CN108232160B - Method for preparing porous metal-carbon composite - Google Patents

Method for preparing porous metal-carbon composite Download PDF

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CN108232160B
CN108232160B CN201810012614.XA CN201810012614A CN108232160B CN 108232160 B CN108232160 B CN 108232160B CN 201810012614 A CN201810012614 A CN 201810012614A CN 108232160 B CN108232160 B CN 108232160B
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ball milling
porous
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carbide
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CN108232160A (en
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金先波
袁亚庭
王志勇
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Wuhan University WHU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method of a porous metal-carbon composite material with high metal content and high dispersity. The compound MX of the target metal and the carbide of the active metal A are subjected to mechanical ball milling reaction, and the carbide of the A is a reducing agent and a carbon source. Thus, carbon is generated in situ when MX is reduced to a metal, thereby achieving highly dispersed complexing of the metal particles with the carbon material, and the content of the metal is determined by the stoichiometric ratio of the chemical reaction. In the porous composite material prepared by the invention, the size of the metal particles is adjustable, and the porosity is controllable. The prepared material shows good sodium and lithium storage performance.

Description

Method for preparing porous metal-carbon composite
Technical Field
The invention relates to a preparation method of a nano-porous metal-carbon composite, belonging to the technical field of material preparation.
Background
The metal-carbon composite material is widely applied to the fields of energy conversion, environmental monitoring, aerospace, catalysis, energy storage and the like. In the field of new energy, some metal materials can provide higher specific capacity, so that the energy density of lithium ion batteries and sodium ion batteries can be greatly improved. However, pure phase metallic materials have proven unsuitable for use in making electrodes due to the large volume change during charging and discharging. The study finds that the cycle stability of the composite material can be remarkably improved after the composite material is compounded with the carbon material. In addition, since the pore structure of the material can buffer the volume change, the porosity of the material also has a great influence on the cycle performance. The preparation of a highly dispersed metal-carbon composite with suitable porosity is key to ensure its cycling stability.
Some methods of making metal-carbon composites generally involve high temperature processing. However, some metals, such as tin antimony bismuth and the like, which are alloyed with lithium ions or sodium ions by a multi-electron reaction to provide a higher specific capacity, have a lower melting point. The high temperature treatment process can cause serious sintering growth of metal particles, and the electrochemical performance of the material is influenced. In addition, the existing method for preparing the metal-carbon composite material usually adopts a top-down mode, so that the size of metal particles is usually larger, the content of cyclic carbon for pursuing the material is usually higher, and the specific capacity of the material is reduced. For example, in the antimony-carbon composite materials reported in the literature, the size of the antimony particles is usually from tens to hundreds of nanometers, and the materials are often difficult to maintain the cycle life in a sodium ion battery and cannot meet the commercial requirements. Moreover, the preparation of these materials also often involves a multi-step process, increasing costs. Therefore, the invention of the preparation method of the composite material with high metal content and controllable metal particle size and porosity is the current technical problem.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel technology for preparing a porous metal-carbon composite material from bottom to top. The method has the advantages of low cost, simple operation, short process flow, cheap and easily-obtained raw materials, and suitability for expanded production. The metal-carbon composite material prepared by the method has high metal content; the particle size of the metal can be controlled from crystals of tens of nanometers to amorphous metal of sub-nanometer scale (less than 1 nanometer); the porosity of the material can be adjusted. The prepared material has good sodium and lithium storage performance.
The main technical idea of the invention is as follows: a compound MX (X ═ O, S, P, F, Cl, Br and I) of a certain metal and the carbide of an active metal A are subjected to solid phase reaction by mechanical ball milling, wherein the carbide of the A is a reducing agent and a carbon source. Thus, carbon is generated in situ when MX is reduced to metal, thereby realizing highly dispersed compounding of metal particles and carbon material. And removing the generated by-product compound AX of the active metal in the subsequent washing process to obtain the porous metal/carbon composite material. The ratio of metal to carbon in the metal-carbon composite material prepared by the method is determined by the stoichiometric ratio of the chemical reaction, so that the content of the metal is high. The porosity of the composite product can be controlled by adding excessive A carbide, and the metal particle size of the composite product can be influenced.
The technical scheme of the invention can be realized by the following technical measures:
a preparation method of a porous metal-carbon composite material comprises the following steps: putting a compound MX of a target metal M and carbide powder of an active metal A into a ball-milling tank according to a certain proportion, isolating air, carrying out ball-milling solid-phase reaction, taking out a product after the reaction is finished, and washing and drying the product to obtain a porous metal-carbon composite material; the obtained porous metal-carbon composite material can be sintered as required.
The target metal M is one or more of B, Ga, Al, Si, Ge, Sn, Sb, Bi, Te and transition metals of other subgroups except IIIB and IVB subgroups; x is one or more of O, S, P, F, Cl, Br and I; a is one or more of alkali metal or alkaline earth metal.
Preferably, the carbide of A is added in a desired excess with respect to the reduction of MX to M.
Preferably, the mass ratio of the milling beads to the reactants added in the ball-milling solid-phase reaction is not less than 3: 1.
Preferably, the ball milling tank is a stainless steel or hard alloy ball milling tank, and the ball milling mode is planetary ball milling or vibration ball milling.
Preferably, the ball milling speed used is not less than 300 revolutions per minute.
Preferably, the ball milling reaction is carried out under an inert gas blanket, such as high purity argon.
Preferably, the size of the metal particles in the prepared porous metal-carbon composite is in the sub-nanometer range.
Preferably, the ball milled reaction product is washed with water, an organic solvent (e.g., ethanol) or an acid (e.g., hydrochloric acid, acetic acid, etc.).
A porous metal-carbon composite material is prepared by the method.
The method is applied to the porosity of the porous metal-carbon composite material and the size adjustment of metal particles in the composite material, the porosity is adjusted by adjusting the addition amount of the carbide of the active metal A, and the size of the metal particles in a product is adjusted by adjusting the addition amount of the carbide of the active metal A or the degree of ball milling or the degree of subsequent sintering.
Compared with the prior art, the method has the advantages of low cost, simple operation, short process flow, cheap and easily obtained raw materials, and suitability for expanded production. The metal-carbon composite material prepared by the method has high metal content; the particle size of the metal can be controlled from crystals of tens of nanometers to amorphous metal of sub-nanometer level; the porosity of the material can be adjusted. The prepared material has good sodium and lithium storage performance.
Drawings
The invention is further illustrated by means of the attached drawings, the examples of which are not to be construed as limiting the invention in any way.
FIG. 1, XRD analysis of the Sb/C material prepared in example 2, shows that Sb is crystalline structure;
FIG. 2, Raman analysis of the Sb/C material prepared in example 2, shows that C is an amorphous structure;
FIG. 3, BET analysis of the Sb/C material of the material prepared in example 2, shows that it is a porous structure;
FIG. 4, TEM analysis of the Sb/C material of the material prepared in example 2, shows Sb particle size in the range of 20-30 nm;
FIG. 5, XRD analysis of the Sb/C material prepared in example 5, showing it is amorphous;
FIG. 6, BET analysis of the Sb/C material of the material prepared in example 5, shows that it is a porous structure;
FIG. 7, TEM analysis of the Sb/C material of the material prepared in example 5, shows that the Sb particle size is sub-nanometer;
FIG. 8 is an XPS analysis of the Sb/C material of the material prepared in example 5, showing that the material is an Sb-C composite;
FIG. 9, XRD analysis of Sn/C material of the material prepared in example 11, showing that Sn is in a crystalline structure;
figure 10, sodium storage performance of the material prepared in example 5, shows high capacity and high cycle stability.
Detailed Description
In order that the invention may be more readily understood, specific embodiments thereof will be described further below.
Example 1:
2g of Sb2O3Powder with 1.6g CaC2The powder was placed in a stainless steel ball mill jar filled with argon and then 30g of stainless steel balls were placed. The jar was mounted on a vibratory ball mill and subjected to vibratory ball milling at 1000 revolutions per minute for 8 hours. And then washing the product with dilute hydrochloric acid and purified water to obtain the porous Sb/C composite. The pore volume of the composite material is 0.12cm3The mass ratio content of the metal material Sb is about 74 percent, and the grain diameter of the obtained crystalline metal Sb is about 30-50 nm.
Example 2:
2g of Sb2O3Powder with 2g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and then 30g of stainless steel balls were placed. The jar was set in a vibratory ball mill at 1000 revolutions per minute for 10 hours. And then washing the product with dilute hydrochloric acid and purified water to obtain the porous Sb/C composite.
XRD, Raman, BET and TEM analyses were performed on the obtained porous Sb/C composite, and the results are shown in FIGS. 1 to 4, respectively. From the test results, the pore volume of the obtained composite material is 0.15cm3The mass ratio content of the metal material Sb is about 74 percent, and the grain diameter of the obtained crystalline metal Sb is about 20-30 nm.
Example 3:
2g of Sb2O3Powder and 4g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and then 30g of stainless steel balls were placed. The jar was set in a vibratory ball mill at 500 revolutions per minute for 10 hours. And then washing the product with dilute hydrochloric acid and purified water to obtain the porous Sb/C composite. The pore volume of the composite material is 0.25cm3The mass ratio content of the metal material Sb is about 74 percent, and the grain diameter of the obtained crystalline metal Sb is about 10-20 nm.
Example 4:
2g of Sb2O3Powder and 4g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and then 30g of stainless steel balls were placed. Fixing the ball milling pot on a vibration ball mill to perform vibration ball milling at the frequency of 800 revolutions per minute 10 hour. And then washing the product with dilute hydrochloric acid and purified water to obtain the porous Sb/C composite. The pore volume of the composite material is 0.25cm3The mass ratio content of the metal material Sb is about 74 percent, and the grain diameter of the obtained crystalline metal Sb is about 5-10 nm.
Example 5:
2g of Sb2O3Powder and 4g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and then 30g of stainless steel balls were placed. The jar was set in a vibratory ball mill at 1000 revolutions per minute for 10 hours. And then washing the product with dilute hydrochloric acid and purified water to obtain the porous Sb/C composite.
XRD, BET, TEM and XPS analyses were performed on the obtained porous Sb/C composite, and the results are shown in FIGS. 5 to 8, respectively. From the test results, the pore volume of the obtained composite material is 0.25cm3The mass ratio content of the metal material Sb is about 72 percent, and the particle size of the obtained amorphous metal Sb is less than 1 nm.
The obtained porous Sb/C composite is subjected to sodium storage performance test at a voltage of between 0.01 and 2V on the basis of 1M sodium perchlorate (the solvent is ethylene carbonate and diclohexyl carbonate in a volume ratio of 1: 1) and a metal sodium negative electrode, and the cycle curve and the coulombic efficiency under the condition of 1A/g multiplying power are shown in FIG. 10. Therefore, the circulation capacity is as high as 400mAh/g, the circulation Kunlun efficiency is basically 100%, and good circulation stability is shown.
Example 6:
2g of Sb2O3Powder with 2g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and then 30g of stainless steel balls were placed. The jar was mounted on a vibratory ball mill and subjected to vibratory ball milling at 1500 rpm for 10 hours. And then washing the product with dilute hydrochloric acid and purified water to obtain the porous Sb/C composite. The pore volume of the composite material is 0.15cm3The mass ratio content of the metal material Sb is about 74 percent, and the grain diameter of the obtained crystalline metal Sb is about 2-5 nm.
Example 7:
5g of CuCl2Powder with 2g of CaC2The powder was placed in a tungsten carbide ball mill jar filled with argon and then 50g of tungsten carbide balls were placed. Fixing the ball milling tank on a vibratorThe ball was milled on a dynamic ball mill with vibration at 1000 rpm for 3 hours. And then washing the product with purified water to obtain the porous Cu/C composite.
Example 8:
2g of Sb2O3Powder and 4g of CaC2The powder was placed in a tungsten carbide ball mill jar filled with argon and then 50g of tungsten carbide balls were placed. The jar was mounted on a planetary ball mill and ball milled for 15 hours at a frequency of 1000 revolutions per minute. And washing and drying the product by using dilute acetic acid and purified water to obtain the amorphous metal Sb with the particle size of less than 1nm in the composite material, and sintering the amorphous metal Sb for one hour at 300 ℃ to obtain the crystallized Sb/C composite material.
Example 9:
4g of SbCl3Powder with 1g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and 50g of stainless steel balls were placed. The jar was mounted on a vibratory ball mill and subjected to vibratory ball milling at 1000 revolutions per minute for 3 hours. And then washing the product with ethanol and purified water to obtain the porous Sb/C composite. The pore volume of the composite material is 0.2cm3The mass ratio content of the metal material Sb is about 74 percent, and the grain diameter of the obtained crystalline metal Sb is about 50-100 nm.
Example 10:
4g of SbCl3Powder with 2g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and 50g of stainless steel balls were placed. The jar was mounted on a vibratory ball mill and subjected to vibratory ball milling at 1000 revolutions per minute for 3 hours. And then washing the product with ethanol and purified water to obtain the porous Sb/C composite. The pore volume of the composite material is 0.4cm3The mass ratio content of the metal material Sb is about 74 percent, and the grain diameter of the obtained crystalline metal Sb is about 20-50 nm.
Example 11:
5g of SnCl2Powder with 1g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and 50g of stainless steel balls were placed. The jar was mounted on a vibratory ball mill and subjected to vibratory ball milling at 1000 revolutions per minute for 1 hour. And then washing the product with ethanol and purified water to obtain the porous Sn/C composite. XRD analysis of the resulting porous Sn/C compositeThe results are shown in FIG. 9.
Example 12:
3g of Bi2O3Powder with 3g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and 50g of stainless steel balls were placed. The jar was set in a vibratory ball mill at 1800 rpm for 7 hours. Then washing the product with dilute hydrochloric acid and purified water to obtain the porous Bi/C composite.
Example 13:
3g of PbO2Powder with 1.7g CaC2The powder was placed in a silicon nitride milling jar filled with argon and 40g of silicon nitride milling beads were added. The jar was set in a vibratory ball mill at 1200 rpm for 9 hours. The product was then washed with dilute hydrochloric acid and purified water to give a porous Pb/C complex.
Example 14:
mixing 3g of NiS powder with 4g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and 80g of stainless steel balls were placed. The jar was set in a vibratory ball mill at 1000 rpm for 4 hours. And then washing the product with dilute hydrochloric acid and purified water to obtain the porous Ni/C composite.
Example 15:
2g of SiP powder and 4g of CaC2The powder was placed in a stainless steel ball mill jar filled with argon and then 100g of stainless steel balls were placed. The jar was set in a vibratory ball mill at 1200 rpm for 8 hours. And then washing the product with dilute hydrochloric acid and purified water to obtain the porous Si/C composite.
Example 16:
4g of SnCl2Powder with 0.6g Li2C2The powder was placed in a stainless steel ball mill jar filled with argon and then 100g of stainless steel balls were placed. The jar was set in a vibratory ball mill at 1000 rpm for 5 hours. And then washing the product with ethanol and purified water to obtain the porous Sn/C composite.
Example 17:
1g of ZnBr2Powder and3g CaC2the powder was placed in a stainless steel ball mill jar filled with argon and then 100g of stainless steel balls were placed. The jar was set in a vibratory ball mill at 1000 rpm for 5 hours. And then washing the product with purified water to obtain the porous Zn/C composite.
Example 18:
5g of NiF2Powder with 2.5g CaC2The powder was placed in a stainless steel ball mill jar filled with argon and then 100g of stainless steel balls were placed. The jar was set in a vibratory ball mill at 1000 rpm for 5 hours. And then washing the product with purified water to obtain the porous Ni/C composite.
Example 19:
3g of FeCl3Powder with 1.5g Li2C2The powder was placed in a stainless steel ball mill jar filled with argon and then 100g of stainless steel balls were placed. The jar was set in a vibratory ball mill at 1000 rpm for 5 hours. And then washing the product with purified water to obtain the porous Fe/C composite.
Example 20:
2.5g SnCl2Powder, 5.6g AgCl powder and 2g CaC2The powder was placed in a stainless steel ball mill jar filled with argon and 50g of stainless steel balls were placed. The jar was mounted on a vibratory ball mill and subjected to vibratory ball milling at 1000 revolutions per minute for 1 hour. Then washing the product with ethanol and purified water to obtain the porous Ag3A Sn/C complex.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (9)

1. A method for preparing a porous metal-carbon composite, comprising the steps of: putting a compound MX of a target metal M and carbide powder of an active metal A into a ball milling tank, isolating air, carrying out ball milling solid phase reaction, taking out a product after the reaction is finished, and washing and drying the product to obtain a porous metal-carbon composite material;
the target metal M is one or more of B, Ga, Al, Si, Ge, Sn, Sb, Bi, Te and transition metals of other subgroups except IIIB and IVB subgroups; x is one or more of O, S, P, F, Cl, Br and I; a is one or more of alkali metal or alkaline earth metal.
2. The method of claim 1, wherein the carbide of a is added in a desired excess relative to the reduction of MX to M.
3. The method of claim 1, wherein the mass ratio of milling beads to reactants added in the ball milling solid phase reaction is not less than 3: 1.
4. The method according to claim 1, wherein the ball milling is planetary ball milling or vibratory ball milling.
5. The method according to claim 1, wherein the rotational speed of the ball mill used is not less than 300 revolutions per minute.
6. The method of claim 1, wherein the ball milling reaction is carried out under an inert gas blanket.
7. The method of claim 1, wherein the ball milled reaction product is washed with water, an organic solvent, or an acid.
8. A porous metal-carbon composite material prepared by the method of any one of claims 1 to 7.
9. Use of the method according to any one of claims 1 to 7 for porosity adjustment of porous metal-carbon composites and size adjustment of metal particles in the composites, wherein the porosity is adjusted by adjusting the amount of added carbide of active metal a and the size of the metal particles in the product is adjusted by adjusting the amount of added carbide of active metal a or the degree of ball milling or subsequent sintering.
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CN111313026B (en) * 2020-02-26 2022-07-05 扬州大学 Porous nitrogen-doped carbon/amorphous antimony compound, preparation method and application
CN112510177A (en) * 2020-11-25 2021-03-16 华南理工大学 Sn/C composite negative electrode material for lithium ion battery and preparation method thereof
CN113130873B (en) * 2021-05-20 2022-08-12 武汉科技大学 Porous bismuth-carbon material, preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219540A (en) * 2011-03-01 2011-10-19 山东科技大学 Porous Ti (C, N)-TiB2composite material and its prepn
CN103112854A (en) * 2013-01-31 2013-05-22 黑龙江大学 Method for synthesizing carbide/porous graphitized carbon nano compound through one-step method
CN104507861A (en) * 2012-07-27 2015-04-08 韩化石油化学株式会社 Porous carbon and method for manufacturing same
CN105439131A (en) * 2015-12-17 2016-03-30 成都新柯力化工科技有限公司 Method for preparing graphene with calcium carbide as raw material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219540A (en) * 2011-03-01 2011-10-19 山东科技大学 Porous Ti (C, N)-TiB2composite material and its prepn
CN104507861A (en) * 2012-07-27 2015-04-08 韩化石油化学株式会社 Porous carbon and method for manufacturing same
CN103112854A (en) * 2013-01-31 2013-05-22 黑龙江大学 Method for synthesizing carbide/porous graphitized carbon nano compound through one-step method
CN105439131A (en) * 2015-12-17 2016-03-30 成都新柯力化工科技有限公司 Method for preparing graphene with calcium carbide as raw material

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