CN105609779A - Graphite negative electrode material for power lithium ion battery and preparation method therefor - Google Patents
Graphite negative electrode material for power lithium ion battery and preparation method therefor Download PDFInfo
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- CN105609779A CN105609779A CN201510975839.1A CN201510975839A CN105609779A CN 105609779 A CN105609779 A CN 105609779A CN 201510975839 A CN201510975839 A CN 201510975839A CN 105609779 A CN105609779 A CN 105609779A
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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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- 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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- 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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Abstract
The invention provides a graphite negative electrode material for a power lithium ion battery and a preparation method therefor. Graphite electrode powder is taken as the raw material; the raw material is crushed, shaped, and screened to obtain primary particles with certain appearances and grain fineness distributions; the graphite electrode powder obtained by the steps of crushing, shaping and sieving is uniformly mixed with an adhesive, a graphitizing catalyst and an auxiliary under inert gas protection and a heating condition, and the mixture is subjected to secondary pelleting through mechanical action; secondary particles are obtained by bonding two or more primary particles together; the secondary particles are subjected to catalysis graphitizing high-temperature processing under the inert gas protection; and then the secondary particles are graded or screened to obtain the final product. When the graphite material is used as the power lithium ion battery negative electrode, the advantages of excellent high-current charge-discharge property, long cycling life, good high-and-low temperature performance, low expansion rate, low production cost and the like are realized, so that the graphite negative electrode material is suitable for the power lithium ion battery.
Description
Technical field
The present invention relates to a kind of power lithium-ion battery graphite cathode material and preparation method thereof, belong to lithium battery technology neckTerritory.
Background technology
Compared with the secondary cells such as traditional plumbic acid, NI-G, ni-mh, lithium rechargeable battery has that operating voltage is high, bodyThe advantages such as long-pending little, quality is light, capacity density is high, memory-less effect, pollution-free, self discharge is little and have extended cycle life.Since Sony in 1991 is successfully realized commercialization by lithium ion battery, lithium ion battery has become mobile phone, notesThe leading power supply of this computer and digital product, also more and more extensive in the application in the field such as electric automobile and energy storage. Wherein withThe electric automobile that lithium electricity new forms of energy are power, not only can replace oil, reduce greenhouse gas emission with electricity, can also store upDepositing electric-net valley-electricity, is the competitively rising industry of development of developed country and area. Along with lithium ion battery automobile progressively moves towards city, using with consuming of world's lithium resource will become geometric growth, thus derivative industry chain (supply chain) development prospect wide,Have a high potential. Can predict, who seizes the first chance of lithium electricity New Energy Industry, and who just will win economic developmentInitiatively.
At present, the lithium ion battery negative material that large-scale commercial is used is mainly material with carbon element, comprises native graphite, peopleMake graphite, MCMB (MCMB) etc. As electronic lithium ion battery, negative material used need meet harshnessPerformance indications requirement, as require it to there is high security, high-multiplying power discharge, long circulation life and good technique adapts toProperty etc., so lithium cell for electric bicycle negative material should meet the following conditions: 1) material structure is stable, to obtain lengthCycle life; 2) instantaneous macro-energy there is large current density power, can be provided; 3) with good compatible of electrolyteProperty; 4) stable batches of materials quality. Mostly adopt at present short grained Delanium or MCMB conductPower negative pole, short grained Delanium is because its specific area is large, in battery applications side reaction many, affect batteryCan; MCMB excellent performance, but its cost of raw material is more expensive.
Patent CN201210507903.X discloses a kind of lithium-ion-power cell composite negative pole material and preparation method thereof.Described lithium-ion-power cell composite negative pole material is with the nucleocapsid structure of the coated hard carbon layer composition of native graphite matrix surfaceAnd the secondary modification layer that adopts dressing agent to modify described nucleocapsid structure; Described coating is thermosetting resin warpCross the hard carbon that pyrolysis forms; Described thermosetting resin is at least one in phenolic resins, epoxy resin, furane resins; InstituteThe dressing agent of stating is at least one in coal tar pitch, asphalt. Method coated, secondary modification that the present invention adopts once,Prepare capacity, all lithium-ion-power cell composite negative pole materials preferably of the chemical property such as efficiency, circulation first. ButBe that it exists primary particle larger, cause its high rate during charging-discharging poor. Patent CN201010257822.X is openThe negative material used of a kind of lithium-ion-power cell and preparation method thereof. It is taking spherical, axial ratio as 1.0～3.5Class is spherical, bulk and/or flake graphite are matrix, and matrix is coated with non-graphite material with carbon element, forms composite particles. ThisInvention compared with prior art, the negative material that lithium-ion-power cell is used have high power capacity, high efficiency, low temperature performance excellent,High rate performance excellence, the superior feature of absorbent. But its matrix adopting native graphite, easy delamination in charge and discharge processAffect cycle performance; In addition, it adopts liquid phase method, and productive rate is low.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, discloses a kind of power lithium-ion battery graphite cathode materialPreparation method. The present invention, by secondary granulation, prepares by the granule of multiple laminated structures and is bonded together and forms graphiteParticle, for lithium ion battery negative material.
Another object of the present invention is to, a kind of power lithium-ion battery graphite that uses above-mentioned preparation method to prepare is providedNegative material, for improving the performance of conventional lithium ion battery, thereby is suitable for practicality more.
The object of the invention to solve the technical problems realizes by the following technical solutions. Propose according to the present inventionThe preparation method of graphite cathode material for power lithium-ion battery, is characterized in that, comprises the following steps:
(1) primary particle preparation process, pulverizes graphite electrode powder as raw material, shaping, screening, obtainsGraphite electrode powder primary particle;
(2) secondary granulation step, under the condition of inert gas shielding, heating, by step (1) gained graphite electrodePowder primary particle evenly mixes with adhesive, graphitization catalyst, auxiliary agent, and secondary granulation obtains by two or more graphiteThe second particle that electrode powder primary particle is bonded together;
(3) graphitization step, under inert gas shielding, carries out catalyzed graphitization to step (2) gained second particleProcess;
(4) shaping process, further carries out classification or sieves graphitization afterproduct, obtains final products.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
The preparation method of graphite cathode material for aforesaid power lithium-ion battery, the carbonaceous of wherein said graphite electrode powderAmount content is more than or equal to 99.5wt%.
The preparation method of graphite cathode material for aforesaid power lithium-ion battery, wherein said graphite electrode powder onceGrain is laminated structure, and aspect ratio is 3-15, smooth surface, and its size distribution D10 is more than or equal to 2 microns, D50 and is8-15 micron, D90 are less than or equal to 30 microns.
The preparation method of graphite cathode material for aforesaid power lithium-ion battery, wherein said adhesive is pitch, itsAddition is the 5-30wt% of graphite electrode powder primary particle quality.
The preparation method of graphite cathode material for aforesaid power lithium-ion battery, wherein said graphite catalyst be silicon,One or more in oxide or the nitride of iron, boron, its addition is graphite electrode powder primary particle quality1-10wt％；
The preparation method of graphite cathode material for aforesaid power lithium-ion battery, wherein said auxiliary agent be carbon tetrachloride,One or more in oxolane, washing oil, addition is the 5-30wt% of graphite electrode powder primary particle quality.
The preparation method of graphite cathode material for aforesaid power lithium-ion battery, wherein said secondary granulation adopts reactionStill adds thermal agitation, resistance furnace and adds one or more in mediating of thermal agitation, kneader;
The preparation method of graphite cathode material for aforesaid power lithium-ion battery, wherein said secondary granulation adopts reactionStill adds thermal agitation, resistance furnace, and to add the temperature that thermal agitation, kneader mediate be 200-1400 DEG C, and the time is 0.5-48h;
The preparation method of graphite cathode material for aforesaid power lithium-ion battery, wherein said graphitization processing temperature is2600-3400 DEG C, graphitization time is 10-48h;
The object of the invention to solve the technical problems also adopts following technical scheme to realize. Propose according to the present inventionPower lithium-ion battery graphite cathode material, wherein said power lithium-ion battery graphite cathode material is by above-mentionedPreparation method makes.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid power lithium-ion battery graphite cathode material, is characterized in that, wherein said graphite cathode material isParticle by multiple laminated structures is bonded, and its specific area is less than or equal to 10m2/ g, its size distribution D10 is greater thanEqualing 4 microns, D50 is that 12-25 micron, D90 are less than or equal to 50 microns, and carbon mass content is more than or equal to 99.90wt%.
The power lithium-ion battery graphite cathode material that the inventive method prepares, in its second particle structure onceIntergranular gap can provide electrolyte storage area and expansion space, when having improved the hold facility of electrolyte, fallsThe macroscopic view of low pole piece expands, and a granule has shortened the circulation path of electronics or ion, has improved material thereby playElectrical conductivity reduce the polarization of battery. Therefore there is good cycle, high rate performance excellence, pole piece expansion rate is low etc.Advantage.
Compared with prior art, technical solution of the present invention beneficial effect is:
1. raw material are industrial waste, source is abundant, cheap, technique is simple.
2. second particle structure makes material have higher electrolyte storage area and expansion space.
3. second particle structure has shortened the circulation path of electronics or ion, plays the electrical conductivity effect that has improved material.
Brief description of the drawings
Fig. 1 is embodiment 1 composite SEM collection of illustrative plates.
Fig. 2 is embodiment 1 composite charging and discharging curve.
Detailed description of the invention
Technological means and effect of taking for reaching predetermined goal of the invention for further setting forth the present invention, below in conjunction with attachedFigure and preferred embodiment, to the power lithium-ion battery proposing according to the present invention with graphite cathode material and preparation method thereof itsDetailed description of the invention step, feature and effect thereof, be described in detail as follows, and wherein embodiment 1 produces lithium ion battery to useThe performance of conventional method of graphite cathode material and products thereof, in order to the lithium ion power electricity of the inventive method and production thereofPond compares by the performance of graphite cathode material.
Reference examples:
Be to be more than or equal to 99.5% graphite electrode powder to pulverize through 70 machines by fixed carbon mass content, ball mill shaping,After screening, obtaining size distribution D10, to be more than or equal to 4 microns, D50 be that 18 microns, D90 are less than or equal to the class of 50 micronsSpheric granules; Take this particle of 100 parts of quality, the pitch of 3 parts of quality, the boron carbide of 5 parts of quality, at indifferent gasUnder atmosphere protection, heat and stir and carry out carbon and be coated; Will be after carbon be coated material graphitization 24h at 3000 DEG C, through pointLevel or sieve after obtain final products.
Its charge/discharge capacity is 332.4mAh/g, first 93.2%, 100 week circulation volume conservation rate 94.89% (button of efficiencyThe assembling of formula battery and test are with embodiment 1)
Embodiment 1:
Be to be more than or equal to 99.5% graphite electrode powder to pulverize through 70 machines by fixed carbon mass content, ball mill shaping,After screening, obtaining size distribution D10, to be more than or equal to 2 microns, D50 be that 8-10 micron, D90 are less than or equal to 30 microns,Aspect ratio is the primary particle between 3-15; Take this primary particle of 100 parts of quality, the pitch of 5 parts of quality, 1 part of matterThe tri-iron tetroxide of amount, the carbon tetrachloride of 5 parts of quality, is placed in pyroreaction still, under inert atmosphere protection, heatingAnd stir wherein 300 DEG C of insulation 6h, cooling discharging after 600 DEG C of insulation 6h; Will be after granulation material at 3400 DEG CGraphitization 10h, classified or sieve after obtain final products (accompanying drawing 1 is shown in by SEM collection of illustrative plates).
Active material (graphite material making), conductive agent (superP carbon black), sodium carboxymethylcellulose (CMC),Butadiene-styrene rubber (SBR): deionized water is according to mass ratio 80:10:5:5:100, and 2000r/min speed stirs after 4h, appliesOn 20um thickness Copper Foil, coating thickness 50um obtains battery pole piece after roll extrusion, section, baking, with lithium sheetAs to electrode fabrication half-cell, battery size is CR2032 button cell, and electrolyte is elected conventional lithium ion battery asElectrolyte: 1mol/L lithium hexafluoro phosphate (LiPF6)/ethylene carbonate (EC): dimethyl carbonate (DMC): carbonic acidThe mixed liquor that methyl ethyl ester (EMC) is 10:10:80.
Battery to preparation carries out charge-discharge test, constant current charge-discharge under 0.2C multiplying power, lower voltage limit 0.001V, the upper limitVoltage 2.0V. Charging and discharging curve is shown in accompanying drawing 2, and its charge/discharge capacity is 347.8mAh/g, first efficiency 95.1%, 100All circulation volume conservation rates 99.32%.
Embodiment 2:
Be to be more than or equal to 99.5% graphite electrode powder to pulverize through 70 machines by fixed carbon mass content, ball mill shaping,After screening, obtaining size distribution D10, to be more than or equal to 2 microns, D50 be that 8-10 micron, D90 are less than or equal to 30 microns,Aspect ratio is the primary particle between 3-15; Take this primary particle of 100 parts of quality, the pitch of 15 parts of quality, 5 partsThe tri-iron tetroxide of quality, the carbon tetrachloride of 15 parts of quality, is placed in pyroreaction still, under inert atmosphere protection, addsHeat also stirs, wherein 300 DEG C of insulation 6h, cooling discharging after 800 DEG C of insulation 6h; Will be after granulation material at 2600 DEG CLower graphitization 48h, classified or sieve after obtain final products.
Its charge/discharge capacity is 343.2mAh/g, first 93.7%, 100 week circulation volume conservation rate 99.30% (button of efficiencyThe assembling of formula battery and test are with embodiment 1).
Embodiment 3:
Be to be more than or equal to 99.5% graphite electrode powder to pulverize through 70 machines by fixed carbon mass content, ball mill shaping,After screening, obtaining size distribution D10, to be more than or equal to 2 microns, D50 be that 8-10 micron, D90 are less than or equal to 30 microns,Aspect ratio is the primary particle between 3-15; Take this primary particle of 100 parts of quality, the pitch of 30 parts of quality, 10 partsThe tri-iron tetroxide of quality, the carbon tetrachloride of 30 parts of quality, is placed in pyroreaction still, under inert atmosphere protection, addsHeat also stirs, wherein 300 DEG C of insulation 6h, cooling discharging after 800 DEG C of insulation 6h; Will be after granulation material at 3000 DEG CLower graphitization 24h, classified or sieve after obtain final products.
Its charge/discharge capacity is 351.1mAh/g, first 93.9%, 100 week circulation volume conservation rate 99.27% (button of efficiencyThe assembling of formula battery and test are with embodiment 1).
Embodiment 4:
Be to be more than or equal to 99.5% graphite electrode powder to pulverize through 70 machines by fixed carbon mass content, ball mill shaping,After screening, obtaining size distribution D10, to be more than or equal to 2 microns, D50 be that 10-13 micron, D90 are less than or equal to 30 microns,Aspect ratio is the primary particle between 3-15; Take this primary particle of 100 parts of quality, the pitch of 15 parts of quality, 5 partsThe tri-iron tetroxide of quality, the carbon tetrachloride of 15 parts of quality, is placed in pyroreaction still, under inert atmosphere protection, addsHeat also stirs, wherein 300 DEG C of insulation 12h, cooling discharging after 800 DEG C of insulation 12h; Will be after granulation material at 3000 DEG CLower graphitization 24h, classified or sieve after obtain final products.
Its charge/discharge capacity is 348.3mAh/g, first 95.1%, 100 week circulation volume conservation rate 99.21% (button of efficiencyThe assembling of formula battery and test are with embodiment 1).
Embodiment 5:
Be to be more than or equal to 99.5% graphite electrode powder to pulverize through 70 machines by fixed carbon mass content, ball mill shaping,After screening, obtaining size distribution D10, to be more than or equal to 2 microns, D50 be that 10-13 micron, D90 are less than or equal to 30 microns,Aspect ratio is the primary particle between 3-15; Take this primary particle of 100 parts of quality, the pitch of 15 parts of quality, 5 partsThe tri-iron tetroxide of quality, the carbon tetrachloride of 15 parts of quality, is placed in pyroreaction still, under inert atmosphere protection, addsHeat also stirs, wherein 300 DEG C of insulation 12h, cooling discharging after 800 DEG C of insulation 12h; Will be after granulation material at 3000 DEG CLower graphitization 24h, classified or sieve after obtain final products.
Its charge/discharge capacity is 346.9mAh/g, first 94.3%, 100 week circulation volume conservation rate 99.33% (button of efficiencyThe assembling of formula battery and test are with embodiment 1).
Embodiment 6:
Be to be more than or equal to 99.5% graphite electrode powder to pulverize through 70 machines by fixed carbon mass content, ball mill shaping,After screening, obtaining size distribution D10, to be more than or equal to 2 microns, D50 be that 13-15 micron, D90 are less than or equal to 30 microns,Aspect ratio is the primary particle between 3-15; Take this primary particle of 100 parts of quality, the pitch of 15 parts of quality, 5 partsThe silica of quality, the washing oil of 15 parts of quality, is placed in pyroreaction still, under inert atmosphere protection, heats and stirsMix wherein 300 DEG C of insulation 12h, cooling discharging after 800 DEG C of insulation 12h; Will be after granulation material stone at 3000 DEG CChina inkization 24h, classified or sieve after obtain final products.
Its charge/discharge capacity is 350.4mAh/g, first 94.7%, 100 week circulation volume conservation rate 99.25% (button of efficiencyThe assembling of formula battery and test are with embodiment 1).
Embodiment 7:
Be to be more than or equal to 99.5% graphite electrode powder to pulverize through 70 machines by fixed carbon mass content, ball mill shaping,After screening, obtaining size distribution D10, to be more than or equal to 2 microns, D50 be that 13-15 micron, D90 are less than or equal to 30 microns,Aspect ratio is the primary particle between 3-15; Take this primary particle of 100 parts of quality, the pitch of 15 parts of quality, 5 partsThe boron carbide of quality, the furans of 15 parts of quality, is placed in pyroreaction still, and under inert atmosphere protection, heat and stir,Wherein 300 DEG C of insulation 12h, cooling discharging after 800 DEG C of insulation 12h; Will be after granulation material graphitization at 3000 DEG C24h, classified or sieve after obtain final products.
Its charge/discharge capacity is 349.7mAh/g, first 93.8%, 100 week circulation volume conservation rate 99.23% (button of efficiencyThe assembling of formula battery and test are with embodiment 1).
By relatively can finding out of reference examples and embodiment, in the preferred embodiment of the present invention, utilize the inventive method to obtainPower lithium-ion battery will be better than by the performance of graphite cathode material the lithium ion that in prior art, conventional method obtains far awayCell negative electrode material.
The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction, thoughSo the present invention discloses as above with preferred embodiment, but is not in order to limit the present invention, is anyly familiar with this professional technology peopleMember, is not departing within the scope of technical solution of the present invention, when method and the technology contents that can utilize above-mentioned announcement are made a littleChanging or be modified to the equivalent embodiment of equivalent variations, is the content that does not depart from technical solution of the present invention, according to this in every caseAny simple modification, equivalent variations and modification that bright technical spirit is done above embodiment, all still belong to skill of the present inventionIn the scope of art scheme.
Claims (11)
1. a preparation method for graphite cathode material for power lithium-ion battery, is characterized in that, comprises the following steps:
(1) primary particle preparation process, pulverizes graphite electrode powder as raw material, shaping, screening, obtains graphite electrode powder primary particle;
(2) secondary granulation step, under the condition of inert gas shielding, heating, step (1) gained graphite electrode powder primary particle is evenly mixed with adhesive, graphitization catalyst, auxiliary agent, and secondary granulation obtains the second particle being bonded together by two or more graphite electrode powder primary particles;
(3) graphitization step, under inert gas shielding, carries out catalyzed graphitization processing to step (2) gained second particle;
(4) shaping process, further carries out classification or sieves graphitization afterproduct, obtains final products.
2. the preparation method of graphite cathode material for power lithium-ion battery according to claim 1, is characterized in that, the carbon mass content of described graphite electrode powder is more than or equal to 99.5wt%.
3. the preparation method of graphite cathode material for power lithium-ion battery according to claim 1, it is characterized in that, described graphite electrode powder primary particle is laminated structure, aspect ratio is 3-15, smooth surface, it is that 8-15 micron, D90 are less than or equal to 30 microns that its size distribution D10 is more than or equal to 2 microns, D50.
4. the preparation method of graphite cathode material for power lithium-ion battery according to claim 1, is characterized in that, described adhesive is pitch, and its addition is the 5-30wt% of graphite electrode powder primary particle quality.
5. the preparation method of graphite cathode material for power lithium-ion battery according to claim 1, it is characterized in that, described graphite catalyst is one or more in oxide or the nitride of silicon, iron, boron, and its addition is the 1-10wt% of graphite electrode powder primary particle quality.
6. the preparation method of graphite cathode material for power lithium-ion battery according to claim 1, it is characterized in that, described auxiliary agent is one or more in carbon tetrachloride, oxolane, washing oil, and addition is the 5-30wt% of graphite electrode powder primary particle quality.
7. the preparation method of graphite cathode material for power lithium-ion battery according to claim 1, is characterized in that, described secondary granulation adopts reactor to add thermal agitation, resistance furnace to add one or more in mediating of thermal agitation, kneader.
8. the preparation method of graphite cathode material for power lithium-ion battery according to claim 7, it is characterized in that, described secondary granulation adopt reactor to add thermal agitation, resistance furnace to add the temperature that thermal agitation, kneader mediate be 200-1400 DEG C, the time is 0.5-48h.
9. the preparation method of graphite cathode material for power lithium-ion battery according to claim 1, is characterized in that, described graphitization processing temperature is 2600-3400 DEG C, and graphitization time is 10-48h.
10. one kind by preparation method makes as described in any one in claim 1-9 power lithium-ion battery graphite cathode material.
11. power lithium-ion battery graphite cathode materials according to claim 10, is characterized in that, described graphite cathode material is to be bonded by the particle of multiple laminated structures, and its specific area is less than or equal to 10m2/ g, it is that 12-25 micron, D90 are less than or equal to 50 microns that its size distribution D10 is more than or equal to 4 microns, D50, carbon mass content is more than or equal to 99.90wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110203923A (en) * | 2019-04-24 | 2019-09-06 | 漳州巨铭石墨材料有限公司 | A kind of lithium ion battery negative material and preparation method thereof |
| CN112670466A (en) * | 2020-04-30 | 2021-04-16 | 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 |
| CN114132923A (en) * | 2021-11-26 | 2022-03-04 | 中钢热能金灿新能源科技(湖州)有限公司 | Preparation method of fast-charging graphite cathode material, product and application thereof |
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