CN112875697A - High-energy-density low-temperature quick-charging artificial graphite material and preparation method thereof - Google Patents
High-energy-density low-temperature quick-charging artificial graphite material and preparation method thereof Download PDFInfo
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- 229910021383 artificial graphite Inorganic materials 0.000 title claims abstract description 43
- 239000007770 graphite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000007740 vapor deposition Methods 0.000 claims abstract description 29
- 238000005087 graphitization Methods 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 238000007493 shaping process Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 126
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 115
- 229910002804 graphite Inorganic materials 0.000 claims description 76
- 239000010439 graphite Substances 0.000 claims description 76
- 230000001681 protective effect Effects 0.000 claims description 52
- 229910052799 carbon Inorganic materials 0.000 claims description 39
- 230000003197 catalytic effect Effects 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002006 petroleum coke Substances 0.000 claims description 3
- 239000006253 pitch coke Substances 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 3
- 238000012216 screening Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 229910003481 amorphous carbon Inorganic materials 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
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- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004807 desolvation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
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- 230000002687 intercalation Effects 0.000 description 2
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- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
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- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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 the field of battery cathode materials, in particular to a preparation method of a high-energy-density low-temperature quick-charging artificial graphite material, which comprises the following steps: crushing, shaping and spheroidizing; performing ultra-high temperature graphitization; vapor deposition; cooling; and (6) screening. The invention provides a low-cost high-energy-density low-temperature quick-charging artificial graphite material. The invention also provides a preparation method of the high-energy-density low-temperature quick-charging artificial graphite material with simple process.
Description
Technical Field
The invention relates to the field of battery cathode materials, in particular to a high-energy-density low-temperature quick-charging artificial graphite material and a preparation method thereof.
Background
In recent years, new energy electric vehicles are widely popularized in China, but the electric vehicles have short endurance mileage and long charging time, and the popularization of the electric vehicles is hindered due to the fact that the performance of batteries is greatly reduced in cold weather in winter, so that the energy density and the low-temperature quick charging performance of lithium ion batteries are 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, the method has important significance for improving the energy density of the negative electrode material and maintaining excellent low-temperature quick charge 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 graphite negative electrode material with high energy density and low-temperature fast charging performance and a preparation method thereof.
Disclosure of Invention
In order to solve the technical problems, the invention provides a low-cost high-energy-density low-temperature quick-charging artificial graphite material.
The invention also provides a preparation method of the high-energy-density low-temperature quick-charging artificial graphite material with simple process.
The invention adopts the following technical scheme:
a preparation method of a high-energy-density low-temperature quick-charging artificial graphite material comprises the following steps:
crushing, shaping and spheroidizing the raw materials to obtain graphite precursor powder;
putting the graphite precursor powder into a graphitization furnace, heating to 2800-3200 ℃ at a heating rate of 5-20 ℃/min, preserving heat for 1-96 h, and cooling to obtain a graphite matrix;
putting the graphite matrix into a hearth of a vapor deposition furnace, heating at the speed of 3-15 ℃/min, introducing inert protective gas at the flow rate of 50-500L/h, adjusting the flow rate of the inert protective gas to 100-1000L/h when the temperature reaches 750-1150 ℃, and introducing catalytic gas and carbon source gas;
stopping introducing the catalytic gas and the carbon source gas, adjusting the flow of the inert protective gas to 50-500L/h, naturally cooling to 450-600 ℃ in the furnace, and preserving the heat for 0.5-2 h; turning off the heating power supply, naturally cooling to below 80 ℃ in the furnace, and stopping introducing inert protective gas to obtain the artificial graphite material;
and (3) sieving the artificial graphite material, wherein the mesh number of the ultrasonic vibration sieve is 325 meshes, and obtaining the low-temperature quick-charging artificial graphite material with the average particle size D50 of 3-8 mu m.
The technical scheme is further improved in that in the step of crushing, shaping and spheroidizing the raw materials to obtain the graphite precursor powder, the raw materials are one or more of petroleum coke with the particle size of less than 10mm, pitch coke, mesophase coke and isotropic coke.
The technical scheme is further improved in that in the step of crushing, shaping and spheroidizing the raw materials to obtain the graphite precursor powder, the particle size D50 of the graphite precursor powder is 2-7 microns.
The technical scheme is further improved in that the graphite precursor powder is put into a graphitization furnace, the temperature is raised to 2800-3200 ℃ at the temperature rise speed of 5-20 ℃/min, the temperature is kept for 1-96 h, and the graphite substrate is obtained after cooling, wherein the graphitization furnace is one of a box-type high-temperature graphite furnace, a continuous high-temperature graphitization furnace, a series graphitization furnace and an Acheson graphitization furnace.
The technical scheme is further improved in that the graphite substrate is placed in a hearth of a vapor deposition furnace, the temperature is raised at the speed of 3-15 ℃/min, meanwhile, inert protective gas is introduced at the flow rate of 50-500L/h, when the temperature reaches 750-1150 ℃, the flow rate of the inert protective gas is adjusted to 100-1000L/h, and simultaneously, catalytic gas and carbon source gas are introduced, wherein the flow rate ratio of the inert protective gas to the carbon source gas to the catalytic gas is 1 (0.1-1): (0.01-0.1), and the introduction time is 1-10 h.
The technical scheme is further improved in that the graphite substrate is placed in a hearth of a vapor deposition furnace, the temperature is raised at the speed of 3-15 ℃/min, meanwhile, inert protective gas is introduced at the flow rate of 50-500L/h, when the temperature reaches 750-1150 ℃, the flow rate of the inert protective gas is adjusted to 100-1000L/h, and meanwhile, catalytic gas and carbon source gas are introduced, wherein the vapor deposition furnace is one of a rotary kiln, a tubular furnace and a fluidized bed.
The technical scheme is further improved in that the graphite substrate is placed in a hearth of a vapor deposition furnace, the temperature is raised at the speed of 3-15 ℃/min, meanwhile, inert protective gas is introduced at the flow rate of 50-500L/h, when the temperature reaches 750-1150 ℃, the flow rate of the inert protective gas is adjusted to 100-1000L/h, and in the step of introducing catalytic gas and carbon source gas, the inert protective gas is nitrogen or argon.
The technical scheme is further improved in that the graphite substrate is placed in a hearth of a vapor deposition furnace, the temperature is raised at the speed of 3-15 ℃/min, meanwhile, inert protective gas is introduced at the flow rate of 50-500L/h, when the temperature reaches 750-1150 ℃, the flow rate of the inert protective gas is adjusted to 100-1000L/h, and meanwhile, catalytic gas and carbon source gas are introduced, wherein the catalytic gas is hydrogen.
The technical scheme is further improved in that the graphite substrate is placed in a hearth of a vapor deposition furnace, the temperature is raised at the speed of 3-15 ℃/min, meanwhile, inert protective gas is introduced at the flow rate of 50-500L/h, when the temperature reaches 750-1150 ℃, the flow rate of the inert protective gas is adjusted to 100-1000L/h, and catalytic gas and carbon source gas are introduced at the same time, wherein the carbon source gas is one of methane, ethane, acetylene, ethylene, natural gas, liquefied petroleum gas, benzene or thiophene.
A high-energy-density low-temperature quick-charging artificial graphite material is prepared by the preparation method.
The invention has the beneficial effects that:
1. the small-particle-size graphite particles adopted by the invention have superior high-current charge and discharge performance compared with large-particle-size graphite particles. 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.
2. The invention adopts an ultra-high temperature graphitization mode to enable the graphite to have higher purity and crystallinity, thereby improving the energy density of the material.
3. The invention adopts a two-step cooling CVD vapor deposition coating method to deposit amorphous carbon on the surface of a graphite substrate material. The adoption of the two-step cooling mode is favorable for eliminating the internal stress generated in the material preparation process, so that the surface coating layer has better structural stability.
4. The invention adopts CVD vapor deposition coating to reduce the carbon coating amount, so that the material has higher specific capacity; the interlayer spacing of the amorphous carbon coating layer is larger than that of graphite, so that the diffusion performance of lithium ions in the amorphous carbon coating layer 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 amorphous carbon grown in situ 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. The carbon 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 and discharge efficiency, simultaneously reducing the deposition of Li metal on the graphite surface and improving the safety.
5. Through the combination of the advantages, the graphite cathode material prepared by the invention can realize higher energy density and excellent low-temperature quick charge performance when being applied to batteries.
Drawings
FIG. 1 is an SEM image of a high energy density low temperature fast-charging artificial graphite material of the present invention.
Detailed Description
The present invention will be further described with reference to specific embodiments, and it should be noted that any combination of the embodiments or technical features described below can form a new embodiment without conflict.
As shown in fig. 1, a method for preparing a high-energy-density low-temperature quick-charging artificial graphite material comprises the following steps: crushing, shaping and spheroidizing the raw materials to obtain graphite precursor powder; putting the graphite precursor powder into a graphitization furnace, heating to 2800-3200 ℃ at a heating rate of 5-20 ℃/min, preserving heat for 1-96 h, and cooling to obtain a graphite matrix; putting the graphite matrix into a hearth of a vapor deposition furnace, heating at the speed of 3-15 ℃/min, introducing inert protective gas at the flow rate of 50-500L/h, adjusting the flow rate of the inert protective gas to 100-1000L/h when the temperature reaches 750-1150 ℃, and introducing catalytic gas and carbon source gas; stopping introducing the catalytic gas and the carbon source gas, adjusting the flow of the inert protective gas to 50-500L/h, naturally cooling to 450-600 ℃ in the furnace, and preserving the heat for 0.5-2 h; turning off the heating power supply, naturally cooling to below 80 ℃ in the furnace, and stopping introducing inert protective gas to obtain the artificial graphite material; and (3) sieving the artificial graphite material, wherein the mesh number of the ultrasonic vibration sieve is 325 meshes, and obtaining the low-temperature quick-charging artificial graphite material with the average particle size D50 of 3-8 mu m.
In the step of crushing, shaping and spheroidizing the raw materials to obtain the graphite precursor powder, the raw materials are one or more of petroleum coke with the particle size of less than 10mm, pitch coke, mesophase coke and isotropic coke.
In the step of crushing, shaping and spheroidizing the raw materials to obtain the graphite precursor powder, the particle size D50 of the graphite precursor powder is 2-7 microns.
And putting the graphite precursor powder into a graphitization furnace, heating to 2800-3200 ℃ at a heating rate of 5-20 ℃/min, preserving heat for 1-96 h, and cooling to obtain a graphite matrix, wherein the graphitization furnace is one of a box-type high-temperature graphitization furnace, a continuous high-temperature graphitization furnace, a tandem graphitization furnace and an Acheson graphitization furnace.
Putting the graphite substrate into a hearth of a vapor deposition furnace, heating at the speed of 3-15 ℃/min, introducing inert protective gas at the flow rate of 50-500L/h, adjusting the flow rate of the inert protective gas to 100-1000L/h when the temperature reaches 750-1150 ℃, and introducing catalytic gas and carbon source gas at the same time, wherein the flow rate ratio of the inert protective gas to the carbon source gas to the catalytic gas is 1 (0.1-1) to (0.01-0.1), and the introduction time is 1-10 h.
And putting the graphite substrate into a hearth of a vapor deposition furnace, heating at the speed of 3-15 ℃/min, introducing inert protective gas at the flow rate of 50-500L/h, adjusting the flow rate of the inert protective gas to 100-1000L/h when the temperature reaches 750-1150 ℃, and introducing catalytic gas and carbon source gas, wherein the vapor deposition furnace is one of a rotary kiln, a tubular furnace and a fluidized bed.
Putting the graphite substrate into a hearth of a vapor deposition furnace, heating at the speed of 3-15 ℃/min, introducing inert protective gas at the flow rate of 50-500L/h, adjusting the flow rate of the inert protective gas to 100-1000L/h when the temperature reaches 750-1150 ℃, and introducing catalytic gas and carbon source gas, wherein the inert protective gas is nitrogen or argon.
Putting the graphite substrate into a hearth of a vapor deposition furnace, heating at the speed of 3-15 ℃/min, introducing inert protective gas at the flow rate of 50-500L/h, adjusting the flow rate of the inert protective gas to 100-1000L/h when the temperature reaches 750-1150 ℃, and introducing catalytic gas and carbon source gas, wherein the catalytic gas is hydrogen.
Putting the graphite substrate into a hearth of a vapor deposition furnace, heating at the speed of 3-15 ℃/min, introducing inert protective gas at the flow rate of 50-500L/h, adjusting the flow rate of the inert protective gas to 100-1000L/h when the temperature reaches 750-1150 ℃, and introducing catalytic gas and carbon source gas, wherein the carbon source gas is one of methane, ethane, acetylene, ethylene, natural gas, liquefied petroleum gas, benzene or thiophene.
A high-energy-density low-temperature quick-charging artificial graphite material is prepared by the preparation method.
Example 1
A preparation method of a high-energy-density low-temperature quick-charging artificial graphite material comprises the following steps: crushing, shaping and spheroidizing the raw materials to obtain graphite precursor powder; putting the graphite precursor powder into a graphitization furnace, heating to 2800 ℃ at a heating rate of 5 ℃/min, preserving heat for 20h, and cooling to obtain a graphite matrix; putting the graphite matrix into a hearth of a vapor deposition furnace, heating at the speed of 5 ℃/min, introducing inert protective gas at the flow rate of 200L/h, adjusting the flow rate of the inert protective gas to 200L/h when the temperature reaches 750 ℃, and introducing catalytic gas and carbon source gas; stopping introducing the catalytic gas and the carbon source gas, adjusting the flow of the inert protective gas to 100L/h, adopting a natural cooling mode in the furnace to 450 ℃, and preserving heat for 1 h; turning off the heating power supply, naturally cooling to below 80 ℃ in the furnace, and stopping introducing inert protective gas to obtain the artificial graphite material; sieving the artificial graphite material, wherein the mesh number of the ultrasonic vibration sieve is 325 meshes, and obtaining the low-temperature quick-charging artificial graphite material with the average particle size D50 of 3 mu m.
Example 2
A preparation method of a high-energy-density low-temperature quick-charging artificial graphite material comprises the following steps: crushing, shaping and spheroidizing the raw materials to obtain graphite precursor powder; putting the graphite precursor powder into a graphitization furnace, heating to 3000 ℃ at a heating rate of 10 ℃/min, preserving heat for 40h, and cooling to obtain a graphite matrix; putting the graphite matrix into a hearth of a vapor deposition furnace, heating at the speed of 10 ℃/min, introducing inert protective gas at the flow rate of 250L/h, adjusting the flow rate of the inert protective gas to 600L/h when the temperature reaches 1000 ℃, and introducing catalytic gas and carbon source gas; stopping introducing the catalytic gas and the carbon source gas, adjusting the flow of the inert protective gas to 300L/h, adopting a natural cooling mode in the furnace to 500 ℃, and preserving heat for 1 h; turning off the heating power supply, naturally cooling to below 80 ℃ in the furnace, and stopping introducing inert protective gas to obtain the artificial graphite material; sieving the artificial graphite material, wherein the mesh number of the ultrasonic vibration sieve is 325 meshes, and obtaining the low-temperature quick-charging artificial graphite material with the average particle size D50 of 5 mu m.
Example 3
A preparation method of a high-energy-density low-temperature quick-charging artificial graphite material comprises the following steps: crushing, shaping and spheroidizing the raw materials to obtain graphite precursor powder; putting the graphite precursor powder into a graphitization furnace, heating to 3200 ℃ at a heating rate of 20 ℃/min, preserving heat for 80h, and cooling to obtain a graphite matrix; putting the graphite matrix into a hearth of a vapor deposition furnace, heating at the speed of 15 ℃/min, introducing inert protective gas at the flow rate of 500L/h, adjusting the flow rate of the inert protective gas to 1000L/h when the temperature reaches 1150 ℃, and introducing catalytic gas and carbon source gas; stopping introducing the catalytic gas and the carbon source gas, adjusting the flow of the inert protective gas to 500L/h, adopting a natural cooling mode in the furnace to 600 ℃, and preserving heat for 2 h; turning off the heating power supply, naturally cooling to below 80 ℃ in the furnace, and stopping introducing inert protective gas to obtain the artificial graphite material; sieving the artificial graphite material, wherein the mesh number of the ultrasonic vibration sieve is 325 meshes, and obtaining the low-temperature quick-charging artificial graphite material with the average particle size D50 of 8 mu m.
The small-particle-size graphite particles adopted by the invention have superior high-current charge and discharge performance compared with large-particle-size graphite particles. 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.
The invention adopts an ultra-high temperature graphitization mode to enable the graphite to have higher purity and crystallinity, thereby improving the energy density of the material.
The invention adopts a two-step cooling CVD vapor deposition coating method to deposit amorphous carbon on the surface of a graphite substrate material. The adoption of the two-step cooling mode is favorable for eliminating the internal stress generated in the material preparation process, so that the surface coating layer has better structural stability.
The invention adopts CVD vapor deposition coating to reduce the carbon coating amount, so that the material has higher specific capacity; the interlayer spacing of the amorphous carbon coating layer is larger than that of graphite, so that the diffusion performance of lithium ions in the amorphous carbon coating layer 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 amorphous carbon grown in situ 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. The carbon 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 and discharge efficiency, simultaneously reducing the deposition of Li metal on the graphite surface and improving the safety.
Through the combination of the advantages, the graphite cathode material prepared by the invention can realize higher energy density and excellent low-temperature quick charge performance when being applied to batteries.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-energy-density low-temperature quick-filling artificial graphite material is characterized by comprising the following steps:
crushing, shaping and spheroidizing the raw materials to obtain graphite precursor powder;
putting the graphite precursor powder into a graphitization furnace, heating to 2800-3200 ℃ at a heating rate of 5-20 ℃/min, preserving heat for 1-96 h, and cooling to obtain a graphite matrix;
putting the graphite matrix into a hearth of a vapor deposition furnace, heating at the speed of 3-15 ℃/min, introducing inert protective gas at the flow rate of 50-500L/h, adjusting the flow rate of the inert protective gas to 100-1000L/h when the temperature reaches 750-1150 ℃, and introducing catalytic gas and carbon source gas;
stopping introducing the catalytic gas and the carbon source gas, adjusting the flow of the inert protective gas to 50-500L/h, naturally cooling to 450-600 ℃ in the furnace, and preserving the heat for 0.5-2 h; turning off the heating power supply, naturally cooling to below 80 ℃ in the furnace, and stopping introducing inert protective gas to obtain the artificial graphite material;
and (3) sieving the artificial graphite material, wherein the mesh number of the ultrasonic vibration sieve is 325 meshes, and obtaining the low-temperature quick-charging artificial graphite material with the average particle size D50 of 3-8 mu m.
2. The method for preparing the artificial graphite material with high energy density and low temperature and rapid filling according to claim 1, wherein in the step of crushing, shaping and spheroidizing the raw material to obtain the graphite precursor powder, the raw material is one or more of petroleum coke with a particle size of less than 10mm, pitch coke, mesophase coke and isotropic coke.
3. The method for preparing the artificial graphite material with high energy density and low temperature and high filling speed as claimed in claim 1, wherein in the step of crushing, shaping and spheroidizing the raw materials to obtain the graphite precursor powder, the particle size D50 of the graphite precursor powder is 2-7 microns.
4. The method according to claim 1, wherein the step of placing the graphite precursor powder in a graphitization furnace, heating to 2800-3200 ℃ at a temperature rise rate of 5-20 ℃/min, maintaining the temperature for 1-96 hours, and cooling to obtain the graphite matrix is carried out, wherein the graphitization furnace is one of a box-type high-temperature graphitization furnace, a continuous high-temperature graphitization furnace, a tandem graphitization furnace, and an Acheson graphitization furnace.
5. The method for preparing high energy density low temperature fast-charging artificial graphite material according to claim 1, wherein the graphite substrate is placed in a hearth of a vapor deposition furnace, the temperature is raised at a speed of 3-15 ℃/min, meanwhile, inert shielding gas is introduced at a flow rate of 50-500L/h, when the temperature reaches 750-1150 ℃, the flow rate of the inert shielding gas is adjusted to 100-1000L/h, and simultaneously, catalytic gas and carbon source gas are introduced, wherein the flow rate ratio of the inert shielding gas to the carbon source gas to the catalytic gas is 1 (0.1-1): 0.01-0.1), and the introduction time is 1-10 h.
6. The method for preparing the artificial graphite material with high energy density and low temperature fast filling as claimed in claim 1, wherein the graphite substrate is placed into a hearth of a vapor deposition furnace, the temperature is raised at a speed of 3-15 ℃/min, meanwhile, inert shielding gas is introduced at a flow rate of 50-500L/h, when the temperature reaches 750-1150 ℃, the flow rate of the inert shielding gas is adjusted to 100-1000L/h, and meanwhile, catalytic gas and carbon source gas are introduced, wherein the vapor deposition furnace is one of a rotary kiln, a tubular furnace and a fluidized bed.
7. The preparation method of the high-energy-density low-temperature fast-charging artificial graphite material according to claim 1, wherein the graphite substrate is placed in a hearth of a vapor deposition furnace, the temperature is raised at a speed of 3-15 ℃/min, meanwhile, inert shielding gas is introduced at a flow rate of 50-500L/h, when the temperature reaches 750-1150 ℃, the flow rate of the inert shielding gas is adjusted to 100-1000L/h, and in the step of introducing the catalytic gas and the carbon source gas, the inert shielding gas is nitrogen or argon.
8. The preparation method of the high-energy-density low-temperature fast-charging artificial graphite material according to claim 1, wherein the graphite substrate is placed in a hearth of a vapor deposition furnace, the temperature is raised at a speed of 3-15 ℃/min, meanwhile, inert protective gas is introduced at a flow rate of 50-500L/h, when the temperature reaches 750-1150 ℃, the flow rate of the inert protective gas is adjusted to 100-1000L/h, and in the step of introducing catalytic gas and carbon source gas, the catalytic gas is hydrogen.
9. The method for preparing the high-energy-density low-temperature fast-charging artificial graphite material according to claim 1, wherein the graphite substrate is placed in a hearth of a vapor deposition furnace, the temperature is raised at a speed of 3-15 ℃/min, meanwhile, inert protective gas is introduced at a flow rate of 50-500L/h, when the temperature reaches 750-1150 ℃, the flow rate of the inert protective gas is adjusted to 100-1000L/h, and meanwhile, a catalytic gas and a carbon source gas are introduced, wherein the carbon source gas is one of methane, ethane, acetylene, ethylene, natural gas, liquefied petroleum gas, benzene or thiophene.
10. A high energy density low temperature fast charging artificial graphite material, characterized by being produced by the production method as claimed in any one of claims 1 to 9.
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| PCT/CN2021/099071 WO2022166058A1 (en) | 2021-02-02 | 2021-06-09 | High-energy-density low-temperature artificial graphite material for fast-charge and preparation method therefor |
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| WO2022166058A1 (en) * | 2021-02-02 | 2022-08-11 | 广东凯金新能源科技股份有限公司 | High-energy-density low-temperature artificial graphite material for fast-charge and preparation method therefor |
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| CN115893400B (en) * | 2022-11-15 | 2023-10-10 | 贵州晖阳科技创新研究有限公司 | Preparation method of negative electrode material for long-cycle lithium ion battery |
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