CN112164784B - Quaternary concentration gradient core-shell lithium ion battery positive electrode material and preparation method thereof - Google Patents

Quaternary concentration gradient core-shell lithium ion battery positive electrode material and preparation method thereof Download PDF

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CN112164784B
CN112164784B CN202010875417.8A CN202010875417A CN112164784B CN 112164784 B CN112164784 B CN 112164784B CN 202010875417 A CN202010875417 A CN 202010875417A CN 112164784 B CN112164784 B CN 112164784B
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CN112164784A (en
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范亮姣
张坤
许开华
李聪
黎俊
孙海波
陈康
薛晓斐
陈小飞
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Jingmen GEM New Material Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—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
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    • C01P2006/40—Electric properties
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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 quaternary concentration gradient core-shell lithium ion battery anode material, which has a chemical formula of LiNixCoyMn1‑x‑y‑zMzO2Wherein x is more than 0.7 and less than 0.9, y is more than 0.05 and less than 0.2, z is more than 0.01 and less than 0.03, and M is one of Al, Cr, Mg, Zn, Mo, Ti and W. The preparation method of the material comprises the following steps: adding a first salt solution containing nickel, cobalt and manganese, a sodium hydroxide solution and an ammonia water solution into a reaction kettle for reaction, and mixing a second salt solution containing nickel, cobalt and manganese with the rest of the first salt solution to obtain a mixed solution; and adding the mixed solution and the doped salt solution into a reaction kettle, centrifugally washing, drying, screening to remove iron, mixing with lithium hydroxide, and roasting to obtain the quaternary concentration gradient core-shell lithium ion battery anode material. The invention ensures that the particle nucleus is rich in nickel and has high capacity, and the surface nickel is insufficient (or rich in manganese) and has cycle stability and thermal stability.

Description

Quaternary concentration gradient core-shell lithium ion battery positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a quaternary concentration gradient core-shell lithium ion battery anode material and a preparation method thereof.
Background
Lithium Ion Batteries (LIBs) are currently the most promising energy storage technology for Electric Vehicles (EVs) and have been widely used. The main drawbacks of LIB are high cost, insufficient energy density, poor cycling stability, which is largely limited by the positive electrode material. Therefore, development of a positive electrode material having high energy density and good cycle stability is urgently required. Among the numerous positive electrode candidates, Li [ Ni ] rich in nickel1-x-yCoxMny]O2(NCM) layered oxides are most promising due to their high capacity and low cost.
The high nickel anode material is made of Ni2+/3+And Ni3+/4+The redox reaction of (a) provides the primary reversible capacity, so high nickel enrichment is generally employed to achieve maximum reversible capacity. However, nickel enrichment in NCM leads to a significant reduction in capacity upon cycling, mainly due to structural instability of micron-sized spherical secondary particles agglomerated from primary grains. After many cycles, the secondary particles are internally fractured. Such cracking will result in poor grain-to-grain connection and electrical contact, resulting in a rapid increase in resistance. At the same time, the electrolyte will penetrate into the secondary particles along the cracks, causing further side reactions and irreversible phase changes. The concentration of transition metals in conventional concentration gradient materials varies linearly from the core to the surface. The overall Ni content is significantly reduced to an average value at the core and surface. At the same time, the structure does not contribute to the mitigation in Li+Internal stress caused by lattice change during insertion/extraction. Thus, the reversible capacity and structural stability of conventional concentration gradient materials remain undesirable, and there remains a lack of an effective method to enhance the structural and surface stability of Ni-rich NCMs particles.
Disclosure of Invention
In order to overcome the inherent instability of the nickel-rich NCM positive electrode in the prior art, the invention introduces a composition gradual change method, so that the nickel-rich particle core has high capacity, and the insufficient nickel (or manganese-rich) surface has cycling stability and thermal stability. Book (I)The invention designs the gradient change of component concentration, and synthesizes a precursor material for a mixed quaternary lithium ion battery with a high nickel NCM as an inner core and a doped concentration gradient as an outer layer by regulating and controlling the pH value of a reaction solid-liquid mixture. Chemical formula composition Ni of quaternary mixed precursor materialxCoyMn1-x-y-zMz(OH)2Wherein x is more than 0.7 and less than 0.9, y is more than 0.05 and less than 0.2, z is more than 0.01 and less than 0.03, and M is any one of Al, Cr, Mg, Zn, Mo, Ti, W and the like. And then the quaternary concentration gradient core-shell lithium ion battery anode material is synthesized by mixed lithium calcination.
The invention adopts the following technical scheme:
the quaternary concentration gradient core-shell lithium ion battery positive electrode material is characterized in that the chemical formula of the positive electrode material is LiNixCoyMn1-x-y-zMzO2Wherein x is more than 0.7 and less than 0.9, y is more than 0.05 and less than 0.2, z is more than 0.01 and less than 0.03, and M is one of Al, Cr, Mg, Zn, Mo, Ti and W.
The preparation method of the quaternary concentration gradient core-shell lithium ion battery cathode material is characterized by comprising the following steps of:
(1) preparing a first salt solution containing nickel, cobalt and manganese, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the first salt solution is (90-100): (1-5): (1-5), the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the first salt solution is 2.00-4.00 mol/L, and the first salt solution is placed in a first salt solution tank; preparing a second salt solution containing nickel, cobalt and manganese, wherein the molar ratio of nickel ions, cobalt ions and manganese ions in the second salt solution is (20-60): (20-50): (20-50), wherein the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the second salt solution is 2.00-4.00 mol/L;
(2) preparing a doped salt solution, wherein the concentration of metal ions in the doped salt solution is 0.2-0.45 mol/L, and the doping element in the doped salt solution is one of Al, Cr, Mg, Zn, Mo, Ti and W;
(3) adding the first salt solution into a reaction kettle in a nitrogen atmosphere at the speed of 2.5L/h-5L/h, and simultaneously carrying out reactionAdding sodium hydroxide solution and ammonia water solution into the kettle to carry out first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is NimConMn1-m-n(OH)2Wherein m is more than or equal to 0.9 and less than 1, and n is more than or equal to 0.01 and less than or equal to 0.05; the concentration of the sodium hydroxide solution is 2-4 mol/L, the concentration of the ammonia water solution is 1-4 mol/L, and the technological conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 4g/L and 12g/L, the pH value of the reaction is between 10 and 12, the reaction time is between 20 and 50 hours, and the rotating speed of the reaction is between 300 and 450 rpm;
(4) when the reaction time of the first coprecipitation reaction is reached, immediately pumping a second salt solution into the residual first salt solution in the first salt solution tank at the rate of 3L/h-4L/h, stirring to obtain a mixed solution, simultaneously pumping the mixed solution into the reaction kettle at the rate of 9L/h-12L/h, simultaneously adding a doped salt solution into the reaction kettle at the rate of 0.8L/h-3L/h, and carrying out a second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 5g/L and 15g/L, the pH value of the reaction is between 10 and 12, the reaction time is between 50 and 60 hours, and the rotating speed of the reaction is between 300 and 450 rpm;
(5) sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a quaternary concentration gradient precursor, wherein the chemical formula of the quaternary concentration gradient precursor is NixCoyMn1-x-y-zMz(OH)2Wherein x is more than 0.7 and less than 0.9, y is more than 0.05 and less than 0.2, z is more than 0.01 and less than 0.03, and M is one of Al, Cr, Mg, Zn, Mo, Ti and W; the drying temperature is 100-150 ℃, and the drying time is 8-10 h;
(6) uniformly mixing the quaternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.05-1.2, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain the quaternary concentration gradient core-shell lithium ion battery anode material.
The preparation method of the quaternary concentration gradient core-shell lithium ion battery cathode material is characterized in that the first salt solution is one of a sulfate solution, a nitrate solution and a chloride solution; the second saline solution is one of a sulfate solution, a nitrate solution and a chloride solution.
The preparation method of the quaternary concentration gradient core-shell lithium ion battery anode material is characterized in that in the step (6), oxygen atmosphere is kept in the whole roasting process, the roasting process comprises first-stage roasting and second-stage roasting which are sequentially carried out, and the process conditions of the first-stage roasting are as follows: heat treatment is carried out for 1h-5h at the temperature of 250 ℃ to 500 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 5h to 12h at the temperature of 500 ℃ to 900 ℃.
The invention has the beneficial technical effects that: in order to overcome the inherent instability of the nickel-rich NCM anode, the invention adopts a composition gradual change method to ensure that the particle core is enriched with nickel element, the nickel content of the gradient layer is gradually reduced, the manganese content is increased, the insufficient nickel (or manganese-rich) on the surface has the cycle stability and the thermal stability, and other elements are doped simultaneously, thereby realizing the functional composition and complementation of the core part and the outer layer part and improving the cycle stability of the material. The invention designs the concentration gradient change of components, and synthesizes the quaternary mixed type anode material with high nickel NCM as the inner core and doped concentration gradient as the outer layer by regulating and controlling the pH value of a reaction solid-liquid mixture. And then the doped quaternary concentration gradient core-shell lithium ion battery anode material is synthesized by mixed lithium calcination. Through the design of the gradual concentration gradient material, the capacity advantage of a high-nickel core can be exerted, and the internal stress can be remarkably relieved, so that the mechanical stability of the fine particles after repeated circulation is effectively improved; meanwhile, the Ni generated by the high-nickel material in the lithium-deficient state is increased due to the increase of the manganese content in the outer layer doping concentration gradient material4+The material is not easy to contact with electrolyte to react to release a large amount of gas, and simultaneously, the bonding strength of oxygen ions and metal ions can be increased by doping other elements in a small amount, so that the cycling stability of the material is increased. During second salt solution was gone into first salt solution with the rate pump, first salt solution groove continuously stirred, and during first salt solution added reation kettle with the rate simultaneously, these two kinds of solutions can finish through the accurate control of autonomous control equipment simultaneous feeding, do not waste the material.
Drawings
FIG. 1 is a schematic diagram of the coprecipitation reaction process of the present invention;
FIG. 2 is a schematic cross-sectional view of a gradient doping precursor in example 1;
fig. 3 is a gradient doping element distribution diagram in example 1.
Detailed Description
The invention relates to a quaternary concentration gradient core-shell lithium ion battery anode material with a chemical formula of LiNixCoyMn1-x-y- zMzO2Wherein x is more than 0.7 and less than 0.9, y is more than 0.05 and less than 0.2, z is more than 0.01 and less than 0.03, and M is one of Al, Cr, Mg, Zn, Mo, Ti and W.
Referring to fig. 1, the preparation method of the quaternary concentration gradient core-shell lithium ion battery cathode material comprises the following steps:
(1) preparing a first salt solution (ternary salt solution A in figure 1) containing nickel, cobalt and manganese, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the first salt solution is (90-100): (1-5): (1-5), the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the first salt solution is 2.00-4.00 mol/L, and the first salt solution is placed in a first salt solution tank; preparing a second salt solution (a ternary salt solution B in the figure 1) containing nickel, cobalt and manganese, wherein the molar ratio of nickel ions, cobalt ions and manganese ions in the second salt solution is (20-60): (20-50): (20-50), wherein the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the second salt solution is 2.00-4.00 mol/L; the first salt solution is one of sulfate solution, nitrate solution and chloride solution; the second saline solution is one of a sulfate solution, a nitrate solution and a chloride solution.
(2) Preparing a doped salt solution, wherein the concentration of metal ions in the doped salt solution is 0.2-0.45 mol/L, and the doping element in the doped salt solution is one of Al, Cr, Mg, Zn, Mo, Ti and W;
(3) adding the first salt solution into a reaction kettle in a nitrogen atmosphere at the speed of 2.5L/h-5L/h (Q1), simultaneously adding a sodium hydroxide solution and an ammonia water solution into the reaction kettle for carrying out a first coprecipitation reaction, and obtaining a precursor core part after the first salt solution with a certain volume of V1 is reacted, wherein the molecular formula of the precursor core part is NimConMn1-m-n(OH)2Wherein m is more than or equal to 0.9 and less than 1, and n is more than or equal to 0.01 and less than or equal to 0.05; the concentration of the sodium hydroxide solution is 2-4 mol/L, the concentration of the ammonia water solution is 1-4 mol/L, and the technological conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 4g/L and 12g/L, the pH value of the reaction is between 10 and 12, the reaction time (V1/Q1) is between 20 and 50 hours, and the rotating speed of the reaction is between 300 and 450 rpm.
(4) When the reaction time of the first coprecipitation reaction is reached, immediately pumping a second salt solution (volume V3) into the residual first salt solution (volume V2) in the first salt solution tank at the rate of 3L/h-4L/h (Q2), stirring to obtain a mixed solution, simultaneously pumping the mixed solution into the reaction kettle at the rate of 9L/h-12L/h (Q3), simultaneously adding a doping salt solution into the reaction kettle at the rate of 0.8L/h-3L/h, and carrying out a second coprecipitation reaction to obtain a solid-liquid mixture; and continuously adding a sodium hydroxide solution and an ammonia water solution into the first coprecipitation reaction and the second coprecipitation reaction. The process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 5g/L and 15g/L, the pH value of the reaction is between 10 and 12, the reaction time (V2/(Q3-Q2)) is between 50 and 60 hours, and the rotating speed of the reaction is between 300 and 450 rpm. Continuously adding a sodium hydroxide solution, an ammonia water solution, a mixed solution and a doped salt solution into the reaction kettle in the second coprecipitation reaction process, and continuously pumping a second salt solution into the remaining first salt solution in the first salt solution tank; namely, the reaction time of the second coprecipitation reaction is the time for adding the sodium hydroxide solution, the ammonia water solution, the mixed solution and the doped salt solution into the reaction kettle in the nitrogen atmosphere respectively, and the reaction time of the second coprecipitation reaction is the time for pumping the second salt solution into the remaining first salt solution in the first salt solution tank (V3/Q2). The second saline solution and the mixed solution are fed simultaneously, so that materials are not wasted through accurate control.
(5) Sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a quaternary concentration gradient precursor, wherein the chemical formula of the quaternary concentration gradient precursor is NixCoyMn1-x-y-zMz(OH)2Wherein x is more than 0.7 and less than 0.9, y is more than 0.05 and less than 0.2, z is more than 0.01 and less than 0.03, and M is one of Al, Cr, Mg, Zn, Mo, Ti and W; what is needed isThe drying temperature is 100-150 ℃, and the drying time is 8-10 h;
(6) uniformly mixing the quaternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.05-1.2, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain the quaternary concentration gradient core-shell lithium ion battery anode material. The whole roasting process is kept in an oxygen atmosphere, the roasting comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, and the process conditions of the first-stage roasting are as follows: heat treatment is carried out for 1h-5h at the temperature of 250 ℃ to 500 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 5h to 12h at the temperature of 500 ℃ to 900 ℃.
Example 1
(1) Preparing a first salt solution and a second salt solution containing nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the first salt solution is 90: 5: and 5, the sum of the concentration of the nickel ions, the concentration of the cobalt ions and the concentration of the manganese ions in the first salt solution is 2.00mol/L, and the first salt solution is placed in the first salt solution tank. The molar ratio of nickel ions, cobalt ions and manganese ions in the second salt solution is 60: 20: and 20, the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the second salt solution is 2.00 mol/L.
(2) Preparing 0.2mol/L aluminum salt solution by taking sodium metaaluminate as a raw material;
(3) adding 150L of first salt solution into a reaction kettle in a nitrogen atmosphere at the speed of 5L/h, and simultaneously adding sodium hydroxide solution and ammonia water solution into the reaction kettle to carry out a first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is Ni0.9Co0.05Mn0.05(OH)2(ii) a The concentration of the sodium hydroxide solution is 4mol/L, the concentration of the ammonia water solution is 4mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 7 and 8g/L, the pH value of the reaction is between 11.2 and 12, the reaction time is 30 hours, and the rotating speed of the reaction is 400 rpm;
(4) when the coprecipitation reaction is carried out for 30 hours, 240L of second salt solution is pumped into the remaining 480L of first salt solution in the first salt solution tank at the rate of 4L/h, and the mixture is stirred to obtain a mixed solution; simultaneously pumping the mixed solution into a reaction kettle at the speed of 12L/h, adding an aluminum salt solution into the reaction kettle at the speed of 3L/h when reaching 30h of the first coprecipitation reaction, and carrying out the second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 7.5g/L and 8.5g/L, the pH value of the reaction is 11 to 11.8, the reaction time is 60 hours, and the rotating speed of the reaction is 380 rpm;
(5) sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a quaternary concentration gradient precursor, wherein the chemical formula of the quaternary concentration gradient precursor is Ni0.80Co0.09Mn0.09Al0.02(OH)2(ii) a The drying temperature is 140 ℃, and the drying time is 8 hours; fig. 2 is a schematic cross-sectional view of a gradient doping precursor in example 1.
(6) Uniformly mixing the quaternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.18, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain the LiNi with the chemical formula0.80Co0.09Mn0.09Al0.02O2The quaternary concentration gradient core-shell lithium ion battery positive electrode material; the whole roasting process is kept in an oxygen atmosphere, the roasting comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, and the process conditions of the first-stage roasting are as follows: heat treatment is carried out for 2h at 500 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 8h at 800 ℃.
(7) The tap density, the discharge specific capacity, the capacity retention rate after circulation, the decomposition temperature, the heat release and the high-temperature circulation retention rate of the quaternary concentration gradient core-shell lithium ion battery anode material are tested. Fig. 3 is a gradient doping element distribution diagram in example 1.
Example 2
(1) Preparing a first salt solution and a second salt solution containing nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the first salt solution is 92: 5: and 3, the sum of the concentration of the nickel ions, the concentration of the cobalt ions and the concentration of the manganese ions in the first salt solution is 2.17mol/L, and the first salt solution is placed in the first salt solution tank. The molar ratio of nickel ions, cobalt ions and manganese ions in the second salt solution is 48: 23: 30, the sum of the concentration of the nickel ions, the concentration of the cobalt ions and the concentration of the manganese ions in the second salt solution is 2.02 mol/L.
(2) Magnesium sulfate is used as a raw material to prepare 0.3mol/L magnesium salt solution;
(3) adding 200L of first salt solution into a reaction kettle in nitrogen atmosphere at the speed of 4L/h, and simultaneously adding sodium hydroxide solution and ammonia water solution into the reaction kettle to carry out primary coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is Ni0.92Co0.05Mn0.03(OH)2(ii) a The concentration of the sodium hydroxide solution is 3mol/L, the concentration of the ammonia water solution is 3mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept at 8-10g/L, the pH value of the reaction is 11.0-11.8, the reaction time is 50h, and the rotating speed of the reaction is 410 rpm;
(4) when the coprecipitation reaction is carried out for 50 hours, 210L of second salt solution is pumped into the remaining 450L of first salt solution in the first salt solution tank at the rate of 3.5L/h, and the mixture is stirred to obtain a mixed solution; simultaneously pumping the mixed solution into a reaction kettle at the speed of 11L/h, adding a magnesium salt solution into the reaction kettle at the speed of 2.5L/h when 50h of the first coprecipitation reaction is reached, and carrying out the second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 9g/L and 10.5g/L, the pH value of the reaction is 11.1 to 11.6, the reaction time is 60 hours, and the rotating speed of the reaction is 390 rpm;
(5) sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a quaternary concentration gradient precursor, wherein the chemical formula of the quaternary concentration gradient precursor is Ni0.80Co0.09Mn0.09Mg0.02(OH)2(ii) a The drying temperature is 130 ℃, and the drying time is 9 h;
(6) uniformly mixing the quaternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.2, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain the LiNi with the chemical formula0.80Co0.09Mn0.09Mg0.02O2The quaternary concentration gradient core-shell lithium ion battery positive electrode material; the whole roasting process is kept in an oxygen atmosphere, the roasting comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, and the process conditions of the first-stage roasting are as follows: heat at 400 deg.CThe treatment is carried out for 3 hours, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 10h at 600 ℃.
(7) The tap density, the discharge specific capacity, the capacity retention rate after circulation, the decomposition temperature, the heat release and the high-temperature circulation retention rate of the quaternary concentration gradient core-shell lithium ion battery anode material are tested.
Example 3
(1) Preparing a first salt solution and a second salt solution containing nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the first salt solution is 95: 3: and 2, the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the first salt solution is 3.37mol/L, and the first salt solution is placed in the first salt solution tank. The molar ratio of nickel ions, cobalt ions and manganese ions in the second salt solution is 28: 38: 42, the sum of the concentration of the nickel ions, the concentration of the cobalt ions and the concentration of the manganese ions in the second salt solution is 2.16 mol/L.
(2) Preparing 0.4mol/L titanium salt solution by taking titanium sulfate as a raw material;
(3) adding 60L of first salt solution into a reaction kettle in nitrogen atmosphere at the speed of 3L/h, and simultaneously adding sodium hydroxide solution and ammonia water solution into the reaction kettle to carry out primary coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is Ni0.95Co0.03Mn0.02(OH)2(ii) a The concentration of the sodium hydroxide solution is 2mol/L, the concentration of the ammonia water solution is 1mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 10.5 and 11.5g/L, the pH value of the reaction is between 10.4 and 11.2, the reaction time is 20 hours, and the rotating speed of the reaction is 450 rpm;
(4) when the coprecipitation reaction is carried out for 20 hours, immediately pumping 180L of second salt solution into the remaining 420L of first salt solution in the first salt solution tank at the rate of 3L/h, and stirring to obtain a mixed solution; simultaneously pumping the mixed solution into a reaction kettle at the speed of 10L/h; adding a titanium salt solution into the reaction kettle at a rate of 1L/h when the reaction time reaches 20h of the first coprecipitation reaction, and carrying out a second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept at 11-12g/L, the pH value of the reaction is 11.2-12, the reaction time is 60h, and the rotating speed of the reaction is 420 rpm;
(5) sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a quaternary concentration gradient precursor, wherein the chemical formula of the quaternary concentration gradient precursor is Ni0.80Co0.09Mn0.09Ti0.02(OH)2(ii) a The drying temperature is 120 ℃, and the drying time is 10 hours;
(6) uniformly mixing the quaternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.1, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain the LiNi with the chemical formula0.80Co0.09Mn0.09Ti0.02O2The quaternary concentration gradient core-shell lithium ion battery positive electrode material; the whole roasting process is kept in an oxygen atmosphere, the roasting comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, and the process conditions of the first-stage roasting are as follows: heat treatment is carried out for 2h at 300 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 8h at 700 ℃.
(7) The tap density, the discharge specific capacity, the capacity retention rate after circulation, the decomposition temperature, the heat release and the high-temperature circulation retention rate of the quaternary concentration gradient core-shell lithium ion battery anode material are tested.
Example 4
(1) Preparing a first salt solution and a second salt solution containing nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the first salt solution is 98: 1: 1, the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the first salt solution is 3.06mol/L, and the first salt solution is placed in a first salt solution tank. The molar ratio of nickel ions, cobalt ions and manganese ions in the second salt solution is 56: 45: 45, the sum of the concentration of the nickel ions, the concentration of the cobalt ions and the concentration of the manganese ions in the second salt solution is 2.92 mol/L.
(2) Preparing a tungsten salt solution with the concentration of 0.45mol/L by taking tungsten trioxide as a raw material;
(3) adding 80L of first salt solution into a reaction kettle in nitrogen atmosphere at the speed of 2.5L/h, simultaneously adding sodium hydroxide solution and ammonia water solution into the reaction kettle for carrying out first coprecipitation reaction to obtain a precursor core part, and dividing the precursor core partHas the sub-formula of Ni0.98Co0.01Mn0.01(OH)2(ii) a The concentration of the sodium hydroxide solution is 2mol/L, the concentration of the ammonia water solution is 1mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 4 and 6g/L, the pH value of the reaction is between 10 and 10.8, the reaction time is 32 hours, and the rotating speed of the reaction is 300 rpm;
(4) when the coprecipitation reaction is carried out for 32 hours, immediately pumping 150L of second salt solution into the remaining 300L of first salt solution in the first salt solution tank at the rate of 3L/h, and stirring to obtain a mixed solution; simultaneously pumping the mixed solution into a reaction kettle at the speed of 9L/h; adding a tungsten salt solution into the reaction kettle at a rate of 0.8L/h when the reaction time reaches 32h of the first coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 5 and 6g/L, the pH value of the reaction is between 10.2 and 10.6, the reaction time is 50h, and the rotating speed of the reaction is 320 rpm;
(5) sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a quaternary concentration gradient precursor, wherein the chemical formula of the quaternary concentration gradient precursor is Ni0.80Co0.09Mn0.09W0.02(OH)2(ii) a The drying temperature is 110 ℃, and the drying time is 9 hours;
(6) uniformly mixing the quaternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.05, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain the LiNi with the chemical formula0.80Co0.09Mn0.09W0.02O2The quaternary concentration gradient core-shell lithium ion battery positive electrode material; the whole roasting process is kept in an oxygen atmosphere, the roasting comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, and the process conditions of the first-stage roasting are as follows: heat treatment is carried out for 5 hours at 350 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 6h at 800 ℃.
(7) The tap density, the discharge specific capacity, the capacity retention rate after circulation, the decomposition temperature, the heat release and the high-temperature circulation retention rate of the quaternary concentration gradient core-shell lithium ion battery anode material are tested.
Comparative example 1
(1) Preparing a salt solution containing nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the salt solution is 8: 1: and 1, the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the salt solution is 2 mol/L.
(3) Adding 1000L of salt solution into a reaction kettle with nitrogen atmosphere and 350rpm of rotation speed at the speed of 10L/h, adding 4mol/L ammonia water serving as a complexing agent into the reaction kettle, simultaneously pumping 4mol/L NaOH solution into the reaction kettle, adjusting the flow rate of the alkali solution, keeping the pH value between 10.4 and 11.8, and carrying out coprecipitation reaction for 100 hours to obtain a precursor;
(5) and centrifugally separating and washing the solid-liquid mixture after reaction to be neutral, and drying for 10-12h at 130 ℃.
(6) Uniformly mixing the reacted precursor with lithium hydroxide according to the molar ratio of 1: 1.1, roasting for 12 hours in a muffle furnace at 800 ℃, crushing and sieving the roasted material to obtain uniform LiNi0.8Co0.1Mn0.1O2A ternary material.
(7) The tap density, specific discharge capacity, capacity retention rate after cycling, decomposition temperature, heat release and high-temperature cycle retention rate of the ternary material are tested.
The physical properties of the quaternary concentration gradient core-shell lithium ion battery anode material obtained in examples 1-4 and the common ternary material obtained in comparative example 1 after calcination are compared, and the detection results are as follows:
table 1 physical properties of positive electrode materials for batteries obtained in examples 1 to 4 and comparative example 1
pH BET(m2/g) Moisture (ppm) Tap density (g/cm)3)
Example 1 11.5 0.46 241.5 2.3
Example 2 11.3 0.51 254.4 2.6
Example 3 11.6 0.42 237.0 2.2
Example 4 11.5 0.45 248.9 2.4
Comparative example 1 10.99 0.52 273.3 1.9
From table 1, it can be derived: examples 1-4 had lower moisture than the comparative example 1 sample, while examples 1-4 had a higher pH than the comparative example 1 sample. Generally, the pH value of the lithium ion battery anode material is lower than 11, and lithium precipitation is likely to be caused during the charge and discharge test of the material, so that capacity attenuation is further caused; the higher tap densities of the samples of examples 1-4 compared to the sample of comparative example 1 indicate a higher battery capacity.
Assembling a button cell and detecting:
the positive electrode material of the quaternary concentration gradient core-shell lithium ion battery obtained in the examples 1 to 4 and the common ternary material obtained in the comparative example 1 are used as positive electrodes, the metal lithium sheet is used as a negative electrode, and the positive electrodes and the negative electrode are respectively assembled into 5 button batteries to carry out charge-discharge comparative tests, wherein the detection results are as follows:
table 2 specific discharge capacity test data of the battery positive electrode materials of examples 1 to 4 and comparative example 1
Figure BDA0002652531390000091
From table 2, it can be derived: by adopting the quaternary concentration gradient core-shell lithium ion battery positive electrode material obtained in the embodiments 1-4 as a positive electrode and a metal lithium sheet as a negative electrode to assemble a button battery for charge-discharge comparative test, the first discharge specific capacity can reach 199.5mAh/g under 0.1C multiplying power, the capacity retention rate can reach 99.3% after 100 charge-discharge cycles, the capacity retention rate can still reach 93.1% after 50 ℃ high-temperature cycle, while the first discharge specific capacity of the common high-nickel positive electrode material is 185.7mAh/g, the capacity retention rate is 93.4% after 100 charge-discharge cycles, and the capacity retention rate is 86.3% after 50 ℃ high-temperature cycle; therefore, the specific discharge capacity of the battery prepared from the quaternary concentration gradient core-shell lithium ion battery anode material obtained by the invention is superior to that of the battery prepared from the conventional high-nickel battery anode material.

Claims (2)

1. The preparation method of the quaternary concentration gradient core-shell lithium ion battery positive electrode material is characterized in that the positive electrode material has a chemical formula of LiNixCoyMn1-x-y-zMzO2Wherein x is more than 0.7 and less than 0.9, y is more than 0.05 and less than 0.2, z is more than 0.01 and less than 0.03, and M is Cr, Mg, Zn, Mo, Ti, Mo, Ti, B, V,one of W; the method comprises the following steps:
(1) preparing a first salt solution containing nickel, cobalt and manganese, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the first salt solution is (90-100): (1-5): (1-5), the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the first salt solution is 2.00-4.00 mol/L, and the first salt solution is placed in a first salt solution tank; preparing a second salt solution containing nickel, cobalt and manganese, wherein the molar ratio of nickel ions, cobalt ions and manganese ions in the second salt solution is (20-60): (20-50): (20-50), wherein the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the second salt solution is 2.00-4.00 mol/L;
(2) preparing a doped salt solution, wherein the concentration of metal ions in the doped salt solution is 0.2-0.45 mol/L, and the doping element in the doped salt solution is one of Cr, Mg, Zn, Mo, Ti and W;
(3) adding the first salt solution into a reaction kettle in a nitrogen atmosphere at the speed of 2.5L/h-5L/h, and simultaneously adding a sodium hydroxide solution and an ammonia water solution into the reaction kettle to perform a first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is NimConMn1-m-n(OH)2Wherein m is more than or equal to 0.9 and less than 1, and n is more than or equal to 0.01 and less than or equal to 0.05; the concentration of the sodium hydroxide solution is 2-4 mol/L, the concentration of the ammonia water solution is 1-4 mol/L, and the technological conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 4g/L and 12g/L, the pH value of the reaction is between 10 and 12, the reaction time is between 20 and 50 hours, and the rotating speed of the reaction is between 300 and 450 rpm;
(4) when the reaction time of the first coprecipitation reaction is reached, immediately pumping a second salt solution into the residual first salt solution in the first salt solution tank at the rate of 3L/h-4L/h, stirring to obtain a mixed solution, simultaneously pumping the mixed solution into the reaction kettle at the rate of 9L/h-12L/h, simultaneously adding a doped salt solution into the reaction kettle at the rate of 0.8L/h-3L/h, and carrying out a second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 5g/L and 15g/L, the pH value of the reaction is between 10 and 12, the reaction time is between 50 and 60 hours, and the rotating speed of the reaction is between 300 and 450 rpm;
(5) sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a quaternary concentration gradient precursor, wherein the chemical formula of the quaternary concentration gradient precursor is NixCoyMn1-x-y-zMz(OH)2Wherein x is more than 0.7 and less than 0.9, y is more than 0.05 and less than 0.2, z is more than 0.01 and less than 0.03, and M is one of Cr, Mg, Zn, Mo, Ti and W; the drying temperature is 110-150 ℃, and the drying time is 8-10 h;
(6) uniformly mixing the quaternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.05-1.2, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain the quaternary concentration gradient core-shell lithium ion battery anode material; the roasting process is characterized in that oxygen atmosphere is kept in the whole roasting process, the roasting process comprises a first-stage roasting process and a second-stage roasting process which are sequentially carried out, and the first-stage roasting process comprises the following process conditions: heat treatment is carried out for 1h-5h at the temperature of 250 ℃ to 350 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 5h to 6h at the temperature of 500 ℃ to 900 ℃.
2. The method of claim 1, wherein the first salt solution is one of a sulfate solution, a nitrate solution, and a chloride solution; the second saline solution is one of a sulfate solution, a nitrate solution and a chloride solution.
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