CN111925232A - Graphite surface silicon/carbon double-layer coated negative electrode material and preparation method thereof - Google Patents

Graphite surface silicon/carbon double-layer coated negative electrode material and preparation method thereof Download PDF

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Publication number
CN111925232A
CN111925232A CN202010727837.1A CN202010727837A CN111925232A CN 111925232 A CN111925232 A CN 111925232A CN 202010727837 A CN202010727837 A CN 202010727837A CN 111925232 A CN111925232 A CN 111925232A
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silicon
layer
negative electrode
electrode material
carbon double
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岳之浩
周浪
徐国军
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Jiangxi Changda High Tech Energy Material Technology Co ltd
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Jiangxi Changda High Tech Energy Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • 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
    • H01M4/362—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
    • 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
    • H01M4/36—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 provides a preparation method of a graphite surface silicon/carbon double-layer coated cathode material, which comprises the following steps of (1) placing graphite particles in a vacuum heat treatment furnace; (2) after the set temperature is reached, introducing a gaseous silicon source to coat a silicon layer on the surface of the graphite particles; (3) and introducing a gaseous carbon source after the set temperature is reached, so that the surface of the silicon film is coated with a carbon layer. The invention also discloses the graphite surface silicon/carbon double-layer coated negative electrode material prepared by the method. The preparation method of the negative electrode material can ensure that the silicon material is very uniformly distributed in the whole negative electrode material system, and the phenomenon of nonuniform expansion can not be generated in the charging and discharging processes. The negative electrode material structure provided by the invention is expected to have excellent rate characteristic, cycling stability and high specific capacity.

Description

Graphite surface silicon/carbon double-layer coated negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a graphite surface silicon/carbon double-layer coated negative electrode material and a preparation method thereof.
Background
At present, the theoretical capacity of the conventional graphite cathode material for the lithium ion battery is 372mAh/g, wherein the commercial graphite cathode product reaches about 355mAh/g, and basically no promotion space exists. The theoretical capacity of silicon as the lithium ion battery negative electrode material can reach about 4200mAh/g, and the silicon is rich in the earth crust and is second to oxygen, so the silicon-based lithium ion battery negative electrode material becomes a research hotspot. However, the huge lithium storage expansion effect of the silicon material limits the exertion of the charge and discharge performance, so that the silicon material cannot be applied on a large scale. Therefore, most enterprises in the industry adopt a compromise scheme, namely a small amount (generally not more than 5%) of nano silicon particles and graphite particles are compounded for use, the method relieves the lithium storage expansion effect of the silicon material to a certain extent, but the cycle life of the silicon material is still not ideal, and the main reason is that the nano silicon particles are not uniformly dispersed in graphite powder, so that the whole negative electrode system expands unevenly, and partial areas on the negative electrode plate are cracked and fall off.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention aims to provide a graphite surface silicon/carbon double-layer coated negative electrode material and a preparation method thereof.
The invention is realized by the following technical scheme:
a preparation method of a graphite surface silicon/carbon double-layer coated negative electrode material comprises the following steps:
step (1), placing graphite particles in a vacuum heat treatment furnace;
step (2), after the set temperature is reached, introducing a gaseous silicon source to coat a silicon layer on the surface of the graphite particles;
and (3) introducing a gaseous carbon source after the set temperature is reached, so that the surface of the silicon layer is coated with a carbon layer.
Further, the vacuum heat treatment furnace is preferably a rotary vacuum tube furnace.
Further, the set temperature in the step (2) is preferably 600 to 1000 ℃.
Further, the gaseous silicon source in step (2) is preferably silane.
Further, the thickness of the silicon layer in the step (2) is preferably 100 to 500 nm.
Further, the set temperature in the step (3) is preferably 600 to 1000 ℃.
Further, the gaseous carbon source in step (3) is preferably acetylene or methane.
Further, the carbon layer of step (3) preferably has a thickness of 5 to 20 nm.
The invention also provides a graphite surface silicon/carbon double-layer coated negative electrode material which is prepared by the method.
According to the invention, a gaseous silicon source and a gaseous carbon source are sequentially filled in a vacuum high-temperature environment, so that a uniform silicon layer film and a uniform carbon layer film are sequentially formed on the surface of graphite particles, and further the composite material of the silicon/carbon double-layer coated graphite particles is formed.
According to the invention, the silicon-carbon composite negative electrode material is formed by depositing the gaseous silicon source on the surface of the graphite particle after thermal decomposition, and is more uniformly mixed than the traditional silicon particle and graphite particle, and the structure of the silicon film coating the graphite particle can ensure that silicon is more uniformly dispersed in a graphite system; the gaseous carbon source has the effect that the carbon layer is wrapped on the surface of the silicon film, so that silicon is not directly contacted with electrolyte, and the surface of the silicon film is not provided with an SEI (solid electrolyte interface) film, otherwise, a new SEI film is always generated on the surface of the silicon film, so that the electrolyte is always consumed, and the capacity of the battery is always attenuated; the traditional carbon-coated silicon material is coated by adopting a liquid phase, and the coating of a gaseous carbon source is deposited layer by layer, so that a carbon layer is more uniform and the thickness is more controllable.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the negative electrode material can ensure that the silicon material is very uniformly distributed in the whole negative electrode material system, and the phenomenon of nonuniform expansion can not be generated in the charging and discharging processes.
(2) The negative electrode material structure provided by the invention is expected to have excellent rate characteristic, cycling stability and high specific capacity.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Illustration of the drawings: 1-graphite particles, 2-silicon layer, 3-carbon layer.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
The preparation method of the graphite surface silicon/carbon double-layer coated negative electrode material shown in the attached figure 1 is as follows: (1) placing graphite particles 1 with the particle size of 10 mu m in a rotary vacuum tube furnace; (2) introducing silane after the temperature reaches 1000 ℃ to coat a silicon layer 2 with the thickness of 500nm on the surface of the graphite particles; (3) and introducing acetylene at 1000 ℃ without changing the temperature to coat the surface of the silicon layer with a carbon layer 3 with the thickness of 20 nm.
The first discharge capacity of the prepared negative electrode material is 500mAh/g, the capacity retention rate is 90% after 500 times of 0.2C circulation, and the capacity retention rate is 83% after 500 times of 2C circulation.
Example 2
The preparation method of the graphite surface silicon/carbon double-layer coated negative electrode material shown in the attached figure 1 is as follows: (1) placing graphite particles 1 with the particle size of 10 mu m in a rotary vacuum tube furnace; (2) introducing silane after the temperature reaches 600 ℃ to coat a silicon layer 2 with the thickness of 100nm on the surface of the graphite particles; (3) the temperature is not changed, methane is introduced at 600 ℃, and a carbon layer 3 with the thickness of 5nm is coated on the surface of the silicon layer.
The first discharge capacity of the prepared negative electrode material is 390mAh/g, the capacity retention rate is 93% after 500 times of 0.2C circulation, and the capacity retention rate is 88% after 500 times of 2C circulation.
Example 3
The preparation method of the graphite surface silicon/carbon double-layer coated negative electrode material shown in the attached figure 1 is as follows: (1) placing graphite particles 1 with the particle size of 10 mu m in a rotary vacuum tube furnace; (2) introducing silane after the temperature reaches 800 ℃ to coat a silicon layer 2 with the thickness of 200nm on the surface of the graphite particles; (3) and cooling to 700 ℃, introducing methane, and coating a carbon layer 3 with the thickness of 10nm on the surface of the silicon layer.
The first discharge capacity of the prepared negative electrode material is 420mAh/g, the capacity retention rate is 92% after 500 times of 0.2C circulation, and the capacity retention rate is 87% after 500 times of 2C circulation.
The foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. A preparation method of a graphite surface silicon/carbon double-layer coated negative electrode material is characterized by comprising the following steps:
step (1), placing graphite particles in a vacuum heat treatment furnace;
step (2), after the set temperature is reached, introducing a gaseous silicon source to coat a silicon layer on the surface of the graphite particles;
and (3) introducing a gaseous carbon source after the set temperature is reached, so that the surface of the silicon layer is coated with a carbon layer.
2. The method for preparing the silicon/carbon double-layer coated anode material on the surface of the graphite according to claim 1, wherein the vacuum heat treatment furnace is a rotary vacuum tube furnace.
3. The method for preparing the negative electrode material with the graphite surface coated by the silicon/carbon double layer is characterized in that the set temperature of the step (2) is 600-1000 ℃.
4. The method for preparing the graphite surface silicon/carbon double-layer coated anode material as claimed in claim 1, wherein the gaseous silicon source in the step (2) is silane.
5. The method for preparing the graphite surface silicon/carbon double-layer coated anode material as claimed in claim 1, wherein the silicon layer formed in the step (2) has a thickness of 100-500 nm.
6. The method for preparing the negative electrode material with the graphite surface coated by the silicon/carbon double layer is characterized in that the set temperature in the step (3) is 600-1000 ℃.
7. The method for preparing the graphite surface silicon/carbon double-layer coated anode material as claimed in claim 1, wherein the gaseous carbon source in the step (3) is acetylene or methane.
8. The method for preparing the anode material coated with the silicon/carbon double layer on the graphite surface according to claim 1, wherein the carbon layer formed in the step (3) has a thickness of 5-20 nm.
9. A graphite surface silicon/carbon double-layer coated negative electrode material, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
CN202010727837.1A 2020-07-24 2020-07-24 Graphite surface silicon/carbon double-layer coated negative electrode material and preparation method thereof Pending CN111925232A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114744172A (en) * 2022-04-06 2022-07-12 广东海洋大学 Silicon-carbon composite negative electrode material and preparation method and application thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114744172A (en) * 2022-04-06 2022-07-12 广东海洋大学 Silicon-carbon composite negative electrode material and preparation method and application thereof
CN114744172B (en) * 2022-04-06 2024-03-22 广东海洋大学 Silicon-carbon composite anode material and preparation method and application thereof

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