阅读说明：本技术 石墨烯铅合金的制造方法 (Method for manufacturing graphene-lead alloy ) 是由 赖中平 张国兴 于 2018-06-14 设计创作，主要内容包括：本发明提供一种石墨烯铅合金的制造方法,包括：将石墨烯氧化物分散于含铅离子或其它金属离子的水溶液中；使用还原剂将金属离子与石墨烯氧化物同步还原成含有金属纳米颗粒的石墨烯产物；过滤干燥前一步骤的含有金属纳米颗粒的石墨烯产物,获得金属纳米颗粒改性的石墨烯粉体；以及将前述金属纳米颗粒改性的石墨烯粉体加入铅熔炼液中,搅拌分散后浇铸冷却成块,进而获得石墨烯铅合金块。本发明方法可以增加石墨烯在金属熔炼液中的湿润性,提升石墨烯分散程度。(The invention provides a method for manufacturing a graphene-lead alloy, which comprises the following steps: dispersing graphene oxide in an aqueous solution containing lead ions or other metal ions; synchronously reducing metal ions and graphene oxide into a graphene product containing metal nanoparticles by using a reducing agent; filtering and drying the graphene product containing the metal nano particles in the previous step to obtain metal nano particle modified graphene powder; and adding the graphene powder modified by the metal nanoparticles into a lead smelting solution, stirring and dispersing, and then casting and cooling into blocks to obtain the graphene-lead alloy blocks. The method can increase the wettability of the graphene in the metal smelting liquid and improve the dispersion degree of the graphene.)

1. A method for manufacturing a graphene-lead alloy is characterized by comprising the following steps:

dispersing graphene oxide in an aqueous solution containing lead ions or other metal ions;

synchronously reducing the metal ions and the graphene oxide into a graphene product containing metal nanoparticles by using a reducing agent;

filtering and drying the graphene product containing the metal nano particles in the previous step to obtain metal nano particle modified graphene powder; and

and adding the metal nanoparticle modified graphene powder into a lead smelting solution, stirring and dispersing, and then casting and cooling into blocks to obtain the graphene-lead alloy blocks.

2. The method for producing a graphene-lead alloy according to claim 1, wherein: the aqueous solution containing lead ions or other metal ions comprises: any one of lead, iron, cobalt, nickel, copper, zinc, manganese, silver and other ionic solutions; the metal ion material is any one of the materials of sulfate, nitrate, hypochlorite, chloride, acetate, etc. of the above metals.

3. The method for producing a graphene-lead alloy according to claim 1, wherein: the reducing agent comprises: sodium borohydride, sodium dithionite, sodium thiosulfate, hydrazine, vitamin C, SnCl2, and the like.

Technical Field

The invention relates to a manufacturing process of a lead alloy, in particular to a manufacturing method of a graphene lead alloy.

Background

The graphene is introduced into the alloy structure and can be used as a framework inside the alloy structure, so that the strength of the whole alloy is enhanced. In the graphene lead alloy part, related reports and products show that the performance and the cycle life of the lead-acid battery can be greatly improved when the graphene lead alloy is applied to the lead-acid battery. Therefore, the graphene lead-acid battery has sufficient competitiveness in the aspect of industrial products. In the production process of the graphene alloy industry, the dispersion condition of graphene in the alloy is a key influencing the physical properties of the graphene-lead alloy. Known related manufacturing techniques are listed below.

The published Chinese patent application publication No. CN104263994A shows a graphene alloy composite conductive material and a preparation method thereof, and the graphene alloy composite material is an alloy of 0.01-5% of graphene on indium, bismuth, tin and zinc substrates. The preparation method comprises the steps of heating the metal powder in a crucible to form an alloy liquid, directly adding the graphene powder into the alloy liquid, stirring the graphene powder and a graphite rod, casting and molding, and naturally cooling to form the graphene alloy. It can be understood that graphene has a low density, a strong cohesive force of a molten metal, and poor wettability of graphene mixed solution, and uniformly dispersed graphene alloy is difficult to achieve by direct stirring.

In published chinese patent application publication No. CN102719719A, which is basically a powder metallurgy method for preparing graphene alloy, a cemented carbide material containing 0.01-0.5 wt% of graphene is disclosed. The preparation process comprises the steps of uniformly dispersing a graphene material in water or an organic solvent to form a graphene dispersion liquid, mixing the graphene dispersion liquid with hard alloy powder, and performing ball milling, drying, granulation, compression molding, degreasing and sintering in sequence to obtain a target product. The patented technology improves the dispersion problem of graphene in the molten liquid by adopting a powder metallurgy mode.

The published Chinese patent application publication No. CN106312045A provides a formula alloy of a graphene-lead grid of a lead-acid storage battery and a manufacturing method thereof, and basically, nickel-plated graphene and aluminum metal powder are mixed by ball milling and then a graphene aluminum alloy is prepared by adopting a powder metallurgy mode. The nickel-plated graphene adopted in the aluminum alloy powder metallurgy can have higher wettability and bonding force. However, among them, nickel-plated graphene needs to be obtained through a plurality of manufacturing processes such as sensitization, activation, and electroless nickel plating, and the manufacturing process is relatively troublesome.

In other graphene alloy manufacturing processes, for example, published chinese patent application publication No. CN105551839A discloses a graphene copper alloy preparation method, which comprises depositing copper metal on the surface of graphene by a direct current magnetron sputtering method to obtain copper-plated graphene composite powder, then performing ball milling and mixing, cold press molding, and arc melting and sintering to obtain a target product.

Published Chinese patent application publication No. CN106148748A proposes a graphene titanium alloy preparation method, which comprises the steps of mixing titanium sponge and graphene to enable the graphene to be uniformly absorbed in a titanium sponge body, pressing the titanium sponge absorbed with the graphene into a fixed shape, and then smelting in a vacuum arc smelting mode to finally obtain the graphene titanium alloy.

Published chinese patent application publication No. CN106058267A proposes a process for preparing graphene-lead alloy by an in-situ synthesis method, in which a metal carbide or a solid organic substance is added to a lead smelting solution to dissolve a carbonaceous substance in the metal smelting solution, and then, in a casting cooling process, carbon atoms are separated out in a grain boundary and arranged into graphene, thereby obtaining the graphene-lead alloy.

From the viewpoint of cost and mass production, the smelting method is a relatively feasible and adopted mass production process.

Regarding the improvement of the dispersion problem of graphene in a smelting method, a multi-step smelting method is used as a main process. Published chinese patent application publication No. CN103943865A proposes a multi-step melting method for preparing graphene-lead alloy, which contains lead alloy of tin, aluminum, strontium, copper and graphene, and is applied to lead-acid battery grid alloy.

Firstly, mixing graphene oxide or a small amount of graphene powder with tin oxide, strontium oxide, copper oxide and aluminum oxide, adding a proper amount of reducing agent, reducing the metal oxide in a high-temperature vacuum electric furnace, and synchronously smelting to obtain a preliminary graphene base alloy matrix; then, the graphene base matrix is added into the lead melt according to the proportion to obtain the lead alloy containing tin, aluminum, strontium, copper and graphene.

From the above-mentioned many graphene alloy patents, it can be found that the direct use of graphene powder has the problems of graphene wettability and dispersibility; the powder metallurgy adopts ball milling mixing and cannot be efficiently produced in large quantities; other manufacturing processes have problems of complicated processes and expensive equipment.

Disclosure of Invention

The invention aims to provide a method for manufacturing a graphene lead alloy, which is simple and can solve the problems of wetting and dispersion of graphene powder in a metal alloy smelting solution.

In order to solve the above technical problem, an embodiment of the present invention of a method for manufacturing a graphene-lead alloy includes:

1. dispersing Graphene Oxide (GO) in an aqueous solution containing lead ions or other metal ions;

2. synchronously reducing metal ions and graphene oxide into a graphene product containing metal nanoparticles by using a reducing agent;

3. filtering and drying the graphene product containing the metal nano particles in the previous step to obtain metal nano particle modified graphene powder; and

4. and adding the metal nanoparticle modified graphene powder into a lead smelting solution, stirring and dispersing, and then casting and cooling into blocks to obtain the graphene-lead alloy blocks.

As a preferred embodiment of the method for producing the graphene lead alloy of the present invention, the aqueous solution containing lead ions or other metal ions includes: any one of lead, iron, cobalt, nickel, copper, zinc, manganese, silver and other ionic solutions; the metal ion material is any one of the materials of sulfate, nitrate, hypochlorite, chloride, acetate, etc. of the above metals.

As a preferred embodiment of the method for manufacturing the graphene-lead alloy of the present invention, the reducing agent includes: sodium borohydride (NaBH4), sodium dithionite (Na2S2O4), sodium thiosulfate (Na2S2O3), hydrazine (N2H4), vitamin C, SnCl2, and the like.

The method for manufacturing the graphene-lead alloy has the advantages that functional groups on the surface of the oxidized graphene can adsorb metal ions, so that the metal nanoparticles and the graphene after the reduction process have chemical bonding relevance; on the other hand, the surface of the graphene powder modified by the metal nanoparticles can increase the wettability of the graphene in the lead metal smelting liquid and improve the dispersion degree of the graphene.

Other features and embodiments of the present invention will be described in detail below with reference to the drawings.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.

Fig. 1 is a flowchart illustrating steps of a method for manufacturing a graphene-lead alloy according to the present invention.

Description of the symbols

1. Dispersing Graphene Oxide (GO) in an aqueous solution containing lead ions or other metal ions

2. Simultaneous reduction of metal ions with graphene oxide to graphene products containing metal nanoparticles using a reducing agent

3. Filtering and drying the graphene product containing the metal nano particles in the previous step to obtain metal nano particle modified graphene powder

4. Adding the metal nanoparticle modified graphene powder into a lead smelting solution, stirring and dispersing, then casting and cooling to form a block, and further obtaining a graphene-lead alloy block

Detailed Description

The positional relationship described in the following embodiments includes: the top, bottom, left and right, unless otherwise indicated, are based on the orientation of the elements in the drawings.

Fig. 1 is a flow chart of steps of a method for manufacturing a graphene-lead alloy according to the present invention. The steps of one embodiment of the method for producing a graphene-lead alloy according to the present invention include:

1. dispersing Graphene Oxide (GO) in an aqueous solution containing lead ions or other metal ions to enable surface functional groups of the graphene oxide to adsorb the lead ions or other metal ions; the aqueous solution containing lead ions or other metal ions comprises: any one of lead, iron, cobalt, nickel, copper, zinc, manganese, silver and other ionic solutions; the metal ion material is any one of the materials of sulfate, nitrate, hypochlorite, chlorate, acetate and the like of the metal;

2. reducing metal ions simultaneously with graphene oxide to a graphene product containing metal nanoparticles using a reducing agent, wherein the reducing agent can remove the content of functional groups, said reducing agent comprising: sodium borohydride (NaBH4), sodium dithionite (Na2S2O4), sodium thiosulfate (Na2S2O3), hydrazine (N2H4), vitamins C, SnCl2, and the like; by this step, lead ions or other metal ions will be chemically reduced into metal nanoparticles and deposited on the graphene surface;

3. filtering and drying the graphene product containing the metal nano particles in the previous step to obtain metal nano particle modified graphene powder; and

4. and adding the metal nanoparticle modified graphene powder into a lead smelting solution, stirring and dispersing, and then casting and cooling into blocks to obtain the graphene-lead alloy blocks.

Through the steps of the method for manufacturing the graphene-lead alloy, the carbon-oxygen functional group on the surface of the graphene oxide can adsorb metal ions, so that the reduced metal nanoparticles and graphene have chemical bonding relevance. On the other hand, the surface of the graphene powder modified by the metal nanoparticles can increase the wettability of the graphene in the metal smelting liquid and improve the dispersion degree of the graphene.

The above-described embodiments and/or implementations are only for illustrating the preferred embodiments and/or implementations of the present technology, and are not intended to limit the implementations of the present technology in any way, and those skilled in the art may make modifications or changes to other equivalent embodiments without departing from the scope of the technical means disclosed in the present disclosure, but should be construed as the technology or implementations substantially the same as the present technology.