CN113851614A - Low-temperature quick-charging artificial graphite cathode material, preparation method thereof and low-temperature quick-charging battery - Google Patents
Low-temperature quick-charging artificial graphite cathode material, preparation method thereof and low-temperature quick-charging 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a low-temperature quick-charging artificial graphite cathode material, a preparation method thereof and a low-temperature quick-charging battery, wherein the composite material comprises a graphite substrate, and a carbon nano tube and amorphous carbon which are coated on the surface of the graphite substrate; the mass of the carbon nano tube and the amorphous carbon is 0.5-5% of that of the graphite matrix; in the preparation process, petroleum coke, pitch coke or graphite electrode joint powder is used as a raw material, and the low-temperature quick-charging artificial graphite negative electrode material is obtained by crushing, shaping and spheroidizing, purifying at high temperature and then carrying out CVD vapor deposition carbon coating. Compared with the prior art, the small-particle-size graphite single particles used in the invention have better low-temperature quick-charging performance; the graphite has higher purity and crystallinity by adopting a high-temperature purification mode; the adoption of the two-step cooling mode is beneficial to eliminating the internal stress generated in the material preparation process; the battery prepared by using the low-temperature quick-charging artificial graphite cathode material has higher energy density and good low-temperature quick-charging performance.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a low-temperature fast-charging artificial graphite cathode material and a preparation method thereof.
Background
In recent years, new energy electric vehicles are widely popularized in China, but the electric vehicle battery is long in charging time, and the popularization of the electric vehicle is hindered due to the fact that the performance of the battery is greatly reduced in cold weather in winter, so that the low-temperature quick-charging performance of the lithium ion battery is urgently needed to be improved. The improvement of the performance of the lithium ion battery is mainly determined by the improvement of the electrochemical performance of the electrode material. Therefore, it is important to improve the charge-discharge characteristics of the negative electrode material while maintaining excellent cycle performance. In the prior art, the low-temperature quick-charging graphite cathode material is basically formed by carbonizing secondary particles, but the secondary particle carbonization has the defects of coating modification, complex process, high cost and the like. Meanwhile, the energy density loss to a certain degree is caused by the fact that the coating layer is too thick; in addition, the technical scheme is restricted by larger secondary particle size, so that the low-temperature quick charge performance of the graphite cathode material can not be further improved, and the performance requirement of the lithium ion battery on low-temperature quick charge is difficult to meet.
In view of the above, there is a need to develop a low-temperature fast-charging graphite negative electrode material with small particle size, single particle surface coating, simple process, and excellent low-temperature and fast-charging performance, and a preparation method thereof.
Chinese patents CN102299308A and CN103199254A respectively report a negative electrode material of a lithium ion battery and a preparation method thereof, which adopts a vapor deposition method to form a composite material by in-situ grown reticular carbon nanotubes and/or carbon fibers on the surface of a graphite matrix, and/or reticular carbon nanotubes and/or carbon fibers mixed between graphite matrices. The rate capability, the liquid absorption and the cycle performance of the lithium ion battery are improved by using the material. However, the method adopts the metal catalyst, so that a large amount of metal impurities remain on the surface of the obtained material, the charge and discharge performance of the material is influenced, and the specific capacity of the material is reduced. The material stress is released too fast by adopting a one-step cooling mode, so that a surface coating layer falls off, and the low-temperature quick-charging performance of the material is still poor.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a low-temperature fast-charging artificial graphite cathode material and a preparation method thereof, a small-particle-size single-particle surface coating structure is prepared by a simple process, and excellent low-temperature fast-charging performance is realized.
The purpose of the invention can be realized by the following technical scheme:
the low-temperature quick-charging artificial graphite cathode material is a coated carbon composite material; the composite material comprises a graphite substrate, and a carbon nano tube and amorphous carbon which are coated on the surface of the graphite substrate; the mass of the carbon nano tube and the amorphous carbon is 0.5-5% of that of the graphite matrix.
Further, the graphitization degree of the composite material is 85-95%, the particle size D50 is 3-8 mu m, and the tap density is 0.7-1.2 g/cm3The specific surface area is 1 to 6m2/g。
The preparation method of the low-temperature quick-charging artificial graphite cathode material is characterized by comprising the following steps of:
s1: crushing, shaping and spheroidizing the raw materials to obtain graphite precursor powder;
s2: placing the graphite precursor powder in a high-temperature purification furnace, and purifying at high temperature to obtain a graphite matrix;
s3: placing the graphite matrix in a vapor deposition furnace, heating to a set deposition temperature under the protection of inert protective gas, and performing vapor deposition at the set deposition temperature under the atmosphere of inert protective gas, catalytic gas and carbon source gas to obtain a carbon-coated artificial graphite cathode material;
s4: and screening the carbon-coated artificial graphite negative electrode material obtained in the step S3 to obtain the low-temperature quick-charging artificial graphite negative electrode material with the average particle size D50 of 3-8 microns.
Further, the raw material in S1 is one or more of petroleum coke with a particle size of less than 10mm, pitch coke and graphite electrode joint powder.
Furthermore, the particle size D50 of the graphite precursor powder in S1 is 2-7 μm.
Further, in S2, the graphite substrate is placed in the hearth of the vapor deposition furnace, and the hearth is rotated at a rotation speed of 0 to 30 rpm.
Further, the high-temperature purification process in S2 is: and introducing inert protective gas, heating to 2600-3000 ℃ at the heating rate of 1-20 ℃/min, simultaneously introducing purified gas chlorine or freon, preserving heat for 1-96 h, then stopping introducing purified gas chlorine or freon, and cooling along with the furnace under the condition of the inert protective gas.
Further, the purified gas is chlorine or freon.
Further, the vapor deposition furnace is one of a rotary furnace, a tube furnace and a fluidized bed.
Further, the process of vapor deposition in S3 is:
s3-1: heating to a set deposition temperature at the speed of 3-15 ℃/min, and introducing inert protective gas into a hearth of the vapor deposition furnace at the flow rate of 10-500L/h, wherein the set deposition temperature is 800-1100 ℃;
s3-2: when the temperature reaches the set deposition temperature, adjusting the flow of inert protective gas to 100-2000L/h, and simultaneously introducing catalytic gas and carbon source gas for 0.5-5 h;
s3-3: stopping introducing the catalytic gas and the carbon source gas, adjusting the flow of the inert protective gas to 10-500L/h, and preserving heat for 0.5-2 h when the temperature is reduced to 500-700 ℃; stopping heating, cooling to below 60 ℃, and stopping introducing inert protective gas to obtain the carbon-coated artificial graphite cathode material.
Further, the carbon source gas is one or more of methane, ethane, acetylene, ethylene, natural gas, liquefied petroleum gas, benzene or thiophene;
the catalytic gas is hydrogen;
the inert protective gas is nitrogen or argon;
the inert shielding gas flow rate is as follows: carbon source gas flow rate: the hydrogen flow rate is 1 (1/3-1) and (1/20-1/10).
Further, in S4, the screen was sieved with an ultrasonic vibration sieve having a mesh size of 325 mesh.
Compared with the prior art, the invention has the following advantages:
1) the technical scheme adopts petroleum coke, pitch coke and graphite electrode joint powder as raw materials, a graphite matrix is prepared by a high-temperature purification method, and a carbon nano tube and amorphous carbon grow in situ on the surface of the graphite matrix material by a two-step cooling CVD vapor deposition coating method. The technical scheme adopts CVD vapor deposition coating to reduce the carbon coating capacity, so that the material has higher specific capacity and compaction density; the coating layer has low graphitization degree and high lithium intercalation potential, thereby preventing the electrolyte from obtaining electrons on the graphite surface and being reduced, improving the charge-discharge efficiency, simultaneously reducing the deposition of Li metal on the graphite surface and improving the safety.
2) The small-particle graphite adopted in the technical scheme has superior high-current charge and discharge performance compared with large-particle graphite. On one hand, the small particles can reduce the current loaded in unit area, thereby being beneficial to reducing the overpotential; on the other hand, the edge of the small-particle carbon microcrystal can provide more migration channels for lithium ions; meanwhile, the lithium ion migration path is short, and the diffusion resistance is small.
3) The technical scheme adopts a high-temperature purification mode to ensure that the graphite has higher purity and crystallinity; the technical scheme adopts a two-step cooling mode, which is favorable for eliminating internal stress generated in the material preparation process, so that the graphite has better structural stability, and the coating layer on the surface of the graphite is more tightly combined.
4) The interlayer spacing of the amorphous carbon prepared in the technical scheme is larger than that of graphite, so that the diffusion performance of lithium ions in the amorphous carbon can be improved, namely a lithium ion buffer layer is formed on the outer surface of the graphite, and the high-current charge and discharge performance of the material is improved; the in-situ growth of the carbon nano tube and the amorphous carbon can improve the interaction with lithium ions, improve the desolvation speed, improve the interface reaction speed and improve the low-temperature charge and discharge performance.
Through the combination of the advantages, when the graphite cathode material prepared in the technical scheme is applied to a battery, higher energy density and excellent low-temperature quick charge performance can be realized.
Drawings
Fig. 1 is an SEM image of the low-temperature rapid-charging artificial graphite negative electrode material in example 1.
Detailed Description
The following examples are given for the detailed embodiments and specific procedures of the present invention, but the scope of the present invention is not limited to the following examples.
The invention relates to a low-temperature quick-charging artificial graphite cathode material, which is a composite material consisting of a graphite matrix and carbon nano tubes and amorphous carbon, wherein the carbon nano tubes and the amorphous carbon are coated on the surface of the graphite matrix. Wherein the graphitization degree of the composite material is 85-95%, the granularity D50 is 3-8 microns, and the tap density is 0.7-1.2 g/cm3The specific surface area is 1-6 m2Between/g; wherein the mass of the carbon nano tube and the amorphous carbon is 0.5-5% of that of the graphite matrix.
The preparation method of the low-temperature quick-charging artificial graphite cathode material comprises the following steps:
firstly, crushing, shaping and spheroidizing:
the raw materials are crushed, shaped and spheroidized to obtain the graphite precursor powder. Wherein the adopted raw material is one or more of petroleum coke with the grain diameter less than 10mm, pitch coke or graphite electrode joint powder. The particle size D50 of the graphite precursor powder is 2-7 microns.
Secondly, high-temperature purification:
putting the graphite precursor powder into a high-temperature purification furnace, introducing inert protective gas, heating to 2600-3000 ℃ at the heating rate of 1-20 ℃/min, simultaneously introducing purified gas chlorine or freon, preserving the heat for 1-96 h, then stopping introducing the purified gas chlorine or freon, and cooling along with the furnace under the inert protective gas condition to obtain the graphite matrix.
Wherein the high-temperature purifying furnace is a box-type high-temperature graphite purifying furnace, a continuous high-temperature graphite purifying furnace or a push boat-type high-temperature graphite purifying furnace. Wherein the adopted purified gas is chlorine or Freon.
Thirdly, vapor deposition:
putting a graphite matrix into a hearth of a vapor deposition furnace, heating at the speed of 3-15 ℃/min, introducing inert protective gas nitrogen or argon at the flow rate of 10-500L/h, adjusting the flow rate of the inert protective gas nitrogen or argon to 100-2000L/h when the temperature reaches 800-1100 ℃, and introducing catalytic gas hydrogen and carbon source gas, wherein the inert protective gas flow rate is as follows: carbon source gas flow rate: the hydrogen flow rate is 1 (1/3-1) and (1/20-1/10), and the feeding time is 0.5-5 h.
Wherein the vapor deposition furnace is a rotary kiln, a tubular furnace or a fluidized bed; wherein the inert protective gas is nitrogen or argon. Wherein the carbon source gas is methane, ethane, acetylene, ethylene, natural gas, liquefied petroleum gas, benzene or thiophene.
Fourthly, cooling:
stopping introducing the catalytic gas and the carbon source gas, adjusting the flow of the inert protective gas to 10-500L/h, and preserving heat for 0.5-2 h at 500-700 ℃ in a furnace cooling mode; and (3) closing the heating power supply, cooling to below 60 ℃ along with the furnace, and stopping introducing inert protective gas nitrogen or argon to obtain the vapor deposition carbon-coated artificial graphite cathode material.
And fifthly, screening:
and (3) screening the vapor deposition carbon-coated artificial graphite cathode material, wherein the mesh number of the ultrasonic vibration screen is 325 meshes, so as to obtain the low-temperature fast-charging artificial graphite cathode material with the average particle size D50 of 3-8 mu m.
The method of the invention selects petroleum coke, pitch coke and graphite electrode joint powder as raw materials, and greatly reduces the cost in the selection of the raw materials because of higher impurity content and lower price.
In the prior art, the low-temperature quick-charging graphite cathode material is basically formed by carbonizing secondary particles, but the secondary particle carbonization has the defects of coating modification, complex process, high cost and the like. The common solid phase or liquid phase is not good in coating uniformity, so that the electrochemical performance of the material is not improved, the thickness of a coating layer is difficult to accurately control, and energy density loss to a certain degree is caused by too thick coating layer; in addition, the method in the prior art can cause the particle size of the material to be increased, is not beneficial to improving the low-temperature quick charge performance of the graphite cathode material, and is difficult to meet the performance requirement of the lithium ion battery on the low-temperature quick charge.
The method comprises the steps of crushing raw materials to 2-7 microns, purifying at high temperature, and carrying out CVD (chemical vapor deposition) carbon coating to obtain the 3-8 micron carbon-coated small-particle-size graphite single-particle negative electrode material. The small-particle-size graphite single particles have better low-temperature quick-charging performance; the graphite has higher purity and crystallinity by adopting a high-temperature purification mode; the vapor deposition preparation method adopted by the invention has simple process, and can realize the accurate control of the coating layer of the electrode material by controlling the factors such as the concentration, the flow, the reaction time and the like of the carbon source gas, thereby leading the material to have higher specific capacity and compaction density; the adoption of the two-step cooling mode is favorable for eliminating the internal stress generated in the material preparation process, so that the graphite has better structural stability, and the coating layer on the surface of the graphite is more tightly combined. The battery prepared by using the low-temperature quick-charging artificial graphite cathode material has higher energy density and good low-temperature quick-charging performance.
For ease of understanding, the following examples are further illustrated.
Example 1:
crushing petroleum coke with the particle size of less than 10mm by using a mechanical mill and a shaping machine, and shaping the petroleum coke into balls until the particle size D50 is 5 microns to obtain graphite precursor powder. Putting the graphite precursor powder into a push boat type high-temperature graphite purification furnace, introducing inert protective gas, heating to 2600 ℃ at the heating rate of 10 ℃/min, introducing purified gas chlorine, preserving the temperature for 96 hours, then stopping introducing the purified gas chlorine, and cooling along with the furnace under the condition of the inert protective gas to obtain the graphite substrate.
Putting 10Kg of the obtained graphite substrate into a hearth of a rotary kiln; rotating a hearth at the rotating speed of 10rpm, heating at the speed of 15 ℃/min, simultaneously introducing inert protective gas nitrogen at the flow rate of 500L/h, adjusting the flow rate of the inert protective gas nitrogen to 2000L/h when the temperature reaches 1100 ℃, and simultaneously introducing catalytic gas hydrogen and carbon source gas methane, wherein in order to ensure the CVD vapor deposition effect, the inert protective gas flow rate: carbon source gas flow rate: the hydrogen flow rate is 1, (1), (1/10), the flowing time is 0.5 h. After stopping introducing the carbon source gas and the catalytic gas, adjusting the flow of the inert protective gas to 500L/h, and preserving heat for 2h to 700 ℃ by adopting a furnace cooling mode; and (3) closing the heating power supply, cooling to below 60 ℃ along with the furnace, and stopping introducing the inert protective gas to obtain the vapor deposition carbon-coated artificial graphite cathode material. And screening the obtained vapor deposition carbon-coated artificial graphite cathode material, wherein the mesh number of an ultrasonic vibration screen is 325 meshes, so as to obtain the low-temperature quick-charging artificial graphite cathode material with the average particle size D50 of 3-8 mu m.
In this embodiment, as shown in fig. 1, an SEM image of the low-temperature rapid-charging artificial graphite negative electrode material can clearly represent morphology structures of the carbon nanotube and the amorphous carbon coated on the surface of the graphite substrate.
And (3) performing electrochemical performance test on the half-cell formed by the obtained low-temperature fast-charging artificial graphite cathode material and the metal lithium, wherein the test current density and the charge-discharge voltage are 0-2.0V. The button cell can reach 336mAh/g in specific discharge capacity under the charge-discharge multiplying power of 0.2C/0.2C, the first efficiency is 92.7%, the charge-discharge capacity of 5C is 91% of that of 0.2C, and the capacity of 89% can still be maintained under the discharge at the temperature of minus 20 ℃.
Example 2:
crushing petroleum coke with the particle size of less than 10mm by using a mechanical mill and a shaping machine, and shaping the petroleum coke into balls until the particle size D50 is 2 microns to obtain graphite precursor powder. Putting the graphite precursor powder into a push boat type high-temperature graphite purification furnace, introducing inert protective gas, heating to 2800 ℃ at the heating rate of 1 ℃/min, introducing purified gas Freon, preserving heat for 48 hours, then stopping introducing the purified gas Freon, and cooling along with the furnace under the inert protective gas condition to obtain the graphite substrate.
Putting 10Kg of the obtained graphite substrate into a hearth of a rotary kiln; rotating a hearth at the rotating speed of 10rpm, heating at the speed of 3 ℃/min, simultaneously introducing an inert protective gas nitrogen at the flow rate of 250L/h, adjusting the flow rate of the inert protective gas nitrogen to 1000L/h when the temperature reaches 1100 ℃, and simultaneously introducing catalytic gas hydrogen and carbon source gas acetylene, wherein in order to ensure the CVD vapor deposition effect, the inert protective gas flow rate: carbon source gas flow rate: the hydrogen flow rate is 1, (1/3), (1/20), and the flowing time is 2.5 h. After stopping introducing the carbon source gas and the catalytic gas, adjusting the flow of the inert protective gas to 250L/h, and preserving heat for 0.5h to 600 ℃ in a furnace cooling mode; and (3) closing the heating power supply, cooling to below 60 ℃ along with the furnace, and stopping introducing the inert protective gas to obtain the vapor deposition carbon-coated artificial graphite cathode material. And screening the obtained vapor deposition carbon-coated artificial graphite cathode material, wherein the mesh number of an ultrasonic vibration screen is 325 meshes, so as to obtain the low-temperature quick-charging artificial graphite cathode material with the average particle size D50 of 3-8 mu m.
And (3) testing the electrochemical performance of the half-cell formed by the obtained low-temperature quick-charging artificial graphite cathode material and the metal lithium, wherein the charging and discharging voltage is 0-2.0V. The button cell can reach 347mAh/g of specific discharge capacity under the charge-discharge multiplying power of 0.2C/0.2C, the first efficiency is 93.4%, the charge-discharge capacity of 5C is 89% of that of 0.2C, and the capacity of 85% can still be maintained under the discharge at the temperature of minus 20 ℃.
Example 3:
crushing petroleum coke with the particle size of less than 10mm by using a mechanical mill and a shaping machine, and shaping the petroleum coke into balls until the particle size D50 is 7 microns to obtain graphite precursor powder. Putting the graphite precursor powder into a push boat type high-temperature graphite purification furnace, introducing inert protective gas, heating to 3000 ℃ at the heating rate of 5 ℃/min, introducing purified gas chlorine, preserving the temperature for 1h, then stopping introducing the purified gas chlorine, and cooling along with the furnace under the condition of the inert protective gas to obtain the graphite substrate.
Putting 10Kg of the obtained graphite substrate into a hearth of a rotary kiln; rotating a hearth at the rotating speed of 30rpm, heating at the speed of 15 ℃/min, introducing an inert protective gas argon at the flow rate of 250L/h, adjusting the flow rate of the inert protective gas argon to 1000L/h when the temperature reaches 950 ℃, and introducing catalytic gas hydrogen and carbon source gas natural gas at the same time, wherein in order to ensure the CVD vapor deposition effect, the inert protective gas flow rate: carbon source gas flow rate: the hydrogen flow rate is 1, (1/3), (1/10) and the flowing time is 5 h. After stopping introducing the carbon source gas and the catalytic gas, adjusting the flow of the inert protective gas to 250L/h, and preserving heat for 0.5h to 600 ℃ in a furnace cooling mode; and (3) closing the heating power supply, cooling to below 60 ℃ along with the furnace, and stopping introducing the inert protective gas to obtain the vapor deposition carbon-coated artificial graphite cathode material. And screening the obtained vapor deposition carbon-coated artificial graphite cathode material, wherein the mesh number of an ultrasonic vibration screen is 325 meshes, so as to obtain the low-temperature quick-charging artificial graphite cathode material with the average particle size D50 of 3-8 mu m.
And (3) testing the electrochemical performance of the half-cell formed by the obtained low-temperature quick-charging artificial graphite cathode material and the metal lithium, wherein the charging and discharging voltage is 0-2.0V. The button cell can reach 353mAh/g of specific discharge capacity under the charge-discharge multiplying power of 0.2C/0.2C, the first efficiency is 94.2%, the charge-discharge capacity of 5C is 85% of that of 0.2C, and the capacity of 81% can still be maintained under the discharge at the temperature of minus 20 ℃.
Example 4:
crushing petroleum coke with the particle size of less than 10mm by using a mechanical mill and a shaping machine, and shaping the petroleum coke into balls until the particle size D50 is 5 microns to obtain graphite precursor powder. Putting the graphite precursor powder into a push boat type high-temperature graphite purification furnace, introducing inert protective gas, heating to 2600 ℃ at the heating rate of 20 ℃/min, introducing purified gas chlorine, preserving the temperature for 96 hours, then stopping introducing the purified gas chlorine, and cooling along with the furnace under the condition of the inert protective gas to obtain the graphite substrate.
Putting 10Kg of the obtained graphite substrate into a hearth of a rotary kiln; rotating a hearth at the rotating speed of 0rpm, heating at the speed of 5 ℃/min, introducing inert protective gas nitrogen at the flow rate of 10L/h, adjusting the flow rate of the inert protective gas nitrogen or argon to 100L/h when the temperature reaches 800 ℃, and introducing catalytic gas hydrogen and carbon source gas acetylene at the same time, wherein in order to ensure the CVD vapor deposition effect, the flow rate of the inert protective gas is as follows: carbon source gas flow rate:
the hydrogen flow rate is 1, (1/3), (1/20), and the flowing time is 2.5 h. After stopping introducing the carbon source gas and the catalytic gas, adjusting the flow of the inert protective gas to 10L/h, and preserving heat for 1h to 500 ℃ in a furnace cooling mode; and (3) closing the heating power supply, cooling to below 60 ℃ along with the furnace, and stopping introducing the inert protective gas to obtain the vapor deposition carbon-coated artificial graphite cathode material. And screening the obtained vapor deposition carbon-coated artificial graphite cathode material, wherein the mesh number of an ultrasonic vibration screen is 325 meshes, so as to obtain the low-temperature quick-charging artificial graphite cathode material with the average particle size D50 of 3-8 mu m.
And (3) testing the electrochemical performance of the half-cell formed by the obtained low-temperature quick-charging artificial graphite cathode material and the metal lithium, wherein the charging and discharging voltage is 0-2.0V. The button cell can reach 338mAh/g in specific discharge capacity under the charge-discharge rate of 0.2C/0.2C, the first efficiency is 93.6%, the charge-discharge rate of 5C is 90% of the charge-discharge rate of 0.2C, and the button cell can still maintain 87% of the charge capacity under the discharge at the temperature of minus 20 ℃.
Example 5:
crushing petroleum coke with the particle size of less than 10mm by using a mechanical mill and a shaping machine, and shaping the petroleum coke into balls until the particle size D50 is 7 microns to obtain graphite precursor powder. Putting the graphite precursor powder into a push boat type high-temperature graphite purification furnace, introducing inert protective gas, heating to 3000 ℃ at the heating rate of 10 ℃/min, introducing purified gas Freon, preserving heat for 48 hours, then stopping introducing the purified gas Freon, and cooling along with the furnace under the inert protective gas condition to obtain the graphite substrate.
Putting 10Kg of the obtained graphite substrate into a hearth of a rotary kiln; rotating a hearth at the rotating speed of 30rpm, heating at the speed of 3 ℃/min, simultaneously introducing inert protective gas nitrogen at the flow rate of 500L/h, adjusting the flow rate of the inert protective gas nitrogen to 2000L/h when the temperature reaches 1100 ℃, and simultaneously introducing catalytic gas hydrogen and carbon source gas natural gas, wherein in order to ensure the CVD vapor deposition effect, the inert protective gas flow rate: carbon source gas flow rate: the hydrogen flow rate is 1, (1/3), (1/15) and the flowing time is 5 h. After stopping introducing the carbon source gas and the catalytic gas, adjusting the flow of the inert protective gas to 500L/h, and preserving heat for 0.5h to 600 ℃ in a furnace cooling mode; and (3) closing the heating power supply, cooling to below 60 ℃ along with the furnace, and stopping introducing the inert protective gas to obtain the vapor deposition carbon-coated artificial graphite cathode material. And screening the obtained vapor deposition carbon-coated artificial graphite cathode material, wherein the mesh number of an ultrasonic vibration screen is 325 meshes, so as to obtain the low-temperature quick-charging artificial graphite cathode material with the average particle size D50 of 3-8 mu m.
And (3) testing the electrochemical performance of the half-cell formed by the obtained low-temperature quick-charging artificial graphite cathode material and the metal lithium, wherein the charging and discharging voltage is 0-2.0V. The button cell can reach 351mAh/g of specific discharge capacity under the charge-discharge rate of 0.2C/0.2C, the first efficiency is 94.4%, the charge-discharge capacity of 5C is 84% of that of 0.2C, and 82% of capacity can still be maintained under the discharge at the temperature of minus 20 ℃.
Comparative example 1:
crushing petroleum coke with the particle size of less than 10mm by using a mechanical mill and a shaping machine, and shaping the petroleum coke into balls until the particle size D50 is 7 microns to obtain graphite precursor powder. Putting the graphite precursor powder into a push boat type high-temperature graphite purification furnace, heating to 3000 ℃ at the heating rate of 10 ℃/min, preserving the heat for 48h, introducing purified gas Freon, and performing high-temperature purification to obtain a graphite matrix. Putting 10Kg of the obtained graphite matrix and 500g of asphalt with the particle size of 2 microns into a hearth of a rotary kiln; rotating the hearth at the rotating speed of 30rpm, heating at the speed of 3 ℃/min, introducing inert protective gas nitrogen at the flow rate of 500L/h, and preserving heat for 5h when the temperature reaches 1100 ℃; continuously introducing inert protective gas at the flow rate of 500L/h, and cooling to below 60 ℃ in a furnace; and (4) closing the heating power supply, and stopping introducing the inert protective gas to obtain the vapor deposition carbon-coated artificial graphite cathode material. And screening the obtained vapor deposition carbon-coated artificial graphite cathode material, wherein the mesh number of the ultrasonic vibration screen is 325 meshes, so as to obtain the low-temperature quick-charging artificial graphite cathode material.
And (3) testing the electrochemical performance of the half-cell formed by the obtained low-temperature quick-charging artificial graphite cathode material and the metal lithium, wherein the charging and discharging voltage is 0-2.0V. The button cell can reach 331mAh/g of specific discharge capacity under the charge-discharge rate of 0.2C/0.2C, the first efficiency is 92.1%, the charge-discharge rate of 5C is 81% of that of 0.2C, and the capacity retention rate is 73% under the discharge at-20 ℃.
The performance parameters of the examples and comparative examples are shown in the following table:
as can be seen from the data in the table, the comparative example 1 has lower capacity and first efficiency, the 5C charge-discharge capacity is 81% of the 0.2C charge-discharge capacity, and the capacity retention rate is only 73% under the discharge at-20 ℃. The capacity of the material prepared by the method is greatly improved to 347mAh/g, the charge-discharge capacity retention rate of 5C is 89%, and the capacity retention rate reaches 85% under the discharge at-20 ℃.
According to the analysis, the reversible capacity, the first coulombic efficiency, the low-temperature performance and the quick charge performance of the lithium ion battery manufactured by the lithium ion battery cathode material prepared by the method are improved, the graphitization degree of the material is improved through high-temperature purification, and the electrochemical performance of the material is improved through forming a compact coating layer on the surface of a graphite matrix through vapor deposition.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The low-temperature fast-charging artificial graphite cathode material is characterized in that the low-temperature fast-charging artificial graphite cathode material is a coated carbon composite material;
the composite material comprises a graphite substrate, and a carbon nano tube and amorphous carbon which are coated on the surface of the graphite substrate;
the mass of the carbon nano tube and the amorphous carbon is 0.5-5% of that of the graphite matrix.
2. The low-temperature fast-charging artificial graphite cathode material as claimed in claim 1, wherein the composite material is prepared by mixing a graphite powder and a binderThe graphitization degree is 85-95%, the granularity D50 is 3-8 mu m, and the tap density is 0.7-1.2 g/cm3The specific surface area is 1 to 6m2/g。
3. A preparation method of the low-temperature quick-charging artificial graphite cathode material in the claim 1 or 2 is characterized by comprising the following steps:
s1: crushing, shaping and spheroidizing the raw materials to obtain graphite precursor powder;
s2: placing the graphite precursor powder in a high-temperature purification furnace, and purifying at high temperature to obtain a graphite matrix;
s3: placing the graphite matrix in a vapor deposition furnace, heating to a set deposition temperature under the protection of inert protective gas, and performing vapor deposition at the set deposition temperature under the atmosphere of inert protective gas, catalytic gas and carbon source gas to obtain a carbon-coated artificial graphite cathode material;
s4: and screening the carbon-coated artificial graphite negative electrode material obtained in the step S3 to obtain the low-temperature quick-charging artificial graphite negative electrode material with the average particle size D50 of 3-8 microns.
4. The preparation method of the low-temperature quick-charging artificial graphite negative electrode material as claimed in claim 3, wherein the raw material in S1 is one or more of petroleum coke with a particle size of less than 10mm, pitch coke and graphite electrode joint powder.
5. The preparation method of the low-temperature fast-charging artificial graphite negative electrode material as claimed in claim 3, wherein the particle size D50 of the graphite precursor powder in S1 is 2-7 μm.
6. The preparation method of the low-temperature fast-charging artificial graphite anode material as claimed in claim 3, wherein the high-temperature purification process in S2 is as follows: and introducing inert protective gas, heating to 2600-3000 ℃ at the heating rate of 1-20 ℃/min, simultaneously introducing purified gas, preserving the heat for 1-96 hours, then stopping introducing the purified gas, and cooling along with the furnace under the inert protective gas condition, wherein the purified gas is chlorine or Freon.
7. The preparation method of the low-temperature fast-charging artificial graphite anode material as claimed in claim 3, wherein the process of gas phase deposition in S3 is as follows:
s3-1: heating to a set deposition temperature at the speed of 3-15 ℃/min, and introducing inert protective gas into a hearth of the vapor deposition furnace at the flow rate of 10-500L/h, wherein the set deposition temperature is 800-1100 ℃;
s3-2: when the temperature reaches the set deposition temperature, adjusting the flow of inert protective gas to 100-2000L/h, and simultaneously introducing catalytic gas and carbon source gas for 0.5-5 h;
s3-3: stopping introducing the catalytic gas and the carbon source gas, adjusting the flow of the inert protective gas to 10-500L/h, and preserving heat for 0.5-2 h when the temperature is reduced to 500-700 ℃; stopping heating, cooling to below 60 ℃, and stopping introducing inert protective gas to obtain the carbon-coated artificial graphite cathode material.
8. The preparation method of the low-temperature fast-charging artificial graphite cathode material according to claim 7, wherein the carbon source gas is one or more of methane, ethane, acetylene, ethylene, natural gas, liquefied petroleum gas, benzene or thiophene;
the catalytic gas is hydrogen;
the inert protective gas is nitrogen or argon;
the inert shielding gas flow rate is as follows: carbon source gas flow rate: the hydrogen flow rate is 1 (1/3-1) and (1/20-1/10).
9. The preparation method of the low-temperature fast-charging artificial graphite anode material as claimed in claim 3, wherein the screening is performed in S4 by an ultrasonic vibration screen with the screen mesh number of 325.
10. A low-temperature fast-charging battery, which comprises the low-temperature fast-charging artificial graphite negative electrode material as claimed in claim 1 or 2.
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