CN113921784A - Negative electrode material and preparation method and application thereof - Google Patents
Negative electrode material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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Images
Classifications
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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
-
- 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
-
- 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
- H01M4/58—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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Abstract
The invention provides a negative electrode material and a preparation method and application thereof. The preparation method comprises the following steps: taking metal as a catalyst, depositing artificial graphite and a low-molecular-weight gas-phase carbon source by adopting a chemical vapor deposition method, and pickling to obtain the negative electrode material; the micromolecular gas-phase carbon source is gas with the number of carbon atoms less than or equal to 4. According to the invention, a quick-charging graphite/carbon nanofiber composite material is formed by adopting metal as a catalyst, a low-molecular-weight gas-phase carbon source as a raw material and a chemical vapor deposition method, so that the capacity is considered, lithium separation of a lithium iron phosphate battery under the condition of quick charging can be avoided, and the problems of quick charging of an electric automobile and high energy density incompatibility are effectively solved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to a negative electrode material, and a preparation method and application thereof, and particularly relates to a negative electrode material in a lithium ion power battery, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, low self-discharge rate, no memory effect and the like, becomes a main driving power supply of a pure electric vehicle, a plug-in electric vehicle and a hybrid electric vehicle, and is also a main energy storage element of a mobile phone, a notebook computer and the like. However, the lithium ion battery has a slow charging speed, and a charging time of several hours is required in a general charging procedure, which causes inconvenience to the use of a pure electric vehicle, a mobile phone, and the like. In order to increase the charging speed of lithium ion batteries, fast charging methods are receiving attention.
At present, research on new energy automobiles is increasing day by day, and with the gradual increase of the quantity of new energy automobiles, more and more users hope that the new energy automobiles can also supplement energy quickly like traditional automobiles, namely, the new energy automobiles can be charged quickly, but the design of the quick charging type material is usually sacrificed by reducing capacity, and meanwhile, the problems of great increase of battery temperature, great battery temperature difference, battery service life attenuation, increase of cooling energy consumption and the like can be caused. Therefore, the method becomes a very important means in the development process of the fast charging field by developing new fast charging materials and optimizing the fast charging strategy.
At present, hard carbon or soft carbon is used for coating the surface of graphite at home and abroad, but the method not only reduces the capacity of a finished product, but also causes the storage performance of the graphite to be poor.
CN105024043A discloses a quick-charging graphite lithium ion battery cathode material and a preparation method thereof. The preparation method of the negative electrode material of the quick-charging graphite lithium ion battery comprises the following steps: (1) mixing, heating, kneading and crushing a mixture containing natural graphite and asphalt; wherein the average particle size D50 of the natural graphite is 5-10 μm, and the mass ratio of the natural graphite to the asphalt is 50: 50-90: 10; (2) carrying out heat treatment at 300-700 ℃ under the protection of inert gas; (3) and (6) graphitizing. In the document, natural graphite is used as a raw material, and the fast charging performance of a graphite negative electrode is improved by means of coating and granulation respectively, but the natural graphite has poor compatibility with an electrolyte, so that the cycle performance is poor, and the application range of the graphite negative electrode is small.
CN109244392A discloses a composite graphite negative electrode material, a preparation method thereof and a lithium ion battery, comprising the following steps: 1) coating a metal oxide layer on the surface of the graphite powder by adopting an atomic layer deposition method; 2) then, uniformly mixing the lithium salt powder with the metal oxide powder, sintering the mixture for 9-12 hours at the temperature of 300-1200 ℃, reacting the metal oxide with the lithium salt to form a lithium ion conductor layer, and enabling the metal oxide and the lithium salt to enter a graphite layered structure to form doping; 3) then washing with water and drying. In the document, the metal oxide is coated on the surface of graphite by an atomic deposition method to improve the rate capability of the graphite, but the existing electrolyte system and the metal oxide have poor wettability, so that the energy density of a battery monomer is low, and the battery monomer cannot be applied on a large scale at present.
Therefore, how to provide a negative electrode material that can achieve both fast charging and no loss of energy density is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a negative electrode material and a preparation method and application thereof. According to the invention, a quick-charging graphite/carbon nanofiber composite material is formed by adopting metal as a catalyst, a low-molecular-weight gas-phase carbon source as a raw material and a chemical vapor deposition method, so that the capacity is considered, lithium separation of a lithium iron phosphate battery under the condition of quick charging can be avoided, and the problems of quick charging of an electric automobile and high energy density incompatibility are effectively solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an anode material, the method comprising:
and (3) taking metal as a catalyst, depositing the artificial graphite and the low-molecular-weight gas-phase carbon source by adopting a chemical vapor deposition method, and pickling to obtain the cathode material.
According to the invention, a quick-charging graphite/carbon nanofiber composite material is formed by adopting metal as a catalyst, a low-molecular-weight gas-phase carbon source as a raw material and a chemical vapor deposition method, so that the capacity is considered, lithium separation of a lithium iron phosphate battery under the condition of quick charging can be avoided, and the problems of quick charging of an electric automobile and high energy density incompatibility are effectively solved.
In the present invention, the metal is used as a catalyst to act as a catalyst, and if a liquid catalyst such as an acid or a base is used, side reactions are increased.
In the present invention, the low molecular weight gas phase carbon source is a gas having a carbon number of 4 or less, and the number of carbon atoms may be 1, 2, 3, or 4, for example.
In the invention, the low molecular weight gas-phase carbon source is more beneficial to preparing the power battery with higher energy density, and if the carbon source with the carbon atom number more than 4 is selected, the power battery with higher energy density is difficult to obtain.
Preferably, the low molecular weight gas phase carbon source comprises methane and/or acetylene.
Preferably, the flow rate of the small molecular weight gas phase carbon source is 400-800 mL/min, such as 400mL/min, 450mL/min, 500mL/min, 550mL/min, 600mL/min, 650mL/min, 700mL/min, 750mL/min or 800 mL/min.
In the invention, the small molecular weight gas-phase carbon source is not easy to improve the productivity because the flow rate is too small, but is not easy to form the graphite/carbon nanofiber composite material because the flow rate is too large.
Preferably, the mass ratio of the metal to the graphite is 1 (10-20), such as 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1: 20.
Preferably, the metal comprises any one or a combination of at least two of copper, nickel, palladium, silver, gold or rhodium.
Preferably, the preparation method of the artificial graphite comprises the following steps:
crushing petroleum coke to obtain single particles, and then carrying out graphitization treatment to obtain the artificial graphite.
In the invention, the petroleum coke is used as a raw material to prepare the artificial graphite, and the obtained artificial graphite has the advantages of capacity and quick charging.
Preferably, the median particle diameter of the single particles is 7 to 20 μm, such as 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm, and the like.
Preferably, the graphitization treatment is performed at a temperature of 2000 to 2800 ℃, for example, 2000 ℃, 2100 ℃, 2200 ℃, 2300 ℃, 2400 ℃, 2500 ℃, 2600 ℃, 2700 ℃, 2800 ℃, or the like.
Preferably, the graphitization treatment time is 10-15 h, such as 10h, 11h, 12h, 13h, 14h or 15 h.
Preferably, the temperature rise rate in the chemical vapor deposition process is 1-20 ℃/min, such as 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min, 15 ℃/min, 16 ℃/min, 17 ℃/min, 18 ℃/min, 19 ℃/min or 20 ℃/min, and the like, preferably 5-10 ℃/min.
According to the invention, the graphite/carbon nanofiber composite material with a good structure can be formed at the temperature rise rate of 1-20 ℃/min, and the temperature rise rate is further optimized to be 5-10 ℃/min, so that the graphite/carbon nanofiber composite material can be formed more favorably.
Preferably, the temperature of the chemical vapor deposition method is 500 to 800 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃.
In the invention, in the chemical vapor deposition process, too high temperature can cause too high energy consumption, and too low temperature is not beneficial to the formation of the graphite/carbon nanofiber composite material.
Preferably, the time of the chemical vapor deposition method is 0.5 to 6 hours, such as 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours.
Preferably, the chemical vapor deposition process is carried out under a protective atmosphere.
Illustratively, the protective atmosphere in the present invention includes, but is not limited to, any one or a combination of at least two of nitrogen, argon, or helium, and the like.
In the invention, the chemical vapor deposition process is carried out in a protective atmosphere, and the graphite/carbon nanofiber composite material with single component can be formed.
Preferably, the acid used in the acid washing is an inorganic acid.
Preferably, the inorganic acid comprises any one of hydrochloric acid, sulfuric acid or nitric acid or a combination of at least two thereof.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) crushing petroleum coke to obtain single particles with the median particle size of 7-20 mu m, and then carrying out graphitization treatment at 2000-2800 ℃ for 10-15 h to obtain artificial graphite;
(2) taking metal as a catalyst, heating the artificial graphite and the low-molecular-weight gas-phase carbon source in the step (1) to 500-800 ℃ at a heating rate of 5-10 ℃/min in a protective atmosphere, depositing for 0.5-6 h by adopting a chemical vapor deposition method, and pickling to obtain the negative electrode material;
the metal comprises any one or a combination of at least two of copper, nickel, palladium, silver, gold and rhodium, the flow of the low-molecular-weight gas-phase carbon source is 400-800 mL/min, and the acid adopted in the acid washing is any one or a combination of at least two of hydrochloric acid, sulfuric acid or nitric acid.
In a second aspect, the present invention provides an anode material, which is prepared by the preparation method of the anode material according to the first aspect, and the anode material is a graphite/carbon nanofiber composite material.
In a third aspect, the invention further provides a lithium ion battery, which includes the negative electrode material according to the second aspect.
Preferably, the lithium ion battery is a lithium ion power battery.
Preferably, the positive electrode material in the lithium ion battery is a lithium iron phosphate positive electrode material.
The cathode material prepared by the invention is matched with the lithium iron phosphate cathode material for use, and is more favorable for safety.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a quick-charging graphite/carbon nanofiber composite material is formed by adopting metal as a catalyst, a low-molecular-weight gas-phase carbon source as a raw material and a chemical vapor deposition method, so that the capacity is considered, lithium separation of a lithium iron phosphate battery under the condition of quick charging is avoided, the problem of incompatibility of quick charging and high energy density of an electric automobile is effectively solved, the energy density of the obtained power battery can reach above 189.9Wh/kg, the battery is charged from 0% SOC to 50% from 3C, from 2.5C to 60% from 2C to 70% from 1.5C to 80% from 2C, and the capacity retention rate can reach above 89.7% after 0.2C discharge cycle for 2000 circles.
Drawings
Fig. 1 is an SEM image of the anode material provided in example 1.
Fig. 2 is a graph of the cycle performance of the battery provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a negative electrode material, and the negative electrode material is a graphite/carbon nanofiber composite material.
The preparation method of the negative electrode material comprises the following steps:
(1) crushing petroleum coke to obtain single particles with the median particle size of 13 mu m, and then carrying out graphitization treatment for 12h at 2400 ℃ to obtain artificial graphite;
(2) taking copper and nickel as catalysts, heating the artificial graphite and methane in the step (1) to 650 ℃ at a heating rate of 5 ℃/min under a helium atmosphere, depositing for 3h by adopting a chemical vapor deposition method, wherein the introduction flow rate of methane is 600mL/min, cooling to room temperature after deposition, and cleaning by using a hydrochloric acid (1mol/L) solution to obtain the cathode material, wherein: the mass ratio of the catalyst (copper and nickel) to the artificial graphite was 1: 15.
Fig. 1 shows an SEM image of the anode material provided in example 1, and as can be seen from fig. 1, the formed graphite/carbon nanofiber composite is structurally intact; fig. 2 shows a cycle performance chart of the battery provided in example 1, and as can be seen from fig. 2(17.4min refers to the time taken for charging from 10% to 80% of the corresponding current), the capacity retention of the material is still 90% after 2000 weeks of cycle, and it can be further inferred that the cycle life of the material can reach more than 3000 weeks (measured by the cycle retention falling below 80% as the battery failure).
Example 2
The embodiment provides a negative electrode material, and the negative electrode material is a graphite/carbon nanofiber composite material.
The preparation method of the negative electrode material comprises the following steps:
(1) crushing petroleum coke to obtain single particles with the median particle size of 20 mu m, and then carrying out graphitization treatment for 10h at 2800 ℃ to obtain artificial graphite;
(2) taking gold as a catalyst, heating the artificial graphite and acetylene in the step (1) to 800 ℃ at a heating rate of 10 ℃/min under a helium atmosphere, depositing for 1h by adopting a chemical vapor deposition method, wherein the introducing flow of acetylene is 500mL/min, cooling to room temperature after deposition is finished, and cleaning by using a sulfuric acid (1mol/L) solution to obtain the cathode material, wherein: the mass ratio of the catalyst (gold) to the artificial graphite is 1: 10.
Example 3
The embodiment provides a negative electrode material, and the negative electrode material is a graphite/carbon nanofiber composite material.
The preparation method of the negative electrode material comprises the following steps:
(1) crushing petroleum coke to obtain single particles with the median particle size of 7 mu m, and then carrying out graphitization treatment for 15h at 2000 ℃ to obtain artificial graphite;
(2) taking palladium and silver as catalysts, heating the artificial graphite and methane in the step (1) to 500 ℃ at a heating rate of 8 ℃/min under an argon atmosphere, depositing for 6h by adopting a chemical vapor deposition method, wherein the introducing flow of the methane is 800mL/min, cooling to room temperature after deposition is finished, and cleaning by using a nitric acid (1mol/L) solution to obtain the cathode material, wherein: the mass ratio of the catalyst (palladium and silver) to the artificial graphite was 1: 20.
Example 4
The present example is different from example 1 in that the temperature increase rate in step (2) of the present example is 1 ℃/min.
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
The present example is different from example 1 in that the temperature increase rate in step (2) of the present example is 20 ℃/min.
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
The difference between this example and example 1 is that the deposition temperature in step (2) of this example is 900 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 7
The difference between this example and example 1 is that the deposition temperature in step (2) of this example is 400 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The comparative example differs from example 1 in that the catalyst of step (2) in the comparative example is MnO2。
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 2
This comparative example differs from example 1 in that methane was replaced by pentane in step (2) of this comparative example.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 3
The comparative example is different from example 1 in that methane is replaced by a phenolic resin in the step (2) in the comparative example, and the preparation method comprises the following steps:
in the comparative example, the step (1) is consistent with the step (1), the obtained petroleum coke single particles and phenolic resin are mixed and stirred, and after uniform mixing, the mixture is transferred into a crucible and carbonized at 900 ℃ for 12 hours to obtain the hard carbon coated graphite cathode.
The negative electrode materials prepared in examples 1 to 7 and comparative examples 1 to 3, CMC (sodium carboxymethylcellulose), SBR (styrene butadiene rubber) and SP (conductive carbon black) are prepared into a negative electrode plate according to the mass ratio of 95.5:2.0:1.5:1, and a lithium iron phosphate positive electrode is prepared into a positive electrode plate, and the soft package battery is prepared in a lamination mode.
Carrying out formation-capacity grading on the batteries provided in the examples 1 to 7 and the comparative examples 1 to 3 to obtain specific discharge capacity and first effect; the batteries provided in examples 1 to 7 and comparative examples 1 to 3 were charged from 0% SOC to 50%, 2.5C to 60%, 2C to 70%, and 1.5C to 80% from 3C, and then discharged at 0.2C to obtain the cycle capacity retention rates, the results of which are shown in table 1, and the energy densities of which are also shown in table 1;
TABLE 1
From the data results of example 1 and examples 4 and 5, it is clear that the electrochemical performance is good, but on the other hand, the temperature rise rate is too low, which is favorable for growing the graphite/carbon nanofiber composite material with a good structure, but is not favorable for improving the productivity, and the temperature rise rate is too high, which is not favorable for forming the graphite/carbon nanofiber composite material.
From the data results of example 1 and examples 6 and 7, it can be seen that the electrochemical performance is good, however, from the practical use point of view, the temperature during the vapor deposition process is too high, which is not favorable for the subsequent temperature reduction and cost control, and the temperature is too low, which cannot realize the formation of the graphite/carbon nanofiber composite.
As is clear from the data results of example 1 and comparative example 1, the use of a non-metal catalyst is not favorable for the reaction.
From the data results of example 1 and comparative example 2, it is understood that when the number of C atoms in the carbon source is more than 4, it is difficult to obtain a power battery having a high energy density.
From the data results of example 1 and comparative example 3, it can be seen that compared with the conventional hard carbon-coated graphite anode material, the anode material provided by the invention not only has better fast charging performance, but also has capacity at the same time.
In conclusion, the invention adopts metal as a catalyst, a low-molecular-weight gas-phase carbon source as a raw material and a chemical vapor deposition method to form a quick-charging graphite/carbon nanofiber composite material, not only is the capacity considered, but also lithium separation of a lithium iron phosphate battery can be avoided under the condition of quick charging, the problem of incompatibility of quick charging and high energy density of an electric automobile is effectively solved, the energy density of the obtained power battery can reach above 189.9Wh/kg, the battery can be charged from 0% SOC to 50% from 3C, from 2.5C to 60%, from 2C to 70% and from 1.5C to 80%, and the capacity retention rate can reach above 89.7% after 0.2C discharge cycle of 2000 circles.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a negative electrode material is characterized by comprising the following steps:
taking metal as a catalyst, depositing artificial graphite and a low-molecular-weight gas-phase carbon source by adopting a chemical vapor deposition method, and pickling to obtain the negative electrode material;
wherein the micromolecular gas-phase carbon source is gas with the number of carbon atoms less than or equal to 4.
2. The method for producing the anode material according to claim 1, wherein the low-molecular-weight gas-phase carbon source includes methane and/or acetylene;
preferably, the flow rate of the small molecular weight gas-phase carbon source is 400-800 mL/min.
3. The preparation method of the anode material is characterized in that the mass ratio of the metal to the artificial graphite is 1 (10-20).
4. The method for producing an anode material according to claim 1 or 3, wherein the metal includes any one of copper, nickel, palladium, silver, gold, or rhodium or a combination of at least two of them.
5. The method for preparing the anode material according to claim 1 or 3, wherein the method for preparing the artificial graphite comprises:
crushing petroleum coke to obtain single particles, and then carrying out graphitization treatment to obtain artificial graphite;
preferably, the median particle diameter of the single particles is 7-20 μm;
preferably, the temperature of the graphitization treatment is 2000-2800 ℃;
preferably, the graphitization treatment time is 10-15 h.
6. The method for preparing the negative electrode material according to any one of claims 1 to 5, wherein the temperature rise rate in the chemical vapor deposition method is 1 to 20 ℃/min, preferably 5 to 10 ℃/min;
preferably, the temperature of the chemical vapor deposition method is 500-800 ℃;
preferably, the time of the chemical vapor deposition method is 0.5-6 h;
preferably, the chemical vapor deposition process is carried out under a protective atmosphere.
7. The method for producing the anode material according to any one of claims 1 to 6, wherein an acid used in the acid washing is an inorganic acid;
preferably, the inorganic acid is any one of hydrochloric acid, sulfuric acid or nitric acid or a combination of at least two of them.
8. The method for producing the anode material according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) crushing petroleum coke to obtain single particles with the median particle size of 7-20 mu m, and then carrying out graphitization treatment at 2000-2800 ℃ for 10-15 h to obtain artificial graphite;
(2) taking metal as a catalyst, heating the artificial graphite and the low-molecular-weight gas-phase carbon source in the step (1) to 500-800 ℃ at a heating rate of 5-10 ℃/min in a protective atmosphere, depositing for 0.5-6 h by adopting a chemical vapor deposition method, and pickling to obtain the negative electrode material;
the metal comprises any one or a combination of at least two of copper, nickel, palladium, silver, gold and rhodium, the flow of the low-molecular-weight gas-phase carbon source is 400-800 mL/min, and the acid adopted in the acid washing is any one or a combination of at least two of hydrochloric acid, sulfuric acid or nitric acid.
9. An anode material prepared by the method for preparing the anode material according to any one of claims 1 to 8, wherein the anode material is a graphite/carbon nanofiber composite material.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the negative electrode material of claim 9;
preferably, the lithium ion battery is a lithium ion power battery;
preferably, the positive electrode material in the lithium ion battery is a lithium iron phosphate positive electrode material.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2205767A1 (en) * | 1996-05-23 | 1997-11-23 | Sharp Kabushiki Kaisha | Nonaqueous secondary battery and a method of manufacturing a negative electrode active material |
| CN1789120A (en) * | 2004-12-14 | 2006-06-21 | 中国科学院物理研究所 | Carbon wool ball material and its preparation method and uses |
| CN1812168A (en) * | 2005-01-26 | 2006-08-02 | 中国科学院金属研究所 | Modified method for lithium ion cell negative electrode material |
| CN101106192A (en) * | 2006-07-14 | 2008-01-16 | 锦湖石油化学株式会社 | Anode active material hybridizing carbon nano fibers for lithium secondary battery |
| CN101969112A (en) * | 2010-09-30 | 2011-02-09 | 湛江市聚鑫新能源有限公司 | Anode material and cathode material for lithium ion battery and modifying method thereof |
| CN102299308A (en) * | 2011-09-03 | 2011-12-28 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery cathode material, and preparation method and lithium ion battery thereof |
| CN103199254A (en) * | 2013-04-03 | 2013-07-10 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite negative material of lithium-ion battery and preparation method of negative material |
| CN106507692A (en) * | 2014-05-08 | 2017-03-15 | Sei株式会社 | Lithium secondary battery |
| JP2017054815A (en) * | 2015-09-11 | 2017-03-16 | Ｊｆｅケミカル株式会社 | Carbon material for lithium ion secondary battery negative electrode, manufacturing method thereof, lithium ion secondary battery negative electrode, and lithium ion secondary battery |
| CN108807996A (en) * | 2018-08-17 | 2018-11-13 | 东莞市凯金新能源科技股份有限公司 | A kind of preparation method and material of high magnification fast charge graphite cathode material |
| CN111620331A (en) * | 2020-05-29 | 2020-09-04 | 湖北亿纬动力有限公司 | Artificial graphite negative electrode material, preparation method thereof and application thereof in lithium ion battery |
| CN112875697A (en) * | 2021-02-02 | 2021-06-01 | 广东凯金新能源科技股份有限公司 | High-energy-density low-temperature quick-charging artificial graphite material and preparation method thereof |
-
2021
- 2021-09-29 CN CN202111149905.1A patent/CN113921784A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2205767A1 (en) * | 1996-05-23 | 1997-11-23 | Sharp Kabushiki Kaisha | Nonaqueous secondary battery and a method of manufacturing a negative electrode active material |
| CN1789120A (en) * | 2004-12-14 | 2006-06-21 | 中国科学院物理研究所 | Carbon wool ball material and its preparation method and uses |
| CN1812168A (en) * | 2005-01-26 | 2006-08-02 | 中国科学院金属研究所 | Modified method for lithium ion cell negative electrode material |
| CN101106192A (en) * | 2006-07-14 | 2008-01-16 | 锦湖石油化学株式会社 | Anode active material hybridizing carbon nano fibers for lithium secondary battery |
| CN101969112A (en) * | 2010-09-30 | 2011-02-09 | 湛江市聚鑫新能源有限公司 | Anode material and cathode material for lithium ion battery and modifying method thereof |
| CN102299308A (en) * | 2011-09-03 | 2011-12-28 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery cathode material, and preparation method and lithium ion battery thereof |
| CN103199254A (en) * | 2013-04-03 | 2013-07-10 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite negative material of lithium-ion battery and preparation method of negative material |
| CN106507692A (en) * | 2014-05-08 | 2017-03-15 | Sei株式会社 | Lithium secondary battery |
| JP2017054815A (en) * | 2015-09-11 | 2017-03-16 | Ｊｆｅケミカル株式会社 | Carbon material for lithium ion secondary battery negative electrode, manufacturing method thereof, lithium ion secondary battery negative electrode, and lithium ion secondary battery |
| CN108807996A (en) * | 2018-08-17 | 2018-11-13 | 东莞市凯金新能源科技股份有限公司 | A kind of preparation method and material of high magnification fast charge graphite cathode material |
| CN111620331A (en) * | 2020-05-29 | 2020-09-04 | 湖北亿纬动力有限公司 | Artificial graphite negative electrode material, preparation method thereof and application thereof in lithium ion battery |
| CN112875697A (en) * | 2021-02-02 | 2021-06-01 | 广东凯金新能源科技股份有限公司 | High-energy-density low-temperature quick-charging artificial graphite material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114975974A (en) * | 2022-07-11 | 2022-08-30 | 焦作聚能能源科技有限公司 | High-energy-density graphite composite material, preparation method thereof and lithium ion battery |
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