CN111825082A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN111825082A CN111825082A CN202010702369.2A CN202010702369A CN111825082A CN 111825082 A CN111825082 A CN 111825082A CN 202010702369 A CN202010702369 A CN 202010702369A CN 111825082 A CN111825082 A CN 111825082A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/06—Etching of iron or steel
Abstract
The invention relates to a preparation method of graphene, in particular to a preparation method of an ultra-stable silicon-based lithium ion battery cathode material capable of being industrially produced and a preparation method of a silicon-based cathode material coated by nitrogen-doped graphene. The method comprises the following steps: firstly, preparing nano silicon particles by using thermal plasma, secondly, preparing a nano silicon template by using a mechanical method, and finally preparing the nitrogen-doped graphene-coated silicon-based negative electrode material by using DMF (dimethyl formamide) as a nitrogen-carbon source. The method is characterized in that: (1) the preparation method of the spherical silicon nano-particles is established by taking silicon powder as a raw material, adopting industrial-grade purity argon or hydrogen as a raw material and utilizing a direct-current thermal plasma heating mode, so that the preparation of the spherical silicon nano-particles is realized. (2) The nano-silicon prepared by the method has the advantages of smaller particle size, better dispersibility, higher yield and the like. (3) The size of the nano silicon particles is adjusted by controlling the atmosphere composition, the gas flow and the like. (4) DMF is used as a nitrogen source and a carbon source, and doped sites exist at the edge of graphene and inside the graphene.
Description
Technical Field
The invention belongs to the field of material processing, and particularly relates to a preparation method of graphene.
Background
The graphene has the characteristics of extremely high electron mobility, good conductivity, extremely large specific surface area, transparency and the like, and is expected to be used for new-generation electronic devices, optoelectronic devices, energy devices and the like. The main preparation methods of graphene include a micro-mechanical lift-off method, an epitaxial growth method, a CVD growth method, and a graphite oxide reduction method. The graphene prepared by the first three methods has controllable number of layers, few defects and high quality, but the process is relatively complex, the preparation efficiency is low and the cost is high. The graphite oxide reduction method can prepare graphene in a large scale at low cost, is one of the widely used preparation methods at present, but needs to use a large amount of strong oxidant and reducing agent in the preparation process, and has dangerous process and great harm to the environment. The methods for preparing graphene include a carbon nanotube cutting method, a graphite intercalation method, an ion implantation method, a high temperature and high pressure HPHT growth method, an explosion method, an organic synthesis method, and the like, but each of these methods has limitations and cannot be mass-produced.
Disclosure of Invention
The invention aims to provide a preparation method for preparing large-area and high-quality graphene at low cost in a large scale.
The technical scheme of the invention is as follows: a preparation method of graphene comprises the following steps: etching the carbon alloy by using etching liquid, and removing non-carbon elements in the carbon-containing alloy to obtain graphene; the etching liquid comprises one to three of hydrochloric acid, sulfuric acid or nitric acid.
Preferably, the carbon alloy is synthesized by the existing smelting method, metal and a carbon source are uniformly mixed and heated until the mixture is completely melted to form uniform alloy liquid. The carbon element is distributed in the alloy by heating. And cooling to obtain the carbon alloy.
The preparation of the carbon-containing alloy can be realized by uniformly mixing a carbon source and one or more metals according to a certain proportion, heating to a molten state, and cooling to obtain the carbon-containing alloy. The carbon source can be selected from carbon simple substance or carbon-containing compound such as coke, activated carbon, carbon black, carbon nanotube, etc., and the metal can be one or more of iron, nickel, copper, chromium, aluminum, titanium, manganese, zinc, magnesium, tin, molybdenum and silicon. The heating temperature varies with the type of the metal to be selected, so that a uniform molten state with fluidity can be formed.
And chemically and electrochemically etching the carbon alloy by using the etching solution. And cleaning the product to remove residual ions, and etching off non-carbon elements in the alloy to form graphene. Other non-carbon metallic non-metals are also retained in the alloy to form a graphene composite.
Preferably, the carbon in the carbon alloy is present in an amount of 0.5 to 6.18% by mass.
Preferably, the carbon in the carbon alloy is present in an amount of 2.18 to 4.23% by mass.
Preferably, the etching solution also comprises ferric trichloride with the concentration of not more than 12 mol/L.
Preferably, the etching solution is hydrochloric acid with the concentration of 0.01 mol/L-12 mol/L, and the temperature of the etching solution is 20 ℃ to 90 ℃.
Preferably, the etching solution is sulfuric acid with the concentration of 0.01-11.5 mol/L, and the temperature of the etching solution is 20-90 ℃.
Preferably, the etching solution is nitric acid with the concentration of 0.01-16 mol/L, and the temperature of the etching solution is 20-86 ℃.
Preferably, the etching solution is a mixed solution of nitric acid, sulfuric acid and hydrochloric acid with the mass ratio of 1:1: 1.
Preferably, the etching solution is hydrochloric acid with the concentration of 1 mol/L-12 mol/L and ferric trichloride with the concentration of 1 mol/L-12 mol/L.
The invention is characterized in that the carbon precipitation phenomenon in the process of melting, cooling and dealloying the carbon-containing alloy is utilized, one or more non-carbon elements in the alloy are removed by chemical electrochemical etching, and the carbon in the alloy body is utilized to form the graphene. Different from a CVD method, graphene is precipitated on the surface of metal. Compared with the existing micro-mechanical stripping method, epitaxial growth method, CVD growth method and graphite oxide reduction method, the method has the advantages of relatively simple process, high preparation efficiency, low cost and easy industrial production, and can directly utilize the carbon-containing alloy prepared in the steel industry to prepare the graphene.
Drawings
FIG. 1 is a transmission electron microscope image of graphene prepared by etching a nickel-carbon alloy with 12mol/L hydrochloric acid;
FIG. 2 is a Raman spectrum of graphene prepared by etching a nickel-carbon alloy with 12mol/L hydrochloric acid;
FIG. 3 is a Raman spectrum of graphene prepared by etching a grey iron standard sample with 0.01mol/L hydrochloric acid;
FIG. 4 is a transmission electron microscope image of graphene prepared by etching a grey iron standard sample with 0.01mol/L hydrochloric acid;
FIG. 5 is a Raman spectrum of graphene prepared by etching an alloy cast iron standard sample with 0.01mol/L sulfuric acid;
FIG. 6 is a transmission electron microscope image of graphene prepared by etching a cast alloy iron standard sample with 0.01mol/L sulfuric acid;
FIG. 7 is a Raman spectrum of graphene prepared by etching an alloy cast iron standard sample with 11.5mol/L sulfuric acid;
FIG. 8 is a Raman spectrum of graphene prepared by etching a grey iron standard sample with 16mol/L nitric acid;
FIG. 9 is a Raman spectrum of graphene prepared by etching a grey iron standard sample with 0.01mol/L nitric acid;
FIG. 10 is a Raman spectrum of graphene prepared by etching a grey iron standard sample with a mixed solution of hydrochloric acid, sulfuric acid and nitric acid;
FIG. 11 is a graph of graphene prepared by etching white cast iron containing 6.18% of carbon by using 12mol/L hydrochloric acid as a raw material;
FIG. 12 is a graph of graphene prepared by etching white cast iron containing 4.23% of carbon by using 12mol/L ferric trichloride and 3mol/L hydrochloric acid as raw materials;
FIG. 13 is a schematic illustration of a mixture of a carbon source and a metal;
FIG. 14 is a distribution diagram of carbon atoms in a molten state;
FIG. 15 is a schematic illustration of a carbon alloy;
fig. 16 is a schematic representation of graphene obtained by the method of the invention.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention in any way.
Example 1
A. Putting 2.85g of nickel powder and 0.15g of carbon nano tube into a mortar, uniformly mixing, putting the mixed powder into an electron beam evaporation table, heating by adopting an electron beam, observing the state of the mixture through a stripping window of the evaporation table, continuously increasing the intensity of the electron beam until the powder is completely melted into a liquid bead shape with fluidity, and naturally cooling to obtain the nickel-carbon alloy with the carbon mass fraction of 0.5%.
B. And etching the obtained nickel-carbon alloy by using etching liquid, wherein the etching liquid comprises hydrochloric acid with the concentration of 12mol/L and ferric trichloride with the concentration of 1mol/L, the etching temperature is 90 ℃, and the reaction time is 1 week. And centrifuging the floating substances in the solution, and repeatedly washing with deionized water to obtain the graphene.
Fig. 1 is a transmission electron micrograph of the graphene prepared in example 1, which shows that the graphene is multilayered and the number of layers is 5. Fig. 2 is a raman spectrum of the graphene prepared in example 1, and the appearance of a 2D peak in the graph proves that the product is graphene. Compared with the graphite oxide reduction method generally adopted at present, the graphene prepared by the method has fewer defects.
Example 2
The carbon alloy prepared by the existing process is used as a raw material to directly prepare the graphene. The carbon alloy used is cast iron standard sample gray iron (QD 2004-1E), and the components of the carbon alloy are C2.18%, S0.072%, Si 1.32%, Mn 0.671%, P0.092%, Cr0.074%, Ni 0.021%, Cu 0.053%, Ti 0.037% and V0.024%.
Corroding the grey iron by using 0.01mol/L hydrochloric acid, removing elements such as iron, sulfur and the like in the grey iron, collecting black substances formed after reaction at the reaction temperature of 90 ℃, and cleaning by using deionized water and alcohol to obtain the graphene containing a certain proportion of silicon impurities. Fig. 3 is a raman spectrum of the graphene prepared in example 2. Fig. 4 is a transmission electron micrograph of graphene prepared in example 2. It can be seen that the graphene is multilayered with 10 layers.
In the example, cheap grey iron is used as a raw material to prepare the graphene, so that the cost is greatly reduced. The preparation method is expected to partially replace the current graphene production process.
Example 3
An alloy cast iron standard sample (YSB C37022-09) is used as a raw material for preparing graphene, and the components of the alloy cast iron standard sample are C2.40%, S0.084%, Si 2.47%, Mn1.19%, P0.072%, Cr 0.94%, Ni 0.23%, Mo 0.11%, Cu 2.18%, Ti0.13%, Re 0.025% and V0.16%.
0.01mol/L sulfuric acid is used for corroding the alloy cast iron to remove elements such as iron, sulfur and the like in the alloy cast iron, and the reaction temperature is 90 ℃. And collecting black substances formed after the reaction, and cleaning the black substances by using deionized water and alcohol to obtain the graphene. Fig. 5 is a raman spectrum of the graphene prepared in this example, and the appearance of a 2D peak in the graph proves that the product is graphene. Fig. 6 is a transmission electron micrograph of the prepared graphene, which shows that the graphene is multi-layered, and the number of layers is 4.
Example 4
An alloy cast iron standard sample (2018-1C) is used as a raw material for preparing graphene, and the components of the alloy cast iron standard sample are C3% and S0.008%.
Corroding the alloy cast iron by using 11.5mol/L sulfuric acid to remove elements such as iron, sulfur and the like in the alloy cast iron, wherein the reaction temperature is 20 ℃; and collecting black substances formed after the reaction, and cleaning the black substances by using deionized water and alcohol to obtain the graphene. Fig. 7 is a raman spectrum of the graphene prepared in this example, and the appearance of a 2D peak in the graph proves that the product is graphene.
Example 5
Carbon alloy is used as a gray iron standard sample (QD 2004-1E) as a raw material for preparing graphene,
corroding the alloy cast iron by using 16mol/L nitric acid to remove elements such as iron, sulfur and the like in the alloy cast iron, wherein the reaction temperature is 20 ℃; and collecting black substances formed after the reaction, and cleaning the black substances by using deionized water and alcohol to obtain the graphene. Fig. 8 is a raman spectrum of the graphene prepared in this example, and the appearance of the 2D peak in the graph proves that the product is graphene.
Example 6
Carbon alloy is used as a gray iron standard sample (QD 2004-1E) as a raw material for preparing graphene.
Corroding the alloy cast iron by using 0.01 mol/nitric acid to remove elements such as iron, sulfur and the like in the alloy cast iron, wherein the reaction temperature is 85 ℃; and collecting black substances formed after the reaction, and cleaning the black substances by using deionized water and alcohol to obtain the graphene. Fig. 9 is a raman spectrum of the graphene prepared in this example, and the appearance of the 2D peak in the graph proves that the product is graphene.
Example 7
Carbon alloy is used as a gray iron standard sample (QD 2004-1E) as a raw material for preparing graphene.
The alloy cast iron is subjected to acid corrosion by using a mixed solution of nitric acid, sulfuric acid and hydrochloric acid in a mass ratio of 1:1:1, elements such as iron and sulfur in the alloy cast iron are removed, graphene is prepared, fig. 10 is a raman spectrum of the graphene prepared in the example 7, and a 2D peak in the graph shows that the product is graphene.
Example 8
The graphene prepared by adopting white cast iron with 6.18% of carbon content as a raw material is corroded by hydrochloric acid with the concentration of 12mol/L to remove elements such as iron, sulfur and the like in the alloy cast iron, and the reaction temperature is 60 ℃. And collecting black substances formed after the reaction, and cleaning the black substances by using deionized water and alcohol to obtain the graphene. Fig. 11 is a raman spectrum of graphene prepared in example, and the appearance of 2D peak in the graph proves that the product is graphene.
Example 9
The carbon alloy is used as cast iron (YSBC 37048B-12) and is used as a raw material for preparing graphene, and the carbon content of the graphene is 4.23%. The raw cast iron is corroded by using a mixed solution of hydrochloric acid with the concentration of 3mol/L and ferric trichloride with the concentration of 12mol/L, elements such as iron, sulfur and the like in the alloy cast iron are removed, and the reaction temperature is 85 ℃. And collecting black substances formed after the reaction, and cleaning the black substances by using deionized water and alcohol to obtain the graphene. Fig. 12 is a raman spectrum of graphene prepared in example, and the appearance of 2D peak in the graph proves that the product is graphene.
Example 10
The carbon alloy is used as cast iron (YSBC 37048B-12) and is used as a raw material for preparing graphene, and the carbon content of the graphene is 4.23%. The mixed solution of hydrochloric acid with the concentration of 1mol/L and ferric trichloride with the concentration of 1mol/L is used for corroding the raw cast iron to remove elements such as iron, sulfur and the like in the alloy cast iron, and the reaction temperature is 85 ℃. And collecting black substances formed after the reaction, and cleaning the black substances by using deionized water and alcohol to obtain the graphene.
Examples 2 to 8 show that graphene can be prepared when the mass fraction of ferric trichloride in the etching solution is zero. Excessive use of ferric chloride can cause waste, in example 10, when the concentration of the hydrochloric acid and the ferric chloride is 1mol/L, the corrosion effect is good, and the relative usage amount of the hydrochloric acid and the ferric chloride is small.
The traditional CVD method utilizes the supersaturation segregation phenomenon of carbon atoms on the surface of metal in the cooling process to form graphene on the surface of metal. Since graphene can only be formed on the surface of metal, the efficiency of preparing graphene by the conventional CVD method is low.
The method of the invention prepares graphene by a dealloying method, firstly mixes a carbon source and metal, the mixture is shown in fig. 13, and heats the mixture until the mixture is molten, at the moment, carbon atoms are uniformly distributed in the alloy, and as shown in fig. 14, a large amount of metal atoms isolate the carbon atoms (black dots in the figure). Cooling to obtain the carbon alloy, as shown in fig. 15. Finally, the metal in the alloy is removed by using an etching solution, and carbon atoms separated by the metal form a more stable graphite state, and finally form graphene, as shown in fig. 16. Compared with the traditional CVD method for preparing graphene, the method disclosed by the invention has the greatest difference that the graphene is prepared by utilizing carbon atoms in the alloy. The carbon atoms for forming the graphene are not limited on the metal surface by utilizing the dealloying method, so that the preparation efficiency of the graphene is greatly improved.
Claims (10)
1. A preparation method of graphene is characterized by comprising the following steps:
etching the carbon alloy by using etching liquid, and removing non-carbon elements in the carbon-containing alloy to obtain graphene; the etching liquid comprises one to three of hydrochloric acid, sulfuric acid or nitric acid.
2. The method for producing graphene according to claim 1, wherein: the synthesis of the carbon alloy is prepared by a smelting method, metal and a carbon source are uniformly mixed and heated until the mixture is completely melted to form uniform alloy liquid; and cooling to obtain the carbon alloy.
3. The method for producing graphene according to claim 1 or 2, characterized in that: the mass fraction of carbon in the carbon alloy is 0.5-6.18%.
4. The method for producing graphene according to claim 3, wherein: the mass fraction of carbon in the carbon alloy is 2.18-4.23%.
5. The method for producing graphene according to claim 4, wherein: the etching solution also comprises ferric trichloride with the concentration of not more than 12 mol/L.
6. The method for producing graphene according to claim 5, wherein: the etching solution is hydrochloric acid with the concentration of 0.01 mol/L-12 mol/L, and the temperature of the etching solution is 20 ℃ to 90 ℃.
7. The method for producing graphene according to claim 5, wherein: the etching solution is sulfuric acid with the concentration of 0.01-11.5 mol/L, and the temperature of the etching solution is 20-90 ℃.
8. The method for producing graphene according to claim 5, wherein: the etching solution is nitric acid with the concentration of 0.01-16 mol/L, and the temperature of the etching solution is 20-86 ℃.
9. The method for producing graphene according to claim 5, wherein: the etching solution is a mixed solution of nitric acid, sulfuric acid and hydrochloric acid with the mass ratio of 1:1: 1.
10. The method for producing graphene according to claim 4, wherein: the etching solution is hydrochloric acid with the concentration of 1 mol/L-12 mol/L and ferric trichloride with the concentration of 1 mol/L-12 mol/L.
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| CN202010702369.2A CN111825082A (en) | 2020-07-17 | 2020-07-17 | Preparation method of graphene |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134067A (en) * | 2011-04-18 | 2011-07-27 | 北京大学 | Method for preparing single-layer graphene |
| US20110206934A1 (en) * | 2010-02-22 | 2011-08-25 | International Business Machines Corporation | Graphene formation utilizing solid phase carbon sources |
| CN102583347A (en) * | 2012-02-17 | 2012-07-18 | 北京化工大学 | Method for preparing graphene by using interlaminar two-dimensional confinement space of inorganic laminar material |
| CN103265018A (en) * | 2013-05-21 | 2013-08-28 | 上海大学 | Method for directly preparing graphene on insulation base |
| CN105016329A (en) * | 2015-07-06 | 2015-11-04 | 兰州大学 | Preparation method for graphene |
| CN105399089A (en) * | 2015-12-15 | 2016-03-16 | 深圳市国创新能源研究院 | Graphene generation method, device and equipment based on arbitrary substrate |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110206934A1 (en) * | 2010-02-22 | 2011-08-25 | International Business Machines Corporation | Graphene formation utilizing solid phase carbon sources |
| CN102134067A (en) * | 2011-04-18 | 2011-07-27 | 北京大学 | Method for preparing single-layer graphene |
| CN102583347A (en) * | 2012-02-17 | 2012-07-18 | 北京化工大学 | Method for preparing graphene by using interlaminar two-dimensional confinement space of inorganic laminar material |
| CN103265018A (en) * | 2013-05-21 | 2013-08-28 | 上海大学 | Method for directly preparing graphene on insulation base |
| CN105016329A (en) * | 2015-07-06 | 2015-11-04 | 兰州大学 | Preparation method for graphene |
| CN105399089A (en) * | 2015-12-15 | 2016-03-16 | 深圳市国创新能源研究院 | Graphene generation method, device and equipment based on arbitrary substrate |
Non-Patent Citations (1)
| Title |
|---|
| SHAAHIN AMINI ET AL.: "Growth of graphene and graphite nanocrystals from a molten phase", 《JOURNAL OF MATERIALS SCIENCE》 * |
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