WO2022265586A1 - A method for preparing graphene oxide fibers by wet spinning - Google Patents

A method for preparing graphene oxide fibers by wet spinning Download PDF

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Publication number
WO2022265586A1
WO2022265586A1 PCT/TH2022/000023 TH2022000023W WO2022265586A1 WO 2022265586 A1 WO2022265586 A1 WO 2022265586A1 TH 2022000023 W TH2022000023 W TH 2022000023W WO 2022265586 A1 WO2022265586 A1 WO 2022265586A1
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Prior art keywords
graphene oxide
fibers
wet spinning
preparing graphene
spinning according
Prior art date
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PCT/TH2022/000023
Other languages
French (fr)
Inventor
Apichai JOMPHOAK
Kata JARUWONGRUNGSEE
Noppadon Nuntawong
Tawee POGFAY
Uraiwan WAIWIJIT
Thitima MATUROS DANIELS
Kotchaporn JARIYAKUN
Wanida PONGSAKSAWAD
Piya KHAMSUK
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National Science And Technology Development Agency
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Publication of WO2022265586A1 publication Critical patent/WO2022265586A1/en

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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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/06—Feeding liquid to the spinning head
    • D01D1/09—Control of pressure, temperature or feeding rate
    • 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
    • C01B32/198—Graphene oxide
    • 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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • 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
    • 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
    • D01F11/121—Halogen, halogenic acids or their salts
    • 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

  • This invention generally relates to the fields of chemistry, materials science, and materials engineering related to fabrication of graphene oxide (GO) fibers by wet- spinning method.
  • Carbon fiber is a functional fiber material that can be applied in various industries due to its properties and performance in many aspects.
  • CF is generally synthesized from cellulose or natural fibers.
  • Remarkable advantages of CF are its mechanical properties such as high tensile strength, flexibility, and light weight. When it is molded into synthetic fibers it can have a performance up to 1.7 GPa and a tensile strength of 400 GPa. It also is resistant to chemicals and harsh environments, as well as being stable at high temperatures. Because of these advantages that make CF into an indispensable part of structure or the key component in other technologies such as aircraft, vehicles, and cables, etc. However, CF also has disadvantages, its electrical conductivity is not as good as metal due to the arrangement of carbon atoms within its molecular structure.
  • Graphene is a material whose entire structure composed of hexagonally arranged carbon atoms connected in a two-dimensional plane network which has structure that resembles the shape of a honeycomb in nature. It is a nano-scale sheet of graphene because it is only one carbon atom thick. The molecular structure of graphene sheet also forms the basic structure of other carbon-based materials, such as carbon nanotube (CNT), graphite, and buckyball. Since the discovery of graphene, there has widely been numerous research and development in various fields and applications because it has many outstanding properties than other materials, for example conductivity properties, coexistence with other types of organic matter, transparency, chemically inert reaction, electron mobility, light weight, high specific surface area, strength, and toughness. Because of these outstanding properties that are superior to other materials, as a result, graphene has been more widely used in electronic and sensor applications than other carbon-based materials.
  • CNT carbon nanotube
  • the sheet structure also has limitations, i.e. it cannot directly be used by itself because a single layer of graphene is only one carbon atom thick. Consequently, there must be a base material to support it from the beginning of the synthesis process all the way through to its applications. Some base materials may affect or alter some properties of graphene.
  • KR 101830797 Bl reveals the development of graphene fiber fabrication using polymer fiber as a substrate for GO bonding and then separate the substrate from GO fiber that will only left with the basic structure, but the length of produced fiber does not exceed 5 micrometers.
  • US patent, document No. US 10480099 B2 reveals a continuous graphite fiber synthesis process containing at least 90% of graphene by weight and less than 5% of oxygen by weight, the process consists of preparing GO as a gel-like colloidal solution and allows it to flow through by substrate. Then, the fiber is heat to more than 1000 ° C to intentionally increase the strength of fibers.
  • the invention involves a method of preparing GO fibers by wet spinning technique using a coagulant solution to fabricate GO or rGO fibers with consistent length that can maintain their shape continuously without the use of additive.
  • the above methods comprising the steps of a) Preparing graphene oxide mixtures in solvent selected from water, N-methyl- 2-pyrrolidone (NMP), N,N-dimethyl formamide (DMF), or the mixture thereof which the concentration of graphene oxide in the ranges of 5 to 30 mg/ml; b) Injecting the graphene oxide mixtures obtained from step a) through a nozzle with a diameter of 0.5 to 1.5 mm at a speed of 0.1 to 0.5 ml/min into a coagulation bath rotated at 5 to 30 rpm to obtain graphene oxide fibers, where the coagulation bath contains a coagulant of a silver nitrate (AgNOi) in a solvent mixture of ethanol and water with a volumetric ratio of ethanol to water in
  • FIG. 1 Image of rGO fibers and its morphology.
  • FIG. 2 Demonstrate electrical conductivity of rGO fibers.
  • the invention involves a method of preparing rGO fibers by wet spinning technique using a coagulant to fabricate GO or rGO fibers with consistent length that can maintain their shape continuously without the use of additives while sustaining good electrical conductivity.
  • any tools, equipment, methods, or chemicals mentioned herein refer to tools, equipment, methods, or chemicals commonly practiced or used by those who are skilled in the arts and sciences in this field unless expressly stated as a tool, device, method, or special chemical, or specific to this invention.
  • estimate is used to indicate that any value appears or is expressed herein may change or may deviate where the variation or deviation may be caused by device discrepancy.
  • this invention involves a method of preparing GO fibers by wet spinning that comprising the steps of c) Preparing graphene oxide mixtures in solvent selected from water, N-methyl- 2-pyrrolidone (NMP), N,N-dimethyl formamide (DMF), or the mixture thereof which the concentration of graphene oxide in the ranges of 5 to 30 mg/ml; d) Injecting the graphene oxide mixtures obtained from step a) through a nozzle with a diameter of 0.5 to 1.5 mm at a speed of 0.1 to 0.5 ml/min into a coagulation bath rotated at 5 to 30 rpm to obtain graphene oxide fibers, where the coagulation bath contains a coagulant of a silver nitrate (AgNOi) in a solvent mixture of ethanol and water with a volumetric ratio of ethanol to water in the range of 1:1 to 1:5, wherein concentrations of silver nitrate solution is in the range of
  • solvent selected from water, N-methyl- 2-pyrrol
  • the concentration of silver nitrate solution is in the range of 0.2 to 0.3 Molar.
  • the volumetric ratio of ethanol to water is in the range of 1:2 to 1:3.
  • the concentration of graphene oxide is in the ranges of 8 to 15 mg/ml.
  • the used solvent is water.
  • the graphene oxide has a particle size in the range of 150 to 300 microns.
  • the graphene oxide mixture is injected through a nozzle with a diameter of 0.8 to 1.0 mm
  • the graphene oxide mixture is injected through the nozzle at a speed in the range of 0.2 to 0.4 ml/min.
  • the coagulation bath is rotated at a speed of 10 to 20 rpm.
  • the method also consists of a step c) an acid reduction of GO fibers. This is performed by soaking the GO fibers obtained from step b) in concentrated acid for a period of 15 to 60 minutes.
  • the concentrated acid is selected from hydroiodic acid, ascorbic acid, hydrazine, hydrochloric acid, or a mixture thereof. In one of the desirable features of invention, the concentrated acid is hydroiodic acid.
  • the method also consists of a step of drying of the GO or rGO fibers by the method chosen from baking, annealing under an atmosphere of inert gases, annealing under vacuum, annealing under ultraviolet (UV) rays, either or several together.
  • a step of drying of the GO or rGO fibers by the method chosen from baking, annealing under an atmosphere of inert gases, annealing under vacuum, annealing under ultraviolet (UV) rays, either or several together.
  • the precursors used in the synthesis process consist of graphite powder with an approximate diameter of 180 microns which containing more than 95% carbon, sulfuric acid (H2SO4, 98% concentration), ethanol, potassium permanganate (KMn0 4 ), hydrochloric acids (HC1, 37 % concentration), hydrogen peroxide (H2O2, 30% concentration), silver nitrate (AgNOs) and hydroiodic acid (HI, 55% concentration).
  • the first step, preparation of expanded graphite is to increase the spacing between the graphene plates in the graphite crystals via thermal expansion. This is performed by calcining approximately 1 g of graphite at 800°C for approximately 1 minute.
  • the second step the preparation of GO by modified Hummers’ method is initiated by mixing approximately 1 g of thermally expanded graphite obtained from the first step and concentrated acid. The concentrations of approximately 45 ml of sulfuric acid were mixed by stirring for approximately 30 minutes.
  • the third step approximately 3 g of KMn0 4 is added to the mixture from the second step, and then put it in an ice bath for approximately 4 hours with constant stirring. Then it is heated at about 35°C for about 2 hours.
  • the fourth step the temperature of the mixture is reduced to room temperature, and then add approximately 200 ml of deionized water and approximately 6 ml of hydrogen peroxide to the mixture and stir until the mixture turns yellowish brown.
  • the fifth step the mixture is rinsed with deionized water mixed with hydrochloric acid.
  • the volumetric ratio of deionized water to hydrochloric acid is approximately 9:1 by centrifuge at approximately 6,000 rpm until the mixture reaches a pH of approximately 3. It is centrifuged at high speed to separate the liquid from GO particles.
  • the GO concentration can be adjusted by dissolving the obtained GO particles in deionized water to approximately 10 mg/ml for next procedure.
  • the first step GO solution is prepared for fabricating GO fibers by wet spinning process. It can be started by adding the GO solution with a concentration of approximately 10 mg/ml, which is already prepared into a 10 ml syringe, and a 20G needle, approximately 0.9 mm in diameter, is used.
  • the second step, preparation of a coagulation bath can be conducted with various coagulants such as calcium chloride (CaCh) at a concentration of 0.25 molar in an aqueous and ethanol solvent at a volumetric ratio of 3:1 , silver chloride (AgCl) at a concentration of 0.2 molar in aqueous solvent with ethanol at a volumetric ratio of 3 : 1 , and silver nitrate
  • the third step, fabrication of GO fibers by wet spinning process can be conducted by injecting the solution prepared in the first step at a speed of 0.3 ml per minute into the coagulant bath rotated at approximately 20 rpm, in which allows GO solution to be injected from the needle tip and stretched according to the rotational force of the solution and can produce continuous GO fibers according to the whole amount of GO solution.
  • Reduction of GO fibers with HI is performed by immersing the obtained fibers in concentrated HI at different times: approximately 15, 30, 45, and 60 minutes to obtain rGO fibers by eliminating oxygen content.
  • FIG. 1 shows the characteristics of the graphene fibers prepared by this fabrication method. From the figure, the prepared rGO fiber is cohesive to form a continuous long fiber. It is shown on the left-hand side of FIG. 1 , and the morphology of the homogeneous surface area is determined by scanning electron microscope (SEM) images on the right-hand side of FIG. 1.
  • SEM scanning electron microscope
  • the electrical conductivity is tested by using a two-probe method by digital multimeter with a two-probe method by digital multimeter, the measurements are repeated 10 times in each sample, and the comparison is made among rGO fibers fabricated by the same method but with different coagulants.
  • the test results are shown in FIG. 2, and it is found that the electrical conductivity of rGO fibers can be obtained from CaCF with a concentration of 0.25 molar in an aqueous ethanol solution at a volumetric ratio of 3 : 1 , which is the most common coagulant for the preparation.
  • AgCl coagulant is used in a water-ethanol mixture at a volumetric ratio of 3 : 1 by starting the same procedure, AgCl is found to have low solubility in usable solvents. This makes it impossible to use AgCl as a coagulant at the desired concentration (approximately 0.25 molar), and thus requires a lower concentration of 0.2 molar.
  • rGO fibers obtained from the use of AgCl have lower electrical conductivity than that of CaCF.

Abstract

A method of preparing graphene oxide (GO) fibers by wet spinning that can obtain a fiber with consistent in length and maintains its shape continuously which comprising the steps of a) Preparing graphene oxide mixtures in solvent selected from water, N-methyl- 2-pyrrolidone (NMP), N,N-dimethyl formamide (DMF), or the mixture thereof which the concentration of graphene oxide in the ranges of 5 to 30 mg/ml; b) Injecting the graphene oxide mixtures obtained from step a) through a nozzle with a diameter of 0.5 to 1.5 mm at a speed of 0.1 to 0.5 ml/min into a coagulation bath rotated at 5 to 30 rpm to obtain graphene oxide fibers, where the coagulation bath contains a coagulant of a silver nitrate (AgNO3) in a solvent mixture of ethanol and water with a volumetric ratio of ethanol to water in the range of 1:1 to 1:5, wherein concentrations of silver nitrate solution is in the range of 0.1 to 0.5 Molar.

Description

A METHOD FOR PREPARING GRAPHENE OXIDE FIBERS BY WET
SPINNING
FIELD OF THE INVENTION
This invention generally relates to the fields of chemistry, materials science, and materials engineering related to fabrication of graphene oxide (GO) fibers by wet- spinning method.
BACKGROUND OF THE INVENTION
Carbon fiber (CF) is a functional fiber material that can be applied in various industries due to its properties and performance in many aspects. CF is generally synthesized from cellulose or natural fibers. Remarkable advantages of CF are its mechanical properties such as high tensile strength, flexibility, and light weight. When it is molded into synthetic fibers it can have a performance up to 1.7 GPa and a tensile strength of 400 GPa. It also is resistant to chemicals and harsh environments, as well as being stable at high temperatures. Because of these advantages that make CF into an indispensable part of structure or the key component in other technologies such as aircraft, vehicles, and cables, etc. However, CF also has disadvantages, its electrical conductivity is not as good as metal due to the arrangement of carbon atoms within its molecular structure.
In materials science, CF has been the beginning of carbon-based fiber technology. There has been an increase in the development of new carbon fibers that can overcome several limitations of conventional CF. Due to the breakthrough in nanotechnology of materials, especially with the discovery of graphene in 2004, a novel carbon material that holds many outstanding properties. And it has great potential to be synthesized as a new infrastructure for carbon-based fibers.
Graphene is a material whose entire structure composed of hexagonally arranged carbon atoms connected in a two-dimensional plane network which has structure that resembles the shape of a honeycomb in nature. It is a nano-scale sheet of graphene because it is only one carbon atom thick. The molecular structure of graphene sheet also forms the basic structure of other carbon-based materials, such as carbon nanotube (CNT), graphite, and buckyball. Since the discovery of graphene, there has widely been numerous research and development in various fields and applications because it has many outstanding properties than other materials, for example conductivity properties, coexistence with other types of organic matter, transparency, chemically inert reaction, electron mobility, light weight, high specific surface area, strength, and toughness. Because of these outstanding properties that are superior to other materials, as a result, graphene has been more widely used in electronic and sensor applications than other carbon-based materials.
At present day, industrial productions of graphene sheets that demand large area and high quality are sheet-forming synthesized by chemical vapor deposition (CVD) process, which requires high production resources resulting in high production costs. To reduce the cost of such production; therefore, graphene synthesis by other processes was correspondingly developed, for example chemical synthesis from powdered precursors of crystalline graphite. However, the product obtained from this method yields GO derivatives. Then, applications of GO derivatives have been developed by preparing to reduce the oxygen content of the structure into reduced graphene oxide (rGO) because it is one of the hassle-free production processes. In addition, some of the outstanding properties of graphene are still used to enhance the properties of various products, such as printing with graphene-based inks for sensor electrodes. The sheet structure also has limitations, i.e. it cannot directly be used by itself because a single layer of graphene is only one carbon atom thick. Consequently, there must be a base material to support it from the beginning of the synthesis process all the way through to its applications. Some base materials may affect or alter some properties of graphene.
Later, the conceptual idea to form graphene into fibers like carbon fiber was initiated. For example, by wet spinning method, the production of GO fibers can be applied in many products because it can be woven into a piece of cloth to increase the area and strength. In wet spinning process, additive polymers are commonly added to increase the stability of graphene fiber because they make the process easier to form into fibers. However, the use of stabilizers reduces the specific surface area of graphene and lead to less efficient performance. Subsequently, a binder-free process was developed, or binders will be later separated from the graphene, but still continuously needed to support the fiber formation until the end of production.
Therefore, the continuous processes of synthesizing GO and rGO fiber was developed. This means that there is no binders or any substrate materials. The fibers will have excellent electrical conductivity and better adhesion to benzene and aromatic compounds due to the greater surface area of GO or rGO, and the molecular structure will not be affected by binders added during the synthesis process.
The publication of patent application of the People's Republic of China, CN 109750391 A, reveals a positive pressure filament spinning process with a platform in which positive pressure synthesis is initiated at the grating of GO suspension nozzle and continued to extract fibers from tape molding. The fibers are moved on the support until dry and rolled up.
South Korean patent, KR 101830797 Bl, reveals the development of graphene fiber fabrication using polymer fiber as a substrate for GO bonding and then separate the substrate from GO fiber that will only left with the basic structure, but the length of produced fiber does not exceed 5 micrometers.
US patent, document No. US 10480099 B2, reveals a continuous graphite fiber synthesis process containing at least 90% of graphene by weight and less than 5% of oxygen by weight, the process consists of preparing GO as a gel-like colloidal solution and allows it to flow through by substrate. Then, the fiber is heat to more than 1000°C to intentionally increase the strength of fibers.
However, methods for preparing GO and rGO fibers according to the revelation described above, there is also the use of binder or substrate during the preparation process. This is because the fiber cannot maintain their own shape as soon as they are formed into fiber. Therefore, this invention developed a method for preparing GO and rGO fibers by wet spinning technique using a coagulant solution to produce a consistent length of continuously stable GO or rGO fiber without the use of a additive but still has good electrical conductivity.
SUMMARY OF THE INVENTION
The invention involves a method of preparing GO fibers by wet spinning technique using a coagulant solution to fabricate GO or rGO fibers with consistent length that can maintain their shape continuously without the use of additive. The above methods comprising the steps of a) Preparing graphene oxide mixtures in solvent selected from water, N-methyl- 2-pyrrolidone (NMP), N,N-dimethyl formamide (DMF), or the mixture thereof which the concentration of graphene oxide in the ranges of 5 to 30 mg/ml; b) Injecting the graphene oxide mixtures obtained from step a) through a nozzle with a diameter of 0.5 to 1.5 mm at a speed of 0.1 to 0.5 ml/min into a coagulation bath rotated at 5 to 30 rpm to obtain graphene oxide fibers, where the coagulation bath contains a coagulant of a silver nitrate (AgNOi) in a solvent mixture of ethanol and water with a volumetric ratio of ethanol to water in the range of 1:1 to 1:5, wherein concentrations of silver nitrate solution is in the range of 0.1 to 0.5 Molar.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 Image of rGO fibers and its morphology.
FIG. 2 Demonstrate electrical conductivity of rGO fibers.
DETAILED DESCRIPTION OF THE INVENTION The invention involves a method of preparing rGO fibers by wet spinning technique using a coagulant to fabricate GO or rGO fibers with consistent length that can maintain their shape continuously without the use of additives while sustaining good electrical conductivity.
Any inventive nature shown herein shall also include its application to other aspects of this invention unless otherwise stated. DEFINITION
The technical or scientific terms used herein shall be interpreted in the context in which they are used in the present invention and shall be defined as understood by those who are skilled in the arts and sciences in this field as well as any other definitions of technical or scientific terms that may be specifically discussed in other contexts of the full disclosure of the invention.
Any tools, equipment, methods, or chemicals mentioned herein refer to tools, equipment, methods, or chemicals commonly practiced or used by those who are skilled in the arts and sciences in this field unless expressly stated as a tool, device, method, or special chemical, or specific to this invention.
Using singular noun or singular pronoun when used with the word "included" in the claim or in the details of the invention shall mean “one” and shall include “one or more,” “at least one, and “one or more than one”.
Throughout this patent application, the term “estimate” is used to indicate that any value appears or is expressed herein may change or may deviate where the variation or deviation may be caused by device discrepancy. A method used to determine any values or by the person who uses the device or performs following that method.
All disclosed elements and/or methods and the claim are intended to cover the nature of the invention obtained by the act, performance, modification, or alteration of any factors without experimentation that are significantly different from this invention and obtain the qualified product and produce a similar effect with the nature of the present invention according to the opinion of a person who has an ordinary level of expertise in the arts or sciences that although not specified in any specific claim. Therefore, the substitutable or similar elements and/or methods to the nature of the present invention including modifications a small change that appears clearly to those who are skilled in this field of art and science should be considered within the intent, scope, and concept of invention as shown by the claim attached.
The following illustrates the invention in detail without any intention of limiting the scope of the invention.
In one method of invention, this invention involves a method of preparing GO fibers by wet spinning that comprising the steps of c) Preparing graphene oxide mixtures in solvent selected from water, N-methyl- 2-pyrrolidone (NMP), N,N-dimethyl formamide (DMF), or the mixture thereof which the concentration of graphene oxide in the ranges of 5 to 30 mg/ml; d) Injecting the graphene oxide mixtures obtained from step a) through a nozzle with a diameter of 0.5 to 1.5 mm at a speed of 0.1 to 0.5 ml/min into a coagulation bath rotated at 5 to 30 rpm to obtain graphene oxide fibers, where the coagulation bath contains a coagulant of a silver nitrate (AgNOi) in a solvent mixture of ethanol and water with a volumetric ratio of ethanol to water in the range of 1:1 to 1:5, wherein concentrations of silver nitrate solution is in the range of
0.1 to 0.5 Molar. In one of the desirable features of invention, the concentration of silver nitrate solution is in the range of 0.2 to 0.3 Molar.
In one of the desirable features of invention, the volumetric ratio of ethanol to water is in the range of 1:2 to 1:3.
In one of the desirable features of invention in the step a), the concentration of graphene oxide is in the ranges of 8 to 15 mg/ml.
In one of the desirable features of invention in the step a), the used solvent is water.
In one of the desirable features of invention in the step a), the graphene oxide has a particle size in the range of 150 to 300 microns.
In one of the desirable features of invention in the step b), the graphene oxide mixture is injected through a nozzle with a diameter of 0.8 to 1.0 mm
In one of the desirable features of invention in the step b), the graphene oxide mixture is injected through the nozzle at a speed in the range of 0.2 to 0.4 ml/min.
In one of the desirable features of invention in the step b), the coagulation bath is rotated at a speed of 10 to 20 rpm. In one of the features of invention, the method also consists of a step c) an acid reduction of GO fibers. This is performed by soaking the GO fibers obtained from step b) in concentrated acid for a period of 15 to 60 minutes.
In one of the desirable features of invention, the concentrated acid is selected from hydroiodic acid, ascorbic acid, hydrazine, hydrochloric acid, or a mixture thereof. In one of the desirable features of invention, the concentrated acid is hydroiodic acid.
In one of the desirable features of invention, the method also consists of a step of drying of the GO or rGO fibers by the method chosen from baking, annealing under an atmosphere of inert gases, annealing under vacuum, annealing under ultraviolet (UV) rays, either or several together.
To better understand the invention, an example of the method based on this invention will be given. The following examples are only to illustrate the features of this invention. This does not limit the scope of this invention.
EXAMPLE
Graphene Oxide Synthesis
The precursors used in the synthesis process consist of graphite powder with an approximate diameter of 180 microns which containing more than 95% carbon, sulfuric acid (H2SO4, 98% concentration), ethanol, potassium permanganate (KMn04), hydrochloric acids (HC1, 37 % concentration), hydrogen peroxide (H2O2, 30% concentration), silver nitrate (AgNOs) and hydroiodic acid (HI, 55% concentration).
The first step, preparation of expanded graphite is to increase the spacing between the graphene plates in the graphite crystals via thermal expansion. This is performed by calcining approximately 1 g of graphite at 800°C for approximately 1 minute.
The second step, the preparation of GO by modified Hummers’ method is initiated by mixing approximately 1 g of thermally expanded graphite obtained from the first step and concentrated acid. The concentrations of approximately 45 ml of sulfuric acid were mixed by stirring for approximately 30 minutes.
The third step, approximately 3 g of KMn04 is added to the mixture from the second step, and then put it in an ice bath for approximately 4 hours with constant stirring. Then it is heated at about 35°C for about 2 hours.
The fourth step, the temperature of the mixture is reduced to room temperature, and then add approximately 200 ml of deionized water and approximately 6 ml of hydrogen peroxide to the mixture and stir until the mixture turns yellowish brown. The fifth step, the mixture is rinsed with deionized water mixed with hydrochloric acid. The volumetric ratio of deionized water to hydrochloric acid is approximately 9:1 by centrifuge at approximately 6,000 rpm until the mixture reaches a pH of approximately 3. It is centrifuged at high speed to separate the liquid from GO particles. The sixth step, the GO concentration can be adjusted by dissolving the obtained GO particles in deionized water to approximately 10 mg/ml for next procedure.
Preparation of Graphene Oxide Fiber by Wet Spinning
The first step, GO solution is prepared for fabricating GO fibers by wet spinning process. It can be started by adding the GO solution with a concentration of approximately 10 mg/ml, which is already prepared into a 10 ml syringe, and a 20G needle, approximately 0.9 mm in diameter, is used.
The second step, preparation of a coagulation bath can be conducted with various coagulants such as calcium chloride (CaCh) at a concentration of 0.25 molar in an aqueous and ethanol solvent at a volumetric ratio of 3:1 , silver chloride (AgCl) at a concentration of 0.2 molar in aqueous solvent with ethanol at a volumetric ratio of 3 : 1 , and silver nitrate
(AgNOs) at a concentration of 0.25 molar in an aqueous ethanol solvent at a volumetric ratio of 3:1.
The third step, fabrication of GO fibers by wet spinning process can be conducted by injecting the solution prepared in the first step at a speed of 0.3 ml per minute into the coagulant bath rotated at approximately 20 rpm, in which allows GO solution to be injected from the needle tip and stretched according to the rotational force of the solution and can produce continuous GO fibers according to the whole amount of GO solution.
Graphene Oxide Fiber Reduction Process
Reduction of GO fibers with HI is performed by immersing the obtained fibers in concentrated HI at different times: approximately 15, 30, 45, and 60 minutes to obtain rGO fibers by eliminating oxygen content.
Process of Drying reduced Graphene Oxide Fibers The obtained rGO fibers from previous procedure is then washed several times with deionized water, and then dried in a vacuum incubator at a temperature of about 60°C with a pressure of about 5xl02 millibars for approximately 2 hours to obtain rGO fibers.
Characteristics and Conductivity of Reduced Graphene Oxide Fiber
FIG. 1 shows the characteristics of the graphene fibers prepared by this fabrication method. From the figure, the prepared rGO fiber is cohesive to form a continuous long fiber. It is shown on the left-hand side of FIG. 1 , and the morphology of the homogeneous surface area is determined by scanning electron microscope (SEM) images on the right-hand side of FIG. 1.
In addition, the electrical conductivity is tested by using a two-probe method by digital multimeter with a two-probe method by digital multimeter, the measurements are repeated 10 times in each sample, and the comparison is made among rGO fibers fabricated by the same method but with different coagulants. The test results are shown in FIG. 2, and it is found that the electrical conductivity of rGO fibers can be obtained from CaCF with a concentration of 0.25 molar in an aqueous ethanol solution at a volumetric ratio of 3 : 1 , which is the most common coagulant for the preparation.
Then, AgCl coagulant is used in a water-ethanol mixture at a volumetric ratio of 3 : 1 by starting the same procedure, AgCl is found to have low solubility in usable solvents. This makes it impossible to use AgCl as a coagulant at the desired concentration (approximately 0.25 molar), and thus requires a lower concentration of 0.2 molar. In addition, rGO fibers obtained from the use of AgCl have lower electrical conductivity than that of CaCF.
However, when a solution of AgN03 at a concentration of 0.25 molar is used in an aqueous ethanol solution at a volumetric ratio of approximately 3:1, it is found that the precipitate agent can form a long and strong rGO fiber with better electrical conductivity than other coagulants.
Although this invention is fully described, but it is understandable that the modification or various edits by those who have general expertise in the related arts and sciences involved within the scope and purpose of this invention may be the scope of this invention shall be in accordance with the nature of the invention set forth in the attached claim. It also covers any features of the invention that is not specifically stated in the claim, but it is useful application and has the similar effect as the features of this invention specified in the claim.
The best method of invention is as already described in detailed description of the invention.

Claims

1. Method for preparing graphene oxide (GO) fibers by wet spinning comprising: e) Preparing graphene oxide mixtures in solvent selected from water, N-methyl- 2-pyrrolidone (NMP), N,N-dimethyl formamide (DMF), or the mixture thereof which the concentration of graphene oxide in the ranges of 5 to 30 mg/ml; f) Injecting the graphene oxide mixtures obtained from step a) through a nozzle with a diameter of 0.5 to 1.5 mm at a speed of 0.1 to 0.5 ml/min into a coagulation bath rotated at 5 to 30 rpm to obtain graphene oxide fibers, where the coagulation bath contains a coagulant of a silver nitrate (AgNOi) in a solvent mixture of ethanol and water with a volumetric ratio of ethanol to water in the range of 1:1 to 1:5, wherein concentrations of silver nitrate solution is in the range of 0.1 to 0.5 Molar.
2. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 1, wherein the concentration of silver nitrate solution is in the range of 0.2 to 0.3 Molar.
3. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 1, wherein the volumetric ratio of ethanol to water is in the range of 1:2 to 1:3.
4. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 1, wherein the concentration of graphene oxide is in the ranges of 8 to 15 mg/ml.
5. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 1, wherein the solvent in step a) is water.
6. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 1, wherein the graphene oxide has a particle size in the range of 150 to 300 microns.
7. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 1, wherein the graphene oxide mixture is injected through a nozzle with a diameter of 0.8 to 1.0 mm
8. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 1, wherein the graphene oxide mixture is injected through the nozzle at a speed in the range of 0.2 to 0.4 ml/min.
9. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 1, wherein the coagulation bath is rotated at a speed of 10 to 20 rpm.
10. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 1 further comprising the step of reducing graphene oxide fiber by immersing the graphene oxide fibers obtained from step b) into concentrated acid for a period of 15 to 60 minutes.
11. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 10, wherein the concentrated acid is selected from hydroiodic acid, ascorbic acid, hydrazine, hydrochloric acid , or a mixture thereof.
12. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 11, wherein the concentrated acid is hydroiodic acid.
13. The method for preparing graphene oxide (GO) fibers by wet spinning according to claim 1 or 12, further comprising the step of drying by the method chosen from baking, annealing under inert gases, annealing under atmosphere, annealing under vacuum, annealing under ultraviolet (UV) rays, either or several together.
PCT/TH2022/000023 2021-06-19 2022-06-15 A method for preparing graphene oxide fibers by wet spinning WO2022265586A1 (en)

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Citations (3)

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CN104894692A (en) * 2015-06-03 2015-09-09 东华大学 Preparation method of high-strength graphene fibers
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