CN109455772A - A kind of preparation method of the lithium ion battery presoma of modification, positive electrode and the presoma and positive electrode - Google Patents

A kind of preparation method of the lithium ion battery presoma of modification, positive electrode and the presoma and positive electrode Download PDF

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CN109455772A
CN109455772A CN201711456555.7A CN201711456555A CN109455772A CN 109455772 A CN109455772 A CN 109455772A CN 201711456555 A CN201711456555 A CN 201711456555A CN 109455772 A CN109455772 A CN 109455772A
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salt
presoma
ion battery
lithium ion
reaction
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CN109455772B (en
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宋顺林
张朋立
郑长春
刘亚飞
陈彦彬
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Beijing Easpring Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides the preparation method of a kind of lithium ion battery presoma, positive electrode and the presoma and positive electrode.The presoma is spherical metal hydroxide, molecular formula NixCoyMzM1 aM2 d(OH)2+e, M is Mn or Al, M1It is greater than 0.76 element, M for ionic radius2It is less than or equal to 0.76 element for ionic radius, wherein 0.55≤x≤0.96,0.02≤y≤0.25,0.01≤z≤0.25,0.0005≤a≤0.005,0.0002≤d≤0.005, x+y+z+a+d=1,0≤e≤0.06；M1Element is uniformly distributed in material bodies phase, M2Element is uniformly distributed in material surface；The precursor construction is novel, and manufactured positive electrode has superior capacity, circulation and security performance.Preparation method is easy stability contorting, at low cost, is suitable for large-scale industrial production.

Description

A kind of lithium ion battery presoma of modification, positive electrode and the presoma and just The preparation method of pole material
Technical field
The present invention relates to a kind of lithium ion battery presomas of modification, positive electrode and preparation method thereof, specifically Be related to a kind of spherical metal hydroxide precursor not only adulterated but also coated, by the positive electrode of the precursor preparation and this before The preparation method for driving body and positive electrode, belongs to technical field of lithium ion.
Background technique
Lithium ion battery is the current most common secondary cell, have big energy density, good cycle, self discharge it is small, Outstanding advantages of memory-less effect, is widely used in various portable power tools, mobile phone, laptop, plate electricity Brain, video camera, weaponry etc., in electric car and all kinds of energy storage fields also large-scale use.
In recent years, new-energy automobile industry development in China's is swift and violent.2016, new-energy automobile sales volume reach 500,000 with On.Power battery is most important as the heart of electric car, and core starting materials of the positive electrode as power battery, directly Influence the performances such as energy density, safety, the cycle life of power battery.Common anode material for lithium-ion batteries mainly has cobalt Sour lithium, LiMn2O4, LiFePO4, lithium nickelate and cobalt nickel lithium manganate ternary material.Wherein, ternary material has specific capacity height, follows Ring better performances, the advantages that cost of material is lower, but with the raising of nickel content, while specific capacity increases, cycle performance and Security performance also deteriorates accordingly.Therefore, although the specific capacity of the especially nickelic ternary material of ternary material is high, practical application When there are still many defects, such as security performance, cycle performance, storge quality and high rate during charging-discharging.
Ternary cathode material of lithium ion battery, which mainly first passes through, at present is prepared into spherical or spherical presoma, then will Presoma and lithium source mixed sintering are made.For example, before Chinese patent CN102916177B discloses a kind of nickel cobalt manganese hydroxide Body and preparation method thereof is driven, is first co-precipitated nickel cobalt manganese mixing salt solution and sodium hydroxide solution, ammonia spirit in patent Reaction controls pH and ammonia dosage in reaction process, while being added to the additive for adjusting granule-morphology, has obtained ball The nickel cobalt manganese hydroxide precursor of shape structure.Chinese patent CN103400973B discloses a kind of nickel cobalt lithium aluminate and its forerunner Aluminium salt and complexing agent are first carried out complex reaction in patent and form stable aluminium complex by the preparation method of body, then with nickel cobalt salt Solution injects reaction kettle simultaneously and carries out coprecipitation reaction, prepares spherical nickel cobalt lithium aluminate presoma, then roasts with lithium source Synthesizing spherical nickel cobalt aluminic acid lithium material.
Although the uniform spherical anode material presoma of component can be made in the above-mentioned published patent, not to presoma Microelement doping and cladding are carried out, while the structure of microelement existence form and material is not designed and is controlled, from And it is unfavorable for the performance of positive electrode performance.
Summary of the invention
For above-mentioned problems of the prior art, the present invention is intended to provide a kind of spherical metal hydroxide forerunner Body can improve the capacity, cycle performance and peace of positive electrode by the promotion of the design and technology that form to material Full performance etc..
The present invention also provides the preparation method of above-mentioned metal hydroxides presoma and positive electrode, simple process, processes It is easy stability contorting, production cost is low, is suitable for large-scale industrial production.
Technical scheme is as follows:
Lithium ion battery presoma provided by the invention, is spherical metal hydroxide, and chemical molecular formula is NixCoyMzM1 aM2 d(OH)2+e, M is Mn or Al, M1For ionic radius greater than 0.76 Elements C a, Sr, Ba, Zr, Y, La, Ce, One or more of Sm, Er, M2For ionic radius less than or equal to 0.76 element M g, Ti, Nb, Ta, Mo, W, Mn, Fe, Zn, One or more of Al, wherein 0.55≤x≤0.96,0.02≤y≤0.25,0.01≤z≤0.25,0.0005≤a≤ 0.005,0.0002≤d≤0.005, x+y+z+a+d=1,0≤e≤0.06；M in the presoma1Element is uniformly distributed in Material bodies phase, M2Element is uniformly distributed in material surface.
In this presoma and the source Li sintering process, M1Element can be uniformly distributed in positive electrode body phase, due to its from Sub- radius is larger, is capable of the space structure of effective backing material, improves the structural stability of material, and be conducive to lithium ion Insertion and abjection；And it is uniformly distributed in the M on persursor material surface2Element during the sintering process can since ionic radius is smaller It is enough to a degree of diffusion is carried out inside particle, certain gradient-structure is formed on the surface layer of positive electrode, thus in stabilization While material surface activity, biggish inert layer not will form to influence the capacity of material and play.The invention had both solved just The poor problem of the cycle performance and security performance of pole material also avoids material surface and forms inert layer, reduces final products Capacity.The doped chemical distributed architecture of presoma of the invention can realize positive electrode for the demand of height ratio capacity, while energy Enough meet requirement of the positive electrode for cycle performance and security performance.
Further, the average particle size of the lithium ion battery presoma is 3~19 μm, and the average particle size refers to grain Diameter percentile reaches partial size corresponding when 50%, can specifically adjust according to actual demand.
The present invention also provides the preparation methods of above-mentioned lithium ion battery presoma, comprising the following steps:
(1) nickel salt, cobalt salt, manganese salt are configured to salting liquid；M will be contained1Compound be added to the water certain density M be made1 Feed liquid；M will be contained2Compound be added to the water certain density M be made2Feed liquid；It is 2~10mol/L's that alkali, which is dissolved into concentration, Aqueous slkali；Complexing agent is dissolved into the enveloping agent solution that concentration is 2~13mol/L.
(2) by salting liquid, the M in step (1)1Cocurrent is added in reaction kettle together for feed liquid, aqueous slkali, enveloping agent solution It is reacted, process is kept stirring invariablenes turning speed, while controlling reaction pH is 10.5~12.5, and reaction temperature is 40~70 DEG C, In reaction system complexing agent concentration control be 1g/L~12g/L, when reaction complete, stop feed liquor, keep reaction solution temperature, Speed of agitator is constant, continues 5~20min of stirring.
(3) M of step (1) is added into reaction kettle according to certain flow velocity2Feed liquid and aqueous slkali adjust reaction solution pH and exist Between 10.5~12.5, reaction temperature is 40~70 DEG C, M2Feed liquid continues 10~60min of stirring after adding, both mixed M1It wraps again M2Hydroxide precursor slurry.
(4) it after being separated by solid-liquid separation, washed by the hydroxide precursor slurry in step (3), being dried, sieve, obtains Spherical hydroxide precursor material NixCoyMzM1 aM2 d(OH)2+e。
In above-mentioned preparation method, the preparation method of salting liquid described in step (1) be by nickel salt, cobalt salt, manganese salt by mole The mixing salt solution that concentration is 1~3mol/L is dissolved into than x:y:z；Or x:y is dissolved into concentration and is in molar ratio by nickel salt, cobalt salt The nickel cobalt salting liquid of 1~3mol/L, aluminium salt be mixed in a certain ratio with alkali be configured to concentration be 0.1~0.5mol/L aluminium salt it is molten Liquid, wherein the molar ratio of the aluminium ion and alkali of aluminium salt and alkali mixed preparing aluminum solutions is 1:5~1:10.
In above-mentioned preparation method, the nickel salt is one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate； The cobalt salt is one or more of cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt acetate；The manganese salt is manganese sulfate, chlorination One of manganese, manganese nitrate, manganese acetate or in which several；The aluminium salt is aluminum sulfate, in aluminum nitrate, aluminium chloride, aluminium acetate One or more；The M1Compound be M1Soluble salt, oxide nonmetallic powder, hydroxide nano powder, hydroxyl oxidation One of object nano powder, colloidal sol or in which several；The M2Compound be M2Soluble salt, oxide nonmetallic powder, hydrogen-oxygen One or more of compound nano powder, oxyhydroxide nano powder, colloidal sol；The alkali is sodium hydroxide, potassium hydroxide, hydrogen One or more of lithia；The complexing agent is salicylic acid, ammonium sulfate, ammonium chloride, ammonium hydroxide, sulfosalicylic acid, second two One or more of amine tetraacethyl.
Anode material for lithium ion battery provided by the invention, has above-mentioned presoma, and chemical molecular formula is LiNixCoyMzM1 aM2 dO2, M is Mn or Al, M1For ionic radius greater than 0.76 Elements C a, Sr, Ba, Zr, Y, La, Ce, Sm, One or more of Er, M2It is less than or equal to 0.76 element M g, Ti, Nb, Ta, Mo, W, Mn, Fe, Zn, Al for ionic radius One or more of, wherein 0.55≤x≤0.96,0.02≤y≤0.25,0.01≤z≤0.25,0.0005≤a≤ 0.005,0.0002≤d≤0.005, x+y+z+a+d=1.
The present invention also provides the preparation methods of above-mentioned anode material for lithium ion battery, comprising the following steps: will be above-mentioned Presoma mix, be sintered with lithium source, is broken, the anode material for lithium ion battery is made in final sizing LiNixCoyMzM1 aM2 dO2。
In above-mentioned preparation method, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium nitrate.
Compared with prior art, the present invention has an advantage that
(1) element that persursor material of the present invention has ionic radius big is uniformly distributed in inside material granule and ionic radius is small Element be uniformly distributed in the structure of material surface, make made of positive electrode structure it is more stable, doped chemical in body phase Ionic radius it is big, can effective backing material space structure, be conducive to the insertion and abjection of lithium ion；Surface doping member The ionic radius of element is small, and doped chemical makes surface layer form certain gradient-structure, make to spreading inside particle during the sintering process The electrode reaction reduction that particle surface occurs, while not will form biggish inert layer and being played to influence the capacity of material, in turn Realize requirement of the positive electrode for height ratio capacity, cycle performance and security performance.
(2) preparation method of the invention can be realized the big element of ionic radius and be uniformly distributed in positive electrode particle Portion, the small element of ionic radius form certain gradient-structure on the surface layer of positive electrode, and it is logical to solve big ionic radius element It crosses and is blended into presoma surface, the problem that effectively can not be uniformly diffused into inside positive electrode during the sintering process；In addition, ion The small element of radius acts only on the surface layer of positive electrode, reduces the content of the inert element of material internal, is conducive to anode The performance of material capacity.The simple process of entire preparation method, process are easy to control, and are suitble to large-scale industrial production.
Detailed description of the invention
Fig. 1 is 2000 times of scanning electron microscope (SEM) figures of the made presoma of the embodiment of the present invention 1.
Fig. 2 is 5000 times of scanning electron microscope (SEM) figures of particle section of the made presoma of the embodiment of the present invention 1.
Fig. 3 is 3000 times of scanning electron microscope (SEM) figures of the made positive electrode of the embodiment of the present invention 1.
Fig. 4 is the XRD figure of the made positive electrode of the embodiment of the present invention 1 and comparative example 1.
Fig. 5 is the made positive electrode of the embodiment of the present invention 1 and button cell under the 3.0-4.5V voltage range of comparative example 1 Normal temperature circulation curve graph.
Fig. 6 is the made positive electrode of the embodiment of the present invention 1 and button cell under the 3.0-4.3V voltage range of comparative example 1 45 DEG C of high temperature circulation curve graphs.
Specific embodiment
It will be helpful to understand the present invention by following examples and drawings, but do not limit the contents of the present invention.
Comparative example 1
The salt-mixture for dissolving to obtain 2mol/L according to the ratio of metal molar ratio 82:12:6 for nickel sulfate, cobaltous sulfate, manganese sulfate is molten Liquid；Sodium hydroxide is dissolved into the aqueous slkali that concentration is 6mol/L；The enveloping agent solution for being 5mol/L at concentration by ammonia solvent.
By 20L mixing salt solution, cocurrent is added in reaction kettle and reacts together with aqueous slkali, enveloping agent solution, process It is constant to be kept stirring revolving speed 400rpm, at the same control mixing salt solution feed liquor flow be 400mL/h, reaction pH be 11.9~ 12.1, reaction temperature is 50 DEG C, and the concentration control of ammonia is 8~10g/L in reaction system, when reaction completion, keeps reaction solution Temperature, speed of agitator are constant, continue to stir 10min, are then separated by solid-liquid separation obtained nickel cobalt manganese hydroxide slurry, wash It washs, is sieved after 115 DEG C of drying 5h of filter cake, obtain spherical hydroxide precursor material Ni0.82Co0.12Mn0.06(OH)2, average grain Spend D50It is 10.2 μm.
The spherical nickel cobalt manganese hydroxide materials are mixed with lithium hydroxide, in oxygen atmosphere, 800 DEG C of sintering 10h, warp Broken, screening is crossed, obtains anode material for lithium ion battery nickle cobalt lithium manganate, chemical molecular formula is LiNi0.82Co0.12Mn0.06O2。
Embodiment 1
The salt-mixture for dissolving to obtain 2mol/L according to the ratio of metal molar ratio 82:12:6 for nickel sulfate, cobaltous sulfate, manganese sulfate is molten Liquid, is dissolved into the calcium nitrate solution that concentration is 0.1mol/L for calcium nitrate, and aluminum nitrate is dissolved into the nitre that concentration is 0.5mol/L Sour aluminum solutions；Sodium hydroxide is dissolved into the aqueous slkali that concentration is 6mol/L；The complexing for being 5mol/L at concentration by ammonia solvent Agent solution.
By 20L mixing salt solution together with calcium nitrate solution, aqueous slkali, enveloping agent solution cocurrent be added in reaction kettle into Row reaction, it is constant that process is kept stirring revolving speed 500rpm, while controlling mixing salt solution feed liquor flow is 400mL/h, calcium nitrate Solution feed liquor flow is 16mL/h, and reaction pH is 11.9~12.1, and reaction temperature is 50 DEG C, the concentration control of ammonia in reaction system It keeps the temperature of reaction solution, speed of agitator constant when reaction completion for 8~10g/L, continues to stir 10min.
160mL aluminum nitrate solution is added according to the flow velocity of 160mL/h into reaction kettle, while aqueous slkali is added and adjusts instead Answer pH between 11.9~12.1, reaction temperature is 50 DEG C, and aluminum nitrate solution continues to stir 30min after adding, and is both mixed Ca The nickel cobalt manganese hydroxide precursor slurry of Al is wrapped again.Then obtained hydroxide slurry is separated by solid-liquid separation, washed, filtered It is sieved after 115 DEG C of drying 5h of cake, obtains spherical hydroxide precursor material Ni0.8167Co0.1195Mn0.0598Ca0.002Al0.002 (OH)2.002, mean particle size D50It is 10.4 μm.
The presoma is mixed with lithium hydroxide, in oxygen atmosphere, 800 DEG C of sintering 10h are obtained by broken, screening Lithium ion battery spherical anode material LiNi0.8167Co0.1195Mn0.0598Ca0.002Al0.002O2。
1 gained persursor material of embodiment is the spheric granules of regular shape as can see from Figure 1.Inside spheric granules Structure is radial oriented growth, and particle denser from inside to outside, as shown in Figure 2.Made of high temperature sintering Positive electrode maintains the spherical morphology of presoma, without adhesion between particle, as shown in Figure 3.
Embodiment 1 and 1 products obtained therefrom XRD of comparative example are linear sharp keen as can see from Figure 4, and two curve comparisons have no Other miscellaneous peaks exist, and show that the crystal of embodiment 1 and 1 gained positive electrode of comparative example is typical α-NaFeO2Structure, Its crystal structure does not change because of the doping vario-property of microelement, but embodiment 1 and 1 gained positive electrode of comparative example spread out Penetrate peak intensity I(003)/I(104)Respectively 1.45 and 1.26, show that the positive electrode crystallization degree of embodiment 1 is higher, crystal structure It is more perfect.
2032 button cells are made in embodiment 1 and 1 gained positive electrode of comparative example, in 3.0-4.5V voltage range, Capacity retention ratio is respectively 92.7% and 91.0% after lower 80 circulations of room temperature 1C charge and discharge, as shown in Figure 5；In 3.0-4.3V electricity It presses in range, capacity retention ratio is respectively 91.1% and 85.8% after lower 80 circulations of 45 DEG C of charge and discharge of 1C@, as shown in Figure 6.On Stating test data can be seen that positive electrode in embodiment 1 compared with the positive electrode in comparative example 1, and room temperature and high temperature follow Ring performance is obviously more excellent.
Embodiment 2
Nickel nitrate, cobalt nitrate are dissolved to obtain the mixing salt solution of 1mol/L according to the ratio of metal molar ratio 88:9；By nitric acid Aluminium and sodium hydroxide obtain the aluminum solutions of aluminium ion concentration 0.3mol/L according to molar ratio 1:5 mixed preparing；Zirconium nitrate is dissolved The zirconium nitrate solution for being 0.05mol/L at concentration；Cerous nitrate is dissolved into the cerous nitrate solution that concentration is 0.05mol/L；By sulphur Sour magnesium is dissolved into the Adlerika that concentration is 0.25mol/L；Sodium hydroxide is dissolved into the aqueous slkali that concentration is 4mol/L；It will The enveloping agent solution that ammonia solvent is 3mol/L at concentration.
Together with aluminum solutions, zirconium nitrate solution, cerous nitrate solution, aqueous slkali, enveloping agent solution simultaneously by 20L mixing salt solution Stream, which is added in reaction kettle, to be reacted, and it is constant that process is kept stirring revolving speed 600rpm, while controlling mixing salt solution feed liquor stream Amount be 400mL/h, aluminum solutions feed liquor flow be 41mL/h, zirconium nitrate solution feed liquor flow be 12.5mL/h, cerous nitrate solution into Flow quantity is 12.5mL/h, and reaction pH is 12.2~12.4, and reaction temperature is 55 DEG C, and the concentration control of ammonia is 9 in reaction system ~11g/L keeps the temperature of reaction solution, speed of agitator constant when reaction completion, continues to stir 15min.
125mL Adlerika is added according to the flow velocity of 80mL/h into reaction kettle, while aqueous slkali is added and adjusts instead Answer pH between 12.2~12.4, reaction temperature be 55 DEG C, Adlerika continue after adding stir 20min, both mixed Zr, Ce wraps the nickel cobalt aluminium hydroxide precursor slurry of Mg again.Then obtained hydroxide slurry is separated by solid-liquid separation, washed, It is sieved after 120 DEG C of drying 5h of filter cake, obtains spherical hydroxide precursor material Ni0.8762Co0.0896Al0.0297Zr0.0015Ce0.0015Mg0.0015(OH)2.036, mean particle size D50It is 8.6 μm.
The presoma is mixed with lithium hydroxide, in oxygen atmosphere, 750 DEG C of sintering 8h are obtained by broken, screening Lithium ion battery spherical anode material LiNi0.8762Co0.0896Al0.0297Zr0.0015Ce0.0015Mg0.0015O2。
Embodiment 3
Nickel sulfate, cobalt chloride, manganese chloride are dissolved to obtain the mixing of 2.5mol/L according to the ratio of metal molar ratio 60:20:20 Salting liquid；Lanthanum nitrate is dissolved into the lanthanum nitrate hexahydrate that concentration is 0.1mol/L；By TiO2Nano powder is configured to concentration The TiO of 0.2mol/L2Suspension；Sodium hydroxide is dissolved into the aqueous slkali that concentration is 10mol/L；It is at concentration by ammonia solvent The enveloping agent solution of 12mol/L.
By 20L mixing salt solution together with lanthanum nitrate hexahydrate, aqueous slkali, enveloping agent solution cocurrent be added in reaction kettle into Row reaction, it is constant that process is kept stirring revolving speed 650rpm, while controlling mixing salt solution feed liquor flow is 200mL/h, lanthanum nitrate Solution feed liquor flow is 10mL/h, and reaction pH is 11.2~11.4, and reaction temperature is 60 DEG C, the concentration control of ammonia in reaction system It keeps the temperature of reaction solution, speed of agitator constant when reaction completion for 6~8g/L, continues to stir 5min.
By 150mLTiO2Suspension is added according to the flow velocity of 75mL/h into reaction kettle, while aqueous slkali is added and adjusts instead Answer pH between 11.2~11.4, reaction temperature is 60 DEG C, TiO2Suspension continues to stir 30min after adding, and is both mixed La The nickel cobalt manganese hydroxide precursor slurry of Ti is wrapped again.Then obtained hydroxide slurry is separated by solid-liquid separation, washed, filtered It is sieved after 130 DEG C of drying 3h of cake, obtains spherical hydroxide precursor material Ni0.5984Co0.1995Mn0.1995La0.002Ti0.0006 (OH)2.003, mean particle size D50It is 14.8 μm.
The presoma is mixed with lithium carbonate, in air atmosphere, 870 DEG C of sintering 13h obtain lithium by broken, screening Ion battery spherical anode material LiNi0.5984Co0.1995Mn0.1995La0.002Ti0.0006O2。
Embodiment 4
Nickel acetate, cobalt acetate, manganese acetate are dissolved to obtain the mixing of 1.5mol/L according to the ratio of metal molar ratio 65:20:15 Salting liquid；Cerous acetate is dissolved into the cerous acetate solution that concentration is 0.05mol/L；It is 0.2mol/L that ammonium tungstate, which is dissolved into concentration, Ammonium tungstate solution；Niobium oxalate is dissolved into the niobium oxalate solution that concentration is 0.2mol/L；Sodium hydroxide, which is dissolved into concentration, is The aqueous slkali of 8mol/L；The enveloping agent solution for being 8mol/L at concentration by ammonia solvent.
By 20L mixing salt solution together with cerous acetate solution, aqueous slkali, enveloping agent solution cocurrent be added in reaction kettle into Row reaction, it is constant that process is kept stirring revolving speed 700rpm, while controlling mixing salt solution feed liquor flow is 200mL/h, cerous acetate Solution feed liquor flow is 20mL/h, and reaction pH is 11.4~11.6, and reaction temperature is 65 DEG C, the concentration control of ammonia in reaction system It keeps the temperature of reaction solution, speed of agitator constant when reaction completion for 5~7g/L, continues to stir 10min.
By 108mL ammonium tungstate solution and 92mL niobium oxalate solution respectively according to the flow velocity of 27mL/h and 23mL/h to reaction kettle Middle addition, while aqueous slkali is added and adjusts reaction pH between 11.4~11.6, reaction temperature is 65 DEG C, ammonium tungstate solution and grass Sour niobium solution continues to stir 15min after adding, and had not only been mixed Ce but also had wrapped the nickel cobalt manganese hydroxide precursor slurry of W, Nb.Then Obtained hydroxide slurry is separated by solid-liquid separation, is washed, is sieved after 120 DEG C of drying 4h of filter cake, obtains spherical hydroxide Persursor material Ni0.647Co0.1991Mn0.1493Ce0.0033W0.0007Nb0.0006(OH)2.01, mean particle size D50It is 8.7 μm.
The presoma is mixed with lithium hydroxide, in air atmosphere, 840 DEG C of sintering 10h are obtained by broken, screening Lithium ion battery spherical anode material LiNi0.647Co0.1991Mn0.1493Ce0.0033W0.0007Nb0.0006O2。
Embodiment 5
Nickel sulfate, cobalt chloride are dissolved to obtain the mixing salt solution of 2mol/L according to the ratio of metal molar ratio 92:4；By nitric acid Aluminium and potassium hydroxide obtain the aluminum solutions of aluminium ion concentration 0.4mol/L according to molar ratio 1:8 mixed preparing；Strontium nitrate is dissolved The strontium nitrate solution for being 0.05mol/L at concentration；Ammonium paramolybdate is dissolved into the molybdenum ammonium solution that molybdenum concentration is 0.3mol/L； Sodium hydroxide and lithium hydroxide are dissolved into the aqueous slkali that concentration is 5mol/L according to the ratio of molar ratio 20:1；By sulfosalisylic It is 2mol/L solution collectively as enveloping agent solution that acid and ammonium chloride are dissolved into concentration respectively.
By 20L mixing salt solution together with strontium nitrate solution, aqueous slkali, enveloping agent solution cocurrent be added in reaction kettle into Row reaction, it is constant that process is kept stirring revolving speed 600rpm, while controlling mixing salt solution feed liquor flow is 200mL/h, aluminum solutions Feed liquor flow is 42mL/h, and strontium nitrate solution feed liquor flow is 10mL/h, and reaction pH is 12.2~12.4, reaction temperature 55 DEG C, the concentration control of ammonia is 3~5g/L in reaction system, when reaction completion, keep the temperature of reaction solution, speed of agitator constant, Continue to stir 15min.
300mL molybdenum ammonium solution is added according to the flow velocity of 50mL/h into reaction kettle, while aqueous slkali adjusting is added PH is reacted between 12.2~12.4, and reaction temperature is 55 DEG C, and molybdenum ammonium solution continues to stir 20min after adding, and is obtained both Mix the nickel cobalt aluminium hydroxide precursor slurry that Sr wraps Mo again.Then obtained hydroxide slurry is separated by solid-liquid separation, washed It washs, is sieved after 120 DEG C of drying 4h of filter cake, obtain spherical hydroxide precursor Ni0.9166Co0.0399Al0.0402Sr0.0012Mo0.0022 (OH)2.045, mean particle size D50It is 7.5 μm.
The presoma is mixed with lithium hydroxide, in oxygen atmosphere, 720 DEG C of sintering 6h are obtained by broken, screening Lithium ion battery spherical anode material LiNi0.9166Co0.0399Al0.0402Sr0.0012Mo0.0022O2。
Embodiment 6
Nickel nitrate, cobalt nitrate, manganese nitrate are dissolved to obtain the salt-mixture of 1.0mol/L according to the ratio of metal molar ratio 95:2:3 Solution；Yttrium nitrate is dissolved into the yttrium nitrate solution that concentration is 0.07mol/L；It is 0.07mol/L that lanthanum chloride, which is dissolved into concentration, Lanthanum chloride solution；Aluminum nitrate is dissolved into the aluminum nitrate solution that concentration is 0.2mol/L；Zinc sulfate, which is dissolved into concentration, is The solution of zinc sulfate of 0.2mol/L；Sodium hydroxide is dissolved into the aqueous slkali that concentration is 4mol/L；Ammonium sulfate is dissolved into concentration For the enveloping agent solution of 2mol/L.
By 20L mixing salt solution, cocurrent is added together with yttrium nitrate solution, lanthanum chloride solution, aqueous slkali, enveloping agent solution It is reacted into reaction kettle, it is constant that process is kept stirring revolving speed 500rpm, while controlling mixing salt solution feed liquor flow and being 300mL/h, yttrium nitrate solution feed liquor flow be 10mL/h, lanthanum chloride solution feed liquor flow be 10mL/h, reaction pH be 12.3~ 12.5, reaction temperature is 50 DEG C, and the concentration control of ammonia is 10~12g/L in reaction system, when reaction completion, keeps reaction solution Temperature, speed of agitator are constant, continue to stir 20min.
250mL aluminum nitrate solution and 250mL solution of zinc sulfate are added according to the flow velocity of 50mL/h into reaction kettle respectively, Aqueous slkali is added simultaneously and adjusts reaction pH between 12.3~12.5, reaction temperature is 50 DEG C, and aluminum nitrate solution and zinc sulfate are molten Liquid continues to stir 30min after adding, and had not only been mixed Y, La but also had wrapped the nickel cobalt manganese hydroxide precursor slurry of Al, Zn.Then will Obtained hydroxide slurry is separated by solid-liquid separation, is washed, and is sieved after 120 DEG C of drying 4h of filter cake, before obtaining spherical hydroxide Drive body Ni0.9411Co0.0198Mn0.0297Y0.0023La0.0023Al 0.0024Zn0.0024(OH)2.007, mean particle size D50It is 9.3 μm.
The presoma is mixed with lithium hydroxide, in oxygen atmosphere, 720 DEG C of sintering 8h are obtained by broken, screening Lithium ion battery spherical anode material LiNi0.9411Co0.0198Mn0.0297Y0.0023La0.0023Al 0.0024Zn0.0024O2。
It is last it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement, and these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims (10)

1. a kind of lithium ion battery presoma of modification, it is characterised in that: the presoma is spherical metal hydroxide, is changed Credit minor is NixCoyMzM1 aM2 d(OH)2+e, M is Mn or Al, M1For ionic radius greater than 0.76 Elements C a, Sr, Ba, Zr, Y, one or more of La, Ce, Sm, Er, M2For ionic radius less than or equal to 0.76 element M g, Ti, Nb, Ta, Mo, W, One or more of Mn, Fe, Zn, Al, wherein 0.55≤x≤0.96,0.02≤y≤0.25,0.01≤z≤0.25, 0.0005≤a≤0.005,0.0002≤d≤0.005, x+y+z+a+d=1,0≤e≤0.06；M in the presoma1Element It is uniformly distributed in material bodies phase, M2Element is uniformly distributed in material surface.
2. lithium ion battery presoma according to claim 1, it is characterised in that the lithium ion battery presoma Average particle size is 3~19 μm.
3. a kind of anode material for lithium ion battery with any one of claim 1~2 presoma, it is characterised in that institute Stating positive electrode molecular formula is LiNixCoyMzM1 aM2 dO2, M is Mn or Al, M1For ionic radius greater than 0.76 Elements C a, Sr, One or more of Ba, Zr, Y, La, Ce, Sm, Er, M2For ionic radius less than or equal to 0.76 element M g, Ti, Nb, Ta, One or more of Mo, W, Mn, Fe, Zn, Al, wherein 0.55≤x≤0.96,0.02≤y≤0.25,0.01≤z≤0.25, 0.0005≤a≤0.005,0.0002≤d≤0.005, x+y+z+a+d=1；M in the positive electrode2Element is in positive material The surface layer of material particle forms certain gradient-structure, and ecto-entad content gradually decreases.
4. the preparation method of described in any item lithium ion battery presomas according to claim 1~2, comprising the following steps:
(1) nickel salt, cobalt salt, manganese salt are configured to salting liquid；M will be contained1Compound be added to the water certain density M be made1Material Liquid；M will be contained2Compound be added to the water certain density M be made2Feed liquid；Alkali is dissolved into the alkali that concentration is 2~10mol/L Solution；Complexing agent is dissolved into the enveloping agent solution that concentration is 2~13mol/L；
(2) by salting liquid, the M in step (1)1Cocurrent is added in reaction kettle and carries out together for feed liquid, aqueous slkali, enveloping agent solution Reaction, process are kept stirring invariablenes turning speed, while controlling reaction pH is 10.5~12.5, and reaction temperature is 40~70 DEG C, reaction The concentration control of complexing agent is 1g/L~12g/L in system, and when reaction is completed, stopping feed liquor keeping temperature, the stirring of reaction solution Revolving speed is constant, continues 5~20min of stirring；
(3) M of step (1) is added into reaction kettle according to certain flow velocity2Feed liquid and aqueous slkali adjust reaction solution pH 10.5 Between~12.5, reaction temperature is 40~70 DEG C, M2Feed liquid continues 10~60min of stirring after adding, both mixed M1M is wrapped again2's Hydroxide precursor slurry；
(4) after being separated by solid-liquid separation, washed by the hydroxide precursor slurry in step (3), being dried, sieve, spherical shape is obtained Hydroxide precursor material NixCoyMzM1 aM2 d(OH)2+e。
5. the preparation method of anode material for lithium ion battery according to claim 3 comprising following steps: by right It is required that 1~2 described in any item presomas are mixed with lithium source, are sintered, is broken, the lithium ion battery is made in final sizing With positive electrode LiNixCoyMzM1 aM2 dO2。
6. the preparation method of lithium ion battery presoma according to claim 4, it is characterised in that described in step (1) The preparation method of salting liquid is that x:y:z is dissolved into the salt-mixture that concentration is 1~3mol/L in molar ratio by nickel salt, cobalt salt, manganese salt Solution；Or x:y is dissolved into the nickel cobalt salting liquid that concentration is 1~3mol/L in molar ratio by nickel salt, cobalt salt, aluminium salt and alkali are by certain Ratio is hybridly prepared into the aluminum salt solution that concentration is 0.1~0.5mol/L.
7. the preparation method of lithium ion battery presoma according to claim 4, it is characterised in that the nickel salt is One or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate；The cobalt salt is cobaltous sulfate, cobalt chloride, cobalt nitrate, second One or more of sour cobalt；The manganese salt is one of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate or in which several； The aluminium salt is one or more of aluminum sulfate, aluminum nitrate, aluminium chloride, aluminium acetate；The alkali is sodium hydroxide, hydrogen-oxygen Change one or more of potassium, lithium hydroxide；The complexing agent is salicylic acid, ammonium sulfate, ammonium chloride, ammonium hydroxide, sulfosalisylic One or more of acid, ethylenediamine tetra-acetic acid.
8. the preparation method of lithium ion battery presoma according to claim 4, it is characterised in that the M1Chemical combination Object is M1Soluble salt, oxide nonmetallic powder, hydroxide nano powder, oxyhydroxide nano powder, one of colloidal sol or its In it is several；The M2Compound be M2Soluble salt, oxide nonmetallic powder, hydroxide nano powder, oxyhydroxide nanometer One or more of powder, colloidal sol.
9. the preparation method of anode material for lithium ion battery according to claim 5, it is characterised in that the lithium source For one or more of lithium carbonate, lithium hydroxide.
10. the preparation method of lithium ion battery presoma according to claim 6, it is characterised in that the aluminium salt with The aluminium ion of alkali mixed preparing aluminum salt solution and the molar ratio of alkali are 1:5~1:10.
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