CN109455772B - Modified precursor and anode material for lithium ion battery and preparation methods of precursor and anode material - Google Patents

Modified precursor and anode material for lithium ion battery and preparation methods of precursor and anode material Download PDF

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CN109455772B
CN109455772B CN201711456555.7A CN201711456555A CN109455772B CN 109455772 B CN109455772 B CN 109455772B CN 201711456555 A CN201711456555 A CN 201711456555A CN 109455772 B CN109455772 B CN 109455772B
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CN109455772A (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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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/40Nickelates
    • C01G53/42Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/006Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a precursor for a lithium ion battery, a positive electrode material and preparation methods of the precursor and the positive electrode material. The precursor is spherical metal hydroxide with a molecular formula of NixCoyMzM1 aM2 d(OH)2+eM is Mn or Al, M1Is an element having an ionic radius greater than 0.76 Å, M2Is an element with an ionic radius of 0.76 Å or less, wherein x is 0.55-0.96, y is 0.02-0.25, z is 0.01-0.25, a is 0.0005-0.005, d is 0.0002-0.005, x + y + z + a + d =1, e is 0-0.06, M1The elements being homogeneously distributed in the bulk phase of the material, M2Elements are uniformly distributed on the surface of the material; the precursor has a novel structure, and the prepared anode material has more excellent capacity, cycle and safety performance. The preparation method is easy to stably control, has low cost and is suitable for large-scale industrial production.

Description

Modified precursor and anode material for lithium ion battery and preparation methods of precursor and anode material
Technical Field
The invention relates to a modified precursor and a positive electrode material for a lithium ion battery and a preparation method thereof, in particular to a doped and coated spherical metal hydroxide precursor, a positive electrode material prepared from the precursor and a preparation method of the precursor and the positive electrode material, and belongs to the technical field of lithium ion batteries.
Background
The lithium ion battery is the most common secondary battery at present, has the outstanding advantages of high energy density, good cycle performance, small self-discharge, no memory effect and the like, is widely applied to various portable electric tools, mobile phones, notebook computers, tablet computers, video cameras, weaponry and the like, and is also widely used in the fields of electric automobiles and various energy storage.
In recent years, the new energy automobile industry in China develops rapidly. In 2016, the sales volume of new energy vehicles reaches over 50 thousands. The power battery is of great importance as the heart of the electric automobile, and the positive electrode material is used as the core raw material of the power battery, which directly influences the energy density, safety, cycle life and other performances of the power battery. Common lithium ion battery anode materials mainly include ternary materials of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickelate and lithium nickel cobalt manganese. The ternary material has the advantages of high specific capacity, good cycle performance, low raw material cost and the like, but the specific capacity is increased along with the increase of the nickel content, and the cycle performance and the safety performance are correspondingly deteriorated. Therefore, although the ternary material, especially the high-nickel ternary material, has a high specific capacity, there still exist many defects in practical applications, such as safety performance, cycle performance, storage performance, and high-current charge and discharge performance.
At present, the ternary anode material of the lithium ion battery is mainly prepared by preparing a spherical or spheroidal precursor and then mixing and sintering the precursor and a lithium source. For example, chinese patent CN102916177B discloses a nickel-cobalt-manganese hydroxide precursor and a preparation method thereof, in which a nickel-cobalt-manganese mixed salt solution, a sodium hydroxide solution and an ammonia water solution are subjected to a coprecipitation reaction, the pH and the ammonia amount in the reaction process are controlled, and an additive with a particle morphology adjusting function is added to obtain the nickel-cobalt-manganese hydroxide precursor with a spherical structure. Chinese patent CN103400973B discloses a method for preparing lithium nickel cobalt aluminate and its precursor, in which an aluminum salt and a complexing agent are subjected to a complex reaction to form a stable aluminum complex, and then the stable aluminum complex and a nickel cobalt salt solution are simultaneously injected into a reaction kettle for a coprecipitation reaction to prepare a spherical lithium nickel cobalt aluminate precursor, and then the spherical lithium nickel cobalt aluminate precursor is calcined with a lithium source to synthesize the spherical lithium nickel cobalt aluminate material.
Although the above-mentioned patent can prepare a spherical precursor of the cathode material with uniform composition, the precursor is not doped and coated with trace elements, and the existing form of the trace elements and the structure of the material are not designed and controlled, which is not favorable for the performance of the cathode material.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a spherical metal hydroxide precursor, which can improve the capacity, the cycle performance, the safety performance, etc. of the cathode material by improving the material composition design and the process technology.
The invention also provides a preparation method of the metal hydroxide precursor and the anode material, which has the advantages of simple process, easy and stable control of the process, low production cost and suitability for large-scale industrial production.
The technical scheme of the invention is as follows:
the precursor for the lithium ion battery is spherical metal hydroxide, and the chemical molecular formula of the precursor is NixCoyMzM1 aM2 d(OH)2+eM is Mn or Al, M1Is one or more of Ca, Sr, Ba, Zr, Y, La, Ce, Sm and Er with the ionic radius larger than 0.76 Å, M2Is one or more of elements Mg, Ti, Nb, Ta, Mo, W, Mn, Fe, Zn and Al with the ionic radius of less than or equal to 0.76 Å, wherein x is more than or equal to 0.55 and less than or equal to 0.96, y is more than or equal to 0.02 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.25, a is more than or equal to 0.0005 and less than or equal to 0.005, d is more than or equal to 0.0002 and less than or equal to 0.005, x + y + z + a + d =1, e is more than or equal to 0 and less than1The elements being homogeneously distributed in the bulk phase of the material, M2The elements are uniformly distributed on the surface of the material.
During sintering of this precursor and the Li source, M1The elements can be uniformly distributed in the positive electrode material phase, and the space structure of the material can be effectively supported due to the larger ionic radius of the elements, so that the structural stability of the material is improved, and the insertion and the extraction of lithium ions are facilitated; and M uniformly distributed on the surface of the precursor material2The element can diffuse to the inside of the particles to a certain degree in the sintering process due to small ionic radius, and a certain gradient structure is formed on the surface layer of the anode material, so that the surface activity of the material is stabilized, and a large inert layer cannot be formed to influence the capacity exertion of the material. The invention not only solves the problem of poor cycle performance and safety performance of the anode material, but also avoids forming an inert layer on the surface of the material and reduces the capacity of the final product. The doping element distribution structure of the precursor can realize the requirement of the anode material on high specific capacity, and can simultaneously meet the requirement of the anode material on circulationRing performance and safety performance requirements.
Further, the average particle size of the precursor for the lithium ion battery is 3-19 μm, wherein the average particle size refers to the corresponding particle size when the particle size distribution percentage reaches 50%, and the average particle size can be specifically adjusted according to actual requirements.
The invention also provides a preparation method of the precursor for the lithium ion battery, which comprises the following steps:
(1) preparing a salt solution from nickel salt, cobalt salt and manganese salt; will contain M1The compound of (A) is added into water to prepare M with a certain concentration1Feed liquid; will contain M2The compound of (A) is added into water to prepare M with a certain concentration2Feed liquid; dissolving alkali into an alkali solution with the concentration of 2-10 mol/L; and dissolving a complexing agent into a complexing agent solution with the concentration of 2-13 mol/L.
(2) Mixing the salt solution obtained in the step (1) and M1And (2) feeding the material liquid, the alkali solution and the complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring rotation speed constant in the process, controlling the reaction pH to be 10.5-12.5, controlling the reaction temperature to be 40-70 ℃, controlling the concentration of the complexing agent in a reaction system to be 1-12 g/L, stopping feeding liquid when the reaction is finished, keeping the temperature of the reaction liquid and the stirring rotation speed unchanged, and continuously stirring for 5-20 min.
(3) Adding M in the step (1) into a reaction kettle according to a certain flow rate2Feed liquid and alkali solution, adjusting the pH of the reaction solution to be 10.5-12.5, and the reaction temperature to be 40-70 ℃, and M2After the feed liquid is added, continuously stirring for 10-60 min to obtain the doped M1Bag M2The hydroxide precursor slurry of (1).
(4) Carrying out solid-liquid separation, washing, drying and screening on the hydroxide precursor slurry in the step (3) to obtain a spherical hydroxide precursor material NixCoyMzM1 aM2 d(OH)2+e
In the preparation method, the preparation method of the salt solution in the step (1) comprises the following steps of mixing nickel salt, cobalt salt and manganese salt according to a molar ratio of x: y: z is dissolved into a mixed salt solution with the concentration of 1-3 mol/L; or mixing nickel salt and cobalt salt according to a molar ratio of x: y is dissolved into a nickel-cobalt salt solution with the concentration of 1-3 mol/L, and an aluminum salt and alkali are mixed according to a certain proportion to prepare an aluminum salt solution with the concentration of 0.1-0.5 mol/L, wherein the molar ratio of aluminum ions and alkali in the aluminum salt and alkali mixed aluminum solution is 1: 5-1: 10.
In the preparation method, the nickel salt is one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; the cobalt salt is one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese salt is one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate; the aluminum salt is one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum acetate; said M1The compound of (A) is M1One or more of soluble salt, oxide nano powder, hydroxide nano powder, oxyhydroxide nano powder and sol; said M2The compound of (A) is M2One or more of soluble salt, oxide nano powder, hydroxide nano powder, oxyhydroxide nano powder and sol; the alkali is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide; the complexing agent is one or more of salicylic acid, ammonium sulfate, ammonium chloride, ammonia water, sulfosalicylic acid and ethylenediamine tetraacetic acid.
The positive electrode material for the lithium ion battery provided by the invention has the precursor, and the chemical molecular formula of the precursor is LiNixCoyMzM1 aM2 dO2M is Mn or Al, M1Is one or more of Ca, Sr, Ba, Zr, Y, La, Ce, Sm and Er with the ionic radius larger than 0.76 Å, M2The ionic radius is less than or equal to 0.76 Å, wherein x is more than or equal to 0.55 and less than or equal to 0.96, y is more than or equal to 0.02 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.25, a is more than or equal to 0.0005 and less than or equal to 0.005, d is more than or equal to 0.0002 and less than or equal to 0.005, and x + y + z + a + d = 1.
The invention also provides a preparation method of the anode material for the lithium ion battery, which comprises the following steps: mixing the precursor with a lithium source, sintering, crushing, and finally screening to obtain the lithium ionPositive electrode material LiNi for sub-batteryxCoyMzM1 aM2 dO2
In the preparation method, the lithium source is one or more of lithium carbonate, lithium hydroxide and lithium nitrate.
Compared with the prior art, the invention has the following advantages:
(1) the precursor material has a structure that elements with large ionic radius are uniformly distributed in material particles and elements with small ionic radius are uniformly distributed on the surface of the material, so that the structure of the prepared anode material is more stable, the ionic radius of doped elements in a bulk phase is large, the spatial structure of the material can be effectively supported, and the insertion and extraction of lithium ions are facilitated; the ionic radius of the surface doping element is small, the doping element diffuses into the particles in the sintering process, so that a certain gradient structure is formed on the surface layer, the electrode reaction generated on the surface of the particles is weakened, and meanwhile, a larger inert layer cannot be formed to influence the capacity exertion of the material, and the requirements of the anode material on high specific capacity, cycle performance and safety performance are further met.
(2) The preparation method can realize that the elements with large ionic radius are uniformly distributed in the positive electrode material particles, and the elements with small ionic radius form a certain gradient structure on the surface layer of the positive electrode material, thereby solving the problem that the elements with large ionic radius cannot be effectively and uniformly diffused into the positive electrode material in the sintering process by being mixed on the surface of the precursor; in addition, the elements with small ionic radius only act on the surface layer of the cathode material, so that the content of inert elements in the material is reduced, and the capacity of the cathode material is favorably exerted. The whole preparation method has simple process and easily controlled process, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a 2000-fold Scanning Electron Microscope (SEM) image of a precursor prepared in example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a precursor prepared in example 1 of the present invention with a particle cross section of 5000 times.
Fig. 3 is a Scanning Electron Microscope (SEM) image at 3000 times of the positive electrode material produced in example 1 of the present invention.
Fig. 4 is XRD patterns of the cathode material prepared in example 1 of the present invention and comparative example 1.
Fig. 5 is a normal temperature cycle curve diagram of the button cell under the voltage range of 3.0-4.5V for the positive electrode material prepared in example 1 of the invention and comparative example 1.
Fig. 6 is a 45 ℃ high temperature cycling curve diagram of the button cell under the voltage range of 3.0-4.3V for the positive electrode material prepared in example 1 of the invention and comparative example 1.
Detailed Description
The present invention will be understood by the following examples and the accompanying drawings, but the present invention is not limited thereto.
Comparative example 1
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the metal molar ratio of 82: 12: 6 to obtain a mixed salt solution of 2 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 6 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 5 mol/L.
Adding 20L of mixed salt solution, aqueous alkali and complexing agent solution into a reaction kettle in a co-current manner for reaction, keeping the stirring rotation speed at 400rpm constant in the process, simultaneously controlling the liquid inlet flow of the mixed salt solution at 400mL/h, the reaction pH at 11.9-12.1, the reaction temperature at 50 ℃, controlling the ammonia concentration in a reaction system at 8-10 g/L, keeping the temperature and the stirring rotation speed of the reaction solution unchanged when the reaction is finished, continuously stirring for 10min, then carrying out solid-liquid separation and washing on the obtained nickel-cobalt-manganese hydroxide slurry, drying the filter cake at 115 ℃ for 5h, and then screening to obtain a spherical hydroxide precursor material Ni0.82Co0.12Mn0.06(OH)2Average particle size D50And 10.2 μm.
Mixing the spherical nickel-cobalt-manganese hydroxide material with lithium hydroxide, sintering for 10h at 800 ℃ in an oxygen atmosphere, crushing and screening to obtain the positive material nickel-cobalt-manganese acid lithium for the lithium ion battery, wherein the chemical molecular formula is LiNi0.82Co0.12Mn0.06O2
Example 1
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the metal molar ratio of 82: 12: 6 to obtain a mixed salt solution with the concentration of 2mol/L, dissolving calcium nitrate into a calcium nitrate solution with the concentration of 0.1mol/L, and dissolving aluminum nitrate into an aluminum nitrate solution with the concentration of 0.5 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 6 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 5 mol/L.
And adding 20L of mixed salt solution, calcium nitrate solution, alkali solution and complexing agent solution into a reaction kettle in a co-current manner for reaction, keeping the stirring rotation speed of 500rpm constant in the process, controlling the liquid inlet flow of the mixed salt solution to be 400mL/h, the liquid inlet flow of the calcium nitrate solution to be 16mL/h, controlling the reaction pH to be 11.9-12.1, the reaction temperature to be 50 ℃, controlling the concentration of ammonia in a reaction system to be 8-10 g/L, and when the reaction is finished, keeping the temperature of the reaction solution and the stirring rotation speed unchanged, and continuing stirring for 10 min.
Adding 160mL of aluminum nitrate solution into a reaction kettle at the flow rate of 160mL/h, adding an alkali solution to adjust the reaction pH to 11.9-12.1 at the reaction temperature of 50 ℃, and continuing stirring for 30min after the aluminum nitrate solution is added to obtain the Ca-doped and Al-coated nickel-cobalt-manganese hydroxide precursor slurry. Then carrying out solid-liquid separation and washing on the obtained hydroxide slurry, drying a filter cake for 5h at 115 ℃, and screening to obtain a spherical hydroxide precursor material Ni0.8167Co0.1195Mn0.0598Ca0.002Al0.002(OH)2.002Average particle size D50And 10.4 μm.
Mixing the precursor with lithium hydroxide, sintering at 800 ℃ for 10h in an oxygen atmosphere, crushing and screening to obtain the spherical positive electrode material LiNi for the lithium ion battery0.8167Co0.1195Mn0.0598Ca0.002Al0.002O2
It can be seen from fig. 1 that the precursor material obtained in example 1 is a spherical particle with a regular shape. The internal structure of the spherical particles is oriented radially from inside to outside, and the particles are relatively dense, as shown in fig. 2. The positive electrode material prepared by high-temperature sintering keeps the spherical morphology of the precursor, and no adhesion exists among particles, as shown in figure 3.
From FIG. 4 can be seenThe XRD lines of the products obtained in example 1 and comparative example 1 are sharp, and the comparison of the two curves shows that no other impurity peak exists, which indicates that the crystals of the cathode materials obtained in example 1 and comparative example 1 are both typical alpha-NaFeO2The structure of the positive electrode material is not changed by doping modification of trace elements, but the diffraction peak intensity I of the positive electrode materials obtained in example 1 and comparative example 1(003)/I(104)1.45 and 1.26 respectively, show that the cathode material of the embodiment 1 has higher crystallization degree and more perfect crystal structure.
The positive electrode materials obtained in the embodiment 1 and the comparative example 1 are made into 2032 button cells, and the capacity retention rates after 80 cycles under normal temperature 1C charge-discharge within the voltage range of 3.0-4.5V are respectively 92.7% and 91.0%, as shown in FIG. 5; the capacity retention rates after 80 cycles at 1C @45 ℃ under charge-discharge within the voltage range of 3.0-4.3V were 91.1% and 85.8%, respectively, as shown in FIG. 6. As can be seen from the above test data, the positive electrode material in example 1 has significantly better cycle performance at normal temperature and high temperature than the positive electrode material in comparative example 1.
Example 2
Nickel nitrate and cobalt nitrate are mixed according to a metal molar ratio of 88: 9 to obtain 1mol/L mixed salt solution; mixing aluminum nitrate and sodium hydroxide according to a molar ratio of 1:5 to prepare an aluminum solution with an aluminum ion concentration of 0.3 mol/L; dissolving zirconium nitrate into a zirconium nitrate solution with the concentration of 0.05 mol/L; dissolving cerium nitrate into a cerium nitrate solution with the concentration of 0.05 mol/L; dissolving magnesium sulfate into a magnesium sulfate solution with the concentration of 0.25 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 4 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 3 mol/L.
Adding 20L of mixed salt solution, aluminum solution, zirconium nitrate solution, cerium nitrate solution, alkali solution and complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring rotation speed at 600rpm constant in the process, simultaneously controlling the liquid inlet flow of the mixed salt solution at 400mL/h, the liquid inlet flow of the aluminum solution at 41mL/h, the liquid inlet flow of the zirconium nitrate solution at 12.5mL/h, the liquid inlet flow of the cerium nitrate solution at 12.5mL/h, the reaction pH at 12.2-12.4, the reaction temperature at 55 ℃, controlling the concentration of ammonia in a reaction system at 9-11 g/L, and when the reaction is finished, keeping the temperature and the stirring rotation speed of the reaction solution unchanged, and continuing stirring for 15 min.
Adding 125mL of magnesium sulfate solution into a reaction kettle at a flow rate of 80mL/h, adding an alkali solution to adjust the reaction pH to 12.2-12.4 at the reaction temperature of 55 ℃, and continuously stirring for 20min after the magnesium sulfate solution is added to obtain the Zr and Ce doped and Mg coated nickel-cobalt-aluminum hydroxide precursor slurry. Then carrying out solid-liquid separation and washing on the obtained hydroxide slurry, drying a filter cake at 120 ℃ for 5h, and then screening to obtain a spherical hydroxide precursor material Ni0.8762Co0.0896Al0.0297Zr0.0015Ce0.0015Mg0.0015(OH)2.036Average particle size D50It was 8.6 μm.
Mixing the precursor with lithium hydroxide, sintering for 8h at 750 ℃ in an oxygen atmosphere, crushing and screening to obtain the spherical positive electrode material LiNi for the lithium ion battery0.8762Co0.0896Al0.0297Zr0.0015Ce0.0015Mg0.0015O2
Example 3
Nickel sulfate, cobalt chloride and manganese chloride are mixed according to a metal molar ratio of 60: 20: 20 to obtain 2.5mol/L mixed salt solution; dissolving lanthanum nitrate into a lanthanum nitrate solution with the concentration of 0.1 mol/L; adding TiO into the mixture2The nanometer powder is prepared into TiO with the concentration of 0.2mol/L2Suspending liquid; dissolving sodium hydroxide into an alkali solution with the concentration of 10 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 12 mol/L.
And adding 20L of mixed salt solution, lanthanum nitrate solution, alkali solution and complexing agent solution into a reaction kettle in a co-current manner for reaction, keeping the stirring rotation speed at 650rpm constant in the process, controlling the liquid inlet flow of the mixed salt solution at 200mL/h, the liquid inlet flow of the lanthanum nitrate solution at 10mL/h, controlling the reaction pH at 11.2-11.4, the reaction temperature at 60 ℃, controlling the concentration of ammonia in a reaction system at 6-8 g/L, and when the reaction is finished, keeping the temperature of the reaction solution and the stirring rotation speed unchanged, and continuing stirring for 5 min.
150ml of TiO2Adding the suspension into the reaction kettle at the flow rate of 75mL/h, and simultaneously adding an alkali solution to adjust the pH of the reaction to 11.2-11.4, the reaction temperature is 60 ℃, and TiO2And continuing stirring for 30min after the suspension is added to obtain the La-doped and Ti-coated nickel-cobalt-manganese hydroxide precursor slurry. Then carrying out solid-liquid separation and washing on the obtained hydroxide slurry, drying a filter cake for 3h at 130 ℃, and screening to obtain a spherical hydroxide precursor material Ni0.5984Co0.1995Mn0.1995La0.002Ti0.0006(OH)2.003Average particle size D50It was 14.8 μm.
Mixing the precursor with lithium carbonate, sintering at 870 ℃ for 13h in air atmosphere, crushing and screening to obtain the spherical positive electrode material LiNi for the lithium ion battery0.5984Co0.1995Mn0.1995La0.002Ti0.0006O2
Example 4
Nickel acetate, cobalt acetate and manganese acetate are mixed according to a metal molar ratio of 65: 20: 15 to obtain 1.5mol/L mixed salt solution; dissolving cerium acetate into a cerium acetate solution with the concentration of 0.05 mol/L; dissolving ammonium tungstate into an ammonium tungstate solution with the concentration of 0.2 mol/L; dissolving niobium oxalate into niobium oxalate solution with the concentration of 0.2 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 8 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 8 mol/L.
And adding 20L of mixed salt solution, a cerium acetate solution, an alkali solution and a complexing agent solution into a reaction kettle in a co-current manner for reaction, keeping the stirring rotation speed at 700rpm constant in the process, controlling the liquid inlet flow rate of the mixed salt solution at 200mL/h, the liquid inlet flow rate of the cerium acetate solution at 20mL/h, the reaction pH at 11.4-11.6, the reaction temperature at 65 ℃, controlling the concentration of ammonia in a reaction system at 5-7 g/L, and when the reaction is finished, keeping the temperature of the reaction solution and the stirring rotation speed unchanged, and continuing stirring for 10 min.
Adding 108mL of ammonium tungstate solution and 92mL of niobium oxalate solution into a reaction kettle respectively according to the flow rates of 27mL/h and 23mL/h, adding an alkali solution to adjust the reaction pH to be 11.4-11.6 at the reaction temperature of 65 ℃, and continuing stirring for 15min after the ammonium tungstate solution and the niobium oxalate solution are added to obtain the Ce-doped W, Nb-coated nickel-cobalt-manganese hydroxide precursor slurry. Then theCarrying out solid-liquid separation and washing on the obtained hydroxide slurry, drying a filter cake for 4h at 120 ℃, and screening to obtain a spherical hydroxide precursor material Ni0.647Co0.1991Mn0.1493Ce0.0033W0.0007Nb0.0006(OH)2.01Average particle size D50It was 8.7 μm.
Mixing the precursor with lithium hydroxide, sintering at 840 ℃ for 10h in air atmosphere, crushing and screening to obtain the spherical anode material LiNi for the lithium ion battery0.647Co0.1991Mn0.1493Ce0.0033W0.0007Nb0.0006O2
Example 5
Nickel sulfate and cobalt chloride are mixed according to a metal molar ratio of 92: 4 to obtain 2mol/L mixed salt solution; mixing aluminum nitrate and potassium hydroxide according to a molar ratio of 1:8 to prepare an aluminum solution with an aluminum ion concentration of 0.4 mol/L; dissolving strontium nitrate into a strontium nitrate solution with the concentration of 0.05 mol/L; dissolving ammonium paramolybdate into an ammonium paramolybdate solution with the molybdenum concentration of 0.3 mol/L; dissolving sodium hydroxide and lithium hydroxide into an alkali solution with the concentration of 5mol/L according to the molar ratio of 20: 1; sulfosalicylic acid and ammonium chloride are respectively dissolved into a solution with the concentration of 2mol/L to be jointly used as a complexing agent solution.
Adding 20L of mixed salt solution, strontium nitrate solution, alkali solution and complexing agent solution into a reaction kettle in a co-current manner for reaction, keeping the stirring rotation speed at 600rpm constant in the process, controlling the liquid inlet flow of the mixed salt solution at 200mL/h, the liquid inlet flow of the aluminum solution at 42mL/h, the liquid inlet flow of the strontium nitrate solution at 10mL/h, controlling the reaction pH at 12.2-12.4, the reaction temperature at 55 ℃, controlling the concentration of ammonia in a reaction system at 3-5 g/L, and continuously stirring for 15min when the reaction is finished and the temperature and the stirring rotation speed of the reaction solution are kept unchanged.
Adding 300mL of ammonium paramolybdate solution into a reaction kettle at the flow rate of 50mL/h, adding an alkali solution to adjust the reaction pH to 12.2-12.4 at the reaction temperature of 55 ℃, and continuing stirring for 20min after the ammonium paramolybdate solution is added to obtain the Sr-doped and Mo-coated nickel-cobalt-aluminum hydroxide precursor slurry. Then the obtained hydroxide slurry is mixedCarrying out solid-liquid separation and washing, drying a filter cake at 120 ℃ for 4h, and screening to obtain a spherical hydroxide precursor Ni0.9166Co0.0399Al0.0402Sr0.0012Mo0.0022(OH)2.045Average particle size D50It was 7.5 μm.
Mixing the precursor with lithium hydroxide, sintering for 6h at 720 ℃ in an oxygen atmosphere, crushing and screening to obtain the spherical positive electrode material LiNi for the lithium ion battery0.9166Co0.0399Al0.0402Sr0.0012Mo0.0022O2
Example 6
Nickel nitrate, cobalt nitrate and manganese nitrate are mixed according to a metal molar ratio of 95: 2: 3 to obtain a mixed salt solution of 1.0 mol/L; dissolving yttrium nitrate into yttrium nitrate solution with the concentration of 0.07 mol/L; dissolving lanthanum chloride into a lanthanum chloride solution with the concentration of 0.07 mol/L; dissolving aluminum nitrate into an aluminum nitrate solution with the concentration of 0.2 mol/L; dissolving zinc sulfate into a zinc sulfate solution with the concentration of 0.2 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 4 mol/L; dissolving ammonium sulfate into a complexing agent solution with the concentration of 2 mol/L.
Adding 20L of mixed salt solution, yttrium nitrate solution, lanthanum chloride solution, alkali solution and complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring rotation speed at 500rpm constant in the process, simultaneously controlling the liquid inlet flow of the mixed salt solution at 300mL/h, the liquid inlet flow of the yttrium nitrate solution at 10mL/h, the liquid inlet flow of the lanthanum chloride solution at 10mL/h, the reaction pH at 12.3-12.5, the reaction temperature at 50 ℃, controlling the concentration of ammonia in a reaction system at 10-12 g/L, and when the reaction is finished, keeping the temperature of the reaction solution and the stirring rotation speed unchanged, and continuing stirring for 20 min.
Adding 250mL of aluminum nitrate solution and 250mL of zinc sulfate solution into a reaction kettle respectively according to the flow rate of 50mL/h, simultaneously adding aqueous alkali to adjust the reaction pH to be 12.3-12.5, controlling the reaction temperature to be 50 ℃, and continuously stirring for 30min after the aluminum nitrate solution and the zinc sulfate solution are added to obtain Y, La-doped nickel-cobalt-manganese hydroxide precursor slurry containing Al and Zn. Then carrying out solid-liquid separation and washing on the obtained hydroxide slurry, and drying a filter cake at 120 ℃ for 4Sieving after h to obtain a spherical hydroxide precursor Ni0.9411Co0.0198Mn0.0297Y0.0023La0.0023Al0.0024Zn0.0024(OH)2.007Average particle size D50And 9.3 μm.
Mixing the precursor with lithium hydroxide, sintering for 8h at 720 ℃ in an oxygen atmosphere, crushing and screening to obtain the spherical positive electrode material LiNi for the lithium ion battery0.9411Co0.0198Mn0.0297Y0.0023La0.0023Al0.0024Zn0.0024O2
Finally, it is to be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: it is to be understood that modifications may be made to the technical solutions described in the foregoing embodiments, or some or all of the technical features may be equivalently replaced, and the modifications or the replacements may not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A modified precursor for a lithium ion battery is characterized in that: the precursor is spherical metal hydroxide, and the chemical molecular formula is NixCoyMzM1 aM2 d(OH)2+eM is Mn or Al, M1Is an ionic radius greater than
Figure FDA0002268396120000011
One or more of Ca, Sr, Ba, Zr, Y, La, Ce, Sm and Er, M2The ionic radius is less than or equal toOne or more of elements Mg, Ti, Nb, Ta, Mo, W, Mn, Fe, Zn and Al, wherein x is more than or equal to 0.55 and less than or equal to 0.96, y is more than or equal to 0.02 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.25, a is more than or equal to 0.0005 and less than or equal to 0.005, d is more than or equal to 0.0002 and less than or equal to 0.005, and x +y + z + a + d is 1, and e is more than or equal to 0 and less than or equal to 0.06; m in the precursor1The elements being homogeneously distributed in the bulk phase of the material, M2The elements are uniformly distributed on the surface of the material.
2. The precursor for a lithium ion battery according to claim 1, wherein the average particle size of the precursor for a lithium ion battery is 3 to 19 μm.
3. A positive electrode material for a lithium ion battery, which comprises the precursor of any one of claims 1 to 2, wherein the molecular formula of the positive electrode material is LiNixCoyMzM1 aM2 dO2M is Mn or Al, M1Is an ionic radius greater than
Figure FDA0002268396120000013
One or more of Ca, Sr, Ba, Zr, Y, La, Ce, Sm and Er, M2The ionic radius is less than or equal to
Figure FDA0002268396120000014
Wherein x is more than or equal to 0.55 and less than or equal to 0.96, y is more than or equal to 0.02 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.25, a is more than or equal to 0.0005 and less than or equal to 0.005, d is more than or equal to 0.0002 and less than or equal to 0.005, and x + y + z + a + d is equal to 1; m in the positive electrode material2The elements form a certain gradient structure on the surface layer of the anode material particles, and the content of the elements is gradually reduced from outside to inside.
4. The method for preparing a precursor for a lithium ion battery according to any one of claims 1 to 2, comprising the steps of:
(1) preparing a salt solution from nickel salt, cobalt salt and manganese salt; will contain M1The compound of (A) is added into water to prepare M with a certain concentration1Feed liquid; will contain M2The compound of (A) is added into water to prepare M with a certain concentration2Feed liquid; dissolving alkali into an alkali solution with the concentration of 2-10 mol/L; dissolving a complexing agent into a complexing agent solution with the concentration of 2-13 mol/L;
(2) Mixing the salt solution obtained in the step (1) and M1Feeding the material liquid, the alkali solution and the complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring rotation speed constant in the process, controlling the reaction pH to be 10.5-12.5, controlling the reaction temperature to be 40-70 ℃, controlling the concentration of the complexing agent in a reaction system to be 1-12 g/L, stopping feeding liquid when the reaction is finished, keeping the temperature of the reaction liquid and the stirring rotation speed unchanged, and continuously stirring for 5-20 min;
(3) adding M in the step (1) into a reaction kettle according to a certain flow rate2Feed liquid and alkali solution, adjusting the pH of the reaction solution to be 10.5-12.5, and the reaction temperature to be 40-70 ℃, and M2After the feed liquid is added, continuously stirring for 10-60 min to obtain the doped M1Bag M2The hydroxide precursor slurry of (1);
(4) carrying out solid-liquid separation, washing, drying and screening on the hydroxide precursor slurry in the step (3) to obtain a spherical hydroxide precursor material NixCoyMzM1 aM2 d(OH)2+e
5. The method for preparing a positive electrode material for a lithium ion battery according to claim 3, comprising the steps of: mixing the precursor of any one of claims 1 to 2 with a lithium source, sintering, crushing, and finally screening to obtain the positive electrode material LiNi for the lithium ion batteryxCoyMzM1 aM2 dO2
6. The method for preparing a precursor for a lithium ion battery according to claim 4, wherein the salt solution in the step (1) is prepared by mixing a nickel salt, a cobalt salt and a manganese salt in a molar ratio of x: y: z is dissolved into a mixed salt solution with the concentration of 1-3 mol/L; or mixing nickel salt and cobalt salt according to a molar ratio of x: y is dissolved into a nickel-cobalt salt solution with the concentration of 1-3 mol/L, and aluminum salt and alkali are mixed according to a certain proportion to prepare an aluminum salt solution with the concentration of 0.1-0.5 mol/L.
7. The method for preparing the precursor for the lithium ion battery according to claim 6, wherein the nickel salt is one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; the cobalt salt is one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese salt is one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate; the aluminum salt is one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum acetate; the alkali is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide; the complexing agent is one or more of salicylic acid, ammonium sulfate, ammonium chloride, ammonia water, sulfosalicylic acid and ethylenediamine tetraacetic acid.
8. The method according to claim 4, wherein M is selected from the group consisting of1The compound of (A) is M1One or more of soluble salt, oxide nano powder, hydroxide nano powder, oxyhydroxide nano powder and sol; said M2The compound of (A) is M2One or more of soluble salt, oxide nano powder, hydroxide nano powder, oxyhydroxide nano powder and sol.
9. The method according to claim 5, wherein the lithium source is one or more of lithium carbonate and lithium hydroxide.
10. The method for preparing the precursor for the lithium ion battery according to claim 6, wherein the molar ratio of the aluminum ions to the alkali in the aluminum salt solution prepared by mixing the aluminum salt and the alkali is 1:5 to 1: 10.
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