CN106654235B - Composite graphite material, preparation method thereof and lithium ion battery containing composite graphite material - Google Patents
Composite graphite material, preparation method thereof and lithium ion battery containing composite graphite material Download PDFInfo
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- CN106654235B CN106654235B CN201710069298.5A CN201710069298A CN106654235B CN 106654235 B CN106654235 B CN 106654235B CN 201710069298 A CN201710069298 A CN 201710069298A CN 106654235 B CN106654235 B CN 106654235B
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Abstract
The invention discloses a composite graphite material, a preparation method and application thereof, wherein the method comprises the following steps: 1) uniformly mixing activated natural graphite, an artificial graphite precursor and asphalt, and fusing and granulating in an inert atmosphere; 2) and uniformly mixing the fused and granulated product with a graphitization catalyst, and performing high-temperature graphitization to obtain the composite graphite material. The electrode plate prepared by the composite graphite material has the advantages of high compaction density, high liquid absorption rate and good compatibility with electrolyte, and the compaction density is 1.75g/cm3The liquid absorption time is less than or equal to 60s, and the further assembled battery has high capacity, good rate performance and cycle performance, the first lithium removal specific capacity is more than 360.5mAh/g, the first efficiency is more than 93.5 percent, and the capacity retention rate of the finished battery after being charged and discharged at normal temperature and 500 cycles is more than 85 percent.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials, and relates to a composite graphite material, a preparation method thereof and a lithium ion battery containing the composite graphite material.
Background
Compared with lead-acid and nickel-hydrogen batteries, the lithium ion battery has the advantages of high energy density, high working voltage, small volume, light weight, no pollution, good safety, long service life and the like, and is an ideal energy storage device. In recent years, lithium ion batteries have been developed vigorously in the aspects of mobile portable devices (mobile phones, notebook computers, digital cameras, tablet computers and the like), energy storage devices, power grid peak shaving and vehicle power batteries, but with the social progress and scientific and technological development, people have more and more urgent needs for miniaturized, lightweight and multifunctional devices, and higher requirements for the performance of the lithium ion batteries are provided, and the improvement of the performance of the lithium ion batteries greatly depends on the development and improvement of a negative electrode material.
At present, Carbon materials are the most successful commercial lithium ion battery negative electrode materials, including natural graphite, artificial graphite, mesocarbon microbeads (MCMB), and the like. Wherein, the natural graphite has the advantages of high specific capacity, low price and the like, but the first irreversible capacity is large, and the cycle performance is poor; the artificial graphite and the MCMB have the advantages of stable structure, good high-current rate capability, good cycle performance and the like, but the cost is higher and the specific capacity is lower. The composite graphite is a composite negative electrode material integrating the advantages of natural graphite and artificial graphite or MCMB, and CN 103311520B discloses a composite graphite negative electrode material of a lithium ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: (1) uniformly mixing spherical natural graphite, mesophase graphite and a graphitization catalyst to obtain a mixture; (2) kneading the mixture and the binder to obtain a kneaded mixture; (3) carbonizing the kneaded mass, cooling, and then carrying out catalytic graphitization high-temperature treatment; (4) crushing and grading the product obtained in the step (3); wherein, the binder in the step (2) is petroleum asphalt and/or coal asphalt. The obtained composite graphite cathode has good electrochemical performance, the discharge capacity is more than 360mAh/g, the composite graphite cathode has high charge-discharge efficiency, high-current charge-discharge performance and good cycle performance, only has small expansion during charging, and has good safety and good adaptability to electrolyte and other additives. However, a large amount of crushing and smashing processes adopted for preparing the material can damage the adhesion among secondary particles, and simultaneously, a large amount of active surfaces can be generated, so that the side reaction of the electrode plate in the charging and discharging process is increased, and in addition, the liquid absorption time of the product is still long.
Disclosure of Invention
In view of the above existing in the prior artThe invention aims to provide a composite graphite material, a preparation method thereof and application in a lithium ion battery, in order to obtain a composite graphite negative electrode material with high capacity, high compaction, low expansion, high multiplying power and long service life by integrating the advantages of natural graphite and artificial graphite, and the electrode plate prepared from the composite graphite material has the advantages of high compaction density, high electrode plate imbibition rate and good electrolyte compatibility, and the compaction density of the electrode plate is 1.75g/cm3The liquid absorption time is less than or equal to 60s, and the battery assembled by the electrode plate has high capacity, good rate capability and cycle performance, the first lithium removal specific capacity is more than 360.5mAh/g, the first efficiency is more than 93.5 percent, and the capacity retention rate of the finished battery after being charged and discharged at normal temperature and circulating for 500 weeks is more than 85 percent.
In a first aspect, the present invention provides a method of preparing a composite graphite material, the method comprising the steps of:
(1) uniformly mixing activated natural graphite, an artificial graphite precursor and asphalt to obtain a mixture;
(2) placing the mixture in a fusion machine, and performing fusion granulation in an inert atmosphere to obtain a fusion granulation product;
(3) and uniformly mixing the fused and granulated product with a graphitization catalyst, and graphitizing to obtain the composite graphite material.
According to the method, activated natural graphite, an artificial graphite precursor and asphalt are mixed, and are fused, granulated and graphitized, so that the obtained composite graphite material has high specific capacity, very good high-current rate capability and cycle performance, and the liquid absorption performance is improved.
As a preferable technical scheme of the method, the activated natural graphite is natural graphite subjected to surface functionalization treatment.
The surface-functionalized natural graphite of the present invention has functional groups on the surface thereof, which are atoms or atomic groups that can determine the chemical properties of the organic compound.
Preferably, the surface-functionalization treated natural graphite is any one of aminated natural graphite, oxidized natural graphite, aminated complex oxidized natural graphite, a mixture of aminated natural graphite and oxidized natural graphite, and preferably a mixture of aminated natural graphite and oxidized natural graphite.
In the invention, ammoniation treatment, oxidation treatment or ammoniation composite oxidation treatment is carried out under the atmosphere of oxygen or ammonia gas, the inert property of the graphite surface is mainly changed, and some functional groups containing O or N are grafted, so that the method is more favorable for more firm bonding of secondary particles and is also favorable for improving the liquid absorption performance.
The "aminated composite oxidation treated natural graphite" in the invention refers to: the modified natural graphite is obtained by firstly carrying out ammoniation treatment and then carrying out oxidation treatment on natural graphite, or the modified natural graphite is obtained by firstly carrying out oxidation treatment and then carrying out ammoniation treatment on natural graphite.
As a further preferable technical solution of the method of the present invention, the natural graphite subjected to surface functionalization treatment is a mixture of aminated natural graphite and oxidized natural graphite, under the condition, the aminated functional group and the oxidized functional group can synergistically promote firm bonding between natural graphite particles and between natural graphite and artificial graphite precursors, and after subsequent granulation and graphitization processes, the performance of the obtained composite graphite material is also greatly improved.
More preferably, in the mixture of aminated natural graphite and oxidized natural graphite, the mass ratio of aminated natural graphite to oxidized natural graphite is 9:1 to 1:9, for example, 1:9, 2:8, 3:7, 3.5:6.5, 4:6, 5:5, 5.5:4.5, 6:4, 6.5:3.5, 7:3, 8:2, or 9:1, and preferably 7:3 to 5: 5.
Preferably, the aminated natural graphite is prepared by the following method: and carrying out heat treatment on the natural graphite in an ammonia atmosphere to obtain the ammonified graphite.
Preferably, the oxidation-treated natural graphite is prepared by the following method: and (3) carrying out heat treatment on the natural graphite in an oxygen atmosphere and/or an air atmosphere to obtain the natural graphite subjected to oxidation treatment.
Preferably, the aminated composite oxidation treated natural graphite is prepared by the first scheme or the second scheme:
the first scheme is as follows: carrying out heat treatment on the aminated natural graphite in an oxygen atmosphere and/or an air atmosphere;
scheme II: and carrying out heat treatment on the oxidized natural graphite in an ammonia atmosphere.
Preferably, the natural graphite has a median particle diameter D50 of 2 to 12 μm, for example, 2, 4, 5, 6, 7, 8, 10, or 12 μm, and preferably D50 of 3 to 8 μm.
Preferably, the sphericity of the natural graphite is 0.80 to 0.95, for example, 0.80, 0.82, 0.83, 0.85, 0.87, 0.88, 0.90, 0.91, 0.92, 0.94, or 0.95.
Preferably, the carbon content of the natural graphite is greater than 99.95 wt.%, e.g., 99.96 wt.%, 99.98 wt.%, or 99.99 wt.%, etc.
Preferably, in the process of preparing the aminated natural graphite, the oxidized natural graphite and the aminated complex-oxidation treated natural graphite, the heat treatment temperature is independently 300 to 1000 ℃, such as 300 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃, and independently preferably 600 to 800 ℃.
In the present invention, the "temperature of the heat treatment is independently 300 to 1000 ℃" means: the heat treatment temperature in the process of preparing the ammoniated natural graphite is 300-1000 ℃; the temperature of heat treatment in the process of preparing the natural graphite subjected to oxidation treatment is 300-1000 ℃; in the first scheme for preparing the natural graphite subjected to ammoniation composite oxidation treatment, the temperature of heat treatment is 300-1000 ℃; the temperature of the heat treatment in the second scheme for preparing the natural graphite subjected to the ammoniation composite oxidation treatment is 300-1000 ℃.
Preferably, in the process of preparing the aminated natural graphite, the oxidized natural graphite and the aminated composite oxidized natural graphite, the heat treatment time is independently 2h to 5h, such as 2h, 2.2h, 2.4h, 2.5h, 2.6h, 2.8h, 3h, 3.3h, 3.5h, 4h, 4.25h, 4.5h, 4.7h or 5h, etc.
In the present invention, the "air atmosphere and/or oxygen atmosphere" means: the atmosphere may be an air atmosphere, an oxygen atmosphere, or a mixed atmosphere of an air atmosphere and an oxygen atmosphere.
Preferably, the flow rate of ammonia gas in the process of preparing the aminated natural graphite is 5L/h.kg-20L/h.kg, such as 5L/h.kg, 8L/h.kg, 10L/h.kg, 11L/h.kg, 12L/h.kg, 14L/h.kg, 15L/h.kg, 17L/h.kg, 18L/h.kg, 19L/h.kg or 20L/h.kg, etc.
Preferably, the flow rate of oxygen and/or air in the process of preparing the oxidation-treated natural graphite is 5L/h.kg to 20L/h.kg, such as 5L/h.kg, 6L/h.kg, 8L/h.kg, 10L/h.kg, 12L/h.kg, 14L/h.kg, 15L/h.kg, 17L/h.kg, 18L/h.kg, 18.5L/h.kg, 20L/h.kg, etc.
Preferably, in the first embodiment, the flow rate of oxygen and/or air is 5L/h.kg to 20L/h.kg, such as 5L/h.kg, 7L/h.kg, 10L/h.kg, 12L/h.kg, 13L/h.kg, 15L/h.kg, 17L/h.kg, 18L/h.kg, 19L/h.kg or 20L/h.kg.
Preferably, in the second embodiment, the flow rate of ammonia gas is 5L/h.kg-20L/h.kg, such as 5L/h.kg, 8L/h.kg, 9L/h.kg, 11L/h.kg, 12L/h.kg, 13L/h.kg, 15L/h.kg, 16L/h.kg, 18L/h.kg or 20L/h.kg.
Preferably, the apparatus used for preparing the surface-functionalization-treated graphite is any one of a rotary kiln, a box-type heating furnace, or a tube furnace.
Preferably, the artificial graphite precursor in the step (1) is coke and/or mesocarbon microbeads.
In the invention, the "artificial graphite precursor is coke and/or mesocarbon microbeads graphite" means: the graphite can be coke, mesocarbon microbeads or a mixture of coke and mesocarbon microbeads.
Preferably, the coke is petroleum-based coke, coal-based coke, or a mixed coke of petroleum-based coke and coal-based coke, and exemplary petroleum-based cokes are: oil-based needle coke, sponge coke, shot coke, and the like, and exemplary coal-based cokes are: coal-based needle coke, asphalt coke, modified asphalt coke, and the like.
The coke preferably has a median particle diameter D50 of 2 to 12 μm, for example, 2, 3, 5, 7, 8, 9, 10, 11 or 12 μm, and preferably D50 of 3 to 8 μm.
Preferably, the mesocarbon microbeads are green pellets.
Preferably, the median particle diameter of the mesocarbon microbeads of graphite is 2 to 12 μm, for example, 2 to 3, 4, 5, 6, 7, 8, 9, 10 or 12 μm, and preferably D50 is 3 to 8 μm.
Preferably, the asphalt in the step (1) is any one or a mixture of at least two of petroleum asphalt, coal-series asphalt or modified asphalt. Exemplary coal-based bitumens are: low temperature coal pitch, medium temperature coal pitch, high temperature coal pitch, and the like, and exemplary modified pitches are: resin-modified asphalt, rubber-modified asphalt, and oxidation-modified asphalt.
Preferably, the mass ratio of the activated natural graphite, the artificial graphite precursor and the pitch in the step (1) is (90-10): (10-90): (5-30), for example, 75:25:20, 60:40:20, 50:50:20, 30:70:15, 80:15:10, 85:15:5, 10:80:30, 10:90:5, 40:60:20, 50:35:15, 45:45:10, 30:40:30, 50:35:15, 70:20:10, 10:70:20, 10:80:10, 90:10:5, 10:10:30 or 10:85: 30.
Preferably, the inert atmosphere in step (2) is any one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere, or a xenon atmosphere, or a combination of at least two of them.
Preferably, the apparatus used for the fusion granulation in step (2) is a fusion machine, such as a commercially available mechanical fusion machine.
Preferably, the temperature for the fusion granulation in step (2) is 600 to 650 ℃, for example 600 ℃, 610 ℃, 615 ℃, 620 ℃, 625 ℃, 630 ℃, 635 ℃, 640 ℃, 650 ℃ or the like.
Preferably, the fusion granulation time in step (2) is 5h to 10h, such as 5h, 5.5h, 6h, 7h, 7.5h, 8h, 9h, 9.5h or 10 h.
Preferably, the graphitization catalyst in the step (3) is any one or a mixture of at least two of carbide, boron oxide or iron oxide, such as silicon carbide, diboron trioxide, ferroferric oxide and ferric oxide, and the like, and is preferably silicon carbide.
Preferably, the median particle diameter of the graphitization catalyst in the step (3) is 2 to 15 μm, for example, 2, 4, 6, 8, 10, 11, 13, 14, or 15 μm.
Preferably, the graphitizing catalyst of step (3) is added in an amount of 3 wt.% to 10 wt.%, e.g., 3 wt.%, 4 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, or 10 wt.%, etc., of the total mass of the graphitizing catalyst and the pelletized product.
Preferably, the graphitization temperature in step (3) is 2600 ℃ to 3200 ℃, e.g., 2600 ℃, 2650 ℃, 2700 ℃, 2750 ℃, 2800 ℃, 2900 ℃, 3000 ℃, 3100 ℃, 3200 ℃, or the like.
Preferably, the method further comprises the step of classifying or screening after the graphitization is completed.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) taking natural graphite with the median particle size of D50-3-8 μm as a raw material, introducing ammonia gas at the flow rate of 5-20L/h.kg, and carrying out heat treatment at 600-800 ℃ for 2-5 h to obtain aminated natural graphite;
(2) taking natural graphite with the median particle size of D50-3-8 μm as a raw material, introducing oxygen at the flow rate of 5-20L/h.kg, and carrying out heat treatment at 600-800 ℃ for 2-5 h to obtain natural graphite subjected to oxidation treatment;
(3) uniformly mixing activated natural graphite, petroleum coke and petroleum asphalt according to the ratio of (90-10) to (10-90) to (5-30), adding the mixture into a high-temperature mechanical fusion machine, introducing inert gas, performing fusion granulation for 5-10 h at the temperature of 600-650 ℃, and cooling to obtain a fusion granulation product;
(4) uniformly mixing the fused and granulated product with silicon carbide, graphitizing at 2600-3200 ℃, and grading or sieving to obtain the composite graphite material.
The negative plate is prepared from the composite graphite material prepared by the preferred technical scheme, and the compaction density of the negative plate reaches 1.8g/cm3The liquid absorption time is less than 46s, the electrochemical performance of a battery assembled by the electrode plate is excellent, the first lithium removal specific capacity reaches more than 362mAh/g, the first efficiency is more than 95%, and the capacity retention rate is more than 89% after 500 cycles of normal-temperature charge and discharge.
The method adopts a surface functionalization process to activate the surface of natural graphite, prepares aminated natural graphite and oxidized natural graphite, and mixes the natural graphite and the artificial graphite to cooperatively promote the formation of firm secondary particles among natural graphite particles and between the natural graphite and an artificial graphite precursor, and the composite graphite material prepared by mixing the natural graphite and the artificial graphite precursor has excellent performance.
In a second aspect, the present invention provides a composite graphite material prepared by the method of the first aspect.
In a third aspect, the present invention provides a negative electrode comprising the composite graphite material according to the second aspect as a negative electrode active material.
In a fourth aspect, the present invention provides a lithium ion battery comprising the composite graphite material of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, activated natural graphite, an artificial graphite precursor and asphalt are mixed, and are fused, granulated and graphitized, so that the obtained composite graphite material has high specific capacity, very good high-current rate capability and cycle performance, and the liquid absorption performance is improved.
(2) The method improves the surface inertia property of the natural graphite through surface functionalization treatment, obtains the activated natural graphite, and promotes the natural graphite to be in contact with each otherThe electrode plate prepared from the composite graphite material has the advantages of high compaction density, high liquid absorption rate of the electrode plate and good compatibility with electrolyte, and the compaction density of the electrode plate is 1.75g/cm3The liquid absorption time is less than or equal to 60s, and the battery assembled by the electrode plate has high capacity, excellent rate performance, cycle life and other performances, the first lithium removal specific capacity is more than 360.5mAh/g, the first efficiency is more than 93.5 percent, and the capacity retention rate of the finished battery after being charged and discharged at normal temperature for 500 cycles is more than 85 percent.
(3) The preparation process is simple, easy to operate and suitable for industrial production.
(4) The composite graphite material is suitable for being used as a negative active material to prepare a negative electrode and further prepare a battery, and is suitable for lithium ion batteries of mobile phones, digital electrical appliances, electric tools, electric automobiles, energy storage and the like.
Drawings
FIG. 1 is an SEM photograph of a composite graphite material prepared in example 1;
fig. 2 is an SEM picture of the composite graphite anode material prepared in comparative example 1.
Detailed Description
Embodiments of the present invention will be described in detail with reference to examples. It will be appreciated by those skilled in the art that the following examples are only preferred embodiments of the invention to facilitate a better understanding of the invention and therefore should not be taken as limiting the scope of the invention.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the experimental materials used, unless otherwise specified, were purchased from conventional biochemical manufacturers.
Example 1
Placing natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, and oxidizing at 600 ℃ for 2h with the oxygen flow rate of 10L/h.kg to obtain oxidized natural graphite (oxidized graphite). According to the mass ratio of 75:25:20,mixing oxidized graphite, petroleum coke (D50 ═ 6-8 μm) and petroleum asphalt, and adding into N2Placing the graphite material in a 600 ℃ fusion machine for mechanical granulation under the atmosphere, cooling the reaction product to room temperature after 5h of mechanical granulation, then adding silicon carbide (D50 ═ 6-8 μm) particles according to the proportion of 92:8, uniformly mixing, and finally graphitizing at 3000 ℃ to obtain the composite graphite material, wherein an SEM picture of the obtained composite graphite material is shown in figure 1.
And (3) electrochemical performance testing:
preparation of a negative electrode:
the composite graphite material obtained in example 1 is used as a negative electrode active material, uniformly mixed according to the mass ratio of CMC to SBR of 96.5:1.5:2, coated on a copper foil current collector, dried and punched for later use.
Assembling the button cell:
the button cell is assembled in a glove box filled with argon, a metal lithium sheet is used as a counter electrode, and the electrolyte is 1mol/LLIPF6And the membrane is a polyethylene/propylene composite microporous membrane, and the button cell is assembled.
Particle size test of the composite graphite material:
the particle size test was carried out with a laser particle sizer according to ISO13320 laser particle sizer standard GB/T19077.1-2003.
Testing the compaction density of the negative pole piece:
adopting hydraulic pressure roll squeezer to press negative pole piece, pressure increases from little to big in proper order, and until the pole piece dies, the following pole piece thickness of record different pressures, then according to formula compaction density become the imbibition speed test of actual surface density/(pole piece thickness-copper foil thickness after the compaction):
the imbibition rate is expressed in imbibition time (seconds, s). Sucking out the electrolyte liquid drop to the rolled negative pole piece by a liquid transfer machine, recording the starting time point, dropping one drop every 5s, recording the ending time point after the electrolyte is dried, wherein the liquid suction time is the ending time point-the starting time point.
And (4) testing standard: the higher the compaction density, the better the performance; the shorter the imbibition time, the better the performance.
And (3) testing capacity and efficiency:
the electrochemical performance test is carried out on a battery tester, the charge-discharge voltage range is 0.001-2V, and the charge-discharge rate is 0.2C.
The particle size, compacted density and liquid absorption rate indexes obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
And (3) testing the cycle performance of the finished battery:
taking the composite graphite materials prepared in examples 1-12 and the composite graphite materials prepared in comparative examples 1-3 as negative active materials, respectively mixing the negative active materials with a conductive agent (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) as binders according to the mass ratio of the SP to the CMC to the SBR of 96 to 1.4 to 1.2 for pulping to obtain slurry with the solid content of 40%, coating the slurry on a copper foil current collector with the thickness of 10 mu m, and preparing a negative plate through vacuum drying and rolling; the positive electrode active material lithium cobaltate (LiCoO)2) Uniformly mixing a conductive agent (SP) and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:2:1, and coating the mixture on an aluminum foil current collector to prepare a positive pole piece. Using 1.0-1.2mol/L LiPF6The positive EC/EMC/DEC is 1/1/1(V: V: V), a proper amount of additive is added, a PE/PP/PE composite film is used as a diaphragm, normal-temperature charge-discharge circulation is carried out at a multiplying power of 1C, and the charge-discharge voltage range is 3.0-4.35V. The cycle capacity retention of the finished battery is shown in table 2.
Example 2
Placing natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, and oxidizing at 500 ℃ for 2h with the oxygen flow rate of 15L/h.kg to obtain oxidized natural graphite (oxidized graphite). Mixing oxidized graphite, petroleum coke (D50 is 6-8 μm) and petroleum asphalt according to the mass ratio of 75:25:20, and then adding the mixture into N2And (2) mechanically granulating in a fusion machine at 650 ℃ in the atmosphere, cooling the reaction product to room temperature after 5 hours of mechanical granulation, adding silicon carbide (D50 is 6-8 mu m) particles according to the ratio of 95:5, uniformly mixing, and finally graphitizing at 3000 ℃ to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Example 3
Placing natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) in a box furnace, introducing oxygen, and oxidizing at 500 ℃ for 5h with the oxygen flow rate of 20L/h.kg to obtain oxidized natural graphite (oxidized graphite). Mixing oxidized graphite, petroleum coke (D50 is 6-8 μm) and petroleum asphalt according to the mass ratio of 60:40:20, and then adding the mixture into N2And (2) mechanically granulating in a fusion machine at 650 ℃ in the atmosphere, cooling the reaction product to room temperature after 5 hours of mechanical granulation, adding silicon carbide (D50 is 6-8 mu m) particles according to the ratio of 95:5, uniformly mixing, and finally graphitizing at 3000 ℃ to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Example 4
Putting natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) into a rotary furnace, introducing ammonia gas, and carrying out ammoniation at 600 ℃ for 2h at the ammonia gas flow rate of 10L/h.kg to obtain ammoniated natural graphite (ammoniated graphite). Mixing ammoniated graphite, petroleum coke (D50 is 6-8 μm) and petroleum asphalt according to the mass ratio of 75:25:20, and then adding the mixture into N2And (2) mechanically granulating in a fusion machine at 650 ℃ in the atmosphere, cooling the reaction product to room temperature after 5 hours of mechanical granulation, adding silicon carbide (D50 is 6-8 mu m) particles according to the proportion of 92:8, uniformly mixing, and finally graphitizing at 3000 ℃ to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Example 5
Putting natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) into a box furnace, introducing ammonia gas, and carrying out ammoniation at 500 ℃ for 5h, wherein the flow rate of the ammonia gas is 20L/h.kg, so as to obtain ammoniated natural graphite (ammoniated graphite). Mixing ammoniated graphite, petroleum coke (D50 is 6-8 μm) and petroleum asphalt according to the mass ratio of 60:40:20, and then adding the mixture into N2And (2) mechanically granulating in a fusion machine at 650 ℃ in the atmosphere, cooling the reaction product to room temperature after 5 hours of mechanical granulation, adding silicon carbide (D50 is 6-8 mu m) particles according to the proportion of 92:8, uniformly mixing, and finally graphitizing at 3000 ℃ to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Example 6
Placing natural spherical graphite (D50 is 4-6 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, and oxidizing at 600 ℃ for 2h with the oxygen flow rate of 10L/h.kg to obtain oxidized natural graphite (oxidized graphite). Mixing oxidized graphite, petroleum coke (D50 is 6-8 μm) and coal pitch according to the mass ratio of 50:50:20, and then adding the mixture into N2And (2) mechanically granulating in a 600 ℃ fusion machine under the atmosphere, cooling the reaction product to room temperature after mechanical granulation for 10h, adding silicon carbide (D50-6-8 mu m) particles according to the ratio of 95:5, uniformly mixing, and finally graphitizing at 2600 ℃ to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Example 7
Putting natural spherical graphite (D50 is 4-6 μm, S50 is 0.80-0.95) into a rotary kiln, introducing ammonia gas, and carrying out ammoniation at 600 ℃ for 2h at the ammonia gas flow rate of 10L/h.kg to obtain ammoniated natural graphite (ammoniated graphite). Mixing ammoniated graphite, petroleum coke (D50 is 6-8 μm) and coal tar pitch according to the mass ratio of 60:40:20, and then adding the mixture into N2And (2) mechanically granulating in a 600 ℃ fusion machine under the atmosphere, cooling the reaction product to room temperature after mechanical granulation for 10h, adding boron oxide (D50-8-10 mu m) particles according to a ratio of 95:5, uniformly mixing, and finally graphitizing at 2600 ℃ to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Example 8
Placing natural spherical graphite (D50 is 4-6 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, and oxidizing at 600 ℃ for 2h with the oxygen flow rate of 10L/h.kg to obtain oxidized natural graphite (oxidized graphite). Mixing oxidized graphite, MCMB (D50 is 6-8 μm) and petroleum asphalt according to the mass ratio of 75:25:20, and then adding the mixture into N2And (2) mechanically granulating in a fusion machine at 650 ℃ in the atmosphere, cooling the reaction product to room temperature after 5 hours of mechanical granulation, adding silicon carbide (D50 is 6-8 mu m) particles according to the proportion of 92:8, uniformly mixing, and finally graphitizing at 3000 ℃ to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Example 9
Natural spherical graphite (D50 ═ 4 μm to 6 μm, S50 ═ 0.80-0.95), placing in a rotary kiln, introducing ammonia gas, and carrying out ammoniation for 5 hours at 500 ℃, wherein the flow of the ammonia gas is 20L/h.kg, so as to obtain the ammoniated natural graphite (ammoniated graphite). Mixing ammoniated graphite, MCMB (D50 is 6-8 μm) and coal tar pitch according to the mass ratio of 50:50:20, and then adding the mixture into N2And (2) mechanically granulating in a fusion machine at 650 ℃ in the atmosphere, cooling the reaction product to room temperature after 5 hours of mechanical granulation, adding silicon carbide (D50 is 6-8 mu m) particles according to the proportion of 92:8, uniformly mixing, and finally graphitizing at 3000 ℃ to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Example 10
Placing natural spherical graphite (D50 is 4-6 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, and oxidizing at 500 ℃ for 5h with the oxygen flow rate of 15L/h.kg to obtain oxidized natural graphite (oxidized graphite). Mixing oxidized graphite, petroleum coke (D50 is 6-8 μm) and coal pitch according to the mass ratio of 30:70:15, and then adding the mixture into N2And (2) mechanically granulating in a fusion machine at 650 ℃ in the atmosphere, cooling the reaction product to room temperature after 5 hours of mechanical granulation, adding silicon carbide (D50 is 6-8 mu m) particles according to a ratio of 90:10, uniformly mixing, and finally graphitizing at 3000 ℃ to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Example 11
Placing natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, oxidizing at 700 ℃ for 2.5h, wherein the oxygen flow is 15L/h.kg, and obtaining the oxidized natural graphite (oxidized graphite).
Putting natural spherical graphite (D50 is 3-5 μm, S50 is 0.80-0.95) into a box furnace, introducing ammonia gas, and ammoniating at 450 ℃ for 5h at the ammonia gas flow rate of 10L/h.kg to obtain ammoniated natural graphite (ammoniated graphite).
Mixing a mixture of oxidizing graphite and aminated graphite (the mass ratio of oxidizing graphite to aminated graphite is 5:5), MCMB (D50 ═ 6 to 8 μm), and coal tar pitch at a mass ratio of 50:40:20, and adding N2And (2) mechanically granulating in a fusion machine at 620 ℃ in the atmosphere, cooling the reaction product to room temperature after mechanical granulation is carried out for 8h, adding silicon carbide (D50 is 6-8 mu m) particles according to the proportion of 92:8, uniformly mixing, and finally graphitizing at 3200 ℃ to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Example 12
Placing natural spherical graphite (D50 is 5-7 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, and oxidizing at 600 ℃ for 3h with the oxygen flow rate of 8L/h.kg to obtain oxidized natural graphite (oxidized graphite).
Putting natural spherical graphite (D50 is 5-6 μm, S50 is 0.80-0.95) into a rotary kiln, introducing ammonia gas, and carrying out ammoniation at 650 ℃ for 4.5h, wherein the flow rate of the ammonia gas is 12.5L/h.kg, so as to obtain ammoniated natural graphite (ammoniated graphite).
Mixing a mixture of oxidized graphite and aminated graphite (the mass ratio of oxidized graphite to aminated graphite is 4:6), MCMB (D50 ═ 6 to 8 μm), and petroleum pitch at a mass ratio of 70:30:15, and adding N2Mechanically granulating at 625 deg.C in a fusion machine, mechanically granulating for 9 hr, cooling to room temperature, adding silicon carbide (D50 ═ 6-8 μm) at a ratio of 92:8, mixing, and graphitizing at 2800 deg.CAnd (5) processing to obtain the composite graphite material.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Comparative example 1
A composite graphite material was prepared in the same manner and under the same conditions as in example 1, except that the oxidized graphite in example 1 was replaced with natural spherical graphite (D50 ═ 6 μm to 8 μm, S50 ═ 0.80 to 0.95), and the SEM image of the obtained composite graphite material is shown in fig. 2.
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Comparative example 2
A composite graphite material was produced in the same manner and under the same conditions as in example 6, except that the oxidized graphite in example 6 was replaced with natural spherical graphite (D50 ═ 4 μm to 6 μm, S50 ═ 0.80 to 0.95).
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
Comparative example 3
A composite graphite material was produced in the same manner and under the same conditions as in example 9, except that the aminated graphite in example 9 was replaced with natural spheroidal graphite (D50 ═ 4 μm to 6 μm, S50 ═ 0.80 to 0.95).
Preparing a negative electrode by the same method as the embodiment 1, assembling the negative electrode into a button cell and carrying out performance test, wherein the indexes of the granularity, the compaction density and the imbibition rate obtained by the test are listed in table 1; the first lithium-removal specific capacity, the first charge-discharge efficiency and the cycle performance index of the battery are shown in table 2.
TABLE 1
TABLE 2
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 (42)
1. A method for preparing a composite graphite material, comprising the steps of:
(1) uniformly mixing activated natural graphite, an artificial graphite precursor and asphalt;
(2) placing the mixture in a fusion machine, and performing fusion granulation in an inert atmosphere to obtain a fusion granulation product;
(3) uniformly mixing the fused and granulated product with a graphitization catalyst, and graphitizing to obtain a composite graphite material;
wherein the activated natural graphite is natural graphite with surface functionalization treatment;
the natural graphite subjected to surface functionalization treatment is aminated and compositely oxidized, or a mixture of aminated natural graphite and oxidized natural graphite;
in the mixture of the aminated natural graphite and the oxidized natural graphite, the mass ratio of the aminated natural graphite to the oxidized natural graphite is 7: 3-5: 5;
the graphitization catalyst in the step (3) is any one or a mixture of at least two of carbide, boron oxide or iron oxide; the adding amount of the graphitizing catalyst in the step (3) accounts for 3-10 wt% of the total mass of the graphitizing catalyst and the granulated product.
2. The method according to claim 1, wherein the surface-functionalization treated natural graphite is a mixture of aminated natural graphite and oxidized natural graphite.
3. The method according to claim 1, wherein the aminated natural graphite is prepared by the following method: and carrying out heat treatment on the natural graphite in an ammonia atmosphere to obtain the aminated natural graphite.
4. The method according to claim 1, wherein the oxidation-treated natural graphite is prepared by: and (3) carrying out heat treatment on the natural graphite in an oxygen atmosphere and/or an air atmosphere to obtain the natural graphite subjected to oxidation treatment.
5. The method according to claim 1, wherein the aminated complex oxidation treated natural graphite is prepared by scheme one or scheme two:
the first scheme is as follows: carrying out heat treatment on the aminated natural graphite in an oxygen atmosphere and/or an air atmosphere;
scheme II: and carrying out heat treatment on the oxidized natural graphite in an ammonia atmosphere.
6. The method according to claim 1, wherein the natural graphite has a median particle diameter D50 of 2 to 12 μm.
7. The method according to claim 6, wherein the natural graphite has a median particle diameter D50-3 μm to 8 μm.
8. The method according to claim 1, wherein the sphericity of the natural graphite is 0.80-0.95% S50.
9. The method of claim 1, wherein the natural graphite has a carbon content of greater than 99.95 wt.%.
10. The method according to any one of claims 3 to 5, wherein the heat treatment temperature during the preparation of the aminated natural graphite, the oxidized natural graphite and the aminated complex oxidized natural graphite is independently 300 ℃ to 1000 ℃.
11. The method as claimed in claim 10, wherein the heat treatment temperature is independently 600 to 800 ℃ in the process of preparing the aminated natural graphite, the oxidized natural graphite and the aminated complex oxidized natural graphite.
12. The method according to any one of claims 3 to 5, wherein the heat treatment time in the preparation of the aminated natural graphite, the oxidized natural graphite and the aminated complex oxidized natural graphite is independently 2 to 5 hours.
13. The method as claimed in claim 3, wherein the flow rate of the ammonia gas is 5L/h.kg-20L/h.kg during the preparation of the aminated natural graphite.
14. The method according to claim 4, wherein the flow rate of oxygen and/or air in the process of preparing the oxidation-treated natural graphite is 5L/h.kg to 20L/h.kg.
15. The method of claim 5, wherein in the first embodiment, the flow rate of oxygen and/or air is 5L/h.kg-20L/h.kg.
16. The method according to claim 5, wherein the flow rate of the ammonia gas in the second scheme is 5L/h.kg-20L/h.kg.
17. The method according to claim 1, wherein the surface-functionalization-treated natural graphite is prepared by using any one of a rotary kiln, a box-type heating furnace, and a tube furnace.
18. The method of claim 1, wherein the artificial graphite precursor of step (1) is coke and/or meso-carbon microsphere graphite (MCMB).
19. The method of claim 18, wherein the coke is petroleum-based coke, coal-based coke, or a mixed coke of petroleum-based coke and coal-based coke.
20. The method of claim 19, wherein the petroleum-based coke comprises any one of oil-based needle coke, sponge coke, or shot coke, or a combination of at least two thereof.
21. The method of claim 19, wherein the coal-based coke comprises any one of or a combination of at least two of coal-based needle coke, pitch coke, or modified pitch coke.
22. The method of claim 18, wherein the coke has a median particle size D50 of 2 to 12 μm.
23. The method of claim 22, wherein the coke has a median particle size D50 of 3 to 8 μm.
24. The method of claim 18, wherein the mesocarbon microbead graphite is a green pellet.
25. The method of claim 18, wherein the meso-carbon microsphere graphite has a median particle size of D50-2 μ ι η to 12 μ ι η.
26. The method of claim 25, wherein the meso-carbon microsphere graphite has a median particle size of D50-3 μ ι η to 8 μ ι η.
27. The method according to claim 1, wherein the asphalt in the step (1) is any one or a mixture of at least two of petroleum asphalt, coal-series asphalt or modified asphalt.
28. The method of claim 27, wherein the coal-based asphalt comprises any one of low-temperature coal asphalt, medium-temperature coal asphalt, or high-temperature coal asphalt, or a combination of at least two of them.
29. The method of claim 27, wherein the modified asphalt comprises any one of resin modified asphalt, rubber modified asphalt, or oxidation modified asphalt, or a combination of at least two thereof.
30. The method as claimed in claim 1, wherein the activated natural graphite, the artificial graphite and the pitch in the step (1) are mixed at a mass ratio of (90-10): (10-90): (5-30).
31. The method according to claim 1, wherein the inert atmosphere in the step (2) is any one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere, or a xenon atmosphere, or a combination of at least two thereof.
32. The method according to claim 1, wherein the fusing granulation in the step (2) is carried out by using a fusing machine.
33. The method according to claim 1, wherein the temperature of the fusion granulation in the step (2) is 600 ℃ to 650 ℃.
34. The method according to claim 1, wherein the time for the fusion granulation in the step (2) is 5 to 10 hours.
35. The method according to claim 1, wherein the graphitization catalyst of step (3) is silicon carbide.
36. The method according to claim 1, wherein the median particle diameter of the graphitization catalyst in step (3) is 2-15 μm.
37. The method according to claim 1, wherein the graphitization temperature in the step (3) is 2600-3200 ℃.
38. The method according to claim 1, further comprising the step of classifying or screening after the completion of graphitization.
39. Method according to claim 1, characterized in that it comprises the following steps:
(1) taking natural graphite with the median particle size of D50-3-8 μm as a raw material, introducing ammonia gas at the flow rate of 5-20L/h.kg, and carrying out heat treatment at 600-800 ℃ for 2-5 h to obtain aminated natural graphite;
(2) taking natural graphite with the median particle size of D50-3-8 μm as a raw material, introducing oxygen at the flow rate of 5-20L/h.kg, and carrying out heat treatment at 600-800 ℃ for 2-5 h to obtain natural graphite subjected to oxidation treatment;
(3) uniformly mixing a mixture of aminated natural graphite and oxidized natural graphite, petroleum coke and petroleum asphalt according to the ratio of (90-10) to (10-90) to (5-30), adding into a mechanical fusion machine, introducing inert gas, fusing and granulating for 5-10 h at the temperature of 600-650 ℃, and cooling to obtain a fused and granulated product;
(4) uniformly mixing the fused and granulated product with silicon carbide, graphitizing at 2600-3200 ℃, and grading or sieving to obtain the composite graphite material.
40. A composite graphite material produced by the method of claim 1.
41. A negative electrode comprising the composite graphite material according to claim 40 as a negative electrode active material.
42. A lithium ion battery comprising the composite graphite material according to claim 40.
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