CN107946556B - Preparation method of graphene-based silicon-carbon composite material - Google Patents
Preparation method of graphene-based silicon-carbon composite material Download PDFInfo
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- CN107946556B CN107946556B CN201711064440.3A CN201711064440A CN107946556B CN 107946556 B CN107946556 B CN 107946556B CN 201711064440 A CN201711064440 A CN 201711064440A CN 107946556 B CN107946556 B CN 107946556B
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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
- H01M4/38—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
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 relates to a preparation method of a graphene-based silicon-carbon composite material, which comprises the steps of firstly dispersing graphene oxide and maleate with the mass ratio of 1-2:1 into water, stirring, carrying out spray drying to obtain a powder, and carrying out high-temperature treatment to obtain spherical graphene microspheres; dispersing nano silicon and spherical graphene microspheres in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, and performing high-temperature treatment under inert gas to obtain a nano silicon/spherical graphene microsphere compound; and dispersing the compound and an organic carbon source in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, and performing high-temperature treatment under inert gas to obtain the graphene-based silicon-carbon composite material. The invention has the beneficial effects that: the spherical graphene microspheres are highly dispersed, the maleate, the silicon and the carbon are uniformly distributed, the first discharge capacity can reach more than 750 percent, the first coulombic efficiency can reach more than 92 percent, the charge and discharge are carried out at 0.1 ℃, and the capacity retention rate is more than 85 percent after 500 cycles.
Description
Technical Field
The invention relates to a preparation method of a graphene-based silicon-carbon composite material, belonging to the technical field of preparation of lithium ion battery cathode materials.
Background
With the improvement of production requirements and environmental protection consciousness, new energy becomes the key point of dispute and development of various countries, and lithium ion batteries already occupy most of markets in the 3C field due to the advantages of large specific energy, high working voltage, small self-discharge rate, small volume, light weight and the like.
The current commercialized lithium ion battery cathode material is mainly graphite, but the theoretical capacity is only 372mAh/g, and the demand of the market for high energy density can not be met gradually.
Silicon has ultrahigh theoretical specific capacity (4200mAh/g) and lower lithium intercalation/deintercalation potential (<0.5V), and the voltage platform of silicon is slightly higher than that of graphite, so that surface lithium precipitation is difficult to cause during charging, and the safety performance is better. The defects of silicon serving as the negative electrode material of the lithium ion battery are obvious. Firstly, silicon is a semiconductor material and has low self conductivity; secondly, in the electrochemical cycle process, the lithium ion intercalation and deintercalation can cause the silicon-based material to expand and contract by more than 300% in volume, the mechanical acting force generated by the expansion and the contraction can gradually pulverize the silicon-based material to cause the structure collapse, and finally, the electrode active substance is separated from the current collector to lose the electric contact, so that the cycle performance of the lithium ion battery is greatly reduced.
Disclosure of Invention
In order to solve the technical problems of low theoretical capacity of graphite and structural collapse caused by lithium intercalation and deintercalation from silicon in the prior art, the invention aims to provide a preparation method of a graphene-based silicon-carbon composite material.
The technical scheme of the invention is as follows:
a preparation method of a graphene-based silicon-carbon composite material comprises the steps of firstly dispersing graphene oxide and maleate with the mass ratio of 1-2:1 into water, stirring at 70-90 ℃ for 2h to obtain a dispersion liquid, then carrying out spray drying at 150-200 ℃ to obtain a powder, treating at 220-250 ℃ for 5h, treating at 300-350 ℃ for 5h, treating at 450-500 ℃ for 5h, and treating at 800-750 ℃ for 5h to obtain spherical graphene microspheres; dispersing nano silicon and spherical graphene microspheres in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, keeping the temperature at 50-100 ℃ for 10-20min, keeping the temperature at 200-300 ℃ for 20-30min and keeping the temperature at 700-800 ℃ for 5-6h under inert gas to obtain a nano silicon/spherical graphene microsphere compound; and dispersing the composite and an organic carbon source in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, and keeping the temperature at 50-100 ℃ for 10-20min, 200-300 ℃ for 20-30min, 700-800 ℃ for 5-6h, and 850-900 ℃ for 8-10h under inert gas to obtain the graphene-based silicon-carbon composite material.
It is preferable that: firstly, dispersing graphene oxide and maleate with the mass ratio of 1.5:1 into water, stirring for 2 hours at 80 ℃ to obtain a dispersion liquid, then carrying out spray drying at 180 ℃ to obtain a powder, treating for 5 hours at 240 ℃, treating for 5 hours at 320 ℃, treating for 5 hours at 480 ℃, and treating for 5 hours at 780 ℃ to obtain spherical graphene microspheres; dispersing nano silicon and spherical graphene microspheres in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, keeping the temperature at 80 ℃ for 10-20min, keeping the temperature at 260 ℃ for 20-30min and keeping the temperature at 780 ℃ for 5-6h under inert gas to obtain a nano silicon/spherical graphene microsphere compound; and dispersing the compound and an organic carbon source in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, and keeping the temperature of 80 ℃ for 10-20min, 260 ℃ for 20-30min, 780 ℃ for 5-6h and 880 ℃ for 8-10h under inert gas to obtain the graphene-based silicon-carbon composite material.
The invention also provides a graphene-based silicon-carbon composite material prepared by the method.
The invention also provides a lithium ion battery cathode material which adopts the graphene-based silicon-carbon composite material.
The invention also provides a lithium ion battery which adopts the cathode material.
The invention has the beneficial effects that: the spherical graphene microspheres are highly dispersed, the maleate, the silicon and the carbon are uniformly distributed, the first discharge capacity can reach more than 750 percent, the first coulombic efficiency can reach more than 92 percent, the charge and discharge are carried out at 0.1 ℃, and the capacity retention rate is more than 85 percent after 500 cycles.
Detailed Description
The technical solution of the present invention will be explained in detail below.
Example 1
Firstly, dispersing graphene oxide and maleate in a mass ratio of 1:1 into water, stirring for 2 hours at 70 ℃ to obtain a dispersion liquid, then carrying out spray drying at 150 ℃ to obtain a powder, treating for 5 hours at 220 ℃, treating for 5 hours at 300 ℃, treating for 5 hours at 450 ℃, and treating for 5 hours at 750 ℃ to obtain spherical graphene microspheres; dispersing nano silicon and spherical graphene microspheres in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, keeping the temperature at 50 ℃ for 10min, keeping the temperature at 200 ℃ for 20min and keeping the temperature at 800 ℃ for 6h under inert gas to obtain a nano silicon/spherical graphene microsphere compound; and dispersing the compound and an organic carbon source in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, and keeping the temperature of 100 ℃ for 20min, 300 ℃ for 20min, 800 ℃ for 5h and 850 ℃ for 8h under inert gas to obtain the graphene-based silicon-carbon composite material.
Example 2
Firstly, dispersing graphene oxide and maleate with the mass ratio of 1.5:1 into water, stirring for 2 hours at 80 ℃ to obtain a dispersion liquid, then carrying out spray drying at 180 ℃ to obtain a powder, treating for 5 hours at 240 ℃, treating for 5 hours at 320 ℃, treating for 5 hours at 480 ℃, and treating for 5 hours at 780 ℃ to obtain spherical graphene microspheres; dispersing nano silicon and spherical graphene microspheres in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, keeping the temperature at 80 ℃ for 10-20min, keeping the temperature at 260 ℃ for 20-30min and keeping the temperature at 780 ℃ for 5-6h under inert gas to obtain a nano silicon/spherical graphene microsphere compound; and dispersing the compound and an organic carbon source in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, and keeping the temperature of 80 ℃ for 10-20min, 260 ℃ for 20-30min, 780 ℃ for 5-6h and 880 ℃ for 8-10h under inert gas to obtain the graphene-based silicon-carbon composite material.
Example 3
Firstly, dispersing graphene oxide and maleate in a mass ratio of 2:1 into water, stirring for 2 hours at 90 ℃ to obtain a dispersion liquid, then carrying out spray drying at 200 ℃ to obtain a powder, treating for 5 hours at 250 ℃, treating for 5 hours at 350 ℃, treating for 5 hours at 500 ℃, and treating for 5 hours at 800 ℃ to obtain spherical graphene microspheres; dispersing nano silicon and spherical graphene microspheres in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, keeping the temperature at 50 ℃ for 20min, keeping the temperature at 200 ℃ for 30min and keeping the temperature at 800 ℃ for 6h under inert gas to obtain a nano silicon/spherical graphene microsphere compound; and dispersing the composite and an organic carbon source in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, and keeping the temperature at 100 ℃ for 20min, 200 ℃ for 300 min, 700 ℃ for 5h and 850 ℃ for 8h under inert gas to obtain the graphene-based silicon-carbon composite material.
The material prepared in the embodiment 1-3 is taken as a negative electrode material, mixed with a binder (L A132), a conductive agent (Super-P) and a dispersant (water and ethanol in a volume ratio of 1: 3) to form slurry, coated on a copper foil, subjected to vacuum drying and rolling to prepare a negative electrode sheet, a positive electrode adopts a metal lithium sheet, an organic electrolyte used in the positive electrode is 1M L iPF6/EC + PC + DEC (a molar ratio of 1: 1: 1), a diaphragm is polypropylene, and a CR2025 type button cell is prepared, and the test condition is normal temperature, the charge and discharge are carried out at 0.1C, and the charge and discharge voltage is limited to 0.005-1.5V.
TABLE 1 half cell test Performance
Claims (5)
1. A preparation method of a graphene-based silicon-carbon composite material is characterized by comprising the following steps: firstly, dispersing graphene oxide and maleate with the mass ratio of 1-2:1 into water, stirring for 2h at 70-90 ℃ to obtain a dispersion liquid, then carrying out spray drying at 150-200 ℃ to obtain a powder, treating for 5h at 220-350 ℃, treating for 5h at 450-500 ℃ and treating for 5h at 750-800 ℃ to obtain spherical graphene microspheres; dispersing nano silicon and spherical graphene microspheres in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, keeping the temperature at 50-100 ℃ for 10-20min, keeping the temperature at 200-300 ℃ for 20-30min and keeping the temperature at 700-800 ℃ for 5-6h under inert gas to obtain a nano silicon/spherical graphene microsphere compound; and dispersing the composite and an organic carbon source in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, and keeping the temperature at 50-100 ℃ for 10-20min, 200-300 ℃ for 20-30min, 700-800 ℃ for 5-6h, and 850-900 ℃ for 8-10h under inert gas to obtain the graphene-based silicon-carbon composite material.
2. The method for preparing graphene-based silicon-carbon composite material according to claim 1, wherein the method comprises the following steps: firstly, dispersing graphene oxide and maleate with the mass ratio of 1.5:1 into water, stirring for 2 hours at 80 ℃ to obtain a dispersion liquid, then carrying out spray drying at 180 ℃ to obtain a powder, treating for 5 hours at 240 ℃, treating for 5 hours at 320 ℃, treating for 5 hours at 480 ℃, and treating for 5 hours at 780 ℃ to obtain spherical graphene microspheres; dispersing nano silicon and spherical graphene microspheres in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, keeping the temperature at 80 ℃ for 10-20min, keeping the temperature at 260 ℃ for 20-30min and keeping the temperature at 780 ℃ for 5-6h under inert gas to obtain a nano silicon/spherical graphene microsphere compound; and dispersing the compound and an organic carbon source in a solvent, performing ultrasonic treatment and stirring, removing the solvent after uniform mixing, and keeping the temperature of 80 ℃ for 10-20min, 260 ℃ for 20-30min, 780 ℃ for 5-6h and 880 ℃ for 8-10h under inert gas to obtain the graphene-based silicon-carbon composite material.
3. A graphene-based silicon-carbon composite material is characterized in that: prepared by the process of claim 1 or 2.
4. A lithium ion battery negative electrode material is characterized in that: the graphene-based silicon-carbon composite material according to claim 3 is adopted.
5. A lithium ion battery, characterized by: the negative electrode material according to claim 4 is used.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306757A (en) * | 2011-08-26 | 2012-01-04 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| CN104591177A (en) * | 2015-02-03 | 2015-05-06 | 辽宁工程技术大学 | Method for preparing self-supporting three-dimensional porous graphene composite microsphere |
| CN105304884A (en) * | 2015-05-18 | 2016-02-03 | 深圳市国创新能源研究院 | Graphene-based silicon-carbon composite anode material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306757A (en) * | 2011-08-26 | 2012-01-04 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| CN104591177A (en) * | 2015-02-03 | 2015-05-06 | 辽宁工程技术大学 | Method for preparing self-supporting three-dimensional porous graphene composite microsphere |
| CN105304884A (en) * | 2015-05-18 | 2016-02-03 | 深圳市国创新能源研究院 | Graphene-based silicon-carbon composite anode material and preparation method thereof |
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