CN102347481A - Superfine spherical graphite as well as preparation method and application thereof - Google Patents
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Abstract
The invention relates to superfine spherical graphite which is applied to a negative electrode material of a lithium ion battery and a preparation method thereof. The average particle size of the spherical graphite provided by the invention is 5-8 microns, the length/diameter ratio is 1-2, the specific surface area is 9-11 m<2>/g, the tap density is 0.6-0.92 g/cm<3>, and the crystal interlamellar spacing d002 is 0.335-0.338 nm. The preparation method comprises the following steps: crushing graphite micro-powder until the average particle size is 1-4 microns; subjecting the graphite particles to spheroidization so that the average particle size of the graphite particles is 5-8 microns; mixing the obtained graphite particles with mixed acid according to a proportion, reacting for 12 hours in an environment with a temperature of 100-150 DEG C, washing the material until the material is neutral; and finally, drying the obtained graphite particles to obtain the product. The spherical graphite provided by the invention is smaller in average particle size and good in degree of sphericity, so that the prepared negative electrode material of a lithium power battery is of rapid charge-discharge property and excellent cycle performance; and the preparation method provided by the invention is simple in preparation process, low in cost, and high in output and yield.
Description
Technical field
The present invention relates to a kind of artificial spherical graphite and preparation method thereof, particularly relate to a kind of superfine spherical graphite that is used for lithium ion battery negative material and its production and application.
Background technology
21st century oil crisis and the continuous increase of population, the contradiction of shortage of resources is become increasingly conspicuous, particularly in today that people more and more pay attention to environmental protection, green power supply has obtained develop rapidly.Lithium-ion-power cell has been exactly the secondary cell of new generation after lead acid accumulator since the eighties of last century the nineties; And because of it has the operating voltage height, the high current charge-discharge ability is strong; Energy density is big, have extended cycle life, advantages such as self discharge is little, memory-less effect; Become present electric bicycle, the most potential chemical power source of electric automobile, and be penetrated into sophisticated technology fields such as Aero-Space, military affairs.Be accompanied by the demand that it grows with each passing day, lithium-ion-power cell is just becoming the emphasis and the focus of new century scientific and technical research and exploitation.
The negative material of commercialization lithium-ion-power cell is material with carbon element at present; Wherein graphite type material comprises native graphite and the Delanium through the preparation of graphitizations such as coke, pitch and various organic substances etc., is used widely because of it has high charge/discharge capacity, favorable charge-discharge platform, wide material sources, cost is low.In the market the spherical graphite that generally uses be average grain diameter at 14～25 microns, wherein 17.5 ± 0.5 microns use is maximum, because of it has above advantage, extensively is used on mobile phone, notebook computer or other portable type electronic product.But because of its particle diameter is big slightly, lithium ion diffusion therein possibly need the long period, has influenced discharge performance thus, particularly at big electric current or low temperature performance.And electrokinetic cell requires transient large current discharge because of being used in the electric motor car; The faster the better promptly to discharge and recharge speed, therefore just requires the spherical graphite particle more little, and sphericity is good more; Then many more with the quantity of deviating from the graphite nodule layer in the lithium ion embedding graphite nodule layer, speed is fast more; Average grain diameter is that 5～8 microns spherical graphite is compared with 17 microns spherical graphites that generally use in market and had littler bulb diameter; It is near that lithium ion gets into graphite microballoon layer inner distance; Therefore can embed more easily and deviate from; The big graphite microballoon of particle is then because of diameter is big, distance; Embed and deviate from relative prolongation of time, the time that big electric current produces when making battery charging and discharging relatively lags behind.And be difficult to because of its particle diameter is too for a short time grind less than 5 microns more fine spherical grains graphite, can be difficult more with the mechanical grinding method preparation, and yield is extremely low, can not adapt to the needs in market.Identical volume, more little then its amounts of particles of equal in quality graphite granule can be many more, the lithium ion of same quantity is at more graphite granule interlayer, participate in embedding and deviate from the quantity of graphite granule interlayer can be more, speed can be fast more; The lithium ion of greater number embeds simultaneously and just deviates from and could produce instantaneous large-current like this, and it discharges and recharges speed also can be faster! The lithium cell cathode material that 5～8 microns superfine spherical graphite of the present invention are made just has such characteristic! Can well address the above problem, satisfy the electrokinetic cell performance demands!
Summary of the invention
The technical problem that the present invention will solve provides the cathode material of composite carbon in use for lithium ion battery that a kind of superfine artificial spherical graphite and preparation method thereof and superfine spherical graphite thus obtain.
For reaching above-mentioned purpose, a kind of superfine spherical graphite of the present invention, particle average grain diameter 5～8 μ m, draw ratio is 1～2, specific area 9～11m
2/ g, tap density 0.6～0.92g/cm
3, crystal layer spacing d
002Be 0.335～0.338nm.
Superfine spherical graphite of the present invention is shaped as sphere, and draw ratio (being length and its diameter ratio of graphite granule) is 1, also can be elliposoidal, potato shape or other types sphere, and draw ratio is 1-2.
The preparation method of the above-mentioned spherical graphite of the present invention may further comprise the steps:
(1) be 5～15 microns with average grain diameter, the graphite microparticles of carbon content >=90.0%, being crushed to average grain diameter is the 1-4 micron;
(2) graphite granule that step (1) is obtained carries out spheroidising, carries out fine gradedly through Ultrafine Classifier again, and the average grain diameter that makes graphite granule is 5～8 microns;
(3) graphite granule and the mixed acid that step (2) is obtained is even by weight 1: 1 mixed; It in temperature reaction 12 hours under 100-150 ℃ the environment; Its objective is impurity such as the potassium oxide removed in the graphite, sodium oxide molybdena, magnesia; Calcium oxide; Iron oxide, aluminium oxide, impurity such as disilicon trioxide and calcium carbonate; Again material is repeatedly washed, to neutral;
(4) graphite granule that step (3) is obtained carries out drying with drying plant, promptly gets.
Graphite microparticles is pulverized with the high pressure draught pulverizer among the preparation method of spherical graphite of the present invention, said step (1), and pressure is 0.7MPa, and said high pressure draught pulverizer is a fluidized bed type steam flow pulverizer, and this pulverizer is this area common equipment.
The preparation method of spherical graphite of the present invention, said mode of washing can adopt centrifuge washing, and the washing facility that this areas such as press filtration washing or sedimentation washing are commonly used preferably carries out the sedimentation washing with the decanter type washing tank.Its method is that the mixture of graphite granule and mix acid liquor is put into settling tank from retort; Sedimentation through one to four hour; Each valve of opening is from top to bottom emitted the top supernatant liquid successively; Draining again after adding depositing in water once more and falling; After ph value of mixture is neutrality, upper clear supernate is emitted, only stay the mixture of pulpous state graphite and water.
The preparation method of spherical graphite of the present invention, said drying plant can adopt this areas such as spray drying, expansion drying or boiling drying equipment drying equipment commonly used, dries to the graphite granule moisture less than 0.2%.
The preparation method of spherical graphite of the present invention; Wherein preferred said mixed acid contains following substances in parts by weight; Hydrofluoric acid 1-3 part, hydrochloric acid 3-6 part and nitric acid 1-2 part; Be hydrofluoric acid; Hydrochloric acid, nitric acid, the part by weight of its mixing are (1～3): (3～6): (1～2); Corrosivity and dissolubility that its effect mainly is a mixed acid are stronger, and be under equal conditions fast than the speed of the reaction of the impurity in single acid and the graphite.Make more thorough sooner that chemical reaction can carry out, generate water-soluble material and remove through mode of washing such as centrifugal, sedimentations, its graphite purity is improved.
The application of the above-mentioned spherical graphite of the present invention is applied to prepare the lithium dynamical battery negative material.
A kind of lithium dynamical battery of the present invention, its negative material contains above-mentioned spherical graphite, and its reversible specific capacity is 350mAh/g～372mAh/g, and the coulombic efficiency that circulates first is 85%～95%, and 500 capability retentions that circulate are 80%～92%.
Spherical graphite of the present invention compared with prior art has littler average grain diameter; Good sphericity; The lithium dynamical battery negative material reversible specific capacity that is prepared by graphite of the present invention is greater than 350mAh/g; Coulombic efficiency circulate first greater than 85%; Circulate 500 capability retentions greater than 80%; Have fast charging and discharging performance and good cycle performance; The preparation method of spherical graphite of the present invention; With graphite microparticles is the 1-4 micron through ultra-fine grinding to average grain diameter earlier; Carry out spheroidising again; Obtain the graphite granule that average grain diameter is the 5-8 micron; Compared with prior art; The spherical graphite that obtains has littler average grain diameter, and it is simple to have the preparation process; Cost is low; The characteristics that output and yield are high.
Below in conjunction with accompanying drawing superfine spherical graphite of the present invention and preparation method thereof is described further.
Description of drawings
Fig. 1 a-1b is the raw material electromicroscopic photograph of superfine spherical graphite of the present invention;
Fig. 2 a-2b is the electromicroscopic photograph of the finished product of superfine spherical graphite of the present invention.
Embodiment
Below in conjunction with accompanying drawing, embodiment and test data, do more detailed explanation with other technical characterictic and advantage to the present invention is above-mentioned.
Embodiment 1:
With average grain diameter 10 μ m; The native graphite micro mist 100g (shown in Fig. 1 a-1b) of phosphorus content 95%; Add in the high pressure steam flow pulverizer and pulverize; Pressure is 0.7MPa; Adjust material granularity to 1～4 micron; Again this ultra-fine material is added in the ACM-30 type balling machine and carry out nodularization; Carry out fine graded through Ultrafine Classifier again; The average grain diameter that makes graphite granule is 5～8 microns; Drop in the retort; The hydrofluoric acid that adds 18g; The hydrochloric acid of 54g; The nitric acid of 28g is reaction 12 hours under 150 ℃ the environmental condition in temperature, and material is put into the sedimentation washing tank; The washing depickling obtains 5～8 microns ultra-fine spherical graphites to neutral with oven dry in this ultra-fine material slurry entering spray dryer.Find out (shown in Fig. 2 a-2b) by this stereoscan photograph; Its most of particle is potato shape, sphere, elliposoidal or other types sphere; Detecting its carbon amount by the GB/T3521-95 standard method is 99.965%, measures its D50=6.11um D10=3.81um D90=10.16um with the MS2000 laser particle analyzer; Adopting BET method test specific area is 10.16m
2/ g, the tap density that adopts QuantachromeAutoTap tap density appearance to record powder is 0.85g/cm
3, adopt Ka Er. and taking not, coulometric titration appearance test moisture content adopts the wide angle of powder X-ray RD diffraction approach to measure its d less than 0.2%
002Be 0.3358nm.
The preparation of lithium ion battery:
Adopt following method prepare 053048A (the 05th, thickness; The 30th, width; The 48th, height; A is an aluminum hull) rectangular lithium ion battery; Negative electrode active material adopts the superfine spherical graphite of above-mentioned steps preparation to coat negative material, with binding agent butadiene-styrene rubber breast SBR, suspending agent carboxyl methyl cellulose, conductive black Super-P according to 95: 3: 2: 1 weight ratio is mixed, and adds an amount of pure water and sizes mixing as dispersant; Evenly be coated on the Copper Foil, process negative plate through vacuumize, roll-in; Use LiCoO
2Be positive electrode active materials; Mix according to 95: 2: 2 weight ratio with binding agent polyvinylidene fluoride (PVDF), conductive agent Super-P, add an amount of N-methyl pyrrolidone (NMP), be coated on the aluminium foil as dispersant furnishing slurry; And, be prepared into positive plate through vacuumize, roll-in; Use 1mol/LLiPF
6The solution of three component mixed solvent EC (ethylene carbonate): DMC (dimethyl carbonate): EMC (methyl ethyl carbonate)=1: 1: 1 (v/v) be electrolyte, microporous polypropylene membrane is a barrier film, is assembled into battery.Test result is seen table 1.
The constant current charge-discharge data of table 1MSG6 (coating spherical graphite) sample
Embodiment 2:
With crystalline flake graphite-192; Its granularity is 100 orders; The native graphite 100g of phosphorus content 92%; Add in the high pressure steam flow pulverizer and pulverize; Adjust material granularity to 1～4 micron; Again this ultra-fine material is sent in the AMC-50 type balling machine and carried out nodularization; Carry out fine graded through Ultrafine Classifier again; The average grain diameter that makes graphite granule is 5～8 microns; Drop in the retort; The hydrofluoric acid that adds 30g, the hydrochloric acid of adding 60g, the nitric acid of adding 10g; It in temperature reaction 12 hours under 150 ℃ the environmental condition; Material is put into the sedimentation washing tank, and the washing depickling obtains ultra-fine 5～8 microns spherical graphites to neutral with drying in this ultra-fine material slurry entering spray dryer.Find out by this stereoscan photograph; Its most of particle is potato shape, sphere, elliposoidal or other types sphere; Detecting its carbon amount by the GB/T3521-95 standard method is 99.960%, measures its D50=7.59um D10=4.17umD90=10.30um with the MS2000 laser particle analyzer; Adopting BET method test specific area is 9.98m
2/ g, the tap density that adopts Quantachrome Auto Tap tap density appearance to record powder is 0.91g/cm
3, adopt Ka Er. and taking not, coulometric titration appearance test moisture content adopts the wide angle of powder X-ray RD diffraction approach to measure its d less than 0.2%
002Be 0.3360nm.
The preparation of lithium ion battery:
Adopt following method to prepare 053048A (the 05th, thickness 30 is that width 48 is that height A is an aluminum hull) rectangular lithium ion battery; Negative electrode active material adopts the superfine spherical graphite of above-mentioned steps preparation to coat negative material; With binding agent butadiene-styrene rubber breast SBR, suspending agent carboxyl methyl cellulose, conductive black Super-P according to 95: 3: 2: 1 weight ratio is mixed; Adding an amount of pure water sizes mixing as dispersant; Evenly be coated on the Copper Foil, process negative plate through vacuumize, roll-in; Use LiCoO
2Be positive electrode active materials; Mix according to 95: 2: 2 weight ratio with binding agent polyvinylidene fluoride (PVDF), conductive agent Super-P, add an amount of N-methyl pyrrolidone (NMP), be coated on the aluminium foil as dispersant furnishing slurry; And, be prepared into positive plate through vacuumize, roll-in; Use 1mol/LLiPF
6The solution of three component mixed solvent EC (ethylene carbonate): DMC (dimethyl carbonate): EMC (methyl ethyl carbonate)=1: 1: 1 (v/v) be electrolyte, microporous polypropylene membrane is a barrier film, is assembled into battery.Test result is seen table 2.
The constant current charge-discharge data of table 2MSG7.5 sample
Embodiment 3:
With average grain diameter 15 μ m; The native graphite micro mist 100g of phosphorus content 90%; Add in the high pressure steam flow pulverizer and pulverize; Adjust material granularity to 1～4 micron; Again this ultra-fine material is added in the AMC-20 type steam flow vortex balling machine and carry out nodularization; The average grain diameter that makes graphite granule is 5～8 microns; Drop in the retort; The hydrofluoric acid that adds 25g; The hydrochloric acid that adds 50g; The nitric acid that adds 25g is reaction 12 hours under 120 ℃ the environmental condition in temperature, and material is dropped into the sedimentation washing tank; The washing depickling is to neutral, this ultra-fine material slurry sent into drying obtains ultra-fine 5～8 microns spherical graphites in the spray dryer.Find out that by this stereoscan photograph its most of particle is potato shape, sphere, elliposoidal or other types sphere, measure its D50=5.86um D10=4.09umD90=9.88um with the MS2000 laser particle analyzer; Adopting BET method test specific area is 10.56m
2/ g, the tap density that adopts Quantachrome Auto Tap tap density appearance to record powder is 0.88g/cm
3, adopt Ka Er. and taking not, coulometric titration appearance test moisture content adopts the wide angle of powder X-ray RD diffraction approach to measure its d less than 0.2%
002Be 0.3357nm.
The preparation of lithium ion battery:
Adopt following method to prepare 053048A (the 05th, thickness 30 is that width 48 is that height A is an aluminum hull) rectangular lithium ion battery; Negative electrode active material adopts the superfine spherical graphite of above-mentioned steps preparation to coat negative material; With binding agent butadiene-styrene rubber breast SBR, suspending agent carboxyl methyl cellulose, conductive black Super-P according to 95: 3: 2: 1 weight ratio is mixed; Adding an amount of pure water sizes mixing as dispersant; Evenly be coated on the Copper Foil, process negative plate through vacuumize, roll-in; Use LiCoO
2Be positive electrode active materials; Mix according to 95: 2: 2 weight ratio with binding agent polyvinylidene fluoride (PVDF), conductive agent Super-P, add an amount of N-methyl pyrrolidone (NMP), be coated on the aluminium foil as dispersant furnishing slurry; And, be prepared into positive plate through vacuumize, roll-in; Use 1mol/LLiPF
6The solution of three component mixed solvent EC (ethylene carbonate): DMC (dimethyl carbonate): EMC (methyl ethyl carbonate)=1: 1: 1 (v/v) be electrolyte, microporous polypropylene membrane is a barrier film, is assembled into battery.Test result is seen table 3.
The constant current charge-discharge data of table 3MSG58 sample
Comparative Examples 1
The Delanium micro mist is crushed to average grain diameter 23 μ m, obtains the graphite granule of laminated structure, draw ratio is 5-6, specific area 8m
2/ g, crystal layer spacing d
002Be 0.3357nm.
Adopt to prepare battery with embodiment 1 identical method, carry out electrochemical property test, the result sees table 4.
The constant current charge-discharge data of the sample that table 4 Comparative Examples 1 obtains
Found out that by data in the above table with the lithium ion battery of comparative sample preparation, the coulombic efficiency that circulates first is 81.83%, discharge capacity has only 338.6mAhg first
-1, far below the lithium ion battery for preparing with superfine spherical graphite of the present invention among the embodiment 1-3.
Prove that through lot of test as particle average grain diameter 5～8 μ m of spherical graphite, draw ratio is 1～2, specific area 9～11m
2/ g, tap density 0.6～0.92g/cm
3, crystal layer spacing d
002When being 0.335～0.338nm; Lithium dynamical battery with this graphite granule preparation has higher discharge capacity first with the superfine spherical graphite cathode material; Cycle performance and multiplying power discharging property are excellent; Reversible specific capacity is higher first to compare it with other Delaniums; The fast charging and discharging ability is stronger; Its cycle efficieny is higher, and cycle life is longer.Graphite granule of the present invention compared with prior art has littler average grain diameter (5～8 μ m); Good sphericity (contrast can be known like Fig. 1 a-1b and Fig. 2 a-2b ESEM picture) is particularly useful for making the negative material that lithium-ion-power cell with fast charging and discharging performance and good cycle performance is used.
The present invention also provides a kind of more reasonably production method of superfine spherical graphite; Adopt high pressure steam flow pulverizer earlier graphite microparticles to be carried out ultra-fineization and be crushed to 1～4 micron; Re-use balling machine and steam flow vortex Ultrafine Classifier carries out nodularization and surperficial shaping to graphite granule; Pass through the shaping classification again, obtain spherical graphite of the present invention at last.And existing spherical graphite production method adopts crystalline flake graphite like-190～-199 (negative 100 order carbon amounts are 90%～99%); Directly get into steam flow vortex pulverizer earlier through broken; Pass through the shaping classification again; The graphite granule that obtains at last is inhomogeneous; Granularity is bigger; All have from the 10-50 micron, the graphite granule granularity is big, and sphericity is low.The raw material that the inventive method is used can use byproduct-native graphite micro mist that cheap general spherical shape graphite produces and Delanium micro mist as raw material; Its granularity of the spherical graphite of producing is little; Good sphericity; There are above data can find out that its chemical property is more excellent; It is faster that it discharges and recharges speed; Unit volume endoparticle quantity is many; Has the high current charge-discharge ability; The by-product utilization of general spherical shape graphite is produced superfine spherical graphite improved the graphite utilization rate; Saved the graphite resource of non-renewable product; Spherical graphite output and yield have been improved on the whole; Reduced cost; For lithium dynamical battery provides a kind of battery material of Cheap highly effective, will promote the popularization and application of lithium dynamical battery and electric motor car after the batch process.
Prove through lot of test, use the superfine spherical graphite granule of the inventive method preparation, uniform granularity, average grain diameter is little, is 5～8 μ m, and the nodularization degree is good, and draw ratio is 1-2, and specific area is bigger, is 9-11m
2/ g, tap density is 0.6～0.92g/cm
3, crystal layer spacing d
002Be 0.335～0.338nm, use the cathode material of composite carbon in use for lithium ion battery that superfine spherical graphite of the present invention makes, have less irreversible capacity loss first, fast charging and discharging performance and cycle performance excellent characteristics.With the lithium dynamical battery that this negative material is processed, reversible specific capacity is 350mAh/g～372mAh/g, and the coulombic efficiency that circulates first is 85%～95%, and 500 capability retentions that circulate are 80%～92%.
The present invention is in other execution mode, and used mixed acid can also be the above mixed acid of other inorganic acids both or both such as any hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, the mixed acid that is not limited to use in the foregoing description.
Above-described embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that those of ordinary skills make technical scheme of the present invention all should fall in the definite protection range of claims of the present invention.
Claims (9)
1. superfine spherical graphite, it is characterized in that: particle average grain diameter 5～8 μ m, draw ratio is 1～2, specific area 9～11m
2/ g, tap density 0.6～0.92g/cm
3, crystal layer spacing d
002Be 0.335～0.338nm.
2. spherical graphite according to claim 1 is characterized in that: be shaped as sphere, potato shape or elliposoidal.
3. the preparation method of each described spherical graphite of claim 1-2 is characterized in that, may further comprise the steps:
(1) be 5～15 microns with average grain diameter, the graphite microparticles of carbon content >=90.0%, being crushed to average grain diameter is the 1-4 micron;
(2) graphite granule that step (1) is obtained carries out spheroidising, and the average grain diameter that makes graphite granule is 5～8 microns;
(3) graphite granule and the mixed acid that step (2) is obtained is even by weight 1: 1 mixed, is reaction 12 hours under 100-150 ℃ the environment in temperature, material is repeatedly washed to neutrality again;
(4) graphite granule that step (3) is obtained carries out drying with drying plant, promptly gets.
4. method according to claim 3 is characterized in that: graphite microparticles is pulverized with the high pressure draught pulverizer in the said step (1), and pressure is 0.7MPa, and said high pressure draught pulverizer is a fluidized bed type steam flow pulverizer.
5. method according to claim 3 is characterized in that: the decanter type washing tank is adopted in said washing.
6. method according to claim 3 is characterized in that: said drying plant adopts spray drying, expansion drying or boiling drying equipment.
7. method according to claim 3 is characterized in that: said mixed acid contains following substances in parts by weight, hydrofluoric acid 1-3 part, hydrochloric acid 3-6 part and nitric acid 1-2 part.
8. the application of each described spherical graphite of claim 1-2 is characterized in that: be applied to prepare the lithium dynamical battery negative material.
9. lithium dynamical battery; It is characterized in that: its negative material contains each described spherical graphite of claim 1-2; Its reversible specific capacity is 350mAh/g～372mAh/g, and the coulombic efficiency that circulates first is 85%～95%, and 500 capability retentions that circulate are 80%～92%.
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Cited By (8)
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| CN108063234A (en) * | 2017-12-22 | 2018-05-22 | 林荣铨 | A kind of carbon nanotubes/application of micro- swollen graphite composite material as lithium ion battery negative material |
| CN108565460A (en) * | 2017-12-23 | 2018-09-21 | 林荣铨 | A kind of application of the spherical shape micro crystal graphite as lithium ion battery negative material |
| CN108933276A (en) * | 2017-05-29 | 2018-12-04 | Sk新技术株式会社 | Lithium secondary battery |
| CN112408382A (en) * | 2020-11-19 | 2021-02-26 | 萝北瑞喆烯碳新材料有限公司 | Preparation method of high-sphericity graphite powder |
| CN112689919A (en) * | 2020-04-24 | 2021-04-20 | 宁德新能源科技有限公司 | Negative electrode active material, and electrochemical device and electronic device using same |
| CN113526501A (en) * | 2021-07-12 | 2021-10-22 | 中国矿业大学 | Spherical graphite material and preparation method and application thereof |
| JP7119131B2 (en) | 2018-11-29 | 2022-08-16 | 貝特瑞新材料集団股▲ふん▼有限公司 | Natural graphite, modified natural graphite material prepared from natural graphite, preparation method and use thereof |
| CN116281996A (en) * | 2023-03-27 | 2023-06-23 | 青岛洛唯新材料有限公司 | Preparation method of high-interlayer-spacing graphite, negative electrode and lithium battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1558458A (en) * | 2004-01-21 | 2004-12-29 | 敏 岳 | Graphite powder for negative electrode of lithium ion secondary cell and manufacturing method thereof |
| CN1635650A (en) * | 2003-12-26 | 2005-07-06 | 比亚迪股份有限公司 | A negative electrode graphite material for lithium-ion secondary battery and preparation method thereof |
| CN101323447A (en) * | 2008-07-21 | 2008-12-17 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite powder of lithium ionic cell cathode and preparation thereof |
| CN101905883A (en) * | 2010-08-11 | 2010-12-08 | 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 | Production method of spherical graphite |
| CN101939865A (en) * | 2008-02-04 | 2011-01-05 | 三菱化学株式会社 | Carbonaceous material having multilayer structure, process for producing the carbonaceous material, and nonaqueous rechargeable battery using the carbonaceous material |
-
2011
- 2011-10-14 CN CN2011103114176A patent/CN102347481A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1635650A (en) * | 2003-12-26 | 2005-07-06 | 比亚迪股份有限公司 | A negative electrode graphite material for lithium-ion secondary battery and preparation method thereof |
| CN1558458A (en) * | 2004-01-21 | 2004-12-29 | 敏 岳 | Graphite powder for negative electrode of lithium ion secondary cell and manufacturing method thereof |
| CN101939865A (en) * | 2008-02-04 | 2011-01-05 | 三菱化学株式会社 | Carbonaceous material having multilayer structure, process for producing the carbonaceous material, and nonaqueous rechargeable battery using the carbonaceous material |
| CN101323447A (en) * | 2008-07-21 | 2008-12-17 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite powder of lithium ionic cell cathode and preparation thereof |
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