CN112713271B - Modified graphite material, preparation method thereof, lithium ion battery and application - Google Patents
Modified graphite material, preparation method thereof, lithium ion battery and application Download PDFInfo
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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
- H01M4/58—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention discloses a modified graphite material, a preparation method thereof, a lithium ion battery and application. The preparation method of the modified graphite material comprises the following steps: mixing and granulating graphite particles and a coating material to obtain a precursor; sequentially carrying out carbonization treatment, acid washing and drying on the precursor to obtain a modified graphite material; the mass ratio of the graphite particles to the coating material is 100 (1-8); the coating material comprises a soft carbon material and an organic acid metal salt, and the mass ratio of the soft carbon material to the organic acid metal salt is 1: (0.1-10). The modified graphite material has uniform particle size and higher specific surface area, and after the modified graphite material is used for a lithium ion battery, the battery has higher first discharge efficiency and discharge capacity and good battery stability, and the capacity retention rate of the battery is still higher (more than 83.6%) after the battery is circulated for 500 weeks at 1C/1C; the multiplying power performance is good, and the constant current ratio at 3C is still more than 11.3 percent.
Description
Technical Field
The invention relates to a modified graphite material, a preparation method thereof, a lithium ion battery and application.
Background
A lithium ion battery is a battery that operates by movement of lithium ions between a positive electrode and a negative electrode, has many advantages of high energy density, long cycle life, small self-discharge, no memory effect, environmental friendliness, and the like, and has been widely used in the field of consumer electronics. Meanwhile, with the development of the automobile industry and the requirement of environmental friendliness, the lithium ion battery begins to show the head in the field of pure electric vehicles, hybrid electric vehicles and extended-range electric passenger cars, and the share of the electric vehicles in the whole automobile market is gradually increased. Meanwhile, the continuous development in the field of electric vehicles puts higher demands on the endurance mileage (i.e., the capacity of the battery), the rate charge/discharge capacity, the service life, and the like of the lithium ion battery.
The lithium ion battery mainly comprises four parts, namely a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the capacity, the multiplying power charge-discharge capacity, the service life and the like of the lithium ion battery are closely related to a negative electrode material, so that the negative electrode material is often required to be modified to realize the regulation and optimization of the negative electrode material in order to ensure that the lithium ion battery has better electrochemical performance. The existing modification modes generally comprise: coating, blending, special shape design, doping and the like, wherein coating modification is an effective way for improving electrochemical comprehensive performance and stability of the material, and is worthy of intensive research.
Chinese patent document CN101582503A discloses a negative electrode material of a lithium ion battery with graphite coated with asphalt and a preparation method thereof, wherein asphalt is used for coating the surface of a natural graphite sphere, a mixed solution of asphalt and washing oil and the spheroidized natural graphite are uniformly mixed according to a certain mass ratio, the prepared mixed solution is filtered at normal temperature, the obtained filter cake is dried, carbonized and graphitized under a protective atmosphere, and finally, the obtained product is crushed and graded to obtain the coated graphite. The negative electrode material is simple to produce, and the product has high cost performance, but after the lithium ion battery prepared by the negative electrode material is cycled for 300 times, the capacity retention rate is only 88.3%, and the application range is limited.
Chinese patent document CN106495143A discloses a preparation method of a modified graphite negative electrode material for a lithium ion battery, which comprises the steps of crushing and mixing graphite and asphalt, and performing heat treatment to obtain asphalt-coated graphite precursor powder; coating the pitch-coated graphite precursor powder in N2And (3) carrying out high-temperature heat treatment under protection, naturally cooling, mixing with a phenolic resin diluted solution, filtering, drying, curing, carbonizing, and grading to obtain the modified lithium ion battery graphite cathode material. TheThe method needs to be mixed with asphalt and phenolic resin in sequence, and the control is strict, so the operation is complex and the industrial production is difficult to realize; and the first discharge efficiency is only 90% at most, which is relatively low.
Therefore, there is a need for an electrode material that is beneficial for improving the rate capability, capacity, first discharge rate and capacity retention rate of lithium ion batteries.
Disclosure of Invention
The invention aims to overcome the defects that a lithium ion battery in the prior art cannot simultaneously have high electric capacity, high first discharge efficiency, good rate capability and high capacity retention rate, and provides a modified graphite material, a preparation method thereof, the lithium ion battery and application thereof.
The invention solves the technical problems through the following technical scheme:
a preparation method of a modified graphite material comprises the following steps:
(1) mixing and granulating graphite particles and a coating material to obtain a precursor;
(2) sequentially carrying out carbonization treatment, acid washing and drying on the precursor to obtain a modified graphite material;
the mass ratio of the graphite particles to the coating material is 100 (1-8);
the coating material comprises a soft carbon material and an organic acid metal salt, and the mass ratio of the soft carbon material to the organic acid metal salt is 1: (0.1-10).
In the step (1), the median diameter of D50 of the graphite particles is preferably 6 to 10 μm, for example, 9.6 μm.
In step (1), the graphite particles may be artificial graphite particles and/or natural graphite particles, preferably artificial graphite particles, which are conventional in the art.
The artificial graphite particles may be uncoated artificial graphite particles or primary coated artificial graphite particles, preferably primary coated artificial graphite particles, which are conventional in the art.
The uncoated synthetic graphite particles may be commercially available or may be prepared according to conventional methods in the art. Preferably, the method for preparing the uncoated artificial graphite particles comprises the following steps: the carbon raw material is subjected to heat treatment and graphitization treatment.
The carbonaceous feedstock may be conventional in the art, such as one or more of carbon fiber, pyrolytic carbon, graphite foam, coal needle coke, and petroleum coke. The carbonaceous feedstock is preferably petroleum coke and/or coal needle coke, more preferably petroleum coke, such as petroleum coke available from the national branch of oil and gas, ltd. The S (sulfur) content in the petroleum coke or the coal needle coke is preferably less than or equal to 0.45 percent. The ash content in the petroleum coke or the coal needle coke is preferably less than or equal to 0.2 percent. The moisture in the petroleum coke or the coal needle coke is preferably less than or equal to 0.65 percent. The volatile content in the petroleum coke or the coal needle coke is preferably less than or equal to 7.1 percent.
Before the heat treatment, preferably, the carbonaceous raw material is sequentially crushed, shaped and finely powdered to obtain a shaped material. The crushed material obtained after crushing can have a D50 median particle size of 6.0-10.0 μm, for example 6.5 μm. Preferably, the D50 median particle size of the shaping material is 5.5-12.0 μm, such as 6.8 μm. The comminution process may be a process conventionally practiced in the art, such as by roll milling. The shaping and the de-powdering process may be operations conventional in the art, for example by a shaping machine.
The temperature of the heat treatment may be conventional in the art, for example 550 to 850 ℃, for example 700 ℃. The equipment for the heat treatment may be conventional in the art, for example a horizontal reactor. The heat treatment time may be conventional in the art, for example 6 to 20 hours, for example 8 hours.
The graphitization treatment temperature can be conventional in the art, such as 2800-3200 ℃, such as 3000 ℃. The graphitization treatment time may be conventional in the art, for example 20 to 60 hours, for example 30 hours.
Preferably, the preparation method of the primary-coated artificial graphite particles comprises the following steps: and sequentially coating and carbonizing the uncoated artificial graphite particles. The process of coating may be conventional in the art, for example the coating may be carried out by a fusion machine. In the coating process, the rotation speed of the fusion machine is preferably 200 to 1500r/min, such as 280 r/min. The coating agent employed in the coating may be conventional in the art, such as coal tar, again, for example, coal tar available from new energy limited, dongri, dongshan. In the coating process, the mass ratio of the coating agent to the uncoated artificial graphite particles is (2-6): 100, e.g. 4: 100. the coking value of the coating agent can be conventional in the field, and is preferably 10-30%. The coating time can be 10-70 min, for example 20 min.
The equipment for the carbonization treatment may be conventional in the art, such as a calciner. The temperature of the carbonization treatment may be conventional in the art, and is preferably 950 ℃ to 1350 ℃, for example 1250 ℃.
In a preferred embodiment, the uncoated artificial graphite particles and the coal tar are coated according to a mass ratio of 100:4, and are carbonized at 1250 ℃, so that the D50 median diameter of the primary coated artificial graphite particles is 9.6 mu m.
In the present invention, the soft carbon material may be conventional in the art, such as petroleum residuum or asphalt, preferably asphalt, such as asphalt available from the division, mallow, china oil and gas, ltd. Wherein the softening point of the asphalt is generally 110-130 ℃. The organic acid metal salt may be an organic acid metal salt conventional in the art, such as magnesium acetate or magnesium citrate, preferably magnesium citrate. The mass ratio of the soft carbon material to the organic acid metal salt is preferably (1:9) to (5:1), more preferably (1:7) to (3:1), for example, 1:5, 1:3, or 1: 1.
In a preferred embodiment, the coating material comprises bitumen and magnesium citrate; the mass ratio of the magnesium citrate to the asphalt is 1:9, or 1:7, or 1:5, or 1:3, or 1:1, or 3:1, or 5: 1.
in a preferred embodiment, the coating material comprises asphalt and magnesium acetate; the mass ratio of the magnesium acetate to the asphalt is 1: 9.
In the step (1), the preparation method of the coating material may include the steps of: the soft carbon material may be mixed with the organic acid metal salt. Wherein the mixing temperature of the soft carbon material and the organic acid metal salt may be 50 to 150 ℃. The mixing time of the soft carbon material and the organic acid metal salt may be 20 to 60min, for example, 50 min. The mixing of the soft carbon material with the metal salt of an organic acid is generally carried out by a mixer. The compounder may be a compounder conventional in the art, such as a CDLW-8000 ribbon blender. During the mixing process of the soft carbon material and the organic acid metal salt, the rotating speed of the mixer can be 200-800 r/min, such as 500 r/min.
In the step (1), preferably, the mass ratio of the graphite particles to the coating material is 100: (5-8).
In a preferred embodiment, the mass ratio of the graphite particles to the coating material is 20:1, wherein the graphite particles are primary coated artificial graphite particles, and the coating material comprises magnesium citrate and asphalt in a mass ratio of 1: 9.
In step (1), the mixing process may be conventional in the art, for example, mixing by a fusion machine. The mixing time can be 30-80 min, such as 60 min.
In the step (1), the granulation process may be conventional in the art, for example, granulation is performed by a horizontal kettle, a vertical kettle, or an electrically heated high-speed modifying and mixing coating machine, preferably by an electrically heated high-speed modifying and mixing coating machine. The granulation temperature is preferably 500 to 700 ℃, more preferably 630 to 670 ℃. The granulation time can be 3-20 h. Preferably, the D50 median particle size of the product obtained after granulation is 9.0-15.0 μm, such as 9.8 μm.
In step (2), the equipment for the carbonization treatment may be conventional in the art, such as a calciner. The temperature of the carbonization treatment can be conventional in the art, and is preferably 700-1350 ℃, for example 1250 ℃.
In step (2), the acid used in the acid washing may be an acid that dissolves the metal oxide, such as dilute hydrochloric acid or dilute sulfuric acid, which are conventional in the art. The concentration of the acid can be 0.01-1 mol/L. In the pickling process, the mass ratio of the acid to the object to be pickled is preferably (4-10): 1. In the acid washing process, the mixing speed of the acid and the object to be washed by acid can be 200-1000 r/min, such as 800 r/min. In the acid washing process, the mixing time of the acid and the object to be washed by acid can be 30-120 min, such as 30 min.
In the step (2), preferably, a step of washing with water is further included after the acidity. The water wash may be a process conventional in the art, such as washing to neutrality with deionized water.
In step (2), the drying may be a process conventional in the art, such as suction filtration followed by drying. The drying temperature can be 90-120 ℃. The drying time can be 6-12 h, such as 10 h.
The invention also provides a modified graphite material which is prepared according to the preparation method.
Wherein the modified graphite material preferably satisfies the following criteria: the tap density is 0.98-1.25 g/cm3The D50 median particle size is 10.1-12.5 μm, the D50 particle size distribution range is 0.5-45.26 μm, and the specific surface area is 2.87-3.7 m2The density of the particles is 1.61-1.8 g/cm3(ii) a More preferably: the distribution range of the D50 particle size is 0.9-40 μm.
The invention also provides a modified graphite material, which is of a core-shell structure, wherein the core in the core-shell structure is graphite particles, the shell layer in the core-shell structure contains carbon element, and the content of the carbon element is more than 99.99%;
the thickness of the shell layer is 0.5-mum;
the mass ratio of the carbon element in the shell layer to the graphite particles is (2.5-6): 100.
In the present invention, the thickness of the shell layer is preferably 1 to 2.5 μm, such as 1.6 μm, 1.7 μm, 2.2 μm, 1.8 μm, 2.1 μm, 1.9 μm, 2 μm or 2.8 μm;
in the present invention, the mass ratio of the carbon element in the shell layer to the graphite particles is preferably (3-6): 100, for example, 3.31:100, 3.22:100, 3.15:100, 3.1:100, 3.06:100, 3.01:100, 3.17:100, 3.27:100, 3.22:100, 3.18:100, or 5.78: 100.
In the present invention, the shell layer generally further contains impurity elements such as one or more of Na, Mg, Al, Si, S, K, Ca, Ti, V, Cr, Mn, Ni, Fe, Cu and Zn.
The content of Fe in the shell is preferably 50ppm or less, more preferably 20ppm or less, and still more preferably 17ppm or less, for example, 4.60ppm, 6.10ppm, 6.00ppm, 7.50ppm, 10.00ppm, 16.30ppm, 8.30ppm, 7.80ppm, 6.90ppm, 7.10ppm, or 7.70.
Wherein the Ni content in the shell layer is preferably 50ppm or less, more preferably 5ppm or less, such as 2.70ppm, 3.10ppm, 2.80ppm, 2.50ppm, 3.80ppm, 2.80ppm, 2.90ppm, 3.50ppm, 2.80ppm, 3.00ppm or 3.50 ppm.
The Mn content in the shell layer is preferably 50ppm or less, more preferably 0.5ppm or less, for example, 0.38ppm, 0.07ppm, 0ppm, 0.33ppm, 0.37ppm, 0.40ppm, 0.25ppm, 0.27ppm or 0.48 ppm.
The invention also provides application of the modified graphite material in a lithium ion battery.
The invention also provides a lithium ion battery, and the electrode material of the lithium ion battery comprises the modified graphite material.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1) the modified graphite material has uniform particle size and higher specific surface area;
2) after the modified graphite material is used as an electrode material of a lithium ion battery, the first discharge efficiency and the discharge capacity of the battery are high and can respectively reach 93.1 percent and 358.9 mAh/g;
3) after the modified graphite material is used as a lithium ion battery, the battery stability is good, and the capacity retention rate after 500 weeks of circulation at 1C/1C is still high (more than 83.6%); the multiplying power performance is good, and the constant current ratio at 3C is still more than 11.3 percent.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a modified graphite material according to example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples:
the petroleum coke is purchased from Jinzhou branch of China Petroleum and Natural gas Co., Ltd, and mainly comprises carbon atoms and hydrogen atoms, the moisture content is 0.65%, the ash content is 0.2%, the volatile matter is 7.1%, and the S content is less than or equal to 0.45%.
The asphalt is purchased from the Jinzhou branch of China Petroleum and Natural gas Co., Ltd, and has a softening point of 110-130 ℃.
The coal tar is purchased from New energy Limited company of Dongri of Tangshan, and the coking value is 20-30%.
Example 1
The preparation method of the soft and hard carbon-coated graphite negative electrode material of the embodiment specifically comprises the following steps:
(1) preparation of one-step coated artificial graphite particles
Grinding and crushing petroleum coke by a roller, wherein the median particle size D50 of the crushed material is 6.5 mu m, and shaping to remove fine powder, so that the median particle size D50 of the obtained shaped material is 6.8 mu m; carrying out heat treatment on the shaping material in a horizontal reaction kettle under the protection of inert gas, wherein the temperature is 700 ℃, and the time is 8 hours; then, graphitizing the heat-treated material at 3000 ℃ for 30h to obtain uncoated artificial graphite particles; then coating the uncoated artificial graphite particles in a fusion machine, wherein the rotating speed of the fusion machine is 280r/min, the time is 20min, the coating agent is coal tar, and the mass ratio of the uncoated artificial graphite particles to the coal tar is 100: 4; finally, heating the granulated material in a calcining device for carbonization treatment, keeping the temperature at 1250 ℃ for 12 hours to obtain primary coated artificial graphite particles, wherein the median particle size of D50 is 9.6 mu m;
(2) preparation of the coating Material
Uniformly mixing magnesium citrate and asphalt in a CDLW-8000 ribbon mixer, wherein the ratio of the magnesium citrate: the mass ratio of the asphalt is equal to 1:9, and the mixing time is 50 minutes; the rotating speed of the mixer is 500 r/min;
(3) preparation of modified graphite material
Putting the primary coated artificial graphite particles in the step (1) and the coating material in the step (2) into a fusion machine according to the ratio of 20:1, mixing for 60 minutes at the speed of 40hz/min, adding the mixture into a Jianuo SHR high-speed mixer, and performing high-speed modified mixing at the granulation temperature of 630 ℃ for 3 hours; then under the protection of inert gas, heating in a calcining furnace for carbonization treatment, keeping the temperature at 1250 ℃ for 12 hours to obtain a granulated graphite material, wherein the median particle size D50 is 9.8 mu m;
mixing and stirring the granulated graphite material and hydrochloric acid solution with the concentration of 0.01mol/L, wherein the mass ratio of the granulated graphite material to the hydrochloric acid solution is 10:1, the stirring speed is 800r/min, and the stirring time is 30min, so as to obtain graphite slurry; and (3) carrying out suction filtration on the graphite slurry through a suction filtration device, and then drying at 90 ℃ for 10h to obtain the modified graphite material. Wherein the D50 median diameter is 12.1 μm, the particle diameter distribution range is 0.78-22.8 μm, and the tap density is 0.98g/cm3Specific surface area of 3.3m2/g。
Example 2
The present embodiment is different from embodiment 1 in that: in the step (2), the mass ratio of the magnesium citrate to the asphalt is 1: 7. The modified graphite material of this example had a D50 median particle size of 11.2 μm, a particle size distribution of 0.98-43.5 μm, and a tap density of 1.07g/cm3The specific surface area is 3.39m2/g。
Example 3
This example and implementationExample 1 differs in that: in the step (2), the mass ratio of the magnesium citrate to the asphalt is 1: 5. The modified graphite material of this example had a D50 median particle size of 11.3 μm, a particle size distribution range of 0.96-41.7 μm, and a tap density of 1.1g/cm3Specific surface area of 3.7m2/g。
Example 4
The present embodiment is different from embodiment 1 in that: in the step (2), the mass ratio of the magnesium citrate to the asphalt is 1: 3. The modified graphite material of this example had a D50 median particle size of 11.8 μm, a particle size distribution in the range of 0.97 to 39.4 μm, and a tap density of 1.13g/cm3Specific surface area of 3.52m2/g。
Example 5
The present embodiment is different from embodiment 1 in that: in the step (2), the mass ratio of the magnesium citrate to the asphalt is 1: 1; the modified graphite material of this example had a D50 median particle size of 11.4 μm, a particle size distribution in the range of 0.91-38.8 μm, and a tap density of 1.18g/cm3The specific surface area is 3.68m2/g。
Example 6
The present embodiment is different from embodiment 1 in that: in the step (2), the mass ratio of the magnesium citrate to the asphalt is 3: 1; the modified graphite material of this example had a D50 median particle size of 11.7 μm, a particle size distribution range of 0.90-40.5 μm, and a tap density of 1.09g/cm3Specific surface area of 3.15m2/g。
Example 7
The present embodiment is different from embodiment 1 in that: in the step (2), the mass ratio of the magnesium citrate to the asphalt is 5: 1; the modified graphite material of this example had a D50 median particle size of 11.5 μm, a particle size distribution of 0.90-36.9 μm, and a tap density of 1.21g/cm3Specific surface area of 3.01m2/g。
Example 8
Example 8 differs from example 1 in that: the temperature of the carbonization treatment in the step (3) is 700 ℃. The D50 median particle diameter of the modified graphite material in this comparative example was 11.4. mu.m, the particle size distribution range was 0.94-41.1. mu.m, and the tap density was 1.08g/cm3Specific surface area of 3.17m2/g。
Example 9
The present embodiment is different from embodiment 1 in that: the graphite particles selected in the step (1) are uncoated artificial graphite single particles (10.4 mu m of D50) purchased from Neptune graphite; the modified graphite material of this example had a D50 median particle size of 15.6 μm, a particle size distribution in the range of 2.31-31.5 μm, and a tap density of 1.21g/cm3Specific surface area of 1.86m2/g。
Example 10
The present embodiment is different from embodiment 1 in that: the graphite particles selected in the step (1) are natural graphite single particles (10.4 mu m is D50) purchased from the Xingxcheng graphite on the net; the modified graphite material of this example had a D50 median particle size of 13.2 μm, a particle size distribution range of 5.34-40.2 μm, and a tap density of 2.33g/cm3Specific surface area of 1.81m2/g。
Example 11
The present embodiment is different from embodiment 1 in that: and (3) replacing magnesium citrate and asphalt with magnesium acetate and asphalt in the step (2). The D50 median particle size of the modified graphite material in this example was 12.4. mu.m, the particle size distribution ranged from 0.96-41.7 μm, the tap density was 1.1g/cm3, and the specific surface area was 2.75m2/g。
Comparative example 1
Comparative example 1 differs from example 1 in that: and (4) changing the mass ratio of the artificial graphite particles coated once in the step (3) to the coating material into 10: 1. The modified graphite material of this example had a D50 median particle size of 13.4 μm, a particle size distribution in the range of 1.08-45.7 μm, and a tap density of 1.16g/cm3Specific surface area of 3.6m2/g。
Comparative example 2
Comparative example 1 differs from example 1 in that: and (4) changing the mass ratio of the artificial graphite particles coated once in the step (3) to the coating material into 50: 1. The D50 median particle size of the modified graphite material in this comparative example was 10.3 μm, the particle size distribution range was 0.80-38.8 μm, and the tap density was 1.31g/cm3A specific surface area of 3.07m2/g。
Comparative example 3
Comparative example 3 differs from example 1 in that: in the step (3), the mixture of the primary coated artificial graphite particles and the coating material is directly carbonized without a granulation process. The D50 median particle size of the modified graphite material in this comparative example was 10.8 μm, the particle size distribution range was 0.95-40.9 μm, and the tap density was 1.07g/cm3Specific surface area of 2.87m2/g。
Comparative example 4
Comparative example 4 differs from example 1 in that: in the step (2), asphalt and phenolic resin are selected as coating agents to coat the graphite single particles. The D50 median particle size of the modified graphite material in this comparative example was 15.3 μm, the particle size distribution range was 0.94-70.2 μm, and the tap density was 0.98g/cm3Specific surface area of 3.12m2/g。
Comparative example 5
Comparative example 5 differs from example 1 in that: and (4) the pickling process is cancelled in the step (3). The D50 median particle size of the modified graphite material in this comparative example was 12.4 μm, the particle size distribution range was 1.24-41.1. mu.m, and the tap density was 1.01g/cm3Specific surface area of 2.13m2/g。
Effects of the embodiment
1. Detection of shell elements of modified graphite materials
According to the conventional detection method in the field, the XRF detection is performed on the examples 1 to 11 and the comparative examples 1 to 5 by using an HD Prime desktop high-definition X-ray fluorescence spectrometer, and the detection results are shown in the following table 1 (the content units of other elements except C are ppm):
TABLE 1
| Na | Mg | Al | Si | S | K | Ca | Ti | V | Cr | Mn | Fe | Ni | Cu | Zn | C(％) | |
| Example 1 | 2.80 | 1.15 | 0.65 | 3.70 | 20.60 | 0.34 | 7.80 | 2.75 | 2.14 | 0.27 | 0.38 | 4.60 | 2.70 | 0.60 | 0.60 | 99.9964 |
| Example 2 | 0.72 | 1.53 | 1.67 | 0 | 4.57 | 0.48 | 5.02 | 3.35 | 2.23 | 0.20 | 0.07 | 6.10 | 3.10 | 0.50 | 0.60 | 99.9964 |
| Example 3 | 1.36 | 1.54 | 3.01 | 0 | 4.34 | 0.44 | 4.82 | 3.71 | 2.58 | 0.00 | 0.00 | 6.00 | 2.80 | 0.50 | 0.80 | 99.9965 |
| Example 4 | 0.38 | 1.00 | 1.97 | 6.6 | 12.54 | 1.12 | 10.34 | 2.98 | 11.27 | 0.58 | 0.33 | 7.50 | 2.50 | 0.70 | 0.70 | 99.9928 |
| Example 5 | 0.09 | 2.06 | 2.72 | 7.5 | 12.76 | 0.81 | 11.45 | 2.87 | 11.48 | 0.60 | 0.37 | 10.00 | 3.80 | 0.80 | 0.70 | 99.9916 |
| Example 6 | 5.88 | 1.00 | 2.44 | 19 | 11.66 | 0.52 | 11.22 | 2.39 | 6.54 | 0.29 | 0.40 | 16.30 | 2.80 | 0.80 | 1.40 | 99.9936 |
| Example 7 | 1.90 | 1.26 | 2.73 | 3.3 | 12.31 | 0.60 | 8.91 | 2.24 | 5.81 | 0.44 | 0.00 | 8.30 | 2.90 | 0.90 | 0.70 | 99.9940 |
| Example 8 | 1.33 | 1.00 | 3.63 | 1.9 | 4.63 | 0.67 | 7.44 | 2.92 | 1.91 | 0.14 | 0.25 | 7.80 | 3.50 | 0.80 | 0.50 | 99.9955 |
| Example 9 | 0.80 | 1.00 | 1.73 | 2.7 | 4.23 | 0.60 | 3.32 | 1.33 | 1.67 | 0.08 | 0.27 | 6.90 | 2.80 | 0.60 | 0.70 | 99.9969 |
| Example 10 | 0.28 | 1.50 | 2.57 | 1.1 | 7.48 | 0.02 | 2.92 | 2.21 | 0.92 | 0.52 | 0.48 | 7.10 | 3.00 | 0.50 | 0.60 | 99.9967 |
| Example 11 | 1.69 | 2.00 | 3.28 | 6.3 | 7.09 | 0.71 | 6.67 | 2.62 | 3.45 | 0.12 | 0.00 | 7.70 | 3.50 | 0.90 | 0.70 | 99.9953 |
| Comparative example 1 | 0.87 | 1.33 | 2.53 | 1 | 10.19 | 0.93 | 9.93 | 3.13 | 9.58 | 0.00 | 0.39 | 8.30 | 3.70 | 0.90 | 0.50 | 99.9933 |
| Comparative example 2 | 2.00 | 0.33 | 4.14 | 1.2 | 9.79 | 0.50 | 10.11 | 3.13 | 8.71 | 0.44 | 0.21 | 7.70 | 3.60 | 0.80 | 0.70 | 99.9934 |
| Comparative example 3 | 2.06 | 1.33 | 4.12 | 1.23 | 9.39 | 0.53 | 13.11 | 3.13 | 5.71 | 0.45 | 0.31 | 7.23 | 4.60 | 0.98 | 0.50 | 99.9936 |
| Comparative example 4 | 0.19 | 2.36 | 2.13 | 8.5 | 12.21 | 0.49 | 10.43 | 1.97 | 9.48 | 0.48 | 0.82 | 11.04 | 4.40 | 0.67 | 0.54 | 99.9965 |
| Comparative example 5 | 4.68 | 1.40 | 2.24 | 125 | 11.56 | 0.54 | 9.25 | 1.78 | 5.56 | 0.62 | 0.47 | 13.20 | 2.74 | 0.45 | 1.65 | 99.9916 |
The mass ratio of carbon element to graphite particles in the shell layer of the modified graphite material in each example and comparative example was as follows:
TABLE 2
2. Performance testing of modified graphite materials
The modified graphite materials prepared in examples 1 to 11 and comparative examples 1 to 5 were subjected to the following tests according to the routine in the art:
(1) the modified graphite material prepared in example 1 was subjected to a scanning electron microscope Phenom XL, and an electron microscope picture of the modified graphite material was tested according to a conventional test method in the field, and the test result is shown in FIG. 1. As can be seen from fig. 1, the modified graphite material of the present application has a single-particle structure and no agglomeration.
(2) Testing the D50 median particle size and the particle size distribution range of the modified graphite material by using a laser particle size distribution instrument MS 3000; the test results are shown in table 3, and compared with the comparative example, the modified graphite materials in examples 1 to 11 have moderate particle sizes and relatively uniform distribution.
(3) Testing the tap density of the modified graphite material by adopting a tap meter TF-100B; as shown in table 3, the tap densities of the modified graphite materials in the examples were comparable and were still maintained at a higher level than in the comparative examples.
(4) Testing the specific surface area of the modified graphite material by using a specific surface area tester NOVATouch 2000; the test results are shown in table 3, and the specific surface area of the modified graphite material in the examples is significantly higher than that of the comparative example.
(5) Testing the compaction density of the modified graphite material by adopting an FT-100F powder automatic compaction density instrument; as shown in table 3.
(6) As is conventional in the art, the shell thickness of the modified graphite material-the D50 median particle diameter of the modified graphite material-the D50 median particle diameter of the graphite particles.
TABLE 3
3. Electrical Performance testing
1) The modified graphite materials prepared in examples 1 to 11 and comparative examples 1 to 5 were used to prepare half-cells according to the following methods:
respectively weighing the modified graphite materials, the conductive carbon black SP, the CMC and the SBR in the embodiments 1-11 and the comparative examples 1-5 according to the mass ratio of 95:1:2:2, uniformly stirring in water to prepare negative electrode slurry, uniformly coating the negative electrode slurry on copper foil by using a coater, putting the coated electrode piece into a vacuum drying oven at the temperature of 110 ℃ for vacuum drying for 4 hours, and then pressing the electrode piece to prepare a negative electrode; and the compacted density is the mass of the pole piece/(the thickness of the pole piece after rolling-the thickness of the current collector). The CR-2430 button cell was assembled in an argon-filled German Braun glove box with an electrolyte of 1M LiPF6+ EC: EMC: DMC 1:1 (volume ratio) and a metallic lithium plate as counter electrode.
The prepared half-cell was tested for discharge capacity and first discharge efficiency on an arbinbbt 2000 model us cell tester, and the discharge capacity and first discharge efficiency were measured according to conventional test methods in the art under the conditions of a charge-discharge voltage range of 0.005V to 1.0V and a charge-discharge rate of 0.1C, with the test results shown in table 3. As can be seen from table 3, after the modified graphite materials prepared in examples 1 to 11 are used for preparing batteries, the discharge capacity is higher and can reach 358.9mAh/g, the first discharge efficiency is overall higher and can reach 93.1%, the capacity retention rate after 500 cycles at 1C/1C can reach over 90%, and the stability of the batteries is good.
2) The modified graphite materials prepared in examples 1 to 7 and comparative examples 1 to 4 were used to prepare full cells according to the following methods:
the modified graphite materials prepared in examples 1 to 7 and comparative examples 1 to 4 were used as battery negative electrodes, and lithium cobaltate: PVDF: adding NMP as solvent, homogenizing, coating on the surface of aluminum foil, drying, and tabletting to obtain positive electrode; the polypropylene is used as a diaphragm, and a solution with the volume ratio of 1:1 (1M) of iPF6+ EC: DMC: EMC is used as an electrolyte to assemble a full cell.
The prepared full cell was subjected to the following tests on a us ArbinBT bt2000 type cell tester:
rate capability: the test process is as follows, first week 0.6mA constant current discharge to 5mV, then constant voltage discharge, cutoff current 0.06mA, 0.1C constant current charge to 2V; a constant current of 0.1C was discharged to 5mV (representing a capacity of "0.1C constant") and then discharged at constant voltage (representing a capacity of "0.1C total"), with a cutoff current of 0.06mA, with a 0.2C constant current charge to 2V; then multiplying discharge current is 0.2C, 0.5C, 1C, 2C, 3C; after 3C, returning to 0.2C again, the rate charging current is 0.1C, and the constant current ratio is constant current charging capacity/total charging capacity, where the total charging capacity is constant current charging capacity + constant voltage charging capacity. The results are shown in Table 4.
TABLE 4
From the results in table 4, it can be seen that the constant current ratios of the modified graphite materials in examples 1 to 11 when the "rate discharge current 0.2C, 0.5C, 1C, 2C, and 3C" were calculated respectively after the full cell was prepared, and the constant current ratios of the examples were overall superior to the comparative examples, and the rate performance was better.
As can be seen from the test results in tables 3 and 4, after the modified graphite material is used in a battery, the battery can simultaneously maintain higher discharge capacity, first discharge efficiency, capacity retention rate, and better rate performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments disclosed and described, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (43)
1. The preparation method of the modified graphite material is characterized by comprising the following steps:
(1) mixing and granulating graphite particles and a coating material to obtain a precursor;
the granulation temperature is 500-700 ℃; d50 median particle size of the product obtained after granulation is 9.0-15.0 μm;
(2) sequentially carrying out carbonization treatment, acid washing and drying on the precursor to obtain a modified graphite material;
the mass ratio of the graphite particles to the coating material is 100 (1-8);
the coating material comprises asphalt and magnesium citrate, wherein the mass ratio of the asphalt to the magnesium citrate is 1: (0.1 to 10);
the D50 median particle size of the graphite particles is 6-10 mu m;
the graphite particles are primary coated artificial graphite particles; the coating agent for coating the artificial graphite particles at one time is coal tar;
the modified graphite material meets the following indexes: the tap density is 0.98-1.25 g/cm3D50, the median particle size is 10.1-12.5 μm, the particle size distribution range of the modified graphite material is 0.5-45.26 μm, and the specific surface area is 2.87-3.7 m2The density of the particles is 1.61-1.8 g/cm3。
2. The method for producing a modified graphite material according to claim 1,
the mass ratio of the asphalt to the magnesium citrate is (1:9) - (5: 1).
3. The method of preparing a modified graphite material according to claim 1, wherein the magnesium citrate and the pitch are present in a mass ratio of 1:9, or 1:7, or 1:5, or 1:3, or 1:1, or 3:1, or 5: 1.
4. the method for preparing a modified graphite material according to claim 1, wherein the method for preparing the clad material in the step (1) comprises the steps of: and mixing the asphalt with the magnesium citrate.
5. The method for preparing a modified graphite material according to claim 1, wherein in the step (1), the mass ratio of the graphite particles to the coating material is 100: (5-8).
6. The method of preparing a modified graphite material according to claim 5, wherein the mass ratio of the graphite particles to the coating material is 20:1, and the coating material comprises magnesium citrate and asphalt in a mass ratio of 1: 9.
7. The method for preparing a modified graphite material according to claim 1, wherein in the step (1), the mixing is performed by a fusion machine;
the granulation process is carried out by a horizontal kettle, a vertical kettle or an electric heating high-speed modified material mixing coating machine;
the granulation time is 3-20 h.
8. The method for producing a modified graphite material according to claim 1,
in step (1), the graphite particles had a D50 median particle size of 9.6 μm.
9. The process for producing a modified graphite material according to claim 2,
the mass ratio of the asphalt to the magnesium citrate is (1:7) - (3: 1);
the mixing temperature of the asphalt and the magnesium citrate is 50-150 ℃;
the mixing time of the asphalt and the magnesium citrate is 20-60 min;
mixing the asphalt and the magnesium citrate by a mixer;
when the mixing process is carried out through a fusion machine, the mixing time is 30-80 min.
10. The process for producing a modified graphite material according to claim 1,
the granulation process is carried out by an electric heating high-speed modified mixing and cladding machine;
the granulation temperature is 630-670 ℃;
the D50 median particle size of the product obtained after the granulation was 9.8. mu.m.
11. The process for preparing a modified graphite material according to claim 9, wherein the asphalt is an asphalt obtained from the national branch of oil and gas, ltd, china;
the mass ratio of the asphalt to the magnesium citrate is 1:5, 1:3 or 1: 1;
in the step (1), the mixing time of the asphalt and the magnesium citrate is 50 min; the mixer is a CDLW-8000 spiral mixer;
the rotating speed of the mixer is 200-800 r/min;
when the mixing process is carried out by a fusion machine, the mixing time is 60 min.
12. The method for preparing a modified graphite material according to claim 11,
in the step (1), the rotating speed of the mixer is 500 r/min.
13. The method for preparing a modified graphite material according to claim 1, wherein the method for preparing the primary-coated artificial graphite particles comprises the steps of: and (3) sequentially coating and carbonizing the uncoated artificial graphite particles.
14. The method for preparing a modified graphite material according to claim 13,
the coating process is carried out by a fusion machine.
15. The method for preparing a modified graphite material according to claim 13,
the coating agent adopted in the coating is coal tar purchased from New energy Co., Ltd in Dongri of Tangshan;
the mass ratio of the coating agent adopted in the coating to the uncoated artificial graphite particles is (2-6): 100, respectively;
the coking value of the coating agent adopted in the coating is 10-30%;
the coating time is 10-70 min.
16. The method for preparing a modified graphite material according to claim 13,
the temperature of the carbonization treatment is 950 ℃ to 1350 ℃.
17. The method of claim 13, wherein the uncoated artificial graphite particles and the coal tar are coated at a mass ratio of 100:4, and the primary coated artificial graphite particles obtained by carbonizing at 1250 ℃ have a median particle size of D50 of 9.6 μm.
18. The method for preparing a modified graphite material according to claim 14, wherein the rotation speed of the fusing machine is 200 to 1500 r/min.
19. The method for preparing a modified graphite material according to claim 15,
the mass ratio of the coating agent used in the coating to the uncoated artificial graphite particles is 4: 100, respectively; the coating time is 20 min.
20. The method of preparing a modified graphite material according to claim 16, wherein the carbonization treatment temperature is 1250 ℃.
21. The method of preparing a modified graphite material according to claim 18, wherein the rotation speed of the fusing machine is 280 r/min.
22. The method for producing a modified graphite material according to claim 1, wherein in the step (2), the carbonization treatment is performed by a calciner; the temperature of the carbonization treatment is 700-1350 ℃.
23. The method for producing a modified graphite material according to claim 1, wherein in the step (2), the acid used in the acid washing is an acid for dissolving a metal oxide;
the mass ratio of acid to an object to be pickled in the pickling process is (4-10) to 1;
the mixing speed of acid and the object to be pickled in the pickling process is 200-1000 r/min;
in the pickling process, the mixing time of acid and the object to be pickled is 30-120 min;
the step of washing with water is also included after the acid washing;
the drying temperature is 90-120 ℃;
the drying time is 6-12 h.
24. The method of preparing a modified graphite material according to claim 22, wherein the carbonization treatment temperature is 1250 ℃.
25. The method of preparing a modified graphite material according to claim 23,
the acid adopted in the acid washing is dilute hydrochloric acid or dilute sulfuric acid;
the mixing speed of the acid and the object to be pickled is 800 r/min;
the mixing time of the acid and the object to be pickled is 30 min;
the washing process is to adopt deionized water to wash until the solution is neutral;
the drying time is 10 h.
26. The method of preparing a modified graphite material according to claim 25,
the concentration of the acid is 0.01-1 mol/L.
27. A modified graphite material, which is produced by the method for producing a modified graphite material according to any one of claims 1 to 26.
28. The modified graphite material of claim 27, wherein the modified graphite material has a particle size distribution in the range of 0.9 to 40 μm.
29. The modified graphite material according to claim 27, wherein the modified graphite material is a core-shell structure, the core in the core-shell structure is graphite particles, the shell layer in the core-shell structure contains carbon, and the content of the carbon is 99.99% or more;
the thickness of the shell layer is 0.5-3 mu m;
the mass ratio of the carbon element in the shell layer to the graphite particles is (2.5-6): 100.
30. The modified graphite material of claim 29,
the thickness of the shell layer is 1-2.5 mu m;
the mass ratio of the carbon element in the shell layer to the graphite particles is (3-6): 100;
the shell layer also contains one or more impurity elements of Na, Mg, Al, Si, S, K, Ca, Ti, V, Cr, Mn, Ni, Fe, Cu and Zn.
31. The modified graphite material of claim 30, wherein,
the thickness of the shell layer is 1.6 μm, 1.7 μm, 2.2 μm, 1.8 μm, 2.1 μm, 1.9 μm, 2 μm or 2.8 μm;
the mass ratio of the carbon element in the shell layer to the graphite particles is 3.31:100, 3.22:100, 3.15:100, 3.1:100, 3.06:100, 3.01:100, 3.17:100, 3.27:100, 3.18:100 or 5.78: 100.
32. The modified graphite material of claim 29, wherein the Fe content in the shell layer is 50ppm or less.
33. The modified graphite material of claim 29, wherein the Ni content in the shell layer is 50ppm or less.
34. The modified graphite material of claim 29, wherein the Mn content in the shell layer is 50ppm or less.
35. The modified graphite material of claim 32, wherein the Fe content in the shell layer is 20ppm or less.
36. The modified graphite material of claim 33, wherein the Ni content in the shell layer is 5ppm or less.
37. The modified graphite material of claim 34, wherein the Mn content in the shell layer is 0.5ppm or less.
38. The modified graphite material of claim 35, wherein the Fe content in the shell layer is 17ppm or less.
39. The modified graphite material of claim 36, wherein the Ni content in the shell layer is 2.70ppm, 3.10ppm, 2.80ppm, 2.50ppm, 3.80ppm, 2.90ppm, 3.50ppm, 3.00ppm, or 3.50 ppm.
40. The modified graphite material of claim 37, wherein the Mn content in the shell layer is 0.38ppm, 0.07ppm, 0ppm, 0.33ppm, 0.37ppm, 0.40ppm, 0.25ppm, 0.27ppm, or 0.48 ppm.
41. The modified graphite material of claim 38,
the Fe content in the shell layer is 4.60ppm, 6.10ppm, 6.00ppm, 7.50ppm, 10.00ppm, 16.30ppm, 8.30ppm, 7.80ppm, 6.90ppm, 7.10ppm or 7.70 ppm.
42. Use of the modified graphite material of any one of claims 21 to 41 in a lithium ion battery.
43. A lithium ion battery, characterized in that the electrode material of the lithium ion battery comprises the modified graphite material of any one of claims 21 to 41.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794765A (en) * | 2012-10-30 | 2014-05-14 | 上海杉杉科技有限公司 | Lithium ion battery graphite negative electrode material and preparation method thereof |
| CN104733705A (en) * | 2013-12-20 | 2015-06-24 | 上海杉杉科技有限公司 | Negative pole material for lithium ion power cell and preparation method thereof |
| CN105024075A (en) * | 2014-12-18 | 2015-11-04 | 上海杉杉科技有限公司 | Negative electrode material for quickly rechargeable graphite lithium-ion battery and preparation method of negative electrode material |
| CN106558685A (en) * | 2015-09-30 | 2017-04-05 | 比亚迪股份有限公司 | Porous core shell structure negative material and preparation method thereof and battery |
| CN108899551A (en) * | 2018-07-19 | 2018-11-27 | 桑德集团有限公司 | Composite material and preparation method, lithium ion battery negative material and lithium ion battery |
| CN109911892A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of the powerful composite graphite negative electrode material of high capacity |
| CN110642247A (en) * | 2019-09-30 | 2020-01-03 | 广东凯金新能源科技股份有限公司 | Artificial graphite negative electrode material, preparation method thereof and lithium ion battery |
| CN111153392A (en) * | 2019-12-26 | 2020-05-15 | 合肥国轩高科动力能源有限公司 | High-rate lithium ion battery negative electrode material and preparation method thereof |
| CN112018386A (en) * | 2019-05-31 | 2020-12-01 | 宁波杉杉新材料科技有限公司 | Artificial graphite material, composite material, preparation method of composite material and lithium ion secondary battery |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585172A (en) * | 2004-06-12 | 2005-02-23 | 深圳市贝特瑞电子材料有限公司 | Graphite negative material of lithium ion battery and producing method thereof |
| CN101445232A (en) * | 2008-11-18 | 2009-06-03 | 中国海洋石油总公司 | Porous carbon and preparation method thereof |
| KR101291050B1 (en) * | 2011-02-23 | 2013-08-01 | 주식회사 엘지화학 | Negative Active Material Having High Density and Anode for Lithium Secondary Battery Containing The Same |
| CN102956889B (en) * | 2012-11-05 | 2015-12-09 | 江西正拓新能源科技股份有限公司 | Composite cathode material for lithium ion cell and preparation method thereof |
| CN106058304A (en) * | 2016-08-10 | 2016-10-26 | 广东东岛新能源股份有限公司 | Artificial graphite negative electrode material used for lithium ion power batteries, and preparation method thereof |
| CN106602067B (en) * | 2017-02-08 | 2020-01-24 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite-based composite material, preparation method thereof and lithium ion battery containing composite material |
| CN107369823B (en) * | 2017-07-25 | 2020-07-07 | 广东海洋大学 | Artificial graphite composite negative electrode material for lithium ion battery and preparation method thereof |
| CN108383116A (en) * | 2018-02-11 | 2018-08-10 | 珠海光宇电池有限公司 | Artificial plumbago negative pole material and preparation method thereof and negative electrode of lithium ion battery |
| CN111081989A (en) * | 2018-10-22 | 2020-04-28 | 海门市源美美术图案设计有限公司 | Preparation method of asphalt-coated spherical natural graphite negative electrode material |
| CN111620332A (en) * | 2020-06-08 | 2020-09-04 | 湖北亿纬动力有限公司 | Negative electrode material, preparation method thereof, negative plate and lithium ion battery |
-
2020
- 2020-12-29 CN CN202011599914.6A patent/CN112713271B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794765A (en) * | 2012-10-30 | 2014-05-14 | 上海杉杉科技有限公司 | Lithium ion battery graphite negative electrode material and preparation method thereof |
| CN104733705A (en) * | 2013-12-20 | 2015-06-24 | 上海杉杉科技有限公司 | Negative pole material for lithium ion power cell and preparation method thereof |
| CN105024075A (en) * | 2014-12-18 | 2015-11-04 | 上海杉杉科技有限公司 | Negative electrode material for quickly rechargeable graphite lithium-ion battery and preparation method of negative electrode material |
| CN106558685A (en) * | 2015-09-30 | 2017-04-05 | 比亚迪股份有限公司 | Porous core shell structure negative material and preparation method thereof and battery |
| CN109911892A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of the powerful composite graphite negative electrode material of high capacity |
| CN108899551A (en) * | 2018-07-19 | 2018-11-27 | 桑德集团有限公司 | Composite material and preparation method, lithium ion battery negative material and lithium ion battery |
| CN112018386A (en) * | 2019-05-31 | 2020-12-01 | 宁波杉杉新材料科技有限公司 | Artificial graphite material, composite material, preparation method of composite material and lithium ion secondary battery |
| CN110642247A (en) * | 2019-09-30 | 2020-01-03 | 广东凯金新能源科技股份有限公司 | Artificial graphite negative electrode material, preparation method thereof and lithium ion battery |
| CN111153392A (en) * | 2019-12-26 | 2020-05-15 | 合肥国轩高科动力能源有限公司 | High-rate lithium ion battery negative electrode material and preparation method thereof |
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