CN114628646A - Composite negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Composite negative electrode material, preparation method thereof and lithium ion battery 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Abstract
The invention discloses a composite negative electrode material, a preparation method thereof and a lithium ion battery. The composite negative electrode material not only keeps the advantage of high capacity of graphite, but also keeps the higher rate capability of soft carbon; and the stability of the electrical property is good in the charging and discharging process.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a composite negative electrode material, a preparation method thereof and a lithium ion battery.
Background
With the rapid development of new energy industry, higher requirements are put forward in the aspects of mileage and rapid charging of new energy automobiles, and secondary lithium ion batteries with high capacity and high multiplying power are increasingly required. If on the basis of guaranteeing new energy automobile duration, can realize quick charge, that will greatly alleviate the difficult problem of new energy automobile charging, promote its practical application, have wide commercial prospect.
The soft carbon is widely applied to secondary battery materials by virtue of the excellent rate capability of the soft carbon, and the graphite also becomes an ideal cathode material in the application of lithium ion batteries due to the advantages of high capacity, low voltage platform and the like. In addition, graphite as a battery negative electrode material also has some disadvantages, such as poor compatibility of graphite with an electrolyte, non-uniformity of the graphite surface, and difficulty in forming a uniform and dense SEI film (passivation film) during the first charge and discharge of the battery. Therefore, how to modify and modify a graphite material and how to combine high-capacity graphite with soft carbon with excellent rate to obtain a lithium ion battery fast-charging composite negative electrode material with high capacity, high rate and good stability is obviously a great hotspot of industrial research. For example, the graphite, the soft carbon precursor and the hard carbon precursor are subjected to composite granulation, crushing, screening, mixing and other operation procedures to prepare the soft and hard carbon modified negative electrode material of the lithium ion battery, the method effectively solves the problem of compatibility of the material and electrolyte, but the rate capability is not obviously improved.
Disclosure of Invention
In view of the above, it is necessary to provide a composite anode material capable of improving rate performance, a preparation method thereof, and a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite negative electrode material comprises a carbon material core and a carbon coating layer formed on the surface of the core, wherein the carbon material core comprises soft carbon and artificial graphite.
The composite cathode material has a core-shell structure, so that the advantage of high capacity of graphite is kept, and the high rate performance of soft carbon is also kept; the lithium ion fast-charging composite material with a core-shell structure is obtained by a coating technology. The carbon coating ensures the stability of the electrical property of the material in the charging and discharging process. In the fast-charging cathode material, graphite and soft carbon are beneficial to improving the compaction density and improving the capacity and rate capability, and the core-shell structure can improve the stability of the composite material.
In one embodiment, the mass ratio of the soft carbon to the artificial graphite is 1: 1-5;
in one embodiment, the soft carbon is dispersed in the artificial graphite;
in one embodiment, the soft carbon and artificial graphite are spheroidal in shape;
in one embodiment, the soft carbon has a graphite interlayer spacing of 0.35nm to 0.36nm, I110/I0020.03 to 0.05.
In one embodiment, the carbon coating layer is an amorphous carbon coating layer, and the thickness of the carbon coating layer is 1 μm to 3 μm.
In one embodiment, the composite negative electrode material has a D50 of 7 to 15 μm; the compacted density of the composite negative electrode material is 1.50g/cm3～1.60g/cm3。
A preparation method of the composite anode material comprises the following steps:
carbonizing the coke source material to obtain a soft carbon material;
graphitizing the coke source material to obtain artificial graphite;
mixing the soft carbon material and the artificial graphite to obtain a mixture; and
and carrying out carbon coating on the mixture to obtain the composite negative electrode material.
The preparation method of the composite negative electrode material is low in cost and excellent in performance, the soft carbon material is obtained by carbonizing coke source materials such as petroleum coke firstly, the artificial graphite is obtained by graphitizing the coke source materials such as petroleum coke, and then the two materials are mixed. And carbonizing the uniform mixture to obtain the required lithium ion battery quick-charging composite negative electrode material with the core-shell structure.
In one embodiment, the temperature of the carbonization treatment is 600-1800 ℃, and the time of the carbonization treatment is 9-14 h;
in one embodiment, the temperature of the graphitization treatment is 2800-3000 ℃, and the time of the graphitization treatment is 5-8 h;
in one embodiment, the graphitization treatment is performed under a protective atmosphere, wherein the gas of the protective atmosphere comprises at least one of nitrogen, helium, neon, argon, krypton, and xenon; and/or
In an embodiment, the coke source material comprises at least one of petroleum coke, pitch coke, natural pitch coke, and needle coke.
In one embodiment, the mixture is prepared by physically mixing the soft carbon material and the artificial graphite;
in one embodiment, the mass ratio of the soft carbon material to the artificial graphite is 1: 1-5 mixing;
in one embodiment, the soft carbon material and the artificial graphite are mixed by a mixer, wherein the mixing speed is 200r/min to 400r/min, and the mixing time is 1h to 1.5 h.
In one embodiment, the carbon coating process is an amorphous carbon coating process, and the method of the carbon coating process comprises liquid phase coating;
in one embodiment, the liquid phase coating step comprises: dispersing the mixture and an organic carbon source in an organic solvent system, drying and carbonizing to obtain a carbon-coated mixture composite material;
in one embodiment, the organic carbon source comprises at least one of coal pitch, petroleum pitch, coal tar, heavy oil from the petroleum industry, and heavy aromatic hydrocarbons;
in one embodiment, the organic solvent comprises at least one of tetrahydrofuran, quinoline, pyridine, tetrahydrofuran, and toluene;
in one embodiment, the mass ratio of the mixture to the bitumen is from 5 to 20: 1.
In one embodiment, the step of dispersing the mixture and organic carbon source in an organic solvent system comprises: dissolving an organic carbon source in an organic solvent to obtain a mixed solution; adding the mixture into the mixed solution, stirring and carrying out ultrasonic treatment for 10-30 min;
in one embodiment, the drying condition is that the temperature is kept for 1.5 to 3 hours at the temperature of 80 to 100 ℃;
in one embodiment, the carbonization condition is that the reaction is carried out for 3 to 5 hours at 700 to 900 ℃ in a protective atmosphere;
in one embodiment, the carbon-coated mixture composite material is further subjected to a shaping treatment to obtain a composite negative electrode material.
The lithium ion battery comprises the composite negative electrode material or the composite negative electrode material prepared by the preparation method of the composite negative electrode material.
Advantages of embodiments of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
FIG. 1 is an SEM scan of a composite anode material of example 1;
fig. 2 is an XRD spectrum of the composite anode material of example 1.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
At present, soft carbon is widely applied to secondary battery materials by virtue of excellent rate performance per se, and graphite is an ideal negative electrode material in lithium ion battery application due to the advantages of high capacity, low voltage platform and the like. In addition, graphite as a battery negative electrode material also exhibits some disadvantages, such as poor compatibility of graphite with an electrolyte, non-uniformity of graphite surface, and difficulty in forming a uniform and dense SEI film (passivation film) during the first charge and discharge of a battery. Therefore, how to obtain a fast-charging composite cathode material of a lithium ion battery with high capacity, high rate and good stability is obviously a great hotspot of industrial research.
The composite negative electrode material of an embodiment comprises a carbon material core and a carbon coating layer formed on the surface of the core, wherein the material of the carbon material core comprises soft carbon and artificial graphite.
The composite cathode material has a core-shell structure, so that the advantage of high capacity of graphite is kept, and the high rate performance of soft carbon is also kept; the lithium ion fast-charging composite material with a core-shell structure is obtained by a coating technology. The carbon coating ensures the stability of the electrical property of the material in the charging and discharging process. In the fast-charging cathode material, graphite and soft carbon are beneficial to improving the compaction density and improving the capacity and rate capability, and the core-shell structure can improve the stability of the composite material.
In some embodiments, the mass ratio of soft carbon to artificial graphite is 1: 1-5; the proper proportion is beneficial to matching materials and is more beneficial to improving the capacity and rate capability. Specifically, the mass ratio of the soft carbon to the artificial graphite may be 1:1, 1:2, 1:3, 1:4, or 1: 5.
In some embodiments, the material distribution of the carbonaceous material core is such that the soft carbon is dispersed in the artificial graphite;
in some embodiments, the soft carbon and artificial graphite are spheroidal in shape; in the fast-charging negative electrode material, the graphite and the soft carbon which are all in the shape of sphere-like shapes are beneficial to improving the compaction density and improving the capacity and rate capability.
In some embodiments, the carbon coating layer is an amorphous carbon coating layer, and the amorphous carbon has good compatibility with an electrolyte, so that the stability of electrical properties of the material in the charging and discharging processes is ensured.
In some embodiments, the carbon coating layer has a thickness of 1 μm to 3 μm.
In some embodiments, the amorphous carbon in the amorphous carbon coating layer may be at least one of coal pitch, petroleum pitch, coal tar, petroleum industry heavy oil, and heavy aromatic hydrocarbons; wherein the softening point of the asphalt is 75-120 ℃;
in some embodiments, the composite anode material has a D50 of 7 to 15 μm; specifically, D50 may be 7 μm, 8 μm, 10 μm, 10.92 μm, 10.94 μm, 10.95 μm, 10.98 μm, 10.99 μm, 11.08 μm, or 11.12 μm.
In some embodiments, the composite anode material has a compacted density of 1.50g/cm3～1.60g/cm3. The composite negative electrode material has higher compaction density, and can effectively improve the capacity and rate capability.
A method for preparing a composite anode material according to another embodiment includes the following steps S100 to S400:
s100, carbonizing the coke source material to obtain a soft carbon material;
specifically, the coke source material includes at least one of petroleum coke, pitch coke, natural pitch coke, and needle coke;
specifically, the soft carbon material obtained by using the coke source material has more excellent rate performance, and in a specific example, petroleum coke is used as a raw material, the soft carbon material has excellent anisotropy observed under a polarization microscope, and the graphite layer spacing and orientation of the prepared soft carbon can be adjusted by controlling carbonization treatment conditions, so that the soft carbon material has more excellent rate performance.
Specifically, the temperature of the carbonization treatment is controlled to be 600 ℃ to 1800 ℃, for example, 600 ℃, 800 ℃, 1000 ℃, 1200 ℃, 1400 ℃, 1600 ℃ and the like. The carbonization time is 9-14 h; such as 9h, 10h, 11h or 12 h; under the carbonization treatment condition, the graphite interlayer spacing of the soft carbon is 0.35-0.36 nm, and the orientation I is110/I0020.03 to 0.05; compared with the conventional soft carbon, the soft carbon preparation step of the embodiment has the advantages that the lower heat treatment temperature and the better heat treatment time are adopted for soft carbon preparation, and the cost is reduced;
s200, graphitizing the coke source material to obtain artificial graphite;
the preparation process of the artificial graphite only needs heat treatment, the preparation process is simple, and the preparation cost is low.
In some embodiments, the coke source material comprises at least one of petroleum coke, pitch coke, natural pitch coke, and needle coke; in a preferred embodiment, petroleum coke is used as a raw material, and the petroleum coke has excellent anisotropy when observed under a polarization microscope, so that the artificial graphite has higher capacity.
In some embodiments, the temperature of the graphitization treatment is 2800-3000 ℃, and the time of the graphitization treatment is 5-8 h; further, the graphitization treatment is performed under a protective atmosphere, and the gas of the protective atmosphere includes at least one of nitrogen, helium, neon, argon, krypton, and xenon.
It should be noted that the preparation of the soft carbon material and the preparation of the artificial graphite are not in sequence, and the soft carbon material and the artificial graphite can be prepared first, or the artificial graphite and the soft carbon material can be prepared first; i.e. S100 and S200 do not have a precedence order.
S300, mixing the soft carbon material with artificial graphite to obtain a mixture;
in some embodiments, the mixture is prepared by physically mixing the soft carbon material and the artificial graphite;
specifically, the soft carbon material and the artificial graphite are mixed using a mixer, and more specifically, the mixture is prepared by at least one of mixing, fusing, or stirring by a VC mixer.
Wherein the mixing speed is 200 r/min-400 r/min, and the mixing time is 1 h-1.5 h.
In some embodiments, the ratio of the soft carbon material to the artificial graphite is 1: 1-5, mixing; the proper proportion is beneficial to matching materials and is more beneficial to improving the capacity and rate capability. Specifically, the mass ratio of the soft carbon to the artificial graphite may be 1:1, 1:2, 1:3, 1:4, or 1: 5.
And S400, carrying out carbon coating treatment on the mixture to obtain the composite negative electrode material.
In some embodiments, the carbon coating is an amorphous carbon coating, and the amorphous carbon has good compatibility with an electrolyte, so that the stability of electrical properties of the material in the charging and discharging processes is ensured.
Specifically, the carbon coating method may adopt a liquid phase coating method, and the liquid phase coating method includes the following specific steps: dispersing the mixture and an organic carbon source in an organic solvent system, drying and carbonizing to obtain a carbon-coated mixture composite material;
in some embodiments, the dispersing method is to dissolve the organic carbon source in the organic solvent to obtain a mixed solution; ultrasonic treatment is adopted for dissolution, and the time is 10-30 min; then adding the mixture into the mixed solution for stirring and ultrasonic treatment for 10-30 min;
further, mixing the mixture and the asphalt in a mass ratio of 5-20: 1;
wherein, the drying treatment is carried out after the ultrasonic stirring treatment, and the drying condition is that the temperature is kept for 1.5 to 3 hours at the temperature of 80 to 100 ℃; to evaporate the organic solvent to dryness, leaving only the mixture and the organic carbon source;
in a specific embodiment, the organic carbon source comprises at least one of coal pitch, petroleum pitch, coal tar, heavy oil of petroleum industry, and heavy aromatic hydrocarbon to obtain an amorphous carbon coating; wherein the asphalt softening point is 75-120 ℃, and the organic solvent comprises at least one of tetrahydrofuran, quinoline, pyridine and toluene.
In some embodiments, the carbonization conditions are reaction at 700 ℃ to 900 ℃ for 3h to 5h under a protective atmosphere; the gas of the protective atmosphere comprises at least one of nitrogen, helium, neon, argon, krypton and xenon.
In some embodiments, the mixture is subjected to a carbon coating treatment and then to a crushing and shaping treatment to obtain the composite anode material with the particle size of 7-15 μm. Wherein the shaping processing mode adopts a shaping method which is conventional in the field.
The preparation method of the composite negative electrode material is low in cost and excellent in performance, the soft carbon material is obtained by carbonizing coke source materials such as petroleum coke, the artificial graphite is obtained by graphitizing the coke source materials such as petroleum coke, and the two materials are physically mixed. And carbonizing the uniform mixture, crushing and shaping to obtain the required lithium ion battery quick-charging composite negative electrode material with the core-shell structure.
The composite negative electrode material prepared by the embodiment comprises a carbon material core and a carbon coating layer formed on the surface of the core, wherein the carbon material core comprises soft carbon and artificial graphite.
According to the scheme, the asphalt is coated on the soft carbon-graphite composite material through a coating technology to form the fast-filling composite material with a double-yellow core-shell structure or a multi-yellow core-shell structure. The core-shell structure not only keeps the advantage of high capacity of graphite, but also keeps the higher rate capability of soft carbon; in addition, the amorphous carbon shell layer is adopted, the amorphous carbon has good compatibility with electrolyte, and the stability of the electrical property of the material in the charging and discharging process is ensured.
The embodiment of the invention also provides a lithium ion secondary battery cathode pole piece and a lithium ion secondary battery, and the composite cathode material provided by the embodiment of the invention is adopted.
The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific embodiments. The present invention can be modified and implemented as appropriate within the scope of the main claim.
Example 1
A preparation method of the composite anode material comprises the following steps:
1) selecting petroleum coke as a raw material, carbonizing the petroleum coke powder at 1800 ℃ for 11h, and carbonizing to obtain the soft carbon material.
2) Putting the petroleum coke in a nitrogen atmosphere, and carrying out high-temperature heat treatment on the petroleum coke powder for 5 hours at the temperature of 3000 ℃ to graphitize the petroleum coke powder to obtain the artificial graphite.
3) According to the mass ratio of the soft carbon material to the graphite of 1: and 4, mixing the soft carbon material and the graphite by using a mixer at the rotating speed of 400r/min for 1.5h to obtain the uniformly mixed soft carbon-graphite composite material.
4) Firstly dissolving asphalt into tetrahydrofuran by ultrasonic dissolution for 30min, then adding the soft carbon-graphite composite material into the mixed solution for stirring and ultrasonic treatment for 30min, wherein the mass ratio of the soft carbon-graphite composite material to the asphalt is 15: 1. Then, the mixed solution is placed at the temperature of 110 ℃ and is subjected to heat preservation for 3 hours; and carbonizing the obtained sample, namely putting the sample into a reaction kettle, introducing nitrogen, and keeping the temperature of the reaction kettle at 800 ℃ in a heating environment for 4 hours to obtain the large-size carbon-coated soft carbon graphite material. And finally, crushing and shaping the carbon-coated soft carbon graphite material to finally obtain the lithium ion battery quick-charging composite material with the particle size of about 10.9 microns.
The composite negative electrode material provided by the embodiment comprises a carbon material core and an amorphous carbon coating layer formed on the surface of the core, wherein the carbon material core comprises soft carbon and artificial graphite. The thickness of the amorphous carbon coating layer was 1.58 μm.
Fig. 1 is an electron micrograph of the lithium ion battery rapid-charging composite negative electrode material of the embodiment.
Fig. 2 is an XRD pattern of the lithium ion battery fast-charging composite negative electrode material of this example.
As shown in fig. 1, in an electron micrograph of the fast-charging composite negative electrode material of the lithium ion battery of this embodiment, it can be seen that the composite material is in a spheroidal structure and is relatively uniform.
As shown in fig. 2, in the XRD spectrum of the fast-charging composite negative electrode material of the lithium ion battery of this example, it can be seen that the 002 peak of graphite is located at about 26 ° of the spectrum, and at the same time, it can also be seen that a steamed bread peak located at about 25 °, and this peak belongs to a soft carbon material.
Example 2
A preparation method of the composite anode material comprises the following steps:
1) selecting petroleum coke as a raw material, carbonizing the petroleum coke at 1600 ℃ for 14h, and carbonizing to obtain a soft carbon material;
2) placing petroleum coke in a nitrogen atmosphere, and performing high-temperature heat treatment on petroleum coke powder at the temperature of 2800 ℃ for 8 hours to graphitize the petroleum coke powder to obtain artificial graphite;
3) according to the mass ratio of the soft carbon material to the graphite of 1:2, mixing the soft carbon material and graphite by using a mixer at the rotating speed of 300r/min for 1.5 hours to obtain a soft carbon-graphite composite material;
4) firstly, dissolving asphalt into tetrahydrofuran by ultrasonic dissolution for 25min, then adding a soft carbon-graphite composite material into a mixed solution for stirring and ultrasonic treatment for 25min, wherein the mass ratio of the soft carbon-graphite composite material to the asphalt is 20: 1; the mixed solution was then incubated at 110 ℃ for 3h in order to evaporate off the tetrahydrofuran to dryness. And carbonizing the obtained sample, namely putting the sample into a reaction kettle, introducing nitrogen, and keeping the temperature of the reaction kettle in a heating environment of 700 ℃ for 5 hours to obtain the large-size carbon-coated soft carbon graphite material. And finally, crushing and shaping the carbon-coated soft carbon graphite material to finally obtain the lithium ion battery quick-charging composite material with the particle size of about 10.9 microns.
The composite negative electrode material provided by the embodiment comprises a carbon material core and an amorphous carbon coating layer formed on the surface of the core, wherein the carbon material core comprises soft carbon and artificial graphite. The thickness of the amorphous carbon coating layer was 1.52 μm.
Example 3
The preparation method of the composite anode material provided by the embodiment comprises the following steps:
1) selecting petroleum coke as a raw material, and carbonizing petroleum coke powder at 1200 ℃ for 13 h; and carbonizing to obtain the soft carbon material.
2) Putting the petroleum coke in a nitrogen atmosphere, and carrying out high-temperature heat treatment on the petroleum coke powder for 9 hours at the temperature of 3000 ℃ to graphitize the petroleum coke powder to obtain the artificial graphite.
3) According to the mass ratio of the soft carbon material to the graphite of 1: and 3, mixing the soft carbon material and the graphite by using a mixer at the rotating speed of 200r/min for 1.5 hours to obtain the soft carbon-graphite composite material.
4) Dissolving asphalt into tetrahydrofuran by ultrasonic dissolution for 10min, then adding the soft carbon-graphite composite material into the mixed solution for stirring and ultrasonic treatment for 10min, wherein the mass ratio of the soft carbon-graphite composite material to the asphalt is 10: 1; the mixed solution was then incubated at 110 ℃ for 3h in order to evaporate off the tetrahydrofuran to dryness. And carbonizing the obtained sample, namely putting the sample into a reaction kettle, introducing nitrogen, and keeping the temperature of the reaction kettle at 800 ℃ in a heating environment for 4 hours to obtain the large-size carbon-coated soft carbon graphite material. And finally, crushing and shaping the carbon-coated soft carbon graphite material to finally obtain the lithium ion battery quick-charging composite material with the particle size of about 11 microns.
Example 4
The preparation method of the composite anode material provided by the embodiment comprises the following steps:
1) carbonizing petroleum coke at 1100 deg.c for 10 hr; carbonizing to obtain a soft carbon material;
2) placing petroleum coke powder in a nitrogen atmosphere, and performing high-temperature heat treatment on the petroleum coke powder at the temperature of 2900 ℃ for 6 hours to graphitize the petroleum coke powder to obtain artificial graphite;
3) according to the mass ratio of the soft carbon material to the graphite of 1:4, mixing the soft carbon material and graphite by using a mixer at the rotating speed of 300r/min for 1h to obtain a soft carbon-graphite composite material;
4) dissolving asphalt into tetrahydrofuran by ultrasonic dissolution for 10min, then adding the soft carbon-graphite composite material into the mixed solution for stirring and ultrasonic treatment for 10min, wherein the mass ratio of the soft carbon-graphite composite material to the asphalt is 5: 1; then, the mixed solution is kept at the temperature of 110 ℃ for 3 hours, so that tetrahydrofuran is volatilized to be dry; and carbonizing the obtained sample, namely putting the sample into a reaction kettle, introducing nitrogen, and keeping the temperature of the reaction kettle at 900 ℃ for 3 hours to obtain the large-size carbon-coated soft carbon graphite material. And finally, crushing and shaping the carbon-coated soft carbon graphite material to finally obtain the lithium ion battery quick-charging composite material with the particle size of about 11 microns.
Example 5
The preparation method of the composite anode material provided by the embodiment comprises the following steps:
1) selecting petroleum coke as a raw material, and carbonizing the petroleum coke powder at 800 ℃ for 12 h; carbonizing to obtain a soft carbon material;
2) putting petroleum coke powder in a nitrogen atmosphere, and carrying out high-temperature heat treatment on the petroleum coke powder at the temperature of 3000 ℃ for 7h to graphitize the petroleum coke powder to obtain artificial graphite;
3) according to the mass ratio of the soft carbon material to the graphite of 1:5, mixing the soft carbon material and graphite by using a mixer at the rotating speed of 300r/min for 1h to obtain a soft carbon-graphite composite material;
4) dissolving asphalt into tetrahydrofuran by ultrasonic dissolution for 20min, then adding the soft carbon-graphite composite material into the mixed solution for stirring and ultrasonic treatment for 20min, wherein the mass ratio of the soft carbon-graphite composite material to the asphalt is 20: 1; the mixed solution is then kept at 110 ℃ for 3h in order to evaporate the tetrahydrofuran to dryness. And carbonizing the obtained sample, namely putting the sample into a reaction kettle, introducing nitrogen, and keeping the temperature of the reaction kettle at 800 ℃ in a heating environment for 5 hours to obtain the large-size carbon-coated soft carbon graphite material. And finally, crushing and shaping the carbon-coated soft carbon graphite material to finally obtain the lithium ion battery quick-charging composite material with the particle size of about 11.1 mu m.
Example 6
The difference between the embodiment and the embodiment 1 is only that the mass ratio of the soft carbon material and the graphite in the step 3) is 1: 1.
example 7
A preparation method of the composite anode material comprises the following steps:
1) selecting petroleum coke as a raw material, carbonizing the petroleum coke powder for 14 hours at 600 ℃, and carbonizing to obtain the soft carbon material.
2) Putting the petroleum coke in a nitrogen atmosphere, and carrying out high-temperature heat treatment on the petroleum coke powder for 5 hours at the temperature of 3000 ℃ to graphitize the petroleum coke powder to obtain the artificial graphite.
3) According to the mass ratio of the soft carbon material to the graphite of 1: and 4, mixing the soft carbon material and the graphite by using a mixer at the rotating speed of 400r/min for 1.5h to obtain the uniformly mixed soft carbon-graphite composite material.
4) Dissolving asphalt into tetrahydrofuran by ultrasonic dissolution for 30min, then adding the soft carbon-graphite composite material into the mixed solution for stirring and ultrasonic treatment for 30min, wherein the mass ratio of the soft carbon-graphite composite material to the asphalt is 15: 1. Then, the mixed solution is placed at the temperature of 110 ℃ and is subjected to heat preservation for 3 hours; and carbonizing the obtained sample, namely putting the sample into a reaction kettle, introducing nitrogen, and keeping the temperature of the reaction kettle at 800 ℃ in a heating environment for 4 hours to obtain the large-size carbon-coated soft carbon graphite material. And finally, crushing and shaping the carbon-coated soft carbon graphite material to obtain the lithium ion battery quick-charging composite material.
Comparative example 1
The preparation method of the lithium ion battery rapid charging cathode material provided by the comparative example comprises the following steps:
1) selecting petroleum coke as a raw material, carbonizing the petroleum coke powder at 800 ℃ for 12h, and obtaining approximately spherical soft carbon after carbonization treatment;
2) putting petroleum coke powder in a nitrogen atmosphere, and carrying out high-temperature heat treatment on the petroleum coke powder for 6 hours at the temperature of 3000 ℃ to graphitize the petroleum coke powder to obtain artificial graphite;
3) according to the mass ratio of the soft carbon material to the graphite of 1:1, mixing the soft carbon material and graphite by using a mixer at the rotating speed of 300r/min for 1h to obtain the quick-charging composite cathode material of the lithium ion battery.
And (3) testing:
the lithium ion battery quick-charging composite negative electrode materials prepared in the examples 1 to 5 and the comparative example 1, the binder LA132 and the conductive agent Super-P are mixed according to the weight ratio of 9.35: 0.5: mixing the raw materials according to the solid content ratio of 0.15, adding water serving as a dispersing agent to prepare slurry, coating the uniformly mixed slurry on a copper foil current collector, wherein the thickness of a copper foil is about 10 mu m, drying, pressing the copper foil current collector into a sheet, and preparing a circular carbon film with the diameter of 1cm for later use. The battery is assembled in a glove box filled with argon, a metal lithium sheet is used for an electrode, 1mol/L LiPF6 three-component mixed solvent is used for mixing electrolyte according to the volume ratio of EC to DMC to EMC of 1:1:1, a polyethylene/propylene composite microporous membrane is used as a diaphragm, the electrochemical performance test is carried out on a battery tester, the charging and discharging voltage is limited to 0.001-1.5V, 0.1C, 1C, 4C and 10C, and the first reversible capacity, the first coulombic efficiency and the rate capability are tested.
The test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the capacity of the composite negative electrode material exceeds 350mAh/g, the first efficiency exceeds 90%, and the 4C/1C charge capacity retention ratio and 10C/based on the ion exchange capacity are greater than 10C/based on the ion exchange capacityThe retention rate of 1C discharge capacity exceeds 92 percent, and the compacted density is not less than 1.50g/cm3. Comparative example 1 is not carbon-coated, the capacity of the prepared composite anode material is not more than 320mAh/g, and the first charge efficiency and the charge-discharge capacity retention rate are low. The fast-charging composite material prepared by the preparation method provided by the invention has more excellent performance, and the capacity, the first-time charging efficiency and the rate capability are higher, wherein the fast-charging composite negative electrode material of the human lithium ion battery prepared in the embodiment 1 has the best performance.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The composite negative electrode material is characterized by comprising a carbon material core and a carbon coating layer formed on the surface of the core, wherein the carbon material core comprises soft carbon and artificial graphite.
2. The composite anode material according to claim 1, wherein the mass ratio of the soft carbon to the artificial graphite is 1: 1-5; and/or
The soft carbon is dispersed in the artificial graphite; and/or
The soft carbon and the artificial graphite are spherical-like in shape; and/or
The graphite interlayer spacing of the soft carbon is 0.35-0.36 nm, I110/I0020.03 to 0.05.
3. The composite anode material according to claim 1, wherein the carbon coating layer is an amorphous carbon coating layer; and/or
The thickness of the carbon coating layer is 1-3 μm.
4. The composite negative electrode material according to any one of claims 1 to 3, wherein D50 of the composite negative electrode material is 7 to 15 μm; and/or
The compacted density of the composite negative electrode material is 1.50g/cm3～1.60g/cm3。
5. The preparation method of the composite anode material is characterized by comprising the following steps of:
carbonizing the coke source material to obtain a soft carbon material;
graphitizing the coke source material to obtain artificial graphite;
mixing the soft carbon material and the artificial graphite to obtain a mixture; and
and carrying out carbon coating on the mixture to obtain the composite negative electrode material.
6. The preparation method of the composite anode material according to claim 5, wherein the temperature of the carbonization treatment is 600-1800 ℃, and the time of the carbonization treatment is 9-14 h; and/or
The temperature of the graphitization treatment is 2800-3000 ℃, and the time of the graphitization treatment is 5-8 h; and/or
The graphitization treatment is carried out under the condition of protective atmosphere, and the gas of the protective atmosphere comprises at least one of nitrogen, helium, neon, argon, krypton and xenon; and/or
The coke source material comprises at least one of petroleum coke, asphalt coke, natural asphalt coke and needle coke.
7. The method for preparing a composite anode material according to claim 5, wherein the mixture is prepared by physically mixing the soft carbon material and the artificial graphite; and/or
According to the mass ratio of the soft carbon material to the artificial graphite of 1: 1-5 mixing; and/or
And mixing the soft carbon material and the artificial graphite by a mixer at the mixing speed of 200-400 r/min for 1-1.5 h.
8. The method for preparing the composite anode material according to claim 5, wherein the carbon coating treatment is an amorphous carbon coating treatment, and the method of the carbon coating treatment comprises liquid phase coating; and/or
The liquid phase coating step comprises: dispersing the mixture and an organic carbon source in an organic solvent system, drying and carbonizing to obtain a carbon-coated mixture composite material; and/or
The organic carbon source comprises at least one of coal pitch, petroleum pitch, coal tar, heavy oil in petroleum industry and heavy aromatic hydrocarbon; and/or
The organic solvent comprises at least one of tetrahydrofuran, quinoline, pyridine, tetrahydrofuran and toluene; and/or
The mass ratio of the mixture to the asphalt is 5-20: 1.
9. The method of preparing the composite anode material according to claim 8, wherein the step of dispersing the mixture and the organic carbon source in an organic solvent system comprises: dissolving an organic carbon source in an organic solvent to obtain a mixed solution; adding the mixture into the mixed solution, stirring and carrying out ultrasonic treatment for 10-30 min; and/or
The drying condition is that the temperature is kept for 1.5 to 3 hours at the temperature of 80 to 100 ℃; and/or
The carbonization condition is that the reaction is carried out for 3 to 5 hours at the temperature of 700 to 900 ℃ under the protective atmosphere; and/or
And shaping the carbon-coated mixture composite material to obtain the composite cathode material.
10. A lithium ion battery is characterized by comprising the composite negative electrode material of any one of claims 1 to 4 or the composite negative electrode material prepared by the preparation method of the composite negative electrode material of any one of claims 5 to 9.
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