CN114361427A - Method for coating silicon cathode material with carbon nano tube - Google Patents
Method for coating silicon cathode material with carbon nano tube Download PDFInfo
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- CN114361427A CN114361427A CN202111622360.1A CN202111622360A CN114361427A CN 114361427 A CN114361427 A CN 114361427A CN 202111622360 A CN202111622360 A CN 202111622360A CN 114361427 A CN114361427 A CN 114361427A
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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
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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
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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
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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
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Abstract
A method for coating a silicon cathode material with a carbon nano tube comprises the following steps: a. taking the components in a weight ratio of 0.1-2: feeding 99.9-98 parts of carbon nano tube powder and silicon negative electrode material powder into coating equipment; b. starting coating equipment, and running for 1-20 minutes at a rotating speed of 3-40 m/s to enable the carbon nano tube to form a coating layer on the surface of the silicon cathode material, so as to obtain the silicon cathode material coated by the carbon nano tube; c. the obtained silicon cathode material coated by the nano tube is powder formed by micron-sized particles, and the particle size of the particles is 5-10 microns. The invention has the characteristics of uniform coating, good conductivity, small volume expansion, high capacity, no introduction of other metal impurities, low manufacturing cost, strong practicability and the like.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of preparation of lithium battery cathode materials, in particular to a method for coating a silicon cathode material with a carbon nano tube.
[ background of the invention ]
Currently, a commercial lithium ion battery generally uses a graphite carbon material as a negative electrode, and the theoretical capacity of graphite is 372mAh/g, so that the energy density of the lithium ion battery is limited by the lower capacity. The theoretical capacity of the silicon negative electrode material is 4200mAh/g, and the theoretical capacity of the silicon monoxide is 2000mAh/g, so that the silicon negative electrode material is the first choice of the negative electrode material of the new-generation battery. However, during the process of lithium ion intercalation and deintercalation, the volume of the silicon oxide can be greatly expanded, which is very likely to cause the capacity reduction and even the short circuit of the lithium ion battery.
Much work has been done to improve the electrochemical stability of silicon and silica. The carbon nano tube has larger length-diameter ratio, so that the conductivity and mechanical property of the silicon material can be increased, and the adverse effect of volume expansion of the silicon material is relieved. However, most of the silicon material aggregates and the carbon nanotubes are mixed in slurry during battery preparation or in-situ growth methods, which not only have complex process and high cost, but also have complex process and poor uniformity.
In the prior art, one of the solutions is to prepare a catalyst solution from a catalyst and a solvent, add a silicon material into the catalyst solution to load the catalyst on the surface of the silicon material, and then add the silicon material into a carbon source solution to load a carbon source on the surface of the silicon material. In the method, the catalyst cannot be uniformly loaded on the surface of the silicon material, the gram capacity of the obtained battery is low, and the battery needs to be cleaned by hydrochloric acid, nitric acid and hydrofluoric acid at the later stage. In addition, the silicon material is easy to agglomerate in the drying process after cleaning, and the complex use of the silicon material and the graphite cathode material is influenced. The other proposal relates to a method for coating carbon nano-tubes and amorphous carbon in situ by silicon, but the obtained carbon tubes are thick and short, the length of the carbon nano-tubes is about 3-4 microns, the diameter is about 500 nanometers, the length-diameter ratio is 6-8, the obtained lithium ion negative electrode has poor conductivity, so the obtained product has limited performance, the specific capacity is about 1000-1360mAh/g, and the obtained product has low commercial value. In other schemes, a method for growing carbon tubes in situ by using silicon or oxides thereof is adopted, a metal catalyst is attached to the surface of the silicon or oxides thereof, and the silicon or silicon oxides thereof coated with the carbon nanotubes are prepared in a mode of generating the carbon nanotubes on the surface of the silicon or oxides thereof by a chemical vapor deposition method. However, the scheme cannot remove metal catalyst impurities, so that self-discharge of the battery is aggravated, and the storage performance is influenced. And the yield is limited, the mass production is difficult, and the cost is higher.
[ summary of the invention ]
The invention aims to solve the problems and provides a method for coating a silicon cathode material by a carbon nano tube, which has the advantages of uniform coating, good conductivity, small volume expansion, high capacity, no introduction of other metal impurities, low manufacturing cost and strong practicability.
In order to achieve the above object, the present invention provides a method for coating a silicon negative electrode material with carbon nanotubes, the method comprising the steps of:
a. taking the components in a weight ratio of 0.1-2: feeding 99.9-98 parts of carbon nano tube powder and silicon negative electrode material powder into coating equipment;
b. starting coating equipment, and running for 1-20 minutes at a rotating speed of 3-40 m/s to enable the carbon nano tube to form a coating layer on the surface of the silicon cathode material, so as to obtain the silicon cathode material coated by the carbon nano tube;
c. the obtained silicon cathode material coated by the nano tube is powder formed by micron-sized particles, and the particle size of the particles is 2-10 microns.
The carbon nanotube is a single-walled carbon nanotube, a double-walled carbon nanotube, a multi-walled carbon nanotube or a mixture of any two of them.
The carbon nano tube is a fibrous aggregate with a tube diameter of 2-100 nanometers, a length of 5-50 micrometers and a bulk density of 0.01-0.1 g/cc.
The silicon cathode material is silicon monoxide.
The silicon monoxide is a particle with the particle size of 2-10 microns and the density of 1.1 g/cubic centimeter.
The thickness of the coating layer is 2-500 nanometers.
In a particular embodiment, the method comprises the steps of:
a. putting carbon nanotube powder and silicon cathode material powder in a weight ratio of 2:98 into coating equipment;
b. starting coating equipment, and running at the rotating speed of 20m/s for 10 minutes to enable the carbon nano tube to form a coating layer on the surface of the silicon cathode material, so as to obtain the silicon cathode material coated by the carbon nano tube;
c. the obtained silicon cathode material coated by the nano tube is powder formed by micron-sized particles, and the particle size of the particles is 2-10 microns.
The contribution of the present invention is that it effectively solves the problems existing in the prior art. The invention realizes the carbon nano tube coating of the silicon cathode material by a physical method, and the obtained product has the advantages of uniform carbon nano tube coating, good conductivity, small volume expansion and no other metal impurities brought in. The method can remarkably reduce the manufacturing cost, thereby having higher commercial value and practicability.
[ detailed description ] embodiments
The following examples are further illustrative and explanatory of the present invention and are not to be construed as limiting the invention in any way.
Example 1
And (3) putting 500 g of silica powder and 4 g of multi-wall carbon nano tube powder into a coating device, starting the coating device, and running for 5 minutes at a linear speed of 15 m/s. In the embodiment, the particle size of the silicon monoxide particles is 5-10 microns, and the density is 1.1 g/cc. The multi-walled carbon nanotubes are fibrous aggregates with a tube diameter of 50 nanometers, a length of 25 micrometers, and a bulk density of 0.1 g/cc. In the operation process of the coating equipment, the multi-walled carbon nanotubes are dispersed into a net shape, and the carbon nanotubes are embedded into a carbon black layer on the surface of the oxidized silica due to the fact that the linear velocity and the shearing force are large and the surface of the oxidized silica is coated with a layer of carbon black. And after the coating is finished, forming a carbon nano tube coating layer on the surface of the silicon oxide, wherein the thickness of the coating layer is 100 nanometers, and obtaining the silicon cathode material coated by the carbon nano tube. The coating apparatus is commercially available. In this embodiment, the coating apparatus is a nobileta powder processing apparatus, and can mix or precisely mix the two different types of materials in a short time. The silicon cathode material coated by the nano tube obtained by the coating equipment is powder formed by micron-sized particles, the particle size of the particles is about 5-10 microns, and the silicon cathode material can be used as a lithium ion battery cathode material.
Example 2
500 g of silica powder and 4 g of multi-walled carbon nanotube powder are put into a coating device, wherein the composition and the form of the silica and the multi-walled carbon nanotubes are the same as those in example 1. The coating apparatus was started and run at a line speed of 10m/s for 5 minutes. In the operation process of the coating equipment, the multi-walled carbon nanotubes are dispersed into a net shape, and the carbon nanotubes are embedded into a carbon black layer on the surface of the oxidized silica due to the fact that the linear velocity and the shearing force are large and the surface of the oxidized silica is coated with a layer of carbon black. And after the coating is finished, forming a carbon nano tube coating layer on the surface of the silicon oxide, wherein the thickness of the coating layer is 100 nanometers, and obtaining the silicon cathode material coated by the carbon nano tube. The coating apparatus was the same as in example 1. The silicon cathode material coated by the nano tube obtained by the coating equipment is powder formed by micron-sized particles, the particle size of the particles is about 5-10 microns, and the silicon cathode material can be used as a lithium ion battery cathode material.
Example 3
500 g of silica powder, 0.5 g of 8012 single-walled carbon nanotube and 2 g of multi-walled carbon nanotube are put into coating equipment, wherein the single-walled carbon nanotube is a fibrous aggregate with the pipe diameter of 2 nanometers, the length of 50 micrometers and the bulk density of 0.01 g/cubic centimeter. The composition and form of the above-mentioned silica and multi-walled carbon nanotubes were the same as those of example 1. The coating apparatus was started and run at a line speed of 15m/s for 5 minutes. During the operation of the coating equipment, the single-walled carbon nanotubes and the multi-walled carbon nanotubes are dispersed into a net shape, and the carbon nanotubes are embedded into a carbon black layer on the surface of the silica because the linear velocity and the shearing force are both large and the surface of the silica is coated by a layer of carbon black. And after the coating is finished, forming a carbon nano tube coating layer on the surface of the oxidized silicon, wherein the thickness of the coating layer is 80 nanometers, and obtaining the silicon cathode material coated by the carbon nano tube. The coating apparatus was the same as in example 1. The silicon cathode material coated by the nano tube obtained by the coating equipment is powder formed by micron-sized particles, the particle size of the particles is about 5-10 microns, and the silicon cathode material can be used as a lithium ion battery cathode material.
Example 4
500 g of silica powder, 0.5 g of 8012 single-walled carbon nanotube and 2 g of NTP3003 multi-walled carbon nanotube are put into a coating device, wherein the composition and the form of the silica, the single-walled carbon nanotube and the multi-walled carbon nanotube are the same as those of the embodiment 3. The coating apparatus was started and run at a line speed of 15m/s for 10 minutes. During the operation of the coating equipment, the single-walled carbon nanotubes and the multi-walled carbon nanotubes are dispersed into a net shape, and the carbon nanotubes are embedded into a carbon black layer on the surface of the silica because the linear velocity and the shearing force are both large and the surface of the silica is coated by a layer of carbon black. And after the coating is finished, forming a carbon nano tube coating layer on the surface of the oxidized silicon, wherein the thickness of the coating layer is 80 nanometers, and obtaining the silicon cathode material coated by the carbon nano tube. The coating apparatus is commercially available. The silicon cathode material coated by the nano tube obtained by the coating equipment is powder formed by micron-sized particles, the particle size of the particles is about 5-10 microns, and the silicon cathode material can be used as a lithium ion battery cathode material.
Example 5
500 g of silica powder and 1 g of 9012 double-wall carbon nano tube are put into coating equipment, wherein the double-wall carbon nano tube is a fibrous aggregate with the tube diameter of 4 nanometers, the length of 50 micrometers and the bulk density of 0.02 g/cubic centimeter. The composition and form of the above-mentioned silica are the same as those of example 1. The coating apparatus was started and run at a line speed of 25m/s for 5 minutes. In the operation process of the coating equipment, the double-wall carbon nano tubes are dispersed into a net shape, and the linear velocity and the shearing force are both large, and the surface of the oxidized silica is coated by a layer of carbon black, so that the carbon nano tubes are embedded into the carbon black layer on the surface of the oxidized silica, a carbon nano tube coating layer is formed on the surface of the oxidized silica, the thickness of the coating layer is 50 nanometers, and the silicon cathode material coated by the carbon nano tubes is obtained. The coating apparatus is commercially available. The silicon cathode material coated by the nano tube obtained by the coating equipment is powder formed by micron-sized particles, the particle size of the particles is about 5-10 microns, and the silicon cathode material can be used as a lithium ion battery cathode material.
Example 6
500 g of silica powder and 10.2 g of NTP3023 multi-walled carbon nanotube are put into a coating device, wherein the composition and the form of the silica powder and the multi-walled carbon nanotube are the same as those of example 1. The coating apparatus was started and run at a line speed of 25m/s for 20 minutes. In the operation process of the coating equipment, the multi-walled carbon nanotubes are dispersed into a net shape, and the linear velocity and the shearing force are both large, and the surface of the oxidized silica is coated with a layer of carbon black, so that the carbon nanotubes are embedded into the carbon black layer on the surface of the oxidized silica, a carbon nanotube coating layer is formed on the surface of the oxidized silica, the thickness of the coating layer is 500 nanometers, and the silicon cathode material coated with the carbon nanotubes is obtained. The coating apparatus is commercially available. The silicon cathode material coated by the nano tube obtained by the coating equipment is powder formed by micron-sized particles, the particle size of the particles is about 2-10 microns, and the silicon cathode material can be used as a lithium ion battery cathode material.
Although the present invention has been described with reference to the above embodiments, the scope of the present invention is not limited thereto, and modifications, substitutions and the like of the above members are intended to fall within the scope of the claims of the present invention without departing from the spirit of the present invention.
Claims (7)
1. A method for coating a silicon cathode material with a carbon nano tube is characterized by comprising the following steps:
a. taking the components in a weight ratio of 0.1-2: feeding 99.9-98 parts of carbon nano tube powder and silicon negative electrode material powder into coating equipment;
b. starting coating equipment, and running for 1-20 minutes at a rotating speed of 3-40 m/s to enable the carbon nano tube to form a coating layer on the surface of the silicon cathode material, so as to obtain the silicon cathode material coated by the carbon nano tube;
c. the obtained silicon cathode material coated by the nano tube is powder formed by micron-sized particles, and the particle size of the particles is 2-10 microns.
2. The method of claim 1, wherein the carbon nanotubes are single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, or a mixture of any two.
3. The method of claim 2, wherein the carbon nanotubes are fibrous agglomerates having a tube diameter of 2 to 100 nm, a length of 5 to 50 μm, and a bulk density of 0.01 to 0.1 g/cc.
4. The method of claim 1, wherein the silicon negative electrode material is silica.
5. The method of claim 4, wherein the silica is in the form of particles having a particle size of 2 to 10 microns and a density of 1.1 g/cc.
6. The method of claim 1, wherein the coating has a thickness of 2 nm to 500 nm.
7. The method of claim 1, characterized in that it comprises the following steps:
a. putting carbon nanotube powder and silicon cathode material powder in a weight ratio of 2:98 into coating equipment;
b. starting coating equipment, and running at the rotating speed of 20m/s for 10 minutes to enable the carbon nano tube to form a coating layer on the surface of the silicon cathode material, so as to obtain the silicon cathode material coated by the carbon nano tube;
c. the obtained silicon cathode material coated by the nano tube is powder formed by micron-sized particles, and the particle size of the particles is 2-10 microns.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111622360.1A CN114361427A (en) | 2021-12-28 | 2021-12-28 | Method for coating silicon cathode material with carbon nano tube |
| PCT/CN2022/079205 WO2023123658A1 (en) | 2021-12-28 | 2022-03-04 | Method for coating silicon negative electrode material with carbon nanotubes |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111622360.1A CN114361427A (en) | 2021-12-28 | 2021-12-28 | Method for coating silicon cathode material with carbon nano tube |
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| CN114361427A true CN114361427A (en) | 2022-04-15 |
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| WO (1) | WO2023123658A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114899398A (en) * | 2022-04-20 | 2022-08-12 | 同济大学 | Preparation and application of boron-nitrogen co-doped carbon nanotube coated silicon oxide composite material |
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Cited By (2)
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|---|---|---|---|---|
| CN114899398A (en) * | 2022-04-20 | 2022-08-12 | 同济大学 | Preparation and application of boron-nitrogen co-doped carbon nanotube coated silicon oxide composite material |
| CN114899398B (en) * | 2022-04-20 | 2024-01-26 | 同济大学 | Preparation and application of boron-nitrogen co-doped carbon nanotube coated silicon oxide composite material |
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| WO2023123658A1 (en) | 2023-07-06 |
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