CN109713252A

CN109713252A - The high nickelic tertiary cathode material and its preparation method and application of electrical property consistency

Info

Publication number: CN109713252A
Application number: CN201811457823.1A
Authority: CN
Inventors: 赵孝连; 曾国城; 杨亮亮; 李诗文; 农廷峰
Original assignee: Guizhou Gaodian Technology Co Ltd; High Point (shenzhen) Technology Co Ltd
Current assignee: Guizhou Gaodian Technology Co Ltd; High Point (shenzhen) Technology Co Ltd
Priority date: 2018-11-30
Filing date: 2018-11-30
Publication date: 2019-05-03

Abstract

The present invention relates to field of lithium ion battery fields, and in particular to a kind of high nickelic tertiary cathode material and its preparation method and application of electrical property consistency.The present invention provides a kind of high nickelic tertiary cathode materials of electrical property consistency, which is characterized in that chemical structural formula Li_xNi_aCo_bM_cR_dO₂Wherein, R is doped chemical, 0.95 < x <, 1.15,0.60 < a <, 0.85,0 < b < 0.2,0 < c < 0.2,0.98≤a+b+c≤1.00,0≤d < 0.1, M are selected from one of Mn or Al.Nickelic tertiary cathode material of the present invention, partial size consistency is high, can effectively improve the physical property and chemical property of nickelic lithium ion secondary battery.

Description

The high nickelic tertiary cathode material and its preparation method and application of electrical property consistency

Technical field

The present invention relates to lithium-ion-power cell fields, and in particular to a kind of high nickelic tertiary cathode of electrical property consistency Material and its preparation method and application.

Background technique

Lithium ion secondary battery is and extensive due to having many advantages, such as that energy density is high, operating voltage is high, having extended cycle life Power supply as various mobile devices, energy-accumulating power station, or even in the fields such as Aeronautics and Astronautics, navigation, automobile, Medical Devices by Step replaces other conventional batteries.

As the lithium battery motor-car occurred in recent years, (if Japanese Toyota Company produces Jim Press, tesla, U.S. automobile is public Take charge of the tesla's electric vehicle etc. produced, the electric bus that BYD company produces F6 iron cell electric vehicle and various regions are released in recent years Deng), and electric energy storage station etc., handling characteristics are to deposit the high lithium ion battery of a large amount of energy densities (electrochmical power source) concentration It puts together, charge and discharge etc. is carried out by electric energy management system and are used.In the commercialization process of above equipment, lithium ion secondary The charge/discharge high rate performance of battery and the height of cobalt content are always that each production firm and application terminal client pay close attention to Major fields are usually carried out in 3.0-4.2V either 2.75-4.4V when lithium ion battery material specific capacity detects, but in reality For safety actually the voltage petiolarea (range) on both sides is reduced in application process, such as 3.4-4.2V passes through people For operating voltage range is arranged on protection board come the security reliability of strengthening lithium battery, nevertheless, due to lithium battery capacity Charge and discharge be process that the energy accumulation for a relative time either discharges, if the especially positive material of lithium battery material If the consistency of material is bad, then can be had differences between battery core different in above-mentioned operating voltage range, if any battery core Cause a part of capacity that cannot be utilized in the presence of electric discharge trailing phenomenon.In commercialized lithium battery, in order to overcome battery core Performance difference when in groups, it usually needs artificial grouping is carried out to the lithium battery of shipment and selects that (as by measure, internal resistance, voltage is flat The indexs such as platform), it further needs exist for managing performance difference battery according to characteristic parameter using more complicated battery management system (BMS) Group, when lithium battery quantity increases in groups, the complexity of BMS system can be multiplied, this is also to drive tesla, the U.S. public The reason of taking charge of the important measure for replacing 18650 type batteries to reduce battery pack cost using 21700 type batteries (http: // libattery.ofweek.com/2017-07/ART-36003-8500-30154661.html).Investigate the knot of lithium ion battery Structure is the bottle that entire lithium ion battery chemical property plays it is found that due to only having the electric conductivity of positive electrode worst in battery The performance limitation in neck region, most lithium batteries can find reason from positive electrode.Therefore as can by simple and effective Method improve the consistency of positive electrode and be possible to the consistency of General Promotion lithium battery performance.

On the other hand, be current conventional Powder Processing Technology in China as crushing and classification technology, usually by first to powder into Promoting the circulation of qi body aerosol dispersion carries out sizing screening again, and action principle is similar to sieve classification.It is produced in natural graphite and inorganic chemical industry It usually requires to be classified the material of crushing under fluidising conditions and collect processing in product production process, with natural scale stone For tampon shape metaplasia produces, it usually needs the crushing and classification equipment of 5 grades of concatenation or more constantly to carry out broken classification, is closed with preparing Granularity requirements ball-type graphite, for the process due to being only physical mechanical cracking and sorting, material loss rate is bigger, actual receipts Rate is between 35-45%.Different with natural machining graphite, the presoma of nickelic tertiary cathode material preparation itself is also a kind of Spheric granules, with lithium source carry out decompose and solid-state diffusion react after by the noncrystal spherical or sharp ball for increasingly generating layer structure Type positive electrode.But during the sintering process and the introducing link of raw material, it will usually which the local growth for particle occur is too fast and broken It splits, on the other hand during the sintering process because lithium melts the bulky grain formed due to effect has part granular precursor mutual gluing, table It is hardened to there is hardening for material in sight, therefore inevitably has small particle and large particle appearance in process, In the case where current positive electrode price height enterprise, Equilibrium yield and manufacturing process, the feasibility and economy of manufacturing cost are needed.

In lithium ion electrochmical power source system, the output of energy is usually realized by the transfer of lithium ion, is related to just Pole, cathode, isolation film, (electrochemistry of lithium ion battery hinders the electronics transfer between a variety of solid-liquid body porous medias such as electrolyte Anti- spectrum analysis, Zhuan Quanchao；Xu Shoudong；Qiu Xiangyun；Cui Yongli；Fang Liang；2010.22 (6) P 1044- of Sun Shigang " chemical progress " 1057), work as discharge current if different size of positive electrode stroke in de-/process of intercalation is different in charge and discharge process When excessive, lithium ion has little time to be embedded in positive electrode, and often in cathode/isolation fenestra, positive electrode surface (containing particle) is formed The metal lithium simple substance of high activity, long-time service can bring serious safety problem, can equally go out because electric current is excessive in charging process Existing lithium metal is enriched in the problem of each interface of lithium battery interior.It is bad in the consistency for macroscopically showing as lithium battery, finally Influence the comprehensive performance of lithium battery in groups.

Therefore how to start with optimizing from positive electrode and be wanted as lithium ion battery especially power battery urgent need It solves the problems, such as.

The modified side for improving battery security in surface by positive electrode has been proposed in many open and patent documents Method.

Chinese patent CN201280070138.8 discloses a kind of nickel complex hydroxide and its manufacturing method, non-water system electricity Solve matter positive active material manufacturing method and lithium ion secondary battery, a kind of non-aqueous electrolyte secondary battery positive electrode active material The manufacturing method of matter, the hexagonal crystalline positive active material is with general formula Li_(1+u)Ni_xCo_yAl_zMn_tM_sO₂It indicates, -0.05≤u ≤ 0.20, x+y+z+t+s=1,0≤y≤0.3,0 < z≤0.1,0.001 < t≤0.05,0≤s≤0.05, M be selected from by The addition element of at least one of the group that Mg, Ca, Ti, V, Cr, Zr, Nb, Mo and W are constituted, and by multiple primary particles The substantially spherical offspring that agglutination is formed is constituted, and preparation section includes: heat treatment procedure, by nickel cobalt aluminum complex hydroxide It is heat-treated in 105~750 DEG C of temperature；Mixed processes are 1:0.95 by the ratio of the sum of metal atomicity and lithium atom number ~1.2 are mixed to form lithium mixture with lithium source；And firing process, the process is in oxidative environment with 700~800 DEG C of temperature Degree is burnt into the aforementioned lithium mixture formed in aforementioned mixed processes.The technique is first first to decompose presoma hydroxide Product is generated at oxide, then with oxide and lithium salts hybrid reaction.However this method is due to the presence of moisture in decomposable process Cause the chemical valence of nickel in reactant unstable.

Chinese patent CN200810052730.0 discloses the preparation method of spherical aluminum-doped nickel cobalt lithium for lithium ion battery. By precursor spherical nickel cobalt aluminum hydroxide and lithium source (one of LITHIUM BATTERY lithium hydroxide, lithium nitrate and lithium carbonate or in which several Kind mixture) mixing after.It is roasted 20~24 hours at 700~800 DEG C.Cooling and broken classification is carried out after roasting, obtains ball Shape aluminum-doped nickel lithium carbonate for lithium.The technique is that presoma hydroxide is directly mixed to a step to generate product with lithium salts, it is contemplated that moisture Removing influence the preparation of material, lithium source volatile matter (moisture) content is more, and equipment seriously corroded is easy to cause under high temperature, practical On be not industrial method.

Patent document CN201610650420.3 is disclosing nickel cobalt aluminium ternary precursor and preparation method thereof and preparation just Pole material and method.Using high-speed mixer, by a certain percentage by obtained nickel cobalt aluminium ternary precursor and monohydrate lithium hydroxide (Li/ (Ni+Co+Al) molar ratio is 0.9~1.2:1) is uniformly mixed, in bell-type roaster, with the rate of 2~10 DEG C/min 600~800 DEG C are warming up to, 5~20h is kept the temperature, oxygen is passed through into bell-type roaster, guarantees that oxygen content is greater than 70% in furnace, Room temperature is naturally cooling to after heat preservation, the blank roasted obtains nickel cobalt aluminium tertiary cathode material after crushing, being sieved.

Patent document CN201610638474.8 discloses soft carbon composite cathode material of silicon/carbon/graphite, preparation method and lithium-ion electric Pond.Natural spherical plumbago, pitch mixing, the hot submersion under default pressure, pitch softening flowing are filled to day after mixing Right ball-type graphite internal void, obtains intermediate product after cooling；Intermediate product is carbonized, obtains soft carbon using crushing, being classified Composite cathode material of silicon/carbon/graphite.The average grain diameter of soft carbon composite cathode material of silicon/carbon/graphite after being crushed and classified is 5~15 μm, fixed carbon Content is greater than 99%.

Above-mentioned patent and document are related to the preparation method of nickelic tertiary cathode material and the classification granulation side of cathode graphite Method, but do not refer to using 2 times or more concatenation type crushing and classification processing and prepare positive electrode.

Summary of the invention

For this purpose, the problem of technology solved by the invention, is: being prepared in the prior art using nickelic tertiary cathode material Lithium ion battery storage consistency is not high, causes nickelic lithium ion battery applications limited.

Adjustable and narrowly distributing the nickelic tertiary cathode material the object of the present invention is to provide a kind of partial size, the material due to Particle diameter distribution is narrow, and lithium ion is de-/and embedding lithium path is relatively uniform, is conducive to improve the property of nickelic lithium ion battery in a state of use Energy inconsistency, improves excellent rate and yield, reduces production cost, expands the application range of lithium ion battery.

The present invention provides a kind of high nickelic tertiary cathode materials of electrical property consistency, which is characterized in that chemical structure Formula is Li_xNi_aCo_bM_cR_dO₂, wherein R is doped chemical, 0.95 < x <, 1.15,0.61 < a <, 0.85,0 < b <, 0.2,0 < c < 0.2,0.98≤a+b+c≤1.00,0≤d < 0.1, M are selected from one of Mn or Al, preferably 0.0008≤d≤0.006.

The present invention provides a kind of preparation methods of positive electrode, and it includes following step:

(1) by lithium source, nickel cobalt M presoma and the source R be in molar ratio 1.0-1.2:1:0.00-0.003 mix, then into Row first sintering；

(2) the obtained product of step (1) is subjected to crushing and classification processing, obtains classification product；

(3) the obtained classification product of step (2) is mixed with the residue source R, obtains semi-finished product；

(4) the obtained semi-finished product of step (3) are carried out second to be sintered, then carries out crushing and classification processing, mixing obtains To the positive electrode.

The present invention also provides a kind of lithium ion batteries, and it includes positive electrodes described above.

The present invention also provides positive electrodes described above or shown lithium ion battery in mobile digital product (3C), electricity Application in electrical automobile (xEV) or the field energy storage (ESS).

Specifically, the invention proposes following technical solutions.

The present invention provides a kind of nickelic tertiary cathode materials, wherein chemical structural formula Li_xNi_aCo_bM_cR_dO₂, wherein R is doped chemical, 0.95 < x <, 1.15,0.61 < a <, 0.85,0 < b < 0.2,0 < c < 0.2,0.98≤a+b+c≤ 1.00,0≤d < 0.1, M are selected from one of Mn or Al, preferably 0.0008≤d≤0.006.

Preferably, for positive electrode described above, wherein the D of the positive electrode_v50=2-18 μm, it is preferred that D_v50=2.5-10.1 μm；Preferably, size distribution half-peak breadth is 0.5 μm -4.2 μm, preferably 0.72-4.06 μm.

Preferably, for positive electrode described above, wherein the positive electrode is secondary spherical structure.

Preferably, for positive electrode described above, wherein the R element is in titanium, yttrium, zirconium, cobalt and lanthanum It is one or more kinds of.

The present invention provides the preparation methods of material described above, wherein the preparation method includes following step:

Preferably, for preparation method described above, wherein in step (1), the lithium source selected from lithium carbonate, One or more of monohydrate lithium hydroxide, lithium acetate and lithium oxalate.

Preferably, for preparation method described above, wherein in step (1), the source R is the change containing R element Object is closed, the compound is selected from hydroxide, oxide or its solubility salt.

Preferably, for preparation method described above, wherein in step (1), the nickel cobalt M presoma is nickel cobalt Manganese presoma or nickel cobalt aluminium presoma.

Preferably, for preparation method described above, wherein in step (1), the temperature of the first sintering is 400-900 DEG C, preferably 400 DEG C.

Preferably, for preparation method described above, wherein in step (1), the time of the first sintering is 8-20 hours, preferably 10 hours.

Preferably, for preparation method described above, wherein in step (4), the temperature of second of sintering is 500-1000 DEG C, preferably 700-1000 DEG C are more preferably 700 DEG C.

Preferably, for preparation method described above, wherein in step (4), the time of second of sintering is 8-20 hours, preferably 10 hours.

Preferably, for preparation method described above, wherein the first sintering and the atmosphere of second of sintering are Oxygen-enriched air, oxygen volume content are 40-99.8%, it is preferred that the air mass flow of the first sintering is 200-400Nm³/ The air mass flow of h, second of sintering are 200-500Nm³/h。

Preferably, for preparation method described above, wherein in step (2) and step (4), the crushing and classification For 2 times or more concatenation type crushing and classifications.

The present invention provides a kind of anode material for lithium-ion batteries, are prepared by preparation method described above.

The present invention provides a kind of lithium ion batteries, and it includes positive electrodes described above.

The present invention provides positive electrodes described above or lithium ion battery described above in mobile digital product Application in (3C), electric car (xEV) or the field energy storage (ESS).

Beneficial effect obtained by the present invention is:

1. the crystal structure of the obtained positive electrode of the present invention is complete, particle diameter distribution is narrow, good sphericity.

2. the high nickelic tertiary cathode material of the obtained partial size consistency of the present invention, with other existing positive electrode phases Than the physical property and chemical property of nickelic lithium ion secondary battery can be efficiently modified.

Detailed description of the invention

Fig. 1 is embodiment one, embodiment three, comparative example one and the preparation-obtained size distribution schematic diagram of comparative example two.

Fig. 2-1 is the scanning electron microscope sem schematic diagram of the preparation-obtained positive electrode of embodiment one.

Fig. 2-2 is the scanning electron microscope sem schematic diagram of the preparation-obtained positive electrode of comparative example one.

Fig. 2-3 is the scanning electron microscope sem schematic diagram of the preparation-obtained positive electrode of embodiment three.

Fig. 2-4 is the scanning electron microscope sem schematic diagram of the preparation-obtained positive electrode of comparative example two.

Fig. 3 is the button electricity of embodiment three, embodiment seven, comparative example two and the preparation-obtained positive electrode of comparative example four Pond result schematic diagram.

Specific embodiment

Usual size distribution refers to that the particle of all size in powder sample accounts for the ratio of total number of particles.When all in sample When the real density of grain is identical, the distribution of weight of particle is consistent with volume distribution.When being not particularly illustrated, granularity that instrument provides Distribution refers generally to weight or volume distribution.It in volume distribution map, is characterized using peak shape figure, abscissa is granularity, ordinate For the accounting of granularity, size distribution often shows as the peak of a multiple approximate normal distributions.The width and height at peak respectively have not Together, but its area integral value is 1.For the characterizing method of size distribution width, dispersion is generallyd use to indicate, i.e. dispersion =the dispersion of distribution/average particle size.If using D_V50Average grain diameter is represented, wherein D_v0It can not read, therefore be simplified to (D again_v90-D_v10) Represent particle size distribution, D in formula_v0The partial size that granularity Detection is represented when having response, the value are usually examined due to adopting several frequencies It does not detect, D_v10Represent the average grain diameter of 10% particle, D_v90Represent the average grain diameter of 90% particle.

But since test material average grain diameter is different, the method for above-mentioned dispersion for the comparison between different powders exist compared with Big difference, characterizes the distribution situation of particle using the half-peak breadth method in spectrum analysis thus in the present invention, half-peak breadth is It is the peak width at peak height half, also known as half peak breadth.Be parallel to the straight line of peak base by the midpoint of peak height, this straight line and Intersect the distance between two o'clock in peak two sides.

As described above, the nickelic tertiary cathode material high the present invention provides a kind of electrical property consistency, the anode material The chemical structural formula of material is Li_xNi_aCo_bM_cR_dO₂, wherein R is doped chemical, 0.95 < x <, 1.15,0.61 < a < 0.85,0 < b < 0.2,0 < c < 0.2,0.98≤a+b+c≤1.00,0≤d < 0.1, M are selected from one of Mn or Al, preferably 0.0008≤d≤0.006。

In a kind of currently preferred specific embodiment, the D of the positive electrode_v50=2-18 μm, it is preferred that D_v50 =2.5-10.1 μm；Preferably, size distribution half-peak breadth is 0.5 μm -4.2 μm, preferably 0.72-4.06 μm.

In a kind of currently preferred specific embodiment, the positive electrode is secondary spherical structure.

In more preferably a kind of specific embodiment of the present invention, the R element is in titanium, yttrium, zirconium, cobalt and lanthanum It is one or more kinds of.

The present invention provides a kind of preparation methods of positive electrode comprising following step: (1) by lithium source, nickel cobalt M Presoma and the source R are 1.0-1.2:1:0.00-0.003 mixing in molar ratio, then carry out first sintering；

In a kind of currently preferred specific embodiment, wherein in step (1), the lithium source is selected from carbonic acid One or more of lithium, monohydrate lithium hydroxide, lithium acetate and lithium oxalate.

In a kind of currently preferred specific embodiment, wherein in step (1), the R was containing R element originally Compound, the compound be selected from hydroxide, oxide or its solubility salt.

In a kind of currently preferred specific embodiment, wherein in step (1), the nickel cobalt M presoma is nickel Cobalt manganese presoma or nickel cobalt aluminium presoma.

In a kind of currently preferred specific embodiment, wherein in step (1), the temperature of the first sintering Degree is 400-900 DEG C, preferably 400 DEG C.

In a kind of currently preferred specific embodiment, wherein in step (1), the time of first sintering It is 8-20 hours, preferably 10 hours.

It further include by sintered production after first sintering in more preferably a kind of specific embodiment of the present invention The step of object is cooled to room temperature under the protection of dry nitrogen.

In a kind of currently preferred specific embodiment, wherein in step (4), the temperature of second of sintering Degree is 500-1000 DEG C, and preferably 700-1000 DEG C, be more preferably 700 DEG C.

In a kind of currently preferred specific embodiment, wherein in step (4), second of sintering when Between be 8-20 hours, preferably 10 hours.

In a kind of currently preferred specific embodiment, wherein in step (1) and step (4), the first time The atmosphere of second of sintering of sintering is oxygen-enriched air, and oxygen volume content is 40-99.8%, it is preferred that the first sintering Air mass flow be 200-400Nm³The air mass flow of/h, second of sintering are 200-500Nm³/h。

In a kind of currently preferred specific embodiment, in step (2) and step (4), the crushing and classification is 2 The secondary above concatenation type crushing and classification, it is preferred that the crushing and classification uses 3 concatenation type crushing and classifications.

Preferably, the equipment used that is classified is grading wheel and cyclone separator, and the grading wheel is gridiron structure, Material is ceramic material, and the grid spacing is 0.3-3.0cm.

Preferably, the linear velocity of the grading wheel is 0.5-62m/s.

Preferably, the cyclone separator is plastic material or liner radio frequency coating media, to reduce anode The magnetic impurity of material.

In a kind of currently preferred specific embodiment, the present invention provides a kind of preparation sides of positive electrode Method, it includes following step:

A) (physical dispersion) is mixed, i.e., by lithium salts, the presoma of nickelic ternary material, the use such as target doped chemical raw material Wet process, the material of the fluffy powder state material of the quasi- dry process of dry method either part slightly agglomeration.Lithium salts is lithium carbonate, The compositions such as monohydrate lithium hydroxide, lithium acetate and/or lithium oxalate.

B) material that high temperature first sintering obtains is introduced into pulverizer and groups of grader/whirlwind after cooling Separator is classified, and pulse dust collector is arranged from the semi-finished product of different cyclone collection different-grain diameters, and in terminal The semi-finished product of different particle size distribution are prepared in dust.

C) mixing.The granular material that b) step obtains will be rejoined in mixing plant and be stirred again, and be added few Amount energy modified additive is simultaneously uniformly mixed, and optionally adds or do not add solvent.

D) is sintered.The granular material that c) step obtains is carried out 500 DEG C or more in oxygen-enriched air to be sintered, then is protected Protect atmosphere (N₂) under natural cooling.Agglomerating plant refers to roller kilns, the equipment such as ventilation controlled atmosphere kiln.

The material that d) step obtains is repeated b) step and carries out crushing and classification, is prepared by e) second of crushing and classification of The nickelic tertiary cathode material of the low specific surface of target product.Disintegrating apparatus refers to the equipment such as cyclone vortex pulverizer, airslide disintegrating mill.

The present invention provides positive electrodes described above or lithium ion battery in mobile digital product (3C), electric car (xEV) or the application in the field energy storage (ESS).

To be improved in view of the electrochemistry consistent performance of current lithium ion battery, the present invention is based on nickelic tertiary cathode materials Preparation angle propose a kind of method for preparing the narrow positive electrode of particle diameter distribution, the positive electrode use materials synthesis/ The method of multiple multi-step classification carries out in preparation process.The positive electrode particle diameter distribution of preparation is narrow, the lithium ion of later period preparation Battery charging and discharging consistency is good, stable electrochemical property, is conducive to the application scenarios for expanding nickelic tertiary cathode material.

The equipment and analysis that manufacturer to raw material used in the present embodiment and equipment and product analysis below uses Method is described as follows, wherein the chemical substance do not indicate be conventional reagent the pure rank of chemistry.Embodiment The information and experimental facilities of used raw material are as shown in Table 1 and Table 2

The information of used raw material in 1 embodiment of table

The information of used experimental facilities in 2 embodiment of table

The preparation of one positive electrode of embodiment

(1) 200L plough batch mixer is selected.Stirring (revolving speed 25rpm) is opened, the nickel cobalt of 100kg is added under agitation Manganese presoma (Ni_0.61Co_0.19Mn_0.20(OH)₂(granularity D_v50: 7 μm, substance content 99.5%), then press Li/ (Ni+Co+Mn) Molar ratio=1.01 ratios weigh 46.1kg monohydrate lithium hydroxide powder (granularity D_v50: 25 μm, substance content 99.5%) it is added Into mixing machine, 37.0kg deionized water is added by 80wt% solid content under agitation, adds 1.43kg basic carbonate Cobalt (is added cobalt amount based on finished product and accounts for 7000ppm), and speed (5rpm) stirring 6h is further decreased after stirring 2h and discharges to be formed has The plaster material discharging of certain forming degree；Then using ventilation 24m roller kilns, setting heating zone temperature is 400 DEG C, is passed through oxygen-enriched (oxygen-enriched air oxygen content 40%, flow 400Nm under air conditions³/ h) charge material into ceramic alms bowl carry out the 1st time sintering, It is sintered 10h, material is cooled to room temperature under the protection of dry nitrogen, weighs the weight of disengaging material, burn tinctuer is calculated as with raw material 34.7%；

(2) step (1) obtained product is crushed with cyclone vortex pulverizer, smashed material passes through respectively 1st grade of grading wheel (linear velocity 25m/s) and cyclone separator, the 2nd grade of pulverizer, grading wheel (linear velocity 28m/s) and rotation Wind separator, 3rd level pulverizer, grading wheel (linear velocity 32m/s) and cyclone separator and pulse dust collector, through whirlwind Separator and pulse dust collector obtain varigrained material.The inspection of wet process granularity is carried out to material respectively using Malvern ParticleSizer It surveys, the granularity for obtaining 4 kinds of materials is as shown in table 3, and above-mentioned material is obtained to classification product after evenly mixing；

(3) the obtained classification product of step (2) is rejoined into 200L plough batch mixer, opens stirring, and be added 1.43kg basic cobaltous carbonate (based on finished product be added cobalt amount account for 7000ppm) is simultaneously uniformly mixed and obtains semi-finished product；

(4) using ventilation 24m roller kilns.It is 700 DEG C that heating zone temperature, which is arranged, is passed through (oxygen-enriched sky under the conditions of oxygen-enriched air Gas oxygen content 99.8%, flow 300Nm³/ h) charge material into ceramic alms bowl carry out the 2nd time sintering, be sintered 10h.By material It is cooled to room temperature under the protection of dry nitrogen, weighs the weight of disengaging material, burn tinctuer is calculated as 1.2% with raw material；With cyclone whirlpool Stream pulverizer crushes double sintering material, and smashed material passes through the 1st grade of grading wheel (linear velocity 30m/s) respectively And cyclone separator, the 2nd grade of pulverizer, grading wheel (linear velocity 35m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 33m/s) and cyclone separator and pulse dust collector respectively obtain tool through cyclone separator and pulse dust collector There are the classification product of certain particle size, will uniformly be mixed to get positive electrode again after the analysis of classification product.

5g positive electrode is weighed, using diluted hydrochloric acid dissolution, then with taking a small amount of low-concentration liquid again after deionized water constant volume Secondary dilution constant volume, and calculated through ICP detection and obtain positive electrode chemical formula as Li_0.98Ni_0.61Co_0.196Mn_0.20O₂, magnetisable material (iron (Fe)+nickel (Ni)+chromium (Cr)+zinc (Zn)) about 103ppb.

Wet process granularity Detection is carried out to material respectively using Malvern ParticleSizer, obtains granularity such as 4 institute of table of 4 kinds of materials Show.

The preparation of two positive electrode of embodiment

(1) 200LY type mixing machine is selected.Stirring (revolving speed 50rpm) is opened, the nickel cobalt of 100kg is added under agitation Manganese presoma (Ni_0.61Co_0.20Mn_0.20(OH)₂(granularity D_v50: 7 μm, substance content 99.5%), then press Li/ (Ni+Co+Mn) Molar ratio=1.04 ratios weigh 41.5kg carbonic acid powder for lithium (granularity D_v50: 5 μm, substance content 99.8%) it is added to mixing In machine, 20.0kg deionized water is added by 90% solid content under agitation, further decreases speed (3- after stirring 2h 5rpm) stirring 1h discharge to be formed with certain forming degree plaster material discharging；One is carried out using method same as Example 1 Secondary sintering (oxygen-enriched air oxygen content 99.5%, flow 200Nm³/ h), burn tinctuer is calculated as 33.8% with raw material；

(2) step (1) obtained product is crushed with cyclone vortex pulverizer, smashed material passes through respectively 1st grade of grading wheel (linear velocity 45m/s) and cyclone separator, the 2nd grade of pulverizer, grading wheel (linear velocity 28m/s) and rotation Wind separator, 3rd level pulverizer, grading wheel (linear velocity 28m/s) and cyclone separator and pulse dust collector, through whirlwind Separator and pulse dust collector obtain varigrained material.The inspection of wet process granularity is carried out to material respectively using Malvern ParticleSizer It surveys, the granularity for obtaining 4 kinds of materials is as shown in table 3, and above-mentioned material is obtained to classification product after evenly mixing；

(3) the obtained classification product of step (2) is rejoined into 200L Y type batch mixer, opens stirring, and be added And positive four butyl ester of 7.45kg metatitanic acid (technical grade, effective component content 20%, content Ti content in terms of finished product is 2000ppm) is simultaneously It is uniformly mixed and obtains semi-finished product；

(4) double sintering (oxygen-enriched air oxygen content 99.5%, flow are carried out using method same as Example 1 400Nm³/ h), burn tinctuer is calculated as 5.4% with raw material；Then double sintering material is crushed using cyclone vortex pulverizer (material 1), smashed material pass through the 1st grade of grading wheel (linear velocity 62m/s) and cyclone separator, the 2nd grade of crushing respectively Machine, grading wheel (linear velocity 25m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 20m/s) and whirlwind Separator and pulse dust collector respectively obtain the classification product with certain particle size through cyclone separator and pulse dust collector, will It is uniformly mixed to get positive electrode again after the analysis of classification product.

It uses dilute hydrochloric acid to clear up and calculate through ICP detection and obtains positive electrode chemical formula as Li_1.01Ni_0.61Co_0.20Mn_0.20 Ti_0.004O₂, magnetisable material (iron (Fe)+nickel (Ni)+chromium (Cr)+zinc (Zn)) about 41ppb.

The preparation of three positive electrode of embodiment

(1) it selects 200L to merge machine, opens stirring (revolving speed 600rpm), the nickel cobalt manganese of 100kg is added under agitation Presoma (Ni_0.70Co_0.15Mn_0.15(OH)₂(granularity D_v50: 10 μm, substance content 99.5%), then rub by Li/ (Ni+Co+Mn) You weigh 58.6kg oxalic acid powder for lithium (granularity D in ratio=1.06_v50: 4.5 μm, substance content 99.5%) it is added in fusion machine, And 0.27kg yttrium oxide (ceramic grade, granularity D_v50: 0.3 μm, purity 99.0%, content yttrium content in terms of finished product is 200ppm), Speed (50rpm) stirring 20min discharging is further decreased after stirring 2h；It is once burnt using method same as Example 1 Tie (oxygen-enriched air oxygen content 78.3%, flow 350Nm³/ h), burn tinctuer is calculated as 33.8% with raw material；

(2) step (1) obtained product is crushed (material 1) with cyclone vortex pulverizer, smashed material Respectively by the 1st grade of grading wheel (linear velocity 0.5m/s) and cyclone separator, the 2nd grade of pulverizer, (linear velocity is grading wheel 20m/s) and cyclone separator and pulse dust collector, varigrained material is obtained through cyclone separator and pulse dust collector. Wet process granularity Detection is carried out to material respectively using Malvern ParticleSizer, the granularity for obtaining 3 kinds of materials is as shown in table 3, will be above-mentioned Material obtains classification product after evenly mixing；

(3) the obtained classification product of step (2) is rejoined into 200L fusion machine, opens stirring, and 0.3kg is added Five water zirconium nitrate of deionized water and 0.12kg (technical grade, purity 98.5%, content zirconium content in terms of finished product is 300ppm), And it is uniformly mixed and obtains semi-finished product；

(4) double sintering (oxygen-enriched air oxygen content 78.3%, flow are carried out using method same as Example 1 230Nm³/ h), burn tinctuer is calculated as 0.9% with raw material；Then double sintering material is crushed using cyclone vortex pulverizer (material 1), smashed material pass through the 1st grade of grading wheel (linear velocity 40m/s) and cyclone separator, the 2nd grade of crushing respectively Machine, grading wheel (linear velocity 30m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 28m/s) and whirlwind Separator and pulse dust collector respectively obtain the classification product with certain particle size through cyclone separator and pulse dust collector, will It is uniformly mixed to get positive electrode again after the analysis of classification product.

It uses dilute hydrochloric acid to clear up and calculate through ICP detection and obtains positive electrode chemical formula as Li_1.02Ni_0.70Co_0.15Mn_0.1 ₅Y_0.0010Zr_0.0004O₂, magnetisable material (iron (Fe)+nickel (Ni)+chromium (Cr)+zinc (Zn)) about 73ppb.

The preparation of example IV positive electrode

(1) 400L kneader is selected, stirring (revolving speed 40rpm) is opened, before the nickel cobalt manganese of 100kg is added under agitation Drive body (Ni_0.79Co_0.08Mn_0.11(OH)₂(granularity D_v50: 10 μm, substance content 99.5%), then press Li/ (Ni+Co+Mn) mole 48.4kg monohydrate lithium hydroxide powder (granularity D is weighed than=1.05_v50: 15 μm, substance content 99.8%) and 0.125kg Four water acetic acid yttriums (chemical pure, purity 95.5%, content yttrium content in terms of finished product is 300ppm) are added in kneader, stir 1h After further decrease speed (20rpm) stirring 20min discharging；It is carried out using method same as Example 1 once sintered (oxygen-enriched Air oxygen content 65.0%, total charge flow rate 350Nm³/ h), burn tinctuer is calculated as 33.8% with raw material；

(2) step (1) obtained product is crushed (material 1) with cyclone vortex pulverizer, smashed material Respectively by the 1st grade of grading wheel (linear velocity 40m/s) and cyclone separator, the 2nd grade of pulverizer, (linear velocity is grading wheel 28m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 35m/s) and cyclone separator and pulsating collection Device obtains varigrained material through cyclone separator and pulse dust collector.Wet process is carried out to material using Malvern ParticleSizer Granularity Detection, the granularity for obtaining 4 kinds of materials is as shown in table 3, and above-mentioned material is obtained to classification product after evenly mixing；

(3) the obtained classification product of step (2) is rejoined into 400L kneader, opens stirring, and 0.3kg is added Deionized water and 0.096kg cobalt acetate (chemical pure, purity 99.5%, content cobalt content in terms of finished product is 300ppm), and mix It closes and uniformly obtains semi-finished product；

(4) double sintering (oxygen-enriched air oxygen content 65.0%, flow are carried out using method same as Example 1 400Nm³/ h), burn tinctuer is calculated as 1.3% with raw material；Then double sintering material is crushed using cyclone vortex pulverizer (material 1), smashed material pass through the 1st grade of grading wheel (linear velocity 30m/s) and cyclone separator, the 2nd grade of crushing respectively Machine, grading wheel (linear velocity 29m/s) and cyclone separator and pulse dust collector, through cyclone separator and pulse dust collector The classification product with certain particle size are respectively obtained, classification product are uniformly mixed to get positive electrode again after grain size analysis.

It uses dilute hydrochloric acid to clear up and calculate through ICP detection and obtains positive electrode chemical formula as Li_1.02Ni_0.79Co_0.0804Mn_0.1 ₁Y_0.0004O₂, magnetisable material (iron (Fe)+nickel (Ni)+chromium (Cr)+zinc (Zn)) about 116ppb.

Wet process granularity Detection is carried out to material respectively using Malvern ParticleSizer, obtains granularity such as 4 institute of table of 3 kinds of materials Show.

The preparation of five positive electrode of embodiment

(1) 400L kneader is selected, stirring (revolving speed 30rpm) is opened, before the nickel cobalt manganese of 100kg is added under agitation Drive body Ni_0.80Co_0.11Mn_0.09(OH)₂(granularity D_v50: 10 μm, substance content 99.5%), then press Li/ (Ni+Co+Mn) mole 47.7kg monohydrate lithium hydroxide powder (granularity D is weighed than=1.05_v50: 25 μm, substance content 99.8%) and 0.071kg Zirconium oxide (technical grade, purity 95.5%, content zirconium content in terms of finished product is 500ppm) is added in kneader, stirs 50min After further decrease speed (20rpm) stirring 20min discharging；It is carried out using method same as Example 1 once sintered (oxygen-enriched Air oxygen content 95.0%, flow 280Nm³/ h), 5 burn tinctuer of embodiment is calculated as 33.8% with raw material；

(2) step (1) obtained product is crushed (material 1) with cyclone vortex pulverizer, smashed material Respectively by the 1st grade of grading wheel (linear velocity 25m/s) and cyclone separator, the 2nd grade of pulverizer, (linear velocity is grading wheel 28m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 40m/s) and cyclone separator and pulsating collection Device obtains varigrained material through cyclone separator and pulse dust collector.Wet process is carried out to material using Malvern ParticleSizer Granularity Detection, the granularity for obtaining 4 kinds of materials is as shown in table 3, and above-mentioned material is obtained to classification product after evenly mixing；

(3) the obtained classification product of step (2) is rejoined into 400L kneader, opens stirring, 0.054kg is added Nano-titanium dioxide (D_v50: 0.3 μm, technical grade, purity 98.0%, content Ti content in terms of finished product is 300ppm), and mix equal It is even to obtain semi-finished product；

(4) double sintering (oxygen-enriched air oxygen content 95.0%, flow are carried out using method same as Example 1 350Nm³/ h), burn tinctuer is calculated as 0.7% with raw material；Then double sintering material is crushed with cyclone vortex pulverizer, powder Material after broken passes through the 1st grade of grading wheel (linear velocity 30m/s) and cyclone separator, the 2nd grade of pulverizer, grading wheel respectively (linear velocity 35m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 40m/s) and cyclone separator, with And pulse dust collector, the classification product with certain particle size are respectively obtained through cyclone separator and pulse dust collector, by classification product warp Positive electrode is uniformly mixed to get after grain size analysis again.

It uses dilute hydrochloric acid to clear up and calculate through ICP detection and obtains positive electrode chemical formula as Li_1.02Ni_0.80Co_0.11Mn_0.09 Ti_0.0007Zr_0.0006O₂, magnetisable material (iron (Fe)+nickel (Ni)+chromium (Cr)+zinc (Zn)) about 54ppb.

The preparation of six positive electrode of embodiment

(1) 200L plough batch mixer is selected, stirring (revolving speed 25rpm) is opened, the nickel cobalt of 100kg is added under agitation Manganese presoma Ni_0.81Co_0.15Al_0.05(OH)₂, (granularity D_v50: 7 μm, substance content 99.5%), then press Li/ (Ni+Co+Al) Molar ratio=1.06 ratios weigh 42.7kg carbonic acid powder for lithium (granularity D_v50: 3.5 μm, substance content 99.8%) be added to it is mixed In conjunction machine, under agitation by 90wt% solid content addition 20.0kg deionized water and tetra- water acetic acid yttrium (work of 0.167kg Industry grade, purity 95.5%, content zirconium content in terms of finished product is 400ppm), it further decreases speed (3-5rpm) after stirring 2h and stirs 6h is mixed to discharge to form the plaster material with certain forming degree；It is carried out using method same as Example 1 once sintered (oxygen-enriched Air oxygen content 99.5%, flow 380Nm³/ h), burn tinctuer is calculated as 33.5% with raw material；

(2) step (1) obtained product is crushed (material 1) with cyclone vortex pulverizer, smashed material Respectively by the 1st grade of grading wheel (linear velocity 25m/s) and cyclone separator, the 2nd grade of pulverizer, (linear velocity is grading wheel 28m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 35m/s) and cyclone separator, the 4th grade of pulverizer, Grading wheel (linear velocity 35m/s) and cyclone separator and pulse dust collector, obtain through cyclone separator and pulse dust collector With varigrained material.Wet process granularity Detection is carried out to material respectively using Malvern ParticleSizer, obtains the grain of 4 kinds of materials Degree obtains classification product after evenly mixing as shown in table 3, by above-mentioned semi-product material；

(3) the obtained classification product of step (2) is rejoined into 200L plough batch mixer, opens stirring, be added 0.068kg hydroxide cobalt (D_v50: 0.3 μm, technical grade, purity 98.0%, content Ti content in terms of finished product is 400ppm), and It is uniformly mixed and obtains semi-finished product；

(4) double sintering (oxygen-enriched air oxygen content 99.5%, flow are carried out using method same as Example 1 400Nm³/ h), burn tinctuer is calculated as 1.2% with raw material；Then double sintering material is crushed using cyclone vortex pulverizer, Smashed material passes through the 1st grade of grading wheel (linear velocity 30m/s) and cyclone separator, the 2nd grade of pulverizer, grading wheel respectively (linear velocity 35m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 35m/s) and cyclone separator, with And pulse dust collector, the classification product with certain particle size are respectively obtained through cyclone separator and pulse dust collector, by classification product point Positive electrode is uniformly mixed to get after analysis again.

It uses dilute hydrochloric acid to clear up and calculate through ICP detection and obtains positive electrode chemical formula as Li_1.02Ni_0.81Co_0.1507Al_0.0 ₅Y_0.0005O₂, magnetisable material (iron (Fe)+nickel (Ni)+chromium (Cr)+zinc (Zn)) about 20ppb.

Wet process granularity Detection is carried out to material respectively using Malvern part particle size analyzer, obtains granularity such as 4 institute of table of 3 kinds of materials Show.

The preparation of seven positive electrode of embodiment

(1) 400L kneader is selected, stirring (revolving speed 30rpm) is opened, before the nickel cobalt aluminium of 100kg is added under agitation Drive body Ni_0.80Co_0.15Al_0.04(OH)₂(granularity D_v50: 8 μm, substance content 99.5%), then press Li/ (Ni+Co+Al) molar ratio =1.05 weigh 42.7kg carbonic acid powder for lithium (granularity D_v50: 3.5 μm, substance content 99.8%) and 0.075kg nanometers of hydrogen Zirconium oxide (ceramic grade, purity 98.0%, content zirconium content in terms of finished product is 400ppm) is added in kneader, stirs 50min After further decrease speed (20rpm) stirring 20min discharging；It is carried out using method same as Example 1 once sintered (oxygen-enriched Air oxygen content 99.8%, flow 300Nm³/ h), burn tinctuer is calculated as 33.8% with raw material；

(2) step (1) obtained product is crushed (material 1) with cyclone vortex pulverizer, smashed material Respectively by the 1st grade of grading wheel (linear velocity 25m/s) and cyclone separator, the 2nd grade of pulverizer, (linear velocity is grading wheel 28m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 33m/s) and cyclone separator and pulsating collection Device respectively obtains the semi-finished product with certain particle size through cyclone separator and pulse dust collector.Using Malvern part particle size analyzer point Other to carry out wet process granularity Detection to material, the granularity for obtaining 4 kinds of materials is as shown in table 3, and above-mentioned material is obtained after evenly mixing It is classified product；

(3) the obtained classification product of step (2) is rejoined into 400L kneader, opens stirring, 0.3kg is added and goes Ionized water and 0.129kg cobalt acetate (chemical pure, purity 98.0%, content Ti content in terms of finished product is 400ppm), and mix Uniformly obtain semi-finished product；

(4) double sintering (oxygen-enriched air oxygen content 99.8%, flow are carried out using method same as Example 1 300Nm³/ h), burn tinctuer is calculated as 0.8% with raw material；Then double sintering material is crushed using cyclone vortex pulverizer (material 1), smashed material pass through the 1st grade of grading wheel (linear velocity 30m/s) and cyclone separator, the 2nd grade of crushing respectively Machine, grading wheel (linear velocity 35m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 30m/s) and whirlwind Separator and pulse dust collector respectively obtain the classification product with certain particle size through cyclone separator and pulse dust collector, will It is uniformly mixed to get positive electrode again after the analysis of classification product.

It uses dilute hydrochloric acid to clear up and calculate through ICP detection and obtains positive electrode chemical formula as Li_1.02Ni_0.80Co_0.1505Al_0.0 ₄Zr_0.0004O₂, magnetisable material (iron (Fe)+nickel (Ni)+chromium (Cr)+zinc (Zn)) about 53ppb.

Wet process granularity Detection is carried out to material respectively using Malvern part particle size analyzer, obtains granularity such as 4 institute of table of 4 kinds of materials Show.

The preparation of eight positive electrode of embodiment

(1) 200L plough batch mixer is selected, stirring (revolving speed 25rpm) is opened, is added 100kg's under agitation Ni_0.80Co_0.11Mn_0.09(OH)₂(granularity D_v50: 10 μm, substance content 99.5%), then by Li/ (Ni+Co+Mn) molar ratio= 1.0 ratios weigh 42.7kg carbonic acid powder for lithium (granularity D_v50: 3.5 μm, substance content 99.8%) it is added in mixing machine, By 90wt% solid content addition 20.0kg deionized water and 0.167kg tetra- water acetic acid yttrium (technical grade, purity under stirring state 95.5%, content zirconium content in terms of finished product is 400ppm), speed (3-5rpm) stirring 6h discharging shape is further decreased after stirring 2h At the plaster material with certain forming degree；Using method same as Example 1 carry out it is once sintered (900 DEG C of * 8h, it is oxygen-enriched Air oxygen content 98.0%, flow 350Nm³/ h), burn tinctuer is calculated as 33.5% with raw material；

(2) step (1) obtained product is crushed (material 1) with cyclone vortex pulverizer, smashed material Respectively by the 1st grade of grading wheel (linear velocity 25m/s) and cyclone separator, the 2nd grade of pulverizer, (linear velocity is grading wheel 28m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 35m/s) and cyclone separator and pulsating collection Device obtains having varigrained material through cyclone separator and pulse dust collector.Using Malvern ParticleSizer respectively to material Wet process granularity Detection is carried out, the granularity for obtaining 3 kinds of materials is as shown in table 3, and above-mentioned semi-product material is divided after evenly mixing Grade product；

(4) double sintering (1000 DEG C of * 8h, oxygen-enriched air oxygen content are carried out using method same as Example 1 98.0%, flow 400Nm³/ h), burn tinctuer is calculated as 1.2% with raw material；Then using cyclone vortex pulverizer to double sintering object Material is crushed (material 1), and smashed material passes through the 1st grade of grading wheel (linear velocity 30m/s) and cyclone separator respectively, 2nd grade of pulverizer, grading wheel (linear velocity 35m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 35m/ S) and cyclone separator and pulse dust collector, respectively obtain through cyclone separator and pulse dust collector with certain particle size Classification product will uniformly be mixed to get positive electrode after the analysis of classification product again.

It uses dilute hydrochloric acid to clear up and calculate through ICP detection and obtains positive electrode chemical formula as Li_1.02Ni_0.80Co_0.1107Mn_0.0 ₉Y_0.0005O₂, magnetisable material (iron (Fe)+nickel (Ni)+chromium (Cr)+zinc (Zn)) about 20ppb.

The preparation of nine positive electrode of embodiment

(1) 400L kneader is selected, stirring (revolving speed 30rpm) is opened, before the nickel cobalt aluminium of 100kg is added under agitation Drive body Ni_0.80Co_0.15Al_0.04(OH)₂(granularity D_v50: 8 μm, substance content 99.5%), then press Li/ (Ni+Co+Al) molar ratio =1.2 weigh 42.7kg carbonic acid powder for lithium (granularity D_v50: 3.5 μm, substance content 99.8%) and 0.075kg nanometers of hydrogen-oxygens Change zirconium (ceramic grade, purity 98.0%, content zirconium content in terms of finished product is 400ppm) to be added in kneader, after stirring 50min Further decrease speed (20rpm) stirring 20min discharging；Once sintered (500 DEG C of * are carried out using method same as Example 1 20h, oxygen-enriched air oxygen content 99.8%, flow 200Nm³/ h), burn tinctuer is calculated as 33.8% with raw material；

(2) step (1) obtained product is crushed (material 1) with cyclone vortex pulverizer, smashed material Respectively by the 1st grade of grading wheel (linear velocity 25m/s) and cyclone separator, the 2nd grade of pulverizer, (linear velocity is grading wheel 28m/s) and cyclone separator, the 2nd grade of pulverizer, grading wheel (linear velocity 33m/s) and cyclone separator and pulsating collection Device respectively obtains the semi-finished product with certain particle size through cyclone separator and pulse dust collector.Using Malvern part particle size analyzer point Other to carry out wet process granularity Detection to material, the granularity for obtaining 4 kinds of materials is as shown in table 3, and above-mentioned material is obtained after evenly mixing It is classified product；

(4) double sintering (500 DEG C of * 20h, oxygen-enriched air oxygen content are carried out using method same as Example 1 99.8%, flow 200Nm³/ h), burn tinctuer is calculated as 0.8% with raw material；Then using cyclone vortex pulverizer to double sintering object Material is crushed (material 1), and smashed material passes through the 1st grade of grading wheel (linear velocity 30m/s) and cyclone separator respectively, 2nd grade of pulverizer, grading wheel (linear velocity 35m/s), 3rd level pulverizer (linear velocity 30m/s), (linear velocity is grading wheel 35m/s) and cyclone separator and pulse dust collector, it respectively obtains through cyclone separator and pulse dust collector with certain grain The classification product of degree will uniformly be mixed to get positive electrode after the analysis of classification product again.

The preparation of ten positive electrode of embodiment

(1) 200L plough batch mixer is selected, stirring (revolving speed 25rpm) is opened, is added 100kg's under agitation Ni_0.80Co_0.11Mn_0.09(OH)₂(granularity D_v50: 10 μm, substance content 99.5%), then by Li/ (Ni+Co+Mn) molar ratio= 1.08 ratios weigh 42.7kg carbonic acid powder for lithium (Dv50:3.5 μm of granularity, substance content 99.8%) and are added in mixing machine, Under agitation by 90wt% solid content addition 20.0kg deionized water and tetra- water acetic acid yttrium of 0.167kg (technical grade, it is pure Degree 95.5%, content zirconium content in terms of finished product is 400ppm), speed (3-5rpm) stirring 6h discharging is further decreased after stirring 2h Form the plaster material with certain forming degree；Once sintered (800 DEG C of * 18h, richness are carried out using method same as Example 1 Oxygen air oxygen content 95.0%, flow 300Nm³/ h), burn tinctuer is calculated as 33.5% with raw material；

(2) step (1) obtained product is crushed (material 1) with cyclone vortex pulverizer, smashed material Respectively by the 1st grade of grading wheel (linear velocity 25m/s) and cyclone separator, the 2nd grade of pulverizer, (linear velocity is grading wheel 28m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 35m/s) and cyclone separator, the 4th grade of pulverizer, Grading wheel (linear velocity 30m/s) and cyclone separator and pulse dust collector, obtain through cyclone separator and pulse dust collector With varigrained material.Wet process granularity Detection is carried out to material respectively using Malvern ParticleSizer, obtains the grain of 4 kinds of materials Degree obtains classification product after evenly mixing as shown in table 3, by above-mentioned semi-product material；

(3) the obtained classification product of step (2) is rejoined into 200L plough batch mixer, opens stirring, be added 0.068kg hydroxide cobalt (Dv50:0.3 μm, technical grade, purity 98.0%, content Ti content in terms of finished product is 400ppm), and It is uniformly mixed and obtains semi-finished product；

(4) double sintering (900 DEG C of * 15h, oxygen-enriched air oxygen content are carried out using method same as Example 1 98.0%, flow 400Nm³/ h), burn tinctuer is calculated as 1.2% with raw material；Then using cyclone vortex pulverizer to double sintering object Material is crushed (material 1), and smashed material passes through the 1st grade of grading wheel (linear velocity 30m/s) and cyclone separator respectively, 2nd grade of pulverizer, grading wheel (linear velocity 35m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 35m/ S) and cyclone separator and pulse dust collector, respectively obtain through cyclone separator and pulse dust collector with certain particle size Classification product will uniformly be mixed to get positive electrode after the analysis of classification product again.

The preparation of 11 positive electrode of embodiment

(1) 200L kneader is selected, the nickel cobalt manganese presoma (Ni of 30kg is first added_0.70Co_0.15Mn_0.15(OH)₂(granularity Dv50:10 μm, substance content 99.5%), stirring (revolving speed 40rpm) is opened, is added remaining 70kg's under agitation Nickel cobalt manganese presoma, then 42.5kg carbonic acid powder for lithium (granularity D is weighed by molar ratio=1.04 Li/ (Ni+Co+Mn)_v50: 3.5 μm, Substance content 99.8%) it is added in kneader, speed (50rpm) stirring 20min discharging is further decreased after stirring 2h；It adopts Once sintered (oxygen-enriched air oxygen content 95.0%, flow 400Nm are carried out with method same as Example 1³/ h), burn tinctuer with Raw material is calculated as 33.8%；

(3) double sintering (oxygen-enriched air oxygen content 95%, flow 400Nm are carried out using method same as Example 1³/ H), burn tinctuer is calculated as 0.3% with raw material；Then (material 1) is crushed to double sintering material using cyclone vortex pulverizer, Smashed material passes through the 1st grade of grading wheel (linear velocity 40m/s) and cyclone separator, the 2nd grade of pulverizer, grading wheel respectively (linear velocity 30m/s) and cyclone separator, 3rd level pulverizer, grading wheel (linear velocity 28m/s) and cyclone separator, with And pulse dust collector, the classification product with certain particle size are respectively obtained through cyclone separator and pulse dust collector, by classification product point Positive electrode is uniformly mixed to get after analysis again.

Use dilute hydrochloric acid clear up and through ICP detection calculate obtain positive electrode chemical formula for Li_1.01Ni_0.70Co_0.15Mn_0.15O₂, magnetisable material (iron (Fe)+nickel (Ni)+chromium (Cr)+zinc (Zn)) about 87ppb.Using Malvern Particle size analyzer carries out wet process granularity Detection to material respectively, and the granularity for obtaining 4 kinds of materials is as shown in table 4.

The preparation of the common positive electrode of comparative example one

(1) 200L plough batch mixer is selected.Stirring (revolving speed 25rpm) is opened, the nickel cobalt of 100kg is added under agitation Manganese presoma (Ni_0.61Co_0.19Mn_0.20(OH)₂(granularity D_v50: 7 μm, substance content 99.5%), then press Li/ (Ni+Co+Mn) Molar ratio=1.01 ratios weigh 46.1kg monohydrate lithium hydroxide powder (granularity D_v50: 25 μm, substance content 99.5%) it is added Into mixing machine, 37.0kg deionized water is added by 80wt% solid content under agitation, adds 1.43kg basic carbonate Cobalt (is added cobalt amount based on finished product and accounts for 7000ppm), and speed (5rpm) stirring 6h is further decreased after stirring 2h and discharges to be formed has The plaster material discharging of certain forming degree；Then using ventilation 24m roller kilns, setting heating zone temperature is 400 DEG C, is passed through oxygen-enriched (oxygen-enriched air oxygen content 45%, flow 400m under air conditions³/ h) charge material into ceramic alms bowl carry out the 1st time sintering, It is sintered 10h, material is cooled to room temperature under the protection of dry nitrogen, weighs the weight of disengaging material, burn tinctuer is calculated as with raw material 34.7%；

(2) step (1) obtained product crush with cyclone vortex pulverizer and be obtained using pulse dust collector Product carries out wet process granularity Detection to product using Malvern ParticleSizer, and the granularity for obtaining product is as shown in table 3；

(3) step (2) obtained product is rejoined into 200L plough batch mixer, opens stirring, and be added 1.43kg basic cobaltous carbonate (based on finished product be added cobalt amount account for 7000ppm) is simultaneously uniformly mixed and obtains semi-finished product；

(4) using ventilation 24m roller kilns.It is 700 DEG C that heating zone temperature, which is arranged, is passed through (oxygen-enriched sky under the conditions of oxygen-enriched air Gas oxygen content 98%, flow 300m³/ h) charge material into ceramic alms bowl carry out the 2nd time sintering, be sintered 10h.By material dry It is cooled to room temperature under dry nitrogen protection, weighs the weight of disengaging material, burn tinctuer is calculated as 1.2% with raw material；With cyclone vortex powder Broken machine crushes double sintering material, and smashed material obtains positive electrode through pulse dust collector.

Wet process granularity Detection is carried out to anode using Malvern ParticleSizer, the granularity for obtaining material is as shown in table 4.

The preparation of the common positive electrode of comparative example two

(1) it selects 200L to merge machine, opens stirring (revolving speed 600rpm), the nickel cobalt manganese of 100kg is added under agitation Presoma (Ni_0.70Co_0.15Mn_0.15(OH)₂(granularity D_v50: 10 μm, substance content 99.5%), then rub by Li/ (Ni+Co+Mn) You weigh 58.6kg oxalic acid powder for lithium (granularity D in ratio=1.06_v50: 4.5 μm, substance content 99.5%) it is added in fusion machine, And 0.27kg yttrium oxide (ceramic grade, granularity D_v50: 0.3 μm, purity 99.0%, content yttrium content in terms of finished product is 200ppm), Speed (50rpm) stirring 20min discharging is further decreased after stirring 2h；It is once burnt using method same as Example 1 Tie (oxygen-enriched air oxygen content 99.8%, flow 300Nm³/ h), burn tinctuer is calculated as 33.8% with raw material；

(2) step (1) obtained product is crushed with cyclone vortex pulverizer, smashed material is received through pulse Dirt device obtains product, carries out wet process granularity Detection to product using Malvern ParticleSizer, the granularity for obtaining product is as shown in table 3；

(3) by step (2) obtained product rejoin 200L fusion machine, open stirring, and be added 0.3kg go from Five water zirconium nitrate of sub- water and 0.12kg (technical grade, purity 98.5%, content zirconium content in terms of finished product is 300ppm), and mix It closes and uniformly obtains semi-finished product；

(4) double sintering (oxygen-enriched air oxygen content 95.0%, flow are carried out using method same as Example 1 300Nm³/ h), burn tinctuer is calculated as 0.9% with raw material；Then double sintering material is crushed using cyclone vortex pulverizer, Smashed material pulse dust collector obtains positive electrode.

Wet process granularity Detection is carried out to anode using Malvern ParticleSizer, the granularity for obtaining positive electrode is as shown in table 4.

The preparation of the common positive electrode of comparative example three

(1) 400L kneader is selected, stirring (revolving speed 40rpm) is opened, before the nickel cobalt manganese of 100kg is added under agitation Drive body (Ni_0.79Co_0.08Mn_0.11(OH)₂(granularity D_v50: 10 μm, substance content 99.5%), then press Li/ (Ni+Co+Mn) mole 48.4kg monohydrate lithium hydroxide powder (granularity D is weighed than=1.05_v50: 15 μm, substance content 99.8%) and 0.125kg Four water acetic acid yttriums (chemical pure, purity 95.5%, content yttrium content in terms of finished product is 300ppm) are added in kneader, stir 1h After further decrease speed (20rpm) stirring 20min discharging；It is carried out using method same as Example 1 once sintered (oxygen-enriched Air oxygen content 65.0%, flow 400Nm³/ h), burn tinctuer is calculated as 33.8% with raw material；

(3) step (2) obtained product is rejoined into 400L kneader, opens stirring, and be added 0.3kg go from Sub- water and 0.096kg cobalt acetate (chemical pure, purity 99.5%, content cobalt content in terms of finished product is 300ppm), and mix equal It is even to obtain semi-finished product；

(4) double sintering (oxygen-enriched air oxygen content 65.0%, flow are carried out using method same as Example 1 400Nm³/ h), burn tinctuer is calculated as 1.3% with raw material；Then double sintering material is crushed using cyclone vortex pulverizer, Smashed material obtains positive electrode through pulse dust collector.

Wet process granularity Detection is carried out to positive electrode using Malvern ParticleSizer, obtains granularity such as 4 institute of table of positive electrode Show.

The preparation of the common positive electrode of comparative example four

(1) 400L kneader is selected, stirring (revolving speed 30rpm) is opened, before the nickel cobalt aluminium of 100kg is added under agitation Drive body Ni_0.80Co_0.15Al_0.04(OH)₂(granularity D_v50: 8 μm, substance content 99.5%), then press Li/ (Ni+Co+Al) molar ratio =1.05 weigh 42.7kg carbonic acid powder for lithium (granularity D_v50: 3.5 μm, substance content 99.8%) and 0.075kg nanometers of hydrogen Zirconium oxide (ceramic grade, purity 98.0%, content zirconium content in terms of finished product is 400ppm) is added in kneader, stirs 50min After further decrease speed (20rpm) stirring 20min discharging；It is carried out using method same as Example 1 once sintered (oxygen-enriched Air oxygen content 99.8%, flow 200Nm³/ h), burn tinctuer is calculated as 33.8% with raw material；

(2) step (1) obtained product is crushed with cyclone vortex pulverizer, smashed material is received through pulse Dirt device obtains product, carries out wet process granularity Detection to product using Malvern part particle size analyzer, obtains granularity such as 3 institute of table of product Show；

(3) step (2) obtained product is rejoined into 400L kneader, opens stirring, 0.3kg deionization is added Water and 0.129kg cobalt acetate (chemical pure, purity 98.0%, content Ti content in terms of finished product is 400ppm), and be uniformly mixed Obtain semi-finished product；

(4) double sintering (oxygen-enriched air oxygen content 99.8%, flow are carried out using method same as Example 1 200Nm³/ h), burn tinctuer is calculated as 0.8% with raw material；Then double sintering material is crushed using cyclone vortex pulverizer, Smashed material obtains positive electrode through pulse dust collector.

Wet process granularity Detection is carried out to positive electrode using Malvern part particle size analyzer, obtains the granularity such as table 4 of positive electrode It is shown.

3 embodiment semi-finished product partition size of table and yield

4 embodiment finished product partition size of table and yield

It can be seen from table 3 and table 4 for semi-finished product, the 1st time and the 2nd time smashed material particular diameter difference is not Greatly, the total accounting of the two is in 70wt% or so.The material obtained in 3rd level is also relatively more, while can by the half-peak breadth result of table 3 See, the half-peak breadth of embodiment is generally small compared with comparative example, while crushing and classification process it is less semi-finished product its half-peak breadths it is larger, table Bright crushing and progressive operation have a certain impact to particle diameter distribution；By table 4 as it can be seen that being then the 2nd crushing and classification to after finished product Obtained material is more (accounting is in 65wt% or so), and the material that the 3rd time and pulse dust arrester obtain is less, and half-peak breadth is equally in Existing above-mentioned rule, the half-peak breadth of finished product are between 0.72 μm~4.2 μm, and showing can by adjusting crushing and clasfficiator collective effect To obtain material similar in the partial size of higher yields, and partial size can be adjusted in biggish amplitude range, while adjustable Peak width is to obtain the more consistent product of particle diameter distribution.The granularity of comparative example and the granularity of presoma are not much different, while dust arrester Material ratio in 4wt% or so, higher than the collecting amount of embodiment 1wt%, thus from this aspect can also obtain using classification receive Collection material is conducive to balance the little particle in material, and the convenient granularity for adjusting shipment product can be needed according to market, together When guarantee product narrow size distribution, to obtain preferable chemical property.

Performance test

1. size distribution

The granularity of embodiment one, embodiment three, comparative example one and the obtained positive electrode of comparative example two is used into wet process Granularity is detected, and particle size distribution figure is as shown in Figure 1.

It will be seen from figure 1 that granularity of the size distribution of comparative example one and comparative example two compared with embodiment one and embodiment three Distribution is obvious wide in range and close with the partial size of presoma, unadjustable.

2. sem test

The positive electrode that above-described embodiment one, comparative example one, embodiment three and comparative example two obtain is scanned respectively Shown in Electronic Speculum SEM test, result such as Fig. 2-1,2-2,2-3 and 2-4.

By Fig. 2-1 and Fig. 2-2 as it can be seen that having biggish area on embodiment one and the obtained positive electrode pattern of comparative example one Not, the granule-morphology of the positive electrode of embodiment one is uniform in size, and a ball particle therein is (0.02-0.5 μm) in the same size, And the primary particle and second particle of the obtained positive electrode of comparative example one are not of uniform size, primary particle growth is in disorder, and There are more small particles materials.

By 2-4, partial size is significantly greater compared with Fig. 2-3, and particle is oval.In nickel cobalt manganese anode material, nickel cobalt manganese The size and consistency of the primary particle of positive electrode have highly important influence, primary particle size to the performance of positive electrode Unanimously, material ball-type degree is good, then the specific capacity of material and platform are high, slurrying viscosity stablization in process, the lithium battery of preparation Gas production is few, and circulation of battery etc. is preferably.

3. button cell result

By above-described embodiment three, embodiment seven, the nickelic tertiary cathode material that comparative example two and comparative example four are prepared Button cell is prepared by the following method, and the corresponding button cell being prepared is respectively button cell 8, button cell 9, button Formula battery 10 and button cell 12.

It weighs 70gN- methyl pyrrole and omits alkanone (NMP) in experiment dispersion cup, open stirring, 5g is added under stiring As Kynoar (PVDF Solef6020) powder of adhesive, 5g conductive carbon black is weighed after waiting adhesives to be completely dissolved again (SP) it is added in above-mentioned solution, after high speed dispersion 60min, takes respectively

Final nickelic tertiary cathode material 90g prepared by embodiment two, embodiment seven, comparative example two and comparative example four is added Into above-mentioned solution, reduction mixing speed discharging is spare after dispersing 1~1.5h.

It takes with a thickness of 16 μm of aluminium foils as collector, the slurry of above-mentioned preparation is spread evenly across on aluminium foil and in drying box Middle drying, baking temperature are 105 DEG C, and positive plate is prepared in baking time 1h.

Electrode film is obtained after the positive plate of preparation is compacted, the compacted density of electrode film active material layer is 3.4g/ cm³, active matter thickness is about 85 μm, and the overall thickness of positive plate is about 100 μm, prepares CR2032 type button cell；It is corresponding negative Electrode is metal lithium sheet (is produced from Tianjin, 99.9%), and electrolyte LBC301 stands 6~10h after button cell production, then makes It is filled enamel electric test equipment with 8, carries out examination with computer.Discharge voltage is 0.05V~2.50V for the first time when test, in charge and discharge process Voltage range be 1.0~2.5V, charge-discharge magnification 0.1C, corresponding current density is 1mA/cm², obtained result is such as Shown in Fig. 3.

As seen from Figure 3, in the normal range, compared with comparative example, the button of embodiment material is electric for the specific capacity of embodiment Testing result platform voltage is slightly higher, while specific capacity is slightly promoted, and reason is that embodiment can be square after multiple fractionation Just the partial size of adjusting product, the access of lithium ion disengaging positive electrode ontology can be reduced slightly in the lesser situation of particle, Be conducive to the transfer of lithium ion in this way, simultaneously because positive electrode granular size is consistent, pattern is close, disengaging step when charge and discharge It cuts down than more consistent, the chemical property for being likewise advantageous to material is promoted.

4. full battery preparation and Performance Evaluation

Embodiment one, embodiment three and embodiment seven and corresponding comparative example one, comparative example two, comparative example four are prepared into As a positive electrode active material, be prepared into capacity respectively by 21700 cylindrical batteries is 4.86Ah left and right moving to the positive electrode powder arrived Power battery, for investigating high voltage cycle and security impact.Applicable 21700 fashioned iron housing battery of winding-structure is wherein assessed, Cell diameter is 21mm, and height is about 70mm, and preparation process is common process.

Anode pole piece is made by preparing slurry, coating and cold pressing, the techniques such as cutting.Effective positive active material in pole piece Content is 97.5%, and pole coating average weight is 0.0260g/cm³, pole coating width is 62mm, and pole piece active material is total Area is 937.4cm², for Al foil substrate with a thickness of 13 μm, pole piece compaction density is calculated as 3.2g/cm with active material³。

Cathode pole piece is coated with, cold pressing, the processes preparation such as cutting by preparing slurry.It is living as cathode using artificial graphite Property substance when, pole piece effective negative electrode active material (artificial graphite) content after preparation is 96.0%, and pole coating weight is 0.0164g/cm², pole coating width is 63.5mm, and the pole piece active material gross area is 1009.65cm², copper foil base material with a thickness of 9 μm, pole piece compaction density is calculated as 1.65g/cm with active material³。

The positive plates of aluminium pole ears, isolation film will be welded with (for the PP/ through nano aluminium oxide coating problems with a thickness of 16 μm PE/PP composite isolated film), winding is prepared into the naked battery core of cylinder in order for the negative electrode tab that is welded with nickel tab etc., and by tab set Enter shell after upper dead ring, using laser welding by nickel tab welding in cylinder bottom, it is reeded naked to be then prepared into tool through curling Battery core cools down fluid injection after drying.And upper CID is welded, PTC and Vent component encapsulates after standing in LIP-10AHB06 type high temperature Chemical conversion machine chemical conversion (formation voltage 0~4.2V, 0.1C charging, 0.2C electric discharge, temperature 45 C ± 2 DEG C), carries out volume test (test Voltage 3.0~4.2V, 0.2C, 0.5C), up-to-standard battery core is selected for subsequent Performance Evaluation.

By it is above-mentioned use embodiment one, embodiment three, embodiment seven, comparative example one, comparative example two, comparative example four make 21700 type cylinder type lithium ion secondary batteries of positive electrode preparation carry out lateral pressure test by UL-1642, first expire lithium battery and fill To 4.2V, open-circuit voltage and internal resistance are tested, then lithium battery is placed in and starts to squeeze battery with certain speed between two pieces of plates Until the upper limit value of pressure sensor reaches 13kN, pressing device is unclamped again, test lithium battery is because of temperature caused by internal short-circuit It rises and other is not as a result, battery is smoldered, on fire and electrolyte leakage, which is considered as, has passed through extruding test.By above-described embodiment and Comparative example is tested to obtain representative result as shown in table 5.

5 embodiment of table and comparative example lithium battery squeeze test result

As can be seen from Table 5, using the present embodiment one, embodiment three, embodiment seven, lithium battery side prepared by comparative example one Can pass through under pressure abuse condition, but lithium battery prepared by comparative example one smoke event occurs in test, comparative example two and There is phenomenon on fire in lithium battery prepared by comparative example four, this is because the security risk of usually lithium battery mostlys come from anode Material and battery charge state, for positive electrode due to being a kind of semiconductor, electric conductivity is poor, either extraneous logical in applied voltage The abjection and insertion of lithium ion are not moment completion behind road, but the lithium richness that there is part is gathered and lithium gradient, and safety is past Toward being caused by the poly- active lithium of richness, if material is in the same size and pattern is identical, there is no potential energy between material granule Difference should can reduce safe probability of happening in this way, to illustrate that the safety of comparative example battery is poor, adopt through the invention The electricity of nickelic tertiary cathode material can be obviously improved with the size distribution that multi-level hierarchical method controls nickelic tertiary cathode material Chemical property consistency and security performance have reached the imagination and purpose of exploitation.

Embodiment two, example IV, embodiment five, embodiment six, embodiment eight to embodiment 11 have similar skill Art effect.

The above is only the preferred embodiment that the present invention is implemented, and not does limitation in any form to the present invention, all The modifications, equivalent substitutions and improvements etc. done within the spirit and principles in the present invention are required to be included in protection of the invention Within the scope of.

Claims

1. a kind of nickelic tertiary cathode material, which is characterized in that chemical structural formula Li_xNi_aCo_bM_cR_dO₂, wherein R is doping Element, 0.95 < x <, 1.15,0.61 < a <, 0.85,0 < b < 0.2,0 < c < 0.2,0.98≤a+b+c≤1.00,0≤d < 0.1, M is selected from one of Mn or Al, preferably 0.0008≤d≤0.006.

2. positive electrode according to claim 1, wherein the D of the positive electrode_v50=2-18 μm, it is preferred that D_v50= 2.5-10.1μm；Preferably, size distribution half-peak breadth is 0.5 μm -4.2 μm, preferably 0.72-4.06 μm.

3. positive electrode according to claim 1 or 2, wherein the positive electrode is secondary spherical structure.

4. positive electrode according to claim 1-3, wherein the R element is selected from titanium, yttrium, zirconium, cobalt and lanthanum One or more of.

5. the preparation method of any one of the claim 1-4 positive electrode, wherein the preparation method includes following step:

(1) in molar ratio it is that 1.0-1.2:1:0.00-0.003 is mixed by lithium source, nickel cobalt M presoma and the source R, then carries out the It is once sintered；

(4) the obtained semi-finished product of step (3) are carried out second to be sintered, then carries out crushing and classification processing, mixing obtains institute State positive electrode.

6. preparation method according to claim 5, wherein in step (1), the lithium source is selected from lithium carbonate, Dan Shui One or more of lithium hydroxide, lithium acetate and lithium oxalate.

7. preparation method according to claim 5 or 6, wherein in step (1), the source R is the change containing R element Object is closed, the compound is selected from hydroxide, oxide or its solubility salt.

8. according to the described in any item preparation methods of claim 5-7, wherein in step (1), the nickel cobalt M presoma is Nickel cobalt manganese presoma or nickel cobalt aluminium presoma.

9. according to the described in any item preparation methods of claim 5-8, wherein in step (1), the temperature of the first sintering Degree is 400-900 DEG C, preferably 400 DEG C.

10. according to the described in any item preparation methods of claim 5-9, wherein in step (1), the first sintering Time is 8-20 hours, preferably 10 hours.

11. according to the described in any item preparation methods of claim 5-10, wherein in step (4), second of sintering Temperature is 500-1000 DEG C, and preferably 700-1000 DEG C, be more preferably 700 DEG C.

12. according to the described in any item preparation methods of claim 5-11, wherein in step (4), second of sintering Time is 8-20 hours, preferably 10 hours.

13. according to the described in any item preparation methods of claim 5-12, wherein the first sintering and for the second time sintering Atmosphere is oxygen-enriched air, and oxygen volume content is 40-99.8%, it is preferred that the air mass flow of the first sintering is 200- 400Nm³The air mass flow of/h, second of sintering are 200-500Nm³/h。

14. according to the described in any item preparation methods of claim 5-14, wherein in step (2) and step (4), the powder The broken concatenation type crushing and classification for being classified as 2 times or more.

15. a kind of anode material for lithium-ion batteries is prepared by the described in any item preparation methods of claim 5-14.

16. a kind of lithium ion battery, it includes described in the described in any item positive electrodes of claim 1-4 or claim 15 Positive electrode.

17. positive electrode or claim 16 described in the described in any item positive electrodes of claim 1-4 or claim 15 Application of the lithium ion battery in mobile digital product (3C), electric car (xEV) or the field energy storage (ESS).