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CN108346797B - Preparation method of high-nickel ternary material - Google Patents

Preparation method of high-nickel ternary material Download PDF

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CN108346797B
CN108346797B CN201810205025.3A CN201810205025A CN108346797B CN 108346797 B CN108346797 B CN 108346797B CN 201810205025 A CN201810205025 A CN 201810205025A CN 108346797 B CN108346797 B CN 108346797B
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CN108346797A (en
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吴振豪
陈步青
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Zoltrix Material Guangzhou 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
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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
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    • H01M4/02—Electrodes composed of, or comprising, active material
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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
    • H—ELECTRICITY
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    • 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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Abstract

The application provides a preparation method of a high-nickel ternary material, wherein the high-nickel ternary material is Li(1+a)NixCoyMzO2+bWherein a is more than or equal to-0.10 and less than or equal to 0.50, and x is more than or equal to 0.8<0.9，0.1≤y≤0.25，0<z is less than or equal to 0.25, b is less than or equal to 0.05 and less than or equal to 0.10, M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V and Cu, and the method comprises the following steps: mixing a precursor with a lithium source, adding a sintering aid, uniformly mixing, and sintering by adopting a three-stage sintering mode, wherein the three-stage sintering mode is as follows: the sintering of the first stage is firstly carried out, then the sintering of the second stage is carried out, and finally the sintering of the third stage is carried out, wherein the sintering temperature of the second stage is higher than that of the first stage and that of the third stage. By adopting a three-stage sintering mode, and the sintering temperature of the second stage is higher than that of the first stage and the third stage, the prepared high-nickel ternary material has high crystallinity and less Li/Ni mixed row, so that the structural stability is high, the first efficiency is high, and the power is good.

Description

Preparation method of high-nickel ternary material
Technical Field
The application relates to the field of ternary materials, in particular to a preparation method of a high-nickel ternary material.
Background
As a new green energy source, the lithium ion battery has the advantages of high specific energy, small self-discharge, high open circuit voltage, no memory effect, long cycle life, no environmental pollution and the like, so the lithium ion battery is widely used as a power source of electronic products such as mobile phones, notebook computers, digital cameras and the like, and meanwhile, the lithium ion battery is also a power source of electric automobiles and is an energy storage power source of solar renewable energy.
The core link in the lithium ion battery industry is the manufacture of battery materials, the battery performance depends on the performance of the anode material to a great extent, and the nickel-cobalt-manganese or nickel-cobalt-aluminum ternary material is one of the hot spots in the research of the new generation of lithium ion anode materials.
At present, when a nickel-cobalt-manganese or nickel-cobalt-aluminum ternary material is prepared, a precursor and a lithium salt are mixed and then mostly synthesized by adopting a two-stage sintering process, wherein the temperature of the two-stage sintering process is set in the following mode: and arranging a section of heat preservation platform at a temperature slightly higher than the melting point of the lithium salt for melting the lithium salt to construct a liquid phase sintering environment, and then arranging a section of heat preservation platform at a temperature slightly higher than the crystallization temperature of the nickel-cobalt-manganese or nickel-cobalt-aluminum ternary material for crystallizing the material. The sintering process is suitable for preparing nickel-cobalt-manganese or nickel-cobalt-aluminum ternary materials with low nickel content, but for nickel-cobalt-manganese or nickel-cobalt-aluminum ternary materials with the nickel content of more than 80%, if the performance of the obtained material is poor by adopting the sintering mode, the performance is mainly due to the following reasons: the crystallization window temperature of the nickel-cobalt-manganese or nickel-cobalt-aluminum ternary material is generally 750-; when sintering is carried out in a window temperature range, the sintering of the material is controlled by the kinetic speed due to a low thermodynamic environment, the crystallinity of the material is improved by keeping the temperature of the material in the temperature range for more than 15 hours, and the diffusion of Li ions to a transition metal layer is greatly accelerated by too long heat-preservation time, so that a high Li/Ni mixed-discharging phenomenon is formed, and the reversibility of the material is poor. Because of oxygen defect and Li/Ni mixed row, the prepared material has poor structural stability and lower first efficiency and power.
Therefore, the preparation of the high-nickel ternary material with excellent performance is still a difficult problem to be overcome by research personnel.
Disclosure of Invention
The application aims to prepare the high-nickel ternary material, so that the problem that the high-nickel ternary material with excellent performance is difficult to prepare is solved, and the high-nickel ternary material with good structural stability and high initial efficiency and power is obtained.
In order to achieve the purpose, the application provides a preparation method of a high-nickel ternary material, wherein the high-nickel ternary material is Li(1+a)NixCoyMzO2+bWherein a is more than or equal to-0.10 and less than or equal to 0.50, and x is more than or equal to 0.8<0.9，0.1≤y≤0.25，0<z is less than or equal to 0.25, b is less than or equal to 0.05 and less than or equal to 0.10, M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V and Cu, and the method comprises the following steps: mixing the precursor with a lithium sourceMixing, adding a sintering aid, uniformly mixing, and sintering by adopting a three-section sintering mode: the sintering of the first stage is firstly carried out, then the sintering of the second stage is carried out, and finally the sintering of the third stage is carried out, wherein the sintering temperature of the second stage is higher than that of the first stage and that of the third stage.
The preparation method adopts a three-stage sintering mode, the sintering temperature of the second stage is higher than that of the first stage and the third stage, and the material can be pre-crystallized while lithium salt is melted due to the low temperature of the first stage, so that Li is reduced2The high sintering temperature of the second stage can improve the crystallinity of the material, and the oxygen defect caused by the high sintering temperature of the second stage can be eliminated through the low-temperature annealing procedure of the third stage, so that the prepared high-nickel ternary material has high crystallinity and less Li/Ni mixed row, and therefore, the high-nickel ternary material has high structural stability, high first efficiency and good power.
Detailed Description
The technical solutions of the present application are further described below by the specific embodiments, but the present application is not limited thereto.
The application provides a preparation method of a high-nickel ternary material, wherein the high-nickel ternary material is Li(1+a)NixCoyMzO2+bWherein a is more than or equal to-0.10 and less than or equal to 0.50, and x is more than or equal to 0.8<0.9，0.1≤y≤0.25，0<z is less than or equal to 0.25, b is less than or equal to 0.05 and less than or equal to 0.10, M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V and Cu, the method comprises the following steps of mixing a precursor with a lithium source, adding a sintering aid, uniformly mixing, and sintering by adopting a three-stage sintering mode: the sintering of the first stage is firstly carried out, then the sintering of the second stage is carried out, and finally the sintering of the third stage is carried out, wherein the sintering temperature of the second stage is higher than that of the first stage and that of the third stage.
Further, the sintering in the first stage is: and (3) heating the mixture added with the sintering aid and mixed to 650-750 ℃ at the heating rate of 0.5-10 ℃/min in the air atmosphere, and preserving the heat for 3-6h to obtain an intermediate I. At the position which is slightly lower than the lower limit of the crystallization window temperature (750-800 ℃) of the high-nickel ternary material and is 0-150 DEG CThe first temperature platform is arranged, the heat preservation time is short, and the platform has the function of pre-crystallizing the material while melting lithium salt to reduce Li2And forming O.
Further, the second stage sintering is as follows: and (3) placing the intermediate I in an oxidizing atmosphere, heating to 800-950 ℃ at the heating rate of 5-15 ℃/min, and preserving heat for 5-8h to obtain an intermediate II. A second temperature platform is arranged at the position 50-150 ℃ higher than the upper limit of the crystallization window temperature (750-2O is volatilized, the heat preservation time is short, and the Li/Ni mixed discharging degree is greatly reduced.
Further, the third stage sintering is: and (5) placing the intermediate II in an oxidizing atmosphere, cooling to 650 plus 750 ℃ at a cooling rate of 0.5-5 ℃/min, and preserving heat for 5-8 h. And arranging a third temperature platform at the position which is 0-150 ℃ lower than the lower limit of the crystallization window temperature (750-800 ℃) of the high-nickel ternary material, wherein the heat preservation time is 5-8h, and the function of the platform is to eliminate the oxygen defect caused by the high sintering temperature of the second temperature platform by using a low-temperature annealing procedure. The process of converting spinel phase into layered structure exists in the annealing process, which is similar to the pre-crystallization process, thereby overcoming the oxygen defect.
The sintering temperatures of the first and third stages may be the same or different, preferably different, because the third stage does not need to take into account melting of the lithium salt, the energy provided by the annealing is provided by the product of temperature and time, i.e. heat flux, theoretically lower temperatures require longer times, higher temperatures require lower times, but must be below the crystallization temperature.
Further, the oxidizing atmosphere in the second stage and the third stage is an atmosphere having an oxygen content of more than 99% by mass. Under the oxidizing atmosphere of 99%, an environment close to pure oxygen is provided, and sufficient oxidation of Ni and elimination of oxygen defects are guaranteed.
Further, the precursor is a hydroxide precursor, a carbonate precursor, or a hydroxide-carbonate core-shell precursor. The hydroxide precursor is hydroxide containing Ni, Co and M and has a chemical formula of NixCoyMz(OH)2Wherein, 0.8 is less than or equal tox<0.9，0.1≤y≤0.25，0<z is less than or equal to 0.25, and M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V and Cu. The carbonate precursor is carbonate containing Ni, Co and M and has a chemical formula of NixCoyMzCO3Wherein x is more than or equal to 0.8<0.9，0.1≤y≤0.25，0<z is less than or equal to 0.25, and M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V and Cu. The core of the precursor with the hydroxide-carbonate core-shell structure is carbonate, the shell is hydroxide, and the chemical formulas are respectively NixCoyMzCO3And NixCoyMz(OH)2Wherein x is more than or equal to 0.8<0.9，0.1≤y≤0.25，0<z is less than or equal to 0.25, and M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V and Cu.
The hydroxide precursor can be prepared by a currently common hydroxide precipitation method, for example, a Ni source, a Co source and an M source are dissolved in deionized water to obtain an aqueous solution, the aqueous solution, a morphology control agent ammonia water and a NaOH solution are mixed in a parallel flow manner, the PH value is controlled to be 9-12, the mixture is subjected to constant temperature reaction at the temperature of 60-90 ℃ for 3-12h, the mixture is cooled to 25-30 ℃, and the precursor Ni is obtained by filteringxCoyMz(OH)2。
The carbonate precursor can be prepared by a common carbonate precipitation method at present, for example, dissolving a Ni source, a Co source and an M source in deionized water to obtain an aqueous solution, carrying out cocurrent flow mixing on the aqueous solution, ammonia water as a morphology control agent and a carbonate solution in a reaction kettle, controlling the pH to be 9-12, carrying out constant temperature reaction at 60-90 ℃ for 3-12h, cooling to 25-30 ℃, and filtering to obtain a precursor NixCoyMzCO3。
The hydroxide-carbonate core-shell structure precursor can be prepared by firstly preparing precursor core NixCoyMzCO3And then preparing a precursor with a core-shell structure. Specifically, the following steps can be carried out:
a. precursor nucleus NixCoyMzCO3Preparation of
Dissolving Ni source, Co source and M source in deionized water to obtain aqueous solution, dissolving the aqueous solution, ammonia water as morphology control agent and carbonateMixing the solution in a reaction kettle in parallel flow, controlling the pH value to be 9-12, reacting at the constant temperature of 60-90 ℃ for 3-12h, cooling to 25-30 ℃, and filtering to obtain a precursor NixCoyMzCO3；
b. Preparation of precursor with core-shell structure
In precursor nucleus NixCoyMzCO3Adding Ni source, Co source, M source, shape control agent ammonia water and NaOH solution, parallel-flow mixing, controlling PH to 9-12, reacting at constant temperature of 60-90 ℃ for 3-12h, cooling to 25-30 ℃, and filtering to obtain the precursor with the core-shell structure.
Further, the lithium source is one or more of lithium hydroxide, lithium carbonate and lithium nitrate, and the dosage of the lithium source is 1.03-1.12 times of the stoichiometric ratio. The Ni source, Co source and M source are water soluble and non-oxidizing salts such as sulfates, chlorides. The carbonate solution is preferably sodium carbonate, potassium carbonate or sodium bicarbonate.
Generally speaking, the precursor is a hydroxide precursor and a carbonate precursor, and the high-nickel ternary material is sintered to obtain secondary particles, and after lithium salt is added into the hydroxide-carbonate core-shell structure precursor and sintering is carried out, the shrinkage ratio of the core is greater than that of the shell, so that the shell of the precursor is broken, and the high-nickel ternary material with a single crystal morphology can be obtained.
Further, the sintering aid accounts for 1-20% of the mass of the precursor, specifically 1%, 2%, 5%, 8%, 10%, 15%, 20%. The sintering aid can be a water-insoluble aid or a water-soluble aid, and the water-insoluble aid can be boron oxide or lithium fluoride; the water-soluble auxiliary agent can be water-soluble sulfate and water-soluble chloride, preferably sodium sulfate or sodium chloride. The sintering aid is preferably a water-soluble aid, but if the water-soluble aid is selected, the product sintered in the third stage is preferably leached for 10min under the oxygen-free water nitrogen atmosphere, dried at 120 ℃, and the water-soluble aid is removed to obtain a finished product.
The preparation method of the high nickel ternary material of the present application is described in detail below with reference to examples.
Example 1
High nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2.005The preparation method comprises the following steps:
a. preparation of the precursor
Adding sulfate solution of metal Ni, Co and Mn, ammonia water as morphology control agent and NaOH solution into a reaction kettle, carrying out parallel flow mixing, controlling the pH to be 12, carrying out constant temperature reaction at 65 ℃, continuously reacting until the particle size D50 is 10 mu m, filtering and washing to obtain precursor Ni0.8Co0.1Mn0.1(OH)2；
b. Mixing
Mixing the precursor with lithium hydroxide according to a molar ratio of 1:1.10, adding a water-insoluble auxiliary agent boron oxide accounting for 10% of the mass of the precursor, and uniformly mixing;
c. three-stage sintering
B, sintering the mixture mixed in the step b in a first stage: placing the mixture in an air atmosphere, heating to 650 ℃ at the heating rate of 1 ℃/min, and preserving heat for 4h to obtain an intermediate I;
and then carrying out second-stage sintering: placing the intermediate I in an oxidizing atmosphere with oxygen mass content more than 99%, heating to 900 ℃ at a heating rate of 8 ℃/min, and preserving heat for 6 hours to obtain an intermediate II;
finally, a third stage of sintering is carried out: and placing the intermediate II in an oxidizing atmosphere with the oxygen mass content of more than 99%, cooling to 680 ℃ at the cooling rate of 2 ℃/min, preserving heat for 6h, leaching for 10min in an oxygen-free water nitrogen atmosphere, and drying at 120 ℃ to obtain a finished product.
Example 2
High nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2.005The preparation method comprises the following steps:
a. preparation of the precursor
Adding sulfate solution of metal Ni, Co and Mn, ammonia water as morphology control agent and sodium carbonate solution into a reaction kettle, carrying out cocurrent flow mixing in the reaction kettle, controlling the pH to be 12, carrying out constant temperature reaction at 65 ℃, continuously reacting until the particle size D50 is 9um, filtering and washing to obtain precursor Ni0.8Co0.1Mn0.1CO3；
b. Mixing
Mixing the precursor with lithium hydroxide according to a molar ratio of 1:1.10, adding a water-insoluble auxiliary agent boron oxide accounting for 10% of the mass of the precursor, and uniformly mixing;
c. three-stage sintering
B, sintering the mixture mixed in the step b in a first stage: placing the mixture in an air atmosphere, heating to 650 ℃ at the heating rate of 1 ℃/min, and preserving heat for 4h to obtain an intermediate I;
and then carrying out second-stage sintering: placing the intermediate I in an oxidizing atmosphere with oxygen mass content more than 99%, heating to 900 ℃ at a heating rate of 8 ℃/min, and preserving heat for 6 hours to obtain an intermediate II;
finally, a third stage of sintering is carried out: and placing the intermediate II in an oxidizing atmosphere with the oxygen mass content of more than 99%, cooling to 680 ℃ at the cooling rate of 2 ℃/min, preserving heat for 6h, leaching for 10min in an oxygen-free water nitrogen atmosphere, and drying at 120 ℃ to obtain a finished product.
Example 3
High nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2.005The preparation method comprises the following steps:
a. preparation of the precursor
Dissolving sulfates of metal Ni, Co and Mn in deionized water to obtain an aqueous solution, carrying out parallel flow mixing on the aqueous solution, a sodium carbonate solution and ammonia water in a reaction kettle, controlling the pH value of the reaction kettle to be 11, carrying out constant-temperature reaction at 80 ℃ for 10 hours, cooling to 25 ℃, and filtering to obtain a precursor core Ni0.8Co0.1Mn0.1CO3Seed crystal of Ni in precursor nucleus0.8Co0.1Mn0.1CO3Adding a sulfate solution of metal Ni, Co and Mn, ammonia water as a morphology control agent and a NaOH solution, carrying out parallel flow mixing, controlling the pH to be 12, carrying out constant temperature reaction at 65 ℃, continuously reacting until the particle size D50 is 3um, filtering and washing to obtain a precursor with a core-shell structure;
b. mixing
Mixing the precursor with lithium hydroxide according to a molar ratio of 1:1.10, adding a water-soluble auxiliary agent sodium sulfate accounting for 10% of the mass of the precursor, and uniformly mixing;
c. three-stage sintering
B, sintering the mixture mixed in the step b in a first stage: placing the mixture in an air atmosphere, heating to 650 ℃ at the heating rate of 1 ℃/min, and preserving heat for 4h to obtain an intermediate I;
and then carrying out second-stage sintering: placing the intermediate I in an oxidizing atmosphere with oxygen mass content more than 99%, heating to 900 ℃ at a heating rate of 8 ℃/min, and preserving heat for 6 hours to obtain an intermediate II;
finally, a third stage of sintering is carried out: and placing the intermediate II in an oxidizing atmosphere with the oxygen mass content of more than 99%, cooling to 680 ℃ at the cooling rate of 2 ℃/min, preserving heat for 6h, leaching for 10min in an oxygen-free water nitrogen atmosphere, and drying at 120 ℃ to obtain a finished product.
Example 4
High nickel ternary material Li1.02Ni0.8Co0.15Al0.05O2.01The preparation method comprises the following steps:
a. preparation of the precursor
Adding a sulfate solution of metal Ni, Co and Al, a morphology control agent ammonia water and a sodium carbonate solution into a reaction kettle, carrying out parallel flow mixing in the reaction kettle, controlling the pH to be 12, carrying out constant temperature reaction at 65 ℃, continuously reacting until the particle size D50 is 9um, filtering and washing to obtain a precursor Ni0.8Co0.15Al0.05CO3；
b. Mixing
Mixing the precursor with lithium hydroxide according to a molar ratio of 1:1.05, adding a water-insoluble auxiliary agent lithium fluoride accounting for 15% of the mass of the precursor, and uniformly mixing;
c. three-stage sintering
B, sintering the mixture mixed in the step b in a first stage: placing the mixture in an air atmosphere, heating to 700 ℃ at a heating rate of 10 ℃/min, and preserving heat for 6 hours to obtain an intermediate I;
and then carrying out second-stage sintering: and (3) placing the intermediate I in an oxidizing atmosphere with the oxygen mass content of more than 99.5%, heating to 950 ℃ at the heating rate of 12 ℃/min, and preserving heat for 5 hours to obtain an intermediate II.
Finally, a third stage of sintering is carried out: and placing the intermediate II in an oxidizing atmosphere with the oxygen mass content of more than 99%, cooling to 750 ℃ at the cooling rate of 5 ℃/min, preserving heat for 5h, leaching for 10min in an oxygen-free water nitrogen atmosphere, and drying at 120 ℃ to obtain a finished product.
Example 5
High nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2.005The preparation method comprises the following steps:
a. preparation of the precursor
Adding sulfate solution of metal Ni, Co and Mn, ammonia water as morphology control agent and NaOH solution into a reaction kettle, carrying out parallel flow mixing, controlling the pH to be 12, carrying out constant temperature reaction at 65 ℃, continuously reacting until the particle size D50 is 10 mu m, filtering and washing to obtain precursor Ni0.8Co0.1Mn0.1(OH)2；
b. Mixing
Mixing the precursor with lithium hydroxide according to a molar ratio of 1:1.10, adding a water-soluble auxiliary agent sodium sulfate accounting for 10% of the mass of the precursor, and uniformly mixing;
c. three-stage sintering
B, sintering the mixture mixed in the step b in a first stage: placing the mixture in an air atmosphere, heating to 650 ℃ at the heating rate of 1 ℃/min, and preserving heat for 4h to obtain an intermediate I;
and then carrying out second-stage sintering: placing the intermediate I in an oxidizing atmosphere with oxygen mass content more than 99%, heating to 900 ℃ at a heating rate of 8 ℃/min, and preserving heat for 6 hours to obtain an intermediate II;
finally, a third stage of sintering is carried out: and placing the intermediate II in an oxidizing atmosphere with the oxygen mass content of more than 99%, cooling to 680 ℃ at the cooling rate of 2 ℃/min, preserving heat for 6h, leaching for 10min in an oxygen-free water nitrogen atmosphere, and drying at 120 ℃ to obtain a finished product.
Comparative example 1
High nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2.005Preparation method ofThe method comprises the following steps:
a. preparation of the precursor
Adding sulfate solution of metal Ni, Co and Mn, ammonia water as morphology control agent and NaOH solution into a reaction kettle, carrying out parallel flow mixing, controlling the pH to be 12, carrying out constant temperature reaction at 65 ℃, continuously reacting until the particle size D50 is 10 mu m, filtering and washing to obtain precursor Ni0.8Co0.1Mn0.1(OH)2；
b. Mixing
Mixing the precursor with lithium hydroxide according to a molar ratio of 1:1.10, adding a water-insoluble auxiliary agent boron oxide accounting for 10% of the mass of the precursor, and uniformly mixing;
c. one-stage sintering
B, performing one-stage sintering on the mixture mixed in the step b: placing in an oxidizing atmosphere with oxygen mass content more than 99%, heating to 900 ℃ at a heating rate of 8 ℃/min, keeping the temperature for 15h, rinsing for 10min in an oxygen-free water nitrogen atmosphere, and drying at 120 ℃ to obtain a finished product.
Comparative example 2
High nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2.005The preparation method comprises the following steps:
a. preparation of the precursor
Adding sulfate solution of metal Ni, Co and Mn, ammonia water as morphology control agent and NaOH solution into a reaction kettle, carrying out parallel flow mixing, controlling the pH to be 12, carrying out constant temperature reaction at 65 ℃, continuously reacting until the particle size D50 is 10 mu m, filtering and washing to obtain precursor Ni0.8Co0.1Mn0.1(OH)2；
b. Mixing
Mixing the precursor with lithium hydroxide according to a molar ratio of 1:1.10, adding a water-insoluble auxiliary agent boron oxide accounting for 10% of the mass of the precursor, and uniformly mixing;
c. two-stage sintering
B, sintering the mixture mixed in the step b in a first stage: placing the mixture in an oxidizing atmosphere with the oxygen mass content of more than 99%, heating to 650 ℃ at the heating rate of 2 ℃/min, and preserving heat for 10 hours to obtain an intermediate I;
and then carrying out second-stage sintering: and (3) placing the intermediate I in an oxidizing atmosphere with the oxygen mass content of more than 99%, heating to 950 ℃ at the heating rate of 10 ℃/min, preserving the heat for 8h, rinsing for 10min in an oxygen-free water nitrogen atmosphere, and drying at 120 ℃ to obtain a finished product.
Comparative example 3
High nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2.005The preparation method comprises the following steps:
a. preparation of the precursor
Adding sulfate solution of metal Ni, Co and Mn, ammonia water as morphology control agent and NaOH solution into a reaction kettle, carrying out parallel flow mixing, controlling the pH to be 12, carrying out constant temperature reaction at 65 ℃, continuously reacting until the particle size D50 is 10 mu m, filtering and washing to obtain precursor Ni0.8Co0.1Mn0.1(OH)2；
b. Mixing
Mixing the precursor with lithium hydroxide according to a molar ratio of 1:1.10, adding a water-insoluble auxiliary agent boron oxide accounting for 10% of the mass of the precursor, and uniformly mixing;
c. two-stage sintering
B, sintering the mixture mixed in the step b in a first stage: placing the mixture in an oxidizing atmosphere with the oxygen mass content of more than 99%, heating to 650 ℃ at the heating rate of 2 ℃/min, and preserving heat for 10 hours to obtain an intermediate I;
and then carrying out second-stage sintering: and (3) placing the intermediate I in an oxidizing atmosphere with the oxygen mass content of more than 99%, heating to 800 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 20h, rinsing for 10min in the oxygen-free water nitrogen atmosphere, and drying at 120 ℃ to obtain a finished product.
Comparative example 4
High nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2.005The preparation method comprises the following steps:
a. preparation of the precursor
Adding sulfate solution of metal Ni, Co and Mn, ammonia water as morphology control agent and NaOH solution into a reaction kettle, carrying out parallel flow mixing, controlling the pH to be 12, andreacting at a constant temperature of 65 ℃, continuously reacting until the grain diameter D50 is 10um, filtering and washing to obtain a precursor Ni0.8Co0.1Mn0.1(OH)2；
b. Mixing
Mixing the precursor with lithium hydroxide according to a molar ratio of 1:1.10, adding a water-insoluble auxiliary agent boron oxide accounting for 10% of the mass of the precursor, and uniformly mixing;
c. three-stage sintering
B, sintering the mixture mixed in the step b in a first stage: placing the mixture in an air atmosphere, heating to 650 ℃ at the heating rate of 1 ℃/min, and preserving heat for 4h to obtain an intermediate I;
and then carrying out second-stage sintering: and (3) placing the intermediate I in an oxidizing atmosphere with the oxygen mass content of more than 99%, heating to 750 ℃ at the heating rate of 5 ℃/min, and preserving heat for 6 hours to obtain an intermediate II.
Finally, a third stage of sintering is carried out: and (3) placing the intermediate II in an oxidizing atmosphere with the oxygen mass content of more than 99%, heating to 900 ℃ at the heating rate of 2 ℃/min, preserving the heat for 8h, rinsing for 10min in the oxygen-free water nitrogen atmosphere, and drying at 120 ℃ to obtain a finished product.
TABLE 1 XRD test results of examples 1-5 and comparative examples 1-4
Figure BDA0001595679290000111
XRD examination of the high-nickel ternary materials prepared in examples 1-5 and comparative examples 1-4 showed results shown in Table 1, and it was found that the high-nickel ternary materials obtained in examples 1-5 had a larger ratio c/a of c-axis length to a-axis length in lattice parameters, indicating a more perfect layered structure, and I, as compared with the one-stage sintering (comparative example 1), the two-stage sintering (comparative examples 2 and 3) and the three-stage sintering (comparative example 4) in which the sintering temperature was gradually increased003Peak and I104Intensity ratio of peaks I003/I104And is also larger, indicating less Li/Ni misclassification, indicating that the material made by the three-stage sintering process of the present application has less Li/Ni misclassification and higher crystallinity.
TABLE 2 results of chemical composition test of examples 1 to 5 and comparative examples 1 to 4
Figure BDA0001595679290000112
Figure BDA0001595679290000121
The high nickel ternary materials prepared in examples 1 to 5 and comparative examples 1 to 4 were subjected to chemical titration analysis and ICP analysis, and the results of chemical formulas of the respective samples were shown in table 2. It can be seen from the table that the high nickel ternary materials prepared in examples 1-5 have less Li/Ni mixed-out and no oxygen defect, compared to the one-stage sintering (comparative example 1), the two-stage sintering (comparative examples 2 and 3) and the three-stage sintering (comparative example 4) in which the sintering temperature is gradually increased, which shows that the oxygen defect of the material can be eliminated, the Li/Ni mixed-out degree can be reduced, and the structural stability of the material can be improved by adopting the three-stage sintering method of the present application.
TABLE 3 first efficiency and Power test results for the high nickel ternary materials of examples 1-5 and comparative examples 1-4
Item First efficiency/%) Rct/Ω
Example 1 90.7 9
Example 2 90.4 8.7
Example 3 91.6 9.3
Example 4 91.2 7.9
Example 5 91.0 8.5
Comparative example 1 83.7 233.5
Comparative example 2 85.3 92.6
Comparative example 3 87.5 34.4
Comparative example 4 88.9 78
The high nickel ternary materials prepared in examples 1-5 and comparative examples 1-4 were assembled into button cells and tested for electrochemical performance, and the first efficiency and EIS test results are shown in Table 3. As can be seen from Table 3, the first efficiency of examples 1-5 is significantly higher than that of comparative examples 1-4, further illustrating the more complete crystal structure of the materials prepared in examples 1-5. Charge transfer resistance R of the materials prepared in examples 1 to 5ctIs obviously lower than that of the comparative example1-4, from P ═ Δ U2It can be seen that, when constant power discharge is performed, the voltage drop Δ U of the material having the smaller resistance R is smaller, and the power performance is better. The preparation method adopts a three-stage sintering mode, and the sintering temperature of the second stage is higher than that of the first stage and the third stage, so that the material can be pre-crystallized while lithium salt is melted due to the low temperature of the first stage, and Li is reduced2The formation of O, the high sintering temperature of the second stage can improve the crystallinity of the material, and the shorter sintering time can reduce Li2O is volatilized, and then the oxygen defect caused by high sintering temperature in the second stage can be eliminated through the low-temperature annealing procedure in the third stage, so that the Li/Ni mixed row of the prepared high-nickel ternary material is less, and the first efficiency is high and the power is good.
And the comparative example 1 adopts a one-stage sintering process, sintering is carried out at the upper limit of the temperature far higher than the crystallization window temperature of the nickel-rich ternary material, and the produced Li2More O exists, obvious oxygen defect exists, and the diffusion of Li ions to the transition metal layer is greatly accelerated by overlong heat preservation time, so that a high Li/Ni mixed discharging phenomenon is formed, and the first efficiency and the power of the obtained material are poorer.
While comparative examples 2 and 3 used a two-stage sintering process, despite Li compared to comparative example 12The generation of O is suppressed, but in comparative example 2, the sintering temperature is high, which causes tetravalent nickel ions on the surface layer of the material to lose oxygen atoms and generate a spinel phase, thereby generating oxygen defects, and in comparative example 3, when sintering is performed within the crystallization window temperature range, the too long holding time greatly aggravates the diffusion of Li ions to the transition metal layer, thereby forming a high Li/Ni mixed-row phenomenon, and thus the first efficiency and power of the obtained material are poor.
Comparative example 4 is a three-stage sintering, but the sintering temperature is changed in a gradient manner, and the problem of oxygen defect caused by the fact that tetravalent nickel ions on the surface layer of the material lose oxygen atoms to form a spinel phase due to the fact that the sintering temperature is too high cannot be overcome.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications and alterations to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles disclosed herein.

Claims (6)

1. The preparation method of the high-nickel ternary material is characterized in that the high-nickel ternary material is Li(1+a)NixCoyMzO2+bWherein a is more than or equal to-0.10 and less than or equal to 0.50, and x is more than or equal to 0.8<0.9，0.1≤y≤0.25，0<z is less than or equal to 0.25, b is less than or equal to 0.05 and less than or equal to 0.10, M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V and Cu, the method comprises the steps of mixing a precursor with a lithium source, adding a sintering aid, uniformly mixing, and sintering by adopting a three-stage sintering mode: firstly sintering at a first stage, then sintering at a second stage, and finally sintering at a third stage, wherein the sintering temperature at the second stage is higher than that at the first stage and that at the third stage, the precursor is a hydroxide-carbonate core-shell structure precursor, the core of the hydroxide-carbonate core-shell structure precursor is carbonate, the shell of the hydroxide-carbonate core-shell structure precursor is hydroxide, and the chemical formulas of the precursors are NixCoyMzCO3And NixCoyMz(OH)2Wherein x is more than or equal to 0.8<0.9，0.1≤y≤0.25，0<z is less than or equal to 0.25, M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V and Cu, the sintering aid is a water-soluble aid, and the water-soluble aid is water-soluble sulfate and water-soluble chloride.
2. The method for preparing the high-nickel ternary material according to claim 1, wherein the first-stage sintering is as follows: and (3) heating the mixture added with the sintering aid and mixed to 650-750 ℃ at the heating rate of 0.5-10 ℃/min in the air atmosphere, and preserving the heat for 3-6h to obtain an intermediate I.
3. The method for preparing the high-nickel ternary material according to claim 2, wherein the second-stage sintering is as follows: and (3) placing the intermediate I in an oxidizing atmosphere, heating to 800-950 ℃ at the heating rate of 5-15 ℃/min, and preserving heat for 5-8h to obtain an intermediate II.
4. The method for preparing a high-nickel ternary material according to claim 3, wherein the third-stage sintering is: and (5) placing the intermediate II in an oxidizing atmosphere, cooling to 650 plus 750 ℃ at a cooling rate of 0.5-5 ℃/min, and preserving heat for 5-8 h.
5. The method for preparing a high-nickel ternary material according to claim 3 or 4, wherein the oxidizing atmosphere is an atmosphere having an oxygen content of more than 99% by mass.
6. The method for preparing the high-nickel ternary material according to claim 1, wherein the sintering aid accounts for 1-20% of the mass of the precursor.
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