) * | 2018-09-21 | 2019-02-01 | 杭州高烯科技有限公司 | A kind of graphene oxide fibrous paper and preparation method thereof from fusion |
| CN110512311B (en) * | 2019-09-09 | 2022-12-30 | 苏州大学 | Method for controllably preparing graphene fibers by utilizing microfluidic technology |
| CN112647159B (en) * | 2019-10-10 | 2022-04-19 | 中国科学技术大学 | Graphene-based micron rod with multi-capsule-hole structure and preparation method thereof |
| CN110699779B (en) * | 2019-11-01 | 2022-05-13 | 常州富烯科技股份有限公司 | Graphene oxide fiber cloth and preparation method thereof, and graphene gas diffusion film and preparation method thereof |
| CN111214962B (en) * | 2019-12-10 | 2021-04-13 | 中国科学院过程工程研究所 | Folded graphene oxide/nanofiber composite membrane and preparation method and application thereof |
| CN112760813B (en) * | 2021-01-28 | 2022-01-07 | 广东春夏新材料科技股份有限公司 | Hot-air cloth for diaper and preparation method thereof |
| CN112941894A (en) * | 2021-02-01 | 2021-06-11 | 河北工业大学 | Preparation method of microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles |
| CN113388905B (en) * | 2021-06-15 | 2022-07-05 | 广西大学 | A kind of self-crimping preparation method of hollow graphene fiber and its application |
| CN113896186A (en) * | 2021-09-10 | 2022-01-07 | 山东建筑大学 | A kind of preparation method of defective graphene |
| CN115000355B (en) * | 2022-06-06 | 2024-01-30 | 中汽创智科技有限公司 | Three-dimensional metal lithium-oxide composite negative electrode, preparation method and application thereof |
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| KR101195490B1 (en) * | 2011-03-15 | 2012-10-29 | 한양대학교 산학협력단 | Graphene composite fiber and the method for preparing the fiber |
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| WO2014078423A1 (en) * | 2012-11-13 | 2014-05-22 | Ndsu Research Foundation | Nanostructured materials |
| CN103726133B (en) * | 2014-01-02 | 2016-04-06 | 东华大学 | High strength, compact neat porous graphene fiber and continuous production method thereof |
| CN104451959B (en) * | 2014-11-28 | 2016-10-05 | 华南理工大学 | A kind of graphene fiber of porous surface high-specific surface area 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 |
| CN106192201B (en) * | 2016-07-18 | 2018-09-14 | 浙江大学 | A kind of graphene fiber non-woven fabrics and preparation method thereof |
| CN106948165B (en) * | 2017-04-28 | 2019-06-21 | 浙江大学 | A kind of self-fusion graphene fiber 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 |
| 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 |
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2017
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2018
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| Publication number | Publication date |
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| WO2019029191A1 (en) | 2019-02-14 |
| CN107502995A (en) | 2017-12-22 |
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