CN113461069A - Lithium ion battery positive electrode material precursor, preparation method thereof and lithium ion battery positive electrode material - Google Patents

Lithium ion battery positive electrode material precursor, preparation method thereof and lithium ion battery positive electrode material Download PDF

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CN113461069A
CN113461069A CN202110539720.5A CN202110539720A CN113461069A CN 113461069 A CN113461069 A CN 113461069A CN 202110539720 A CN202110539720 A CN 202110539720A CN 113461069 A CN113461069 A CN 113461069A
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precursor
lithium ion
ion battery
sintering
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雷天起
陈龙
李道聪
杨茂萍
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • 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
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a precursor of a lithium ion battery anode material, which comprises an inner core and a shell coated on the outer surface of the inner core by regulating and controlling raw material components and reaction conditions at different stages of a coprecipitation method, wherein the inner core is loose and has a porous structure, and the chemical composition of the inner core is shown as a general formula (Ni)aCobMnc)1‑xAlx(OH)2Shown; the shell is compact, and the chemical composition of the shell is shown as the general formula NidCoeMnf(OH)2As shown. Hair brushThe preparation method of the precursor has the advantages of simple process, low ammonia consumption, good element precipitation uniformity and suitability for large-scale industrial production, the cathode material prepared from the precursor has an obvious hollow structure, and the wettability of the electrolyte can be improved and the power performance of the battery can be improved after the lithium ion battery is prepared.

Description

Lithium ion battery positive electrode material precursor, preparation method thereof and lithium ion battery positive electrode material
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a lithium ion battery anode material precursor, a preparation method thereof and a lithium ion battery anode material.
Background
In recent years, with the rapid development of new energy automobiles, higher requirements are made on the capacity, power, safety, cycle and other performances of lithium ion power batteries. Particularly, the hybrid electric vehicle has a significant requirement on the power performance of the battery, and the current main development direction of the power battery is in the aspect of the structural design of the power battery, and the research on the bottleneck condition of the positive electrode material is less. The main modification direction of the anode material of the power type lithium ion battery at present is to control the particle size distribution and the size of the material, and then the stability of a crystal structure is improved in a doping and cladding mode. Patent publication No. CN 110931772A proposes to prepare a cathode material with a hollow structure by optimizing the microstructure of a precursor of the cathode material, so as to improve the wettability of an electrolyte in a battery system, and to improve the power performance of the material and the battery. The idea is mainly to prepare a structure with fine and loose primary particles at the inner layer and a structure with thick and compact particles at the outer layer in a mode of regulating and controlling the concentration of ammonium ions. But the main problem that this kind of scheme leads to is that the aqueous ammonia uses more, leads to later stage to retrieve the aqueous ammonia cost higher, and increases the ammonia easily and leaks the risk. On the other hand, in the preparation of the core of smaller particles, ammonia was used at a lower concentration according to the thermodynamic equilibrium during the coprecipitation reaction (Ni-Co-Mn)2+-NH4 +-NH3-H2In the O system, due to Ni2+、Co2+、Mn2+The hydroxide ion product of the metal ions is greatly different, and NH with certain concentration3The existence of (2) is the key of uniform precipitation of nickel-cobalt-manganese metal ions. Therefore, CN 110931772A is liable to have a risk of low capacity of the cathode material due to element segregation. In addition, the size difference of the primary particles of the inner layer and the outer layer cannot completely ensure that a hollow structure is formed after sintering in the practical application process, and a more porous inner core structure is needed to be more suitable.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a lithium ion battery anode material precursor, a preparation method thereof and a lithium ion battery anode material.
The invention provides a preparation method of a precursor of a lithium ion battery anode material, which comprises the following steps:
s1, the reaction product is (Ni) according to the coprecipitationaCobMnc)1-xAlx(OH)2Dissolving nickel salt, cobalt salt, manganese salt and aluminum salt in water to obtain a first mixed solution, wherein x is more than or equal to 0.01 and less than or equal to 0.07, a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.2, c is more than or equal to 0.05 and less than or equal to 0.3, and a + b + c is equal to 1;
s2, taking Ni as a coprecipitation reaction productdCoeMnf(OH)2Dissolving nickel salt, cobalt salt and manganese salt in water to obtain a second mixed solution, wherein d is more than or equal to 0.5 and less than or equal to 0.9, e is more than or equal to 0.05 and less than or equal to 0.2, f is more than or equal to 0.05 and less than or equal to 0.3, and d + e + f is equal to 1;
and S3, continuously adding the first mixed solution, the alkali solution and the ammonia water solution into the reaction kettle, carrying out a first-stage coprecipitation reaction to form a precursor core part, then stopping adding the first mixed solution, continuously adding the second mixed solution, the alkali solution and the ammonia water solution into the reaction kettle, carrying out a second-stage coprecipitation reaction, and coating the outer surface of the precursor core part to form a precursor shell part, thereby obtaining the lithium ion battery anode material precursor.
Preferably, NH in the reaction system of the first-stage coprecipitation reaction3The concentration of (A) is 5-10g/L, and the pH value is 11.2-12.0; NH in the reaction system of the second-stage coprecipitation reaction3The concentration of (A) is 5-10g/L, and the pH value is 11.2-12.0.
Preferably, the temperature of the first stage coprecipitation reaction is 50-55 ℃, the reaction is carried out under stirring, and the stirring speed is 600-900 rpm; the temperature of the second stage coprecipitation reaction is 50-55 ℃, the reaction is carried out under stirring, and the stirring speed is 600-900 rpm; and the first-stage coprecipitation reaction and the second-stage coprecipitation reaction are carried out under the protection of inert gas.
Preferably, the particle size of the core part of the precursor is 1.5-3 μm, and the particle size of the precursor is 4-6 μm.
Preferably, the concentration of the metal ions in the first mixed solution is 1.8-2.2 mol/L; the concentration of metal ions in the second mixed solution is 1.8-2.2 mol/L; the concentration of the ammonia water solution is 7-10 mol/L; the concentration of the alkali solution is 4-6 mol/L; the alkali solution is at least one aqueous solution of sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium carbonate; the nickel salt is at least one of nickel sulfate, nickel nitrate and nickel chloride; the cobalt salt is at least one of cobalt sulfate, cobalt nitrate and cobalt chloride; the manganese salt is at least one of manganese sulfate, manganese nitrate and manganese chloride; the aluminum salt is at least one of aluminum sulfate, aluminum nitrate and aluminum chloride.
The invention also provides a precursor of the lithium ion battery anode material, which is prepared by the preparation method; the precursor comprises an inner core and an outer shell wrapping the outer surface of the inner core, wherein the inner core is loose and has a porous structure, and the chemical composition of the inner core is shown as the general formula (Ni)aCobMnc)1-xAlx(OH)2Wherein x is 0.01-0.07, a is 0.5-0.9, and a + b + c is 1; the shell is compact, and the chemical composition of the shell is shown as the general formula NidCoeMnf(OH)2Wherein d is 0.5. ltoreq. d.ltoreq.0.9 and d + e + f is 1.
The invention also provides the application of the precursor of the lithium ion battery anode material in the preparation of the lithium ion battery anode material.
The invention also provides a power type lithium ion battery anode material, and the preparation method comprises the following steps:
(1) uniformly mixing the lithium ion battery anode material precursor, a lithium source and a nano oxide to obtain a first mixture, and performing primary sintering to obtain a primary sintered material;
(2) and uniformly mixing the primary sintering material, the boron source, the nano aluminum oxide and the cobalt hydroxide to obtain a second mixture, and sintering for the second time to obtain the secondary sintering material.
Preferably, in the first mixture, the ratio of the sum of the number of moles of Ni, Co, Mn to the number of moles of Li is 1: (1.01-1.05), the ratio of the sum of the mole numbers of Ni, Co and Mn to the mole number of the nano oxide is 1: (0.01-0.04); in the second mixture, the sum of the mass of boron source, boron element, aluminum element and cobalt element in the nano alumina and the cobalt hydroxide is 0.2-0.5% of the mass of the primary sintering material; preferably, the lithium source is lithium carbonate, lithium hydroxide or a combination thereof, the nano oxide is at least one of nano alumina, nano zirconia and nano titania, and the boron source is boric acid.
Preferably, the sintering atmosphere of the primary sintering is pure oxygen atmosphere, the sintering temperature is 710-900 ℃, the sintering time is 12-20h, the sintering atmosphere of the secondary sintering is pure oxygen atmosphere, the sintering temperature is 300-600 ℃, and the sintering time is 2-5 h.
The invention has the following beneficial effects:
(1) the process for preparing the precursor of the lithium ion battery anode material with the internal porous structure has the advantages of simple parameters required to be adjusted, low ammonia water consumption and good element precipitation uniformity, and is suitable for large-scale industrial production;
(2) the anode material prepared from the precursor has an obvious porous structure, and after the lithium ion battery is prepared, the wettability of electrolyte can be increased, so that the power performance of the battery is improved;
(3) furthermore, when the precursor is used as a raw material to prepare the cathode material, the processability and structural stability of the cathode material can be improved through doping and coating processes, and the comprehensive performance index of the cathode material is further improved.
Drawings
Fig. 1 is a cross-sectional SEM image of the positive electrode material of the lithium ion battery prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Preparing a precursor of the lithium ion battery anode material:
s1, the reaction product is (Ni) according to the coprecipitation0.85Co0.1Mn0.05)0.99Al0.01(OH)2Dissolving nickel sulfate, cobalt sulfate, manganese sulfate and aluminum sulfate in water to obtain a first mixed solution with the metal ion concentration of 2 mol/L;
s2, taking Ni as a coprecipitation reaction product0.85Co0.1Mn0.05(OH)2Dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to obtain a second mixed solution with the metal ion concentration of 2 mol/L;
s3, under the protection of nitrogen, continuously adding the first mixed solution, a sodium hydroxide solution with the concentration of 4.5mol/L and an ammonia water solution with the concentration of 9mol/L into the reaction kettle, controlling the feeding flow rate of the first mixed solution to be 30mL/min, and controlling NH in the reaction system3The concentration of the second mixed solution is 9g/L, the pH of the reaction system is 11.8, the first-stage coprecipitation reaction is carried out under the conditions that the temperature is 52 ℃ and the stirring speed is 700rpm to form a precursor core part, the granularity of the precursor core part is 2 mu m, then the first mixed solution is stopped to be added, the second mixed solution, the sodium hydroxide solution with the concentration of 4.5mol/L and the ammonia water solution with the concentration of 9mol/L are continuously added into a reaction kettle, the feeding flow rate of the second mixed solution is controlled to be 30mL/min, and NH in the reaction system is carried out3The concentration of the precursor is 9g/L, the pH of the reaction system is 11.8, the second stage coprecipitation reaction is carried out under the conditions that the temperature is 52 ℃ and the stirring speed is 700rpm, and the outer surface of the inner core part of the precursor is coated to form a precursor shell part, so that the lithium ion battery anode material precursor with the granularity of 4 mu m is obtained.
The precursor of the lithium ion battery anode material prepared by the method comprises an inner core and a shell wrapping the outer surface of the inner core, wherein the inner core is loose and has a porous structure, and the chemical composition of the inner core is shown as a general formula (Ni)0.85Co0.1Mn0.05)0.99Al0.01(OH)2Shown; the shell is compact, and the chemical composition of the shell is shown as the general formula Ni0.85Co0.1Mn0.05(OH)2As shown.
Preparing a power type lithium ion battery anode material:
(1) uniformly mixing the lithium ion battery positive electrode material precursor, lithium hydroxide monohydrate and nano-alumina to obtain a first mixture, wherein the ratio of the sum of the molar numbers of Ni, Co and Mn to the molar number of Li in the first mixture is 1: 1.04, the ratio of the sum of the mole numbers of Ni, Co and Mn to the mole number of the nano alumina is 1: 0.03; carrying out primary sintering on the first mixture in a pure oxygen atmosphere, wherein the sintering temperature is 790 ℃, and the sintering time is 15h, so as to obtain a primary sintered material;
(2) uniformly mixing the primary sintering material, boric acid, nano-alumina and cobalt hydroxide to obtain a second mixture, wherein in the second mixture, the mass of boron element in the boric acid is 0.1% of the mass of the primary sintering material, the mass of aluminum element in the nano-alumina is 0.1% of the mass of the primary sintering material, and the mass of cobalt element in the cobalt hydroxide is 0.1% of the mass of the primary sintering material; and (3) sintering the second mixture for the second time in a pure oxygen atmosphere at the sintering temperature of 400 ℃ for 3 hours to obtain the composite material.
Example 2
Preparing a precursor of the lithium ion battery anode material:
s1, the reaction product is (Ni) according to the coprecipitation0.6Co0.2Mn0.2)0.99Al0.01(OH)2Dissolving nickel sulfate, cobalt sulfate, manganese sulfate and aluminum sulfate in water to obtain a first mixed solution with the metal ion concentration of 2.2 mol/L;
s2, taking Ni as a coprecipitation reaction product0.6Co0.2Mn0.2(OH)2Dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to obtain a second mixed solution with the metal ion concentration of 2.2 mol/L;
s3, under the protection of nitrogen, continuously adding the first mixed solution, a sodium hydroxide solution with the concentration of 6mol/L and an ammonia water solution with the concentration of 10mol/L into the reaction kettle, controlling the feeding flow rate of the first mixed solution to be 30mL/min, and controlling NH in the reaction system3The concentration of (A) is 10g/L, the pH of the reaction system is 11.8, the reaction system is stirred at a temperature of 55 DEG CCarrying out a first-stage coprecipitation reaction at the speed of 800rpm to form a precursor core part, wherein the granularity of the precursor core part is 3 microns, then stopping adding the first mixed solution, continuously adding the second mixed solution, a sodium hydroxide solution with the concentration of 6mol/L and an ammonia water solution with the concentration of 10mol/L into a reaction kettle, controlling the feeding flow rate of the second mixed solution to be 30mL/min, and carrying out NH reaction in a reaction system3The concentration of the precursor is 10g/L, the pH of a reaction system is 11.8, the second stage coprecipitation reaction is carried out under the conditions that the temperature is 55 ℃ and the stirring speed is 800rpm, and the outer surface of the inner core part of the precursor is coated to form a precursor shell part, so that the lithium ion battery anode material precursor with the granularity of 6 mu m is obtained.
The precursor of the lithium ion battery anode material prepared by the method comprises an inner core and a shell wrapping the outer surface of the inner core, wherein the inner core is loose and has a porous structure, and the chemical composition of the inner core is shown as a general formula (Ni)0.6Co0.2Mn0.2)0.99Al0.01(OH)2Shown; the shell is compact, and the chemical composition of the shell is shown as the general formula Ni0.6Co0.2Mn0.2(OH)2As shown.
Preparing a power type lithium ion battery anode material:
(1) uniformly mixing the lithium ion battery positive electrode material precursor, lithium hydroxide monohydrate and nano zirconia to obtain a first mixture, wherein the ratio of the sum of the molar numbers of Ni, Co and Mn to the molar number of Li in the first mixture is 1: 1.05, the ratio of the sum of the mole numbers of Ni, Co and Mn to the mole number of the nano zirconia is 1: 0.02; carrying out primary sintering on the first mixture in a pure oxygen atmosphere, wherein the sintering temperature is 830 ℃, and the sintering time is 18h, so as to obtain a primary sintering material;
(2) uniformly mixing the primary sintering material, boric acid, nano-alumina and cobalt hydroxide to obtain a second mixture, wherein in the second mixture, the mass of boron element in the boric acid is 0.1% of the mass of the primary sintering material, the mass of aluminum element in the nano-alumina is 0.2% of the mass of the primary sintering material, and the mass of cobalt element in the cobalt hydroxide is 0.1% of the mass of the primary sintering material; and (3) sintering the second mixture for the second time in a pure oxygen atmosphere, wherein the sintering temperature is 600 ℃, and the sintering time is 5 hours.
Example 3
Preparing a precursor of the lithium ion battery anode material:
s1, the reaction product is (Ni) according to the coprecipitation0.5Co0.2Mn0.3)0.99Al0.01(OH)2Dissolving nickel sulfate, cobalt sulfate, manganese sulfate and aluminum sulfate in water to obtain a first mixed solution with the metal ion concentration of 1.8 mol/L;
s2, taking Ni as a coprecipitation reaction product0.5Co0.2Mn0.3(OH)2Dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to obtain a second mixed solution with the metal ion concentration of 1.8 mol/L;
s3, under the protection of nitrogen, continuously adding the first mixed solution, a sodium hydroxide solution with the concentration of 4mol/L and an ammonia water solution with the concentration of 7mol/L into the reaction kettle, controlling the feeding flow rate of the first mixed solution to be 30mL/min, and controlling NH in the reaction system3The concentration of the second mixed solution is 5g/L, the pH of the reaction system is 11.2, the first-stage coprecipitation reaction is carried out under the conditions that the temperature is 50 ℃ and the stirring speed is 900rpm to form a precursor core part, wherein the granularity of the precursor core part is 2 mu m, then the first mixed solution is stopped to be added, the second mixed solution, the sodium hydroxide solution with the concentration of 4mol/L and the ammonia water solution with the concentration of 7mol/L are continuously added into a reaction kettle, the feeding flow rate of the second mixed solution is controlled to be 30mL/min, and NH in the reaction system3The concentration of the precursor is 5g/L, the pH value of the reaction system is 11.2, the second stage coprecipitation reaction is carried out under the conditions that the temperature is 50 ℃ and the stirring speed is 900rpm, and the outer surface of the inner core part of the precursor is coated to form a precursor shell part, so that the lithium ion battery anode material precursor with the granularity of 4 mu m is obtained.
The precursor of the lithium ion battery anode material prepared by the method comprises an inner core and a shell wrapping the outer surface of the inner core, wherein the inner core is loose and has a porous structure, and the chemical composition of the inner core is shown as a general formula (Ni)0.5Co0.2Mn0.3)0.99Al0.01(OH)2Shown; the shell is compact, and the chemical composition of the shell is shown as the general formula Ni0.5Co0.2Mn0.3(OH)2As shown.
Preparing a power type lithium ion battery anode material:
(1) uniformly mixing the lithium ion battery positive electrode material precursor, lithium hydroxide monohydrate and nano titanium dioxide to obtain a first mixture, wherein in the first mixture, the ratio of the sum of the molar numbers of Ni, Co and Mn to the molar number of Li is 1: 1.01, the ratio of the sum of the mole numbers of Ni, Co and Mn to the mole number of the nano titanium dioxide is 1: 0.01; carrying out primary sintering on the first mixture in a pure oxygen atmosphere, wherein the sintering temperature is 900 ℃, and the sintering time is 20 hours, so as to obtain a primary sintered material;
(2) uniformly mixing the primary sintering material, boric acid, nano-alumina and cobalt hydroxide to obtain a second mixture, wherein in the second mixture, the mass of boron element in the boric acid is 0.1% of the mass of the primary sintering material, the mass of aluminum element in the nano-alumina is 0.3% of the mass of the primary sintering material, and the mass of cobalt element in the cobalt hydroxide is 0.1% of the mass of the primary sintering material; and (3) sintering the second mixture for the second time in a pure oxygen atmosphere, wherein the sintering temperature is 500 ℃, and the sintering time is 4 hours, thus obtaining the composite material.
Example 4
Preparing a precursor of the lithium ion battery anode material:
s1, the reaction product is (Ni) according to the coprecipitation0.9Co0.05Mn0.05)0.99Al0.01(OH)2Dissolving nickel sulfate, cobalt sulfate, manganese sulfate and aluminum sulfate in water to obtain a first mixed solution with the metal ion concentration of 1.8 mol/L;
s2, taking Ni as a coprecipitation reaction product0.9Co0.05Mn0.05(OH)2Dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to obtain a second mixed solution with the metal ion concentration of 1.8 mol/L;
s3, continuously adding the first mixed solution and sodium hydroxide with the concentration of 4mol/L into the reaction kettle under the protection of nitrogenThe solution and 7mol/L ammonia water solution are added, the feeding flow rate of the first mixed solution is controlled to be 30mL/min, and NH in the reaction system3The concentration of the second mixed solution is 7g/L, the pH of the reaction system is 11.6, the first-stage coprecipitation reaction is carried out under the conditions that the temperature is 52 ℃ and the stirring speed is 600rpm to form a precursor core part, the granularity of the precursor core part is 3 mu m, then the first mixed solution is stopped to be added, the second mixed solution, the sodium hydroxide solution with the concentration of 4mol/L and the ammonia water solution with the concentration of 7mol/L are continuously added into a reaction kettle, the feeding flow rate of the second mixed solution is controlled to be 30mL/min, and NH in the reaction system3The concentration of the precursor is 7g/L, the pH of a reaction system is 11.6, the second stage coprecipitation reaction is carried out under the conditions that the temperature is 52 ℃ and the stirring speed is 600rpm, and the outer surface of the inner core part of the precursor is coated to form a precursor shell part, so that the lithium ion battery anode material precursor with the granularity of 5 mu m is obtained.
The precursor of the lithium ion battery anode material prepared by the method comprises an inner core and a shell wrapping the outer surface of the inner core, wherein the inner core is loose and has a porous structure, and the chemical composition of the inner core is shown as a general formula (Ni)0.9Co0.05Mn0.05)0.99Al0.01(OH)2Shown; the shell is compact, and the chemical composition of the shell is shown as the general formula Ni0.9Co0.05Mn0.05(OH)2As shown.
Preparing a power type lithium ion battery anode material:
(1) and uniformly mixing the lithium ion battery positive electrode material precursor, a lithium source and nano zirconia to obtain a first mixture, wherein in the first mixture, the ratio of the sum of the molar numbers of Ni, Co and Mn to the molar number of Li is 1: 1.03, the ratio of the sum of the mole numbers of Ni, Co and Mn to the mole number of the nano zirconia is 1: 0.04; carrying out primary sintering on the first mixture in a pure oxygen atmosphere, wherein the sintering temperature is 710 ℃, and the sintering time is 12h, so as to obtain a primary sintering material;
(2) uniformly mixing the primary sintering material, boric acid, nano-alumina and cobalt hydroxide to obtain a second mixture, wherein in the second mixture, the mass of boron in the boric acid is 0.1% of the mass of the primary sintering material, the mass of aluminum in the nano-alumina is 0.2% of the mass of the primary sintering material, and the mass of cobalt in the cobalt hydroxide is 0.2% of the mass of the primary sintering material; and (3) sintering the second mixture for the second time in a pure oxygen atmosphere, wherein the sintering temperature is 300 ℃, and the sintering time is 2 hours, so as to obtain the composite material.
The lithium ion battery positive electrode materials obtained in the examples 1 to 4 are assembled into a 2016 button battery and tested in a discharge interval of 2.75 to 4.3V under the condition that the 1C theoretical capacity is 200 mAh/g. Table 1 shows the electrochemical properties of the materials of examples 1-4, and it can be seen that the materials of the examples have high capacity, good rate capability and excellent cycle performance.
Table 1 electrochemical performance of the materials of examples 1-4
0.1C 1C 2C 3C Capacity retention @1C at 100 weeks
Example 1 205.2 198.2 192.1 187.2 94.2％
Example 2 173.2 163.5 157.3 152.1 99.5％
Example 3 182.2 175.3 167.4 162.6 98.1％
Example 4 212.3 204.1 198.2 192.5 92.1％
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. A preparation method of a precursor of a lithium ion battery positive electrode material is characterized by comprising the following steps:
s1, the reaction product is (Ni) according to the coprecipitationaCobMnc)1-xAlx(OH)2Dissolving nickel salt, cobalt salt, manganese salt and aluminum salt in water to obtain a first mixed solution, wherein x is more than or equal to 0.01 and less than or equal to 0.07, a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.2, c is more than or equal to 0.05 and less than or equal to 0.3, and a + b+c＝1；
S2, taking Ni as a coprecipitation reaction productdCoeMnf(OH)2Dissolving nickel salt, cobalt salt and manganese salt in water to obtain a second mixed solution, wherein d is more than or equal to 0.5 and less than or equal to 0.9, e is more than or equal to 0.05 and less than or equal to 0.2, f is more than or equal to 0.05 and less than or equal to 0.3, and d + e + f is equal to 1;
and S3, continuously adding the first mixed solution, the alkali solution and the ammonia water solution into the reaction kettle, carrying out a first-stage coprecipitation reaction to form a precursor core part, then stopping adding the first mixed solution, continuously adding the second mixed solution, the alkali solution and the ammonia water solution into the reaction kettle, carrying out a second-stage coprecipitation reaction, and coating the outer surface of the precursor core part to form a precursor shell part, thereby obtaining the lithium ion battery anode material precursor.
2. The method for preparing the precursor of the lithium ion battery cathode material according to claim 1, wherein NH is contained in the reaction system of the first-stage co-precipitation reaction3The concentration of (A) is 5-10g/L, and the pH value is 11.2-12.0; NH in the reaction system of the second-stage coprecipitation reaction3The concentration of (A) is 5-10g/L, and the pH value is 11.2-12.0.
3. The method for preparing the precursor of the lithium ion battery cathode material according to claim 1 or 2, wherein the temperature of the first-stage coprecipitation reaction is 50-55 ℃, the reaction is performed under stirring, and the stirring speed is 600-900 rpm; the temperature of the second stage coprecipitation reaction is 50-55 ℃, the reaction is carried out under stirring, and the stirring speed is 600-900 rpm; and the first-stage coprecipitation reaction and the second-stage coprecipitation reaction are carried out under the protection of inert gas.
4. The method for preparing the precursor of the positive electrode material for the lithium ion battery according to any one of claims 1 to 3, wherein the particle size of the core part of the precursor is 1.5 to 3 μm, and the particle size of the precursor is 4 to 6 μm.
5. The method for preparing the precursor of the lithium ion battery positive electrode material according to any one of claims 1 to 4, wherein the concentration of the metal ions in the first mixed solution is 1.8 to 2.2 mol/L; the concentration of metal ions in the second mixed solution is 1.8-2.2 mol/L; the concentration of the ammonia water solution is 7-10 mol/L; the concentration of the alkali solution is 4-6 mol/L; the alkali solution is at least one aqueous solution of sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium carbonate; the nickel salt is at least one of nickel sulfate, nickel nitrate and nickel chloride; the cobalt salt is at least one of cobalt sulfate, cobalt nitrate and cobalt chloride; the manganese salt is at least one of manganese sulfate, manganese nitrate and manganese chloride; the aluminum salt is at least one of aluminum sulfate, aluminum nitrate and aluminum chloride.
6. A precursor of a lithium ion battery positive electrode material, which is prepared by the preparation method of any one of claims 1 to 5; the precursor comprises an inner core and an outer shell wrapping the outer surface of the inner core, wherein the inner core is loose and has a porous structure, and the chemical composition of the inner core is shown as the general formula (Ni)aCobMnc)1-xAlx(OH)2Wherein x is more than or equal to 0.01 and less than or equal to 0.07, a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.2, c is more than or equal to 0.05 and less than or equal to 0.3, and a + b + c is equal to 1; the shell is compact, and the chemical composition of the shell is shown as the general formula NidCoeMnf(OH)2Wherein d is more than or equal to 0.5 and less than or equal to 0.9, e is more than or equal to 0.05 and less than or equal to 0.2, f is more than or equal to 0.05 and less than or equal to 0.3, and d + e + f is equal to 1.
7. The use of the lithium ion battery positive electrode material precursor of claim 6 in the preparation of a lithium ion battery positive electrode material.
8. The preparation method of the power type lithium ion battery anode material is characterized by comprising the following steps:
(1) uniformly mixing the lithium ion battery anode material precursor, the lithium source and the nano oxide to obtain a first mixture, and performing primary sintering to obtain a primary sintered material;
(2) and uniformly mixing the primary sintering material, the boron source, the nano aluminum oxide and the cobalt hydroxide to obtain a second mixture, and sintering for the second time to obtain the secondary sintering material.
9. The power lithium ion battery positive electrode material according to claim 8, wherein the ratio of the sum of the number of moles of Ni, Co, Mn to the number of moles of Li in the first mixture is 1: (1.01-1.05), the ratio of the sum of the mole numbers of Ni, Co and Mn to the mole number of the nano oxide is 1: (0.01-0.04); in the second mixture, the sum of the mass of boron source, boron element, aluminum element and cobalt element in the nano alumina and the cobalt hydroxide is 0.2-0.5% of the mass of the primary sintering material; preferably, the lithium source is lithium carbonate, lithium hydroxide or a combination thereof, the nano oxide is at least one of nano alumina, nano zirconia and nano titania, and the boron source is boric acid.
10. The power type lithium ion battery anode material as claimed in claim 8 or 9, wherein the sintering atmosphere of the primary sintering is pure oxygen atmosphere, the sintering temperature is 710-900 ℃, and the sintering time is 12-20h, the sintering atmosphere of the secondary sintering is pure oxygen atmosphere, the sintering temperature is 300-600 ℃, and the sintering time is 2-5 h.
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