CN102290572B - Cathode active substance and cathode used for lithiumion secondary battery - Google Patents
Cathode active substance and cathode used for lithiumion secondary battery Download PDFInfo
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Abstract
The invention discloses a cathode active substance and cathode used for a lithiumion secondary battery. In the cathode active substance used for the lithiumion secondary battery, a mixture of spherical or torispherical graphite, massive artificial graphite the particle length-width ratio of which is 1.0-3.0 and needle-like artificial graphite the particle length-width ratio of which is 1.0-4.0 is taken as a substrate; non-graphite carbon materials are cladded outside the mixed substrate; the cladding amount is 1-20% of the mass of the mixed substrate; the non-graphite carbon material is asphalt or resin; the gram specific capacity of the cathode active substance is 350-370mAh/g, the particle size is 4.0-45mu m, the specific surface area is 1.0-4.0m<2>/g, the compacted density of the powder body is 1.65-2.10g/cm<3>, and the layer space (d002) is 0.3354-0.3370nm. The cathode active substance provided by the invention has the beneficial effects of improving the conductivity performance of materials, ensuring the excellent multiplying power and circular stability of materials, and satisfying different high-end requirements, especially the requirements of electric automobiles (EV), hybrid electric vehicles (HEV) and batteries in the energy storage field.
Description
Technical field
The present invention relates to a kind of negative electrode active material and negative pole, relate in particular to a kind of lithium ion secondary battery cathode active material and negative pole.
Background technology
Lithium rechargeable battery, as the filled secondary cell of high power capacity, high voltage, small-sized and lightweight, is widely used in the mobile electronic devices such as mobile phone, notebook computer, panel computer, video camera.Due to the requirement of the further miniaturization of mobile electronic device, high cruising ability, need lithium rechargeable battery more small-sized light materialization, higher energy density and excellent cycle performance.On the other hand, from environmental problem, consider, exploitation electric automobile (EV), mixed power electric car (HEV) substitute original fuel-engined vehicle, lithium-ion energy storage battery substitutes original lead-acid battery and has great importance, and the power supply that the lithium rechargeable battery that energy density is high, voltage is high is used as follow-on EV, HEV and energy storage field receives much attention, so just the electrode for lithium ion secondary battery material is had higher requirement, require constantly improvement and bring new ideas of electrode material, wherein the improvement and bring new ideas of negative material is one of first-selection.
At present, silicon/carbon/graphite in lithium ion batteries class negative material is mainly main with three substantially: modified natural graphite, Delanium and carbonaceous mesophase spherules (being also a kind of Delanium).The modified natural graphite main advantage is the characteristics such as the gram specific capacity is high, compacted density is high, good processability, but the compatibility of itself and electrolyte etc. is poor, cycle life is bad, and especially under the high compacted density condition, the cycle performance decay is very fast, and high-temperature behavior is relatively poor; Simple Delanium has and has extended cycle life, the advantage such as high temperature performance is good, but that it often has compacted density is not high, the shortcomings such as poor processability; The characteristics of carbonaceous mesophase spherules maximum are the cycle performance excellence, good stability, but the gram specific capacity is relatively low, and energy density is too low.For adapting to the development of lithium ion battery negative material, multiple natural and artificial composite graphite has appearred in the market, the advantage of its energy integrated natural graphite and Delanium, reach compromise effect, but generally the gram specific capacity is below 350mAh/g, compacted density is below 1.60, and cycle life is difficult to over 400 times.
Patent documentation 2 " composite graphite negative electrode material of lithium rechargeable battery and preparation method thereof " (patent application publication number is CN 1702892 A) discloses a kind of modified natural graphite and Delanium is undertaken simple the mixing making composite graphite negative electrode material by certain compositely proportional, the advantage of integrated natural graphite and Delanium, obtain performance negative material relatively preferably to a certain extent.But because native graphite and Delanium are simple mechanical mixture, can not form organically compound, the cyclical stability of material is difficult to reach more than 500 times, because the simple stability of mixing of material itself is relatively poor, be difficult to meet the requirement that electric bicycle (E-bike), electric automobile (EV), mixed power electric car (HEV) and energy storage field battery etc. store for a long time and recycle simultaneously.
Based on above context analyzer, in the urgent need to developing a kind of gram specific capacity between 350～370mAh/g, the pole piece compacted density is at 1.50 ~ 1.75 g/cm
3between, cycle life can meet high-end demand at the negative electrode active material that possesses excellent high rate performance, cryogenic property more than 500 times simultaneously, especially the demand of electric automobile (EV), mixed power electric car (HEV) and energy storage field battery.
Summary of the invention
Lithium ion secondary battery cathode active material and negative pole have been the object of the present invention is to provide, solve existing lithium ion secondary battery cathode active material gram volume not high, compacted density is hanged down and the problems of the prior art such as cycle life is long, high gram specific capacity for a kind of lithium rechargeable battery is provided, high compacted density and cycle performance excellence possess excellent high rate performance simultaneously, cryogenic property negative electrode active material and preparation method thereof, and the negative pole that uses this negative electrode active material, reduce the active material for negative pole of Li-ion secondary battery cost when improving the lithium rechargeable battery combination property.
The present invention is achieved like this, a kind of lithium ion secondary battery cathode active material, it is characterized in that described lithium ion secondary battery cathode active material is that to take the mixture of the needle-like Delanium that engineered stone China ink that spherical or torispherical graphite, particle length-width ratio is 1.0 ~ 3.0 and particle length-width ratio be 1.0 ~ 4.0 be matrix, mixed matrix is coated with the non-graphite material with carbon element, and covering amount is 1～20% of mixed matrix quality; Described non-graphite material with carbon element is pitch or resin, and its gram specific capacity of negative electrode active material is 350 ~ 370mAh/g, and granularity is 4.0 ~ 45 μ m, and specific area is 1.0 ~ 4.0m
2/ g, powder body compacted density is 1.65 ~ 2.10g/cm
3, interlamellar spacing (d002) is 0.3354 ~ 0.3370nm.
The mass ratio of the spherical graphite in described negative electrode active material in substrate mixture and Delanium total amount is 5: 95 ~ 95: 5, and wherein preferred proportion is 10: 90 ~ 90: 10, and more preferably ratio is 20: 80 ~ 80: 20; In substrate mixture the ratio of engineered stone China ink and needle-like Delanium be any than.
Described spherical or torispherical graphite behaviour pelletizing shape graphite, natural spherical plumbago or both arbitrarily than mixture.
Described bulk, needle-like Delanium are coal measures bulk, needle-like Delanium or bulk, petroleum needle-like Delanium.
The preparation method of described lithium ion secondary battery cathode active material is characterized in that comprising the following steps:
One, selecting the mass ratio of spherical graphite, Delanium total amount is 5: 95 ~ 95: 5, wherein the ratio of engineered stone China ink and needle-like Delanium is 5: 95 ~ 95: 5, with 1～20% pitch or the resin that are the mixed matrix quality, the total weight of spherical graphite, engineered stone China ink, needle-like Delanium and pitch or resin and solvent are placed in to mixer with the ratio of 1 ~ 10 liter/Kg, mix 30 ~ 240min under the rotating speed of 500 ~ 2000r/min, obtain mixing emulsion;
Two, will mix emulsion in the fusion machine, at the rotating speed of 300 ~ 3000r/min, under the condition that fusion temperature is 20 ~ 100 ℃, merge 30 ~ 240min, obtain merging presoma;
Three, under inert gas shielding, will merge presoma and be placed in high temperature furnace and be warming up to 400 ~ 800 ℃ of charings with 1 ~ 20 ℃/min and process 5 ~ 24h, then the cooling rate with 1 ~ 20 ℃/min is cooled to room temperature; Under 2800～3000 ℃, carry out again obtaining the lithium ion secondary battery cathode active material after graphitization heat treatment.
Described solvent is a kind of or several mixed solvent in water, ethanol, isopropyl alcohol, glycerol, acetone, toluene or dimethylbenzene.
Described inert gas is nitrogen, argon gas, helium, neon or the above-mentioned mist of any ratio.
A kind of preparation method of lithium ion secondary battery cathode, be coated on the mixed uniformly material of the negative electrode active material of above-mentioned preparation, binding agent and conductive agent on metal collector, and dry and compacting forms.
Described lithium ion secondary battery cathode, this negative plate can obtain higher compacted density, reaches 1.50 ~ 1.75 g/cm
3, the lithium rechargeable battery of being made with this negative pole, the capacity after 500 times that circulates still maintains more than 80%, especially at 1.60 ~ 1.75 g/cm
3high compacted density under, the capacity after 500 times that circulates still maintains more than 80%.
Technique effect of the present invention is: obtain a kind of gram specific capacity between 350～370mAh/g, the pole piece compacted density is at 1.50 ~ 1.75 g/cm
3between, cycle life can possess the negative electrode active material of good low temperature performance and high rate performance simultaneously more than 500 times; Adopt spherical graphite, engineered stone China ink, needle-like Delanium and pitch or the polynary raw material of resin as carbon source, can make up the single defect for preparing material as carbon source, the advantage of comprehensive each material, obtain exceeding the negative electrode active material with excellent properties of single carbon source material, can reduce the cost of product simultaneously; Use the mixture of spherical graphite particle, blocky graphite particle and needle-like graphite granule, can reduce the gap between particle, reduce contact resistance, shorten the delivering path of electrolyte between particle simultaneously; The building the carbon layer on surface structure of substrate mixture integral body at charing and graphitizing process medium pitch or resin, improved the electric conductivity of material, thereby guarantee high rate performance and the cyclical stability of material excellence, can meet the demand of high-end different demands, especially electric automobile (EV), mixed power electric car (HEV) and energy storage field battery simultaneously.
The accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 1.
Fig. 2 is first three week gram specific capacity test curve of the embodiment of the present invention 1.
Fig. 3 is that the negative plate of the embodiment of the present invention 1 is at compacted density 1.65 g/cm
3situation under the cycle performance test curve of lithium rechargeable battery.
Embodiment
For further illustrating content of the present invention and characteristics, below in conjunction with embodiment and accompanying drawing, be described in detail.Negative electrode active material of the present invention, the mixture of the needle-like Delanium that engineered stone China ink that spherical or torispherical graphite, particle length-width ratio is 1.0 ~ 3.0 and particle length-width ratio be 1.0 ~ 4.0 of take is matrix, mixed matrix is coated with the non-graphite material with carbon element, and covering amount is 1～20% of mixed matrix quality.
Spherical or the torispherical graphite behaviour pelletizing shape graphite used, natural spherical plumbago or both arbitrarily than mixture.
The needle-like Delanium that spherical or torispherical graphite used, the engineered stone that the particle length-width ratio is 1.0 ~ 3.0 China ink and particle length-width ratio are 1.0 ~ 4.0, their average grain diameter is 3.0 ~ 43 μ m.
The non-graphite material with carbon element coated is pitch or resin.
The preparation method of lithium ion secondary battery cathode active material of the present invention comprises the following steps:
One, selecting the mass ratio of spherical graphite, Delanium total amount is 5: 95 ~ 95: 5(wherein engineered stone ratio black and the needle-like Delanium is 5: 95 ~ 95: 5), with 1～20% pitch or the resin that are the mixed matrix quality, the total weight of spherical graphite, engineered stone China ink, needle-like Delanium and pitch or resin and solvent are placed in to mixer with the ratio of 1 ~ 10 liter/Kg, mix 30 ~ 240min under the rotating speed of 500 ~ 2000r/min, obtain mixing emulsion;
Two, will mix emulsion in the fusion machine, at the rotating speed of 300 ~ 3000r/min, under the condition that fusion temperature is 20 ~ 100 ℃, merge 30 ~ 240min, obtain merging presoma;
Solvent is a kind of in water, ethanol, isopropyl alcohol, glycerol, acetone, toluene or dimethylbenzene or their mixed solvent.
Three, under inert gas shielding, presoma is placed in to high temperature furnace and with 1 ~ 20 ℃/min, is warming up to 400 ~ 800 ℃ of charings processing 5 ~ 24h, then the cooling rate with 1 ~ 20 ℃/min is cooled to room temperature; Under 2800～3000 ℃, carry out again obtaining the lithium ion secondary battery cathode active material after graphitization heat treatment.
Lithium ion secondary battery cathode active material prepared by the present invention, adopt the Britain Malvern-Mastersizer of Ma Erwen instrument company 2000 laser particle size analyzers to measure its average grain diameter, adopt the U.S. Monosorb of Kang Ta instrument company direct-reading dynamic flow method specific surface area analysis instrument to survey its specific area, adopt the crystal structure of multi-functional x-ray diffractometer (XRD DI SYSTEM) the measurement negative electrode active material of Britain Bede company, adopt the surface topography of the FEI QUANTA 200 environmental scanning electron microscopes observation negative electrode active materials of U.S. FEI Co..
Using lithium ion secondary battery cathode active material of the present invention to prepare negative pole, is that the mixed uniformly material of the negative electrode active material of above-mentioned preparation, binding agent and conductive agent is coated on metal collector, and dry and compacting forms.1 mass ratio), conductive carbon black (Super P), deionized water (negative electrode active material: CMC: SBR: Super P=95.0: 1.5: 2.5: 1.0) after mixing according to a certain percentage a kind of concrete preparation method of negative pole is for example: by negative electrode active material and binding agent sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) (CMC: SBR=1:, be coated on the Copper Foil that 10 m are thick, coated diaphragm roll-in is made to negative plate.This negative plate is for high rate performance, cryogenic property and the cycle performance test of following lithium rechargeable battery finished product battery.
The preparation of finished product battery and high rate performance thereof, cryogenic property and cycle performance test process are as follows:
(1) use cobalt acid lithium LiCoO
2as positive active material, with binding agent polyvinylidene fluoride (PVDF), conductive carbon black (Super P) according to the mass ratioes of 94: 3: 3 mix and blend form slurry in 1-METHYLPYRROLIDONE (NMP), be coated on aluminium foil, through 85 ℃ of vacuumizes, roll extrusion, make positive plate.
(2) by the barrier film of the PP/PE/PP three-decker of above negative plate, positive plate, U.S. Celgard and 1mol/L LiPF
6+ EC/DMC/EMC (volume ratio 1: 1: 1) electrolyte is assembled into 523450 polymer lithium ion secondary batteries.
(3) cryogenic property is according to the discharge capacity ratio under-10 ℃ of GB/T18287-2000 " cell phone lithium ion battery general specification " tests; Cycle performance adopts 1.0C to be discharged and recharged, and the charging/discharging voltage scope is 4.2V～3.0V; The multiplying power discharging property test, turns constant voltage charge to electric current to be less than 0.05 C, then respectively with 1.0 C and 15.0 C constant-current discharge to 3.0 V, with 15C/1C with 1.0C constant current charge to 4.2 V for same battery
The discharge capacity ratio characterizes high rate performance.Test result is in Table 1.
It is as follows that the present invention carries out first three week gram specific capacity test process to the negative electrode active material of preparation:
(1) preparation of cathode pole piece: be 90: 5: 5 mix and blend form slurry in 1-METHYLPYRROLIDONE (NMP) according to mass ratio by the negative electrode active material that makes and conductive carbon black (Super P), polyvinylidene fluoride (PVDF), be coated on Copper Foil, then by its 120 ℃ of lower vacuumizes in drying box, be pressed into negative plate.
(2) battery assembling: take metal lithium sheet as anodal, electrolyte adopts 1mol/L LiPF
6the solution of+EC/DMC/EMC (volume ratio 1: 1: 1), barrier film adopts the barrier film of the PP/PE/PP three-decker of U.S. Celgard, in the glove box of logical full argon gas, is assembled into button cell.
(3) the button cell employing discharges and recharges as follows system and tests its capacity and efficiency:
A) constant-current discharge (0.2mA, 0.001V)
B) standing (10min)
C) constant current charge (0.2mA, 2.000V)
As shown in Figure 1, 2, 3, the spherical graphite that is 3: 2 by mass ratio in mixer: Delanium total amount (wherein in Delanium, the ratio of engineered stone China ink and needle-like Delanium is 3: 2), the water of the pitch of graphite quality 5% and 10L/ kilogram solid gross mass mixes, mix 120min under the rotating speed of 1000r/min, obtain mixing emulsion; To mix emulsion in the fusion machine, at the rotating speed of 2500r/min, under the condition that fusion temperature is 60 ℃, merge 30min, obtain merging presoma; Under argon shield gas, will merge presoma and be placed in high temperature furnace and be warming up to 800 ℃ of charings with 10 ℃/min and process 16h, then the cooling rate with 5 ℃/min is cooled to room temperature; Under 3000 ℃, carry out again obtaining the lithium ion secondary battery cathode active material after graphitization heat treatment.
Embodiment 2
The spherical graphite that is 5: 3 by mass ratio in mixer: Delanium total amount (wherein in Delanium, the ratio of engineered stone China ink and needle-like Delanium is 1: 1), the acetone of the pitch of graphite quality 10% and 8L/ kilogram solid gross mass mixes, mix 60min under the rotating speed of 1200r/min, obtain mixing emulsion; To mix emulsion in the fusion machine, at the rotating speed of 2000r/min, under the condition that fusion temperature is 80 ℃, merge 15min, obtain merging presoma; Under nitrogen protection gas, will merge presoma and be placed in high temperature furnace and be warming up to 600 ℃ of charings with 8 ℃/min and process 24h, then the cooling rate with 3 ℃/min is cooled to room temperature; Under 2900 ℃, carry out again obtaining the lithium ion secondary battery cathode active material after graphitization heat treatment.
Embodiment 3
The spherical graphite that is 4: 1 by mass ratio in mixer: Delanium total amount (wherein in Delanium, the ratio of engineered stone China ink and needle-like Delanium is 5: 3), the water of the resin of graphite quality 1% and 5L/ kilogram solid gross mass mixes, mix 30min under the rotating speed of 1500r/min, obtain mixing emulsion; To mix emulsion in the fusion machine, at the rotating speed of 2200r/min, under the condition that fusion temperature is 50 ℃, merge 45min, obtain merging presoma; Under argon shield gas, will merge presoma and be placed in high temperature furnace and be warming up to 700 ℃ of charings with 5 ℃/min and process 18h, then the cooling rate with 4 ℃/min is cooled to room temperature; Under 2800 ℃, carry out again obtaining the lithium ion secondary battery cathode active material after graphitization heat treatment.
Embodiment 4
The spherical graphite that is 3: 4 by mass ratio in mixer: Delanium total amount (wherein in Delanium, the ratio of engineered stone China ink and needle-like Delanium is 2: 3), the isopropyl alcohol of the resin of graphite quality 3% and 3L/ kilogram solid gross mass mixes, mix 60min under the rotating speed of 1100r/min, obtain mixing emulsion; To mix emulsion in the fusion machine, at the rotating speed of 3000r/min, under the condition that fusion temperature is 70 ℃, merge 15min, obtain merging presoma; Under nitrogen protection gas, will merge presoma and be placed in high temperature furnace and be warming up to 750 ℃ of charings with 11 ℃/min and process 20h, then the cooling rate with 6 ℃/min is cooled to room temperature; Under 3000 ℃, carry out again obtaining the lithium ion secondary battery cathode active material after graphitization heat treatment.
Embodiment 5
The spherical graphite that is 1: 4 by mass ratio in mixer: Delanium total amount (wherein in Delanium, the ratio of engineered stone China ink and needle-like Delanium is 3: 5), the water of the pitch of graphite quality 15% and 6L/ kilogram solid gross mass mixes, mix 180min under the rotating speed of 800r/min, obtain mixing emulsion; To mix emulsion in the fusion machine, at the rotating speed of 1600r/min, under the condition that fusion temperature is 30 ℃, merge 90min, obtain merging presoma; Under argon shield gas, will merge presoma and be placed in high temperature furnace and be warming up to 600 ℃ of charings with 6 ℃/min and process 20h, then the cooling rate with 1 ℃/min is cooled to room temperature; Under 2900 ℃, carry out again obtaining the lithium ion secondary battery cathode active material after graphitization heat treatment.
Comparative example 1
In mixer, the water of the pitch of spherical graphite, graphite quality 3% and 2L/ kilogram solid gross mass is mixed, under the rotating speed of 1200r/min, mix 30min, obtain mixing emulsion; To mix emulsion in the fusion machine, at the rotating speed of 3000r/min, under the condition that fusion temperature is 80 ℃, merge 15min, obtain merging presoma; Under nitrogen protection gas, will merge presoma and be placed in high temperature furnace and be warming up to 800 ℃ of charings with 10 ℃/min and process 16h, then the cooling rate with 5 ℃/min is cooled to room temperature; Under 3000 ℃, carry out again obtaining the lithium ion secondary battery cathode active material after graphitization heat treatment.
Comparative example 2
In mixer, the water of the pitch of engineered stone China ink, graphite quality 3% and 2L/ kilogram solid gross mass is mixed, under the rotating speed of 1200r/min, mix 30min, obtain mixing emulsion; To mix emulsion in the fusion machine, at the rotating speed of 3000r/min, under the condition that fusion temperature is 80 ℃, merge 15min, obtain merging presoma; Under nitrogen protection gas, will merge presoma and be placed in high temperature furnace and be warming up to 800 ℃ of charings with 10 ℃/min and process 16h, then the cooling rate with 5 ℃/min is cooled to room temperature; Under 3000 ℃, carry out again obtaining the lithium ion secondary battery cathode active material after graphitization heat treatment.
The physical and chemical index that table 1 is different embodiment and comparative example negative electrode active material and electrical property are relatively.
Table 1: the physical and chemical index of different embodiment and comparative example negative electrode active material and electrical property are relatively
The negative electrode active material of above-mentioned 5 embodiment and 2 comparative examples is tested its physical and chemical index and battery performance according to the method described above.
From test result, can find out, the negative pole that adopts negative electrode active material of the present invention and method to prepare has higher compacted density; The lithium rechargeable battery reversible capacity of preparation is high, and coulombic efficiency is large, multiplying power and low temperature performance excellent; Cycle performance of battery is fine, especially at 1.60 ~ 1.75 g/cm
3high compacted density under, the capacity after 500 times that circulates still maintains more than 80%.
The above embodiment is only the preferred embodiment of the present invention.Should be understood that; for this area or those skilled in the relevant art; under the premise without departing from the principles of the invention, can also prepare the negative electrode active material and the corresponding negative pole thereof that much meet this invention spirit, these also should be considered as belonging to protection scope of the present invention.
Claims (10)
1. a lithium ion secondary battery cathode active material, it is characterized in that described lithium ion secondary battery cathode active material is that to take the mixture of the needle-like Delanium that engineered stone China ink that spherical or torispherical graphite, particle length-width ratio is 1.0～3.0 and particle length-width ratio be 1.0～4.0 be matrix, mixed matrix is coated with the non-graphite material with carbon element, and covering amount is 1～20% of mixed matrix weight; The carbon source of described non-graphite material with carbon element is pitch or resin, and its gram specific capacity of negative electrode active material is 350～370mAh/g, and granularity is 4.0～45.0 μ m, and specific area is 1.0～4.00m
2/ g, powder body compacted density is 1.65～2.10g/cm
3, interlamellar spacing d002 is 0.3354～0.3370nm.
2. lithium ion secondary battery cathode active material according to claim 1, is characterized in that spherical graphite in described negative electrode active material and the mass ratio of Delanium total amount are 5:95～95:5; In substrate mixture, the ratio of engineered stone China ink and needle-like Delanium is any ratio.
3. lithium ion secondary battery cathode active material according to claim 2, is characterized in that spherical graphite in described negative electrode active material and the mass ratio of Delanium total amount are 10:90～90:10; In substrate mixture, the ratio of engineered stone China ink and needle-like Delanium is any ratio.
4. lithium ion secondary battery cathode active material according to claim 3, is characterized in that spherical graphite in described negative electrode active material and the mass ratio of Delanium total amount are 20:80～80:20; In substrate mixture, the ratio of engineered stone China ink and needle-like Delanium is any ratio.
5. lithium ion secondary battery cathode active material according to claim 1, it is characterized in that spherical or torispherical graphite behaviour pelletizing shape graphite, natural spherical plumbago or both arbitrarily than mixture.
6. the preparation method of a lithium ion secondary battery cathode active material claimed in claim 1 is characterized in that comprising the following steps:
One, selecting the mass ratio of spherical graphite, Delanium total amount is 5:95～95:5, wherein the ratio of engineered stone China ink and needle-like Delanium is 5:95～95:5, with 1～20% pitch or the resin that are the mixed matrix quality, the total weight of spherical graphite, engineered stone China ink, needle-like Delanium and pitch or resin and solvent are placed in to mixer with the ratio of 1～10 liter/Kg, mix 30～240min under the rotating speed of 500～2000r/min, obtain mixing emulsion;
Two, by muddy shocking emulsion and fusion machine, at the rotating speed of 300～3000r/min, under the condition that fusion temperature is 20～100 ℃, merge 30～240min, obtain merging presoma;
Three, under inert gas shielding, will merge presoma and be placed in high temperature furnace and be warming up to 400～800 ℃ of charings with 1～20 ℃/min and process 5～24h, then the cooling rate with 1～20 ℃/min is cooled to room temperature; Under 2800～3000 ℃, carry out again obtaining the lithium ion secondary battery cathode active material after graphitization heat treatment.
7. the preparation method of lithium ion secondary battery cathode active material according to claim 6, is characterized in that solvent is one or more in water, ethanol, isopropyl alcohol, glycerol, acetone, toluene or dimethylbenzene.
8. the preparation method of lithium ion secondary battery cathode active material according to claim 6, is characterized in that inert gas is nitrogen, argon gas, helium, neon or the above-mentioned mist of any ratio.
9. the preparation method of a lithium ion secondary battery cathode, is characterized in that the mixed uniformly material of negative electrode active material, binding agent and conductive agent that in claim 6-8 prepared by arbitrary claim is coated on metal collector, and dry and roll-in forms.
10. the preparation method of lithium ion secondary battery cathode according to claim 9, is characterized in that this negative plate can obtain very high compacted density, reaches 1.50～1.75g/cm
3, the lithium rechargeable battery of being made with this negative pole, the capacity after 500 times that circulates still maintains more than 80%; At 1.60～1.75g/cm
3high compacted density under, the capacity after 500 times that circulates still maintains more than 80%.
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| CN103022492A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing improved negative-pole graphite composite material for lithium ion battery |
| EP2945209B1 (en) * | 2013-01-11 | 2018-04-11 | Nec Corporation | Lithium ion secondary battery |
| CN103078088B (en) * | 2013-02-05 | 2015-07-15 | 新乡远东电子科技有限公司 | Lithium ion battery cathode material |
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| CN108808006B (en) * | 2018-04-28 | 2020-12-11 | 宁德时代新能源科技股份有限公司 | Negative pole piece and battery |
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