CN110713187A - Preparation method of silicon material and application of silicon material in lithium ion battery cathode - Google Patents
Preparation method of silicon material and application of silicon material in lithium ion battery cathode Download PDFInfo
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- CN110713187A CN110713187A CN201910902698.9A CN201910902698A CN110713187A CN 110713187 A CN110713187 A CN 110713187A CN 201910902698 A CN201910902698 A CN 201910902698A CN 110713187 A CN110713187 A CN 110713187A
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
A preparation method of a silicon material and an application of the silicon material in a lithium ion battery cathode relate to the field of lithium ion battery materials. Firstly, silicon oxide is used as a raw material to carry out reduction reaction in a molten salt system at the temperature of 200-400 ℃ to obtain a pre-product. And then, treating the pre-product with hydrochloric acid and hydrofluoric acid to obtain the silicon material. According to the invention, the material is prepared into the lithium ion battery cathode material, the material has the first charge specific capacity of more than 2900mAh/g, the first discharge specific capacity of about 3500mAh/g, the first coulombic efficiency of more than 80%, the stable lithium storage specific capacity of about 130 cycles is still 1000-1500 mAh/g under the current density of 0.2A/g, and the lithium ion battery cathode material has higher discharge specific capacity and good cycle stability.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to preparation of a silicon material by a reduction method and application of the silicon material in a lithium ion battery cathode.
Background
With the progress of science and technology, people have higher and higher design requirements on small and convenient electronic products, and in addition, the requirements of high-power electronic products such as new energy electric cars and the like are increased, and silicon materials with high safety and large capacity gradually become the focus of scientific research workers in recent years. Although the silicon Material of the silicon-based negative electrode Material has a serious volume expansion effect (up to 400%) in the battery charging and discharging process, so that the silicon Material is gradually broken and the activity is reduced in the charging and discharging process, thereby causing serious capacity attenuation of the Lithium ion battery, the silicon-based negative electrode Material is the highest known theoretical specific capacity of 4200mAh/g at present, and the performance of the silicon-based negative electrode Material can be improved through modification, so that the silicon-based negative electrode Material is applied to the Lithium battery as a research hotspot at the present stage [ Kim H, Cho J.
At present, the application of the silicon material with low cost and simple process in the preparation of the lithium ion battery cathode material is more and more concerned. Niu J. et al formed Si @ SiOx @ graphene composites by electrostatic self-assembly and performed lithium battery performance tests, and exhibited better capacity and cycle performance [ Niu J, Zhang S, Niu Y, et al direct administration of Si nanoparticles for the preparation of Si @ ultra SiOx @ graphene nanosheeps high performance-on batteries [ J ]. Journal of materials chemistry A,2015,3(39): 19892-. The method is characterized in that natural halloysite clay is selected by the Wan H, the three-dimensional interconnected silicon material is prepared by utilizing molten salt reduction, the halloysite is used as a negative electrode of a lithium ion battery to show higher lithium storage capacity, but the halloysite is subjected to early-stage acid washing and high-temperature hydrothermal treatment and is not beneficial to environmental protection [ Wan H, Xiong H, Liu X, et al, three-dimensional interconnected Si frames of ceramic materials from natural halophysical layers: a high-capacity anode material for lithium-ion batteries [ J ]. Dalton transitions, 2018, 7522-materials 7527 ]. Yu K et al selects rice hulls as a silicon source to prepare a silicon material by magnesiothermic reduction, and the capacity of the silicon material is 537mAh/g after the silicon material is applied to a lithium battery and circulated for 200 circles under the power density of 0.1A/g. The method has the advantages that because the reduction condition is carried out at a higher temperature of 700 ℃, higher energy loss and byproducts are increased, so that the reduction cost is increased [ YuK, Zhang H, Gao X, et al.Rice husks as the Source of Silicon/Carbon inorganic material and Stable Electrochemical Performance [ J ]. Chemistry Select,2018,5439 and 5444 ]. At present, most of silicon materials prepared by a reduction method are silicon oxides reduced by magnesium metal, the preparation process is complex, the required temperature is higher and is usually 650 ℃ or above, and more byproducts are generated, so that the cost of the reduced silicon materials is high, and the realization of industrialization of silicon cathode materials in lithium ion batteries is not facilitated. The main chemical components of the diatomite raw material are siliceous rock formed by animal and plant remains and the like. At present, a large amount of high-quality diatomite ores are found in Jilin, Yunnan, Guangdong and the like, and the prospect reserve is far more than 20 hundred million tons. The diatomite has a large amount of ordered mesoporous pore channel structures, the size of the diatomite is generally dozens of microns, and the diatomite has the characteristics of strong adsorption capacity, small mass specific gravity, poor thermal conductivity, no toxicity, stable chemical property and the like, and is widely applied to the industries of environmental protection, heat preservation, light industry and the like. And for high-quality diatomite, a purification step can be omitted, so that the diatomite is low in price and environment-friendly, and the excellent commercial application prospect of the diatomite is further shown. The diatomite is reduced through magnesiothermic reduction, but complex processes such as diatomite alkali washing, calcining impurity removal, acid washing, magnesiothermic reduction and the like and high-energy consumption treatment are not beneficial to the commercial application of the diatomite for reduction into silicon materials. The invention plays a key role in reducing the cost of the diatomite reduction process by subtracting the diatomite purification process and adopting the improvement of processes such as low-temperature molten salt reduction and the like, and plays a positive role in the commercialization progress of reducing the diatomite into silicon materials and applying the silicon materials to lithium ion batteries.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a method for preparing a silicon material and its application in a negative electrode of a lithium ion battery, which comprises the following steps:
the method comprises the following steps: uniformly mixing a silicon oxide source, a reducing agent and molten salt, then loading the mixture into a high-pressure reaction kettle in an inert atmosphere environment, and reducing the mixture for a plurality of times at a certain temperature to obtain a primary product;
step two: and (3) taking the primary product obtained in the step one, sequentially carrying out acid cleaning for a period of time by using hydrochloric acid and hydrofluoric acid solutions, removing by-products and incompletely reacted reactants, and drying to obtain the silicon material.
Firstly, the silicon oxide source is selected from one or more of diatomite, quartz ore, high-silicon zeolite and silicon oxide compound;
the reduction temperature is 200-400 ℃, and the reduction time is 2-12 h;
the metal reducing agent is one of magnesium powder and aluminum powder;
further preferably, the reduction temperature of magnesium powder is 200-300 ℃, and the reduction temperature of aluminum powder is 250-400 ℃;
the molten salt is one of anhydrous aluminum trichloride and anhydrous zinc chloride;
the mass ratio of the metal reducing agent to the silicon oxide source is (1-6): 1.
the invention adopts different silicon sources to explore different reducing agents, molten salts, reducing temperatures and reducing time. Experiments show that the higher the relative content of silicon is, the better the performance of the reduced silicon material is; the research finds that the reduction temperature of the metal magnesium powder is lower than that of the metal aluminum powder, and the reduction temperature is supposed to be related to the activity of the metal magnesium compared with the metal aluminum; in the process of researching the reduction temperature and the reduction time, the purity of a reduction product is higher along with the increase of the reduction temperature, but when the temperature is too high, the energy consumption is increased, the reduction temperature is preferably 200-400 ℃, the extension of the reduction time plays an important role in the purity of a silicon material, and the reduction time is preferably 2-12 hours; the increase of the mass ratio of the metal oxide to the silicon oxide is beneficial to the improvement of the reduction yield, but when the metal reducing agent is too high, the cost is increased, and the invention preferably selects the mass ratio of the metal reducing agent to the silicon oxide source as (1-6): 1. the material obtained by the method has higher specific discharge capacity and good cycling stability, the first charge/discharge capacity of the silicon material obtained in the preferred scheme as lithium ion battery lithium storage is 2944.9/3562mAh/g, the first coulombic efficiency is 82.7%, and the stable specific lithium storage capacity of 130 cycles of cycling reaches 1503.6mAh/g under the current density of 0.2A/g.
Drawings
FIG. 1 is a scanning electron microscope image of samples obtained in example 4 by reducing metallic aluminum at 300 deg.C for 12h with anhydrous aluminum trichloride in different proportional sizes.
FIG. 2 is a cycle curve of a sample obtained by reducing metallic aluminum at 300 ℃ for 12 hours in example 4 with aluminum trichloride anhydrous at a current density of 0.2A/g.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Mixing diatomite, aluminum powder and anhydrous aluminum trichloride according to a mass ratio of 1: 1: 10, then putting the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 200 ℃, preserving the heat for 12 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material. The obtained silicon material is used for a lithium ion battery, the first charge/discharge capacity is 204.5mAh/g/348.8mAh/g, and 152mAh/g is obtained after 50 times of circulation under the current density of 0.2A/g.
Example 2
Mixing diatomite, aluminum powder and anhydrous aluminum trichloride according to a mass ratio of 1: 1: 10, then putting the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 300 ℃, preserving the heat for 12 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material. The obtained silicon material is used for the lithium ion battery, the first charge/discharge capacity is 1486.9mAh/g/1874.1mAh/g, and the cycle time is 50 times higher than 1400mAh/g under the current density of 0.2A/g.
Example 3
Mixing diatomite, aluminum powder and anhydrous aluminum trichloride according to a mass ratio of 1: 1: 10, then putting the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 400 ℃, preserving the heat for 12 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material. The obtained silicon material still has more than 1500mAh/g after being cycled for 50 times under the current density of 0.2A/g.
Example 4
Mixing diatomite, aluminum powder and anhydrous aluminum trichloride according to a mass ratio of 1: 2: 10, then putting the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 300 ℃, preserving the heat for 12 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material.
FIG. 1 shows a scanning electron microscope image, and the morphology of the product is spherical particles.
FIG. 2 shows that the reversible capacity is still higher than 1500mAh/g after 130 cycles at a current density of 0.2A/g.
Example 5
Mixing diatomite, aluminum powder and anhydrous aluminum trichloride according to a mass ratio of 1: 6: 10, then putting the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 300 ℃, preserving the heat for 12 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material. The obtained silicon material is used for a lithium ion battery, the first charge/discharge capacity is 1263.57mAh/g/1583.3mAh/g, and 1048mAh/g is obtained after 50 times of circulation under the current density of 0.2A/g.
Example 6
Mixing diatomite, aluminum powder and anhydrous aluminum trichloride according to a mass ratio of 1: 1: 10, then putting the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 300 ℃, preserving the heat for 2 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material. The obtained silicon material is used for a lithium ion battery, the first charge/discharge capacity is 934.8mAh/g/1228.1mAh/g, and 724mAh/g is obtained after 50 times of circulation under the current density of 0.2A/g.
Example 7
Mixing diatomite, magnesium powder and anhydrous aluminum trichloride according to a mass ratio of 1: 1: 10, then putting the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 200 ℃, preserving the heat for 12 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material. The obtained silicon material is used for the lithium ion battery, the first charge/discharge capacity is 689.3mAh/g/993.7mAh/g, and the first charge/discharge capacity is higher than 1000mAh/g after the silicon material is cycled for 50 times under the current density of 0.2A/g.
Example 8
Mixing diatomite, magnesium powder and anhydrous aluminum trichloride according to a mass ratio of 1: 1: 10, then placing the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 300 ℃, preserving the heat for 12 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material. The obtained silicon material is used for the lithium ion battery, the first charge/discharge capacity is 1186.4mAh/g/1509.7mAh/g, and the first charge/discharge capacity is higher than 1000mAh/g after the silicon material is cycled for 50 times under the current density of 0.2A/g.
Example 9
Mixing diatomite, aluminum powder and anhydrous zinc chloride according to a mass ratio of 1: 1: 10, then putting the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 300 ℃, preserving the heat for 12 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material. The obtained silicon material is used for the lithium ion battery, the first charge/discharge capacity is 1378.9mAh/g/1737.6.8mAh/g, and the first charge/discharge capacity is higher than 1200mAh/g after the silicon material is cycled for 50 times under the current density of 0.2A/g.
Example 10
Mixing quartz ore, aluminum powder and anhydrous aluminum trichloride according to a mass ratio of 1: 1: 10, then putting the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 300 ℃, preserving the heat for 2 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material.
Example 11
Mixing diatomite, magnesium powder and anhydrous aluminum trichloride according to a mass ratio of 1: 1: 10, then putting the mixture into a high-pressure reaction kettle in an inert atmosphere, heating to 300 ℃, preserving the heat for 12 hours, and sequentially carrying out acid cleaning by using hydrochloric acid and hydrofluoric acid to remove byproducts to obtain the silicon material.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A preparation method of a silicon material is characterized by comprising the following steps:
the method comprises the following steps: uniformly mixing a silicon oxide source, a reducing agent and molten salt, then loading the mixture into a high-pressure reaction kettle in an inert atmosphere environment, and reducing the mixture for a plurality of times at a certain temperature to obtain a primary product;
step two: and (3) taking the primary product obtained in the step one, sequentially carrying out acid cleaning for a period of time by using hydrochloric acid and hydrofluoric acid solutions, removing by-products and incompletely reacted reactants, and drying to obtain the silicon material.
2. A method for preparing a silica material according to claim 1 wherein in step one, the silica source used is selected from one or more of diatomaceous earth, quartz ore, high silica zeolite and silica compounds.
3. The method for preparing a silicon material according to claim 1, wherein the reducing agent used in the step one is one of metal magnesium and metal aluminum.
4. A method for preparing a silicon material according to claim 1, wherein the molten salt used in the first step is one of anhydrous aluminum trichloride and anhydrous zinc chloride.
5. The method for preparing the silicon material according to claim 1, wherein the reduction temperature in the first step is 200-400 ℃ and the reduction time is 2-12 h.
6. The preparation method of the silicon material according to claim 1, wherein the mass ratio of the metal reducing agent to the silicon oxide is (1-6): 1.
7. the method for preparing the silicon material according to claim 1, wherein the reduction temperature of magnesium powder is 200-300 ℃, and the reduction temperature of aluminum powder is 200-400 ℃.
8. Porous silica material prepared according to the process of any one of claims 1 to 7.
9. The porous silicon material prepared by the method of any one of claims 1 to 7 is applied to a lithium ion battery negative electrode material.
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Cited By (3)
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| WO2021217220A1 (en) * | 2020-04-30 | 2021-11-04 | KinAlTek Pty Ltd | Low temperature reduction of metal oxides |
| CN112864366B (en) * | 2021-03-05 | 2024-04-26 | 武汉科技大学 | Alpha-MoC1-xSi@C microsphere and preparation method and application thereof |
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