WO2016037456A1

WO2016037456A1 - Method for preparing graphene and composite film thereof based on i-shaped die

Info

Publication number: WO2016037456A1
Application number: PCT/CN2015/070510
Authority: WO
Inventors: 高超; 刘峥; 寇亮; 李拯; 彭蠡; 许震; 孙海燕; 夏芝香; 黄铁骑
Original assignee: 浙江碳谷上希材料科技有限公司
Priority date: 2014-09-10
Filing date: 2015-01-12
Publication date: 2016-03-17

Abstract

Disclosed are a method for preparing graphene and a composite film thereof based on an I-shaped die. In the method, a preparation device with an I-shaped die is used to prepare a graphene film and a graphene composite film. A tapered runner in the preparation device with a I-shaped die can effectively increase the acting force of a flow field to a graphene sheet, is beneficial for forming a regularly-orientated structure of a graphene dispersion system, and achieves the continuous preparation of a large area of graphene film. The thickness of the prepared graphene film is uniform. The continuous structure stacked layer by layer is highly ordered with less defects, which is beneficial for improving the conductivity of the graphene film material to heat and electricity and excellent mechanical performance, and is also beneficial for combination of graphene with various object materials. The prepared graphene film is beneficial for improving the conductivity of the graphene film material to heat and electricity and excellent mechanical performance.

Description

Method for preparing graphene based on inline die and composite film thereof

Technical field

The invention relates to a method for preparing a graphene film, in particular to a method for preparing graphene and a composite film thereof based on a flat die.

Background technique

In 2010, two professors at the University of Manchester, Andre Geim and Konstantin Novoselov, won the Nobel Prize in Physics for their first successful separation of stable graphene, setting off a worldwide upsurge in graphene research. Graphene is a monolayer of two-dimensional crystals with the highest strength of known materials (Science, 2008, 321, 385-388) and excellent electrical and thermal conductivity. It is currently the most ideal two-dimensional nanomaterial. Commonly used preparation methods are suction filtration, doctor blade method, spin coating method, spray coating method, and dip coating method. However, these preparation methods are difficult to achieve a large-scale continuous preparation of a structurally regular graphene film. At the same time, the internal structure of the graphene or graphene oxide film composed of the nano-scale graphene sheets prepared by these methods is not uniform, and there are often a large number of stress points and defects, which greatly affect the performance and mechanical properties of the film. The preparation of graphene film by suction filtration is limited by the limitation of the suction filtration device, and only a centimeter-scale membrane can be obtained, which requires a lot of time and energy; the scraping film method is determined by the process of scraping the film, the viscosity and surface of the graphene solution. The tension also affects the structure of the film; the spin coating method can only prepare small-area, nano-thickness films, which cannot be scaled at all; although the spray method can produce graphene film materials in a large area, the obtained graphene film is independent. The droplets are fused and dried, which affects the structure and properties of the membrane. Therefore, continuous preparation of a structured, high-performance graphene film is still a challenge, and preparation of a high-strength and high-performance graphene film is more challenging.

Summary of the invention

The object of the present invention is to provide a method for preparing graphene and a composite film thereof based on a one-line die according to the deficiencies of the prior art.

The object of the invention is achieved by the following technical solutions:

A method for preparing a high-strength graphene film, comprising the following steps:

(1) mixing 1 part by weight of graphene, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a graphene dispersion;

(2) The graphene dispersion obtained in the step (1) is extruded in a forming apparatus of an in-line die at an extrusion speed of 10 to 1000 mL/h, and is allowed to stand at 1 to 100 in a coagulating liquid at 10 to 80 °C. Second, solidification into a film, after drying to obtain a high-strength graphene film; the preparation device of the in-line die is a rectangular parallelepiped structure with a gradually narrowing in-line die opening;

The solvent of the step (1) is mainly composed of water, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N-dimethyl B. One or more of an amide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol are mixed according to any ratio;

The coagulating liquid of the step (2) is mainly composed of a methanol solution of sodium hydroxide having a mass fraction of 5-10%, an ethanol solution of sodium hydroxide having a mass fraction of 5-10%, and a hydrogen fraction of 5-8% by mass. a methanol solution of potassium oxide, an ethanol solution of potassium hydroxide having a mass fraction of 5-8%, a sodium hydroxide aqueous solution having a mass fraction of 5-10%, a sodium sulfate aqueous solution having a mass fraction of 10-20%, and a mass fraction of 10 -20% aqueous sodium chloride solution, 5-10% sodium nitrate aqueous solution, 5-10% sodium phosphate aqueous solution, 5-8% potassium chloride aqueous solution, mass fraction 5 One or more of -10% aqueous ammonium chloride solution and 5-15% aqueous ammonia are mixed according to any ratio.

A method for preparing a high-strength graphene film, the steps are as follows:

(1) mixing 1 part by weight of graphene oxide, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a graphene oxide dispersion;

(2) The graphene oxide dispersion prepared in the step (1) is extruded in a forming apparatus of a die-shaped die at an extrusion speed of 10 to 1000 mL/h, and is stopped in a coagulating liquid at 10 to 80 ° C for 1 to Coagulation film formation in 100 seconds, drying to obtain a graphene oxide film;

(3) reducing the graphene oxide film obtained in the step (2) in a reducing agent, washing and drying to obtain a high-strength graphene film;

The device for preparing the inline die in the step (2) is a rectangular parallelepiped structure, and a gradually narrowing in-line die is opened in the middle;

Further, the reducing agent is selected from the group consisting of hydrazine hydrate having a mass fraction of 1% to 40%, an aqueous solution of sodium borohydride having a mass fraction of 1% to 40%, an aqueous solution of phenylhydrazine having a mass fraction of 1% to 40%, and a mass. An aqueous solution of hydrobromic acid having a fraction of 1% to 40%, an aqueous solution of tea polyphenol having a mass fraction of 1% to 40%, an aqueous urea solution having a mass fraction of 1% to 40%, and a thiophene having a mass fraction of 1% to 20% An aqueous solution of sodium sulphate, a 1%-5% aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide having a mass fraction of 1% to 40%, an aqueous solution of vitamin C having a mass fraction of 5% to 50%, and a mass fraction of 1% - 40% aqueous glucose solution, aqueous hydriodic acid solution having a mass fraction of 1% to 40%, aqueous acetic acid having a mass fraction of 1% to 40%, and aqueous phenol solution having a mass fraction of 1% to 40%.

A method for preparing a pure inorganic composite film based on graphene, the steps are as follows:

(1) mixing 1 part by weight of graphene, 0.01 to 2 parts by weight of inorganic nanoparticles, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a mixed dispersion of graphene/inorganic nanoparticles;

(2) The mixed dispersion of the obtained graphene/inorganic nanoparticles obtained in the step 1 is extruded at a rate of 1 to 100 mL/h in a molding apparatus of a die-shaped die, and solidified at 10 to 80 ° C after extrusion. The film is solidified in the liquid for 1 to 100 s to form a film, and a pure inorganic composite film of graphene is obtained;

The inorganic nanoparticles in the step (1) are selected from the group consisting of silicon, gold, silver, aluminum, copper, iron, zinc, chromium, nickel, cobalt, platinum, palladium, rhodium, iridium, ruthenium, titanium, vanadium, magnesium, and indium. , antimony, indium, antimony oxide nanoparticles and montmorillonite, clay, silicic acid Salt, ceramic nanoparticles;

The solvent of the step (1) is water, methanol, ethanol, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N-di One or more of methyl acetamide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol are mixed in any ratio;

The coagulating liquid of the step (2) is mainly composed of a methanol solution of sodium hydroxide having a mass fraction of 5-10%, an ethanol solution of sodium hydroxide having a mass fraction of 5-10%, and a hydrogen fraction of 5-8% by mass. a methanol solution of potassium oxide, an ethanol solution of potassium hydroxide having a mass fraction of 5-8%, a sodium hydroxide aqueous solution having a mass fraction of 5-10%, a sodium sulfate aqueous solution having a mass fraction of 10-20%, and a mass fraction of 10 -20% aqueous sodium chloride solution, 10-20% calcium chloride aqueous solution, 5-10% sodium nitrate aqueous solution, 5-10% calcium nitrate aqueous solution, mass fraction 5 One or more of -10% aqueous sodium phosphate solution, 5-8% potassium chloride aqueous solution, 5-10% ammonium chloride aqueous solution, and 5-15% mass aqueous ammonia water Mix the composition according to any ratio.

(1) mixing 1 part by weight of graphene oxide, 0.01 to 2 parts by weight of inorganic nanoparticles, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a mixed dispersion of graphene oxide/inorganic nanoparticles;

(2) The mixed dispersion of graphene oxide/inorganic nanoparticles obtained in the step 1 is extruded in a preparation apparatus of an in-line die of 1 to 100 mL/h, and a coagulating liquid at 10 to 80 ° C after extrusion. The film is solidified and formed in the film for 1 to 100 s to obtain a graphene oxide/inorganic nanoparticle composite film;

(3) reducing the graphene oxide inorganic composite film obtained in the step (2) in a reducing agent, washing and drying to obtain a pure inorganic composite film of graphene;

The inorganic nanoparticles in the step (1) are selected from the group consisting of silicon, gold, silver, aluminum, copper, iron, zinc, chromium, nickel, cobalt, platinum, palladium, rhodium, iridium, ruthenium, titanium, vanadium, magnesium, and indium. , antimony, indium, antimony oxide nanoparticles and montmorillonite, clay, silicate, ceramic nanoparticles;

Further, the reducing agent is selected from the group consisting of hydrazine hydrate having a mass fraction of 1% to 40%, an aqueous solution of sodium borohydride having a mass fraction of 1% to 40%, an aqueous solution of phenylhydrazine having a mass fraction of 1% to 40%, and a mass. Aqueous hydrobromide solution with a fraction of 1%-40%, quality An aqueous solution of tea polyphenols having a fraction of 1% to 40%, an aqueous urea solution having a mass fraction of 1% to 40%, an aqueous solution of sodium thiosulfate having a mass fraction of 1% to 20%, and a hydrogen having a mass fraction of 1% to 5%. An aqueous solution of sodium oxide, an aqueous solution of potassium hydroxide having a mass fraction of 1% to 40%, an aqueous solution of vitamin C having a mass fraction of 5% to 50%, an aqueous solution of glucose having a mass fraction of 1% to 40%, and a mass fraction of 1% to 40% % aqueous solution of hydriodic acid, aqueous solution of acetic acid having a mass fraction of 1% to 40%, and aqueous phenol solution having a mass fraction of 1% to 40%.

A method for preparing a graphene metal nanoparticle composite film, the method steps are as follows:

(1) mixing 1 part by weight of graphene, 0.01 to 2 parts by weight of metal nanoparticles, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a mixed dispersion of graphene/metal nanoparticles;

(2) The mixed dispersion of graphene/metal nanoparticles obtained in the step 1 is extruded at a speed of 1 to 100 mL/h in a molding apparatus of a die-shaped die, and the coagulating liquid at 10 to 80 ° C after extrusion The film is solidified and formed in the film for 1 to 100 s to obtain a graphene metal nanoparticle composite film;

The metal nanoparticles in the step (1) are selected from the group consisting of gold, silver, aluminum, copper, iron, zinc, chromium, nickel, cobalt, platinum, palladium, rhodium, iridium, ruthenium, titanium, vanadium, magnesium, indium, bismuth. Nanoparticles of indium and antimony;

The solvent of the step (1) is water, methanol, ethanol, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N-di One or more of methyl acetamide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol are composed of any ratio;

The coagulating liquid of the step (2) is mainly composed of a methanol solution of sodium hydroxide having a mass fraction of 5-10%, an ethanol solution of sodium hydroxide having a mass fraction of 5-10%, and a hydrogen fraction of 5-8% by mass. a methanol solution of potassium oxide, an ethanol solution of potassium hydroxide having a mass fraction of 5-8%, a sodium hydroxide aqueous solution having a mass fraction of 5-10%, a sodium sulfate aqueous solution having a mass fraction of 10-20%, and a mass fraction of 10 -20% aqueous sodium chloride solution, 10-20% calcium chloride aqueous solution, 5-10% sodium nitrate aqueous solution, 5-10% calcium nitrate aqueous solution, mass fraction 5 One or more of -10% aqueous sodium phosphate solution, 5-8% potassium chloride aqueous solution, 5-10% ammonium chloride aqueous solution, and 5-15% mass aqueous ammonia water Composition according to any ratio.

A method for preparing a graphene metal nanoparticle composite film, the steps of which are as follows:

(1) mixing 1 part by weight of graphene oxide, 0.01 to 2 parts by weight of metal nanoparticles, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a mixed dispersion of graphene oxide/metal nanoparticles;

(2) The mixed dispersion of graphene oxide/metal nanoparticles obtained in the step 1 is extruded in a preparation apparatus of an in-line die of 1 to 100 mL/h, and a coagulating liquid at 10 to 80 ° C after extrusion. The film is solidified and formed in the film for 1 to 100 s to obtain a graphene oxide/metal nanoparticle composite film;

(3) reducing the graphene oxide/metal nanoparticle composite film obtained in the step (2) in a reducing agent, washing and drying to obtain a graphene metal nanoparticle composite film;

The metal nanoparticles in the step (1) are selected from the group consisting of gold, silver, aluminum, copper, iron, zinc, chromium, nickel, cobalt, platinum, palladium, Nanoparticles of ruthenium, osmium, iridium, titanium, vanadium, magnesium, indium, bismuth, indium and bismuth;

A method for preparing an ion-enhanced graphene film, the steps of which are as follows:

(1) mixing 1 part by weight of graphene, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a graphene solution;

(2) The graphene solution is extruded in a forming apparatus of a die-shaped die at an extrusion speed of 10 to 1000 mL/h, and is allowed to stand in a coagulation liquid containing a coordination ion at 10 to 80 ° C for 1 to 100 seconds to solidify. Film formation, drying to obtain an ion-enhanced graphene film;

The solvent of the step (1) is mainly composed of water, methanol, ethanol, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N- a mixture of one or more of dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol in any ratio;

The coagulating liquid containing the coordination ion in the step (2) is mainly composed of an aqueous solution of calcium chloride having a mass fraction of 5-20%, an aqueous solution of zinc sulfate having a mass fraction of 5-20%, and a sulfuric acid having a mass fraction of 5-20%. One or more of a magnesium aqueous solution, an aqueous solution of ferric chloride having a mass fraction of 5-20%, and an aqueous copper sulfate solution having a mass fraction of 5-20% are mixed in an arbitrary ratio.

(1) 1 part by weight of graphene oxide, 5 to 150 parts by weight of a solvent is mixed, and after ultrasonic treatment, a graphene oxide solution is obtained.

(2) Extrusion of the graphene oxide solution in a preparation apparatus of a die-shaped die at an extrusion speed of 10 to 1000 mL/h, and staying in a coagulating liquid containing a coordination ion at 10 to 80 ° C for 1 to 100 seconds The film was solidified and dried to obtain a graphene oxide film.

(3) The graphene oxide film obtained in the step (2) is reduced in a reducing agent, and washed and dried to obtain ion-enhanced graphite. Alkene film

The invention has the beneficial effects that the invention adopts the preparation device of the inline die to prepare the graphene film and the graphene composite film, compared with the existing suction filtration method, the scraping method, the spin coating method, the spraying method and the dip coating. By the technique and the like, the gradually narrowing flow path in the preparation device of the inline die can effectively increase the force of the flow field on the graphene sheet, facilitate the formation of the regular orientation structure of the graphene dispersion system, and realize the large-area graphene film. Continuously prepared, the prepared graphene film has uniform thickness, and the continuous structure of the layer stacking has high order and low defects, which is beneficial to improve the conduction of heat and electricity of the graphene film material and excellent mechanical properties, and is favorable for graphene. Composite of different guest materials. In addition, the in-line die preparation device can not only control the thickness and width of the graphene film, but also be quick and easy to operate, green and environmentally friendly, and can be prepared in a large-scale continuous manner; the high-strength graphene prepared based on the in-line die The film is made up of graphene stacked in the plane direction, the tensile strength is 20-300 MPa, the elongation at break is 0.3-20%, the electrical conductivity is greater than 10000 S/m, and the thermal conductivity is 10-2000 W/mK. The pure inorganic composite film is composed of graphene and inorganic nanoparticles, and does not contain a filled polymer, and can be used in many harsh environments such as high temperature and chemical corrosiveness; the prepared graphene metal nanoparticle composite film combines different metals in electricity, Magnetic and thermal properties, can be used for high conductivity, magnetic response, high thermal conductivity materials, etc.; prepared ion-enhanced macroscopic graphene film is formed by graphene stacked in the plane direction, tensile strength is 100-300MPa, fracture The elongation is 0.3-20%, the electrical conductivity is greater than 10000 S/m, and the thermal conductivity is 10-2000 W/mK. The tensile strength is 100 to 300 MPa, and the elongation at break is 0.3 to 15%.

DRAWINGS

Figure 1 is a cross-sectional view showing a device for preparing a die-shaped die;

Figure 2 is a front elevational view of the apparatus for preparing a die-shaped die;

Figure 3 is a rear elevational view of the apparatus for preparing a die-shaped die;

4 is a scanning electron micrograph of a tensile section of the graphene film prepared in Example 1;

5 is a scanning electron display of a cross section of a pure inorganic composite film of graphene/ferric oxide nanoparticle prepared in Example 7. Microscopic photo.

6 is a scanning electron micrograph of a cross section and a plane of a graphene/iron nanoparticle film prepared in Example 16;

7 is a current-voltage curve of the graphene/silver nanoparticle film prepared in Example 17;

8 is a scanning electron micrograph of a graphene film prepared in Example 19;

9 is a scanning electron micrograph of a tensile cross section of a graphene film prepared in Example 20.

detailed description

As shown in FIG. 1-3, the device for preparing the inline die has a rectangular parallelepiped structure with a die-shaped die opening therebetween, and the in-line die is a gradually narrowing flow channel. The gradually narrowing flow channel can effectively increase the force of the flow field on the graphene sheet, and is favorable for the formation of the regular orientation structure of the graphene dispersion system. In the present invention, a graphene film and a graphene composite film are prepared by using a device for preparing a die-shaped die, compared with the prior art of suction filtration, scraping, spin coating, spray coating, and dip coating. The graphene film prepared by the invention has uniform thickness, and the continuous structure of the layer stacking has high order order and few defects, which is beneficial to improving the heat and electric conduction of the graphene film material and excellent mechanical properties, and is beneficial to graphene to different objects. Composite of materials.

The present invention will be described in detail below with reference to the embodiments, which are only used to further illustrate the present invention, and are not to be construed as limiting the scope of the present invention. And adjustments are all within the scope of protection of the present invention.

Example 1:

(1) 1 g of graphene oxide and 5 g of deionized water were mixed, and ultrasonicated at 50 kHz for 10 hours at 20 ° C to obtain a graphene oxide dispersion.

(2) Extrusion of the graphene oxide dispersion in a preparation apparatus of a die-shaped die at an extrusion speed of 200 mL/h, and staying in a methanol solution (mass fraction of 10%) of sodium hydroxide at 80 ° C The film was solidified in seconds and dried to obtain a graphene oxide film.

(3) The graphene oxide film obtained in the step (2) is sufficiently reduced in a mass fraction of 20% aqueous glucose solution, and washed and dried to obtain a high-strength graphene film.

As shown in FIG. 4, after the above steps, the graphene film having a thickness of 1 μm has a good layered alignment structure; the tensile strength is 260 MPa, and the elongation at break is 0.68%. The conductivity is more than 10000S/m, the thermal conductivity is 700W/mK, and it has good toughness.

Example 2:

(1) 1 g of graphene oxide, 50 g of tetrahydrofuran, and 100 g of dimethyl sulfoxide were mixed, and ultrasonicated at 50 kHz for 1 hour at 20 ° C to obtain a graphene oxide dispersion.

(2) Extrusion of the graphene oxide dispersion in a preparation apparatus of a die-shaped die at an extrusion speed of 100 mL/h, sodium hydroxide and potassium hydroxide in 10 ° C (sodium hydroxide and hydrogen) The mass fraction of potassium oxide was 2.5%, and the film was solidified for 100 seconds, and after drying, a graphene oxide film was obtained.

(3) The graphene oxide film obtained in the step (2) is sufficiently reduced in hydroiodic acid having a mass fraction of 20%, and washed and dried to obtain a high-strength graphene film.

Through the above steps, the prepared graphene film has a thickness of 1 mm, a tensile strength of 210 MPa, an elongation at break of 1.1%, a conductivity of more than 10,000 S/m, a thermal conductivity of 680 W/mK, and good toughness.

Example 3:

(1) 1 g of graphene oxide, 25 g of N,N-dimethylformamide, 25 g of acetone, and 50 g of methyl ethyl ketone were ultrasonicated at 50 kHz for 1 hour at 20 ° C to obtain a graphene oxide dispersion.

(2) The graphene oxide dispersion was extruded in a molding apparatus at an extrusion speed of 10 mL/h in a die-shaped die, and solidified in a potassium nitrate aqueous solution (mass fraction of 10%) at 40 ° C for 60 seconds. The film was dried to obtain a graphene oxide film.

Through the above steps, the prepared graphene film has a thickness of 30 μm, a tensile strength of 230 MPa, an elongation at break of 1.6%, a conductivity of more than 10000 S/m, a thermal conductivity of 600 W/mK, and good toughness.

Example 4:

(1) 2 g of graphene and 100 g of N-methylpyrrolidone were ultrasonicated at 50 kHz for 2 hours at 20 ° C to obtain a graphene dispersion.

(2) Extrusion of graphene dispersion at a extrusion rate of 500 mL/h in a molding apparatus at a die-shaped die, aqueous solution of sodium sulfate and potassium chloride at 20 ° C (the quality of sodium sulfate and potassium chloride) The score was 10%). The film was solidified for 20 seconds, and dried to obtain a graphene film.

Through the above steps, the prepared graphene film has a thickness of 8 μm, a tensile strength of 280 MPa, an elongation at break of 1.5%, a conductivity of more than 10,000 S/m, a thermal conductivity of 1200 W/mK, and good toughness.

Example 5:

(1) 2 g of graphene and 40 g of N-methylpyrrolidone were ultrasonicated at 50 kHz for 2 hours at 20 ° C to obtain a graphene dispersion.

(2) Extrusion of the graphene dispersion at a extrusion speed of 1000 mL/h in a molding apparatus at a die-shaped die, sodium hydroxide and potassium hydroxide in 60 ° C (sodium hydroxide and hydroxide) The mass fraction of potassium was 5%. The film was solidified for 20 seconds, and dried to obtain a graphene film.

Example 6

(1) 2 g of graphene, 20 g of diethylene glycol, and 40 g of N,N-dimethylacetamide were ultrasonicated at 50 kHz for 2 hours at 20 ° C to obtain a graphene dispersion.

(2) The graphene dispersion was extruded in a molding apparatus at an extrusion speed of 800 mL/h in an in-line die, and left to stand in an ammonia water (mass fraction of 5%) at 80 ° C for 20 seconds to form a film, and dried. A graphene film is obtained later.

Through the above steps, the prepared graphene film has a thickness of 20 μm, a tensile strength of 320 MPa, an elongation at break of 1.1%, a conductivity of more than 10000 S/m, a thermal conductivity of 1500 W/mK, and good toughness.

Example 7

(1) 1 part by weight of graphene oxide, 2 parts by weight of ferroferric oxide nanoparticles, 150 parts by weight of water, and ultrasonically dispersed to obtain a mixed dispersion of graphene oxide/ferric oxide nanoparticles.

(2) Mixing dispersion of graphene oxide/ferric oxide nanoparticle at a speed of 30 mL/h in a die-shaped die The mixture was extruded in a preparation apparatus, and after extrusion, it was solidified in a methanol solution of sodium hydroxide at 80 ° C (mass fraction of 5%) for 10 s to form a film of the graphene oxide/ferric oxide nanoparticle composite film.

(3) The graphene oxide/ferric oxide nanoparticle composite membrane obtained in the step (2) is reduced in an aqueous solution of hydroiodic acid having a mass fraction of 20%, and washed and dried to obtain a graphene/ferric oxide nanoparticle composite. membrane.

Through the above steps, a graphene oxide/ferric oxide nanoparticle composite film having a width of 20 mm and a thickness of 50 μm was prepared.

As shown in FIG. 5, the prepared graphene/ferric oxide nano-particle composite film is layered by graphene nanosheets in a planar direction, and has a good layered alignment structure, and the graphene layers are uniformly filled. Filled with a lot of ferroferric oxide nanoparticles, this highly oriented layered structure and uniformly distributed ferroferric oxide nanoparticles facilitate the realization of magnetic functions. The prepared graphene/ferric oxide nano-particle composite film has obvious response to external magnetic field and can be applied to magnetic control switches and wires and magnetic sensing fields.

Example 8

(1) 1 part by weight of graphene oxide, 0.01 part by weight of alumina nanoparticles, 2 parts by weight of water, and 3 parts by weight of ethanol, and ultrasonically dispersed to obtain a mixed dispersion of graphene oxide/alumina nanoparticles ;

(2) The mixed dispersion obtained in the step 1 was extruded in a molding apparatus at a speed of 1 mL/h in a die-shaped die, and extruded in an ethanol solution of sodium hydroxide at 10 ° C (mass fraction: 10%). The film was solidified for 10 s to form a film, and a graphene oxide/alumina nanoparticle composite film was obtained;

(3) The graphene oxide alumina nanoparticle composite membrane obtained in the step (2) is reduced in a hydrazine hydrate solution having a mass fraction of 1%, and washed and dried to obtain a graphene/alumina nanoparticle composite membrane.

Through the above steps, a graphite/alumina nano-particle inorganic composite film having a width of 50 mm and a thickness of 100 μm is prepared, and the composite film has good flame retardant effect and conductivity of the graphene film without composite alumina nanoparticles. In contrast, the pure inorganic composite film of graphene/alumina nanoparticles has good flame retardancy and can be used in the field of fire retardant.

Example 9

(1) Mixing 1 part by weight of graphene oxide, 2 parts by weight of manganese oxide nanoparticles, 80 parts by weight of ethanol, and 80 parts by weight of acetone, and ultrasonically dispersing to obtain mixed dispersion of graphene oxide/manganese oxide nanoparticles liquid;

(2) The mixed dispersion obtained in the step 1 was extruded at a rate of 100 mL/h in a molding apparatus of a die-shaped die, and extruded in a methanol solution of potassium hydroxide at 20 ° C (mass fraction: 5%). The film is solidified for 100s to obtain a graphene oxide/manganese oxide nanoparticle composite film;

(3) The graphene/manganese oxide nanoparticle composite film obtained in the step (2) is reduced in an aqueous solution of 20% tea polyphenol, and washed and dried to obtain a graphene/manganese oxide nanoparticle composite film.

Through the above steps, a graphene/manganese oxide nanoparticle inorganic composite film having a width of 50 mm and a thickness of 50 μm is prepared, and the graphene composite film can be used as a capacitor material and a graphene film phase without composite manganese oxide nanoparticles. The capacitance of the pure inorganic composite film of graphene/manganese oxide nanoparticles increased from 32 F/g to 116 F/g.

Example 10:

(1) 1 part by weight of graphene, 0.1 part by weight of titanium oxide nanoparticles, 20 parts by weight of N-methylpyrrolidone, 30 parts by weight of acetone, and ultrasonically dispersed to obtain a mixture of graphene/titanium oxide nanoparticles liquid.

(2) The graphene/titanium oxide nanoparticle mixed dispersion was extruded at a speed of 100 mL/h in a molding apparatus of a die-shaped die, and extruded in an ethanol solution of potassium hydroxide at 8 ° C (mass fraction) It was solidified into a film by holding for 1 s in 8%) to obtain a graphene/titanium oxide nanoparticle composite film.

Through the above steps, a graphene/titanium oxide nanoparticle inorganic composite membrane having a width of 200 mm and a thickness of 200 micrometers is prepared, and the graphene composite membrane can be used as a catalyst for preparing hydrogen by photocatalytic cracking water.

Example 11

(1) 1 part by weight of graphene, 0.5 part by weight of montmorillonite nanosheet, 50 parts by weight of N,N-dimethylformamide, and ultrasonically dispersed to obtain a mixture of graphene/montmorillonite nanosheets liquid.

(2) The graphene/montmorillonite nanosheet mixed dispersion was extruded at a speed of 120 mL/h in a molding apparatus at a die-shaped die, and extruded at 40 ° C with sodium hydroxide and potassium hydroxide in methanol. The solution (the mass fraction of sodium hydroxide and potassium hydroxide was 2.5%) was solidified into a film for 50 s to obtain a graphene/montmorillonite nanosheet composite film.

Through the above steps, a graphene/montmorillonite nanosheet inorganic composite film having a width of 500 mm and a thickness of 300 μm was prepared, and the pure inorganic film has good mechanical properties and flame retardancy.

Example 12

(1) 1 part by weight of graphene, 0.5 part by weight of clay nanosheet, 50 parts by weight of N-methylpyrrolidone, and 20 parts by weight of tetrahydrofuran were mixed and ultrasonically dispersed to obtain a graphene/clay nanosheet mixed dispersion.

(2) The graphene/clay nanosheet mixed dispersion was extruded at a speed of 150 mL/h in a molding apparatus of a die-shaped die, and extruded to form a film in a coagulating solution of sodium sulfate aqueous solution at 40 ° C for 50 s. A graphene/clay nanosheet composite film is obtained.

Through the above steps, a graphene/clay nanosheet inorganic composite film having a width of 250 mm and a thickness of 100 μm was prepared.

Example 13

(1) 1 part by weight of graphene, 0.6 part by weight of cubic boron nitride nanoparticles, 100 parts by weight of deionized water, and ultrasonically dispersed to obtain a graphene/cubic boron nitride nanoparticle mixed dispersion.

(2) The graphene/cubic boron nitride nanoparticle mixed dispersion was extruded at a speed of 50 mL/h in a molding apparatus of a die-shaped die, and after extrusion, it was solidified in a coagulation liquid at 60 ° C for 10 s to form a film. A graphene/cubic boron nitride nanoparticle composite film is obtained.

Through the above steps, a graphene/cubic boron nitride nanoparticle inorganic composite film having a width of 500 mm and a thickness of 150 μm was prepared.

Example 14

(1) 1 part by weight of graphene, 0.35 parts by weight of nano ceramic particles, 50 parts by weight of acetone were mixed, and ultrasonicated at 25 kHz for 3 hours at 50 ° C to obtain a graphene/nano ceramic particle mixed dispersion.

(2) The graphene/nano ceramic particle mixed dispersion was extruded at a speed of 300 mL/h in a molding apparatus of a die-shaped die, and after extrusion, it was solidified in a solid solution of calcium nitrate aqueous solution at 50 ° C for 90 s to solidify into a film. A graphene/nano ceramic particle composite film is obtained.

Through the above steps, a graphene/nano ceramic particle inorganic composite film having a width of 500 mm and a thickness of 200 μm was prepared.

Example 15

(1) 1 part by weight of graphene oxide, 0.01 part by weight of gold nanoparticles, 2 parts by weight of ethanol, and 3 parts by weight of ethylene glycol, and ultrasonically dispersed to obtain a mixed dispersion of graphene oxide/gold nanoparticles ;

(2) The mixed dispersion obtained in the step 1 was extruded in a molding apparatus at a speed of 1 mL/h in a die-shaped die, and extruded in an ethanol solution of sodium hydroxide at 80 ° C (mass fraction: 10%). The film is solidified for 1 s to form a film, and a graphene oxide/gold nanoparticle composite film is obtained;

(3) The graphene oxide gold nanoparticle composite film obtained in the step (2) is reduced in a mass fraction of 20% hydrazine hydrate solution, and washed and dried to obtain a graphene/gold nanoparticle composite film.

Through the above steps, a graphene/gold nanoparticle composite film with a width of 50 mm and a thickness of 1 μm is prepared. The composite film can be used as a stationary phase of gold nanoparticles for controlling molecular assembly, molecular recognition template, and catalytic biochemistry. The reaction is applied as a biosensor or the like.

Example 16:

(1) 1 part by weight of graphene, 2 parts by weight of iron nanoparticles, and 150 parts by weight of water are mixed, and ultrasonically dispersed to obtain a graphene/iron nanoparticle mixed dispersion.

(2) The graphene/iron nanoparticle mixed dispersion was extruded at a rate of 30 mL/h in a molding apparatus of a die-shaped die, and extruded at 10 ° C in a methanol solution of sodium hydroxide and potassium hydroxide ( The sodium hydroxide and potassium hydroxide have a mass fraction of 2.5%, and the film is solidified for 100 s. After drying, a graphene/iron nanoparticle composite film is obtained.

Through the above steps, a graphene oxide/iron nanoparticle composite film having a width of 20 mm and a thickness of 50 μm was prepared. As shown in Fig. 6, the iron nanoparticles are uniformly distributed on the surface of the graphene, and the iron nanoparticles and the graphene layer are stacked. The prepared graphene/iron nanoparticle composite film has good paramagnetism and can be applied to magnetic control switches and wires and magnetic sensing fields.

Example 17

(1) mixing 1 part by weight of graphene oxide, 2 parts by weight of silver nanoparticles, 150 parts by weight of dimethyl sulfoxide, and ultrasonically dispersing to obtain a mixed dispersion of graphene oxide/silver nanoparticles;

(2) The mixed dispersion obtained in the step 1 was extruded in a molding apparatus at a speed of 1 mL/h in a die-shaped die, and extruded in a methanol solution of potassium hydroxide at 50 ° C (mass fraction: 6%). The film is solidified for 100 s and dried to obtain a graphene oxide/silver nanoparticle composite film;

(3) The graphene oxide composite film obtained in the step (2) is reduced in a tea polyphenol aqueous solution having a mass fraction of 40%, and washed and dried to obtain a graphene/silver nanoparticle composite film.

After the above steps, a graphene/silver nanoparticle composite film having a width of 50 mm and a thickness of 50 μm is prepared. As shown in FIG. 7, the graphene composite film has high conductivity and no composite silver nanoparticle graphite. Compared with (8500S/m), the graphene/silver nanoparticle nanoparticle composite film has better conductivity, reaching 25000S/m, which can be used as a conductive material instead of metal.

Example 18

(1) 1 part by weight of graphene, 0.1 part by weight of platinum nanoparticles, and 20 parts by weight of N-methylpyrrolidone are mixed, and ultrasonically dispersed to obtain a graphene/platinum nanoparticle mixed dispersion.

(2) The graphene/platinum nanoparticle mixed dispersion was extruded at a speed of 100 mL/h in a molding apparatus of a die-shaped die, and extruded at 60 ° C in an ethanol solution of potassium hydroxide (mass fraction was In 8%), the film was solidified for 100 s and dried to obtain a graphene/platinum nanoparticle composite film.

Through the above steps, a graphene/platinum nano composite film with a width of 200 mm and a thickness of 200 μm is prepared. The graphene composite film can be used as a high-efficiency catalyst for catalytic hydrogenation of organic molecules and coal tar, and can effectively reduce the catalytic reaction. The temperature and catalysis increase the reaction rate.

Example 19

1) 1 g of graphene oxide and 5 g of deionized water were ultrasonicated at 5 to 80 kHz for 10 hours at 20 to 80 ° C to obtain a graphene oxide solution.

2) The graphene oxide solution was extruded in a molding apparatus at an extrusion speed of 1000 mL/h in an in-line die, and solidified into a film by holding in a calcium chloride aqueous solution (mass fraction of 5%) at 80 ° C for 100 seconds. After drying, a graphene oxide film is obtained.

3) The graphene oxide film obtained in the step (2) is placed in a hydrazine hydrate having a mass fraction of 40% for 10 minutes, and washed and dried to obtain an ion-enhanced graphene film.

Through the above steps, as shown in FIG. 8, the prepared graphene film has a thickness of 1 μm and has good toughness. After mechanical properties, the tensile strength is 300 MPa, and the elongation at break is 1.4%.

Example 20

1) 1 part by weight of graphene oxide and 10 parts by weight of N-methylpyrrolidone were ultrasonicated at 50 ° C for 5 hours at 80 ° C to obtain a graphene oxide solution.

2) The graphene oxide solution was continuously extruded at a rate of 50 mL/h in a preparation apparatus having a die-shaped die, and left to stand in a magnesium sulfate aqueous solution (mass fraction of 20%) at 60 ° C for 1 second. The film was formed and dried to obtain a graphene oxide film.

3) The graphene oxide film obtained in the step (2) is placed in an aqueous solution of sodium thiosulfate having a mass fraction of 20% for 1 hour, and washed and dried to obtain an ion-enhanced graphene film.

The prepared graphene film has a thickness of 1 mm. As shown in Fig. 9, the graphene film has a good layered alignment structure, and the tensile strength is 290 MPa and the elongation at break is 2% after mechanical properties test.

Example 21:

1) 1 part by weight of graphene and 5 parts by weight of N,N-dimethylformamide were ultrasonicated at 50 ° C for 1 hour at 50 ° C to obtain a graphene solution.

2) The graphene solution was continuously extruded at a rate of 400 mL/h in a preparation apparatus having a die-shaped die, and solidified in a 25 ° C zinc sulfate aqueous solution (mass fraction of 10%) for 16 seconds. The film was dried to obtain a graphene film.

Through the above steps, the prepared graphene film has a thickness of 30 μm, a tensile strength of 270 MPa, an elongation at break of 1.2%, a conductivity of more than 10,000 S/m, a thermal conductivity of 1200 W/mK, and good toughness.

Example 22

1) 1 part by weight of graphene, 20 parts by weight of diethylene glycol, 20 parts by weight of N-methylpyrrolidone, 20 Parts by weight of pyridine was sonicated at 40 ° C for 2 hours at 60 ° C to obtain a graphene solution.

2) The graphene solution was continuously and continuously extruded in a preparation apparatus having a flat die at an extrusion speed of 500 mL/h, and stayed in an aqueous solution of ferric chloride (mass fraction of 8%) at 25 ° C for 20 seconds. The film was solidified and dried to obtain a graphene film.

Through the above steps, the prepared graphene film has a thickness of 8 μm, a tensile strength of 300 MPa, an elongation at break of 1.5%, a conductivity of more than 10,000 S/m, a thermal conductivity of 1500 W/mK, and good toughness.

Example 23

1) 1 part by weight of graphene oxide, 5 parts by weight of N,N-dimethylacetamide, and 20 parts by weight of dimethyl sulfoxide were sonicated at 25 ° C for 2 hours at 25 ° C to obtain a graphene oxide solution.

2) The graphene oxide solution was continuously and continuously extruded in a preparation apparatus having a flat die at an extrusion speed of 10 mL/h, and a mixed aqueous solution of copper sulfate and calcium chloride at 25 ° C (copper sulfate and calcium chloride) The mass fraction is 10%), the film is solidified for 1 second, and the graphene oxide film is obtained after drying.

3) The graphene oxide film obtained in the step (2) is placed in an aqueous solution of hydroiodic acid having a mass fraction of 20% for 0.1 to 100 hours, and washed and dried to obtain an ion-enhanced graphene film.

Through the above steps, the prepared graphene film has a thickness of 3 μm, a tensile strength of 220 MPa, and an elongation at break of 1.6%.

Example 24:

1) 1 part by weight of graphene oxide, 40 parts by weight of N-methylpyrrolidone, and 20 parts by weight of ethylene glycol were ultrasonicated at 40 ° C for 2 hours at 30 ° C to obtain a graphene oxide solution.

2) The graphene oxide solution was continuously extruded at a rate of 500 mL/h in a preparation apparatus having a flat die, and a mixed aqueous solution of magnesium sulfate and zinc sulfate at 10 ° C (magnesium sulfate mass fraction of 5) %, the mass fraction of zinc sulfate is 10%), and the film is solidified for 16 seconds, and after drying, a graphene oxide film is obtained.

3) The graphene oxide film obtained in the step (2) was placed in a sodium borohydride having a mass fraction of 20% for 2 hours, and washed and dried to obtain an ion-enhanced graphene film.

Through the above steps, the prepared graphene film has a thickness of 1 μm, a tensile strength of 290 MPa, and an elongation at break of 1.8%.

The above-mentioned embodiments are intended to be illustrative of the present invention and are not intended to limit the scope of the invention, and the modifications and variations of the invention are intended to be included within the scope of the invention.

Claims

A method for preparing a high-strength graphene film, comprising the steps of:

(1) mixing 1 part by weight of graphene, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a graphene dispersion;

(2) The graphene dispersion obtained in the step (1) is extruded in a forming apparatus of an in-line die at an extrusion speed of 10 to 1000 mL/h, and is allowed to stand at 1 to 100 in a coagulating liquid at 10 to 80 °C. Second, solidified into a film, dried to obtain a high-strength graphene film;

The device for preparing the inline die in the step (2) is a rectangular parallelepiped structure, and a gradually narrowing in-line die is opened in the middle;

The solvent of the step (1) is mainly composed of water, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N-dimethyl B. One or more of an amide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol are mixed according to any ratio;

The coagulating liquid of the step (2) is mainly composed of a methanol solution of sodium hydroxide having a mass fraction of 5-10%, an ethanol solution of sodium hydroxide having a mass fraction of 5-10%, and a hydrogen fraction of 5-8% by mass. a methanol solution of potassium oxide, an ethanol solution of potassium hydroxide having a mass fraction of 5-8%, a sodium hydroxide aqueous solution having a mass fraction of 5-10%, a sodium sulfate aqueous solution having a mass fraction of 10-20%, and a mass fraction of 10 -20% aqueous sodium chloride solution, 5-10% sodium nitrate aqueous solution, 5-10% sodium phosphate aqueous solution, 5-8% potassium chloride aqueous solution, mass fraction 5 One or more of -10% aqueous ammonium chloride solution and 5-15% aqueous ammonia are mixed according to any ratio.
A method for preparing a high-strength graphene film, characterized in that the steps are as follows:

(1) mixing 1 part by weight of graphene oxide, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a graphene oxide dispersion;

(2) The graphene oxide dispersion prepared in the step (1) is extruded in a forming apparatus of a die-shaped die at an extrusion speed of 10 to 1000 mL/h, and is stopped in a coagulating liquid at 10 to 80 ° C for 1 to Coagulation film formation in 100 seconds, drying to obtain a graphene oxide film;

(3) reducing the graphene oxide film obtained in the step (2) in a reducing agent, washing and drying to obtain a high-strength graphene film;

The device for preparing the inline die in the step (2) is a rectangular parallelepiped structure, and a gradually narrowing in-line die is opened in the middle;

The solvent of the step (1) is mainly composed of water, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N-dimethyl B. One or more of an amide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol are mixed according to any ratio;

The coagulating liquid of the step (2) is mainly composed of a methanol solution of sodium hydroxide having a mass fraction of 5-10%, an ethanol solution of sodium hydroxide having a mass fraction of 5-10%, and a hydrogen fraction of 5-8% by mass. a methanol solution of potassium oxide, an ethanol solution of potassium hydroxide having a mass fraction of 5-8%, a sodium hydroxide aqueous solution having a mass fraction of 5-10%, a sodium sulfate aqueous solution having a mass fraction of 10-20%, and a mass fraction of 10 -20% aqueous sodium chloride solution, 5-10% sodium nitrate aqueous solution, 5-10% sodium phosphate aqueous solution, 5-8% potassium chloride aqueous solution, mass fraction 5 One or more of -10% aqueous ammonium chloride solution and 5-15% aqueous ammonia are mixed according to any ratio.
The method for preparing a high-strength graphene film according to claim 2, wherein the reducing agent It is selected from the group consisting of hydrazine hydrate with a mass fraction of 1%-40%, an aqueous solution of sodium borohydride with a mass fraction of 1%-40%, an aqueous solution of benzoquinone with a mass fraction of 1%-40%, and a mass fraction of 1%-40%. An aqueous solution of hydrobromic acid, an aqueous solution of tea polyphenol having a mass fraction of 1% to 40%, an aqueous urea solution having a mass fraction of 1% to 40%, an aqueous solution of sodium thiosulfate having a mass fraction of 1% to 20%, and a mass fraction of 1 %-5% sodium hydroxide aqueous solution, mass fraction of 1%-40% potassium hydroxide aqueous solution, mass fraction 5%-50% vitamin C aqueous solution, mass fraction 1%-40% glucose aqueous solution, quality The aqueous solution of hydroiodic acid having a fraction of 1% to 40%, an aqueous solution of acetic acid having a mass fraction of 1% to 40%, and an aqueous solution of phenol having a mass fraction of 1% to 40%.
A method for preparing a pure inorganic composite film based on graphene, characterized in that the steps are as follows:

(1) mixing 1 part by weight of graphene, 0.01 to 2 parts by weight of inorganic nanoparticles, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a mixed dispersion of graphene/inorganic nanoparticles;

(2) The mixed dispersion of the obtained graphene/inorganic nanoparticles obtained in the step 1 is extruded at a rate of 1 to 100 mL/h in a molding apparatus of a die-shaped die, and solidified at 10 to 80 ° C after extrusion. The film is solidified in the liquid for 1 to 100 s to form a film, and a pure inorganic composite film of graphene is obtained;

The device for preparing the inline die in the step (2) is a rectangular parallelepiped structure, and a gradually narrowing in-line die is opened in the middle;

The inorganic nanoparticles in the step (1) are selected from the group consisting of silicon, gold, silver, aluminum, copper, iron, zinc, chromium, nickel, cobalt, platinum, palladium, rhodium, iridium, ruthenium, titanium, vanadium, magnesium, and indium. , antimony, indium, antimony oxide nanoparticles and montmorillonite, clay, silicate, ceramic nanoparticles;

The solvent of the step (1) is water, methanol, ethanol, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N-di One or more of methyl acetamide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol are mixed in any ratio;

The coagulating liquid of the step (2) is mainly composed of a methanol solution of sodium hydroxide having a mass fraction of 5-10%, an ethanol solution of sodium hydroxide having a mass fraction of 5-10%, and a hydrogen fraction of 5-8% by mass. a methanol solution of potassium oxide, an ethanol solution of potassium hydroxide having a mass fraction of 5-8%, a sodium hydroxide aqueous solution having a mass fraction of 5-10%, a sodium sulfate aqueous solution having a mass fraction of 10-20%, and a mass fraction of 10 -20% aqueous sodium chloride solution, 10-20% calcium chloride aqueous solution, 5-10% sodium nitrate aqueous solution, 5-10% calcium nitrate aqueous solution, mass fraction 5 One or more of -10% aqueous sodium phosphate solution, 5-8% potassium chloride aqueous solution, 5-10% ammonium chloride aqueous solution, and 5-15% mass aqueous ammonia water Mix the composition according to any ratio.
A method for preparing a pure inorganic composite film based on graphene, characterized in that the steps thereof are as follows:

(1) mixing 1 part by weight of graphene oxide, 0.01 to 2 parts by weight of inorganic nanoparticles, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a mixed dispersion of graphene oxide/inorganic nanoparticles;

(2) The mixed dispersion of graphene oxide/inorganic nanoparticles obtained in the step 1 is extruded in a preparation apparatus of an in-line die of 1 to 100 mL/h, and a coagulating liquid at 10 to 80 ° C after extrusion. The film is solidified and formed in the film for 1 to 100 s to obtain a graphene oxide/inorganic nanoparticle composite film;

(3) reducing the graphene oxide inorganic composite film obtained in the step (2) in a reducing agent, washing and drying to obtain a pure inorganic composite film of graphene;

The device for preparing the inline die in the step (2) has a rectangular parallelepiped structure with a gradually narrowing word in the middle. Mold die

The inorganic nanoparticles in the step (1) are selected from the group consisting of silicon, gold, silver, aluminum, copper, iron, zinc, chromium, nickel, cobalt, platinum, palladium, rhodium, iridium, ruthenium, titanium, vanadium, magnesium, and indium. , antimony, indium, antimony oxide nanoparticles and montmorillonite, clay, silicate, ceramic nanoparticles;

The solvent of the step (1) is water, methanol, ethanol, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N-di One or more of methyl acetamide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol are mixed in any ratio;

The coagulating liquid of the step (2) is mainly composed of a methanol solution of sodium hydroxide having a mass fraction of 5-10%, an ethanol solution of sodium hydroxide having a mass fraction of 5-10%, and a hydrogen fraction of 5-8% by mass. a methanol solution of potassium oxide, an ethanol solution of potassium hydroxide having a mass fraction of 5-8%, a sodium hydroxide aqueous solution having a mass fraction of 5-10%, a sodium sulfate aqueous solution having a mass fraction of 10-20%, and a mass fraction of 10 -20% aqueous sodium chloride solution, 10-20% calcium chloride aqueous solution, 5-10% sodium nitrate aqueous solution, 5-10% calcium nitrate aqueous solution, mass fraction 5 One or more of -10% aqueous sodium phosphate solution, 5-8% potassium chloride aqueous solution, 5-10% ammonium chloride aqueous solution, and 5-15% mass aqueous ammonia water Mix the composition according to any ratio.
The method for preparing a pure inorganic composite film based on graphene according to claim 5, wherein the reducing agent is selected from the group consisting of hydrazine hydrate having a mass fraction of 1% to 40%, and having a mass fraction of 1%- 40% aqueous solution of sodium borohydride, aqueous solution of phenylhydrazine with a mass fraction of 1%-40%, aqueous hydrobromide solution with a mass fraction of 1%-40%, aqueous tea polyphenol solution with mass fraction of 1%-40%, quality Aqueous solution of 1%-40% urea, aqueous sodium thiosulfate with a mass fraction of 1%-20%, aqueous sodium hydroxide with a mass fraction of 1%-5%, hydrogen with a mass fraction of 1%-40% Potassium oxide aqueous solution, 5%-50% vitamin C aqueous solution, mass fraction of 1%-40% aqueous glucose solution, mass fraction of 1%-40% aqueous hydriodic acid, mass fraction of 1%-40 % aqueous solution of acetic acid, aqueous solution of phenol having a mass fraction of 1% to 40%.
A method for preparing a graphene metal nanoparticle composite film, characterized in that the method steps are as follows:

(1) mixing 1 part by weight of graphene, 0.01 to 2 parts by weight of metal nanoparticles, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a mixed dispersion of graphene/metal nanoparticles;

(2) The mixed dispersion of graphene/metal nanoparticles obtained in the step 1 is extruded at a speed of 1 to 100 mL/h in a molding apparatus of a die-shaped die, and the coagulating liquid at 10 to 80 ° C after extrusion The film is solidified and formed in the film for 1 to 100 s to obtain a graphene metal nanoparticle composite film;

The device for preparing the inline die in the step (2) is a rectangular parallelepiped structure, and a gradually narrowing in-line die is opened in the middle;

The metal nanoparticles in the step (1) are selected from the group consisting of gold, silver, aluminum, copper, iron, zinc, chromium, nickel, cobalt, platinum, palladium, rhodium, iridium, ruthenium, titanium, vanadium, magnesium, indium, bismuth. Nanoparticles of indium and antimony;

The solvent of the step (1) is water, methanol, ethanol, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N-di One or more of methyl acetamide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol are composed of any ratio;

The coagulating liquid of the step (2) is mainly composed of a methanol solution of sodium hydroxide having a mass fraction of 5-10%, an ethanol solution of sodium hydroxide having a mass fraction of 5-10%, and a hydrogen fraction of 5-8% by mass. a methanol solution of potassium oxide with a mass fraction of 5-8% An ethanol solution of potassium hydroxide, a sodium hydroxide aqueous solution having a mass fraction of 5-10%, an aqueous sodium sulfate solution having a mass fraction of 10-20%, an aqueous solution of sodium chloride having a mass fraction of 10-20%, and a mass fraction of 10- 20% calcium chloride aqueous solution, 5-10% sodium nitrate aqueous solution, 5-10% calcium nitrate aqueous solution, 5-10% sodium phosphate aqueous solution, mass fraction 5-8 One or more of a % potassium chloride aqueous solution, an ammonium chloride aqueous solution having a mass fraction of 5-10%, and an aqueous ammonia having a mass fraction of 5-15% are composed of any ratio.
A method for preparing a graphene metal nanoparticle composite film, characterized in that the steps thereof are as follows:

(1) mixing 1 part by weight of graphene oxide, 0.01 to 2 parts by weight of metal nanoparticles, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a mixed dispersion of graphene oxide/metal nanoparticles;

(2) The mixed dispersion of graphene oxide/metal nanoparticles obtained in the step 1 is extruded in a preparation apparatus of an in-line die of 1 to 100 mL/h, and a coagulating liquid at 10 to 80 ° C after extrusion. The film is solidified and formed in the film for 1 to 100 s to obtain a graphene oxide/metal nanoparticle composite film;

(3) reducing the graphene oxide/metal nanoparticle composite film obtained in the step (2) in a reducing agent, washing and drying to obtain a graphene metal nanoparticle composite film;

The device for preparing the inline die in the step (2) is a rectangular parallelepiped structure, and a gradually narrowing in-line die is opened in the middle;

The metal nanoparticles in the step (1) are selected from the group consisting of gold, silver, aluminum, copper, iron, zinc, chromium, nickel, cobalt, platinum, palladium, rhodium, iridium, ruthenium, titanium, vanadium, magnesium, indium, bismuth. Nanoparticles of indium and antimony;

The solvent of the step (1) is water, methanol, ethanol, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N-di One or more of methyl acetamide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol are composed of any ratio;

The coagulating liquid of the step (2) is mainly composed of a methanol solution of sodium hydroxide having a mass fraction of 5-10%, an ethanol solution of sodium hydroxide having a mass fraction of 5-10%, and a hydrogen fraction of 5-8% by mass. a methanol solution of potassium oxide, an ethanol solution of potassium hydroxide having a mass fraction of 5-8%, a sodium hydroxide aqueous solution having a mass fraction of 5-10%, a sodium sulfate aqueous solution having a mass fraction of 10-20%, and a mass fraction of 10 -20% aqueous sodium chloride solution, 10-20% calcium chloride aqueous solution, 5-10% sodium nitrate aqueous solution, 5-10% calcium nitrate aqueous solution, mass fraction 5 One or more of -10% aqueous sodium phosphate solution, 5-8% potassium chloride aqueous solution, 5-10% ammonium chloride aqueous solution, and 5-15% mass aqueous ammonia water Composition according to any ratio.
The method for preparing a graphene metal nanoparticle composite film according to claim 8, wherein the reducing agent is selected from the group consisting of hydrazine hydrate having a mass fraction of 1% to 40%, and the mass fraction is 1%-40. % aqueous solution of sodium borohydride, aqueous solution of benzoquinone with a mass fraction of 1% to 40%, aqueous hydrobromide solution with a mass fraction of 1% to 40%, aqueous tea polyphenol solution with a mass fraction of 1% to 40%, mass fraction It is a 1%-40% aqueous urea solution, a 1%-20% sodium thiosulfate aqueous solution, a 1%-5% sodium hydroxide aqueous solution, and a 1%-40% hydroxide. Potassium aqueous solution, 5%-50% vitamin C aqueous solution, mass fraction of 1%-40% aqueous glucose solution, mass fraction of 1%-40% aqueous hydriodic acid, mass fraction of 1%-40% An aqueous solution of acetic acid and an aqueous solution of phenol having a mass fraction of 1% to 40%.
A method for preparing an ion-enhanced graphene film, characterized in that the steps thereof are as follows:

(1) mixing 1 part by weight of graphene, 5 to 150 parts by weight of a solvent, and ultrasonically dispersing to obtain a graphene solution;

(2) The graphene solution is extruded in a forming apparatus of a die-shaped die at an extrusion speed of 10 to 1000 mL/h, and is allowed to stand in a coagulation liquid containing a coordination ion at 10 to 80 ° C for 1 to 100 seconds to solidify. Film formation, drying to obtain an ion-enhanced graphene film;

The device for preparing the inline die in the step (2) is a rectangular parallelepiped structure, and a gradually narrowing in-line die is opened in the middle;

The solvent of the step (1) is mainly composed of water, methanol, ethanol, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N- a mixture of one or more of dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol in any ratio;

The coagulating liquid containing the coordination ion in the step (2) is mainly composed of an aqueous solution of calcium chloride having a mass fraction of 5-20%, an aqueous solution of zinc sulfate having a mass fraction of 5-20%, and a sulfuric acid having a mass fraction of 5-20%. One or more of a magnesium aqueous solution, an aqueous solution of ferric chloride having a mass fraction of 5-20%, and an aqueous copper sulfate solution having a mass fraction of 5-20% are mixed in an arbitrary ratio. 11. A method of preparing an ion-enhanced graphene film, characterized in that the steps are as follows:

(1) 1 part by weight of graphene oxide, 5 to 150 parts by weight of a solvent is mixed, and after ultrasonic treatment, a graphene oxide solution is obtained.

(2) Extrusion of the graphene oxide solution in a preparation apparatus of a die-shaped die at an extrusion speed of 10 to 1000 mL/h, and staying in a coagulating liquid containing a coordination ion at 10 to 80 ° C for 1 to 100 seconds The film was solidified and dried to obtain a graphene oxide film.

(3) The graphene oxide film obtained in the step (2) is reduced in a reducing agent, and washed and dried to obtain an ion-enhanced graphene film;

The device for preparing the inline die in the step (2) is a rectangular parallelepiped structure, and a gradually narrowing in-line die is opened in the middle;

The solvent of the step (1) is mainly composed of water, methanol, ethanol, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N,N-dimethylformamide, N,N- a mixture of one or more of dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, ethylene glycol, and diethylene glycol in any ratio;

The coagulating liquid containing the coordination ion in the step (2) is mainly composed of an aqueous solution of calcium chloride having a mass fraction of 5-20%, an aqueous solution of zinc sulfate having a mass fraction of 5-20%, and a sulfuric acid having a mass fraction of 5-20%. One or more of a magnesium aqueous solution, an aqueous solution of ferric chloride having a mass fraction of 5-20%, and an aqueous copper sulfate solution having a mass fraction of 5-20% are mixed in an arbitrary ratio. The method for preparing an ion-enhanced graphene film according to claim 11, wherein the reducing agent is selected from the group consisting of hydrazine hydrate having a mass fraction of 1% to 40%, and having a mass fraction of 1%-40. % aqueous solution of sodium borohydride, aqueous solution of benzoquinone with a mass fraction of 1% to 40%, aqueous hydrobromide solution with a mass fraction of 1% to 40%, aqueous tea polyphenol solution with a mass fraction of 1% to 40%, mass fraction It is a 1%-40% aqueous urea solution, a 1%-20% sodium thiosulfate aqueous solution, a 1%-5% sodium hydroxide aqueous solution, and a 1%-40% hydroxide. Potassium aqueous solution, 5%-50% vitamin C aqueous solution, mass fraction of 1%-40% aqueous glucose solution, mass fraction of 1%-40% aqueous hydriodic acid, mass fraction of 1%-40% An aqueous solution of acetic acid and an aqueous solution of phenol having a mass fraction of 1% to 40%.