阅读说明：本技术 一种石墨烯导电材料制备方法 (Preparation method of graphene conductive material ) 是由 姬姗姗 全帅 于 2020-05-15 设计创作，主要内容包括：本发明公开一种石墨烯导电材料制备方法,包括以下步骤：将氧化石墨烯加入到去离子水中,加入磷酸,搅拌均匀,加入氢氧化锂,搅拌混合,通入氮气,依次加入硫酸亚铁和葡萄糖,搅拌均匀,送入到反应釜中,保温反应10-12h,出料,将沉淀用无水乙醇洗涤2-3次,干燥10-12h,得改性石墨烯；将改性石墨烯与分散剂混合,超声分散,加入金属盐溶液,再次超声分散；金属基膜放置于上述溶液中,采用水热法反应3-4h,70-80℃烘干得到石墨烯膜导电材料。本发明在改性后的石墨烯中混入金属离子,并附着在金属薄膜上,形成石墨烯与金属的复合薄膜,提高了导电和力学等性能,特别适合于使用在锂电池、印刷电路等应用领域。(The invention discloses a preparation method of a graphene conductive material, which comprises the following steps: adding graphene oxide into deionized water, adding phosphoric acid, stirring uniformly, adding lithium hydroxide, stirring and mixing, introducing nitrogen, sequentially adding ferrous sulfate and glucose, stirring uniformly, feeding into a reaction kettle, carrying out heat preservation reaction for 10-12h, discharging, washing the precipitate with absolute ethyl alcohol for 2-3 times, and drying for 10-12h to obtain modified graphene; mixing the modified graphene with a dispersing agent, performing ultrasonic dispersion, adding a metal salt solution, and performing ultrasonic dispersion again; and placing the metal base film in the solution, reacting for 3-4h by adopting a hydrothermal method, and drying at 70-80 ℃ to obtain the graphene film conductive material. According to the invention, metal ions are mixed into the modified graphene and attached to the metal film to form the composite film of the graphene and the metal, so that the performances of conductivity, mechanics and the like are improved, and the graphene composite film is particularly suitable for application fields such as lithium batteries and printed circuits.)

1. A preparation method of a graphene conductive material is characterized by comprising the following steps: the method comprises the following steps:

a. adding graphene oxide into deionized water, adding phosphoric acid, stirring uniformly, adding lithium hydroxide, stirring and mixing for 30-40min, introducing nitrogen, sequentially adding ferrous sulfate and glucose, stirring uniformly, sending into a reaction kettle, carrying out heat preservation reaction for 10-12h at the temperature of 240 ℃ and 200-;

b. mixing the modified graphene with a dispersing agent, performing ultrasonic dispersion, adding a metal salt solution, and performing ultrasonic dispersion again;

c. and placing the metal-based film in the solution, reacting for 3-4h at 85-95 ℃ by adopting a hydrothermal method, and drying at 70-80 ℃ to obtain the graphene film conductive material.

2. The method for preparing a graphene film conductive material according to claim 1, wherein: in the step a, 90-100 parts of graphene oxide is added into deionized water which is 110 times of 100 times of graphene oxide in weight, 17-20 parts of phosphoric acid is added and uniformly stirred, 20-30 parts of lithium hydroxide is added and mixed for 30-40min, nitrogen is introduced, 8-12 parts of ferrous sulfate and 1-2 parts of glucose are sequentially added and uniformly stirred, and the parts are parts by weight.

3. The method for preparing a graphene film conductive material according to claim 1, wherein: in the step b, the modified graphene and the dispersing agent are mixed according to the mass ratio of 1: 20-40, and the ultrasonic dispersion time is 20-50 min.

4. The method for preparing a graphene film conductive material according to claim 1, wherein: the dispersing agent is one or more of ethylene glycol, glycerol, ethanol, isopropanol, N-methyl pyrrolidone, tetrahydrofuran and water.

5. The method for preparing a graphene film conductive material according to claim 1, wherein: the molar ratio of the modified graphene to the metal salt solution is 1: 0.1-0.5.

6. The method for preparing a graphene film conductive material according to claim 1, wherein: the metal in the metal salt solution is one or more of palladium, platinum, silver, rhodium, aluminum and nickel, and the metal salt is one or more of nitrate, hydrochloride, sulfate, phosphate, oxalate, acetate, formate, propionate, butyrate and valerate.

7. The method for preparing a graphene film conductive material according to claim 1, wherein: the metal-based film is one of palladium, platinum, silver, rhodium, aluminum and nickel.

Technical Field

The invention belongs to the technical field of conductive materials, and particularly relates to a preparation method of a graphene conductive material.

Background

The conductive polymer is a polymer containing a conjugated structure, can enable the conductivity level of the polymer to reach the metal level from the insulation level by doping in a chemical, electrochemical or ionic mode, and has good application prospect in the aspects of capacitors, energy sources, metal corrosion prevention and biosensors; at present, there are many organic raw materials which are compounded with inorganic nano-materials to form organic-inorganic nano-composite materials. The introduction of the inorganic substance improves the original performance, and the synergistic effect between the organic substance and the inorganic substance ensures that the performance of the composite material is superior to the simple addition of the performance of single components.

The special structure of the graphene endows the graphene with a plurality of excellent performances, and the application prospect is wide. However, it is because each carbon atom on the graphene structure is combined together in an sp2 hybridization manner to form a large conjugated pi bond on a two-dimensional plane, and pi-pi interaction occurs between the two large conjugated pi bonds, and meanwhile, graphene has an ultra-high specific surface area, is very easy to agglomerate, and is difficult to be uniformly dispersed in solvents and media, which results in that the application of graphene is greatly limited. Besides excellent electrical properties of the graphene material in the aspect of electronic components, another important application is to prepare high-performance nano composite materials.

Currently, graphene has played a better role as a conductive agent or a composite conductive coating material in the application fields of lithium batteries, printed circuits and the like. However, graphene is generally used only simply, and the use of organic-inorganic composite materials is very rare.

Disclosure of Invention

Aiming at the technical problems in the prior art, the invention provides a preparation method of a graphene conductive material, metal ions are mixed into modified graphene and are attached to a metal film to form a composite film of the graphene and the metal, so that the performances of conductivity, mechanics and the like are improved, and the preparation method is particularly suitable for application fields of lithium batteries, printed circuits and the like.

The technical scheme adopted by the invention is as follows: a preparation method of a graphene conductive material comprises the following steps:

a. adding graphene oxide into deionized water, adding phosphoric acid, stirring uniformly, adding lithium hydroxide, stirring and mixing for 30-40min, introducing nitrogen, sequentially adding ferrous sulfate and glucose, stirring uniformly, sending into a reaction kettle, carrying out heat preservation reaction for 10-12h at the temperature of 240 ℃ and 200-;

b. mixing the modified graphene with a dispersing agent, performing ultrasonic dispersion, adding a metal salt solution, and performing ultrasonic dispersion again;

c. and placing the metal-based film in the solution, reacting for 3-4h at 85-95 ℃ by adopting a hydrothermal method, and drying at 70-80 ℃ to obtain the graphene film conductive material.

Preferably, in the step a, 90-100 parts of graphene oxide is added into deionized water which is 110 times of the graphene oxide by weight of 100, 17-20 parts of phosphoric acid is added, the mixture is uniformly stirred, 20-30 parts of lithium hydroxide is added, the mixture is stirred and mixed for 30-40min, nitrogen is introduced, 8-12 parts of ferrous sulfate and 1-2 parts of glucose are sequentially added, and the mixture is uniformly stirred, wherein the parts are parts by weight.

Preferably, in the step b, the modified graphene and the dispersing agent are mixed according to the mass ratio of 1: 20-40, and the ultrasonic dispersion time is 20-50 min.

Preferably, the dispersant is one or more of ethylene glycol, glycerol, ethanol, isopropanol, N-methylpyrrolidone, tetrahydrofuran and water.

Preferably, the molar ratio of the modified graphene to the metal salt solution is 1: 0.1-0.5.

Preferably, the metal in the metal salt solution is one or more of palladium, platinum, silver, rhodium, aluminum and nickel, and the metal salt is one or more of nitrate, hydrochloride, sulfate, phosphate, oxalate, acetate, formate, propionate, butyrate and valerate.

Preferably, the metal-based film is one of palladium, platinum, silver, rhodium, aluminum and nickel.

Compared with the prior art, the invention has the beneficial effects that: according to the invention, the graphene is modified by phosphoric acid, ferrous sulfate and the like, so that the graphene has good redispersibility, and is attached to a metal film after being combined with metal ions to form an organic-inorganic composite material on a nano layer, and the prepared composite conductive film material has good conductivity, mechanical property and the like, and is particularly suitable for the fields of lithium batteries and printed circuits.

Detailed Description

In order that those skilled in the art will better understand the technical solutions of the present invention, the following detailed description of the present invention is provided in connection with specific embodiments.

Example one

The embodiment of the invention discloses a preparation method of a graphene conductive material, which comprises the following steps:

a. adding 100g of graphene oxide into deionized water with the weight being 110 times that of 100-fold, adding 17.2g of phosphoric acid, uniformly stirring, adding 20g of lithium hydroxide, stirring and mixing for 35min, introducing nitrogen, sequentially adding 10g of ferrous sulfate and 1.6g of glucose, uniformly stirring, feeding into a reaction kettle, carrying out heat preservation reaction at 220 ℃ for 11h, discharging, washing the precipitate with absolute ethyl alcohol for 3 times, and drying at 53 ℃ for 11h to obtain modified graphene;

b. ultrasonically dispersing the modified graphene and ethanol for 50min according to the mass ratio of 1: 20, adding a metal salt solution according to the molar ratio of 1: 0.3 of the modified graphene to the metal salt solution, and ultrasonically dispersing for 20min again; the metal salt solution is prepared by dissolving aluminum chloride in glycol solvent;

c. and placing the metal aluminum-based film in the solution, reacting for 3 hours at 90 ℃ by adopting a hydrothermal method, and drying at 70 ℃ to obtain the graphene film conductive material.

Example two

The embodiment of the invention discloses a preparation method of a graphene conductive material, which comprises the following steps:

a. adding 90g of graphene oxide into deionized water with the weight being 110 times that of 100-fold, adding 17g of phosphoric acid, uniformly stirring, adding 22g of lithium hydroxide, stirring and mixing for 30min, introducing nitrogen, sequentially adding 12g of ferrous sulfate and 2g of glucose, uniformly stirring, feeding into a reaction kettle, carrying out heat preservation reaction at 200 ℃ for 12h, discharging, washing the precipitate with absolute ethyl alcohol for 2 times, and drying at 50 ℃ for 10h to obtain modified graphene;

b. ultrasonically dispersing the modified graphene and ethylene glycol for 40min according to the mass ratio of 1: 40, adding a metal salt solution according to the molar ratio of 1: 0.5 of the modified graphene to the metal salt solution, and ultrasonically dispersing for 30min again; the metal salt solution is prepared by dissolving nickel chloride in a mixed solvent of water and glycol;

c. and placing the metal nickel-based film in the solution, reacting for 4 hours at 85 ℃ by adopting a hydrothermal method, and drying at 80 ℃ to obtain the graphene film conductive material.

EXAMPLE III

The embodiment of the invention discloses a preparation method of a graphene conductive material, which comprises the following steps:

a. adding 98g of graphene oxide into deionized water with the weight being 110 times that of 100-fold, adding 20g of phosphoric acid, uniformly stirring, adding 30g of lithium hydroxide, stirring and mixing for 40min, introducing nitrogen, sequentially adding 8g of ferrous sulfate and 1g of glucose, uniformly stirring, feeding into a reaction kettle, carrying out heat preservation reaction at 240 ℃ for 10h, discharging, washing the precipitate with absolute ethyl alcohol for 3 times, and drying at 55 ℃ for 12h to obtain modified graphene;

b. ultrasonically dispersing the modified graphene, ethylene glycol and glycerol for 20min according to the mass ratio of 1: 25, adding a metal salt solution according to the molar ratio of 1: 0.1 of the modified graphene to the metal salt solution, and ultrasonically dispersing for 50min again; the metal salt solution is prepared by dissolving silver nitrate in a mixed solvent of water and ethanol in volume ratio;

c. and placing the metal silver-based film in the solution, reacting for 3.5h at 90 ℃ by adopting a hydrothermal method, and drying at 75 ℃ to obtain the graphene film conductive material.

Example four

The embodiment of the invention discloses a preparation method of a graphene conductive material, which comprises the following steps:

a. adding 100g of graphene oxide into deionized water with the weight being 110 times that of the graphene oxide, adding 20g of phosphoric acid, uniformly stirring, adding 30g of lithium hydroxide, stirring and mixing for 40min, introducing nitrogen, sequentially adding 10g of ferrous sulfate and 2g of glucose, uniformly stirring, feeding into a reaction kettle, carrying out heat preservation reaction at 220 ℃ for 12h, discharging, washing the precipitate with absolute ethyl alcohol for 3 times, and drying at 55 ℃ for 12h to obtain modified graphene;

b. ultrasonically dispersing the modified graphene and isopropanol for 50min according to the mass ratio of 1: 40, adding a metal salt solution according to the molar ratio of 1: 0.4 of the modified graphene to the metal salt solution, and ultrasonically dispersing for 25min again; the metal salt solution is prepared by dissolving palladium nitrate in a mixed solvent of water and isopropanol;

c. and placing the metal palladium-based membrane in the solution, reacting for 3 hours at 90 ℃ by adopting a hydrothermal method, and drying at 70 ℃ to obtain the graphene membrane conductive material.

The present invention has been described in detail with reference to the embodiments, but the description is only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The scope of the invention is defined by the claims. The technical solutions of the present invention or those skilled in the art, based on the teaching of the technical solutions of the present invention, should be considered to be within the scope of the present invention, and all equivalent changes and modifications made within the scope of the present invention or equivalent technical solutions designed to achieve the above technical effects are also within the scope of the present invention.