CN114411285B - Graphene/graphene quantum dot vertical fiber and preparation method and application thereof - Google Patents
Graphene/graphene quantum dot vertical fiber and preparation method and application thereof Download PDFInfo
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- CN114411285B CN114411285B CN202210216181.6A CN202210216181A CN114411285B CN 114411285 B CN114411285 B CN 114411285B CN 202210216181 A CN202210216181 A CN 202210216181A CN 114411285 B CN114411285 B CN 114411285B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- 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
- Y02E60/10—Energy storage using batteries
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- 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
Abstract
The invention discloses a graphene/graphene quantum dot vertical fiber and a preparation method and application thereof, wherein a graphene oxide aqueous solution is prepared by a Hummers method, and a graphene oxide gel solution is obtained after a part of the graphene oxide aqueous solution is concentrated; mixing and stirring a graphene oxide aqueous solution and a hydrogen peroxide solution to obtain a mixture A; then carrying out hydrothermal reaction on the mixture A to obtain a graphene oxide quantum dot solution; then mixing the graphene oxide gel solution with the graphene oxide quantum dot solution to obtain a graphene oxide/graphene oxide quantum dot solution, and then adjusting the viscosity of the graphene oxide/graphene oxide quantum dot solution; and (3) under the condition of room temperature, pumping the graphene/graphene oxide quantum dot solution with the adjusted viscosity into a sudden-expansion pore channel in a coagulating bath, and spinning to obtain the graphene/graphene oxide quantum dot solution.
Description
Technical Field
The invention belongs to the field of new material preparation, and relates to a graphene/graphene quantum dot vertical fiber and a preparation method and application thereof.
Background
In recent years, with the rapid development of portable intelligent fabrics, flexible and wearable electronic energy storage devices are more and more concerned by people, and the intelligent fabrics can integrate a plurality of different functions, such as sensing, heating, color changing, power generation, electromagnetic shielding and the like, and have infinite prospects in various fields, such as mobile phones, watches, intelligent furniture and the like. The flexible wearable device not only requires the energy storage device to have certain tensile strength and bending performance, but also has the characteristics of easy spinning and weaving. Graphene, as a single-atom-thickness nano-sheet structure, exhibits excellent electrical, mechanical and optical properties, and in recent years, has brought a hot trend in research in various fields. In 2011, a high-class group firstly prepares graphene fibers and initiates the assembly from one-dimensional graphene oxide sheets to two-dimensional graphene fibers. The graphene fiber is used as a macroscopic one-dimensional assembly material of graphene and is formed by orderly arranging a large number of graphene nano sheets. The graphene fiber inherits a series of excellent performances of graphene, such as higher conductivity, mechanical strength, bending performance, flexibility and the like, and shows unique advantages in a plurality of materials, so that the high-performance flexible graphene fiber is an ideal yarn type fiber supercapacitor material. For example, CN201911202193.8, "a method for preparing a fiber", teaches that a stacked graphene oxide fiber is prepared by a wet spinning technique, but in the process of assembling graphene sheets, due to strong van der waals force between graphene sheets, graphene agglomeration is caused, which results in a large reduction in the specific surface area of the graphene fiber, which greatly reduces the accessible specific surface area of solvated ions, and hinders ion transmission and storage, which also results in poor electrochemical properties of the graphene fiber.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problems of small specific surface area, electrode material accumulation, electrochemical reaction kinetics lag and the like of the conventional flexible electrode material, and provides a method for preparing graphene/graphene quantum dot vertical fibers.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of graphene/graphene quantum dot vertical fibers comprises the following steps:
(1) Preparing a graphene oxide aqueous solution by a Hummers method, and concentrating a part of the graphene oxide aqueous solution to obtain a graphene oxide gel solution;
(2) Mixing and stirring the graphene oxide aqueous solution obtained in the step (1) and a hydrogen peroxide solution to obtain a mixture A; then carrying out hydrothermal reaction on the mixture A to obtain a graphene oxide quantum dot solution;
(3) Mixing the graphene oxide gel solution obtained in the step (1) with the graphene oxide quantum dot solution obtained in the step (2) to obtain a graphene oxide/graphene oxide quantum dot solution, and then adjusting the viscosity of the graphene oxide/graphene oxide quantum dot solution;
(4) Pumping the graphene oxide/graphene oxide quantum dot solution with the viscosity adjusted in the step (3) into a sudden-expansion pore channel in a coagulating bath at room temperature, and spinning to obtain a graphene oxide/graphene oxide quantum dot vertical fiber;
(5) And (5) washing and drying the graphene oxide/graphene oxide quantum dot vertical fiber obtained by spinning in the step (4), and reducing by adopting hydroiodic acid to obtain the graphene/graphene quantum dot vertical fiber.
The graphene quantum dot serving as one member of a quantum dot family not only has the characteristics of excellent electrical property, low toxicity, excellent mechanical strength and the like of graphene, but also overcomes the problems of poor electron transmission performance and zero band gap of graphene of the traditional quantum dot, so that the graphene quantum dot has a good application prospect in the field of electrochemistry. In addition, the graphene fiber has remarkable advantages in mechanical flexibility and stability, and has a good application prospect in flexible energy storage equipment.
Specifically, in the step (1), the concentration of the graphene oxide aqueous solution is 2-5mg/ml, which is beneficial to the preparation of the graphene oxide quantum dots in the second step; the graphene oxide gel solution is obtained by rotary evaporation and concentration under the water bath condition, the concentration is 15-20mg/ml, and the stirring and mixing in the third step are facilitated.
In the step (2), the volume concentration of the hydrogen peroxide solution is 25% -30%, and the graphene oxide aqueous solution and the hydrogen peroxide solution are mixed and stirred for 1-3 hours to obtain a mixture A; the volume ratio of the graphene oxide aqueous solution to the hydrogen peroxide solution is 2:1 to 5:1.
in the step (2), the hydrothermal reaction is to place the mixture A in a hydrothermal kettle, heat the mixture A to 90-120 ℃ in a closed state, keep the temperature for 100-120min to obtain a graphene oxide quantum dot solution, and then obtain the graphene oxide quantum dot solution of 0.5-3mg/ml through rotary evaporation and concentration under the water bath condition.
In the step (3), the volume ratio of the graphene oxide gel solution to the graphene oxide quantum dot solution is 10:1 to 20:1.
in the step (3), a nitrate solution B is added into the graphene oxide/graphene oxide quantum dot solution, and the viscosity of the graphene oxide/graphene oxide quantum dot solution is adjusted to 150-250cp.
Preferably, the nitrate solution B is selected from any one of 0.1-0.5mol/L ferric nitrate solution, 0.2-0.6mol/L nickel nitrate solution or 0.1-0.4mol/L magnesium nitrate solution.
In the step (4), the sudden-expansion hole channel consists of a conical pipe sleeve and a cylindrical pipe sleeve; diameter D of front end opening of conical pipe sleeve 1 Is 3mm, the end opening is connected with a cylindrical pipe sleeve, and the diameter D 2 0.1-2mm, length L of the conical pipe sleeve 1 Is 3-4cm; a diameter D of a terminal opening of the cylindrical pipe sleeve 3 2-5mm, cylindrical pipe sleeve length L 2 Is 1.5-3cm.
In the step (4), the coagulation bath is a water tank containing coagulation liquid C; the coagulating liquid C is one or more of 95 vt-99.9 vt% ethanol, water, 0.5-2mg/ml CTAB and 0.4-3mg/ml chitosan solution; the pumping speed of the graphene/graphene oxide quantum dot solution is 0.1-10ml/min, and the rotating speed of the collecting roller is controlled to be 90-120r/min.
In the step (5), the graphene oxide/graphene oxide quantum dot vertical fibers obtained by spinning are respectively washed by 5-10 vt% hydrochloric acid and deionized water, and after freeze drying, hydroiodic acid is added, the mixture is heated to 60-90 ℃ in a sealed state, and the heat preservation time is 5-8h.
Further, the invention also claims the graphene/graphene quantum dot vertical fiber prepared by the preparation method.
Further, the invention also claims application of the prepared graphene/graphene quantum dot vertical fiber in battery materials.
Furthermore, the invention also claims a preparation method of the graphene oxide/graphene oxide quantum dot vertical fiber, which comprises the following steps:
(1) Preparing a graphene oxide aqueous solution by a Hummers method, and concentrating a part of the graphene oxide aqueous solution to obtain a graphene oxide gel solution;
(2) Mixing and stirring the graphene oxide aqueous solution obtained in the step (1) and a hydrogen peroxide solution to obtain a mixture A; then carrying out hydrothermal reaction on the mixture A to obtain a graphene oxide quantum dot solution;
(3) Mixing the graphene oxide gel solution obtained in the step (1) with the graphene oxide quantum dot solution obtained in the step (2) to obtain a graphene oxide/graphene oxide quantum dot solution, and then adjusting the viscosity of the graphene oxide/graphene oxide quantum dot solution;
(4) And (3) pumping the graphene oxide/graphene oxide quantum dot solution with the viscosity adjusted in the step (3) into a sudden-expansion pore channel in a coagulating bath at room temperature, and spinning to obtain the graphene oxide/graphene oxide quantum dot solution.
Furthermore, the invention also claims the graphene oxide/graphene oxide quantum dot vertical fiber prepared by the preparation method.
Furthermore, the invention also claims the application of the prepared graphene oxide/graphene oxide quantum dot vertical fiber in biomedicine, clothing textile and molecular carriers.
The graphene oxide/graphene oxide quantum dot vertical fiber can be used in the fields of clothing textile and the like due to the softness of the fiber, has a certain specific surface area, can be used as a transport carrier of a high polymer, and simultaneously contains rich oxygen-containing functional groups and can be used for catalysis and biomedicine.
The preparation method provided by the invention has the mechanism that certain van der Waals force exists between graphene sheet layers based on the liquid crystal phase phenomenon of graphene oxide. Graphene oxide and graphene oxide quantum dots are mixed, and the graphene oxide quantum dots are inserted between graphene oxide sheet layers, so that stacking of the graphene sheet layers is reduced. Injecting the graphene oxide/graphene oxide quantum dot solution into a coagulating bath to form graphene oxide/graphene oxide quantum dot fibers, and then carrying out freeze drying and hydroiodic acid reduction to prepare the graphene oxide/graphene oxide quantum dot vertical fibers.
Has the advantages that:
the flexible graphene/graphene quantum dot vertical fiber prepared by the method can be directly used as an electrode, so that the use of materials such as an adhesive and acetylene black is reduced; the contact area with the electrolyte is increased, the ion transfer and diffusion paths are shortened, and the free electron transfer capability and the charge storage capability are improved. In addition, the graphene quantum dots are uniformly distributed among the graphene sheet layers, so that the accumulation among the graphene sheet layers is reduced, the specific surface area of the material is further improved, and the electrochemical activity is improved. The flexible graphene/graphene quantum dot vertical fiber obtained by the invention has excellent electrochemical performance, high conductivity and stable cycle performance, and has good application prospect in flexible energy storage equipment.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
Fig. 1 is a flow chart of the preparation of the graphene/graphene quantum dot vertical fiber of the present invention.
Fig. 2 is a pictorial view of a sudden expansion orifice used in the present invention.
Fig. 3 is a camera view of the graphene quantum dots of the product of example 1 under an ultraviolet lamp.
Fig. 4 is a Scanning Electron Microscope (SEM) image of the graphene/graphene quantum dot vertical fibers of the product of example 1.
Fig. 5 is an X-ray diffraction (XRD) pattern of the product graphene/graphene quantum dot vertical fibers of example 2.
Fig. 6 is an infrared image of the graphene/graphene quantum dot vertical fibers of the product of example 2.
Fig. 7 is a Transmission Electron Microscope (TEM) image of graphene quantum dots of the product of example 2.
Fig. 8 is a graphene/graphene vertical fiber Scanning Electron Microscope (SEM) image of the product of example 2.
Fig. 9 is a graphene/graphene vertical fiber Scanning Electron Microscope (SEM) image of the product of example 3.
Fig. 10 is a Scanning Electron Microscope (SEM) image of graphene fibers of the product of comparative example 1.
Detailed Description
The invention will be better understood from the following examples.
The preparation process of the graphene/graphene quantum dot vertical fiber is shown in fig. 1. Wherein, the adopted sudden-expansion hole channel is shown in figure 2 and consists of a conical pipe sleeve and a cylindrical pipe sleeve; diameter D of front end opening of conical pipe sleeve 1 Is 3mm, the end opening is connected with a cylindrical pipe sleeve, and the diameter D 2 0.1-2mm, length L of the conical pipe sleeve 1 Is 3-4cm; a diameter D of a terminal opening of the cylindrical pipe sleeve 3 2-5mm, cylindrical pipe sleeve length L 2 Is 1.5-3cm.
Example 1
(1) Preparing a 2mg/ml graphene oxide aqueous solution by a Hummers method, and further concentrating the graphene oxide solution by rotary evaporation under a water bath condition to obtain a 15mg/ml graphene oxide gel solution;
(2) 70ml of the graphene oxide aqueous solution (2 mg/ml) obtained in the step (1) and 30ml of a 30% hydrogen peroxide solution are weighed, mixed and stirred for 1.5h to obtain a mixture A. Placing the mixture A in a hydrothermal kettle, heating to 100 ℃ in a closed state, preserving heat for 100min to obtain a graphene oxide quantum dot solution, and further performing rotary evaporation and concentration on the graphene oxide quantum dot solution under a water bath condition to obtain a 2mg/ml graphene oxide quantum dot solution;
(3) Stirring and mixing 4ml of the 15mg/ml graphene oxide gel solution obtained in the step (1) and 1.5ml of the 2mg/ml graphene oxide quantum dot solution obtained in the step (2) to obtain a graphene oxide/graphene oxide quantum dot solution. Adding 1ml of 0.3mol/L ferric nitrate solution into the graphene oxide/graphene oxide quantum dot solution, and adjusting the viscosity of the graphene oxide/graphene oxide quantum dot solution to 250cp;
(4) Measuring the graphene oxide/graphene oxide quantum dot solution obtained in the step (3) by using an injector at room temperature, injecting the graphene oxide/graphene oxide quantum dot solution into a water tank containing 99% ethanol in parallel, and suddenly expanding D in a pore channel 1 Is 3mm 2 Is 1mm, D 3 Is 2.5mm 1 Is 3cm, L 2 2cm, the injection speed is 0.5ml/min, and the rotation speed of the collecting roller is controlled to be 100r/min. After injection, washing the graphene oxide/graphene oxide quantum dot vertical fibers with 7% hydrochloric acid and deionized water for three times, and freeze-drying the washed graphene oxide/graphene oxide quantum dot vertical fibers for 24 hours to obtain graphene oxide/graphene oxide quantum dot vertical fibers;
(5) And (3) placing the dried graphene oxide/graphene oxide quantum dot vertical fibers obtained in the step (4) in a beaker, adding 15ml of hydroiodic acid, heating to 60 ℃ in a sealed state, and keeping the temperature for 6 hours to obtain the graphene/graphene quantum dot vertical fibers.
FIG. 3 shows that the graphene oxide quantum dots of example 1 emit green light under the irradiation of an ultraviolet lamp; fig. 4 is a scanning electron microscope image of the graphene/graphene quantum dot vertical fibers of the product of example 1, wherein a large number of sheets are stacked, and only a small amount of graphene is in a vertical structure.
Example 2
(1) Preparing a 2mg/ml graphene oxide aqueous solution by a Hummers method, and further concentrating the graphene oxide solution by rotary evaporation under a water bath condition to obtain a 15mg/ml graphene oxide gel solution;
(2) 70ml of the graphene oxide aqueous solution (2 mg/ml) obtained in the step (1) and 30ml of a 30% hydrogen peroxide solution are weighed, mixed and stirred for 1.5h to obtain a mixture A. Placing the mixture A in a hydrothermal kettle, heating to 100 ℃ in a closed state, preserving heat for 100min to obtain a graphene oxide quantum dot solution, and further performing rotary evaporation and concentration on the graphene oxide quantum dot solution under a water bath condition to obtain a 2mg/ml graphene oxide quantum dot solution;
(3) Stirring and mixing 4ml of the 15mg/ml graphene oxide gel solution obtained in the step (1) and 2ml of the 2mg/ml graphene oxide quantum dot solution obtained in the step (2) to obtain a graphene oxide/graphene oxide quantum dot solution. Adding 0.5ml of 0.3mol/L ferric nitrate solution into the graphene oxide/graphene oxide quantum dot solution, and adjusting the viscosity of the graphene oxide/graphene oxide quantum dot solution to 200cp;
(4) Measuring the graphene oxide/graphene oxide quantum dot solution obtained in the step (3) by using an injector at room temperature, injecting the solution into a water tank containing 99% ethanol in parallel, and suddenly expanding D in a pore channel 1 Is 3mm 2 Is 1mm, D 3 Is 2.5mm 1 Is 3cm 2 2cm, the injection speed is 0.5ml/min, and the rotation speed of the collecting roller is controlled to be 100r/min. After injection, washing the graphene oxide/graphene oxide quantum dot vertical fibers with 7% hydrochloric acid and deionized water for three times, and freeze-drying the washed graphene oxide/graphene oxide quantum dot vertical fibers for 24 hours to obtain graphene oxide/graphene oxide quantum dot vertical fibers;
(5) And (5) placing the dried graphene oxide/graphene oxide quantum dot vertical fiber obtained in the step (4) in a beaker, adding 15ml of hydroiodic acid, heating to 60 ℃ in a closed state, and keeping the temperature for 6 hours to obtain the graphene/graphene quantum dot vertical fiber.
Fig. 5 is an X-ray diffraction pattern of the product graphene/graphene quantum dot vertical fiber of example 2, wherein a characteristic diffraction peak of the pattern completely coincides with a characteristic peak of graphene;
fig. 6 is an infrared spectrum of the product graphene/graphene quantum dot vertical fiber obtained in example 2, and even though the graphene/graphene quantum dot vertical fiber is reduced by hydroiodic acid, a certain amount of hydrophilic groups such as hydroxyl groups and carboxyl groups still exist, so that the hydrophilicity of the vertical fiber electrode material and the wettability of the vertical fiber electrode material to an electrolyte are ensured.
Fig. 7 is a transmission electron microscope image of the graphene oxide quantum dots of the product of example 2, and it can be seen that the size of the graphene oxide quantum dots is substantially around 5 nm.
Fig. 8 is a scanning electron micrograph of the overall structure of example 2, in which graphene oxide and an appropriate amount of graphene oxide quantum dots are mixed, and in which the graphene quantum dots are uniformly dispersed among the graphene oxide sheets in the vertical fibers, so that the stacking among graphene oxide sheet layers is reduced, and the specific surface area of the vertical fibers is significantly increased.
Example 3
1) Preparing a graphene oxide aqueous solution of 2mg/ml by a Hummers method, and further concentrating the graphene oxide aqueous solution by rotary evaporation under a water bath condition to obtain a graphene oxide gel solution of 15 mg/ml;
(2) 70ml of the graphene oxide aqueous solution (2 mg/ml) obtained in the step (1) and 30ml of a 30% hydrogen peroxide solution are weighed, mixed and stirred for 1.5h to obtain a mixture A. Placing the mixture A in a hydrothermal kettle, heating to 100 ℃ in a closed state, preserving heat for 100min to obtain a graphene oxide quantum dot solution, and further performing rotary evaporation and concentration on the graphene oxide quantum dot solution under a water bath condition to obtain a 2mg/ml graphene oxide quantum dot solution;
(3) Stirring and mixing 4ml of the 15mg/ml graphene oxide gel solution obtained in the step (1) and 3ml of the 2mg/ml graphene oxide quantum dot solution obtained in the step (2) to obtain a graphene oxide/graphene oxide quantum dot solution. Adding 0.3ml of 0.3mol/L ferric nitrate solution into the graphene oxide/graphene oxide quantum dot solution, and adjusting the viscosity of the graphene oxide/graphene oxide quantum dot solution to 150cp;
(4) Measuring the graphene oxide/graphene oxide quantum dot solution obtained in the step (3) by using an injector at room temperature, injecting the solution into a water tank containing 99% ethanol in parallel, and suddenly expanding D in a pore channel 1 Is 3mm 2 Is 1mm, D 3 Is 2.5mm 1 Is 3cm 2 2cm, the injection speed is 0.5ml/min, and the rotation speed of the collecting roller is controlled to be 100r/min. After injection, washing the graphene oxide/graphene oxide quantum dot vertical fibers with 7% hydrochloric acid and deionized water for three times respectively, and cooling the washed graphene oxide/graphene oxide quantum dot vertical fibersFreeze-drying for 24 hours to obtain graphene oxide/graphene oxide quantum dot vertical fibers;
(5) And (5) placing the dried graphene oxide/graphene oxide quantum dot vertical fiber obtained in the step (4) in a beaker, adding 15ml of hydroiodic acid, heating to 60 ℃ in a closed state, and keeping the temperature for 6 hours to obtain the graphene/graphene quantum dot vertical fiber.
Fig. 9 is a scanning electron micrograph of the entire structure of example 3, in which graphene oxide and excessive graphene oxide quantum dots are mixed, and at this time, a large number of graphene sheets are stacked in the vertical fiber, the specific surface area of the electrode material is greatly reduced, and the sheets are stacked one another.
Comparative example 1
(1) Preparing a graphene oxide aqueous solution of 2mg/ml by a Hummers method, and further concentrating the graphene oxide solution by rotary evaporation at 40 ℃ in a water bath to obtain a graphene oxide gel solution of 15 mg/ml;
(2) Adding ammonia water into the graphene oxide gel liquid with the concentration of 15mg/ml, and adjusting the pH value of the graphene oxide gel liquid to 8;
(3) Injecting the graphene oxide gel solution (15 mL) obtained in the step (2) into a CTAB solution coagulating bath at an injection speed of 1.5mL/min, and freeze-drying the graphene oxide fiber after the injection is finished to obtain the graphene oxide fiber;
(4) And (4) placing the dried graphene oxide fiber obtained in the step (3) in a beaker, adding hydroiodic acid, heating to 70 ℃ in a closed state, and keeping the temperature for 6 hours to obtain the graphene fiber.
Fig. 10 is a scanning electron micrograph of the graphene fibers of the product of comparative example 1, and it can be seen that interlaminar stacking between the fibers presents a parallel structure, and the specific surface area is greatly reduced.
The samples obtained in examples 1 to 3 and comparative example 1 were tested for their specific mass capacity and specific surface area by the following specific detection methods: the mass specific capacity is tested by adopting an electrochemical constant-current charging and discharging technology. The test is carried out by using a traditional three-electrode system, wherein the reference electrode is a silver/silver chloride electrode, the counter electrode is a platinum sheet electrode, the sample to be tested is a working electrode, and the electrolyte is 1mol L -1 H of (A) to (B) 2 SO 4 And (3) solution. The specific surface area was measured by nitrogen adsorption. The test results are shown in Table 1.
As can be seen from table 1, the graphene/graphene quantum dot vertical fiber provided by the present invention has a higher surface area and a higher electrochemical performance than the comparative example. The main reasons are two reasons: 1. the graphene is vertically arranged by a vertical structure formed by wet spinning, so that the specific surface area of the material is greatly increased. 2. The nano-sized graphene oxide quantum dots can provide certain active sites, and can effectively improve the specific surface area of the material by dispersing the graphene oxide quantum dots between graphene sheets, so that excellent electrochemical performance is further obtained, and the cycling stability is ensured.
TABLE 1
The invention provides a graphene/graphene quantum dot vertical fiber, a preparation method thereof, an application concept thereof and a method thereof, and a method for implementing the technical scheme specifically, the method and the way are many, the above description is only a preferred embodiment of the invention, it should be noted that, for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations should also be regarded as the protection scope of the invention. All the components not specified in this embodiment can be implemented by the prior art.
Claims (10)
1. A preparation method of graphene/graphene quantum dot vertical fibers is characterized by comprising the following steps:
(1) Preparing a graphene oxide aqueous solution by a Hummers method, and concentrating a part of the graphene oxide aqueous solution to obtain a graphene oxide gel solution;
(2) Mixing and stirring the graphene oxide aqueous solution obtained in the step (1) and a hydrogen peroxide solution to obtain a mixture A; then carrying out hydrothermal reaction on the mixture A to obtain a graphene oxide quantum dot solution;
(3) Mixing the graphene oxide gel solution obtained in the step (1) with the graphene oxide quantum dot solution obtained in the step (2) to obtain a graphene oxide/graphene oxide quantum dot solution, and then adjusting the viscosity of the graphene oxide/graphene oxide quantum dot solution to 150-250cp;
(4) Pumping the graphene oxide/graphene oxide quantum dot solution with the viscosity adjusted in the step (3) into a sudden expansion pore channel in a coagulating bath at room temperature, and spinning to obtain a graphene oxide/graphene oxide quantum dot vertical fiber; the sudden-expansion pore passage consists of a conical pipe sleeve and a cylindrical pipe sleeve, and an opening at the tail end of the conical pipe sleeve is connected with the cylindrical pipe sleeve;
(5) And (3) washing and drying the graphene oxide/graphene oxide quantum dot vertical fiber obtained by spinning in the step (4), and reducing by using hydroiodic acid to obtain the graphene/graphene quantum dot vertical fiber.
2. The method for preparing the graphene/graphene quantum dot vertical fiber according to claim 1, wherein in the step (1), the concentration of the graphene oxide aqueous solution is 2-5mg/ml; the graphene oxide gel solution is obtained by rotary evaporation concentration under the water bath condition, and the concentration is 15-20mg/ml.
3. The preparation method of the graphene/graphene quantum dot vertical fiber according to claim 1, wherein in the step (2), the volume concentration of the hydrogen peroxide solution is 25% -30%, and the graphene oxide aqueous solution and the hydrogen peroxide solution are mixed and stirred for 1-3h to obtain a mixture A; the volume ratio of the graphene oxide aqueous solution to the hydrogen peroxide solution is 2:1 to 5:1;
the hydrothermal reaction is that the mixture A is placed in a hydrothermal kettle and heated to 90-120 ℃ in a closed state o And C, preserving the temperature for 100-120min to obtain a graphene oxide quantum dot solution, and then performing rotary evaporation concentration under the water bath condition to obtain the graphene oxide quantum dot solution of 0.5-3 mg/ml.
4. The method for preparing the graphene/graphene quantum dot vertical fiber according to claim 1, wherein in the step (3), the volume ratio of the graphene oxide gel solution to the graphene oxide quantum dot solution is 10:1 to 20:1;
and adding a nitrate solution B into the graphene oxide/graphene oxide quantum dot solution, and adjusting the viscosity of the graphene oxide/graphene oxide quantum dot solution to 150-250cp.
5. The method for preparing the graphene/graphene quantum dot vertical fiber according to claim 1, wherein in the step (4), the front end opening diameter D of the conical pipe sleeve 1 Is 3mm, and has a terminal opening diameter D 2 0.1-2mm, length L of the conical pipe sleeve 1 Is 3-4cm; a diameter D of a terminal opening of the cylindrical pipe sleeve 3 2-5mm, cylindrical pipe sleeve length L 2 Is 1.5-3cm.
6. The method for preparing the graphene/graphene quantum dot vertical fiber according to claim 1, wherein in the step (4), the coagulation bath is a water tank containing a coagulation liquid C; the coagulating liquid C is one or more of 95 vt-99.9 vt% ethanol, water, 0.5-2mg/ml CTAB and 0.4-3mg/ml chitosan solution; the pumping speed of the graphene/graphene oxide quantum dot solution is 0.1-10ml/min, and the rotating speed of the collecting roller is controlled to be 90-120r/min.
7. The method for preparing the graphene/graphene quantum dot vertical fiber according to claim 1, wherein in the step (5), the graphene oxide/graphene oxide quantum dot vertical fiber obtained by spinning is washed with 5 vt% -10 vt% hydrochloric acid and deionized water respectively, and after freeze drying, hydroiodic acid is added, and the fiber is heated to 60-90% in a closed state o C, keeping the temperature for 5-8h.
8. The graphene/graphene quantum dot vertical fiber prepared by the preparation method of any one of claims 1~7.
9. The use of the graphene/graphene quantum dot vertical fibers of claim 8 in battery materials.
10. A preparation method of graphene oxide/graphene oxide quantum dot vertical fibers is characterized by comprising the following steps:
(1) Preparing a graphene oxide aqueous solution by a Hummers method, and concentrating a part of the graphene oxide aqueous solution to obtain a graphene oxide gel solution;
(2) Mixing and stirring the graphene oxide aqueous solution obtained in the step (1) and a hydrogen peroxide solution to obtain a mixture A; then carrying out hydrothermal reaction on the mixture A to obtain a graphene oxide quantum dot solution;
(3) Mixing the graphene oxide gel solution obtained in the step (1) with the graphene oxide quantum dot solution obtained in the step (2) to obtain a graphene oxide/graphene oxide quantum dot solution, and then adjusting the viscosity of the graphene oxide/graphene oxide quantum dot solution to 150-250cp;
(4) Pumping the graphene oxide/graphene oxide quantum dot solution with the viscosity adjusted in the step (3) into a sudden-expansion pore channel in a coagulating bath at room temperature, and spinning to obtain the graphene oxide/graphene oxide quantum dot solution; the sudden expansion hole channel consists of a conical pipe sleeve and a cylindrical pipe sleeve, and an opening at the tail end of the conical pipe sleeve is connected with the cylindrical pipe sleeve.
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