A method for preparing a graphene conductive material

Abstract

The application discloses a preparation method of 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, passing nitrogen, sequentially adding ferrous sulfate and glucose, stirring uniformly, feeding into a reaction kettle, keeping warm for 10-12 hours, discharging, washing the precipitate with anhydrous ethanol for 2-3 times, drying for 10-12 hours, and obtaining modified graphene; mixing the modified graphene with a dispersing agent, ultrasonic dispersing, adding a metal salt solution, and ultrasonic dispersing again; placing a metal film into the above solution, adopting a hydrothermal method to react for 3-4 hours, and drying at 70-80 DEG C to obtain a graphene film conductive material. The metal ions are mixed into the modified graphene, and are attached to the metal film to form a composite film of graphene and metal, so that the conductivity and mechanical properties are improved, and the graphene conductive material is especially suitable for being used in application fields of lithium batteries and printed circuits.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of conductive materials, and particularly relates to a preparation method of graphene conductive material. BACKGROUND

[0002] The conductive polymer is a kind of polymer containing a conjugated structure, and the conductivity level of the polymer can be improved from the insulating level to the metal level through chemical, electrochemical or ionic doping, and the conductive polymer has good application prospects in capacitors, energy sources, metal corrosion prevention and biosensors; at present, many organic raw materials are combined with inorganic nanomaterials to form organic-inorganic nanocomposites. The introduction of inorganic materials improves the original performance, and the synergistic effect between the organic materials and the inorganic materials makes the performance of the composite better than the simple addition of the performance of the single component.

[0003] The special structure of graphene endows it with many excellent properties and wide application prospects. However, due to the fact that each carbon atom in the structure of graphene is combined together in a sp2 hybridization manner to form a large conjugated pi bond on a two-dimensional plane, and the two large conjugated pi bonds produce pi-pi interaction, and graphene has a super-high specific surface area and is prone to aggregation, it is difficult to uniformly disperse in solvents and media, which limits the application of graphene. In addition to the excellent electrical properties of graphene materials in electronic components, another important use is to prepare high-performance nanocomposites.

[0004] At present, graphene has been used as a conductive agent or a composite conductive coating material in the application fields of lithium batteries and printed circuits. However, generally, only graphene is used, and the use of organic-inorganic composite materials is rare. SUMMARY

[0005] The present application provides a preparation method of graphene conductive material, which mixes metal ions into the modified graphene and attaches the metal ions to the metal film to form a composite film of graphene and metal, thereby improving the conductivity and mechanical properties, and is particularly suitable for use in the application fields of lithium batteries and printed circuits.

[0006] The technical scheme adopted by the present application is as follows: a preparation method of graphene conductive material, comprising the following steps:

[0007] a. adding graphene oxide into deionized water, adding phosphoric acid, stirring uniformly, adding lithium hydroxide, stirring and mixing for 30-40 min, passing nitrogen, sequentially adding ferrous sulfate and glucose, stirring uniformly, feeding into a reaction kettle, reacting at 200-240 DEG C for 10-12 h, discharging, washing the precipitate with anhydrous ethanol for 2-3 times, and drying at 50-55 DEG C for 10-12 h to obtain modified graphene;

[0008] b. mixing the modified graphene with a dispersant, ultrasonic dispersion, adding a metal salt solution, and ultrasonic dispersion again;

[0009] c. placing a metal-based film in the above solution, using a hydrothermal method, reacting at 85-95℃ for 3-4h, and drying at 70-80℃ to obtain a graphene film conductive material.

[0010] As preferred, in step a, 90-100 parts of graphene oxide is added to 100-110 times its weight of deionized water, 17-20 parts of phosphoric acid is added, stirred uniformly, 20-30 parts of lithium hydroxide is added, stirred and mixed for 30-40 min, nitrogen is introduced, 8-12 parts of ferrous sulfate and 1-2 parts of glucose are added in sequence, stirred uniformly, and the above parts are weight parts.

[0011] As preferred, in step b, the modified graphene and the dispersant are ultrasonic dispersed at a mass ratio of 1:20-40 for 20-50 min.

[0012] As preferred, the dispersant is one or more of ethylene glycol, glycerol, ethanol, isopropanol, N-methyl pyrrolidone, tetrahydrofuran and water.

[0013] As preferred, the molar ratio of the modified graphene to the metal salt solution is 1:0.1-0.5.

[0014] As preferred, the metal in the metal salt solution is one or more of palladium, platinum, silver, rhodium, aluminum, nickel, and the metal salt is one or more of nitrate, hydrochloride, sulfate, phosphate, oxalate, acetate, formate, propionate, butyrate and valerate.

[0015] As preferred, the metal-based film is one of palladium, platinum, silver, rhodium, aluminum and nickel.

[0016] Compared with the prior art, the present application has the beneficial effects that: the present application uses phosphoric acid, ferrous sulfate and the like to modify graphene, has good redispersibility, and after combining with metal ions, is attached to a metal thin film to form an organic-inorganic composite material at the nanometer level, and the prepared composite conductive film material has good conductivity and mechanical properties, and is particularly suitable for use in the field of lithium batteries and printed circuits. DETAILED DESCRIPTION

[0017] In order for those skilled in the art to better understand the technical solutions of the present application, the present application will be described in detail below in conjunction with specific examples.

[0018] Example One

[0019] The embodiments of the present application disclose a graphene conductive material preparation method, comprising the following steps:

[0020] a. Add 100g of graphene oxide to 100-110 times its weight of deionized water, add 17.2g of phosphoric acid, stir well, add 20g of lithium hydroxide, stir and mix for 35min, introduce nitrogen gas, add 10g of ferrous sulfate and 1.6g of glucose in sequence, stir well, transfer to a reaction vessel, keep the reaction at 220℃ for 11h, discharge the material, wash the precipitate three times with anhydrous ethanol, and dry at 53℃ for 11h to obtain modified graphene;

[0021] b. Modified graphene and ethanol were ultrasonically dispersed at a mass ratio of 1:20 for 50 min. The metal salt solution was then added at a molar ratio of 1:0.3 and ultrasonically dispersed again for 20 min. The metal salt solution was prepared by dissolving aluminum chloride in ethylene glycol solvent.

[0022] c. The aluminum-based film is placed in the above solution and reacted at 90°C for 3 hours using a hydrothermal method. The film is then dried at 70°C to obtain the graphene conductive film material.

[0023] Example 2

[0024] An embodiment of the present invention discloses a method for preparing graphene conductive material, comprising the following steps:

[0025] a. Add 90g of graphene oxide to 100-110 times its weight of deionized water, add 17g of phosphoric acid, stir well, add 22g of lithium hydroxide, stir and mix for 30min, introduce nitrogen gas, add 12g of ferrous sulfate and 2g of glucose in sequence, stir well, transfer to a reaction vessel, keep the reaction at 200℃ for 12h, discharge the material, wash the precipitate twice with anhydrous ethanol, and dry at 50℃ for 10h to obtain modified graphene;

[0026] b. Modified graphene and ethylene glycol were ultrasonically dispersed at a mass ratio of 1:40 for 40 min. Then, the metal salt solution was added at a molar ratio of 1:0.5 to modified graphene, and ultrasonically dispersed again for 30 min. The metal salt solution was prepared by dissolving nickel chloride in a mixture of water and ethylene glycol.

[0027] c. The nickel-based film is placed in the above solution and reacted at 85°C for 4 hours using a hydrothermal method. The film is then dried at 80°C to obtain the graphene conductive film material.

[0028] Example 3

[0029] An embodiment of the present invention discloses a method for preparing graphene conductive material, comprising the following steps:

[0030] a. Add 98g of graphene oxide to 100-110 times its weight of deionized water, add 20g of phosphoric acid, stir well, add 30g of lithium hydroxide, stir and mix for 40min, introduce nitrogen gas, add 8g of ferrous sulfate and 1g of glucose in sequence, stir well, transfer to a reaction vessel, keep the reaction at 240℃ for 10h, discharge the material, wash the precipitate three times with anhydrous ethanol, and dry at 55℃ for 12h to obtain modified graphene;

[0031] b. Modified graphene, ethylene glycol, and glycerol were ultrasonically dispersed at a mass ratio of 1:25 for 20 min. The metal salt solution was then added at a molar ratio of 1:0.1 and ultrasonically dispersed again for 50 min. The metal salt solution was prepared by dissolving silver nitrate in a mixture of water and ethanol in a volume ratio.

[0032] c. The silver-based film is placed in the above solution and reacted at 90°C for 3.5 hours using a hydrothermal method. The film is then dried at 75°C to obtain a graphene conductive film material.

[0033] Example 4

[0034] An embodiment of the present invention discloses a method for preparing graphene conductive material, comprising the following steps:

[0035] a. Add 100g of graphene oxide to 100-110 times its weight of deionized water, add 20g of phosphoric acid, stir well, add 30g of lithium hydroxide, stir and mix for 40min, introduce nitrogen gas, add 10g of ferrous sulfate and 2g of glucose in sequence, stir well, transfer to a reaction vessel, keep the reaction at 220℃ for 12h, discharge the material, wash the precipitate three times with anhydrous ethanol, and dry at 55℃ for 12h to obtain modified graphene;

[0036] b. Modified graphene and isopropanol were ultrasonically dispersed at a mass ratio of 1:40 for 50 min. The metal salt solution was then added at a molar ratio of 1:0.4 and ultrasonically dispersed again for 25 min. The metal salt solution was prepared by dissolving palladium nitrate in a mixture of water and isopropanol.

[0037] c. The palladium-based film is placed in the above solution and reacted at 90°C for 3 hours using a hydrothermal method. The film is then dried at 70°C to obtain the graphene conductive film material.

[0038] The present invention has been described in detail above through embodiments, but the content described is only an exemplary embodiment of the present invention and should not be considered as limiting the scope of the present invention. The scope of protection of the present invention is defined by the claims. Any technical solutions designed by those skilled in the art using the technical solutions described in the present invention, or designed by those skilled in the art under the inspiration of the technical solutions of the present invention, within the substance and protection scope of the present invention, to achieve the above-mentioned technical effects, or any equivalent changes and improvements made to the scope of the application, should still fall within the patent protection scope of the present invention.

Claims

1. A method for preparing a graphene conductive material, characterized in that: Includes the following steps: a. Add graphene oxide to deionized water, add phosphoric acid, stir evenly, add lithium hydroxide, stir and mix for 30-40 minutes, purge with nitrogen, add ferrous sulfate and glucose in sequence, stir evenly, transfer to a reaction vessel, keep the reaction at 200-240℃ for 10-12 hours, discharge the material, wash the precipitate with anhydrous ethanol 2-3 times, dry at 50-55℃ for 10-12 hours to obtain modified graphene. b. Mix the modified graphene with the dispersant, disperse it ultrasonically, add the metal salt solution, and disperse it ultrasonically again; c. The metal substrate film is placed in the above solution and reacted at 85-95℃ for 3-4 hours using a hydrothermal method, and then dried at 70-80℃ to obtain the graphene film conductive material. In step a, 90-100 parts of graphene oxide are added to 100-110 times its weight of deionized water, 17-20 parts of phosphoric acid are added, and the mixture is stirred evenly. Then, 20-30 parts of lithium hydroxide are added and stirred for 30-40 minutes. Nitrogen gas is introduced, and 8-12 parts of ferrous sulfate and 1-2 parts of glucose are added in sequence and stirred evenly. The above figures are by weight. In step b, the modified graphene and the dispersant are mixed at a mass ratio of 1:20-40, and the ultrasonic dispersion time is 20-50 min. The dispersant is one or more of ethylene glycol, glycerol, ethanol, isopropanol, N-methylpyrrolidone, tetrahydrofuran, and water; The molar ratio of the modified graphene to the metal salt solution is 1:0.1-0.5; 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. The metal substrate film is one of palladium, platinum, silver, rhodium, aluminum, and nickel.