CN110867567A - High-safety SiO synthesized by biomass siliconxPreparation method and application of @ C material - Google Patents
High-safety SiO synthesized by biomass siliconxPreparation method and application of @ C material Download PDFInfo
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- CN110867567A CN110867567A CN201911019978.1A CN201911019978A CN110867567A CN 110867567 A CN110867567 A CN 110867567A CN 201911019978 A CN201911019978 A CN 201911019978A CN 110867567 A CN110867567 A CN 110867567A
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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
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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
- 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
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/58—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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides high-safety SiO synthesized by biomass siliconxA preparation method of a @ C material comprises the following steps: acid washing rice hull ash, taking a proper amount of the rice hull ash to carbonize in an inert atmosphere, mixing and ball-milling the carbonized product with metal powder and molten salt uniformly, placing the mixture in a furnace, introducing inert gas, reacting at a high temperature, and acid washing to clean the byproduct to obtain a product of SiOx@ C material. The method has the advantages of simple and easy process, abundant and cheap raw materials, higher safety compared with magnesium thermal reduction, and capability of obtaining SiOxThe @ C particles have a porous structure, are uniform in carbon coating and good in rate capability, and can be applied to the field of lithium battery cathode materials.
Description
Technical Field
The invention belongs to the technical field of new energy material preparation, and particularly relates to high-safety SiO (silicon dioxide) synthesized by biomass siliconxA preparation method of the @ C material.
Background
The method improves the specific energy of the power battery, and is the most effective way for solving the mileage anxiety of the electric automobile at the present stage. The authoritative data show that the lithium ion power battery is required to reach the development target of 300 W.h/kg in 2020, and the only feasible technical route is as follows: the high-nickel ternary positive electrode material NCM 811, NCA or lithium-rich manganese base is matched with the silicon-based negative electrode material.
Research shows that the specific energy of the lithium ion battery can be improved by 15% when the specific capacity of the negative electrode material is increased by 500 mA.h/g. The theoretical specific capacity of the silicon-based negative electrode material can reach 4200 mA.h/g to the maximum extent, is 10 times of the capacity of the traditional graphite negative electrode, has the advantages of rich reserves, low cost, environmental friendliness and the like, and is the first choice of the negative electrode material of the high-specific-energy lithium ion battery. Silicon-based materials that can be used as the negative electrode include: elemental silicon (Si) and silicon monoxide (SiO)x) Silicon dioxide (SiO)2) Silicon carbide (SiC), etc., wherein the introduction of oxygen can significantly improve the stability of the silicon-based material during lithium ion deintercalation.
Conventional SiOxThe material of @ C is prepared by mixing simple substance silicon and silicon dioxide at high temperature above 1300 deg.C, neutralizing under vacuum condition, and rapidly cooling and crystallizing to obtain SiOxThen SiOxAnd (5) performing carbon coating. As described in the patent CN 201810059105.2, the method has harsh synthesis conditions and high requirements on equipment, and is difficult to realize large-scale industrial production. In addition, the method for obtaining the elemental silicon by biomass magnesiothermic reduction is also widely applied, for example, as described in patent CN 201811476229.7, but since magnesium powder is a flammable and explosive controlled drug, only a small amount of experiments can be performed, and large-scale production is not suitable. The invention mainly aims to adopt safer aluminum powder, copper powder, iron powder and the like to carry out metallothermic reduction reaction, change the molar ratio of biomass silicon to metal and change the synthesis conditions to change SiOxThe value of x in @ C (0 < x < 2) gives SiO having more excellent propertiesx@ C material. The whole preparation process is carried out in an inert atmosphere, so that the biomass carbon is kept, the biomass body structure is maintained, and the conductivity, the cycle performance and the rate performance of the material are improved from the inside of the material structure.
Disclosure of Invention
The invention aims to provide a high-safety SiO synthesized by biomass siliconxMethod for preparing @ C material for improving SiOxRate capability and circulation stability of @ C material. The biomass carbon is reserved to achieve the purpose of improving SiOxThe purpose of the conductivity and cycling stability of the @ C material.
In order to achieve the above purpose, the solution of the invention is:
1) mixing a biomass silicon source, pickling and drying, placing in a furnace, introducing protective gas, and reacting for a certain time at a certain temperature to obtain a product A;
2) mixing the product A and metal powder according to a certain proportion, adding a certain amount of molten salt, uniformly ball-milling, placing in a furnace, introducing protective gas, reacting for a certain time at a certain temperature, pickling and drying to obtain a product B, wherein the product B is SiOx@ C material.
The biomass silicon source is one or more than two of coconut shell, rice hull, bamboo leaf and straw.
The acid used for acid cleaning is one or more than two of hydrofluoric acid, hydrochloric acid, phosphoric acid and sulfuric acid, and the concentration is 0.1-10 mol/L.
In the step 1) sintering process, the sintering temperature is 400-700 ℃, and the sintering time is 2-12 hours.
The metal powder is one or more than two of aluminum powder, copper powder, magnesium powder and iron powder, and the molar ratio of silicon to the metal powder in the biomass silicon source is 0.5-1.
The molten salt is halogen salt and comprises one or more than two of sodium chloride, potassium chloride, zinc chloride, calcium chloride and sodium bromide, and the mass ratio of the molten salt to the biomass silicon source is 0.5-5.
The rotating speed of the ball milling process in the step 2) is 100-800 rpm, and the time is 0.5-8 hours.
In the sintering process, one or more than two of inert gases of nitrogen, argon and hydrogen-argon mixed gas are adopted.
In the step 2), the sintering temperature is 600-1000 ℃, and the sintering time is 2-12 hours.
The invention has the advantages that: aiming at the danger of the magnesiothermic reduction method, the invention adopts safer aluminum powder, copper powder, iron powder and the like to carry out metallothermic reduction reaction, so that the reaction can be produced in a larger scale. Because the introduction of oxygen can obviously improve the stability of the silicon-based material in the lithium ion deintercalation process, the invention synthesizes SiO by changing the molar ratio of biomass to metalxInstead of elemental silicon, increaseThe stability of the strong silicon-based material in the charging and discharging process of the battery. According to the invention, molten salt melting is adopted to absorb heat to control the reaction temperature, so that the structure that the original biomass silicon is naturally embedded in organic matters is reserved, and the stability and rate capability of the material are enhanced.
SiO Using the inventionxThe @ C material has excellent stability, can improve the conductivity of the silicon dioxide material, improves the rate capability, and is beneficial to the industrialization process of the power battery. The invention can control SiOxThe oxygen content of the material @ C, and the method is simple and controllable, and is suitable for industrial production.
Drawings
FIG. 1 shows SiO with and without molten salt, which is provided in comparative example 1, which is example 1 of the present inventionxThe X-ray diffraction contrast spectrum of the @ C-800 material.
FIG. 2 shows a synthetic SiO solid provided in example 1 of the present inventionxThe lithium battery cycle performance diagram of the material of @ C-800.
Detailed Description
Example 1
Pickling rice hull ash, carbonizing 5g at 600 ℃ for 1 h under nitrogen, mixing the carbonized product with 0.2g of aluminum powder and 3g of potassium chloride, ball-milling uniformly, placing in a furnace, introducing nitrogen, keeping the temperature at 800 ℃ for 5 h, pickling and cleaning by-product Al2O3To obtain the product of SiOxThe material @ C; the XRD of the product is shown in figure 1, and the electrochemical performance of the lithium battery is shown in figure 2.
Example 2
Pickling rice hull ash, taking 5g of rice hull ash, carbonizing for 1 h under nitrogen, mixing and ball-milling the carbonized product, 0.3g of copper powder and 3g of potassium chloride uniformly, placing the mixture in a furnace, introducing nitrogen, keeping the temperature at 900 ℃ for 4 h, pickling and cleaning a by-product CuO to obtain a product which is SiOx@ C material.
Comparative example
Pickling rice hull ash, carbonizing 5g at 500 deg.C under nitrogen for 2 h, mixing the carbonized product with 0.2g aluminum powder, ball milling, placing in a furnace, introducing nitrogen, maintaining at 800 deg.C for 5 h, pickling to clean byproduct Al2O3To obtain the product of SiOxThe material @ C; the product XRD is shown in figure 1.
Claims (11)
1. Lithium ion battery cathode SiOxThe @ C material is characterized in that: the SiOxThe material @ C being a SiOx(x is more than 0 and less than 2) and carbon.
2. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: the method comprises the following steps:
1) mixing a biomass silicon source, pickling and drying, placing in a furnace, introducing protective gas, and reacting for a certain time at a certain temperature to obtain a product A;
2) mixing the product A and metal powder according to a certain proportion, adding a certain amount of molten salt, uniformly ball-milling, placing in a furnace, introducing protective gas, reacting for a certain time at a certain temperature, pickling and drying to obtain a product B, wherein the product B is SiOx@ C material.
3. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: the biomass silicon source is one or more than two of coconut shell, rice hull, bamboo leaf and straw.
4. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: the acid used for acid cleaning is one or more than two of hydrofluoric acid, hydrochloric acid, phosphoric acid and sulfuric acid, and the concentration is 0.1-10 mol/L.
5. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: in the step 1) sintering process, the sintering temperature is 400-700 ℃, and the sintering time is 2-12 hours.
6. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: the metal powder is one or more than two of aluminum powder, copper powder, magnesium powder and iron powder.
7. The method of preparing a silundum carbon composite material of claim 1, wherein: the molar ratio of silicon to metal powder in the biomass silicon source is 0.5-1.
8. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: the molten salt is halogen salt and comprises one or more than two of sodium chloride, potassium chloride, zinc chloride, calcium chloride and sodium bromide, and the mass ratio of the molten salt to the biomass silicon source is 0.5-5.
9. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: the rotating speed of the ball milling process in the step 2) is 100-800 rpm, and the time is 0.5-8 hours.
10. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: in the sintering process, one or more than two of inert gases of nitrogen, argon and hydrogen-argon mixed gas are adopted.
11. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: in the step 2), the sintering temperature is 600-1000 ℃, and the sintering time is 2-12 hours.
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| CN201911019978.1A CN110867567B (en) | 2019-10-25 | 2019-10-25 | High-safety SiO (silicon dioxide) synthesized by using biomass silicon x Preparation method and application of @ C material |
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| CN201911019978.1A CN110867567B (en) | 2019-10-25 | 2019-10-25 | High-safety SiO (silicon dioxide) synthesized by using biomass silicon x Preparation method and application of @ C material |
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| CN110867567B CN110867567B (en) | 2022-10-18 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112259737A (en) * | 2020-10-27 | 2021-01-22 | 成都新柯力化工科技有限公司 | Preparation method of mesoporous spherical silicon oxide negative electrode material of lithium battery |
| CN112397701A (en) * | 2020-11-20 | 2021-02-23 | 江苏科技大学 | Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof |
| CN112467125A (en) * | 2020-12-29 | 2021-03-09 | 山东硅纳新材料科技有限公司 | Method for preparing novel silicon-carbon negative electrode material by using rice hull ash |
| CN113178564A (en) * | 2021-04-25 | 2021-07-27 | 陈庆 | Silicon dioxide-carbon composite material and preparation method and application thereof |
| CN114566639A (en) * | 2022-01-17 | 2022-05-31 | 苏州科技大学 | SiO (silicon dioxide)x/C composite material and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112259737A (en) * | 2020-10-27 | 2021-01-22 | 成都新柯力化工科技有限公司 | Preparation method of mesoporous spherical silicon oxide negative electrode material of lithium battery |
| CN112397701A (en) * | 2020-11-20 | 2021-02-23 | 江苏科技大学 | Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof |
| CN112467125A (en) * | 2020-12-29 | 2021-03-09 | 山东硅纳新材料科技有限公司 | Method for preparing novel silicon-carbon negative electrode material by using rice hull ash |
| CN113178564A (en) * | 2021-04-25 | 2021-07-27 | 陈庆 | Silicon dioxide-carbon composite material and preparation method and application thereof |
| CN114566639A (en) * | 2022-01-17 | 2022-05-31 | 苏州科技大学 | SiO (silicon dioxide)x/C composite material and preparation method and application thereof |
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