CN107959007B - Preparation method of graphene-silicon-coated lithium ion battery negative electrode material - Google Patents

Preparation method of graphene-silicon-coated lithium ion battery negative electrode material Download PDF

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CN107959007B
CN107959007B CN201711065161.9A CN201711065161A CN107959007B CN 107959007 B CN107959007 B CN 107959007B CN 201711065161 A CN201711065161 A CN 201711065161A CN 107959007 B CN107959007 B CN 107959007B
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graphene
silicon
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lithium ion
ion battery
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CN107959007A (en
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沈晨
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Anhui Zhengxi Biaowang New Energy Co Ltd
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Anhui Zhengxi Biaowang New Energy Co Ltd
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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
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • 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 relates to a preparation method of a graphene-silicon-coated lithium ion battery cathode material, which is characterized by comprising the following steps of: firstly, dispersing graphene oxide and maleate with the mass ratio of 1-2:1 into water, dispersing, spraying, drying to obtain powder, and carrying out high-temperature heat treatment to obtain spherical graphene microspheres; uniformly mixing the silicon-containing slurry and spherical graphene microspheres, evaporating off the solvent, mixing the mixture with high-temperature asphalt at a high speed according to a mass ratio of 1-2:1, stirring, heating for pyrolysis, performing high-temperature heat treatment under an inert atmosphere, and graphitizing to obtain the graphene-silicon lithium ion battery coated negative electrode 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 860, the first coulombic efficiency can reach more than 90%, the charge and discharge are carried out at 0.1 ℃, and the capacity retention rate is more than 82% after 500 cycles.

Description

Preparation method of graphene-silicon-coated lithium ion battery negative electrode material
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery cathode materials, and particularly relates to a preparation method of a graphene-silicon-coated lithium ion battery cathode material.
Background
With the improvement of production requirements and environmental protection awareness, new energy becomes the key point of disputed development of various countries, wherein the development of lithium ion batteries is particularly rapid, and the application of the lithium ion batteries relates to the fields of 3C products, power devices, energy storage equipment 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.
The theoretical capacity of the silicon material can reach 4200mAh/g, which is one order of magnitude higher than that of the carbon negative electrode material which is commercially used at present. However, the silicon material as the negative electrode material of the lithium ion battery has a fatal defect that the volume change is large and reaches 300% in the adsorption and desorption processes of lithium ions, so that the silicon negative electrode is cracked, the charge-discharge cycle performance is extremely poor, and the application is difficult to realize.
At present, a composite material of silicon and graphene is often used for manufacturing a high-capacity graphene negative electrode material, and the adopted technology is basically that the surface of a silicon nanowire or a nanoparticle is coated with graphene or other carbon materials to inhibit the fragmentation of a silicon material in the charging and discharging processes. However, the main problems of these methods are that silicon still exists in the form of small-particle silicon in the negative electrode material, volume change is difficult to avoid during charge and discharge, and long-term charge and discharge performance is still a key problem.
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 coated graphene-silicon lithium ion battery cathode material.
The technical scheme of the invention is as follows:
a preparation method of a coated graphene-silicon lithium ion battery cathode 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 2 hours to obtain a dispersion liquid, then carrying out spray drying at 150-200 ℃ to obtain a powder, treating at 220-250 ℃ for 5 hours, treating at 300-350 ℃ for 5 hours, treating at 450-500 ℃ for 5 hours, and treating at 750-800 ℃ for 5 hours to obtain spherical graphene microspheres; uniformly mixing the silicon-containing slurry and spherical graphene microspheres, evaporating the solvent, mixing the mixture with high-temperature asphalt at a mass ratio of 1-2:1, stirring, heating for pyrolysis, carbonizing in an inert atmosphere at the carbonization temperature of 1000-1200 ℃, and keeping the temperature for 10-12 hours, and then graphitizing at the graphitization temperature of 2800-3000 ℃ and the temperature for 10-12 hours to obtain the coated graphene-silicon lithium ion battery cathode 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; uniformly mixing silicon-containing slurry and spherical graphene microspheres, evaporating off a solvent, mixing the mixture with high-temperature asphalt at a mass ratio of 1.5:1, stirring, heating for pyrolysis, carbonizing in an inert atmosphere at 1100 ℃, keeping the temperature for 12 hours, graphitizing at 2900 ℃, and keeping the temperature for 12 hours to obtain the graphene-silicon lithium ion battery coated negative electrode 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 860, the first coulombic efficiency can reach more than 90%, the charge and discharge are carried out at 0.1 ℃, and the capacity retention rate is more than 82% 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 350 ℃, treating for 5 hours at 450 ℃, and treating for 5 hours at 750 ℃ to obtain spherical graphene microspheres; uniformly mixing silicon-containing slurry and spherical graphene microspheres, evaporating off a solvent, mixing the mixture with high-temperature asphalt at a high speed according to a mass ratio of 1:1, stirring, heating for pyrolysis, carbonizing at 1000 ℃ in an inert atmosphere, keeping the temperature for 10 hours, and graphitizing at 3000 ℃ for 12 hours to obtain the coated graphene-silicon lithium ion battery cathode 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; uniformly mixing silicon-containing slurry and spherical graphene microspheres, evaporating off a solvent, mixing the mixture with high-temperature asphalt at a mass ratio of 1.5:1, stirring, heating for pyrolysis, carbonizing in an inert atmosphere at 1100 ℃, keeping the temperature for 12 hours, graphitizing at 2900 ℃, and keeping the temperature for 12 hours to obtain the graphene-silicon lithium ion battery coated negative electrode material.
Example 3
Firstly, dispersing graphene oxide and maleate with the 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 220 ℃, treating for 5 hours at 350 ℃, treating for 5 hours at 500 ℃ at 450 ℃, and treating for 5 hours at 800 ℃ to obtain spherical graphene microspheres; uniformly mixing the silicon-containing slurry and spherical graphene microspheres, evaporating off a solvent, mixing the mixture with high-temperature asphalt at a mass ratio of 2:1, stirring, heating for pyrolysis, carbonizing at 1200 ℃ in an inert atmosphere, keeping the temperature for 12 hours, graphitizing at 2800 ℃ for 10 hours, and thus obtaining the coated graphene-silicon lithium ion battery cathode material.
Taking the material prepared in the embodiment 1-3 as a negative electrode material, mixing the material with a binder (LA132), a conductive agent (Super-P) and a dispersant (water and ethanol in a volume ratio of 1: 3) to form slurry, coating the slurry on a copper foil, and preparing a negative electrode sheet by vacuum drying and rolling; the positive electrode adopts a metal lithium sheet, the used organic electrolyte is 1MLiPF6/EC + PC + DEC (the molar ratio is 1: 1: 1), the diaphragm is polypropylene, and the CR2025 button cell is prepared. The test conditions are normal temperature, 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
Figure BDA0001455601010000031

Claims (4)

1. A preparation method of a coated graphene-silicon lithium ion battery negative electrode 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; uniformly mixing the silicon-containing slurry and spherical graphene microspheres, evaporating the solvent, mixing the mixture with high-temperature asphalt at a mass ratio of 1-2:1, stirring, heating for pyrolysis, carbonizing in an inert atmosphere at the carbonization temperature of 1000-1200 ℃, and keeping the temperature for 10-12 hours, and then graphitizing at the graphitization temperature of 2800-3000 ℃ and the temperature for 10-12 hours to obtain the coated graphene-silicon lithium ion battery cathode material.
2. The method for preparing the coated graphene-silicon lithium ion battery negative electrode 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; uniformly mixing silicon-containing slurry and spherical graphene microspheres, evaporating off a solvent, mixing the mixture with high-temperature asphalt at a mass ratio of 1.5:1, stirring, heating for pyrolysis, carbonizing in an inert atmosphere at 1100 ℃, keeping the temperature for 12 hours, graphitizing at 2900 ℃, and keeping the temperature for 12 hours to obtain the graphene-silicon lithium ion battery coated negative electrode material.
3. A lithium ion battery negative electrode material is characterized in that: prepared by the process of claim 1 or 2.
4. A lithium ion battery, characterized by: the negative electrode material according to claim 3 is used.
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