CN111115639A - Preparation of SiO by centering reactionxMethod and application of @ C material - Google Patents

Preparation of SiO by centering reactionxMethod and application of @ C material Download PDF

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Publication number
CN111115639A
CN111115639A CN201911354202.5A CN201911354202A CN111115639A CN 111115639 A CN111115639 A CN 111115639A CN 201911354202 A CN201911354202 A CN 201911354202A CN 111115639 A CN111115639 A CN 111115639A
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sio
preparation
silicon
steps
following
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胡培
徐杉
史德友
刘世琦
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HUBEI WANRUN NEW ENERGY TECHNOLOGY DEVELOPMENT CO LTD
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HUBEI WANRUN NEW ENERGY TECHNOLOGY DEVELOPMENT CO LTD
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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
    • C01B33/113—Silicon oxides; Hydrates thereof
    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention provides a method for preparing SiO by using a centering reactionxThe method adopts silicon dioxide and silicon powder to carry out a centering reaction, and the reaction temperature is adjusted to obtain a product SiO under the help of high-temperature protective gasxThe material is coated with carbon by a spray drying method to obtain high-performance SiOx@ C material. The process of the invention does not adopt a flammable and explosive magnesiothermic reduction method, directly adopts the cheap crude silicon and the low-purity silicon dioxide powder on the market to generate the neutralization reaction, the raw materials are cheap and easy to obtain, and the high-quality SiO is obtainedx@ C material. The inventionThe obtained SiOxThe @ C material 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

Preparation of SiO by centering reactionxMethod and application of @ C material
Technical Field
The invention belongs to the technical field of new energy material preparation, and particularly relates to a method for preparing SiO by using a centering reactionxA method and application of the material @ C.
Background
The silicon monoxide (SiO) is a new-generation cathode material, has the characteristics of high capacity, low expansion, long service life and the like, and can effectively promote consumer electronics and electric automobilesThe cruising ability of the vehicle. The theoretical specific capacity of the nano silicon powder is 4200 mAh/g, the theoretical specific capacity of the silicon oxide is 2000 mAh/g, but the process for synthesizing the purer silicon oxide is difficult, a high-temperature vacuum vapor deposition method is generally adopted, the equipment requirement is high, the production cost is high, carbon coating is required to be carried out in the later period, and the working procedure is complex. Therefore, the invention adopts the centering reaction to prepare SiOxThe @ C material and the silicon-based material greatly reduce the expansion coefficient of the material due to the addition of oxygen element, and the cycle life of the material is prolonged. Therefore, the SiO with controllable oxygen content is synthesized by adopting a lower-cost methodxThe @ C material has been the target of researchers.
The conventional SiO @ C material is prepared by mixing simple substance silicon and silicon dioxide at a high temperature of more than 1300 ℃, performing neutralization reaction under a vacuum condition, performing rapid cooling crystallization to obtain SiO, and then performing carbon coating on the SiO. As described in patent CN 201810059105.2, the method has harsh synthesis conditions and high requirements on equipment, and is difficult to realize large-scale industrial production. The invention mainly aims to synthesize SiO by adopting low-cost raw materials without passing through the harsh conditions of high temperature and vacuumxCarbon coating the mixture to obtain SiOx@ C. The invention reduces the production cost from the industrial aspect, ensures the excellent performance of the material under the condition of ensuring the high specific capacity requirement of the cathode material, and improves the conductivity, the cycle performance and the rate capability of the material by regulating and controlling the process parameters.
Disclosure of Invention
The invention aims to provide a method for preparing SiO by using a centering reactionxMethod and application of @ 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 the crude silicon and silicon dioxide by sanding, placing the mixture in a furnace, introducing inert protective gas, and reacting for a certain time at a certain temperature to obtain silicon monoxide;
2) mixing the obtained silica with glucose solution, and spray drying to obtain the final productPutting the powder into a furnace, introducing inert protective gas, and reacting for a certain time at a certain temperature to obtain SiOxThe product of @ C.
The crude silicon is carbon-containing silicon powder obtained after the carbothermic reaction of industrial silicon dioxide.
The silicon dioxide is industrial silicon dioxide.
The sand grinding rotation speed in the step 1) is 400-600 revolutions per minute, and the sand grinding time is 2-4 hours.
The inert gas is one or more than two of nitrogen, argon and hydrogen-argon mixed gas.
In the step 1) sintering process, the sintering temperature is 700-1100 ℃, and the sintering time is 2-12 hours.
The molar ratio of carbon element to silicon oxide in the glucose is 1: 1-3: 1.
In the step 2), the sintering temperature is 400-700 ℃, and the sintering time is 1-5 hours.
The invention has the advantages that: the invention adopts the raw materials with low price, obtains products with excellent performance by the process with lower cost than the traditional process, adopts the spray drying for carbon coating, can remold the microscopic morphology of the material, can accurately master the carbon content of the carbon coating, and enhances the stability and the rate capability of the material.
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.
Drawings
FIG. 1 shows SiO synthesized in examples 1, 2 and 3 of the present inventionxThe X-ray diffraction contrast spectrum of the @ C material.
FIG. 2 is SiO that is provided in example 1 of the present inventionxThe charging and discharging performance diagram of the lithium battery of the @ C material.
Detailed Description
Example 1
Mixing the crude silicon and silicon dioxide by sanding, placing the mixture in a furnace, introducing nitrogen, and reacting for 6 hours at 1100 ℃ to obtain silicon monoxide; dissolving the obtained silica with glucoseMixing the solutions, wherein the molar ratio of carbon to silicon oxide in glucose is 1:1, spray drying to obtain powder, placing in a furnace, introducing nitrogen, reacting at 400 deg.C for 3 hr to obtain SiOxThe product of @ C.
Example 2
Mixing the crude silicon and silicon dioxide by sanding, placing the mixture in a furnace, introducing nitrogen, and reacting for 10 hours at 1000 ℃ to obtain silicon monoxide; mixing the obtained silica with glucose solution with molar ratio of carbon to silica of 1:1, spray drying to obtain powder, placing in a furnace, introducing nitrogen, and reacting at 500 deg.C for 4 hr to obtain SiOxThe product of @ C.
Example 3
Mixing the crude silicon and silicon dioxide by sanding, placing the mixture in a furnace, introducing nitrogen, and reacting for 6 hours at 900 ℃ to obtain silicon monoxide; mixing the obtained silica with glucose solution with molar ratio of carbon to silica of 2:1, spray drying to obtain powder, placing in a furnace, introducing nitrogen, reacting at 500 deg.C for 3 hr to obtain SiOxThe product of @ C.

Claims (9)

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 of:
1) mixing the crude silicon and silicon dioxide by sanding, placing the mixture in a furnace, introducing inert protective gas, and reacting for a certain time at a certain temperature to obtain silicon monoxide;
2) mixing the obtained silicon monoxide with glucose solution, passing through a spray dryer to obtain powder, placing in a furnace, introducing inert shielding gas, and reacting at a certain temperature for a certain time to obtain SiOxThe product of @ C.
3. SiO as claimed in claim 1xPreparation of @ C materialThe method is characterized in that: the crude silicon is carbon-containing silicon powder obtained after the carbothermic reaction of industrial silicon dioxide.
4. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: the silicon dioxide is industrial silicon dioxide.
5. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: the sand grinding rotation speed in the step 1) is 400-600 revolutions per minute, and the sand grinding time is 2-4 hours.
6. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: the inert gas is one or more than two of nitrogen, argon and hydrogen-argon mixed gas.
7. 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 700-1100 ℃, and the sintering time is 2-12 hours.
8. SiO as claimed in claim 1xThe preparation method of the @ C material is characterized by comprising the following steps: the molar ratio of carbon element to silicon oxide in the glucose is 1: 1-3: 1.
9. 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 400-700 ℃, and the sintering time is 1-5 hours.
CN201911354202.5A 2019-12-25 2019-12-25 Preparation of SiO by centering reactionxMethod and application of @ C material Pending CN111115639A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113277518A (en) * 2021-04-27 2021-08-20 郑州市博卓科技有限公司 Silica raw material and preparation method thereof
CN113772678A (en) * 2021-08-30 2021-12-10 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing carbon-coated silicon monoxide negative electrode material and reducing charge transfer impedance of carbon-coated silicon monoxide negative electrode material
CN113816385A (en) * 2021-09-27 2021-12-21 兰州大学 Method for preparing silicon oxide based on silicon rod wire cutting waste
CN114229854A (en) * 2021-12-17 2022-03-25 新疆晶硕新材料有限公司 Preparation method of silicon-oxygen-carbon composite material, negative plate and battery
CN114388770A (en) * 2022-01-24 2022-04-22 浙江锂宸新材料科技有限公司 High-capacity high-first-efficiency silica anode material and preparation method thereof
CN114394599A (en) * 2022-01-18 2022-04-26 郑州炬煌新材料科技有限公司 Preparation method of silicon monoxide and preparation device for realizing method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105789590A (en) * 2016-04-06 2016-07-20 广州有色金属研究院 Preparation method of SiOx/C cathode material
CN106356515A (en) * 2016-11-01 2017-01-25 广东省稀有金属研究所 Preparation method of silicon oxide composite material
CN109037636A (en) * 2018-08-03 2018-12-18 深圳市斯诺实业发展有限公司 A kind of preparation method of SiO/ carbon graphite composite negative pole material
CN110357111A (en) * 2019-07-11 2019-10-22 苏州大学 Oxidation Asia silicium cathode material based on silicon ash, preparation method and lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105789590A (en) * 2016-04-06 2016-07-20 广州有色金属研究院 Preparation method of SiOx/C cathode material
CN106356515A (en) * 2016-11-01 2017-01-25 广东省稀有金属研究所 Preparation method of silicon oxide composite material
CN109037636A (en) * 2018-08-03 2018-12-18 深圳市斯诺实业发展有限公司 A kind of preparation method of SiO/ carbon graphite composite negative pole material
CN110357111A (en) * 2019-07-11 2019-10-22 苏州大学 Oxidation Asia silicium cathode material based on silicon ash, preparation method and lithium ion battery

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113277518A (en) * 2021-04-27 2021-08-20 郑州市博卓科技有限公司 Silica raw material and preparation method thereof
CN113772678A (en) * 2021-08-30 2021-12-10 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing carbon-coated silicon monoxide negative electrode material and reducing charge transfer impedance of carbon-coated silicon monoxide negative electrode material
CN113816385A (en) * 2021-09-27 2021-12-21 兰州大学 Method for preparing silicon oxide based on silicon rod wire cutting waste
CN114229854A (en) * 2021-12-17 2022-03-25 新疆晶硕新材料有限公司 Preparation method of silicon-oxygen-carbon composite material, negative plate and battery
CN114394599A (en) * 2022-01-18 2022-04-26 郑州炬煌新材料科技有限公司 Preparation method of silicon monoxide and preparation device for realizing method
CN114388770A (en) * 2022-01-24 2022-04-22 浙江锂宸新材料科技有限公司 High-capacity high-first-efficiency silica anode material and preparation method thereof

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Application publication date: 20200508