WO2023236351A1 - Fibre d'assemblage au graphène, et son procédé de préparation et son utilisation - Google Patents

Fibre d'assemblage au graphène, et son procédé de préparation et son utilisation Download PDF

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WO2023236351A1
WO2023236351A1 PCT/CN2022/113968 CN2022113968W WO2023236351A1 WO 2023236351 A1 WO2023236351 A1 WO 2023236351A1 CN 2022113968 W CN2022113968 W CN 2022113968W WO 2023236351 A1 WO2023236351 A1 WO 2023236351A1
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graphene
fiber
fibers
aqueous solution
assembly
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Chinese (zh)
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耿凤霞
徐天琪
张家文
嵇锦鹏
宋兆涛
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苏州大学
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to nanosheet assembly technology, and specifically relates to a graphene assembly fiber and its preparation method and application.
  • graphene's single-atom thickness and large area give it a large aspect ratio, it can be assembled into macrostructures such as graphene fibers.
  • the starting point for the synthesis of macroscopic graphene is usually graphene oxide (GO) dispersed in a solvent. Fibers are made from dispersed GO through wet spinning technology, and then graphene-based fibers are obtained through chemical or thermal reduction.
  • GO graphene oxide
  • the existing technology emphasizes the importance of reducing structural defects and improving the regular arrangement of graphene sheets to improve the mechanical and electrical properties of graphene fibers.
  • the tensile strength of the initially obtained chemically reduced graphene oxide fibers was about 200 MPa, recently reaching 2.2 GPa; graphene membranes initially formed by filtration had a strength of 200 MPa, a record-breaking membrane strength of 1.55 GPa was recently achieved using static stretch-induced alignment technology.
  • Existing technology annealing at very high temperatures (3000°C) can eliminate atomic defects on graphene sheets and promote the formation of graphite crystallites, resulting in a tensile strength of 3.4 GPa, graphene fiber with Young's modulus of 342 GPa.
  • the present invention discloses a simple graphene sheet assembly strategy to form a stable 2D connected planar structure, thereby significantly improving the mechanical and conductive properties.
  • the present invention adopts the following technical solution: a graphene assembly fiber, using a graphene oxide aqueous solution as a spinning liquid, an amine compound aqueous solution as a coagulation bath, and obtaining a graphene assembly fiber through spinning and reduction treatment.
  • a graphene oxide fiber uses a graphene oxide aqueous solution as a spinning liquid and an amine compound aqueous solution as a coagulation bath. After spinning, the graphene oxide fiber is obtained.
  • the amine compound is an aromatic amine compound containing two or more amine groups; the chemical structural formula of the amine compound is R (NH 2 ) n , n is greater than 2, such as 2 to 8, preferably 2 to 6, and n represents There are n amine groups connected to R, which does not mean that n amine groups are repeated in series; R is an aryl group, a heterocyclic group, etc., and an aryl group includes a phenyl group, a substituted phenyl group, a biphenyl group, a substituted biphenyl group, and a fused ring Aromatic hydrocarbon group or substituted condensed ring aromatic hydrocarbon group, etc.; preferably, the molecular weight of the amine compound is less than 1000 and it is a small molecular compound.
  • a graphene oxide aqueous solution is injected into an amine compound aqueous solution to obtain graphene oxide fibers; and then the graphene oxide fibers are chemically reduced to obtain graphene assembly fibers.
  • the method for preparing graphene oxide aqueous solution into graphene oxide fibers is a conventional method for preparing graphene oxide fibers.
  • the creativity lies in the fact that the present invention uses an aqueous amine compound solution as a coagulation bath for the first time to obtain graphene oxide fibers.
  • the concentration of the graphene oxide aqueous solution is 0.1mg/mL ⁇ 100mg/mL, preferably 1mg/mL ⁇ 50mg/mL, and more preferably 2mg/mL ⁇ 30mg/mL; the concentration of the amine compound aqueous solution is 0.1mM ⁇ 30mM, preferably The range is 0.5mM to 20mM, more preferably 1mM to 10mM.
  • the amine compound can be prepared in the form of an amine compound salt, such as an amine compound hydrochloride or an amine compound sulfate.
  • the reducing agent for chemical reduction is hydriodic acid, hydrobromic acid, vitamin C, hydrazine hydrate, sodium hydroxide, sodium borohydride, etc.
  • Chemical reduction is performed using reducing agent solution or reducing agent vapor.
  • the temperature of chemical reduction is 50-150°C and the time is 30-200 minutes; the preferred temperature of chemical reduction is 70-120°C and the time is 60-150 minutes.
  • the invention discloses the application of amine compounds in preparing the above-mentioned graphene assembly fibers or graphene oxide fibers, and the amine compounds serve as flocculants.
  • the invention improves the axial stress transfer between connected graphene sheets and the mechanical properties of the assembly.
  • the conjugation of large-area graphene sheets can form an expanded ⁇ electron cloud, thereby achieving high electron mobility on the graphene sheets;
  • no foreign guest material is included between the stacked flakes, and results in a tight stacking of well-aligned graphene flakes, which favors ⁇ - ⁇ interactions and further improves mechanical and conductive properties.
  • the invention discloses the application of the above-mentioned graphene assembly fiber or graphene oxide fiber in the preparation of functional fiber materials, or the application in the preparation of functional fiber composite materials.
  • the so-called fiber composite materials refer to materials containing fibers or materials processed based on fibers through conventional methods. Conventional methods include weaving, spinning, bonding, etc.
  • the so-called functions are electrical conductivity, thermal conductivity, antibacterial, flexibility, etc.
  • the method of the present invention is simple and effective. It can be applied to high-performance fibers.
  • the obtained graphene fibers show very high mechanical properties, with a tensile strength of 3.2 ⁇ 0.2 GPa and a Young’s modulus of 290 ⁇ 54 GPa, which is far from the This is higher than the best recorded values of 2.2 GPa and 183 GPa reported so far.
  • the electrical conductivity measured along the fiber axis was 1.5 ⁇ 10 5 S m -1 , which is an order of magnitude higher than the electrical conductivity of graphene fibers obtained in the prior art. Therefore, the method of assembling graphene of the present invention is expected to be used to produce macroscopic graphene assemblies with mechanical and electrical properties close to those of single graphene.
  • Figure 1 shows the characterization diagram of GO sheets.
  • Figure 2 is a schematic diagram of the preparation of graphene assembly fibers.
  • Figure 4 is an optical microscope image of GO fibers spun from tubular channels of different diameters in the present invention.
  • Figure 5 is an optical microscope image of GO fibers spun from GO aqueous solutions of different concentrations in the present invention.
  • Figure 6 is an optical microscope image of the cross-section of a freshly solidified GO fiber.
  • Figure 7 shows that using a triangular nozzle, fibers with ribbon morphology can also be obtained.
  • Figure 8 is an SEM image of the GO fiber in Example 1, showing the smooth surface morphology and cross-section of the graphene fiber.
  • Figure 9 is an SEM image of the graphene assembly fiber of Example 1, showing a compact structure and good alignment in the stacking and longitudinal directions.
  • Figure 10 shows an example image of a fiber cross-section.
  • Figure 11 shows a dark field TEM image of fiber cross-section.
  • Figure 12 shows X-ray diffraction (XRD) and wide-angle X-ray scattering (WAXS) analysis.
  • Figure 13 shows the WAXS pattern (f) of graphene fiber, the radial (g) and azimuthal scan integration curve (h) of the WAXS mode.
  • Figure 14 shows the swelling behavior of GO fiber in water, where a is the fiber of Example 1 and b is the fiber of Comparative Example.
  • Figure 15 shows the solubility of graphene assembly fibers in acid.
  • Figure 16 shows the mechanical properties of graphene films.
  • Example SEM images show (d) the morphology of the fiber of Example 1 and (e) the fiber of the comparative example after fracture, and (f) the morphology of the fiber of the comparative example after fracture.
  • Figure 17 shows the mechanical properties test of graphene assembly fibers obtained from GO of different sizes.
  • Figure 18 shows the stress transmission of comparative graphene assembly fibers and control graphene assembly fibers.
  • Figure 19 is the stress-strain curve of the fiber before and after chemical reduction in Example 3.
  • Figure 20 shows the mechanical properties test of graphene assembly fibers obtained with different concentrations of 1,2,4,5-tetraaminobenzene hydrochloride aqueous solution.
  • a graphene oxide aqueous solution is injected into an amine compound aqueous solution to obtain graphene oxide fibers; and then the graphene oxide fibers are chemically reduced to obtain graphene assembly fibers.
  • the method for preparing graphene oxide aqueous solution into graphene oxide fibers is a conventional method for preparing graphene oxide fibers.
  • the creativity lies in the fact that the present invention uses an aqueous amine compound solution as a coagulation bath for the first time to obtain graphene oxide fibers.
  • the concentration of the graphene oxide aqueous solution is 0.1mg/mL ⁇ 100mg/mL, preferably 1mg/mL ⁇ 50mg/mL, and more preferably 2mg/mL ⁇ 30mg/mL; the concentration of the amine compound aqueous solution is 0.1mM ⁇ 30mM, preferably The range is 0.5mM to 20mM, more preferably 1mM to 10mM.
  • the amine compound can be prepared in the form of an amine compound salt, such as an amine compound hydrochloride or an amine compound sulfate.
  • the amine compound is an aromatic amine compound containing two or more amine groups; the chemical structural formula of the amine compound is R (NH 2 ) n , n is greater than 2, such as 2 to 8, preferably 2 to 6, and n represents There are n amine groups connected to R, which does not mean that n amine groups are repeated in series; R is an aryl group, a heterocyclic group, etc., and an aryl group includes a phenyl group, a substituted phenyl group, a biphenyl group, a substituted biphenyl group, and a fused ring Aromatic hydrocarbons and substituted condensed ring aromatic hydrocarbons, the substituents involved are halogens, alkyl groups, heteroatoms, etc.; preferably, the molecular weight of the amine compound is less than 1000, and it is a small molecular compound.
  • the benzylamine compound of the present invention is one of the following: .
  • a is 1 to 10, preferably 1 to 5;
  • the phenyl or substituted phenylamine compound is one of the following: .
  • R ⁇ is one or more of hydrogen, halogen, alkyl, alkoxy, heterocyclic group, and aromatic group, and the substitution position is not limited; b represents the number of amine groups, which is 2 to 4.
  • amine compounds include o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 3,4'-diaminodiphenyl ether, 1,2,4,5-tetraaminobenzene, 1,5-naphthylenediamine, 1,4-Naphthalenediamine, 4,4-diaminobiphenyl, 3,3',4,4'-biphenyltetramine, 2,3,5,6-pyridinetetramine, 2,2'-di Aminodiphenyl disulfide, 1,3-phenylenediamine, 4,4'-diaminodiphenylamine, 4,4'-diphenylbiphenyldiamine, 4,4'-diaminobenzoanilide, Meta-aminobenzylamine, 4,4 ⁇ -diamino-2,2 ⁇ -dimethyl-1,1 ⁇ -biphenyl, 2,2 ⁇ -diaminobipheny
  • amine compounds can be prepared in the form of amine compound salts.
  • the solution concentration is based on the amine compound; amine compound hydrochloride or amine compound sulfate can be selected, such as 3,3'-diaminobenzidine hydrochloride.
  • amine compound hydrochloride or amine compound sulfate can be selected, such as 3,3'-diaminobenzidine hydrochloride.
  • (1,1'-Biphenyl)-3,3'4,4'-tetraaminetetrahydrochloride (CAS No.:868272-85-9), 1,2,4,5-tetraaminobenzene hydrochloride salt, ethylenediamine hydrochloride, p-phenylenediamine hydrochloride, naphthalenediamine hydrochloride, benzidine hydrochloride, etc.
  • the present invention adopts an industrially applicable wet spinning scheme, in which aqueous GO is injected with an aromatic amine solution used as a flocculant; the solidified GO is then chemically reduced to prepare graphene fibers.
  • the present invention prefers aromatic amines as flocculants, and their aromatic rings are connected to -NH 2 substituents to achieve rapid solidification of GO sheets; then chemical reduction forms a graphene structure.
  • the graphene oxide aqueous solution can be injected into the coagulation bath through a spinning tube.
  • the inner diameter of the spinning tube can be 1 ⁇ m to 1 cm.
  • the specific injection method is a conventional technology in which the graphene oxide aqueous solution is assembled into fibers.
  • Expandable graphite (approximately 300 ⁇ m) was purchased from Nanjing Pioneer Nanomaterial Technology Co., Ltd.; hydrochloric acid (HCl, 12 mol L -1 ), potassium permanganate (KMnO 4 , ⁇ 99.5%) and sulfuric acid (H 2 SO 4 , 98% ) was purchased from Jiangsu Johnson & Johnson Functional Chemical Co., Ltd.; hydrogen peroxide (H 2 O 2 , 30%) was purchased from Shanghai Lingfeng Chemical Reagent Co., Ltd.; hydroiodic acid (HI, 57 wt%) was purchased from Adamas Beta; 1,2 ,4,5-tetraaminobenzene hydrochloride was obtained from Shanghai Bidepharmatech Co., Ltd., with the following structural formula: .
  • the tensile strength test was performed using a commercial mechanical tensile testing system (HY-0350, Shanghai Hengyi Precision Instrument Co., Ltd.) equipped with a precision force detector program with an accuracy of 0.00001 N.
  • the individual fibers were glued to a rectangular paper frame and mounted to the test system.
  • the specified tensile test length is 5 to 20 mm, and different loading strain rates include 0.01, 0.05, and 0.1 mm min -1 . Adjusting the above parameters has no significant impact on mechanical property measurements.
  • Conductivity was measured using the standard four-probe method. Attach four equally spaced collinear silver probes to the same side of the fiber sample using silver paste. A Keithley2400 multifunctional instrument is used as the current source, current is applied to the probes at both ends, and the corresponding voltage changes of the two inner probes are measured. ⁇ (S m -1 ) is calculated according to the following formula: .
  • I (A) is the applied current
  • U (V) is the corresponding voltage
  • S (m 2 ) is the cross-sectional area measured by SEM
  • L (m) is the distance between electrodes (10 mm).
  • the raw materials used in the present invention are all commercially available products, and the specific preparation operations and testing methods are conventional techniques.
  • GO nanosheets are prepared according to the existing modified Hummers method. 1g of expandable graphite is maintained at 1000°C for 30 seconds, then added to 60ml of sulfuric acid, heated to 80°C, and then 0.84g of potassium persulfate and 1.24g of pentoxide are added. diphosphorus, then add 40ml sulfuric acid and 3g potassium permanganate for oxidation, and then add 2ml hydrogen peroxide. After the reaction, the product is separated, and then washed with hydrochloric acid and water to obtain graphene oxide (GO) dispersed in water.
  • the base and edges of GO sheets are rich in polar oxygen-containing functional groups, which lead to negative surface charges and form stable aqueous dispersions.
  • Figure 1 shows the characterization diagram of GO sheets. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) show that the lateral size of GO sheets is mainly between 10-70 ⁇ m, and the average thickness is about 1 nm; using X-ray photoelectron spectroscopy (XPS) ) and Fourier transform infrared spectroscopy (FTIR) verified the presence of oxygen-containing groups, and elemental analysis showed that the C:O atomic ratio was 1.15.
  • XPS X-ray photoelectron spectroscopy
  • FTIR Fourier transform infrared spectroscopy
  • Example 1 Preparation of graphene assembly fibers: GO aqueous solution (10 mg/mL) is squeezed into 1,2,4,5-tetraaminobenzene hydrochloride aqueous solution (5mM) through a syringe (inner diameter: 160 ⁇ m), and a gel is visible Fibers are formed, and then brown-yellow GO fibers are formed after rotating in the coagulation bath for 5 minutes. The GO fibers are picked out and collected. See Figure 2.
  • a watch glass containing 1,2,4,5-tetraaminobenzene hydrochloride aqueous solution is placed in the Rotate on the rotating table; use glass rods to pick out and collect the fibers; then suspend the GO fibers on parallel rods and expose them to hydriodic acid vapor at 90°C for 12 hours; then wash them 5 times with water and ethanol alternately to remove iodine ions, etc., to obtain graphene assembly fibers.
  • Conventional testing showed no iodine residue, and the weight density was 1.90 g cm -3 , measured using the float-sink method.
  • Example 2 Based on Example 1, the inner diameter of the syringe is 1.5 mm, 500 ⁇ m or 340 ⁇ m, and the rest is the same to obtain graphene assembly fibers.
  • the concentration of the GO aqueous solution is 1 mg/mL or 20 mg/mL, and the rest is the same to obtain graphene assembly fibers.
  • Comparative Example GO was dispersed in DMF, ethyl acetate was used as the coagulation bath, and other conditions were the same as Example 1 to obtain comparative graphene assembly fibers.
  • the graphene assembly fibers formed in the embodiments of the present invention have an unusual ribbon morphology.
  • the unique edge assembly can spontaneously generate a ribbon morphology with an ordered assembly, which can enhance the relationship between the graphene planes.
  • the ⁇ - ⁇ interaction leads to its self-assembly into anisotropic ribbon morphology.
  • Figure 4 is an optical microscope image of GO fibers spun from tubular channels of different diameters.
  • Figure 5 is an optical microscope image of GO fibers spun from GO aqueous solutions with different concentrations. In all cases, the fibers exhibit a ribbon-like morphology.
  • FIG. 10 Atomic-level information of graphene assembly fibers was obtained through transmission electron microscopy (TEM).
  • Figure 10 shows an example image of a fiber cross-section, confirming the presence of a large area of graphite lattice, almost perfectly aligned.
  • SAED selected area electron diffraction
  • the corresponding selected area electron diffraction (SAED) pattern in the inset shows only 00l spots, which are sharp and straight, with The distance is 0.336 nm, close to the stacking distance in an ideal graphite structure, small values of interlayer distance indicate few structural defects, including flake wrinkling, stacking faults, or the presence of guest molecules between stacked flakes.
  • Example 1 graphene assembly fiber is in 12 M HCl for 1 hour
  • Example 3 (ethylenediamine hydrochloride) graphene fiber (II) and control example (Ca 2+ ) graphene assembly fiber (III) immersed in 1 M HCl, (II ), (III) completely dissolved in 5 minutes.
  • the tensile strength of the GO fiber is 1.9 ⁇ 0.09 GPa (the highest value reported so far), and the Young's modulus when the breaking strain is 1.3 ⁇ 0.3% is 153 ⁇ 41 GPa; the tensile strength of the graphene assembly fiber increases to 3.2 ⁇ 0.2 GPa, Young's modulus is 290 ⁇ 54 GPa, and breaking strain is 1.1 ⁇ 0.2%; compared with the highest reported value (2.25 GPa) of graphene fibers prepared by the existing technology, the mechanical strength of the fiber of the present invention is high Out 1.42 times.
  • the strength value of the present invention is comparable to the strength value of graphene fibers graphitized at extremely high temperatures (3.40 GPa) and 1.7 times that of graphitized annealed graphene fibers obtained by microfluidic assembly (1.90 GPa).
  • the significant enhancement in mechanical strength is due to the optimization of inter-chip connections at the atomic scale and the compact stacking at the microscopic scale.
  • the Young's modulus of the fiber of the present invention is also significantly higher than other graphene fibers prepared at near room temperature, and is close to the Young's modulus of the fiber after high-temperature graphitization treatment.
  • Raman spectroscopy is a useful tool for quantitatively observing this effect by measuring the displacement of characteristic bands under strain, as shown in the Raman spectroscopy (bc in Figure 16) where graphene G bands are observed due to tensile strain on the individual flakes redshift.
  • the increase in stress transfer in the control graphene assembly fiber only occurs at low strain values (Fig. 18).
  • the cross-sectional morphology of the fracture surface also confirmed this difference. After continuous sliding fracture, the fiber surface of the invention was smoother than that of the control sample (df in Figure 16).
  • the graphene assembly fiber of the present invention shows a higher Raman shift strain dependence: 9.54 cm -1 /%, the comparative example is 6.57 cm -1 /%, and the comparative example is 5.89 cm -1 /%.
  • the electrical conductivity of graphene-based materials is seriously affected by structural defects.
  • the fiber of the present invention also improves electronic conduction, thereby increasing the overall electronic conductivity, with 1.5 ( ⁇ 0.02) ⁇ 10 5 S m ⁇ 1
  • the excellent electrical conductivity is an order of magnitude higher than the electrical conductivity of graphene fibers prepared at low temperatures using the existing technology (Table 2).
  • Graphene has excellent mechanical and electrical properties. These excellent properties originate from its unique hexagonal lattice composed of carbon atoms. Each carbon atom is connected to three other carbon atoms. The carbon atoms in this unit pass through strong coherence. Valence ⁇ bonds, formed by overlapping sp hybrid orbitals, contribute to graphene's high electrical conductivity. Because graphene's single-atom thickness and large area give it a large aspect ratio, graphene sheets can be assembled into macroscopic structures such as graphene fibers. The starting point for the synthesis of macroscopic graphene is usually graphite oxide dispersed in a solvent. ene (GO), fibers are made from dispersed GO through wet spinning technology, and then graphene-based fibers are obtained through chemical or thermal reduction.
  • GO graphite oxide dispersed in a solvent.
  • the prior art emphasizes the importance of reducing structural defects and improving the regular arrangement of graphene sheets to enhance the mechanical and electrical properties of graphene fibers.
  • High-temperature annealing can eliminate atomic defects on graphene sheets and promote the formation of graphite crystallites, resulting in a tensile strength of 3.4 GPa, graphene fiber with Young's modulus of 342 GPa.
  • the use of high annealing temperatures is generally undesirable from an economic and ecological perspective, and the properties of the resulting macroscopic graphene are still much lower than expected from a single graphene layer. Therefore, it is particularly important to develop new strategies to prepare macroscopic graphene fibers at near room temperature and further prepare conductive graphene components with high mechanical properties.
  • Example 3 GO aqueous solution (10mg/mL) was extruded into ethylenediamine hydrochloride aqueous solution (5mM) through a syringe (inner diameter 160 ⁇ m). It can be seen that gel fibers were formed, and then brown-yellow GO was formed after rotating in the coagulation bath for 5 minutes. fibers, pick out and collect GO fibers.
  • the GO aqueous solution (10mg/mL) was extruded into the octanediamine aqueous solution (5mM) through a syringe (inner diameter 160 ⁇ m). It can be seen that gel fibers were formed, and then brown GO fibers were formed after rotating in the coagulation bath for 5 minutes. Pick out and collect the GO fiber.
  • the GO aqueous solution (10mg/mL) was extruded into the p-phenylenediamine hydrochloride aqueous solution (5mM) through a syringe (inner diameter 160 ⁇ m). It can be seen that gel fibers were formed, and then brown-yellow GO fibers were formed after rotating in the coagulation bath for 5 minutes. Take out and collect the GO fibers.
  • the GO aqueous solution (10mg/mL) was extruded into the naphthalenediamine hydrochloride aqueous solution (5mM) through a syringe (inner diameter 160 ⁇ m). It can be seen that gel fibers were formed, and then after rotating in the coagulation bath for 5 minutes, brown-yellow GO fibers were formed and picked out. and collect GO fibers.
  • the GO aqueous solution (10mg/mL) was extruded into the 4,4-diaminobiphenyl hydrochloride aqueous solution (5mM) through a syringe (inner diameter 160 ⁇ m). It can be seen that gel fibers were formed, and then a brownish yellow color was formed after rotating in the coagulation bath for 5 minutes. GO fibers, pick out and collect GO fibers.
  • the graphene fibers obtained from aromatic amines have a ribbon-like geometric shape different from that of the nozzle, exhibiting the same phenomenon as Example 1.
  • the remaining graphene fibers have a circular geometric shape of the nozzle.
  • Example 4 GO aqueous solution (10mg/mL) is squeezed into 1,2,4,5-tetraaminophenyl hydrochloride aqueous solution (2.5 or 10mM) through a syringe (inner diameter 160 ⁇ m). It can be seen that gel fibers are formed and then solidified. Brown GO fibers were formed after rotating in the bath for 5 minutes. Pick out and collect the GO fibers; use a glass rod to pick out and collect the fibers; then suspend the GO fibers on parallel rods and expose them to hydriodic acid vapor at 90°C for 12 hours; then wash 5 times with water and ethanol alternately to remove iodide ions, etc., and obtain the graphene assembly fiber. There is no iodine residue in the conventional test. The mechanical property test is shown in Figure 20, which is the stress-strain curve of the fiber after chemical reduction.
  • Example 5 GO aqueous solution (10mg/mL) is extruded into 1,2,4,5-tetraaminobenzene hydrochloride aqueous solution (5mM) through a syringe (inner diameter 160 ⁇ m). It can be seen that gel fibers are formed, and then in the coagulation bath After rotating for 5 minutes, brown GO fibers are formed. Pick out and collect the GO fibers with a glass rod; then suspend the GO fibers on the parallel rods and expose them to hydriodic acid vapor at 90°C for 6 or 9 hours. ; Then wash it alternately 5 times with water and ethanol to remove iodide ions, etc., and obtain the graphene assembly fiber. According to conventional tests, there is no iodine residue, the tensile strength is about 3 GPa, and the electrical conductivity is on the order of 10 5 S m -1 .
  • Example 6 GO aqueous solution (10mg/mL) is extruded into 3,3'-diaminobenzidine hydrochloride aqueous solution (5mM) through a syringe (inner diameter 160 ⁇ m). It can be seen that gel fibers are formed, and then rotated in the coagulation bath After 5 minutes, GO fibers were formed, and the GO fibers were picked out and collected; then the GO fibers were suspended on parallel rods and exposed to hydriodic acid vapor at 90°C for 8 hours; then washed 5 times alternately with water and ethanol to remove iodide ions, etc. , obtaining graphene assembly fibers.
  • this invention uses an aromatic amine compound as a coagulation bath to obtain graphene oxide fibers at room temperature under conventional wet spinning processes, and then chemically reduces them into graphene assembly fibers to avoid the introduction of 2D single graphene sheets when assembling them. Fracture occurs due to internal structural defects, and high tensile strength is achieved under the interaction between the edge of the sheet and the in-plane sheet, overcoming the problem of the upper limit bottleneck of the mechanical properties of existing graphene assembly fibers, especially avoiding the existing technology to improve There is a problem of reducing conductive properties due to mechanical properties, because covalent bonding between prior art graphene sheets often reduces conductivity due to interruption of electron transport by the linker, and requires functional modification to restore it.
  • the axial stress transmission between connected graphene sheets and the mechanical properties of the components are improved.
  • the conjugation of large-area graphene sheets can form an extended electron cloud covering the entire connection plane, thereby achieving high electron density on the graphene sheets. mobility, and avoids the entrapment of foreign guest molecules between stacked flakes and forms a compact stack of well-aligned graphene flakes, further improving mechanical and electrical properties.
  • the method of the present invention is simple and effective, and it can be applied to high-performance fibers and films.
  • the graphene fiber obtained by the method of the present invention has very high mechanical properties, with a tensile strength of 3.2 ⁇ 0.2 GPa and a Young's modulus of 290 ⁇ 54 GPa.
  • the connected larger graphene sheets are highly oriented and tightly stacked, and the edge connections and accompanying extended conjugated structure improve the mechanical properties and electronic conductivity of the fiber, especially without the need for high-temperature annealing.
  • the method of the present invention is simple and effective, and can be applied to the manufacture of macroscopic fibers.
  • the fibers produced at near room temperature are simultaneously enhanced in terms of tensile strength, modulus and electrical conductivity, which highlights the use of graphene as a precursor to carbon fiber manufacturing in the present invention.

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Abstract

L'invention concerne une fibre d'assemblage au graphène, et son procédé de préparation et son utilisation. Une solution aqueuse d'oxyde de graphène utilisée en tant que solution de filage et une solution aqueuse de composé amine utilisée en tant que bain de coagulation sont soumises à un filage et à un traitement de réduction pour obtenir une fibre d'assemblage au graphène. Selon l'état de la technique, le recuit à une température très élevée (telle que 3 000 °C) peut éliminer des défauts atomiques sur une feuille de graphène et favoriser la formation de microcristaux de graphite, ce qui permet d'améliorer la résistance à la traction. La fibre d'assemblage au graphène, et son procédé de préparation et son utilisation résolvent le problème d'une température élevée requise pour améliorer les performances mécaniques ; et la fibre de graphène obtenue à basse température présente des propriétés mécaniques très élevées, une résistance à la traction de 3,2 ± 0,2 GPa, un module de Young de 290 ± 54 GPa et une conductivité électrique de 1,5*105 S·m-1, et a un ordre de grandeur supérieur à celui d'une fibre de graphène obtenue selon l'état de la technique.
PCT/CN2022/113968 2022-06-07 2022-08-22 Fibre d'assemblage au graphène, et son procédé de préparation et son utilisation WO2023236351A1 (fr)

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