CN114203978A - High-capacity graphite negative electrode material and preparation method and application thereof - Google Patents
High-capacity graphite negative electrode material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 114
- 239000010439 graphite Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000007773 negative electrode material Substances 0.000 title claims description 45
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 48
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- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000010406 cathode material Substances 0.000 claims abstract description 28
- 239000011268 mixed slurry Substances 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 238000001694 spray drying Methods 0.000 claims abstract description 8
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- 238000012216 screening Methods 0.000 claims abstract description 7
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- 238000000576 coating method Methods 0.000 claims description 25
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
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- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011280 coal tar Substances 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
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- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 239000011300 coal pitch Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000011294 coal tar pitch Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
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- 239000011889 copper foil Substances 0.000 description 2
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- 239000011888 foil Substances 0.000 description 2
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- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
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- 239000012466 permeate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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- Materials Engineering (AREA)
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention discloses a high-capacity graphite cathode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing the flake graphite, the doping compound, the binder and the solvent into mixed slurry, performing spray drying, crushing and spheroidizing to obtain spherical natural graphite with the inner and outer surfaces coated with the binder and the doping compound, carbonizing, and performing magnetic screening to obtain the high-capacity graphite cathode material. The prepared high-capacity graphite cathode material has the advantages of high capacity, good cycle performance, good rate performance and the like, and when the high-capacity graphite cathode material is prepared into a working electrode for preparing a lithium ion battery, the cycle life of the lithium ion battery can be obviously prolonged, and the high-capacity graphite cathode material has high use value and good application prospect. The preparation method has the advantages of simple process, convenient operation, low cost, low energy consumption and the like, is suitable for large-scale production, and is beneficial to technological application.
Description
Technical Field
The invention belongs to the field of negative electrode materials, and relates to a high-capacity graphite negative electrode material, and a preparation method and application thereof.
Background
The natural graphite has been widely used because of its advantages of high charge and discharge capacity, good charge and discharge platform, wide sources, low cost, etc. However, natural graphite has unstable structure and high internal porosity, and is easy to cause co-insertion of solvent molecules, so that the layer falls off and cracks in the charging and discharging process, more surfaces capable of reacting with electrolyte are exposed, the reaction of the natural graphite and the electrolyte is accelerated, and the lithium ion battery has the defects of reduced charging and discharging efficiency, poor cycle performance, poor safety and the like, and the cycle life of the lithium ion battery is directly shortened. In addition, natural graphite has the following disadvantages: the rate capability can not meet the market demand; gram capacity has not been able to meet the higher energy density requirements of batteries. In order to overcome the above disadvantages of the natural graphite, the surface of the natural graphite is usually coated with a layer of amorphous carbon material, however, the existing coating method mainly mixes the natural graphite and the coating modifier by physical mixing, and then makes the natural graphite flow to self-coat by using the liquefaction process of the coating modifier during the carbonization process, and has the following disadvantages: the coating modifier cannot effectively cover the outer surface of the natural graphite, and particularly, the coating modifier cannot easily enter the internal pores of the spherical natural graphite, so that the coating modifier cannot be effectively coated on the inner surface of the spherical natural graphite, and therefore, the amorphous carbon material cannot completely coat the natural graphite, and finally, in the battery circulation process, an electrolyte can gradually permeate into the surface of the uncoated natural graphite to continuously generate a Solid Electrolyte Interface (SEI) film, and the electrolyte is continuously embedded into a natural graphite layer structure, consumes a large amount of active lithium and destroys the natural graphite structure, so that the capacity is continuously reduced. In addition, those skilled in the art have proposed a strategy for increasing the coating amount of the amorphous carbon material, and although the reaction of the natural graphite with the electrolyte can be prevented to some extent by increasing the coating amount of the amorphous carbon material, the capacity of the natural graphite is inevitably reduced, so that the energy density of the material cannot meet the use requirement.
Therefore, how to obtain the graphite cathode material with high capacity and good cycle performance has very important significance for prolonging the cycle life of the lithium ion battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-capacity graphite cathode material with high capacity and good cycle performance as well as a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a high-capacity graphite negative electrode material comprises the following steps:
s1, mixing the crystalline flake graphite, the doping compound, the binder and the solvent to prepare mixed slurry;
s2, spray drying the mixed slurry obtained in the step S1 to obtain a material in which a binder and a doping compound are mixed and coated on the surface of the flake graphite;
s3, mixing the binder and the doping compound obtained in the step S2 and coating the mixture on the material on the surface of the crystalline flake graphite, and crushing and spheroidizing to obtain spherical natural graphite with the inner surface and the outer surface both coated with the binder and the doping compound;
s4, carbonizing the spherical natural graphite with the inner and outer surfaces coated with the binder and the doping compound obtained in the step S3, and performing magnetic screening to obtain the high-capacity graphite cathode material.
In the above preparation method, further improvement is made, in step S1, the solid content of the mixed slurry is 1% to 25%.
In the step S1, the mass ratio of the flake graphite, the doping compound and the binder in the mixed slurry is 55-94: 1-15: 5-30.
In the preparation method, the average particle size of the flake graphite is 3-45 μm; the doping compound is one of phosphoric acid, phosphorus pentoxide, triphenylphosphine, boric acid, boron trioxide and vanadium pentoxide; the binder is at least one of petroleum asphalt, coal asphalt, mesophase asphalt, phenolic resin, epoxy resin, petroleum resin, coal tar or heavy oil.
In a further improvement of the above preparation method, in step S1, the solvent is one or more of acetone, diethyl ether, xylene, carbon tetrachloride, n-hexane or ethanol.
In a further improvement of the above preparation method, in step S3, the spheroidization is performed in a continuous shaping system formed by connecting 2 to 15 micro-nano particle shaping and coating systems in series; the spheroidizing process parameters are as follows: the feeding amount is 50 kg-200 kg/h, the rotating speed is 100 rpm-9000 rpm, and the time is 5 min-45 min.
In a further improvement of the above preparation method, in step S4, the carbonization is performed at a temperature of 600 to 1500 ℃; the heat preservation time in the graphite carbonization process is 5-20 h.
As a general technical concept, the present invention also provides a high-capacity graphite negative electrode material prepared by the above-described preparation method.
In the above high-capacity graphite negative electrode material, the high-capacity graphite negative electrode material further comprises spherical natural graphite; the inner surface and the outer surface of the spherical natural graphite are coated with amorphous carbon material layers to form an inner and outer coating structure which is sequentially provided with the amorphous carbon material layer, the natural graphite layer and the amorphous carbon material layer from inside to outside; the amorphous carbon material layer is doped with at least one element of boron, phosphorus and vanadium.
As a general technical concept, the invention also provides an application of the high-capacity graphite negative electrode material in the preparation of a lithium ion battery.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a preparation method of a high-capacity graphite cathode material, which comprises the steps of preparing mixed slurry by using crystalline flake graphite, a doping compound, a binder and a solvent as raw materials, uniformly coating the binder and the doping compound on the surface of the crystalline flake graphite by a spray drying method, dispersing the crystalline flake graphite which are mutually bonded together by crushing, spheroidizing the crystalline flake graphite coated with the binder and the doping compound to form spherical natural graphite, uniformly coating the inner surface and the outer surface of the spherical natural graphite with the binder and the doping compound, namely the spherical natural graphite coated with the binder and the doping compound on the inner surface and the outer surface, and finally carbonizing, removing magnetic screening and processing to prepare the high-capacity graphite cathode material. In the invention, the method of combining spray drying, crushing and spheroidizing is adopted, so that the inside and outside surfaces of the spherical natural graphite can be uniformly coated with the binder and the doping compound; based on this, after the carbonization, the even amorphous carbon material layer is formed on the internal and external surfaces of spherical natural graphite, thereby forming an internal and external surface coating structure which is the amorphous carbon material layer, the natural graphite layer and the amorphous carbon material layer from inside to outside in sequence, and in the high-capacity graphite cathode material, because the internal and external surfaces of spherical natural graphite are evenly coated with the amorphous carbon material layer, the contact of electrolyte and natural graphite can be effectively prevented, the cycle performance of the material is improved, and simultaneously, the multiplying power performance of the natural graphite can also be improved. In addition, in the carbonization process, the doping of elements of the amorphous carbon material is realized, the doped elements comprise boron, phosphorus, vanadium and other elements, and the reversible charge-discharge capacity of the amorphous carbon material can be improved through doping, so that the gram capacity of the graphite composite material is improved, the energy density of the high-capacity graphite cathode material is obviously improved, and the application range of the high-capacity graphite cathode material is widened. Compared with the conventional natural graphite material, the graphite cathode material prepared by the preparation method has the advantages of high capacity, good cycle performance, good rate performance and the like, and meanwhile, when the high-capacity graphite cathode material is prepared into a working electrode for preparing a lithium ion battery, the cycle life of the lithium ion battery can be obviously prolonged, and the high-capacity graphite cathode material has high use value and good application prospect.
(2) In the preparation method, the solid content of the mixed slurry is optimized to be 1-25%, and the mixed slurry with proper viscosity is obtained by optimizing the solid content of the mixed slurry, so that the adhesive and the doping compound can be more stably coated on the surface of the flake graphite. And because the binder is not cured at high temperature and has strong binding effect, the binder and the doping compound can not fall off in the spray drying, crushing and spheroidizing processes, and the coating layers of the binder and the doping compound can not be damaged, which is the key point for preparing the amorphous carbon material layer with uniformly coated inner and outer surfaces. Meanwhile, the mass ratio of the crystalline flake graphite to the doping compound to the binder in the mixed slurry is optimized to be 55-94: 1-15: 5-30, the mixed slurry with moderate binder content is obtained by optimizing the solid content of the mixed slurry and the dosage ratio of the raw materials, and a coating layer of the binder and the doping compound with proper thickness is favorably formed on the surface of the crystalline flake graphite, so that a compact amorphous carbon material layer with proper thickness is favorably formed on the inner surface and the outer surface of the spherical natural graphite, and finally, a high-capacity graphite cathode material with higher capacity and better cycle performance is obtained. If the content of the binder is too low, the thickness of the amorphous carbon material layer generated in the graphite process is too thin, and the uniformity of the thickness is poor, so that the amorphous carbon material layer cannot be completely and effectively coated on the inner and outer surfaces of the natural graphite, the coating effect is poor, and the performance cycle of the high-capacity graphite cathode material is poor due to side reaction of the natural graphite and the electrolyte. If the content of the binder is too high, the coating layer becomes too thick, which affects the migration rate of lithium ions and deteriorates the rate capability.
(3) The preparation method has the advantages of simple process, convenient operation, low cost, low energy consumption and the like, does not need to adopt organic solvent to wash off redundant binder on the surface of the natural graphite, does not need high-temperature and high-pressure equipment to heat and pressurize, is suitable for large-scale production, and is beneficial to industrialized application.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a flow chart of a preparation process of a high-capacity graphite negative electrode material in example 1 of the present invention.
Fig. 2 is an SEM image of the high capacity graphite negative electrode material prepared in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the processes used were conventional processes, the equipment used were conventional equipment, and the data obtained were average values of three or more experiments.
Example 1
A preparation method of a high-capacity graphite negative electrode material is shown in a preparation flow chart of fig. 1 and comprises the following steps:
(1) adding the crystalline flake graphite with the average particle size of 35 mu m, phosphoric acid (doping compound) and coal tar pitch (binder) into acetone according to the mass ratio of the crystalline flake graphite, the doping compound and the binder of 80: 5: 15, controlling the solid content to be 15%, and fully stirring and ultrasonically treating to obtain mixed slurry.
(2) And (2) carrying out spray drying on the mixed slurry obtained in the step (1) to obtain a material in which coal pitch and phosphoric acid are mixed and coated on the surface of the crystalline flake graphite, namely the material in which the binder and the doping compound are mixed and coated on the surface of the crystalline flake graphite.
(3) And (3) mixing the coal tar pitch obtained in the step (2) with phosphoric acid and coating the mixture on the surface of the flake graphite, crushing the mixture to disperse the flake graphite, and controlling the particle size of the crushed material to be 35 mu m. The adhesive is not cured at high temperature and has strong adhesive effect, so that the adhesive and the doped compound are not dropped off in the crushing process; meanwhile, due to the existence of the binder, the binder and the doping compound can be uniformly coated on the surface of the crystalline flake graphite.
(4) Spheroidizing the crushed product in the step (3), specifically: the crushed product is put into a continuous shaping system (developed by Zhexin New energy Co., Ltd.) consisting of 6 micro-nano particle shaping and coating systems connected in series at a feeding amount of 100kg/h, and the crushed product is shaped (spheroidized) at the main machine rotating speed of 5000rpm for 15 min. During the spheroidization process, the flake graphite is curled into spherical natural graphite, and the mixture of the binder and the doping compound is uniformly coated on the inner surface and the outer surface of the spherical natural graphite to obtain the spherical natural graphite with both the inner surface and the outer surface coated with the coal tar pitch and the phosphoric acid, namely the spherical natural graphite with both the inner surface and the outer surface coated with the binder and the doping compound.
(5) Carbonizing the spherical natural graphite with the inner and outer surfaces coated with the coal pitch and the phosphoric acid obtained in the step (4), heating to 1000 ℃, and preserving heat for 12 hours, wherein in the carbonization process, the coal pitch coated on the inner and outer surfaces of the spherical natural graphite is converted into a compact amorphous carbon material, and the amorphous carbon material is uniformly coated on the inner and outer surfaces of the spherical natural graphite, so that the spherical natural graphite with the inner and outer surfaces coated with the amorphous carbon material is formed, and in the carbonization process, phosphorus is doped into the amorphous carbon material, so that the reversible intercalation and delithiation capacity of the amorphous carbon material is improved, and the high-capacity graphite cathode material is obtained by magnetic screening.
In this embodiment, the prepared high-capacity graphite negative electrode material includes spherical natural graphite, wherein the inner and outer surfaces of the spherical natural graphite are both coated with an amorphous carbon material layer, so as to form an inner and outer coating structure including the amorphous carbon material layer, the natural graphite layer, and the amorphous carbon material layer in sequence from inside to outside, and the amorphous carbon material layer is doped with phosphorus.
Fig. 2 is an SEM image of the high capacity graphite negative electrode material prepared in example 1 of the present invention.
An application of a high-capacity graphite cathode material in the preparation of a lithium ion battery, in particular to a button cell which is assembled by making the high-capacity graphite cathode material into a working electrode of the lithium ion battery, comprising the following steps:
the high-capacity graphite negative electrode material prepared in example 1, CMC and SBR were uniformly mixed at a mass ratio of 96.5: 1.5: 2 to prepare a slurry, which was coated on a copper foil, and then dried, rolled and punched to prepare a working electrode. The button cell is assembled in a glove box filled with argon, a metal lithium foil is taken as a counter electrode, a diaphragm is a polyethylene/propylene composite microporous membrane, and electrolyte is 1M LiPF6/(EC：EMC)(3︰7)。
An application of a high-capacity graphite negative electrode material in the preparation of a lithium ion battery, in particular to a full battery which is assembled by making the high-capacity graphite negative electrode material into a working electrode of the lithium ion battery, comprising the following steps:
mixing the high-capacity graphite negative electrode material, a conductive agent (SP), CMC and SBR according to a mass ratio of 95: 1.5: 2, and coating the mixture on a copper foil to obtain a negative electrode piece. Uniformly mixing a positive active material LiCoO2, a conductive agent (SP) and PVDF according to a mass ratio of 96.5: 2: 1.5, and coating the mixture on an aluminum foil to obtain a positive pole piece. The electrolyte is 1mol/L LiPF6+ EC + EMC, and the diaphragm is a polyethylene/propylene composite microporous membrane. They are assembled into a battery.
Electrochemical performance of the button cell was tested on a battery tester with a charge-discharge rate of 0.1C and a voltage range of 0.005-2V, as shown in table 1.
And (3) carrying out normal-temperature charging and discharging at the multiplying power of 1C, testing the cycle performance of the full cell within the voltage range of 3.0-4.2V, and showing in table 1.
The results show that: the button cell assembled by the high-capacity graphite cathode material prepared in the embodiment 1 has the first lithium removal capacity of 382.2mAh/g and the coulombic efficiency of 92.1 percent; the capacity retention ratio of the full cell assembled by the high-capacity graphite anode material prepared in the embodiment 1 is up to 93.2% after being cycled for 500 cycles at room temperature and 1C, and the capacity retention ratio of the full cell assembled by the high-capacity graphite anode material after being cycled for 1500 cycles at room temperature and 1C is up to 86.8%.
Comparative example 1
A preparation method of a graphite negative electrode material comprises the following steps:
(1) and mixing the crystalline flake graphite with the average particle size of 35 mu m and the coal pitch according to the mass ratio of the crystalline flake graphite to the binder of 90: 10 to obtain a mixed product.
(2) Carbonizing the mixed product obtained in the step (1), heating to 1000 ℃, and keeping the temperature for 12 h. And (4) demagnetizing and screening the carbonized product to obtain the graphite cathode material.
Button cells and full cells were prepared from the graphite negative electrode material prepared in comparative example 1 by the method of example 1, and the electrochemical performance results are shown in table 1.
The results show that: in the comparative example 1, the first lithium removal capacity is 360.1mAh/g, the coulombic efficiency is 90.7%, the capacity retention rate is 85.2% at most after 500 cycles of room temperature 1C circulation, and the capacity retention rate is 75.6% at most after 1500 cycles of room temperature 1C circulation.
Comparative example 2
A preparation method of a graphite negative electrode material comprises the following steps:
(1) adding the crystalline flake graphite with the average particle size of 35 mu m and coal pitch into acetone according to the mass ratio of the crystalline flake graphite to the binder of 85: 15, controlling the solid content to be 15%, and fully stirring and ultrasonically treating to obtain mixed slurry.
(2) And (3) carrying out spray drying on the mixed slurry obtained in the step (1) to obtain a material with the surface of the flake graphite coated with the coal pitch.
(3) And (3) crushing the material of which the surface is coated with the coal tar pitch obtained in the step (2) to disperse the flake graphite, and controlling the particle size of the crushed material to be 35 mu m.
(4) Spheroidizing the crushed product in the step (3), specifically: the crushed product is put into a continuous shaping system (developed by Zhexin New energy Co., Ltd.) consisting of 6 micro-nano particle shaping and coating systems connected in series at a feeding amount of 100kg/h, and the crushed product is shaped (spheroidized) at a main machine rotating speed of 5000rpm for 15min to obtain spherical natural graphite with the inner and outer surfaces coated with the coal pitch.
(5) And (4) carbonizing the spherical natural graphite with the inner and outer surfaces coated with the coal pitch obtained in the step (4), heating to 1000 ℃, preserving heat for 12 hours, and performing magnetic separation and screening to obtain the graphite cathode material.
Button cells and full cells were prepared from the graphite negative electrode material prepared in comparative example 2 by the method of example 1, and the electrochemical performance results are shown in table 1.
Example 2
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in step (1) of example 2, the solid content of the mixed slurry was 1%.
Button cells and full cells were prepared from the high-capacity graphite negative electrode material prepared in example 2 according to the method of example 1, and the electrochemical performance results are shown in table 1.
Example 3
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in step (1) of example 3, the solid content of the mixed slurry was 5%.
Button cells and full cells were prepared from the high-capacity graphite negative electrode material prepared in example 3 by the method of example 1, and the electrochemical performance results are shown in table 1.
Example 4
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in step (1) of example 4, the solid content of the mixed slurry was 10%.
Button cells and full cells were prepared from the high-capacity graphite negative electrode material prepared in example 4 by the method of example 1, and the electrochemical performance results are shown in table 1.
Example 5
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in step (1) of example 5, the solid content of the mixed slurry was 20%.
Button cells and full cells were prepared from the high-capacity graphite negative electrode material prepared in example 5 according to the method of example 1, and the electrochemical performance results are shown in table 1.
Example 6
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in step (1) of example 6, the solid content of the mixed slurry was 25%.
Button cells and full cells were prepared from the high-capacity graphite negative electrode material prepared in example 6 according to the method of example 1, and the electrochemical performance results are shown in table 1.
Example 7
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in the step (1) of example 7, the mass ratio of the crystalline flake graphite, the dopant compound and the binder is 85:5: 10.
And the spheroidizing process parameters in the step (4) are as follows: the crushed product is put into a continuous shaping system formed by connecting 4 micro-nano particle shaping and coating systems in series under the feeding quantity of 100kg/h, and is shaped (spheroidized) at the rotating speed of a main machine of 4000rpm for 5 min.
Button cells and full cells were prepared from the high-capacity graphite negative electrode material prepared in example 7 by the method of example 1, and the electrochemical performance results are shown in table 1.
Example 8
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in the step (1) of example 8, the mass ratio of the crystalline flake graphite, the doping compound and the binder is 85:5: 10.
And in the step (5), the carbonization process parameters are as follows: the temperature is increased to 1200 ℃, and the heat preservation time is 12 h.
Example 9
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in step (1) of example 9, the doping compound is an organic of phosphorus, wherein the organic of phosphorus is triphenylphosphine.
Button cells and full cells were prepared from the high-capacity graphite negative electrode material prepared in example 9 by the method of example 1, and the electrochemical performance results are shown in table 1.
Example 10
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in step (1) of example 10, the dopant compound is boric acid.
Button cells and full cells were prepared from the high-capacity graphite negative electrode material prepared in example 10 according to the method of example 1, and the electrochemical performance results are shown in table 1.
Example 11
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in step (1) of example 11, the doping compound is an oxide of boron, wherein the oxide of boron is diboron trioxide.
Button cells and full cells were prepared from the high-capacity graphite negative electrode material prepared in example 11 by the method of example 1, and the electrochemical performance results are shown in table 1.
Example 12
A method for preparing a high-capacity graphite negative electrode material, which is basically the same as that in example 1, except that: in step (1) of example 12, the doping compound is an oxide of vanadium, wherein the oxide of vanadium is vanadium pentoxide.
Button cells and full cells were prepared from the high-capacity graphite negative electrode material prepared in example 12 by the method of example 1, and the electrochemical performance results are shown in table 1.
TABLE 1 electrochemical Performance test results for button cells and full cells made with different graphite cathode materials
From the results, compared with the conventional natural graphite material, the high-capacity graphite cathode material prepared by the invention has the advantages of high capacity, good cycle performance, good rate performance and the like, can obviously prolong the cycle life of a lithium ion battery when being used as the cathode material of a working electrode for preparing the lithium ion battery, and has high use value and good application prospect.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A preparation method of a high-capacity graphite negative electrode material is characterized by comprising the following steps:
s1, mixing the crystalline flake graphite, the doping compound, the binder and the solvent to prepare mixed slurry;
s2, spray drying the mixed slurry obtained in the step S1 to obtain a material in which a binder and a doping compound are mixed and coated on the surface of the flake graphite;
s3, mixing the binder and the doping compound obtained in the step S2 and coating the mixture on the material on the surface of the crystalline flake graphite, and crushing and spheroidizing to obtain spherical natural graphite with the inner surface and the outer surface both coated with the binder and the doping compound;
s4, carbonizing the spherical natural graphite with the inner and outer surfaces coated with the binder and the doping compound obtained in the step S3, and performing magnetic screening to obtain the high-capacity graphite cathode material.
2. The method according to claim 1, wherein in step S1, the solid content of the mixed slurry is 1% to 25%.
3. The preparation method according to claim 2, wherein in step S1, the mass ratio of the flake graphite, the doping compound and the binder in the mixed slurry is 55-94: 1-15: 5-30.
4. The production method according to claim 3, wherein the average particle size of the flake graphite is 3 to 45 μm; the doping compound is one of phosphoric acid, phosphorus pentoxide, triphenylphosphine, boric acid, boron trioxide and vanadium pentoxide; the binder is at least one of petroleum asphalt, coal asphalt, mesophase asphalt, phenolic resin, epoxy resin, petroleum resin, coal tar or heavy oil.
5. The method according to claim 2, wherein in step S1, the solvent is one or more of acetone, diethyl ether, xylene, carbon tetrachloride, n-hexane, or ethanol.
6. The preparation method according to any one of claims 1 to 5, wherein in step S3, the spheroidization is performed in a continuous shaping system composed of 2 to 15 micro-nano particle shaping and coating systems connected in series; the spheroidizing process parameters are as follows: the feeding amount is 50 kg-200 kg/h, the rotating speed is 100 rpm-9000 rpm, and the time is 5 min-45 min.
7. The production method according to any one of claims 1 to 5, wherein in step S4, the carbonization is performed at a temperature of 600 ℃ to 1500 ℃; the heat preservation time in the graphite carbonization process is 5-20 h.
8. A high-capacity graphite negative electrode material, which is prepared by the preparation method of any one of claims 1 to 7.
9. The high capacity graphite anode material of claim 8, wherein the high capacity graphite anode material comprises spheroidal natural graphite; the inner surface and the outer surface of the spherical natural graphite are coated with amorphous carbon material layers to form an inner and outer coating structure which is sequentially provided with the amorphous carbon material layer, the natural graphite layer and the amorphous carbon material layer from inside to outside; the amorphous carbon material layer is doped with at least one element of boron, phosphorus and vanadium.
10. Use of a high capacity graphite anode material according to claim 8 or 9 in the preparation of a lithium ion battery.
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| CN116364917A (en) * | 2023-03-10 | 2023-06-30 | 内蒙古欣源石墨烯科技股份有限公司 | High-energy-density quick-charging lithium ion battery negative electrode material and preparation method thereof |
Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005158725A (en) * | 2003-11-06 | 2005-06-16 | Showa Denko Kk | Graphite particle for negative pole material, manufacturing method for the same, and battery using the same |
| CN1697215A (en) * | 2005-05-27 | 2005-11-16 | 深圳市贝特瑞电子材料有限公司 | Cathode material of composite carbon in use for lithium ion battery and preparation method |
| CN1702893A (en) * | 2005-04-20 | 2005-11-30 | 深圳市贝特瑞电子材料有限公司 | Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof |
| CN103606680A (en) * | 2013-12-05 | 2014-02-26 | 萝北百吉瑞新能源有限公司 | Preparation method of natural graphite composite N-doped carbon nanofibers webs cathode material |
| JP2014067639A (en) * | 2012-09-26 | 2014-04-17 | Mitsubishi Chemicals Corp | Carbon material for nonaqueous secondary battery, negative electrode for nonaqueous secondary battery, and nonaqueous secondary battery |
| CN103872294A (en) * | 2014-03-26 | 2014-06-18 | 深圳市贝特瑞新能源材料股份有限公司 | Composite material of lithium ion battery, preparation method thereof and lithium ion battery |
| CN103972508A (en) * | 2014-05-20 | 2014-08-06 | 上海第二工业大学 | Inorganic doped/coated modification natural graphite, as well as preparation method and application thereof |
| CN104103820A (en) * | 2013-04-13 | 2014-10-15 | 万台鹏 | Spherical porous channel graphite negative electrode material of lithium ion battery and preparation method thereof |
| CN104201388A (en) * | 2014-07-31 | 2014-12-10 | 湖南德天新能源科技有限公司 | Preparation method for compound lithium ion battery cathode material and application of petroleum resin in preparation method |
| CN104659366A (en) * | 2014-12-30 | 2015-05-27 | 东莞市凯金新能源科技有限公司 | Preparation method of anode material for power lithium ion battery |
| CN105047929A (en) * | 2015-06-08 | 2015-11-11 | 内蒙古瑞盛石墨新材料有限公司 | Lithium ion battery anode material with porous structure and preparation method of lithium ion battery anode material |
| CN105633370A (en) * | 2016-01-06 | 2016-06-01 | 上海第二工业大学 | Modified natural graphite and preparation method and application thereof |
| CN106025277A (en) * | 2016-06-18 | 2016-10-12 | 湖南星城石墨科技股份有限公司 | Low-resilience and high-energy-density composite graphite negative electrode material and preparation method thereof |
| CN106058211A (en) * | 2016-08-03 | 2016-10-26 | 深圳市贝特瑞新能源材料股份有限公司 | Natural graphite composite material, preparation method thereof and lithium ion battery |
| CN106129397A (en) * | 2016-07-27 | 2016-11-16 | 芜湖凯尔电气科技有限公司 | The high/low temperature lithium ion battery of adaptive temperature change |
| KR20170007140A (en) * | 2015-07-09 | 2017-01-18 | 주식회사 엘지화학 | Anode active material comprising mixed graphite, negative electrode comprising thereof and lithium secondary battery using the negative electrode |
| CN106450312A (en) * | 2016-10-18 | 2017-02-22 | 福建翔丰华新能源材料有限公司 | Method for preparing inorganic doped modified natural graphite |
| CN106654271A (en) * | 2016-12-23 | 2017-05-10 | 安徽国威电动车制造有限公司 | Ultrahigh-capacity lithium battery negative electrode material and preparation process |
| CN106784691A (en) * | 2016-12-23 | 2017-05-31 | 安徽国威电动车制造有限公司 | Special electrode material of lithium battery of electric motor car and preparation method thereof |
| 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 |
| CN109768247A (en) * | 2018-12-29 | 2019-05-17 | 湖南中科星城石墨有限公司 | The excellent high-energy density negative electrode material and preparation method thereof of a kind of high-pressure solid, high-temperature behavior |
| CN111232971A (en) * | 2020-01-17 | 2020-06-05 | 广东东岛新能源股份有限公司 | Long-circulation natural graphite-based modified composite material and preparation method and application thereof |
| CN111333063A (en) * | 2020-02-25 | 2020-06-26 | 广东东岛新能源股份有限公司 | Natural graphite-based silicon-carbon composite negative electrode material and preparation method and application thereof |
| CN111463416A (en) * | 2020-04-14 | 2020-07-28 | 广东东岛新能源股份有限公司 | Low-cost low-expansion-rate long-circulation natural graphite-based composite material and preparation method and application thereof |
-
2020
- 2020-09-17 CN CN202010979597.4A patent/CN114203978B/en active Active
Patent Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005158725A (en) * | 2003-11-06 | 2005-06-16 | Showa Denko Kk | Graphite particle for negative pole material, manufacturing method for the same, and battery using the same |
| CN1702893A (en) * | 2005-04-20 | 2005-11-30 | 深圳市贝特瑞电子材料有限公司 | Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof |
| CN1697215A (en) * | 2005-05-27 | 2005-11-16 | 深圳市贝特瑞电子材料有限公司 | Cathode material of composite carbon in use for lithium ion battery and preparation method |
| JP2014067639A (en) * | 2012-09-26 | 2014-04-17 | Mitsubishi Chemicals Corp | Carbon material for nonaqueous secondary battery, negative electrode for nonaqueous secondary battery, and nonaqueous secondary battery |
| CN104103820A (en) * | 2013-04-13 | 2014-10-15 | 万台鹏 | Spherical porous channel graphite negative electrode material of lithium ion battery and preparation method thereof |
| CN103606680A (en) * | 2013-12-05 | 2014-02-26 | 萝北百吉瑞新能源有限公司 | Preparation method of natural graphite composite N-doped carbon nanofibers webs cathode material |
| CN103872294A (en) * | 2014-03-26 | 2014-06-18 | 深圳市贝特瑞新能源材料股份有限公司 | Composite material of lithium ion battery, preparation method thereof and lithium ion battery |
| CN103972508A (en) * | 2014-05-20 | 2014-08-06 | 上海第二工业大学 | Inorganic doped/coated modification natural graphite, as well as preparation method and application thereof |
| CN104201388A (en) * | 2014-07-31 | 2014-12-10 | 湖南德天新能源科技有限公司 | Preparation method for compound lithium ion battery cathode material and application of petroleum resin in preparation method |
| CN104659366A (en) * | 2014-12-30 | 2015-05-27 | 东莞市凯金新能源科技有限公司 | Preparation method of anode material for power lithium ion battery |
| CN105047929A (en) * | 2015-06-08 | 2015-11-11 | 内蒙古瑞盛石墨新材料有限公司 | Lithium ion battery anode material with porous structure and preparation method of lithium ion battery anode material |
| KR20170007140A (en) * | 2015-07-09 | 2017-01-18 | 주식회사 엘지화학 | Anode active material comprising mixed graphite, negative electrode comprising thereof and lithium secondary battery using the negative electrode |
| CN105633370A (en) * | 2016-01-06 | 2016-06-01 | 上海第二工业大学 | Modified natural graphite and preparation method and application thereof |
| CN106025277A (en) * | 2016-06-18 | 2016-10-12 | 湖南星城石墨科技股份有限公司 | Low-resilience and high-energy-density composite graphite negative electrode material and preparation method thereof |
| CN106129397A (en) * | 2016-07-27 | 2016-11-16 | 芜湖凯尔电气科技有限公司 | The high/low temperature lithium ion battery of adaptive temperature change |
| CN106058211A (en) * | 2016-08-03 | 2016-10-26 | 深圳市贝特瑞新能源材料股份有限公司 | Natural graphite composite material, preparation method thereof and lithium ion battery |
| CN106450312A (en) * | 2016-10-18 | 2017-02-22 | 福建翔丰华新能源材料有限公司 | Method for preparing inorganic doped modified natural graphite |
| CN106654271A (en) * | 2016-12-23 | 2017-05-10 | 安徽国威电动车制造有限公司 | Ultrahigh-capacity lithium battery negative electrode material and preparation process |
| CN106784691A (en) * | 2016-12-23 | 2017-05-31 | 安徽国威电动车制造有限公司 | Special electrode material of lithium battery of electric motor car and preparation method thereof |
| 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 |
| CN109768247A (en) * | 2018-12-29 | 2019-05-17 | 湖南中科星城石墨有限公司 | The excellent high-energy density negative electrode material and preparation method thereof of a kind of high-pressure solid, high-temperature behavior |
| CN111232971A (en) * | 2020-01-17 | 2020-06-05 | 广东东岛新能源股份有限公司 | Long-circulation natural graphite-based modified composite material and preparation method and application thereof |
| CN111333063A (en) * | 2020-02-25 | 2020-06-26 | 广东东岛新能源股份有限公司 | Natural graphite-based silicon-carbon composite negative electrode material and preparation method and application thereof |
| CN111463416A (en) * | 2020-04-14 | 2020-07-28 | 广东东岛新能源股份有限公司 | Low-cost low-expansion-rate long-circulation natural graphite-based composite material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 余小军;綦瑞萍;杨绍斌;: "包覆和掺杂对锂离子电池石墨负极材料的影响", 江苏技术师范学院学报, no. 04 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116364917A (en) * | 2023-03-10 | 2023-06-30 | 内蒙古欣源石墨烯科技股份有限公司 | High-energy-density quick-charging lithium ion battery negative electrode material and preparation method thereof |
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