CN110600715B - Graphite cathode composite material of lithium ion battery and preparation method thereof - Google Patents
Graphite cathode composite material of lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN110600715B CN110600715B CN201910987303.XA CN201910987303A CN110600715B CN 110600715 B CN110600715 B CN 110600715B CN 201910987303 A CN201910987303 A CN 201910987303A CN 110600715 B CN110600715 B CN 110600715B
- Authority
- CN
- China
- Prior art keywords
- graphite
- lithium ion
- composite material
- precursor
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 83
- 239000010439 graphite Substances 0.000 title claims abstract description 83
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000011282 treatment Methods 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000007493 shaping process Methods 0.000 claims abstract description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 30
- 239000010426 asphalt Substances 0.000 claims description 24
- 229910021384 soft carbon Inorganic materials 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000007833 carbon precursor Substances 0.000 claims description 22
- 239000011246 composite particle Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 230000004927 fusion Effects 0.000 claims description 14
- 239000011163 secondary particle Substances 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000002006 petroleum coke Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000006253 pitch coke Substances 0.000 claims description 4
- 239000011329 calcined coke Substances 0.000 claims description 3
- 239000002010 green coke Substances 0.000 claims description 3
- 239000011331 needle coke Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 description 17
- 239000011295 pitch Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000011294 coal tar pitch Substances 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- H01M4/362—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
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a graphite cathode composite material of a lithium ion battery and a preparation method thereof, the preparation method of the graphite cathode composite material of the lithium ion battery carries out drying treatment on a graphite precursor, can reduce the water content in the graphite precursor and improve the stability in the process of thinning and crushing; meanwhile, the grain size is further reduced in the thinning process, the lithium ion migration path is favorably shortened, and the quick charge performance of the material can be greatly improved; through shaping treatment, the sphericity of the material is improved, the isotropy of the material is favorably improved, and then high-temperature crystallization treatment is sequentially carried out on the refined precursor powder, so that the energy density is favorably improved and good processing performance is obtained. Through low-temperature heat treatment, the modified coated amorphous carbon is beneficial to forming a uniform coating layer, reducing electrochemical polarization and enhancing current performance; the structure is more stable after modification treatment, and the improvement of the cycle performance is facilitated.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a graphite cathode composite material of a lithium ion battery and a preparation method thereof.
Background
The negative electrode material is one of four main materials of the lithium battery, and occupies an important position in the application of the lithium ion battery, and in recent years, along with the expansion of application scenes, the negative electrode material has more recent requirements on the lithium ion battery material, and is required to have good safety performance, high energy density, good quick charge performance, low temperature performance and the like. On the premise of ensuring the energy density, the improvement of the fast charge rate performance (such as more than 2C) has great significance for the long-term endurance use of the lithium ion battery.
Application number 201410787061.7 discloses a fast-charging graphite lithium ion battery negative electrode material and a preparation method thereof. The preparation method of the negative electrode material of the quick-charging graphite lithium ion battery comprises the following steps: (1) mixing, heating, kneading and crushing a mixture containing a graphite precursor and asphalt; wherein the average particle size D50 of the graphite precursor is 5-10 μm, and the mass ratio of the graphite precursor to the pitch is 50: 50-90: 10; (2) carrying out heat treatment at 300-700 ℃ under the protection of inert gas; (3) and (6) graphitizing. The coating layer of the invention is also converted into graphite after graphitization, so the rate improvement is relatively limited.
Application number 201710186013.6 discloses a preparation method of high-magnification quick-charging graphite, which comprises the following steps: (1) crushing and shaping the raw materials; (2) mixing; (3) graphitizing high-temperature treatment: graphitizing the mixture at 2800-3200 ℃ for 24-48 hours under the protection of inert gas; (4) mixing materials; (5) low-temperature heat treatment; (6) carbonizing and heat treating; (7) and (5) screening the mixed materials. The invention shapes the raw materials, then carries out modification treatment, prepares artificial graphite through high-temperature graphitization, and then prepares the negative electrode material of the quick-charging graphite lithium ion battery through mixing and carbonization with asphalt. Although the method coats the amorphous carbon on the surface of the graphite, the method needs multiple high-temperature heat treatments, and has more complex process route and higher energy consumption.
Application number 201810939161.5 discloses a method for preparing a high-magnification fast-charging graphite cathode material, which comprises the steps of crushing raw materials, graphitizing to obtain artificial graphite, mechanically fusing the artificial graphite and a carbon-containing source adhesive together, and carbonizing to obtain the high-magnification fast-charging graphite cathode material. The graphite particles obtained by the method are irregular in shape, more in surface edges and corners and less in adopted binder, and the uniform coating of the graphite particles cannot be ensured.
The existing method has the defects of complex technical route, high cost, difficult uniform coating effect and difficult better control in actual production.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a graphite cathode composite material of a lithium ion battery and a preparation method thereof.
The invention provides a graphite cathode composite material for a lithium ion battery, which has a secondary composite particle structure, wherein each secondary composite particle structure consists of a plurality of graphite single particles and soft carbon, and the soft carbon is bonded with the graphite single particles and covers the whole secondary composite particle structure.
Further, the precursor of the single graphite particle is one or more of petroleum coke, pitch coke and green coke or calcined coke of needle coke, the average particle size D50 of the precursor of the single graphite particle is 7-13 μm, the precursor of the soft carbon is pitch, and the mass ratio of the precursor of the single graphite particle to the precursor of the soft carbon is 95: 5-80: 20. Furthermore, the average particle diameter D50 of the composite material is 10-16 μm, and the specific surface area is less than 1.5m2And the discharge capacity is more than 350 mAh/g.
The second purpose of the invention provides a preparation method of a graphite cathode composite material of a lithium ion battery, which comprises the following steps:
(1) drying and crushing the graphite precursor until the D50 value is 7-13 mu m, and shaping to obtain amorphous carbon precursor fine powder with the D10 value of 4-6 mu m;
(2) performing high-temperature crystallization treatment on the amorphous carbon precursor fine powder to obtain a crystallized carbon material;
(3) mixing the crystallized carbon material with asphalt to obtain a crystallized carbon material mixture, and then carrying out modification treatment under inert gas to obtain a secondary granular crystallized carbon material;
(4) and carrying out low-temperature heat treatment on the secondary particle crystallized carbon material under the protection of inert gas to obtain the lithium ion battery graphite cathode composite material.
Further, the graphite precursor in the step (1) is one or more of petroleum coke, pitch coke, green coke of needle coke and calcined coke.
Further, the drying temperature in the step (1) is 150-.
Further, coarse crushing is carried out on the graphite precursor in the step (1) before drying to obtain coarse powder, and the particle size of the coarse powder is less than or equal to 2 mm.
Further, the high temperature crystallization treatment in the step (2) is sintering at 2800-3000 ℃ for 1-2 h.
Further, the asphalt in the step (3) is petroleum asphalt and/or coal asphalt, and the D50 value of the asphalt is 1-10 mu m.
Furthermore, the mass ratio of the crystallized carbon material to the asphalt is 95: 5-80: 20.
Further, the mixing mode in the step (3) is mixing by a mixer and then mechanical fusion treatment, the mixing time is 1-3h, the mechanical fusion rotation speed is 200-600rpm, and the time is 3-30 min.
Further, the inert gas in the step (3) is nitrogen or argon, and the modification treatment is heat treatment at 300-600 ℃ for 2-10 h.
Further, the inert gas in the step (4) is nitrogen or argon, and the low-temperature heat treatment is heat treatment at 1000-1300 ℃ for 2-24 h.
The lithium ion battery graphite cathode composite material prepared by the method has the discharge capacity of more than 350mAh/g, the quick charge rate of more than 2C, the D50 value of 10-16 mu m and the tap of more than or equal to 1.05g/cm31.5m or less in the table2The first efficiency is more than or equal to 91.0 percent per gram, and the C004/C110 is less than or equal to 6 percent.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method of the lithium ion battery graphite cathode composite material, the graphite precursor is dried, so that the moisture in the graphite precursor can be reduced, and the stability in the refining and crushing process is improved; meanwhile, the grain size is further reduced in the thinning process, the lithium ion migration path is favorably shortened, and the quick charge performance of the material can be greatly improved; through shaping treatment, the sphericity of the material is improved, the isotropy of the material is favorably improved, and then high-temperature crystallization treatment is sequentially carried out on the refined precursor powder, so that the energy density is favorably improved and good processing performance is obtained. Through low-temperature heat treatment, the modified coated amorphous carbon is beneficial to forming a uniform coating layer, reducing electrochemical polarization and enhancing current performance; the structure is more stable after modification treatment, and the improvement of the cycle performance is facilitated. The first discharge capacity of the prepared lithium ion battery cathode material is larger than 350mAh/g, which shows that the composite material has higher energy density and the quick charge rate can reach more than 2C;
(2) the process route of the invention is simple, the industrial scale production is easy, and the graphite cathode composite material of the lithium ion battery has higher energy density and better quick charging performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The preparation method of the graphite cathode composite material of the lithium ion battery comprises the following steps:
(1) drying and crushing petroleum coke to obtain amorphous carbon precursor fine powder with a D50 value of 7-13 mu m, drying at 150 ℃ for 4h, drying at a drying speed of 20r/min, and shaping to obtain amorphous carbon precursor fine powder with a D10 value of 4-6 mu m;
(2) performing high-temperature crystallization treatment on the amorphous carbon precursor fine powder, wherein the high-temperature crystallization treatment is to fire the amorphous carbon precursor fine powder for 2 hours at 2800 ℃ to obtain a crystallized carbon material;
(3) mixing the crystallized carbon material with petroleum asphalt, wherein the mass ratio of the crystallized carbon material to the petroleum asphalt is 95:5, the D50 value of the petroleum asphalt is 1-10 mu m, the mixing mode is firstly mixing by a mixer, then carrying out mechanical fusion treatment, the mixing time is 1h, the mechanical fusion rotation speed is 600rpm, and the mixing time is 30min, obtaining a crystallized carbon material mixture, then carrying out modification treatment under inert gas nitrogen, and carrying out heat treatment at 300 ℃ for 10h to obtain a secondary particle crystallized carbon material;
(4) and (3) carrying out low-temperature heat treatment on the secondary particle crystallized carbon material under the protection of inert gas nitrogen, wherein the low-temperature heat treatment is carried out for 24 hours at 1000 ℃, and thus the lithium ion battery graphite cathode composite material is obtained.
The lithium ion battery graphite cathode composite material prepared by the embodiment is of a secondary composite particle structure, each secondary composite particle structure is composed of a plurality of graphite single particles and soft carbon, the soft carbon is bonded with the graphite single particles and covers the whole secondary composite particle structure, a precursor of the graphite single particles is petroleum coke, and a precursor of the soft carbon is pitch.
Example 2
The preparation method of the graphite cathode composite material of the lithium ion battery comprises the following steps:
(1) drying and crushing petroleum coke to obtain amorphous carbon precursor fine powder with a D50 value of 7-13 mu m, drying at 250 ℃ for 2.25h and a drying machine rotating speed of 11r/min during drying, and shaping to obtain amorphous carbon precursor fine powder with a D10 value of 4-6 mu m;
(2) performing high-temperature crystallization treatment on the amorphous carbon precursor fine powder, wherein the high-temperature crystallization treatment is to bake the amorphous carbon precursor fine powder for 1.5 hours at 2900 ℃ to obtain a crystallized carbon material;
(3) mixing the crystallized carbon material with coal tar pitch, wherein the mass ratio of the crystallized carbon material to the coal tar pitch is 90:10, the D50 value of the coal tar pitch is 1-10 mu m, the mixing mode is that the crystallized carbon material and the coal tar pitch are mixed by a mixer and then subjected to mechanical fusion treatment, the mixing time is 2 hours, the mechanical fusion rotation speed is 400rpm, and the time is 16.5min, so as to obtain a crystallized carbon material mixture, and then performing modification treatment under inert gas argon, wherein the modification treatment is heat treatment at 300 ℃ for 10 hours, so as to obtain a secondary particle crystallized carbon material;
(4) and (3) carrying out low-temperature heat treatment on the secondary particle crystallized carbon material under the protection of inert gas argon, wherein the low-temperature heat treatment is carried out for 13 hours at 1150 ℃, and thus the graphite cathode composite material of the lithium ion battery is obtained.
The lithium ion battery graphite cathode composite material prepared by the embodiment is of a secondary composite particle structure, each secondary composite particle structure is composed of a plurality of graphite single particles and soft carbon, the soft carbon is bonded with the graphite single particles and covers the whole secondary composite particle structure, a precursor of the graphite single particles is petroleum coke, and a precursor of the soft carbon is pitch.
Example 3
The preparation method of the graphite cathode composite material of the lithium ion battery comprises the following steps:
(1) coke-drying and crushing the asphalt until the D50 value is 7-13 mu m, the drying temperature is 350 ℃, the drying time is 0.5h, the rotating speed of a dryer is 2r/min during drying, and shaping to obtain amorphous carbon precursor fine powder with the D10 value of 4-6 mu m;
(2) performing high-temperature crystallization treatment on the amorphous carbon precursor fine powder, wherein the high-temperature crystallization treatment is to fire the amorphous carbon precursor fine powder for 1 hour at 3000 ℃ to obtain a crystallized carbon material;
(3) mixing the crystallized carbon material with petroleum asphalt at a mass ratio of 80:20, wherein the D50 value of the petroleum asphalt is 1-10 μm, the mixing mode is that the crystallized carbon material and the petroleum asphalt are mixed by a mixer and then subjected to mechanical fusion treatment, the mixing time is 3h, the mechanical fusion rotation speed is 200rpm, and the mixing time is 3min, so as to obtain a crystallized carbon material mixture, and then performing modification treatment under inert gas nitrogen, wherein the modification treatment is that the heat treatment is performed for 2h at 600 ℃ so as to obtain a secondary particle crystallized carbon material;
(4) and (3) carrying out low-temperature heat treatment on the secondary particle crystallized carbon material under the protection of inert gas nitrogen, wherein the low-temperature heat treatment is carried out for 2 hours at 1300 ℃, and thus the lithium ion battery graphite cathode composite material is obtained.
In the lithium ion battery graphite cathode composite material prepared by the embodiment, the composite material is a secondary composite particle structure, each secondary composite particle structure is composed of a plurality of graphite single particles and soft carbon, the soft carbon is bonded with the graphite single particles and coats the whole secondary composite particle structure, a precursor of the graphite single particles is pitch coke, and a precursor of the soft carbon is pitch.
Example 4
The preparation method of the graphite cathode composite material of the lithium ion battery comprises the following steps:
(1) drying and crushing petroleum coke to obtain amorphous carbon precursor fine powder with a D50 value of 7-13 mu m, drying at 200 ℃ for 3h at a drying speed of 15r/min, and shaping to obtain amorphous carbon precursor fine powder with a D10 value of 4-6 mu m;
(2) performing high-temperature crystallization treatment on the amorphous carbon precursor fine powder, wherein the high-temperature crystallization treatment is to fire the amorphous carbon precursor fine powder for 1.2 hours at 2850 ℃ to obtain a crystallized carbon material;
(3) mixing the crystallized carbon material with petroleum asphalt at a mass ratio of 92:8, wherein the D50 value of the petroleum asphalt is 1-10 μm, and the mixing mode is mixing by a mixer and then carrying out mechanical fusion treatment for 1.5h, the mechanical fusion rotation speed is 500rpm and the time is 30min to obtain a crystallized carbon material mixture, and then carrying out modification treatment under inert gas nitrogen, wherein the modification treatment is heat treatment at 300 ℃ for 8h to obtain a secondary particle crystallized carbon material;
(4) and (3) carrying out low-temperature heat treatment on the secondary particle crystallized carbon material under the protection of inert gas nitrogen, wherein the low-temperature heat treatment is carried out for 18 hours at 1100 ℃, and thus the graphite cathode composite material of the lithium ion battery is obtained.
The lithium ion battery graphite cathode composite material prepared by the embodiment is of a secondary composite particle structure, each secondary composite particle structure is composed of a plurality of graphite single particles and soft carbon, the soft carbon is bonded with the graphite single particles and covers the whole secondary composite particle structure, a precursor of the graphite single particles is petroleum coke, and a precursor of the soft carbon is pitch.
Example 5
The preparation method of the graphite cathode composite material of the lithium ion battery comprises the following steps:
(1) drying and crushing petroleum coke to a D50 value of 7-13 mu m, performing coarse crushing treatment before drying a graphite precursor to obtain coarse powder, wherein the granularity of the coarse powder is less than or equal to 2mm, the drying temperature is 300 ℃, the drying time is 2h, the rotating speed of a dryer during drying is 12r/min, and performing shaping treatment to obtain amorphous carbon precursor fine powder with a D10 value of 4-6 mu m;
(2) performing high-temperature crystallization treatment on the amorphous carbon precursor fine powder, wherein the high-temperature crystallization treatment is to fire the amorphous carbon precursor fine powder at 2800 ℃ for 1.5 hours to obtain a crystallized carbon material;
(3) mixing the crystallized carbon material with petroleum asphalt at a mass ratio of 88:12, wherein the D50 value of the petroleum asphalt is 1-10 μm, and the mixing mode is mixing by a mixer and then carrying out mechanical fusion treatment for 2.5h, the mechanical fusion rotation speed is 500rpm and the time is 25min to obtain a crystallized carbon material mixture, and then carrying out modification treatment under the inert gas argon, wherein the modification treatment is heat treatment at 400 ℃ for 5h to obtain a secondary particle crystallized carbon material;
(4) and (3) carrying out low-temperature heat treatment on the secondary particle crystallized carbon material under the protection of inert gas argon, wherein the low-temperature heat treatment is carried out for 15 hours at 1200 ℃, and thus the lithium ion battery graphite cathode composite material is obtained.
The lithium ion battery graphite cathode composite material prepared by the embodiment is of a secondary composite particle structure, each secondary composite particle structure is composed of a plurality of graphite single particles and soft carbon, the soft carbon is bonded with the graphite single particles and covers the whole secondary composite particle structure, a precursor of the graphite single particles is petroleum coke, and a precursor of the soft carbon is pitch.
Comparative example 1
The preparation method of the graphite negative electrode composite material of the lithium ion battery of the comparative example is the same as that of the example 1, except that the step of modification treatment under nitrogen is omitted in the step (3).
Comparative example 2
The preparation method of the graphite cathode composite material of the lithium ion battery in the comparative example is the same as that of the example 1, except that the high-temperature crystallization treatment step in the step (2) is omitted.
Test example 1
The lithium ion battery graphite negative electrode composite materials prepared in examples 1 to 5 and comparative examples 1 and 2 were subjected to the measurement of performance parameters, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the lithium ion battery graphite negative electrode composite material prepared by the invention can improve powder isotropy, and is beneficial to reducing the preferred orientation of lithium intercalation in the charging process of the graphite negative electrode, thereby being beneficial to improving the quick charging performance. Meanwhile, the energy density is high, the specific surface area is low, and the comprehensive performance is excellent. The discharge capacity and charge rate of the composite materials prepared in comparative examples 1 and 2 are obviously reduced, which shows that the inert gas modification treatment and high-temperature crystallization have great influence on the performance.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (3)
1. The graphite cathode composite material for the lithium ion battery is characterized in that the composite material is of a secondary composite particle structure, each secondary composite particle structure is composed of a plurality of graphite single particles and soft carbon, and the soft carbon is bonded with the graphite single particles and coats the whole secondary composite particle structure; the precursor of the single graphite particle is one or more of petroleum coke, pitch coke and green coke or calcined coke of needle coke, the precursor of the soft carbon is pitch, the mass ratio of the precursor of the single graphite particle to the precursor of the soft carbon is 95: 5-80: 20, the average particle size D50 of the composite material is 10-16 mu m, and the specific surface area of the composite material is 10-16 mu mLess than 1.5m2The discharge capacity is more than 350 mAh/g;
the preparation method of the graphite cathode composite material of the lithium ion battery comprises the following steps:
(1) drying and crushing the graphite precursor until the D50 value is 7-13 mu m, wherein the drying temperature is 150-350 ℃, the drying time is 0.5-4h, the rotating speed of a dryer during drying is 2-20r/min, and shaping treatment is carried out to obtain amorphous carbon precursor fine powder with the D10 value of 4-6 mu m;
(2) performing high-temperature crystallization treatment on the amorphous carbon precursor fine powder, namely firing at 2800-3000 ℃ for 1-2h to perform high-temperature crystallization treatment to obtain a crystallized carbon material;
(3) mixing the crystallized carbon material with asphalt to obtain a crystallized carbon material mixture, and then performing modification treatment under nitrogen or argon, wherein the modification treatment is heat treatment at the temperature of 300-600 ℃ for 2-10h to obtain a secondary particle crystallized carbon material;
(4) and carrying out heat treatment on the secondary particle crystallized carbon material at the temperature of 1000-1300 ℃ for 2-24h under nitrogen or argon to obtain the lithium ion battery graphite cathode composite material.
2. The lithium ion battery graphite negative electrode composite material according to claim 1, wherein the asphalt in the step (3) is petroleum asphalt and/or coal asphalt, and the D50 value of the asphalt is 1-10 μm.
3. The graphite cathode composite material of a lithium ion battery as claimed in claim 1, wherein the mixing manner in step (3) is mixing by a mixer and then mechanical fusion treatment, the mixing time is 1-3h, the mechanical fusion rotation speed is 200-600rpm, and the time is 3-30 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910987303.XA CN110600715B (en) | 2019-10-17 | 2019-10-17 | Graphite cathode composite material of lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910987303.XA CN110600715B (en) | 2019-10-17 | 2019-10-17 | Graphite cathode composite material of lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110600715A CN110600715A (en) | 2019-12-20 |
| CN110600715B true CN110600715B (en) | 2021-06-04 |
Family
ID=68849788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910987303.XA Active CN110600715B (en) | 2019-10-17 | 2019-10-17 | Graphite cathode composite material of lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110600715B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111628170B (en) * | 2020-04-23 | 2023-10-17 | 湖南中科星城石墨有限公司 | Porous secondary particle anode material for lithium ion battery and preparation method thereof |
| CN112670466B (en) * | 2020-04-30 | 2022-08-30 | 宁波杉杉新材料科技有限公司 | Composite graphite negative electrode material, preparation method thereof and lithium ion battery |
| CN112652753A (en) * | 2020-12-29 | 2021-04-13 | 湖州杉杉新能源科技有限公司 | Lithium ion battery negative electrode material, lithium ion battery and preparation method and application thereof |
| CN114937758B (en) * | 2022-03-22 | 2024-04-05 | 珠海冠宇电池股份有限公司 | Negative electrode active material, negative electrode sheet and battery containing the negative electrode active material |
| CN114956069A (en) * | 2022-07-07 | 2022-08-30 | 王辅志 | A device for preparing artificial graphite negative electrode material for lithium ion battery and preparation method thereof |
| CN115810729A (en) * | 2022-11-09 | 2023-03-17 | 合肥国轩高科动力能源有限公司 | A kind of high-voltage fast charging type lithium-ion battery and manufacturing method thereof |
| CN115881952A (en) * | 2022-12-22 | 2023-03-31 | 开封瑞丰新材料有限公司 | Negative electrode material and battery |
| CN116161656B (en) * | 2023-03-10 | 2024-09-03 | 蜂巢能源科技股份有限公司 | Quick-charge graphite anode material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2436648A1 (en) * | 2009-05-26 | 2012-04-04 | Incubation Alliance.Inc. | Carbon material and method for producing the same |
| CN102473915A (en) * | 2010-06-30 | 2012-05-23 | 松下电器产业株式会社 | Negative electrode for non-aqueous electrolyte secondary battery and manufacturing method thereof |
| CN103250285A (en) * | 2010-12-08 | 2013-08-14 | 日本焦化工业株式会社 | Negative electrode material for lithium ion secondary batteries, and method for producing same |
| CN105932281A (en) * | 2016-06-03 | 2016-09-07 | 田东 | Preparation method for graphite anode material of lithium ion battery |
| CN107845810A (en) * | 2017-10-26 | 2018-03-27 | 深圳市斯诺实业发展股份有限公司 | A kind of soft or hard carbon of lithium ion battery is modified the preparation method of negative material |
| CN108933240A (en) * | 2018-06-26 | 2018-12-04 | 石家庄尚太科技有限公司 | A kind of preparation method and negative electrode material of high-density lithium ion battery negative electrode material |
| CN109748587A (en) * | 2018-12-29 | 2019-05-14 | 湖南中科星城石墨有限公司 | A kind of high capacity fast charge graphite cathode material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489893A (en) * | 2015-10-28 | 2016-04-13 | 江西正拓新能源科技股份有限公司 | Graphite anode material for lithium-ion battery and preparation method of graphite anode material |
| CN106654269B (en) * | 2017-01-06 | 2019-03-22 | 溧阳紫宸新材料科技有限公司 | Graphite cathode material and its preparation method and application for power lithium-ion battery |
| CN108054357A (en) * | 2017-12-06 | 2018-05-18 | 宁夏博尔特科技有限公司 | Power lithium-ion battery coal base composite negative pole material and preparation method thereof |
| CN108178140A (en) * | 2017-12-28 | 2018-06-19 | 石家庄尚太科技有限公司 | Lithium ion battery, negative material and negative material processing method |
-
2019
- 2019-10-17 CN CN201910987303.XA patent/CN110600715B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2436648A1 (en) * | 2009-05-26 | 2012-04-04 | Incubation Alliance.Inc. | Carbon material and method for producing the same |
| CN102473915A (en) * | 2010-06-30 | 2012-05-23 | 松下电器产业株式会社 | Negative electrode for non-aqueous electrolyte secondary battery and manufacturing method thereof |
| CN103250285A (en) * | 2010-12-08 | 2013-08-14 | 日本焦化工业株式会社 | Negative electrode material for lithium ion secondary batteries, and method for producing same |
| CN105932281A (en) * | 2016-06-03 | 2016-09-07 | 田东 | Preparation method for graphite anode material of lithium ion battery |
| CN107845810A (en) * | 2017-10-26 | 2018-03-27 | 深圳市斯诺实业发展股份有限公司 | A kind of soft or hard carbon of lithium ion battery is modified the preparation method of negative material |
| CN108933240A (en) * | 2018-06-26 | 2018-12-04 | 石家庄尚太科技有限公司 | A kind of preparation method and negative electrode material of high-density lithium ion battery negative electrode material |
| CN109748587A (en) * | 2018-12-29 | 2019-05-14 | 湖南中科星城石墨有限公司 | A kind of high capacity fast charge graphite cathode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110600715A (en) | 2019-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110600715B (en) | Graphite cathode composite material of lithium ion battery and preparation method thereof | |
| CN113213470A (en) | Artificial graphite secondary particle, coating agent, preparation method and application thereof | |
| CN111244400B (en) | Silicon-oxygen-carbon composite material, lithium ion battery, and preparation method and application of silicon-oxygen-carbon composite material | |
| CN112133896B (en) | High-capacity graphite-silicon oxide composite material and preparation method and application thereof | |
| CN106711461A (en) | Spherical porous silicon/carbon composite material as well as preparation method and application thereof | |
| CN109755540B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| US20250125357A1 (en) | Anode material and battery | |
| CN106169582B (en) | A kind of natural needle coke composite graphite negative electrode material production method | |
| CN116715239B (en) | Coal-based porous sodium ion battery hard carbon negative electrode material and preparation method thereof | |
| CN112582592B (en) | High-compaction and fast-filling artificial graphite material and preparation method thereof | |
| CN108682787A (en) | A kind of electrodes of lithium-ion batteries and preparation method thereof | |
| CN114583137B (en) | Method for modifying carbon surface by sulfur doped phosphorus and application thereof | |
| CN112289986A (en) | Preparation method of high-rate quick-charging graphite negative electrode material | |
| CN106299258B (en) | Preparation method of high-density graphite battery negative electrode material | |
| CN112054165B (en) | Mesocarbon microbeads, graphite negative electrode material, preparation method of mesocarbon microbeads and graphite negative electrode material, and lithium ion battery | |
| CN112018366A (en) | Graphite negative electrode material of lithium ion battery and preparation method thereof | |
| CN112768689A (en) | Graphene modified graphite negative electrode material and preparation method thereof | |
| CN110395725A (en) | Quick-charging microcrystalline graphite negative electrode material and preparation method thereof | |
| CN112573517A (en) | Preparation method of asphalt-based hard carbon-coated natural graphite negative electrode material | |
| CN114023958A (en) | A kind of fast-charging graphite anode material and preparation method based on amorphous carbon coating | |
| CN113753882A (en) | Preparation method of artificial graphite negative electrode material | |
| CN112397701A (en) | Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof | |
| CN109301216B (en) | Preparation method of lithium iron phosphate electrode coated with carbon boron composite spheres | |
| CN112713270B (en) | Preparation method of quick-charging graphite negative electrode material | |
| CN112811418B (en) | Quick-charging composite graphite material, preparation method and application thereof, and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 052460 west side of Nansha Road, Licheng road Township, Wuji County, Shijiazhuang City, Hebei Province Applicant after: Shijiazhuang Shangtai Technology Co., Ltd Applicant after: Shanxi Shangtai lithium Technology Co.,Ltd. Address before: 052460 west side of Nansha Road, Licheng road Township, Wuji County, Shijiazhuang City, Hebei Province Applicant before: SHIJIAZHUANG SHANGTAI TECH Co.,Ltd. Applicant before: Shanxi Shangtai lithium Technology Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |