CN111634958A - Precursor for lithium battery, lithium battery positive electrode material and preparation method of lithium battery positive electrode material - Google Patents

Precursor for lithium battery, lithium battery positive electrode material and preparation method of lithium battery positive electrode material Download PDF

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CN111634958A
CN111634958A CN202010488013.3A CN202010488013A CN111634958A CN 111634958 A CN111634958 A CN 111634958A CN 202010488013 A CN202010488013 A CN 202010488013A CN 111634958 A CN111634958 A CN 111634958A
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precursor
reaction
solution
nickel
salt
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张坤
陈康
许开华
蒋振康
薛晓斐
李聪
黎俊
孙海波
范亮姣
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Grammy Corp
GEM Co Ltd China
Jingmen GEM New Material Co Ltd
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Jingmen GEM New Material 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
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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 invention discloses a precursor for a lithium battery, a lithium battery anode material and a preparation method thereof, wherein doping elements such as Y, W, Ti and Al are added when a ternary precursor is prepared by using a chemical coprecipitation method, and the doping elements are only doped on the surface layer of particles, so that the overall doping amount of the doping elements is reduced while the surface structure stability of the material is effectively improved, the reaction process is strictly controlled in the synthesis process of the precursor, primary particles are directionally arranged to form a radial structure from inside to outside, and due to the characteristics of coprecipitation, the doping elements are uniformly distributed on the surface layer of the precursor material, and then the ternary precursor is mixed with a lithium source for sintering, so that the high-nickel multi-element anode material with good multiplying power performance, cycle performance and thermal stability is obtained by utilizing different modification effects of the two methods.

Description

Precursor for lithium battery, lithium battery positive electrode material and preparation method of lithium battery positive electrode material
Technical Field
The invention relates to the field of lithium battery materials, in particular to a precursor for a lithium battery, a lithium battery positive electrode material and a preparation method thereof.
Background
With the development of more and more electronic products toward miniaturization and the rapid development of electric vehicles, the lithium ion battery cathode material is rapidly developing toward higher energy density, volumetric specific energy, cycle life, safety and lower cost.
Currently, the commonly used lithium ion battery anode materials mainly comprise the following materials: lithium manganate with a spinel structure, lithium cobaltate with a layered structure, lithium iron phosphate with a spinel polyanion olivine structure and a ternary material with a layered structure. Among them, the ternary material has the advantages of high specific capacity, stable cycle performance, relatively low cost, good safety performance, etc., and thus becomes a new lithium ion battery positive electrode material which is currently attracting much attention. Under the conventional working voltage of 4.4V, the higher the content of nickel element in the ternary cathode material is, the larger the specific capacity is. Thus, nickel contentHigh nickel ternary positive electrode materials above 0.6 have received increasing attention as a hotspot of research in recent years. However, due to the proximity of the ionic particle size, LiNi increases as the nickel content of the material increases1-x- yCoxMnyO2Ni in the material2+And Li+The cation-mixing phenomenon of (2) is more serious, which inhibits the diffusion of lithium ions; on the other hand, the unstable Ni in the high nickel positive electrode material during charge and discharge4+As a result, the structure of the material is prone to a series of phase transformation processes, which lead to a reduction in the active material of the material, a capacity fade, and a concomitant release of oxygen. Therefore, the thermal stability, the cycle performance and the rate capability of the high-nickel ternary material need to be further improved.
In order to improve the comprehensive electrochemical performance of the high-nickel ternary material, modification means such as ion doping and surface coating are generally adopted. Compared with coating, the doping process is simpler and is easier to realize industrialization, but inactive elements are often used for doping, and when the doping amount is excessive, the specific capacity of the high-nickel ternary material is obviously reduced. In addition, since primary particles of the current polycrystalline positive electrode material are mainly irregular single crystal particles, a phenomenon of charge non-uniformity may occur in the polycrystalline positive electrode material during charge and discharge, and cracks may occur in and between crystals. The growth of these cracks will eventually destroy the electrode structure, causing loss of energy storage active material, reduced cycle performance, and shortened battery life.
Therefore, on the premise of effectively improving the performance of the high-nickel ternary material, the use amount of the doped elements is reduced as much as possible, and the internal structure of the material is adjusted, so that the modified high-nickel ternary material has better cycle performance and rate capability while keeping high capacity, and the method has very important significance for promoting the development of the high-nickel ternary cathode material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a precursor for a surface layer doped lithium battery with a radial structure, a lithium battery positive electrode material and a preparation method thereof.
The invention is realized by the following technical scheme.
The precursor for the lithium battery is characterized in that the physical structure of the precursor comprises a core and a shell layer coated on the outer surface of the core, and the core is made of the following compounds: ni0.8Co0.1Mn0.1(OH)2(I); the shell layer is made of the following compounds: (Ni)0.8Co0.1Mn0.1)1-aMa(OH)2+b(II); wherein, the doping element M is Y, W, Ti and one or more of Al, a is more than 0 and less than or equal to 0.1, and the value of b is determined by the valence of the metal ion M and the doping amount a according to the charge balance principle.
Furthermore, the average particle size of the inner core is 8-10 μm, and the thickness of the shell layer is 1-2 μm.
Furthermore, the cross section of the precursor is in a shape of diverging from the circle center to the circumference.
The preparation method of the precursor is characterized by comprising the following steps:
(1) according to the molar ratio of Ni, Co and Mn of 0.8: 0.1: fully mixing soluble nickel salt, cobalt salt and manganese salt according to the proportion of 0.1 to prepare a mixed salt solution A;
(2) according to the weight ratio of Ni: co: mn: m molar ratio of 0.8-0.8 a: 0.1-0.1 a: 0.1-0.1 a: fully mixing soluble nickel salt, cobalt salt, manganese salt and M salt corresponding to the doping element M according to the proportion of a to prepare a mixed salt solution B, wherein a is more than 0 and less than or equal to 0.1;
(3) adding the mixed salt solution A prepared in the step (1), an alkali solution and ammonia water into a reaction kettle containing a base solution through a metering pump respectively, introducing inert gas into the reaction kettle, and stirring to perform a coprecipitation reaction;
(4) and (3) when the granularity of the material particles in the reaction kettle in the step (3) reaches the target granularity (serving as a core), stopping adding the mixed salt solution A, adding the mixed salt solution B prepared in the step (2) into the reaction kettle, continuously stirring for carrying out coprecipitation reaction, stopping the reaction when the outer surface of the particles grows to a shell layer with the target thickness, transferring the material in the reaction kettle to an ageing tank for ageing, centrifugally washing and drying, and obtaining the surface layer doped precursor with the cross section appearance which is in a divergent shape from the circle center to the circumference.
Further, in the steps (1) and (2), the soluble nickel salt is at least one of nickel sulfate, nickel chloride and nickel nitrate, the soluble cobalt salt is at least one of cobalt sulfate, cobalt chloride and cobalt nitrate, and the soluble manganese salt is at least one of manganese sulfate, manganese chloride and manganese nitrate.
Further, the doping element M in the step (2) is one or a mixture of Y, W, Ti and Al; the salt in the M salt is at least one of sulfate, chloride and nitrate.
Further, the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the mixed salt solution A in the step (1) is 1-3 mol/L.
Further, the sum of the concentrations of nickel ions, cobalt ions, manganese ions and M ions in the mixed salt solution B in the step (2) is 1-3 mol/L.
Further, the molar concentration of the alkali solution in the step (3) is 3-5 mol/L, and the molar concentration of the ammonia water is 6-8 mol/L; the alkali in the alkali solution is sodium hydroxide or potassium hydroxide.
Further, in the step (3), the base solution comprises ammonia water and a sodium hydroxide solution, the pH of the base solution is 12-12.5, and the ammonia concentration is 15-20 g/L.
Further, in the steps (3) and (4), the reaction conditions of the coprecipitation reaction are as follows: the reaction temperature is 40-70 ℃, the pH is 11.5-12.5, the ammonia concentration is 15-25 g/L, the stirring speed is 200-250 rpm, and the reaction time is 80-120 h.
Further, in the step (4), when the average particle size of the material particles in the reaction kettle is 8-10 μm, the addition of the mixed salt solution A is stopped; stopping the reaction when the outer surface of the particle grows to the thickness of 1-2 mu m.
The lithium ion battery positive electrode material prepared by using the precursor is characterized in that the physical structure of the material comprises a core and a shell layer coated on the outer surface of the core; wherein, the material of the inner core is a compound as follows: l isiNi0.8Co0.1Mn0.1O2(I); the shell layer is made of the following compounds: li (Ni)0.8Co0.1Mn0.1)1-aMaO2(II), wherein a is more than 0 and less than or equal to 0.1, and M is Y, W, Ti and one or more of Al.
Furthermore, the cross section of the anode material is in a divergent shape from the circle center to the circumference.
The preparation method of the lithium ion battery positive electrode material is characterized by comprising the following steps: and mixing the precursor with lithium hydroxide, and sintering at high temperature in an atmosphere furnace filled with oxygen to obtain the lithium ion battery anode material.
Further, the precursor and lithium hydroxide are mixed according to a lithium proportion of 1.03-1.10 (the lithium proportion refers to a molar ratio of lithium ions to the total amount of metal ions of the precursor, and Li is lost and excessively added in a sintering process), the sintering temperature is 700-1000 ℃, and the sintering time is 8-16 h.
According to the invention, Y, W, Ti, Al and other doping elements are added when a ternary precursor is prepared by using a chemical coprecipitation method, and the doping elements are only doped on the surface layer of particles, so that the surface structure stability of the material is effectively improved, the overall doping amount of the doping elements is also reduced, the reaction process is strictly controlled in the synthesis process of the precursor, primary particles are directionally arranged to form a radial structure from inside to outside, due to the characteristics of coprecipitation, the doping elements are uniformly distributed on the surface layer of the precursor material, then the ternary precursor is mixed with a lithium source for sintering, and the high-nickel multi-element cathode material with good multiplying power performance, cycle performance and thermal stability is obtained by utilizing different modification effects of the two methods.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the doping elements are directly added in the coprecipitation reaction process, so that the doping elements can be uniformly distributed in the surface layer of the precursor particles at an atomic level, and the doping modification effect is fully exerted. The doping elements can effectively improve the stability of the surface layer structure of the ternary material particles and can improve the cycle performance and the thermal stability of the material. The doping is only carried out on the surface layer of the sample particles, so that the stability of the surface structure of the material is effectively improved, the overall doping amount of elements is reduced, and the influence of doping inactive elements on the capacity of the material is reduced. The primary particles are directionally arranged to form a radial structure from inside to outside by controlling the synthesis process of the precursor, the precursor particles grow radially from inside to outside, the diffusion of lithium salt in the particles of the precursor in the sintering process is facilitated, the reaction is more sufficient, the prepared ternary anode material can form a lithium ion diffusion channel from inside to outside, the radial structure is beneficial to the uniform extraction and the insertion of lithium ions, the nonuniformity of charge distribution in the particles is reduced, and the particle structure is more stable, so that the multiplying power performance and the cycle performance of the material are improved. And meanwhile, surface layer doping and internal structure regulation are carried out on the high-nickel ternary cathode material, and the rate capability and the cycle performance of the high-nickel ternary cathode material are effectively improved by utilizing the synergistic effect of the surface layer doping and the internal structure regulation.
Drawings
Fig. 1 is an SEM sectional view of a high nickel ternary positive electrode material precursor having a radial structure prepared in example 1.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Comparative example 1
Step 1, preparing a mixed salt solution containing nickel ions, cobalt ions and manganese ions; wherein the molar ratio of the nickel ions to the cobalt ions to the manganese ions is 80: 10: 10, and the total concentration of nickel ions, cobalt ions and manganese ions is 2 mol/L;
adding the mixed salt solution, a sodium hydroxide solution and ammonia water into a reaction kettle containing a base solution in a parallel flow mode for coprecipitation reaction, and aging, washing and drying to obtain a nickel-cobalt-manganese ternary positive electrode material precursor;
and 2, uniformly mixing the precursor lithium hydroxide of the nickel-cobalt-manganese ternary cathode material, performing high-temperature treatment, cooling, crushing and sieving to obtain the conventional NCM811 ternary cathode material.
Example 1
The positive electrode material for the lithium ion battery provided by the embodiment has a core-shell structure in element composition, and comprises a core layer and a shell layer coated on the outer surface of the core layer. Wherein, the material of the nuclear layer is the following compound: LiNi0.8Co0.1Mn0.1O2(ii) a The shell layer is made of the following compounds: li (Ni)0.8Co0.1Mn0.1)0.9Y0.05W0.05O2(ii) a The preparation method of the lithium ion battery anode material comprises the following steps:
step 1, mixing the components in a molar ratio of Ni: co: mn is 0.8: 0.1: fully mixing a mixed solution of nickel sulfate and nickel nitrate, a mixed solution of cobalt sulfate and cobalt nitrate and a mixed solution of manganese nitrate and manganese sulfate according to the proportion of 0.1 to prepare a mixed salt solution A with the total metal ion concentration of 1mol/L for later use;
step 2, mixing the components in a molar ratio of Ni: co: mn: y: w is 0.72: 0.09: 0.09: 0.05: 0.05, fully mixing nickel sulfate, cobalt sulfate, manganese sulfate, yttrium sulfate and tungsten sulfate to prepare a mixed salt solution B with the total concentration of metal ions being 3mol/L for later use;
and 3, under the protection of inert gas, respectively adding the mixed salt solution A, a sodium hydroxide solution with the concentration of 5mol/L and ammonia water with the concentration of 6mol/L into a reaction kettle containing the base solution through a metering pump. The base solution comprises ammonia water and a sodium hydroxide solution, the pH value of the base solution is 12, the ammonia concentration is 15g/L, the pH value of a reaction system is controlled to be 11.5-12 in the feeding reaction process, the ammonia concentration is 15g/L, and the coprecipitation reaction is carried out at the temperature of 40 ℃ and the stirring speed of 200 rpm;
step 4, when the granularity D of the material particles in the reaction kettle is larger than the granularity D of the material particles50When the particle size is 8 mu m, the mixed salt solution A in the step 3 is replaced by the mixed salt solution B obtained in the step 2, other process conditions are kept consistent with those in the step 3, the coprecipitation reaction is continued, when the shell layer on the outer surface of the particle grows to be 2 mu m in thickness, the reaction is stopped (the total reaction time is controlled to be 120h), and the materials in the reaction kettle are transferred to be agedAging in a dissolving tank, then centrifugally washing and drying to obtain a surface layer doped precursor with a cross section shape which is in a divergent shape from the circle center to the circumference.
Step 5, uniformly mixing the precursor obtained by the preparation method with lithium hydroxide, and sintering at high temperature for 8 hours in an atmosphere furnace with the temperature of 1000 ℃ and oxygen to obtain the anode material for the lithium ion battery, wherein the cross section of the anode material is in a shape of diverging from the circle center to the circumference; wherein the proportion of lithium is 1.03.
Example 2
In the cathode material for the lithium ion battery provided by the embodiment, the cathode material is of a core-shell structure in terms of element composition, and comprises a core and a shell layer coated on the outer surface of the core. Wherein, the material of the inner core is the following compound: LiNi0.8Co0.1Mn0.1O2(ii) a The shell layer is made of the following compounds: li (Ni)0.8Co0.1Mn0.1)0.95Y0.05O2(ii) a The preparation method of the cathode material for the lithium ion battery comprises the following steps:
step 1, mixing the components in a molar ratio of Ni: co: mn is 0.8: 0.1: fully mixing nickel chloride, cobalt chloride and manganese chloride according to the proportion of 0.1 to prepare a mixed salt solution A with the total concentration of metal ions being 3mol/L for later use;
step 2, mixing the components in a molar ratio of Ni: co: mn: y is 0.76: 0.095: 0.095: fully mixing a mixed solution of nickel chloride and nickel sulfate, a mixed solution of cobalt chloride and cobalt sulfate, a mixed solution of manganese chloride and manganese sulfate and a mixed solution of yttrium chloride and yttrium sulfate according to the proportion of 0.05 to prepare a mixed salt solution B with the total concentration of metal ions being 1mol/L for later use;
and 3, under the protection of inert gas, respectively adding the mixed salt solution A, a potassium hydroxide solution with the concentration of 3mol/L and ammonia water with the concentration of 8mol/L into a reaction kettle containing the base solution through a metering pump. The base solution comprises ammonia water and a potassium hydroxide solution, the pH value of the base solution is 12.5, the ammonia concentration is 20g/L, the pH value of a reaction system is controlled to be 11.5-12.5 in the feeding reaction process, the ammonia concentration is 25g/L, and the coprecipitation reaction is carried out at 70 ℃ and the stirring speed of 250 rpm;
step 4, when the granularity D of the material particles in the reaction kettle50And (2) when the particle size is 10 microns, replacing the mixed salt solution A in the step (3) with the mixed salt solution B in the step (2), keeping other process conditions consistent with those in the step (3), continuing coprecipitation reaction, stopping the reaction (controlling the total reaction time to be 80h) when the shell layer on the outer surface of the particle grows to be 1 micron thick, transferring the materials in the reaction kettle into an ageing tank for ageing, then centrifugally washing and drying to obtain the surface layer doped precursor with the cross section appearance which is in a divergent shape from the circle center to the circumference.
Step 5, uniformly mixing the precursor prepared by the preparation method with lithium hydroxide, and sintering at high temperature for 16 hours in an atmosphere furnace with 700 ℃ and oxygen to obtain the anode material for the lithium ion battery, wherein the cross section of the anode material is in a shape of diverging from the circle center to the circumference; wherein the proportion of lithium is 1.10.
Example 3
In the cathode material for the lithium ion battery provided by the embodiment, the cathode material is of a core-shell structure in terms of element composition, and comprises a core layer and a shell layer coated on the outer surface of the core. Wherein, the material of the inner core is the following compound: LiNi0.8Co0.1Mn0.1O2(ii) a The shell layer is made of the following compounds: li (Ni)0.8Co0.1Mn0.1)0.96W0.04O2(ii) a The preparation method of the cathode material for the lithium ion battery comprises the following steps:
step 1, mixing the components in a molar ratio of Ni: co: mn is 0.8: 0.1: fully mixing nickel sulfate, cobalt sulfate and manganese sulfate according to the proportion of 0.1 to prepare a mixed salt solution A with the total metal ion concentration of 2mol/L for later use;
step 2, mixing the components in a molar ratio of Ni: co: mn: w is 0.768: 0.096: 0.096: 0.04, fully mixing nickel sulfate, cobalt sulfate, manganese sulfate and tungsten sulfate to prepare a mixed salt solution B with the total concentration of metal ions being 2mol/L for later use;
and 3, under the protection of inert gas, respectively adding the mixed salt solution A, a sodium hydroxide solution with the concentration of 4mol/L and ammonia water with the concentration of 7mol/L into a reaction kettle containing the base solution through a metering pump. The base solution comprises ammonia water and a sodium hydroxide solution, the pH value of the base solution is 12.2, the ammonia concentration is 18g/L, the pH value of a reaction system is controlled to be 11.5-12.2 in the feeding reaction process, the ammonia concentration is 20g/L, and the coprecipitation reaction is carried out at 50 ℃ and the stirring speed of 220 rpm;
step 4, when the granularity D of the material particles in the reaction kettle50And (3) when the particle size is 9 micrometers, replacing the mixed salt solution A in the step (3) with the mixed salt solution B in the step (2), keeping other process conditions consistent with those in the step (3), continuing coprecipitation reaction, stopping the reaction when the shell layer on the outer surface of the particle is 1 micrometer long, transferring the material in the reaction kettle into an ageing tank for ageing, centrifugally washing and drying to obtain the surface layer doped precursor with the cross section appearance which is in a divergent shape from the circle center to the circumference.
Step 5, uniformly mixing the precursor prepared by the preparation method with lithium hydroxide, and sintering at high temperature for 10 hours in an atmosphere furnace with the temperature of 800 ℃ and oxygen to obtain the anode material for the lithium ion battery, wherein the cross section of the anode material is in a shape of diverging from the circle center to the circumference; wherein the proportion of lithium is 1.05.
Example 4
In the cathode material for the lithium ion battery provided by the embodiment, the cathode material is of a core-shell structure in terms of element composition, and comprises a core and a shell layer coated on the outer surface of the core. Wherein, the material of the inner core is the following compound: LiNi0.8Co0.1Mn0.1O2(ii) a The shell layer is made of the following compounds: li (Ni)0.8Co0.1Mn0.1)0.92W0.08O2(ii) a The preparation method of the cathode material for the lithium ion battery comprises the following steps:
step 1, mixing the components in a molar ratio of Ni: co: mn is 0.8: 0.1: fully mixing nickel sulfate, cobalt sulfate and manganese sulfate according to the proportion of 0.1 to prepare a mixed salt solution A with the total metal ion concentration of 2mol/L for later use;
step 2, mixing the components in a molar ratio of Ni: co: mn: w is 0.736: 0.092: 0.092: fully mixing nickel sulfate, cobalt sulfate, manganese sulfate and tungsten sulfate according to the proportion of 0.08 to prepare a mixed salt solution B with the total concentration of metal ions being 3mol/L for later use;
and 3, under the protection of inert gas, respectively adding the mixed salt solution A, a sodium hydroxide solution with the concentration of 5mol/L and ammonia water with the concentration of 8mol/L into a reaction kettle containing the base solution through a metering pump. The base solution comprises ammonia water and a sodium hydroxide solution, the pH value of the base solution is 12.4, the ammonia concentration is 19g/L, the pH value of a reaction system is controlled to be 11.5-12.4 in the feeding reaction process, the ammonia concentration is 21g/L, and the coprecipitation reaction is carried out at the temperature of 60 ℃ and the stirring speed of 230 rpm;
step 4, when the granularity D of the material particles in the reaction kettle50And (2) when the particle size is 10 microns, replacing the mixed salt solution A in the step (3) with the mixed salt solution B in the step (2), keeping other process conditions consistent with those in the step (3), continuing coprecipitation reaction, stopping the reaction when the shell layer on the outer surface of the particle grows to be 2 microns thick, transferring the material in the reaction kettle into an ageing tank for ageing, then centrifugally washing and drying to obtain the surface layer doped precursor with the cross section appearance which is in a divergent shape from the circle center to the circumference.
Step 5, uniformly mixing the precursor prepared by the preparation method with lithium hydroxide, and sintering at high temperature for 11 hours in an atmosphere furnace with the temperature of 900 ℃ and oxygen to obtain the anode material for the lithium ion battery, wherein the cross section of the anode material is in a shape of diverging from the circle center to the circumference; wherein the proportion of lithium is 1.09.
Example 5
In the cathode material for the lithium ion battery provided by the embodiment, the cathode material is of a core-shell structure in terms of element composition, and comprises a core and a shell layer coated on the outer surface of the core. Wherein, the material of the inner core is the following compound: LiNi0.8Co0.1Mn0.1O2(ii) a The material of the inner core is a compound as follows: li (Ni)0.8Co0.1Mn0.1)0.98Ti0.02O2(ii) a The preparation method of the cathode material for the lithium ion battery comprises the following steps:
step 1, mixing the components in a molar ratio of Ni: co: mn is 0.8: 0.1: fully mixing nickel nitrate, cobalt nitrate and manganese nitrate according to the proportion of 0.1 to prepare a mixed salt solution A with the total metal ion concentration of 2mol/L for later use;
step 2, mixing the components in a molar ratio of Ni: co: mn: ti is 0.784: 0.098: 0.098: fully mixing nickel nitrate, cobalt nitrate, manganese nitrate and tungsten nitrate according to the proportion of 0.02 to prepare a mixed salt solution B with the total concentration of metal ions being 1mol/L for later use;
and 3, under the protection of inert gas, respectively adding the mixed salt solution A, a sodium hydroxide solution with the concentration of 4mol/L and ammonia water with the concentration of 6mol/L into a reaction kettle containing the base solution through a metering pump. The base solution comprises ammonia water and a sodium hydroxide solution, the pH value of the base solution is 12.1, the ammonia concentration is 16g/L, the pH value of a reaction system is controlled to be 11.5-12.1 in the feeding reaction process, the ammonia concentration is 18g/L, and the coprecipitation reaction is carried out at 65 ℃ and the stirring speed of 210 rpm;
step 4, when the granularity D of the material particles in the reaction kettle50And (3) when the particle size is 9.5 microns, replacing the mixed salt solution A in the step (3) with the mixed salt solution B in the step (2), keeping other process conditions consistent with those in the step (3), continuing coprecipitation reaction, stopping the reaction when the shell layer on the outer surface of the particle grows to be 2 microns thick, transferring the material in the reaction kettle into an ageing tank for ageing, then centrifugally washing and drying to obtain the surface layer doped precursor with the cross section appearance of which is divergent from the circle center to the circumference.
Step 5, uniformly mixing the precursor prepared by the preparation method with lithium hydroxide, and sintering at high temperature for 9 hours in an atmosphere furnace with 850 ℃ and oxygen to obtain the anode material for the lithium ion battery, wherein the cross section of the anode material is in a shape of diverging from the circle center to the circumference; wherein, the proportion of lithium is 1.06.
Example 6
In the cathode material for the lithium ion battery provided by the embodiment, the cathode material is of a core-shell structure in terms of element composition, and comprises a core and a shell layer coated on the outer surface of the core. Wherein, the material of the inner core is the following compound: LiNi0.8Co0.1Mn0.1O2(ii) a The shell layer is made of the following compounds: li (Ni)0.8Co0.1Mn0.1)0.94Ti0.03Al0.03O2(ii) a The lithium ion batteryThe preparation method of the cathode material comprises the following steps:
step 1, mixing the components in a molar ratio of Ni: co: mn is 0.8: 0.1: fully mixing nickel nitrate, cobalt nitrate and manganese nitrate according to the proportion of 0.1 to prepare a mixed salt solution A with the total metal ion concentration of 2mol/L for later use;
step 2, mixing the components in a molar ratio of Ni: co: mn: ti: al is 0.752: 0.094: 0.094: 0.03: fully mixing nickel nitrate, cobalt nitrate, manganese nitrate, titanium nitrate and aluminum nitrate according to the proportion of 0.03 to prepare a mixed salt solution B with the total metal ion concentration of 2mol/L for later use;
and 3, under the protection of inert gas, respectively adding the mixed salt solution A, a sodium hydroxide solution with the concentration of 4mol/L and ammonia water with the concentration of 7mol/L into a reaction kettle containing the base solution through a metering pump. The base solution comprises ammonia water and a sodium hydroxide solution, the pH value of the base solution is 12.3, the ammonia concentration is 17g/L, the pH value of a reaction system is controlled to be 11.5-12.3 in the feeding reaction process, the ammonia concentration is 19g/L, and the coprecipitation reaction is carried out at the temperature of 55 ℃ and the stirring speed of 235 rpm;
step 4, when the granularity D of the material particles in the reaction kettle50And (2) when the particle size is 8 microns, replacing the mixed salt solution A in the step (3) with the mixed salt solution B in the step (2), keeping the technological conditions consistent with those in the step (3), continuing coprecipitation reaction, stopping the reaction when the shell layer on the outer surface of the particle grows to be 1 micron thick, transferring the material in the reaction kettle into an ageing tank for ageing, then centrifugally washing and drying to obtain the surface layer doped precursor with the cross section appearance which is divergent from the circle center to the circumference.
Step 5, uniformly mixing the precursor prepared by the preparation method with lithium hydroxide, and sintering at high temperature for 14 hours in an atmosphere furnace at 750 ℃ and filled with oxygen to obtain the anode material for the lithium ion battery, wherein the cross section of the anode material is in a shape of diverging from the circle center to the circumference; wherein the proportion of lithium is 1.04.
Example 7
In the cathode material for the lithium ion battery provided by the embodiment, the cathode material is of a core-shell structure in terms of element composition, and comprises a core and a shell layer coated on the outer surface of the core. Wherein, insideThe material of the core is a compound as follows: LiNi0.8Co0.1Mn0.1O2(ii) a The shell layer is made of the following compounds: li (Ni)0.8Co0.1Mn0.1)0.97Al0.03O2(ii) a The preparation method of the cathode material for the lithium ion battery comprises the following steps:
step 1, mixing the components in a molar ratio of Ni: co: mn is 0.8: 0.1: fully mixing nickel chloride, cobalt chloride and manganese chloride according to the proportion of 0.1 to prepare a mixed salt solution A with the total metal ion concentration of 2mol/L for later use;
step 2, mixing the components in a molar ratio of Ni: co: mn: al is 0.776: 0.097: 0.097: fully mixing nickel chloride, cobalt chloride, manganese chloride and aluminum chloride according to the proportion of 0.03 to prepare a mixed salt solution B with the total metal ion concentration of 3mol/L for later use;
and 3, under the protection of inert gas, respectively adding the mixed salt solution A, a sodium hydroxide solution with the concentration of 3.5mol/L and ammonia water with the concentration of 6.5mol/L into a reaction kettle containing the base solution through a metering pump. The base solution comprises ammonia water and a sodium hydroxide solution, the pH value of the base solution is 12.4, the ammonia concentration is 18g/L, the pH value of a reaction system is controlled to be 11.5-12.4 in the feeding reaction process, the ammonia concentration is 23g/L, and the coprecipitation reaction is carried out at the temperature of 48 ℃ and the stirring speed of 215 rpm;
step 4, when the granularity D of the material particles in the reaction kettle50And (2) when the diameter is 8.5 mu m, replacing the mixed salt solution A in the step (3) with the mixed salt solution B in the step (2), keeping the technological conditions consistent with those in the step (3), continuing the coprecipitation reaction, stopping the reaction when the shell layer on the outer surface of the particle is 1.5 mu m thick, transferring the materials in the reaction kettle into an ageing tank for ageing, centrifugally washing and drying to obtain the surface layer doped precursor with the section appearance which is divergent from the circle center to the circumference.
Step 5, uniformly mixing the precursor prepared by the preparation method with lithium hydroxide, and sintering at a high temperature for 13 hours in an atmosphere furnace at 880 ℃ and filled with oxygen to obtain the anode material for the lithium ion battery, wherein the cross section of the anode material is in a divergent shape from the center of a circle to the circumference; wherein the proportion of lithium is 1.08.
Example 8
In the cathode material for the lithium ion battery provided by the embodiment, the cathode material is of a core-shell structure in terms of element composition, and comprises a core and a shell layer coated on the outer surface of the core. Wherein, the material of the inner core is the following compound: LiNi0.8Co0.1Mn0.1O2(ii) a The shell layer is made of the following compounds: li (Ni)0.8Co0.1Mn0.1)0.93Al0.07O2(ii) a The preparation method of the cathode material for the lithium ion battery comprises the following steps:
step 1, mixing the components in a molar ratio of Ni: co: mn is 0.8: 0.1: fully mixing nickel sulfate, cobalt sulfate and manganese sulfate according to the proportion of 0.1 to prepare a mixed salt solution A with the total concentration of metal ions of 1.5mol/L for later use;
step 2, mixing the components in a molar ratio of Ni: co: mn: al is 0.744: 0.093: 0.093: 0.07, fully mixing nickel sulfate, cobalt sulfate, manganese sulfate and aluminum sulfate to prepare a mixed salt solution B with the total metal ion concentration of 2.5mol/L for later use;
and 3, under the protection of inert gas, respectively adding the mixed salt solution A, a sodium hydroxide solution with the concentration of 4.5mol/L and ammonia water with the concentration of 7.5mol/L into a reaction kettle containing the base solution through a metering pump. The base solution comprises ammonia water and a sodium hydroxide solution, the pH value of the base solution is 12.2, the ammonia concentration is 17.5g/L, the pH value of a reaction system is controlled to be 11.5-12.2 in the feeding reaction process, the ammonia concentration is 22.5g/L, and the coprecipitation reaction is carried out at the stirring speed of 245rpm at 62 ℃;
step 4, when the granularity D of the material particles in the reaction kettle50And (3) when the particle size is 9.5 microns, replacing the mixed salt solution A in the step (3) with the mixed salt solution B in the step (2), keeping the process conditions consistent with those in the step (3), continuing coprecipitation reaction, stopping the reaction when the shell layer on the outer surface of the particle grows to be 2 microns thick, transferring the material in the reaction kettle into an ageing tank for ageing, centrifugally washing and drying to obtain the surface layer doped precursor with the cross section appearance of which is divergent from the circle center to the circumference.
Step 5, uniformly mixing the precursor prepared by the preparation method with lithium hydroxide, and sintering at high temperature for 15 hours in an atmosphere furnace with 780 ℃ and oxygen to obtain the anode material for the lithium ion battery, wherein the cross section of the anode material is in a shape of diverging from the circle center to the circumference; wherein the proportion of lithium is 1.07.
Assembling a button cell and detecting:
the positive electrode materials for the core-shell doped lithium ion batteries obtained in the comparative example 1 and the examples 1 to 8 are prepared into positive plates, and the positive plates are respectively assembled into button batteries by taking metal lithium plates as negative electrodes to carry out charge-discharge comparative test, wherein the detection results are as follows:
table 1 shows specific discharge capacity test data of the battery positive electrode materials obtained in comparative example 1 and examples 1 to 8 and the button cell positive electrode materials
Figure BDA0002519834920000161
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.

Claims (16)

1. The precursor for the lithium battery is characterized in that the physical structure of the precursor comprises a core and a shell layer coated on the outer surface of the core, and the core is made of the following compounds: ni0.8Co0.1Mn0.1(OH)2(ii) a The shell layer is made of the following compounds: (Ni)0.8Co0.1Mn0.1)1-aMa(OH)2+b(ii) a Wherein, the doping element M is Y, W, Ti and one or more of Al, a is more than 0 and less than or equal to 0.1.
2. Precursor according to claim 1, wherein the average particle size of the core is 8-10 μm and the thickness of the shell is 1-2 μm.
3. The precursor according to claim 1, wherein the cross-sectional topography of the precursor is divergent from the center of the circle to the circumference.
4. A method of preparing a precursor according to any one of claims 1 to 3, wherein the method steps comprise:
(1) according to the molar ratio of Ni, Co and Mn of 0.8: 0.1: fully mixing soluble nickel salt, cobalt salt and manganese salt according to the proportion of 0.1 to prepare a mixed salt solution A;
(2) according to the weight ratio of Ni: co: mn: m molar ratio of 0.8-0.8 a: 0.1-0.1 a: 0.1-0.1 a: fully mixing soluble nickel salt, cobalt salt, manganese salt and M salt corresponding to the doping element M according to the proportion of a to prepare a mixed salt solution B, wherein a is more than 0 and less than or equal to 0.1;
(3) adding the mixed salt solution A prepared in the step (1), an alkali solution and ammonia water into a reaction kettle containing a base solution respectively, introducing inert gas into the reaction kettle, and stirring to perform a coprecipitation reaction;
(4) and (3) stopping adding the mixed salt solution A when the granularity of the material particles in the reaction kettle in the step (3) reaches the target granularity, adding the mixed salt solution B prepared in the step (2) into the reaction kettle, continuously stirring for coprecipitation reaction, stopping the reaction when the outer surface of the particles grows to a shell layer with the target thickness, transferring the material in the reaction kettle to an ageing tank for ageing, centrifugally washing and drying to obtain the surface layer doped precursor with the cross section appearance of which is in a divergent shape from the circle center to the circumference.
5. The method according to claim 4, wherein in the steps (1) and (2), the soluble nickel salt is at least one of nickel sulfate, nickel chloride and nickel nitrate, the soluble cobalt salt is at least one of cobalt sulfate, cobalt chloride and cobalt nitrate, and the soluble manganese salt is at least one of manganese sulfate, manganese chloride and manganese nitrate.
6. The method according to claim 4, wherein the doping element M in the step (2) is one or a mixture of Y, W, Ti and Al; the salt in the M salt is at least one of sulfate, chloride and nitrate.
7. The method according to claim 4, wherein the sum of the concentrations of the nickel ions, the cobalt ions and the manganese ions in the mixed salt solution A in the step (1) is 1-3 mol/L.
8. The method according to claim 4, wherein the sum of the concentrations of the nickel ions, the cobalt ions, the manganese ions and the M ions in the mixed salt solution B in the step (2) is 1-3 mol/L.
9. The method according to claim 4, wherein the molar concentration of the alkali solution in the step (3) is 3-5 mol/L, and the molar concentration of the ammonia water is 6-8 mol/L; the alkali in the alkali solution is sodium hydroxide or potassium hydroxide.
10. The method according to claim 4, wherein in the step (3), the base solution comprises ammonia water and sodium hydroxide solution, the pH of the base solution is 12-12.5, and the ammonia concentration is 15-20 g/L.
11. The method according to claim 4, wherein in the steps (3) and (4), the reaction conditions of the coprecipitation reaction are as follows: the reaction temperature is 40-70 ℃, the pH is 11.5-12.5, the ammonia concentration is 15-25 g/L, the stirring speed is 200-250 rpm, and the reaction time is 80-120 h.
12. The method as claimed in claim 4, wherein in the step (4), when the average particle size of the material particles in the reaction kettle is 8-10 μm, the addition of the mixed salt solution A is stopped; stopping the reaction when the outer surface of the particle grows to the thickness of 1-2 mu m.
13. A lithium ion battery positive electrode material prepared using the precursor according to any one of claims 1 to 3, wherein the physical structure of the material comprisesThe shell layer is coated on the outer surface of the core; wherein, the material of the inner core is a compound as follows: LiNi0.8Co0.1Mn0.1O2(ii) a The shell layer is made of the following compounds: li (Ni)0.8Co0.1Mn0.1)1-aMaO2Wherein a is more than 0 and less than or equal to 0.1, and M is Y, W, Ti and one or more of Al.
14. The positive electrode material as claimed in claim 13, wherein the cross-sectional morphology of the positive electrode material is divergent from the center to the circumference.
15. A method of preparing the positive electrode material of the lithium ion battery according to claim 13, wherein the method comprises: mixing the precursor of claim 1 with lithium hydroxide, and sintering at high temperature in an atmosphere furnace filled with oxygen to obtain the lithium ion battery anode material.
16. The method according to claim 15, wherein the precursor is mixed with lithium hydroxide according to a lithium ratio of 1.03-1.10, the sintering temperature is 700-1000 ℃, and the sintering time is 8-16 h.
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Application publication date: 20200908