CN112652751B - Precursor for lithium ion battery with double-layer structure, positive electrode material and preparation method - Google Patents

Precursor for lithium ion battery with double-layer structure, positive electrode material and preparation method Download PDF

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CN112652751B
CN112652751B CN202011540292.XA CN202011540292A CN112652751B CN 112652751 B CN112652751 B CN 112652751B CN 202011540292 A CN202011540292 A CN 202011540292A CN 112652751 B CN112652751 B CN 112652751B
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precursor
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lithium ion
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CN112652751A (en
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许开华
张坤
陈康
李聪
杨幸
薛晓斐
黎俊
孙海波
范亮姣
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Jingmen GEM New Material Co Ltd
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • 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
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • 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
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    • 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
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    • 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
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    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • 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 ion battery with a double-layer structure, a positive electrode material and a preparation method. The internal compact packing ensures the tap density of the particles, and the loose external part can exert better specific capacity and rate capability, which is beneficial to simultaneously improving the specific capacity, rate capability and energy density of the material; different elements are doped inside and outside the material in a targeted manner, and the rate capability inside the material and the circulation stability outside the material are improved; 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 the atomic level, and the doping modification effect is fully exerted. The comprehensive performance of the layered ternary material can be effectively improved by utilizing different structures inside and outside the particles and using different doping elements.

Description

Precursor for lithium ion battery with double-layer structure, positive electrode material and preparation method
Technical Field
The invention belongs to the field of lithium battery materials, and particularly relates to a precursor for a lithium ion battery with a double-layer structure, a positive electrode material and a preparation method of the precursor.
Background
Lithium Ion Batteries (LIBs) are widely used in the fields of portable electronic products, electric vehicles, energy storage systems, and the like due to their numerous advantages of high energy density, small self-discharge, no memory effect, long cycle life, small environmental pollution, and the like. In the current lithium ion battery technology, the positive electrode material is a key component of the lithium ion battery, and not only participates in electrochemical reaction as an electrode material, but also serves as a lithium ion source, which largely determines the safety, performance, cost and service life of the battery.
Among the commonly used lithium ion battery cathode materials, ternary materials have become a hot point of research in recent years and have been developed rapidly due to the advantages of high capacity density, good cycle performance, relatively low cost and the like. With the continuous expansion and extension of the application scenes of the lithium ion battery, the requirements on the energy density and the rate capability of the lithium ion battery are higher and higher, so that the use requirements of different equipment and application environments are met. High energy density is often associated with high specific capacity and compaction density, and the packing tightness inside the material particles has a certain influence on both energy density and rate capability. Under certain conditions, the loose accumulation in the particles is, the larger the contact surface between the electrolyte and the material is, and more reaction sites are provided, which is beneficial to improving the capacity exertion of the material during charge and discharge, especially high-rate charge and discharge. Therefore, in order to improve the rate capability of the material, the packing density inside the material particles should be reduced to some extent when the material is prepared. However, when the interior is loosely packed, a certain amount of pores may be present in the interior, which may lower the tap density of the material and may be disadvantageous in increasing the compacted density of the material, and therefore, in order to increase the compacted density of the material, the packing density of the interior of the material particles should be increased to some extent when the material is prepared. Therefore, in order to fully exert the performance of the material, the material should be prepared by comprehensively considering the internal packing compactness of the particles, and the compaction density of the material should be improved as much as possible under the condition of keeping high specific capacity and rate capability so as to obtain higher energy density.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a precursor and a positive electrode material for a lithium ion battery, which are of a double-layer structure, wherein primary particles are tightly stacked in a sample, are loosely stacked outside the sample, and are respectively doped with different elements inside and outside the sample, and a preparation method of the precursor and the positive electrode material.
The invention is realized by the following technical scheme:
the precursor for the lithium ion battery with the double-layer structure is characterized by comprising an inner core and an outer layer coated on the outer surface of the inner core; the chemical formula of the material of the inner core is NixCoyMn1-x-y-aMa(OH)2Wherein x is more than 0.3 and less than 1, Y is more than 0 and less than 0.7, a is more than 0 and less than or equal to 0.05, and M is one or more of Mg, Ti and Y; the material of the outer layer has the chemical formula of NixCoyMn1-x-y- bNb(OH)2Wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.7, B is more than 0 and less than or equal to 0.05, and N is one or more of Zr, W, B and Al.
The precursor for a lithium ion battery having a two-layer structure is characterized in that the average particle size of the inner core is 2 to 10 μm, and the thickness of the outer layer is 1 to 5 μm.
The preparation method of the precursor for the lithium ion battery based on the double-layer structure is characterized by comprising the following steps of:
(1) according to a molar ratio of Ni: co: mn: m is x: y: (1-x-y-a): a, mixing soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble M salt corresponding to a doping element M to obtain a first mixed salt solution, wherein x is more than 0.3 and less than 1, Y is more than 0 and less than 0.7, a is more than 0 and less than or equal to 0.05, and the doping element M is one or more of Mg, Ti and Y;
(2) according to a molar ratio of Ni: co: mn: n is x: y: (1-x-y-b): b, mixing soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble N salt corresponding to the doping element N to obtain a second mixed salt solution, wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.7, B is more than 0 and less than or equal to 0.05, and the doping element N is one or more of Zr, W, B and Al;
(3) respectively adding the first mixed salt solution, the alkali solution and ammonia water into a reaction kettle containing the base solution, introducing inert gas into the reaction kettle containing the base solution, and stirring to perform a first coprecipitation reaction to obtain first slurry with the average particle size of 2-10 microns; the technological conditions of the first coprecipitation reaction are as follows: the reaction temperature is 40-70 ℃, the reaction pH is 11.5-12.5, the ammonia concentration is 15-25 g/L, and the stirring speed is 200-250 rpm;
(4) respectively adding the second mixed salt solution, the alkali solution and ammonia water into the reaction kettle in the step (3) to carry out a second coprecipitation reaction, stopping feeding when the outer layer thickness of the particles of the first slurry is 1-5 mu m, and aging, centrifugally washing and drying to obtain a precursor for the lithium ion battery with a double-layer structure; the process conditions of the second coprecipitation reaction are as follows: the reaction temperature is 40-70 ℃, the reaction pH is 11-11.5, the ammonia concentration is 30-50 g/L, and the stirring speed is 150-200 rpm.
The preparation method of the precursor for the lithium ion battery with the double-layer structure is characterized in that the soluble nickel salt in the step (1) is one or more of nickel sulfate, nickel chloride and nickel nitrate; the soluble cobalt salt is one or more of cobalt sulfate, cobalt chloride and cobalt nitrate; the soluble manganese salt is one or more of manganese sulfate, manganese chloride and manganese nitrate; the soluble M salt is one or more of sulfate, chloride and nitrate; in the step (2), the soluble N salt is one or more of sulfate, chloride and nitrate.
The preparation method of the precursor for the lithium ion battery with the double-layer structure is characterized in that the sum of the concentration of nickel ions, the concentration of cobalt ions, the concentration of manganese ions and the concentration of M ions in the first mixed salt solution in the step (1) is 1-3 mol/L; the sum of the concentration of nickel ions, the concentration of cobalt ions, the concentration of manganese ions and the concentration of N ions in the second mixed salt solution in the step (2) is 1-3 mol/L.
The preparation method of the precursor for the lithium ion battery with the double-layer structure is characterized in that the concentration of the alkali solution in the step (3) and the concentration of the alkali solution in the step (4) are both 3-5 mol/L, the alkali solution in the step (3) is a sodium hydroxide solution or a potassium hydroxide solution, and the alkali solution in the step (4) is a sodium hydroxide solution or a potassium hydroxide solution; the concentration of the ammonia water in the step (3) and the concentration of the ammonia water in the step (4) are both 6-8 mol/L.
The preparation method of the precursor for the lithium ion battery with the double-layer structure is characterized in that the base solution in the step (3) is a mixture of ammonia water and a sodium hydroxide solution, the pH value of the base solution is 12-12.5, and the ammonia concentration in the base solution is 15-20 g/L.
The preparation method of the precursor for the lithium ion battery with the double-layer structure is characterized in that the sum of the time of the first coprecipitation reaction and the time of the second coprecipitation reaction is 80-120 h.
The positive electrode material of the precursor for the lithium ion battery based on the double-layer structure is characterized by comprising an inner part and an outer part coated on the outer surface of the inner part; the internal material has the chemical formula LiNixCoyMn1-x-y- aMaO2Wherein x is more than 0.3 and less than 1, Y is more than 0 and less than 0.7, a is more than 0 and less than or equal to 0.05, and M is one or more of Mg, Ti and Y; the chemical formula of the external material is LiNixCoyMn1-x-y-cNcO2Wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.7, c is more than 0 and less than or equal to 0.1, and N is one or more of Zr, W, B and Al.
The preparation method of the positive electrode material of the precursor for the lithium ion battery based on the double-layer structure is characterized by comprising the following steps: mixing the precursor for the lithium ion battery with the double-layer structure with lithium hydroxide or lithium carbonate according to the lithium proportion of 1.03-1.20, and sintering in an oxygen atmosphere furnace to obtain the anode material of the precursor for the lithium ion battery with the double-layer structure; the sintering temperature is 700-1000 ℃, and the sintering time is 8-16 h.
Compared with the prior art, the invention has the beneficial technical effects that: according to the invention, products with primary particles tightly stacked inside and loosely stacked outside are prepared by using different reaction conditions. The internal compact packing ensures the tap density of the particles, and the loose external part can play better specific capacity and rate capability, which is beneficial to simultaneously improving the specific capacity, rate capability and energy density of the material, and purposefully doping different elements into the internal part and the external part, and simultaneously improving the rate capability and the external circulation stability of the material; 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 the atomic level, the doping modification effect is fully exerted, different elements are doped inside and outside in a targeted manner, and the different modification effects of the doping elements are exerted. In the compact interior, relatively speaking, Li+Difficult movement, doping of Mg, Ti and Y, enlarging lithium ion channel and increasing Li in material particles+The transmission speed of (2); and in the loose outer part, the particles can contact with the electrolyte, and the doping of Zr, W, B and Al can improve the stability of the outer part of the material particles. The comprehensive performance of the layered ternary material can be effectively improved by utilizing different structures inside and outside the particles and using different doping elements.
Drawings
FIG. 1 is a schematic diagram of the internal dense and external loose structure of the primary particle accumulation of the precursor material in example 1;
FIG. 2 is an SEM photograph of a sample obtained after the end of the first coprecipitation reaction in example 1;
FIG. 3 is an SEM photograph of a sample obtained after the end of the second coprecipitation reaction in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A double layer structure of the present inventionThe precursor material structurally comprises an inner core and an outer layer coated on the outer surface of the inner core; the chemical formula of the material of the inner core is NixCoyMn1-x-y-aMa(OH)2Wherein x is more than 0.3 and less than 1, Y is more than 0 and less than 0.7, a is more than 0 and less than or equal to 0.05, and the doping element M is one or a mixture of Mg, Ti and Y; the material of the outer layer has the chemical formula of NixCoyMn1-x-y-bNb(OH)2Wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.7, B is more than 0 and less than or equal to 0.05, and the doping element N is one or a mixture of more of Zr, W, B and Al. The average particle size of the inner core is 2-10 μm, and the thickness of the outer layer is 1-5 μm. Inside the particles of the precursor material, the primary particles are tightly packed; the primary particles are loosely stacked outside the particles of the precursor material.
The preparation method of the precursor for the lithium ion battery with the double-layer structure comprises the following steps:
(1) according to a molar ratio of Ni: co: mn: m is x: y: (1-x-y-a): and a, mixing soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble M salt corresponding to the doping element M according to the proportion of a to obtain a first mixed salt solution, wherein x is more than 0.3 and less than 1, Y is more than 0 and less than 0.7, a is more than 0 and less than or equal to 0.05, and the doping element M is one or more of Mg, Ti and Y. The sum of the concentration of nickel ions, the concentration of cobalt ions, the concentration of manganese ions and the concentration of M ions in the first mixed salt solution is 1-3 mol/L. The soluble nickel salt is one or more of nickel sulfate, nickel chloride and nickel nitrate; the soluble cobalt salt is one or more of cobalt sulfate, cobalt chloride and cobalt nitrate; the soluble manganese salt is one or more of manganese sulfate, manganese chloride and manganese nitrate; the soluble M salt is one or more of sulfate, chloride and nitrate.
(2) According to a molar ratio of Ni: co: mn: n is x: y: (1-x-y-b): b, mixing soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble N salt corresponding to the doping element N to obtain a second mixed salt solution, wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.7, B is more than 0 and less than or equal to 0.05, and the doping element N is one or more of Zr, W, B and Al; the sum of the concentration of nickel ions, the concentration of cobalt ions, the concentration of manganese ions and the concentration of N ions in the second mixed salt solution is 1-3 mol/L. The soluble N salt is one or more of sulfate, chloride and nitrate.
(3) Respectively adding the first mixed salt solution, the alkali solution and the ammonia water into a reaction kettle containing the base solution through a metering pump, wherein the flow rate of the first mixed salt solution added into the reaction kettle containing the base solution is 20L/h-100L/h, the base solution is a mixture of the ammonia water and a sodium hydroxide solution, the pH value of the base solution is 12-12.5, and the ammonia concentration of the base solution is 15 g/L-20 g/L. Introducing inert gas into a reaction kettle containing a base solution, stirring to perform a first coprecipitation reaction to obtain a first slurry with the average particle size of 2-10 microns, and stopping feeding to complete the reaction in the first stage; the technological conditions of the first coprecipitation reaction are as follows: the reaction temperature is 40-70 ℃, the reaction pH is 11.5-12.5, the ammonia concentration is 15-25 g/L, and the stirring speed is 200-250 rpm; the concentration of the alkali solution is 3 mol/L-5 mol/L, and the alkali solution is sodium hydroxide solution or potassium hydroxide solution. The concentration of the ammonia water is 6-8 mol/L.
(4) Adjusting the ammonia concentration, the pH value and the rotating speed in the reaction kettle, respectively adding a second mixed salt solution, an alkali solution and ammonia water into the reaction kettle in the step (3) through a metering pump, continuously stirring for a second coprecipitation reaction, wherein the flow rate of the second mixed salt solution added into the reaction kettle containing the base solution is 20L/h-100L/h, and when the thickness of the outer layer of the particles of the first slurry is 1 mu m-5 mu m, stopping feeding to complete the second stage of reaction. Transferring the materials in the reaction kettle to an ageing tank for ageing, centrifugally washing and drying to obtain a precursor for the lithium ion battery with a double-layer structure; the process conditions of the second coprecipitation reaction are as follows: the reaction temperature is 40-70 ℃, the reaction pH is 11-11.5, the ammonia concentration is 30-50 g/L, and the stirring speed is 150-200 rpm. The concentration of the alkali solution is 3 mol/L-5 mol/L, and the alkali solution is sodium hydroxide solution or potassium hydroxide solution. The concentration of the ammonia water is 6-8 mol/L. The sum of the time of the first coprecipitation reaction and the time of the second coprecipitation reaction is 80-120 h.
The anode material of the precursor for the lithium ion battery with the double-layer structure comprises an inner part and an outer part coated on the outer surface of the inner part; the internal material has the chemical formula of LiNixCoyMn1-x-y-aMaO2Wherein x is more than 0.3 and less than 1, Y is more than 0 and less than 0.7, a is more than 0 and less than or equal to 0.05, and M is one or more of Mg, Ti and Y; the chemical formula of the external material is LiNixCoyMn1-x-y-cNcO2Wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.7, c is more than 0 and less than or equal to 0.1, and N is one or more of Zr, W, B and Al. Inside the particles of the anode material, the primary particles are tightly packed; the particles are outside, and the primary particles are loosely stacked.
The preparation method of the precursor anode material for the lithium ion battery with the double-layer structure comprises the following steps: mixing the precursor for the lithium ion battery with the double-layer structure with lithium hydroxide or lithium carbonate according to the lithium proportion of 1.03-1.20, and sintering in an oxygen atmosphere furnace to obtain the anode material of the precursor for the lithium ion battery with the double-layer structure; the lithium proportion refers to the molar ratio of lithium ions to the total amount of metal ions in the precursor; the sintering temperature is 700-1000 ℃, and the sintering time is 8-16 h.
Example 1
According to a molar ratio of Ni: co: mn: mg is 0.8: 0.1: 0.09: and fully mixing the mixed solution of nickel sulfate and nickel nitrate, the mixed solution of cobalt sulfate and cobalt nitrate, the mixed solution of manganese nitrate and manganese sulfate and the mixed solution of magnesium sulfate and magnesium nitrate according to the proportion of 0.01 to prepare a first mixed salt solution with the total metal ion concentration of 3 mol/L.
According to a molar ratio of Ni: co: mn: zr is 0.8: 0.1: 0.05: and fully mixing the nickel sulfate solution, the cobalt sulfate solution, the manganese sulfate solution and the zirconium sulfate solution according to the proportion of 0.05 to prepare a second mixed salt solution with the total metal ion concentration of 3 mol/L.
Under the protection of inert gas, a first mixed salt solution, a sodium hydroxide solution with the concentration of 5mol/L and ammonia water with the concentration of 8mol/L are respectively added into a reaction kettle containing a base solution through a metering pump, and the flow rate of the first mixed salt solution added into the reaction kettle containing the base solution is 20L/h. The base solution is a mixture of ammonia water and sodium hydroxide solution, the pH value of the base solution is 12.5, and the ammonia concentration of the base solution is 15 g/L. And (3) starting the reaction kettle to stir for carrying out the first coprecipitation reaction, wherein the pH of a reaction system is controlled to be 11.5-12.5, the ammonia concentration is 15-25 g/L, the stirring speed is 250rpm, and the reaction temperature is 70 ℃ in the feeding reaction process.
When the particle size D of the material particles in the reaction kettle50When the particle size is 2 mu m, stopping feeding, and finishing the reaction in the first stage; adjusting the ammonia concentration and the rotation speed in the reaction kettle, respectively adding a second mixed salt solution, a sodium hydroxide solution with the concentration of 5mol/L and ammonia water with the concentration of 8mol/L into the reaction kettle through a metering pump, continuously stirring for a second coprecipitation reaction, wherein the flow rate of the second mixed salt solution added into the reaction kettle is 20L/h, and the reaction temperature of a reaction system is controlled to be 70 ℃, the reaction pH value is 11.3-11.5, the ammonia concentration is 30 g/L-35 g/L, and the stirring speed is 200rpm in the process of the second coprecipitation reaction. And stopping feeding when the thickness of the outer layer of the particles in the reaction kettle is 1 mu m, and finishing the reaction of the second stage. The sum of the time of the first coprecipitation reaction and the time of the second coprecipitation reaction is controlled to be 80 h. And transferring the materials in the reaction kettle to an ageing tank for ageing, centrifugally washing and drying after the reaction is finished to obtain the precursor for the lithium ion battery with the double-layer structure.
Uniformly mixing the precursor for the lithium ion battery with the double-layer structure and lithium hydroxide according to the proportion of lithium of 1.03, and sintering at the high temperature of 700 ℃ for 16h in an atmosphere furnace filled with oxygen to obtain the anode material of the precursor for the lithium ion battery with the double-layer structure. The sample particles comprise an inner part and an outer part coated on the outer surface of the inner part; the internal material has the chemical formula LiNi0.8Co0.1Mn0.09Mg0.01O2(ii) a The chemical formula of the external material is LiNi0.8Co0.1Mn0.05Zr0.05O2。
The positive electrode material of the precursor for the lithium ion battery with the double-layer structure is prepared into a positive plate, and the positive plate is assembled into a button battery by taking a metal lithium plate as a negative electrode to carry out charge-discharge comparative test, wherein the discharge specific capacity at 0.2C multiplying power is 194mAh/g, the discharge specific capacity at 0.5C multiplying power is 186mAh/g, and the capacity retention rate after 50 cycles is 92%.
Example 2
According to a molar ratio of Ni: co: mn: ti is 0.9: 0.03: 0.02: 0.05, nickel sulfate, cobalt sulfate, manganese sulfate and titanium sulfate solution are fully mixed to prepare a first mixed salt solution with the total metal ion concentration of 1 mol/L.
According to a molar ratio of Ni: co: mn: w: al is 0.9: 0.03: 0.02: 0.025: 0.025 of the concentration of nickel sulfate, cobalt nitrate, manganese nitrate, tungsten sulfate, tungsten nitrate, and aluminum sulfate, and a second mixed salt solution of metal ions at a total concentration of 1mol/L was prepared.
Under the protection of inert gas, a first mixed salt solution, a sodium hydroxide solution with the concentration of 3mol/L and ammonia water with the concentration of 6mol/L are respectively added into a reaction kettle containing a base solution through a metering pump, and the flow rate of the first mixed salt solution added into the reaction kettle containing the base solution is 100L/h. The base solution is a mixture of ammonia water and sodium hydroxide solution, the pH value of the base solution is 12, and the ammonia concentration of the base solution is 20 g/L. And (3) starting the reaction kettle to stir for carrying out the first coprecipitation reaction, wherein the pH of a reaction system is controlled to be 11.5-12, the ammonia concentration is controlled to be 20-25 g/L, the stirring speed is 200rpm, and the reaction temperature is 40 ℃ in the feeding reaction process.
When the particle size D of the material particles in the reaction kettle50When the thickness is 10 mu m, stopping feeding, and finishing the reaction in the first stage; adjusting the ammonia concentration and the rotation speed in the reaction kettle, respectively adding a second mixed salt solution, a sodium hydroxide solution with the concentration of 3mol/L and ammonia water with the concentration of 6mol/L into the reaction kettle through a metering pump, continuously stirring for a second coprecipitation reaction, wherein the flow rate of the second mixed salt solution added into the reaction kettle is 100L/h, and the reaction temperature of a reaction system is controlled to be 40 ℃, the reaction pH value is 11-11.2, the ammonia concentration is 45-50 g/L, and the stirring speed is 150rpm in the process of the second coprecipitation reaction. And stopping feeding when the thickness of the outer layer of the particles in the reaction kettle is 5 mu m, and finishing the reaction of the second stage. The sum of the time of the first coprecipitation reaction and the time of the second coprecipitation reaction is controlled to be 120 h. After the reaction is finished, transferring the materials in the reaction kettle to an ageing tank for ageing, centrifugally washing and drying to obtain the lithium ion with the double-layer structurePrecursor for subcells.
Uniformly mixing the precursor for the lithium ion battery with the double-layer structure and lithium hydroxide according to the proportion of lithium of 1.20, and sintering at the high temperature of 1000 ℃ in an atmosphere furnace filled with oxygen for 8 hours to obtain the anode material of the precursor for the lithium ion battery with the double-layer structure. The sample particles comprise an inner part and an outer part coated on the outer surface of the inner part; the internal material has the chemical formula LiNi0.9Co0.03Mn0.02Ti0.05O2(ii) a The chemical formula of the external material is LiNi0.9Co0.03Mn0.02W0.025Al0.025O2。
Example 3
According to a molar ratio of Ni: co: mn: y is 0.7: 0.15: 0.12: 0.03, fully mixing the nickel chloride solution, the cobalt chloride solution, the manganese chloride solution and the yttrium chloride solution to prepare a first mixed salt solution with the total metal ion concentration of 2 mol/L.
According to a molar ratio of Ni: co: mn: b is 0.7: 0.15: 0.14: 0.01, and fully mixing nickel sulfate, cobalt sulfate, manganese nitrate and boron sulfate to prepare a second mixed salt solution with the total metal ion concentration of 2 mol/L.
Under the protection of inert gas, a first mixed salt solution, a sodium hydroxide solution with the concentration of 4mol/L and ammonia water with the concentration of 7mol/L are respectively added into a reaction kettle containing a base solution through a metering pump, and the flow rate of the first mixed salt solution added into the reaction kettle containing the base solution is 40L/h. The base solution is a mixture of ammonia water and sodium hydroxide solution, the pH value of the base solution is 12.2, and the ammonia concentration of the base solution is 18 g/L. And (3) starting stirring the reaction kettle to carry out a first coprecipitation reaction, wherein the pH of a reaction system is controlled to be 11.5-12.2, the ammonia concentration is controlled to be 18-23 g/L, the stirring speed is 230rpm, and the reaction temperature is 60 ℃ in the feeding reaction process.
When the particle size D of the material particles in the reaction kettle50When the particle size is 7 mu m, stopping feeding, and finishing the reaction in the first stage; adjusting the ammonia concentration and the rotating speed in the reaction kettle, and passing through a second mixed salt solution, a sodium hydroxide solution with the concentration of 4mol/L and ammonia water with the concentration of 7mol/LAnd respectively adding the measuring pumps into the reaction kettle, continuously stirring for carrying out the second coprecipitation reaction, wherein the flow rate of the second mixed salt solution added into the reaction kettle is 40L/h, and the reaction temperature of a reaction system is controlled to be 60 ℃, the reaction pH is controlled to be 11.1-11.4, the ammonia concentration is 35-40 g/L, and the stirring speed is 170rpm in the process of the second coprecipitation reaction. When the thickness of the outer layer of the particles in the reaction kettle is 2 mu m, the feeding is stopped, and the second stage of reaction is finished. The sum of the time of the first coprecipitation reaction and the time of the second coprecipitation reaction is controlled to be 100 h. And transferring the materials in the reaction kettle to an ageing tank for ageing, centrifugally washing and drying after the reaction is finished to obtain the precursor for the lithium ion battery with the double-layer structure.
Uniformly mixing the precursor for the lithium ion battery with the double-layer structure and lithium hydroxide according to the proportion of lithium of 1.10, and sintering at the high temperature of 850 ℃ in an atmosphere furnace filled with oxygen for 12 hours to obtain the anode material of the precursor for the lithium ion battery with the double-layer structure. The sample particles comprise an inner part and an outer part coated on the outer surface of the inner part; the internal material has the chemical formula LiNi0.7Co0.15Mn0.12Y0.03O2(ii) a The chemical formula of the external material is LiNi0.9Co0.15Mn0.14B0.01O2。
Example 4
According to a molar ratio of Ni: co: mn: mg: y is 0.6: 0.2: 0.15: 0.02: 0.03, fully mixing the nickel sulfate solution, the cobalt sulfate solution, the manganese sulfate solution, the magnesium sulfate solution and the yttrium sulfate solution to prepare a first mixed salt solution with the total metal ion concentration of 2 mol/L.
According to a molar ratio of Ni: co: mn: w is 0.6: 0.2: 0.18: 0.02, fully mixing the nickel sulfate solution, the cobalt sulfate solution, the manganese sulfate solution and the tungsten sulfate solution to prepare a second mixed salt solution with the total metal ion concentration of 3 mol/L.
Under the protection of inert gas, a first mixed salt solution, a sodium hydroxide solution with the concentration of 4mol/L and ammonia water with the concentration of 6mol/L are respectively added into a reaction kettle containing a base solution through a metering pump, and the flow rate of the first mixed salt solution added into the reaction kettle containing the base solution is 75L/h. The base solution is a mixture of ammonia water and sodium hydroxide solution, the pH value of the base solution is 12.1, and the ammonia concentration of the base solution is 16 g/L. And (3) starting the reaction kettle to stir for carrying out the first coprecipitation reaction, wherein the pH of a reaction system is controlled to be 11.5-12.1, the ammonia concentration is controlled to be 16-25 g/L, the stirring speed is 240rpm, and the reaction temperature is 50 ℃ in the feeding reaction process.
When the particle size D of the material particles in the reaction kettle50When the particle size is 4 mu m, stopping feeding, and finishing the reaction in the first stage; adjusting the ammonia concentration and the rotation speed in the reaction kettle, respectively adding a second mixed salt solution, a sodium hydroxide solution with the concentration of 4mol/L and ammonia water with the concentration of 6mol/L into the reaction kettle through a metering pump, continuously stirring for a second coprecipitation reaction, wherein the flow rate of the second mixed salt solution added into the reaction kettle is 75L/h, and the reaction temperature of a reaction system is controlled to be 50 ℃, the reaction pH value is 11.4-11.5, the ammonia concentration is 40 g/L-45 g/L, and the stirring speed is 185rpm in the process of the second coprecipitation reaction. And stopping feeding when the thickness of the outer layer of the particles in the reaction kettle is 3 mu m, and finishing the reaction of the second stage. The sum of the time of the first coprecipitation reaction and the time of the second coprecipitation reaction is controlled to be 95 h. And transferring the materials in the reaction kettle to an ageing tank for ageing, centrifugally washing and drying after the reaction is finished to obtain the precursor for the lithium ion battery with the double-layer structure.
Uniformly mixing the precursor for the lithium ion battery with the double-layer structure and lithium hydroxide according to the proportion of lithium of 1.12, and sintering at the high temperature of 780 ℃ in an atmosphere furnace filled with oxygen for 13h to obtain the anode material of the precursor for the lithium ion battery with the double-layer structure. The sample particles comprise an inner part and an outer part coated on the outer surface of the inner part; the internal material has the chemical formula LiNi0.6Co0.2Mn0.15Mg0.02Y0.03O2(ii) a The chemical formula of the external material is LiNi0.6Co0.2Mn0.18W0.02O2。
Comparative example 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 the nickel ions, the cobalt ions and the manganese ions is 2 mol/L.
And adding the mixed salt solution, a sodium hydroxide solution and ammonia water into a reaction kettle containing a base solution in a parallel flow manner for coprecipitation reaction, and aging, washing and drying to obtain the precursor of the nickel-cobalt-manganese ternary cathode material.
And uniformly mixing the nickel-cobalt-manganese ternary cathode material precursor with lithium hydroxide, performing high-temperature treatment, cooling, crushing and sieving to obtain the conventional NCM811 ternary cathode material.
The positive electrode material is prepared into a positive plate, and a metal lithium plate is used as a negative electrode to be assembled into a button cell to be subjected to charge-discharge comparative test, wherein the discharge specific capacity at 0.2C multiplying power is 195mAh/g, the discharge specific capacity at 0.5C multiplying power is 181mAh/g, and the capacity retention rate after 50 cycles is 86%.

Claims (9)

1. The preparation method of the precursor for the lithium ion battery with the double-layer structure is characterized in that the precursor comprises an inner core and an outer layer coated on the outer surface of the inner core; the chemical formula of the material of the inner core is NixCoyMn1-x-y-aMa(OH)2Wherein x is more than 0.3 and less than 1, Y is more than 0 and less than 0.7, a is more than 0 and less than or equal to 0.05, and M is one or more of Ti and Y; the material of the outer layer has the chemical formula of NixCoyMn1-x-y-bNb(OH)2Wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.7, B is more than 0 and less than or equal to 0.05, and N is one or more of Zr and B; the method comprises the following steps:
(1) according to a molar ratio of Ni: co: mn: m is x: y: (1-x-y-a): a, mixing soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble M salt corresponding to a doping element M to obtain a first mixed salt solution, wherein x is more than 0.3 and less than 1, Y is more than 0 and less than 0.7, a is more than 0 and less than or equal to 0.05, and the doping element M is one or more of Ti and Y;
(2) according to a molar ratio of Ni: co: mn: n is x: y: (1-x-y-b): b, mixing soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble N salt corresponding to the doping element N to obtain a second mixed salt solution, wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.7, B is more than 0 and less than or equal to 0.05, and the doping element N is one or more of Zr and B;
(3) respectively adding the first mixed salt solution, the alkali solution and ammonia water into a reaction kettle containing the base solution, introducing inert gas into the reaction kettle containing the base solution, and stirring to perform a first coprecipitation reaction to obtain first slurry with the average particle size of 2-10 microns; the technological conditions of the first coprecipitation reaction are as follows: the reaction temperature is 40-70 ℃, the reaction pH is 11.5-12.5, the ammonia concentration is 15-25 g/L, and the stirring speed is 200-250 rpm;
(4) respectively adding the second mixed salt solution, the alkali solution and ammonia water into the reaction kettle in the step (3) to carry out a second coprecipitation reaction, stopping feeding when the outer layer thickness of the particles of the first slurry is 1-5 mu m, and aging, centrifugally washing and drying to obtain a precursor for the lithium ion battery with a double-layer structure; the process conditions of the second coprecipitation reaction are as follows: the reaction temperature is 40-70 ℃, the reaction pH is 11-11.5, the ammonia concentration is 30-50 g/L, and the stirring speed is 150-200 rpm.
2. The method according to claim 1, wherein the inner core has an average particle size of 2 to 10 μm, and the outer layer has a thickness of 1 to 5 μm.
3. The method for preparing the precursor for the lithium ion battery with the double-layer structure according to claim 1, wherein the soluble nickel salt in the step (1) is one or more of nickel sulfate, nickel chloride and nickel nitrate; the soluble cobalt salt is one or more of cobalt sulfate, cobalt chloride and cobalt nitrate; the soluble manganese salt is one or more of manganese sulfate, manganese chloride and manganese nitrate; the soluble M salt is one or more of sulfate, chloride and nitrate; in the step (2), the soluble N salt is one or more of sulfate, chloride and nitrate.
4. The method for preparing a precursor for a lithium ion battery having a two-layer structure according to claim 1, wherein the sum of the concentration of nickel ions, the concentration of cobalt ions, the concentration of manganese ions, and the concentration of M ions in the first mixed salt solution in the step (1) is 1 to 3 mol/L; the sum of the concentration of nickel ions, the concentration of cobalt ions, the concentration of manganese ions and the concentration of N ions in the second mixed salt solution in the step (2) is 1-3 mol/L.
5. The method for preparing the precursor for the lithium ion battery with the double-layer structure according to claim 1, wherein the concentration of the alkali solution in the step (3) and the concentration of the alkali solution in the step (4) are both 3mol/L to 5mol/L, the alkali solution in the step (3) is a sodium hydroxide solution or a potassium hydroxide solution, and the alkali solution in the step (4) is a sodium hydroxide solution or a potassium hydroxide solution; the concentration of the ammonia water in the step (3) and the concentration of the ammonia water in the step (4) are both 6-8 mol/L.
6. The method for preparing the precursor for the lithium ion battery with the double-layer structure according to claim 1, wherein the base solution in the step (3) is a mixture of ammonia water and a sodium hydroxide solution, the pH of the base solution is 12-12.5, and the ammonia concentration in the base solution is 15-20 g/L.
7. The method for preparing a precursor for a lithium ion battery having a two-layer structure according to claim 1, wherein the sum of the time of the first coprecipitation reaction and the time of the second coprecipitation reaction is 80 to 120 hours.
8. The cathode material prepared by the preparation method of the precursor for the lithium ion battery with the double-layer structure according to claim 1, wherein the cathode material comprises an inner part and an outer part coated on the outer surface of the inner part; the internal material has the chemical formula LiNixCoyMn1-x-y-aMaO2Wherein x is more than 0.3 and less than 1, Y is more than 0 and less than 0.7, a is more than 0 and less than or equal to 0.05, and M is one or more of Mg, Ti and Y; the chemical formula of the external material is LiNixCoyMn1-x-y-cNcO2Wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.7, c is more than 0 and less than or equal to 0.1, and N is one or more of Zr, W, B and AlSeveral kinds of them.
9. The method for preparing the precursor for the lithium ion battery with the double-layer structure according to claim 8 is characterized by comprising the following steps: mixing the precursor for the lithium ion battery with the double-layer structure with lithium hydroxide or lithium carbonate according to the lithium proportion of 1.03-1.20, and sintering in an oxygen atmosphere furnace to obtain the anode material of the precursor for the lithium ion battery with the double-layer structure; the sintering temperature is 700-1000 ℃, and the sintering time is 8-16 h.
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