WO2021102932A1 - Preparation method for graphene fiber - Google Patents
Preparation method for graphene fiber Download PDFInfo
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- WO2021102932A1 WO2021102932A1 PCT/CN2019/122043 CN2019122043W WO2021102932A1 WO 2021102932 A1 WO2021102932 A1 WO 2021102932A1 CN 2019122043 W CN2019122043 W CN 2019122043W WO 2021102932 A1 WO2021102932 A1 WO 2021102932A1
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- graphene oxide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
- 239000000835 fiber Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 238000000034 method Methods 0.000 claims abstract description 14
- 230000015271 coagulation Effects 0.000 claims abstract description 10
- 238000005345 coagulation Methods 0.000 claims abstract description 10
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 229940071870 hydroiodic acid Drugs 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 2
- 229960005055 sodium ascorbate Drugs 0.000 claims description 2
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 9
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 20
- 229910002804 graphite Inorganic materials 0.000 description 18
- 239000010439 graphite Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000009998 heat setting Methods 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002544 Olefin fiber Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004767 olefin fiber Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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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
-
- 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
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- 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
- D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
-
- 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
- D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
-
- 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
Definitions
- the invention relates to the field of nanomaterials, in particular to a graphene fiber with high thermal conductivity. Compared with the circular graphene fiber, the graphene fiber can better exert the advantages of graphene heat conduction.
- the existing preparation methods of graphene fibers are mainly based on liquid crystal wet spinning.
- the nascent graphene oxide fiber obtained by liquid crystal wet spinning will inevitably introduce defects such as wrinkles during the solidification and drying process. These defects always exist in the fiber during chemical reduction, which affects the succession of graphene fibers to a single sheet of graphene. A big problem with excellent performance.
- the present invention aims to provide an ultra-high thermal conductivity graphene fiber based on full use of large-size graphene oxide raw materials.
- the present invention adopts the following technical scheme: a method for preparing graphene fibers with high thermal conductivity.
- large-size graphene oxide larger than 50 microns
- the upper plasticization stretch makes the large graphene sheets straightly arranged along the axial direction, which is more conducive to the formation of large-size graphite crystals.
- a graphene material composed of graphene crystals is obtained.
- the orientation degree of the graphite crystals is above 85%, and multiple graphite crystals form a conductive and heat conduction path; among them, the orientation degree of the graphene sheet is greater than or equal to 80%, and the density is greater than or equal to 1.8g/cm 3.
- the length of each graphite crystal is above 150nm. Specifically, it includes the following processes:
- the nascent graphene oxide fiber obtained by wet liquid crystal spinning is continuously drawn into a plasticizing bath formulated with a plasticizer, and immersed to make it plasticized.
- the reason for the plasticization is that the intercalation of the plasticizer makes The layer spacing of graphene oxide sheets reaches 1.1-1.8nm; if the layer spacing is less than 1.1nm, the interaction between graphene fibers is too large, and the material does not exhibit or exhibits minimal plastic deformation; if the layer spacing is greater than 1.8nm , The interaction between graphene layers is too weak, and the entire layer slips during the subsequent stretching process, which is directly broken.
- the plasticized and stretched graphene oxide fiber is heat-set. During the heat-set and drying process, external force is applied to maintain the current length.
- the dried graphene oxide fibers are chemically reduced and heat-treated to obtain graphene fibers with high thermal conductivity.
- the plasticization is uniform, and the layer spacing after plasticization is uniform.
- the layer spacing can be obtained by dividing the total thickness by the number of layers and the X-ray diffraction method.
- the layer spacing can be adjusted by adjusting the type of plasticizer.
- the spinneret holes are flat spinneret holes.
- the spinneret hole is changed to a flat shape, after several processes, the large graphene sheets are arranged in a flat arrangement, which greatly improves the transfer efficiency of phonons between the graphene sheets, thereby improving the macroscopic graphene The thermal conductivity of the fiber.
- the graphene oxide liquid crystal spinning solution is prepared from graphene oxide with a size greater than 50 microns.
- the plasticizer is a single solvent with a polarity parameter between 0.3 and 0.75, or a mixture of multiple solvents.
- water with a high polarity and acetone with a low polarity are mutually matched to obtain a mixed solvent with moderate polarity, which can also be used as a plasticizer.
- it may include ethanol, acetone, isopropanol, acetic acid, ethyl acetate, methanol, water, glycerol, propylene glycol, ethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hydrochloric acid, Organic amines, etc. or their mixed plasticizers.
- the plasticizer can be stretched in multiple stages.
- the reagents used in the chemical reduction are hydroiodic acid, hydrazine hydrate, sodium ascorbate, stannous chloride, etc., and the heat treatment temperature is 1300-3000 degrees.
- the spinning solution is graphene oxide aqueous phase dispersion, DMF phase dispersion, DMAc phase dispersion, DMSO phase dispersion, and the coagulation bath is ethyl acetate, dichloromethane, acetic acid, ethanol, water, isopropyl Alcohol, chloroform, acetone, etc. and their mixed coagulation bath.
- the present invention uses the flat spinneret holes to spun flat graphene fibers by the high orientation of large graphene oxide liquid crystals in the flow direction, and uses a plasticizer to skillfully use its plasticity for stretching.
- the large graphene sheets are arranged in a straight line, after chemical reduction and heat treatment, high thermal conductivity graphene fibers are obtained, which make full use of the advantages of super-large graphene oxide arranged completely flat.
- Figure 1 is a cross-section of the fiber.
- the aqueous graphene oxide (sheet diameter: 50 ⁇ m) spinning solution is extruded into the coagulation bath ethyl acetate through the spinneret, and the primary graphene oxide fiber is obtained through wet liquid crystal spinning.
- the plasticized and stretched graphene oxide fiber is placed at 60 degrees Celsius for heat setting. During the heat setting and drying process, external force is applied to maintain the current length.
- the dried graphene oxide fiber is subjected to hydroiodic acid chemical reduction and 3000 degree heat treatment to make its carbon content reach 99%, to obtain graphene fiber with high thermal conductivity, and conduct thermal conductivity, electrical conductivity and stretching test.
- each graphite crystal is 173nm in length; two adjacent graphite crystals are in contact with each other, and multiple graphite crystals form a conductive and heat conduction path.
- the orientation degree of the graphene sheets in the fiber is 93%.
- the density test is 1.94g cm -3 .
- the graphene fiber has a thermal conductivity of 1800 W m -1 K -1 , an electrical conductivity of 1.2 ⁇ 10 6 S m -1 , and a tensile strength of 2 GPa.
- the DMF phase dispersion spinning solution of graphene oxide (sheet diameter 50 ⁇ m) is extruded into the coagulation bath ethanol through the flat spinneret (500 ⁇ 80 ⁇ m), and the primary graphene oxide fiber is obtained through wet liquid crystal spinning. .
- the plasticized and stretched graphene oxide fiber is placed at 60 degrees Celsius for heat setting, and during the heat setting and drying process, an external force is applied to maintain the current length.
- the dried graphene oxide fiber is subjected to hydroiodic acid chemical reduction and 3000 degree heat treatment to make its carbon content reach 99%, to obtain graphene fiber with high thermal conductivity, and conduct thermal conductivity, electrical conductivity and stretching test.
- the graphite crystals in the structure After wide-angle X-ray diffraction test, the graphite crystals in the structure, the length of each graphite crystal is more than 160nm; two adjacent graphite crystals are in contact with each other, and multiple graphite crystals form a conductive and heat conduction path. According to the wide-angle X-ray diffraction test, the orientation degree of the graphene sheets in the fiber is 92%.
- the density test is 1.92g cm -3 .
- the graphene fiber has a thermal conductivity of 1780 W m -1 K -1 , an electrical conductivity of 1.18 ⁇ 10 6 S m -1 , and a tensile strength of 1.85 GPa.
- the plasticized and stretched graphene oxide fiber is placed at 60 degrees Celsius for heat setting, and during the heat setting and drying process, an external force is applied to maintain the current length.
- the dried graphene oxide fiber is subjected to hydroiodic acid chemical reduction and 3000 degree heat treatment to make its carbon content reach 99%, to obtain graphene fiber with high thermal conductivity, and conduct thermal conductivity, electrical conductivity and stretching test.
- the structure of graphite crystals Through wide-angle X-ray diffraction test, the structure of graphite crystals, the length of each graphite crystal is more than 168nm; two adjacent graphite crystals are in contact with each other, and multiple graphite crystals form a conductive and heat conduction path. According to the wide-angle X-ray diffraction test, the orientation degree of the graphene sheets in the fiber is 92%.
- the density test is 1.92g cm -3 .
- the graphene fiber After testing, the graphene fiber has a thermal conductivity of 1790 W m -1 K -1 , an electrical conductivity of 1.17 ⁇ 10 6 S m -1 , and a tensile strength of 1.85 GPa.
Abstract
Disclosed in the present invention is a preparation method for a graphene fiber. The graphene fiber has excellent performances, i.e., high thermal conductivity, high electric conductivity, high strength, and high modulus. The method comprises: spinning a liquid-crystal spinning solution of graphene oxide by means of a spinneret hole in a coagulation bath, performing plastic stretching in a plastic stretching bath to reach an optimal stretch ratio, and performing chemical reduction and thermal treatment to obtain a high-performance graphene fiber.
Description
本发明涉及纳米材料领域，特别是一种高导热石墨烯纤维，相对于圆形石墨烯纤维，石墨烯纤维更能发挥石墨烯导热上的优势。The invention relates to the field of nanomaterials, in particular to a graphene fiber with high thermal conductivity. Compared with the circular graphene fiber, the graphene fiber can better exert the advantages of graphene heat conduction.
2004年，英国曼彻斯特大学A.K.Geim教授课题组运用机械剥离法成功制备石墨烯，并将其悬挂于微型金架上，推翻了完美二维晶体结构无法在非绝对零度下稳定存在的这一论断。换言之，自由态的石墨烯在室温下可以稳定存在；而在相同条件下，其他任何已知材料都会被氧化或分解，甚至在相当于其单层厚度10倍时就变得不稳定。从结构上说，石墨烯(Graphene)是紧密堆积成二维蜂窝状晶格结构的sp2杂化单层碳原子晶体，层内碳原子以共价键的形式连接，具有超高的强度(120GPa)，因此以石墨烯作为源头材料构建特定结构的碳基材料，从而实现碳质功能材料纳米结构的设计和可控以及宏量地制备已经逐渐引起全球科学家的关注。但是由于纳米尺度在向宏观材料组装过程中，难免引入大量缺陷，导致单片的优异性质难以在宏观组装体中实现完美继承，如单层石墨烯拥有的极高的强度、模量、导电率和导热率。尤其在石墨烯纤维材料，目前石墨烯的纤维材料导热率仍难以突破1200W/(m K)，相对于单层石墨烯5400W/(m K)的导热率相差很远，甚至难以媲美商用沥青基碳纤维。因此，探寻如何更精确地控制缺陷，提高组装精度和效率以得到高导热石墨烯纤维，成为了一大难题。In 2004, the research group of Professor A.K. Geim of the University of Manchester successfully prepared graphene by mechanical exfoliation and suspended it on a miniature gold frame, overturning the conclusion that a perfect two-dimensional crystal structure cannot exist stably under non-absolute zero. In other words, free graphene can exist stably at room temperature; and under the same conditions, any other known materials will be oxidized or decomposed, and become unstable even when it is 10 times the thickness of its single layer. From the structural point of view, Graphene is a sp2 hybrid single-layer carbon atom crystal closely packed into a two-dimensional honeycomb lattice structure. The carbon atoms in the layer are connected in the form of covalent bonds, which has ultra-high strength (120GPa). ), therefore, the use of graphene as the source material to construct carbon-based materials with specific structures to realize the design and controllable and macro-preparation of nanostructures of carbonaceous functional materials has gradually attracted the attention of scientists around the world. However, due to the inevitable introduction of a large number of defects in the process of assembling macroscopic materials at the nanoscale, the excellent properties of a single sheet are difficult to achieve perfect inheritance in the macroscopic assembly, such as the extremely high strength, modulus, and conductivity of single-layer graphene. And thermal conductivity. Especially in graphene fiber materials, the current thermal conductivity of graphene fiber materials is still difficult to exceed 1200W/(m K), which is far from the thermal conductivity of single-layer graphene 5400W/(m K), and is even hard to compare with commercial asphalt-based materials. carbon fiber. Therefore, it has become a big problem to explore how to more accurately control defects and improve assembly accuracy and efficiency to obtain high thermal conductivity graphene fibers.
目前，现有石墨烯纤维的制备方法主要基于液晶湿法纺丝。但是通过液晶湿法纺丝得到的初生氧化石墨烯纤维在凝固和干燥过程中不可避免会引入褶皱等缺陷，这些缺陷在化学还原时一直存在于纤维内部，是影响石墨烯纤维继承单片石墨烯优异性能的一大难题。At present, the existing preparation methods of graphene fibers are mainly based on liquid crystal wet spinning. However, the nascent graphene oxide fiber obtained by liquid crystal wet spinning will inevitably introduce defects such as wrinkles during the solidification and drying process. These defects always exist in the fiber during chemical reduction, which affects the succession of graphene fibers to a single sheet of graphene. A big problem with excellent performance.
发明内容Summary of the invention
为了克服上述现有的技术缺陷，本发明旨在充分利用大尺寸氧化石墨烯原料的基础上，提供一种超高导热石墨烯纤维。In order to overcome the above-mentioned existing technical defects, the present invention aims to provide an ultra-high thermal conductivity graphene fiber based on full use of large-size graphene oxide raw materials.
本发明采用以下技术方案：一种高导热石墨烯纤维的制备方法，该方法通过塑化拉伸和热处理，大尺寸的氧化石墨烯(尺寸大于50微米)倾向于生成大尺寸的石墨晶体，加上塑化拉伸使得大片的石墨烯片沿着轴向是平直排列，更加有利于大尺寸的石墨晶体的形成。最终得到由石墨烯晶体构成的石墨烯材料，石墨晶体的取向度在85％以上，多个石墨晶体构成导电导热通路；其中，石墨 烯片取向度大于等于80％，密度大于等于1.8g/cm
3，每个石墨晶体的长度在150nm以上。具体的，包括如下过程：
The present invention adopts the following technical scheme: a method for preparing graphene fibers with high thermal conductivity. Through plasticization, stretching and heat treatment, large-size graphene oxide (larger than 50 microns) tends to generate large-size graphite crystals. The upper plasticization stretch makes the large graphene sheets straightly arranged along the axial direction, which is more conducive to the formation of large-size graphite crystals. Finally, a graphene material composed of graphene crystals is obtained. The orientation degree of the graphite crystals is above 85%, and multiple graphite crystals form a conductive and heat conduction path; among them, the orientation degree of the graphene sheet is greater than or equal to 80%, and the density is greater than or equal to 1.8g/cm 3. The length of each graphite crystal is above 150nm. Specifically, it includes the following processes:
(1)将大片氧化石墨烯的纺丝液通过喷丝孔挤出，进入凝固浴，得到初生氧化石墨烯纤维；(1) Extruding large sheets of graphene oxide spinning solution through spinneret holes and entering the coagulation bath to obtain primary graphene oxide fibers;
(2)将湿法液晶纺丝得到的初生氧化石墨烯纤维，继续牵引入塑化剂配制的塑化浴中，浸泡使其塑化，塑化的原因在于经过塑化剂的插层，使得氧化石墨烯片的层间距达到1.1-1.8nm；如果层间距低于1.1nm，石墨烯纤维层间相互作用太大，材料不表现出或者表现出极小的塑性变形；如果层间距大于1.8nm，石墨烯层间相互作用太弱，在后续拉伸处理过程中整个是层间滑移，直接拉断。(2) The nascent graphene oxide fiber obtained by wet liquid crystal spinning is continuously drawn into a plasticizing bath formulated with a plasticizer, and immersed to make it plasticized. The reason for the plasticization is that the intercalation of the plasticizer makes The layer spacing of graphene oxide sheets reaches 1.1-1.8nm; if the layer spacing is less than 1.1nm, the interaction between graphene fibers is too large, and the material does not exhibit or exhibits minimal plastic deformation; if the layer spacing is greater than 1.8nm , The interaction between graphene layers is too weak, and the entire layer slips during the subsequent stretching process, which is directly broken.
(3)在拉伸浴中对塑化后的纤维进行拉伸，拉伸率为30％，然后保持外力，以保持氧化石墨烯片层的平直排列，释放掉片层间的应力；塑化后的拉伸使得材料内部褶皱被拉直，然后拉伸后，保持拉伸的长度，进行干燥，使去掉褶皱的石墨烯片保持下来，该拉伸-释放过程可以进行一次或两次以上。(3) Stretch the plasticized fiber in a stretching bath with a stretching rate of 30%, and then maintain the external force to maintain the straight arrangement of the graphene oxide sheets and release the stress between the sheets; After the stretching, the internal wrinkles of the material are straightened, and then after stretching, the stretched length is maintained and dried to keep the graphene sheet with the wrinkles removed. The stretching-release process can be performed once or more than twice. .
(4)最后将塑化拉伸后的氧化石墨烯纤维进行热定型，热定型干燥过程中，施加外力以保持当前长度。(4) Finally, the plasticized and stretched graphene oxide fiber is heat-set. During the heat-set and drying process, external force is applied to maintain the current length.
(5)干燥后的氧化石墨烯纤维进行化学还原和热处理，得到具有高导热的石墨烯纤维。(5) The dried graphene oxide fibers are chemically reduced and heat-treated to obtain graphene fibers with high thermal conductivity.
上述过程中，由于浸泡过程的均匀性，塑化作用均匀，塑化后层间距均匀，层间距可以通过总厚度除以层数以及X射线衍射方法来获得。In the above process, due to the uniformity of the immersion process, the plasticization is uniform, and the layer spacing after plasticization is uniform. The layer spacing can be obtained by dividing the total thickness by the number of layers and the X-ray diffraction method.
上述过程中，可以通过调控塑化剂的种类来调控上述层间距。塑化剂极性参数越大，塑化作用越强，层间距越大。In the above process, the layer spacing can be adjusted by adjusting the type of plasticizer. The greater the polar parameter of the plasticizer, the stronger the plasticizing effect and the greater the interlayer spacing.
进一步地，所述步骤1中，所述喷丝孔为扁平状喷丝孔。将喷丝孔换为扁平状，经过数道流程处理后，大片的石墨烯片层在呈平躺排布，大大提升了石墨烯片层之间声子的传递效率，从而能够提高宏观石墨烯纤维的导热率。Further, in the step 1, the spinneret holes are flat spinneret holes. The spinneret hole is changed to a flat shape, after several processes, the large graphene sheets are arranged in a flat arrangement, which greatly improves the transfer efficiency of phonons between the graphene sheets, thereby improving the macroscopic graphene The thermal conductivity of the fiber.
进一步地，所述步骤1中，所述氧化石墨烯的液晶纺丝液由尺寸大于50微米的氧化石墨烯配制。Further, in the step 1, the graphene oxide liquid crystal spinning solution is prepared from graphene oxide with a size greater than 50 microns.
本申请中，所述塑化剂为极性参数为0.3-0.75之间的单一溶剂，或多种溶剂混合液。如极性很高的水和极性较低的丙酮互配，得到极性适中的混合溶剂，也可以作为塑化剂使用。具体的，可以包括乙醇、丙酮、异丙醇、乙酸、乙酸乙酯、甲醇、水、丙三醇、丙二醇、乙二醇、三乙二醇、四乙二醇、五乙二醇、盐酸、有机胺等或其混合塑化剂。In this application, the plasticizer is a single solvent with a polarity parameter between 0.3 and 0.75, or a mixture of multiple solvents. For example, water with a high polarity and acetone with a low polarity are mutually matched to obtain a mixed solvent with moderate polarity, which can also be used as a plasticizer. Specifically, it may include ethanol, acetone, isopropanol, acetic acid, ethyl acetate, methanol, water, glycerol, propylene glycol, ethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hydrochloric acid, Organic amines, etc. or their mixed plasticizers.
进一步地，所述步骤1中，在塑化剂中可以多级拉伸。Further, in the step 1, the plasticizer can be stretched in multiple stages.
进一步地，步骤5中，化学还原所采用的试剂为氢碘酸、水合肼、抗坏血 酸钠、氯化亚锡等，热处理温度为1300-3000度。Further, in step 5, the reagents used in the chemical reduction are hydroiodic acid, hydrazine hydrate, sodium ascorbate, stannous chloride, etc., and the heat treatment temperature is 1300-3000 degrees.
所述的纺丝液为氧化石墨烯的水相分散液、DMF相分散液、DMAc相分散液、DMSO相分散液，凝固浴为乙酸乙酯、二氯甲烷、乙酸、乙醇、水、异丙醇、三氯甲烷、丙酮等及其混合凝固浴。The spinning solution is graphene oxide aqueous phase dispersion, DMF phase dispersion, DMAc phase dispersion, DMSO phase dispersion, and the coagulation bath is ethyl acetate, dichloromethane, acetic acid, ethanol, water, isopropyl Alcohol, chloroform, acetone, etc. and their mixed coagulation bath.
本发明的有益效果在于：本发明借助扁平喷丝孔，利用大片氧化石墨烯液晶在流动方向的高度取向作用纺出扁平的石墨烯纤维，并使用塑化剂，巧妙利用其塑性进行拉伸，使大片的石墨烯片层呈平直排列，后经化学还原和热处理得到了高导热的石墨烯纤维，该纤维充分利用了完全平躺排列的超大尺寸氧化石墨烯的优势。The beneficial effects of the present invention are: the present invention uses the flat spinneret holes to spun flat graphene fibers by the high orientation of large graphene oxide liquid crystals in the flow direction, and uses a plasticizer to skillfully use its plasticity for stretching. The large graphene sheets are arranged in a straight line, after chemical reduction and heat treatment, high thermal conductivity graphene fibers are obtained, which make full use of the advantages of super-large graphene oxide arranged completely flat.
图1为纤维的截面。Figure 1 is a cross-section of the fiber.
实施例1Example 1
(1)将水相氧化石墨烯(片径50μm)纺丝液通过喷丝孔挤出进入凝固浴乙酸乙酯中，经过湿法液晶纺丝得到初生氧化石墨烯纤维。(1) The aqueous graphene oxide (sheet diameter: 50 μm) spinning solution is extruded into the coagulation bath ethyl acetate through the spinneret, and the primary graphene oxide fiber is obtained through wet liquid crystal spinning.
(2)将初生氧化石墨烯纤维，继续牵引入丙酮中浸泡使其塑化，塑化5秒后，经测试，氧化石墨烯纤维的层间距为1.3nm，断裂伸长率为30％以上；(2) The nascent graphene oxide fiber is continuously drawn into acetone and soaked to make it plasticized. After 5 seconds of plasticization, the interlayer spacing of the graphene oxide fiber is tested to be 1.3 nm, and the elongation at break is more than 30%;
(3)对塑化后的氧化石墨烯纤维进行五次塑化拉伸，总拉伸率为30％，然后施加外力以保持当前长度，释放掉片层间的应力；(3) Perform five times of plasticizing and stretching on the plasticized graphene oxide fiber, with a total stretching rate of 30%, and then applying external force to maintain the current length and release the stress between the sheets;
(4)最后将塑化拉伸后的氧化石墨烯纤维置于60摄氏度下，进行热定型，热定型干燥过程中，施加外力以保持当前长度。(4) Finally, the plasticized and stretched graphene oxide fiber is placed at 60 degrees Celsius for heat setting. During the heat setting and drying process, external force is applied to maintain the current length.
(5)干燥后的氧化石墨烯纤维进行氢碘酸化学还原和3000度热处理，使其碳含量达到99％，得到具有高导热的石墨烯纤维，并对其进行导热率、导电率和拉伸测试。(5) The dried graphene oxide fiber is subjected to hydroiodic acid chemical reduction and 3000 degree heat treatment to make its carbon content reach 99%, to obtain graphene fiber with high thermal conductivity, and conduct thermal conductivity, electrical conductivity and stretching test.
经广角X射线衍射测试，其结构中石墨晶体，每个石墨晶体的长度在173nm；相邻两个石墨晶体相互接触，多个石墨晶体构成导电导热通路。经广角X射线衍射测试，该纤维中，石墨烯片取向度93％。After wide-angle X-ray diffraction test, the structure of graphite crystals, each graphite crystal is 173nm in length; two adjacent graphite crystals are in contact with each other, and multiple graphite crystals form a conductive and heat conduction path. According to the wide-angle X-ray diffraction test, the orientation degree of the graphene sheets in the fiber is 93%.
密度测试为1.94g cm
-3。
The density test is 1.94g cm -3 .
该石墨烯纤维导热率达1800W m
-1K
-1,导电率达1.2×10
6S m
-1,拉伸强度达2GPa。
The graphene fiber has a thermal conductivity of 1800 W m -1 K -1 , an electrical conductivity of 1.2×10 6 S m -1 , and a tensile strength of 2 GPa.
实施例2Example 2
(1)将氧化石墨烯(片径50μm)的DMF相分散液纺丝液通过扁平喷丝孔(500×80μm)挤出进入凝固浴乙醇中，经过湿法液晶纺丝得到初生氧化石墨烯纤维。(1) The DMF phase dispersion spinning solution of graphene oxide (sheet diameter 50μm) is extruded into the coagulation bath ethanol through the flat spinneret (500×80μm), and the primary graphene oxide fiber is obtained through wet liquid crystal spinning. .
(2)将初生氧化石墨烯纤维，继续牵引入丙酮中浸泡使其塑化，塑化3秒后，氧化石墨烯纤维的层间距为1.1nm；(2) The nascent graphene oxide fiber is continuously drawn into acetone and soaked to make it plasticized. After plasticizing for 3 seconds, the interlayer spacing of the graphene oxide fiber is 1.1 nm;
(3)对塑化后的氧化石墨烯纤维进行塑化拉伸，拉伸率为30％，然后施加外力以保持当前长度，释放掉片层间的应力；(3) Plasticize and stretch the plasticized graphene oxide fiber with a stretch rate of 30%, and then apply external force to maintain the current length and release the interlayer stress;
(4)最后将塑化拉伸后的氧化石墨烯纤维进行置于60摄氏度下，热定型，热定型干燥过程中，施加外力以保持当前长度。(4) Finally, the plasticized and stretched graphene oxide fiber is placed at 60 degrees Celsius for heat setting, and during the heat setting and drying process, an external force is applied to maintain the current length.
(5)干燥后的氧化石墨烯纤维进行氢碘酸化学还原和3000度热处理，使其碳含量达到99％，得到具有高导热的石墨烯纤维，并对其进行导热率、导电率和拉伸测试。(5) The dried graphene oxide fiber is subjected to hydroiodic acid chemical reduction and 3000 degree heat treatment to make its carbon content reach 99%, to obtain graphene fiber with high thermal conductivity, and conduct thermal conductivity, electrical conductivity and stretching test.
经广角X射线衍射测试，其结构中石墨晶体，每个石墨晶体的长度在160nm以上；相邻两个石墨晶体相互接触，多个石墨晶体构成导电导热通路。经广角X射线衍射测试，该纤维中，石墨烯片取向度92％。After wide-angle X-ray diffraction test, the graphite crystals in the structure, the length of each graphite crystal is more than 160nm; two adjacent graphite crystals are in contact with each other, and multiple graphite crystals form a conductive and heat conduction path. According to the wide-angle X-ray diffraction test, the orientation degree of the graphene sheets in the fiber is 92%.
密度测试为1.92g cm
-3。
The density test is 1.92g cm -3 .
该石墨烯纤维导热率达1780W m
-1K
-1,导电率达1.18×10
6S m
-1,拉伸强度达1.85GPa。
The graphene fiber has a thermal conductivity of 1780 W m -1 K -1 , an electrical conductivity of 1.18×10 6 S m -1 , and a tensile strength of 1.85 GPa.
实施例3Example 3
(1)将氧化石墨烯(片径80μm)的DMSO相分散液纺丝液通过扁平喷丝孔(500×80μm)挤出进入凝固浴异丙醇中，经过湿法液晶纺丝得到初生氧化石墨烯纤维。(1) The DMSO phase dispersion spinning solution of graphene oxide (sheet diameter 80μm) is extruded into the coagulation bath isopropanol through the flat spinneret (500×80μm), and the primary graphite oxide is obtained through wet liquid crystal spinning. Olefin fiber.
(2)将初生氧化石墨烯纤维，继续牵引入丙酮中浸泡使其塑化，塑化10秒后，氧化石墨烯纤维的层间距为1.8nm；(2) Continue to pull the nascent graphene oxide fiber into acetone and soak it for plasticization. After plasticization for 10 seconds, the interlayer spacing of the graphene oxide fiber is 1.8nm;
(3)对塑化后的氧化石墨烯纤维进行塑化拉伸，拉伸率为30％，然后施加外力以保持当前长度，释放掉片层间的应力；(3) Plasticize and stretch the plasticized graphene oxide fiber with a stretch rate of 30%, and then apply external force to maintain the current length and release the interlayer stress;
(4)最后将塑化拉伸后的氧化石墨烯纤维进行置于60摄氏度下，热定型，热定型干燥过程中，施加外力以保持当前长度。(4) Finally, the plasticized and stretched graphene oxide fiber is placed at 60 degrees Celsius for heat setting, and during the heat setting and drying process, an external force is applied to maintain the current length.
(5)干燥后的氧化石墨烯纤维进行氢碘酸化学还原和3000度热处理，使其碳含量达到99％，得到具有高导热的石墨烯纤维，并对其进行导热率、导电率和拉伸测试。(5) The dried graphene oxide fiber is subjected to hydroiodic acid chemical reduction and 3000 degree heat treatment to make its carbon content reach 99%, to obtain graphene fiber with high thermal conductivity, and conduct thermal conductivity, electrical conductivity and stretching test.
经广角X射线衍射测试，其结构中石墨晶体，每个石墨晶体的长度在168nm 以上；相邻两个石墨晶体相互接触，多个石墨晶体构成导电导热通路。经广角X射线衍射测试，该纤维中，石墨烯片取向度92％。Through wide-angle X-ray diffraction test, the structure of graphite crystals, the length of each graphite crystal is more than 168nm; two adjacent graphite crystals are in contact with each other, and multiple graphite crystals form a conductive and heat conduction path. According to the wide-angle X-ray diffraction test, the orientation degree of the graphene sheets in the fiber is 92%.
密度测试为1.92g cm
-3。
The density test is 1.92g cm -3 .
经测试，该石墨烯纤维导热率达1790W m
-1K
-1,导电率达1.17×10
6S m
-1,拉伸强度达1.85GPa。
After testing, the graphene fiber has a thermal conductivity of 1790 W m -1 K -1 , an electrical conductivity of 1.17×10 6 S m -1 , and a tensile strength of 1.85 GPa.
Claims (8)
- 一种石墨烯纤维的制备方法，其特征在于，包括如下过程：A method for preparing graphene fibers, which is characterized in that it includes the following processes:(1)将尺寸大于50微米的大片氧化石墨烯的纺丝液通过喷丝孔挤出，进入凝固浴，得到初生氧化石墨烯纤维；(1) Extruding the spinning solution of large graphene oxide sheets with a size greater than 50 microns through the spinneret holes and entering the coagulation bath to obtain primary graphene oxide fibers;(2)将纺丝得到的初生氧化石墨烯纤维，继续牵引入到塑化剂中，在塑化浴中浸泡使其层间距达到1.1-1.8nm；(2) The nascent graphene oxide fiber obtained by spinning is continuously drawn into the plasticizer, and immersed in the plasticizing bath to make the layer spacing reach 1.1-1.8nm;(3)对纤维进行拉伸，拉伸率为30％，然后保持外力，以保持氧化石墨烯片层的平直排列，释放掉片层间的应力；(3) Stretch the fiber with a stretch rate of 30%, and then maintain the external force to maintain the straight arrangement of the graphene oxide sheets and release the stress between the sheets;(4)最后将拉伸后的氧化石墨烯纤维进行热定型，热定型干燥过程中，施加外力以保持当前长度。(4) Finally, heat-set the stretched graphene oxide fiber. During the heat-set drying process, external force is applied to maintain the current length.(5)干燥后的氧化石墨烯纤维进行化学还原和热处理，得到具有石墨烯纤维。(5) The dried graphene oxide fiber is chemically reduced and heat-treated to obtain a graphene fiber.
- 根据权利要求1所述的高导热石墨烯纤维，其特征在于，所述步骤1中，所述喷丝孔为扁平状喷丝孔。The high thermal conductivity graphene fiber according to claim 1, wherein in the step 1, the spinneret holes are flat spinneret holes.
- 根据权利要求1所述的制备方法，其特征在于，所述塑化剂为极性参数为0.3-0.75之间的单一溶剂，或多种溶剂混合液。The preparation method according to claim 1, wherein the plasticizer is a single solvent with a polarity parameter between 0.3 and 0.75, or a mixture of multiple solvents.
- 根据权利要求1所述的制备方法，其特征在于，所述步骤1中，塑化剂为乙醇、丙酮、异丙醇、乙酸、乙酸乙酯、甲醇、水、丙三醇、丙二醇、乙二醇、三乙二醇、四乙二醇、五乙二醇、盐酸、有机胺等或其混合塑化剂。The preparation method according to claim 1, characterized in that, in the step 1, the plasticizer is ethanol, acetone, isopropanol, acetic acid, ethyl acetate, methanol, water, glycerol, propylene glycol, and ethylene glycol. Alcohol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hydrochloric acid, organic amine, etc. or their mixed plasticizers.
- 根据权利要求1所述的制备方法，其特征在于，经步骤2塑化后的氧化石墨烯纤维的断裂伸长率为30％以上。The preparation method according to claim 1, wherein the elongation at break of the graphene oxide fiber plasticized in step 2 is more than 30%.
- 根据权利要求1所述的制备方法，其特征在于，在塑化浴中可以多级拉伸。The preparation method according to claim 1, characterized in that it can be stretched in multiple stages in a plasticizing bath.
- 根据权利要求1所述的制备方法，其特征在于，步骤5中，化学还原所采用的试剂为氢碘酸、水合肼、抗坏血酸钠、氯化亚锡等，热处理温度为1300-3000度。The preparation method according to claim 1, wherein in step 5, the reagents used in the chemical reduction are hydroiodic acid, hydrazine hydrate, sodium ascorbate, stannous chloride, etc., and the heat treatment temperature is 1300-3000 degrees.
- 根据权利要求1所述的制备方法，其特征在于，所述的纺丝液为氧化石墨烯的水相分散液、DMF相分散液、DMAc相分散液、DMSO相分散液，凝固浴为乙酸乙酯、二氯甲烷、乙酸、乙醇、水、异丙醇、三氯甲烷、丙酮等及其混合凝固浴。The preparation method according to claim 1, wherein the spinning solution is graphene oxide aqueous phase dispersion, DMF phase dispersion, DMAc phase dispersion, DMSO phase dispersion, and the coagulation bath is ethyl acetate. Ester, dichloromethane, acetic acid, ethanol, water, isopropanol, chloroform, acetone, etc. and their mixed coagulation bath.
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| KR20190110726A (en) * | 2018-03-21 | 2019-10-01 | 재단법인차세대융합기술연구원 | Metal-embedded reduced graphene oxide fibers and multi-sensors comprising thereof |
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| CN102534868A (en) * | 2011-12-26 | 2012-07-04 | 浙江大学 | Preparation method for high strength macro graphene conductive fiber |
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| CN105648579A (en) * | 2016-03-31 | 2016-06-08 | 浙江大学 | Superfine graphene fibers and method for preparing same |
| KR20190110726A (en) * | 2018-03-21 | 2019-10-01 | 재단법인차세대융합기술연구원 | Metal-embedded reduced graphene oxide fibers and multi-sensors comprising thereof |
| CN108793149A (en) * | 2018-07-26 | 2018-11-13 | 杭州高烯科技有限公司 | A kind of method enhancing graphene oxide membrane and a kind of preparation method of high-strength graphite alkene film |
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