CN112725843B - Molten salt electrochemical preparation method of carbon-coated low-melting-point metal nano material - Google Patents
Molten salt electrochemical preparation method of carbon-coated low-melting-point metal nano material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a molten salt electrochemical preparation method of a carbon-coated low-melting-point metal nano material, which comprises the following steps of: the method comprises the steps of taking carbonate molten salt as electrolyte, taking low-melting-point metal as an electrode in an inert atmosphere containing carbon dioxide, applying oxidation current to the low-melting-point metal, then applying reduction current to the low-melting-point metal, and washing and drying the low-melting-point metal to obtain the powder of the carbon-coated low-melting-point metal sphere core. The method has simple steps and mild reaction conditions, and the morphology structure of the product can be adjusted by parameters such as reaction time, temperature, electrolytic current and the like. The carbon dioxide which is a greenhouse gas is used as a carbon coating raw material, and an organic matter is not needed to be used as a carbon source, so that the difficulty in controlling the process when the organic matter is violently pyrolyzed and the additional process required for preparing the organic matter in the conventional method can be avoided. The implementation of the method can realize the modification and value-added of the low-melting-point metal and can realize the emission reduction and value-added conversion of greenhouse gas carbon dioxide.
Description
Technical Field
The invention belongs to the technical field of material metallurgy, and particularly relates to a molten salt electrochemical preparation method of a carbon-coated low-melting-point metal nano material.
Background
Metals such as Sn, Bi, Sb, Pb, In, Ga, etc. have low melting points, so the nanostructures of these simple metals are physically unstable, and these metals have a high tendency to oxidize when exposed to air, particularly Sn, Bi, Pb, In, Ga. The carbon-coated low-melting-point metal powder material has the advantages of excellent electronic conductivity, high chemical stability, capability of preventing metal nanoparticles from agglomerating and the like, and is widely applied to the fields of electrocatalysis, batteries, capacitors and the like.
Currently, carbon-coated low-melting-point metal materials are generally prepared by an electrospinning method, a ball milling method, a hydrothermal-carbothermic method and the like. For example, Energy Storage mater, 18(2019) 229-; the patent CN 110400921A adopts a ball milling mode to prepare a carbon-coated metal material; the preparation of carbon-coated metal materials by hydrothermal method and carbonization of precursors is also widely used (Nano Lett.2020,20,4464-4471, J.electrochem.Soc., 152-7) A1452-A1457 (2005); CN 201810055854.8). In all the above methods, organic substances (such as sucrose, glucose, polyacrylonitrile, dimethylformamide, dopamine, etc.) are used as carbon sources, and certain compounds of low-melting point metals are used as metal sources, and the organic substances are prepared first, and then the target structure product is obtained through further carbonization reaction. The regulation and control difficulty is high, the operation steps are complex, and the carbonization temperature is high. .
Disclosure of Invention
The invention aims to provide a molten salt electrochemical preparation method of a carbon-coated low-melting-point metal nano material, which has the advantages of simple steps, mild reaction conditions and controllable product morphology and structure (such as adjustment through parameters of reaction time, temperature, electrolytic current and the like). In particular, the method adopts greenhouse gas carbon dioxide as a carbon coating raw material, does not need organic matters as a carbon source, and can avoid the difficulty in controlling the process when the organic matters are violently pyrolyzed and the additional process required by preparing the organic matters in the prior art. The implementation of the method can realize the modification and value-added of the low-melting-point metal and can realize the emission reduction and value-added conversion of greenhouse gas carbon dioxide.
In order to achieve the purpose, the technical scheme is as follows:
the molten salt electrochemical preparation method of the carbon-coated low-melting-point metal nano material comprises the following steps:
the method comprises the steps of taking carbonate molten salt as electrolyte, taking low-melting-point metal as an electrode in an inert atmosphere containing carbon dioxide, applying oxidation current to the low-melting-point metal, then applying reduction current to the low-melting-point metal, and washing and drying the low-melting-point metal to obtain the powder of the carbon-coated low-melting-point metal sphere core.
According to the scheme, the carbonate is Li2CO3、Na2CO3、K2CO3One or a mixture thereof.
According to the scheme, the inert atmosphere is argon, nitrogen or helium, wherein the volume fraction of carbon dioxide is 0.001-99.99%.
According to the scheme, the electrochemical preparation of the molten salt adopts two electrodes, wherein one electrode is the low-melting-point metal, and the other electrode is graphite, metal, alloy or SnO2Perovskite ceramics, platinum or gold.
According to the scheme, the low-melting-point metal is one or more of Sn, Bi, Sb, Pb, In and Ga.
According to the scheme, the oxidation current is 0.001-5A cm-2。
According to the scheme, the reduction current is 0.001-5A cm-2。
According to the scheme, the time for oxidation or reduction is 1 s-12 h.
According to the scheme, the process of oxidation and reduction is circulated for 1-100 times.
According to the scheme, the method further comprises the following pretreatment steps:
uniformly mixing the carbonates, putting the mixture into a crucible, heating the mixture to 100-300 ℃, and keeping the temperature for 12-48 h to remove water;
then at 5-10 ℃ for min-1Heating to 450-800 ℃ and then carrying out electrolysis.
According to the scheme, the washing process is respectively washed for three times by deionized water and ethanol.
Compared with the prior art, the invention has the beneficial effects that:
the method takes low-melting-point metal (Sn, Bi, Sb, Pb, In and Ga) as an electrode, and carries out electrolysis In a carbonate molten salt In a mode of oxidation and reduction to obtain a carbon-coated low-melting-point metal nano material on the surface of the low-melting-point metal electrode; the formation of a product coating structure and the relative content of metal and carbon are effectively controlled by controlling the reaction time, the temperature and the electrolytic current.
According to the invention, carbon dioxide is used as a carbon source by adopting a molten salt electrolysis method, and is directionally converted into the core-shell structure material of the carbon-coated low-melting-point metal on the liquid metal electrode, so that the modification and value-added of the low-melting-point metal can be realized, and the emission reduction and value-added conversion of greenhouse gas carbon dioxide can be realized.
Drawings
FIG. 1: XRD pattern of carbon-coated Sn nanomaterial obtained in example 1;
FIG. 2: electron micrograph of carbon-coated Sn nanomaterial obtained in example 1.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1:
electrochemical treatment with graphite and low melting point Sn as electrodes, Li2CO3The molten salt is an electrolyte. Firstly at 5 ℃ for min-1Heating to 250 deg.C and maintaining for 24 hr to make Li2CO3The water in the molten salt is completely volatilized. Then at 5 deg.C for min-1Heating to 800 deg.C, introducing argon gas containing carbon dioxide 0.001 vt% as protective atmosphere, maintaining the temperature at 800 deg.C when molten salt is completely melted, and applying 1000mA cm to liquid Sn electrode-2Oxidizing for 1800s, and applying 1000mA cm-2And (4) reducing for 4800 s. And after the electrolysis is finished, taking out the Sn electrode, and respectively washing the Sn electrode for three times by using deionized water and absolute ethyl alcohol to obtain the carbon-coated Sn nano material with the spherical structure.
The XRD of the carbon-coated Sn nano material obtained in the embodiment is shown in figure 1, and the XRD pattern shows that the components in the nano material collected by the cathode are carbon and Sn; an electron microscope (TEM) of the carbon-coated Sn nanomaterial obtained in this example is shown in fig. 2, and the TEM indicates that the morphology of the obtained cathode product is characterized by Sn @ C spheres with a core-shell structure in which metal Sn is used as a core and carbon is used as a shell.
Example 2:
electrochemical treatment with graphite and low melting point Sn as electrodes, Li2CO3-Na2CO3-K2CO3The molten salt is an electrolyte. Firstly at 5 ℃ for min-1Heating to 250 deg.C and maintaining for 24 hr to make Li2CO3-Na2CO3-K2CO3The water in the molten salt is completely removedAnd (4) completely volatilizing. Then at 5 deg.C for min-1Heating to 500 deg.C, introducing argon gas as protective atmosphere, heating to 700 deg.C when molten salt is completely melted, introducing carbon dioxide gas (high purity carbon dioxide gas), and applying 2Acm to liquid Sn electrode-2Oxidizing for 3000s, and applying 5Acm-2Reducing for 3000s, and circulating 100 times in this way. And after the electrolysis is finished, taking out the Sn electrode, and respectively washing the Sn electrode for three times by using deionized water and absolute ethyl alcohol to obtain the carbon-coated tin nano material with the spherical structure.
Example 3:
using graphite and low-melting point bismuth as electrodes, Li2CO3-Na2CO3The molten salt is an electrolyte. Firstly at 5 ℃ for min-1Heating to 300 deg.C and maintaining for 24 hr to make Li2CO3-Na2CO3The water in the molten salt is completely volatilized. Then at 5 deg.C for min-1Heating to 800 ℃, introducing nitrogen containing 90 vol% of carbon dioxide as protective atmosphere, and applying oxidation current of 200mAcm to the liquid bismuth when the molten salt is completely melted-2Oxidizing for 1h, and applying reducing current of 500mAcm-2The reduction time is 2h, and the circulation is carried out for 2 times. And after the electrolysis is finished, taking out the cathode, and respectively washing the cathode for three times by using deionized water and absolute ethyl alcohol to obtain the carbon-coated bismuth nano material.
Example 4:
in SnO2And low melting point indium as an electrode, Li2CO3-Na2CO3-K2CO3The molten salt is an electrolyte. Firstly at 5 ℃ for min-1Heating to 300 deg.C and maintaining for 24 hr to make Li2CO3-Na2CO3-K2CO3The water in the molten salt is completely volatilized. Then at 5 ℃ for min-1Heating to 450 ℃, introducing helium containing 1 vol% of carbon dioxide as protective atmosphere, and applying oxidation current of 1mAcm to liquid indium when molten salt is completely melted-2Oxidizing for 100s, and applying reduction current of 10mAcm-2Reducing for 300s, and circulating 30 times. And after the electrolysis is finished, taking out the cathode, and respectively washing the cathode for three times by using deionized water and absolute ethyl alcohol to obtain the carbon-coated indium nano material.
Example 5:
graphite and low-melting-point lead are used as electrodes, Li2CO3-Na2CO3Molten salt as electrolyte, and heating at 5 deg.C for min-1Heating to 300 deg.C and holding for 24 hr to make Li2CO3-Na2CO3The water in the molten salt is completely volatilized. Then at 5 deg.C for min-1Heating to 800 ℃, introducing nitrogen containing 90 vol% of carbon dioxide as protective atmosphere, and applying oxidation current of 2A cm to the liquid lead when the molten salt is completely melted-2The oxidation time is 1000s, and then a reduction current of 2Acm is applied-2The reduction time is 3000s, and the circulation is carried out for 4 times. And after the electrolysis is finished, taking out the cathode, and respectively washing the cathode for three times by using deionized water and absolute ethyl alcohol to obtain the carbon-coated lead nano material.
Claims (6)
1. The molten salt electrochemical preparation method of the carbon-coated low-melting-point metal nano material is characterized by comprising the following steps of:
taking carbonate molten salt as electrolyte, taking low-melting-point metal as an electrode in an inert atmosphere containing carbon dioxide, firstly applying oxidation current, then applying reduction current, and washing and drying to obtain powder of carbon-coated low-melting-point metal spherical cores;
the carbonate is Li2CO3、Na2CO3、K2CO3One or a mixture of the above;
the low-melting-point metal is one or more of Sn, Bi, Sb, Pb, In and Ga;
the electrochemical preparation of the molten salt adopts two electrodes, wherein one electrode is the low-melting-point metal, and the other electrode is graphite or SnO2Perovskite ceramics, platinum or gold;
the oxidation current is 0.001-5A cm-2(ii) a The reduction current is 0.001-5A cm-2。
2. A molten salt electrochemical method for preparing carbon-coated low-melting point metal nanomaterials according to claim 1, wherein the inert atmosphere is argon, nitrogen or helium, and the volume fraction of carbon dioxide is 0.001-99.99%.
3. A molten salt electrochemical method for preparing carbon-coated low-melting-point metal nano-materials as claimed in claim 1, characterized in that the time for oxidation or reduction is 1 s-12 h.
4. The molten salt electrochemical preparation method of the carbon-coated low-melting-point metal nanomaterial as claimed in claim 1, wherein the oxidation-reduction process is cycled for 1-100 times.
5. A molten salt electrochemical preparation method of a carbon-coated low melting point metal nanomaterial as claimed in claim 1, further comprising a pretreatment step of:
uniformly mixing the carbonates, putting the mixture into a crucible, heating the mixture to 100-300 ℃, and keeping the temperature for 12-48 h to remove water; then at 5-10 ℃ for min-1Heating to 450-800 ℃ and then carrying out electrolysis.
6. A molten salt electrochemical method for preparing carbon-coated low melting point metal nanomaterial as claimed in claim 1, wherein the washing process is performed three times with deionized water and ethanol respectively.
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| JP2012132033A (en) * | 2010-12-17 | 2012-07-12 | Tosoh Corp | Melted salt electrolytic cell and refining method of low melting point metal |
| CN110359068A (en) * | 2019-08-07 | 2019-10-22 | 武汉大学 | A method of carbon nanotube metal material for coating is prepared based on melten salt electriochemistry method |
| CN110400921A (en) * | 2019-07-17 | 2019-11-01 | 湖北锂诺新能源科技有限公司 | A kind of preparation method of carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material |
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