CN109574092B - Preparation method of full-concentration gradient nickel-cobalt-aluminum ternary precursor - Google Patents
Preparation method of full-concentration gradient nickel-cobalt-aluminum ternary precursor Download PDFInfo
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- CN109574092B CN109574092B CN201811452741.8A CN201811452741A CN109574092B CN 109574092 B CN109574092 B CN 109574092B CN 201811452741 A CN201811452741 A CN 201811452741A CN 109574092 B CN109574092 B CN 109574092B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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
- 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
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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
- H01M4/485—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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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of preparation of lithium ion battery anode materials, and particularly relates to a preparation method of a full-concentration gradient nickel-cobalt-aluminum ternary precursor, which comprises the following steps: (1) respectively preparing a nickel-cobalt mixed solution A with high nickel concentration, a nickel-cobalt mixed solution B with high cobalt concentration, an aluminum solution C with certain concentration and a mixed solution D of a complexing agent and a precipitator with certain concentration; (2) adding the solution A into a reaction kettle, and simultaneously adding the solution B into the solution A; adding the solution C into a reaction kettle, and adding deionized water into the solution C at the same time; adding the solution D into a reaction kettle, controlling the reaction temperature to be 50-70 ℃ and the pH value to be 10.5-12, and (3) after the reaction is finished, carrying out solid-liquid separation, washing and drying on the materials to obtain the nickel-cobalt-aluminum ternary precursor with full concentration gradient.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery anode materials, and particularly relates to a preparation method of a full-concentration gradient nickel-cobalt-aluminum ternary precursor.
Background
The lithium ion battery has the advantages of high energy density, long cycle life and the like, and is widely applied to digital products at present. With the environmental protection importance of the country and the vigorous promotion of the development of new energy automobiles, the development and application of lithium ion batteries are advanced to a new level.
In order to meet the development requirements of new energy automobiles, lithium ion batteries with higher energy density must be provided, and the energy density is determined by anode materials to a great extent. The ternary material is found to have a higher capacity density, and the capacity of the material gradually increases with the increase of the nickel content. However, the cycle performance of the battery is drastically reduced with the increase in the nickel content. The reason is as follows: firstly, the nickel ions and the lithium ions have similar ionic radiuses, and during the charging and discharging processes of the battery, the nickel ions gradually occupy lithium positions, so that the laminated structure collapses, and the conduction of the lithium ions is hindered. Secondly, in the battery circulation process, the strong oxidizing property of the quadrivalent nickel ions damages the material and the electrolyte product, and gases such as hydrogen, oxygen and the like are generated along with the release of heat.
In a certain range, the energy density and the cycle performance of the battery show negative correlation, which is against our desire to develop new energy. Research shows that the ternary material with high internal nickel content and low external nickel content has high capacity density and obviously improved cycle performance. For example, chinese patent CN103715424B discloses a core-shell structure cathode material and a preparation method thereof, which comprises first synthesizing a nickel-cobalt precursor, then calcining at high temperature, and then coating a layer of aluminum hydroxide surface on the surface of the calcined product. However, the aluminum layer on the surface does not participate in the electrochemical reaction, and reduces the electronic conductivity and the ion diffusivity of the material, so that the capacity cannot be effectively exerted, and the energy density of the battery is low. For another example, chinese patent CN106207140A discloses a method for preparing a nickel-cobalt-aluminum composite with a multiple core-shell structure, which prepares a precursor with high internal nickel content and low external nickel content through multiple coprecipitation reactions. The precursor prepared by the method consists of a plurality of coating layers with different nickel-cobalt concentrations, interfaces exist among the coating layers, and due to different components among the coating layers, different volume changes occur in the charging and discharging processes of the battery, and the cycle performance of the battery is poor. In addition, the method has complex process and is not suitable for industrial production.
Disclosure of Invention
In order to solve the problems, the inventor skillfully designs a preparation method of a full-concentration gradient nickel-cobalt-aluminum ternary precursor.
In order to realize the technical purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a full concentration gradient nickel-cobalt-aluminum ternary precursor is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a nickel-cobalt mixed solution A with high nickel concentration, a nickel-cobalt mixed solution B with high cobalt concentration, an aluminum solution C and a mixed solution D of a complexing agent and a precipitator;
(2) adding the solution A into a reaction kettle, and simultaneously adding the solution B into the solution A; adding the solution C into a reaction kettle, and adding deionized water into the solution C at the same time; adding the solution D into a reaction kettle until the A, B, C three solutions are completely added, and aging for a certain time;
(3) and after the reaction is finished, performing solid-liquid separation, washing and drying on the materials to obtain the full-concentration gradient nickel-cobalt-aluminum ternary precursor.
Preferably, the salt used for preparing the solutions A and B in the step (1) is nickel sulfate and cobalt sulfate; the salt used for preparing the solution C is sodium metaaluminate.
Preferably, the complexing agent in the step (1) is ammonia water, and the precipitator is sodium hydroxide.
More preferably, the concentration of total metals in the solution in the step (1) A is 1-2M; the concentration of total metals in the solution B is 1-2M; the concentration of the solution C is 0.5-1M; the concentration of ammonia water in the solution D is 1-3M; the concentration of the sodium hydroxide is 3-6M.
Preferably, the molar ratio of nickel to cobalt in the solution A in the step (1) is 10: 1-20: 1; the molar ratio of nickel to cobalt in the solution B is 1: 1-1: 3.
Preferably, in the reaction system of the step (2), the ratio of nickel: cobalt: the molar ratio of aluminum is 0.55-0.80: 0.15-0.40: 0.02-0.06.
Preferably, the addition rate of A, B, C three solutions and DI water in step (2) is controlled to ensure complete addition within a certain time.
More preferably, the A, B, C addition rates for the three solutions and deionized water in step (2) are performed according to the mathematical equation y ═ a-bx, y represents flow rate, x represents time, 0< a <10, 0< b < 1.
In a preferred embodiment, the solution a is added to the reaction kettle at a rate of y ═ 4 to 0.25 x; adding the solution B into the solution A at a rate of y-2-0.125 x; adding the solution C into a reaction kettle at a speed of y being 0.85-0.053 x; deionized water was added to solution C at a rate of y-0.425-0.026 x, while solution D was added to the kettle at a rate.
In a preferred embodiment, the solution a is added to the reaction kettle at a rate of y ═ 6 to 0.375 x; adding the solution B into the solution A at a rate of y-2-0.125 x; adding the solution C into the reaction kettle at a speed of y being 0.675-0.042 x; deionized water was added to solution C at a rate of y-0.337-0.021 x, while solution D was added to the kettle at a rate.
In a preferred embodiment, the solution a is added to the reaction kettle at a rate of y ═ 6 to 0.375 x; adding the solution B into the solution A at a rate of y being 4-0.25 x; adding the solution C into the reaction kettle at a speed of y being 1-0.062 x; deionized water was added to solution C at a rate of y-0.5-0.031, while solution D was added to the kettle at a rate.
Preferably, the pH value in the reaction system in the step (2) is 10.5-12; the temperature is 50-70 ℃, and the aging time is 6-24 h.
Preferably, the materials in the step (3) can be washed by hot alkali solution with the pH of 10.5-12 and the temperature of 50-70 ℃ and deionized water in sequence; more preferably, the alkali solution is a sodium hydroxide solution.
More specifically, the material in the step (3) is subjected to slurry washing in hot alkali solution with the pH of 10.5-11.5 and the temperature of 50-70 ℃ for 2 times, then is washed in purified water for 2 times, is dried at 120 ℃ for 24 hours, and is sieved by a 200-mesh sieve to obtain the nickel-cobalt-aluminum ternary precursor.
The beneficial effects of the method are as follows:
1. the nickel-cobalt-aluminum ternary precursor prepared by the method has a continuous concentration gradient, the nickel concentration is sequentially reduced from inside to outside, the cobalt concentration is sequentially increased from inside to outside, the aluminum concentration is sequentially reduced from inside to outside, and no obvious interface layer exists.
2. The method realizes the full concentration gradient separation of the nickel-cobalt-aluminum ternary precursor by gradually changing the concentration of the nickel-cobalt-aluminum solution, and has the advantages of simple process, good product stability and good cycle performance.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a graph of the addition rates of the solutions of example 1.
FIG. 2 is a graph of the cycling performance of button cells made from the samples of example 1.
Detailed description of the preferred embodiment
The present invention will be further described with reference to the following examples. The described embodiments and their results are only intended to illustrate the invention and should not be taken as limiting the invention described in detail in the claims.
Example 1
Solution preparation
Preparing 16L of mixed solution A with the molar ratio of nickel to cobalt being 10:1 by using deionized water, wherein the total metal concentration is 2M; preparing 16L of mixed solution B with the molar ratio of nickel to cobalt being 1:1, wherein the total metal concentration is 2M; preparing 3.4L of aluminum solution C with the concentration of 1M; and preparing a mixed solution D of ammonia water and sodium hydroxide, wherein the concentration of the ammonia water is 2M, and the concentration of the sodium hydroxide is 4M.
Reaction of
10L of dilute ammonia solution is poured into a 100L reaction kettle, and the pH value is controlled to be about 11. Then adding the solution A into the reaction kettle at a speed of y being 4-0.25 x; adding the solution B into the solution A at a rate of y-2-0.125 x; adding the solution C into a reaction kettle at a speed of y being 0.85-0.053 x; adding deionized water into the solution C at a speed of y-0.425-0.026 x, adding the solution D into the reaction kettle at a certain speed, stopping adding the solution D after the addition of A, B, C three solutions is finished, and aging for 12 hours. The temperature of the whole reaction system is controlled to be 60 ℃, and the pH value is 11.
Post-treatment
Taking the materials out of the reaction kettle, carrying out solid-liquid separation, washing twice by using a sodium hydroxide solution with the pH value of 11 and the temperature of 60 ℃, and washing twice by using deionized water. Drying the cleaned material at 120 deg.C for 24h, sieving with 200 mesh sieve to obtain Ni-Co-Al ternary precursor with full concentration gradient and chemical formula of Ni0.67Co0.28Al0.05(OH)2。
After the button cell prepared by the sample is charged and discharged for 50 times at 0.1 ℃, the capacity retention rate reaches 97.2 percent.
Example 2
Solution preparation
Preparing 32L of mixed solution A with the molar ratio of nickel to cobalt being 20:1 by using deionized water, wherein the total metal concentration is 1M; preparing 16L of mixed solution B with the molar ratio of nickel to cobalt being 1:3, wherein the total metal concentration is 2M; preparing 2.7L of aluminum solution C with the concentration of 1M; and preparing a mixed solution D of ammonia water and sodium hydroxide, wherein the concentration of the ammonia water is 1M, and the concentration of the sodium hydroxide is 3M.
Reaction of
15L of dilute ammonia solution is poured into a 100L reaction kettle, and the pH value is controlled to be about 11.5. Then adding the solution A into the reaction kettle at the speed of y being 6-0.375 x; adding the solution B into the solution A at a rate of y-2-0.125 x; adding the solution C into the reaction kettle at a speed of y being 0.675-0.042 x; adding deionized water into the solution C at a speed of y being 0.337-0.021x, simultaneously adding the solution D into the reaction kettle at a certain speed, stopping adding the solution D after the addition of the A, B, C three solutions is finished, and aging for 6 hours. The temperature of the whole reaction system is controlled to be 65 ℃, and the pH value is 11.5.
Post-treatment
Taking the materials out of the reaction kettle, carrying out solid-liquid separation, washing twice by using a sodium hydroxide solution with the pH value of 11.5 and the temperature of 65 ℃, and then washing twice by using deionized water. Drying the cleaned material at 120 deg.C for 24h, sieving with 200 mesh sieve to obtain Ni-Co-Al ternary precursor with full concentration gradient and chemical formula of Ni0.58Co0.38Al0.04(OH)2。
After the button cell prepared by the sample is charged and discharged for 50 times at 0.1 ℃, the capacity retention rate reaches 97.5 percent.
Example 3
Solution preparation
Preparing 16L of mixed solution A with the molar ratio of nickel to cobalt being 15:1 by using deionized water, wherein the total metal concentration is 2M; preparing 32L of mixed solution B with the molar ratio of nickel and cobalt being 1:2, wherein the total metal concentration is 1M; preparing 4L of aluminum solution C with the concentration of 0.5M; and preparing a mixed solution D of ammonia water and sodium hydroxide, wherein the concentration of the ammonia water is 3M, and the concentration of the sodium hydroxide is 6M.
Reaction of
Pouring 10L of dilute ammonia solution into a 100L reaction kettle, and controlling the pH value to be about 10.5. Then adding the solution A into the reaction kettle at the speed of y being 6-0.375 x; adding the solution B into the solution A at a rate of y being 4-0.25 x; adding the solution C into the reaction kettle at a speed of y being 1-0.062 x; adding deionized water into the solution C at a speed of y being 0.5-0.031, adding the solution D into the reaction kettle at a certain speed, stopping adding the solution D after the addition of A, B, C three solutions is finished, and aging for 24 hours. The temperature of the whole reaction system is controlled to be 55 ℃, and the pH value is 10.5.
Post-treatment
Taking the materials out of the reaction kettle, carrying out solid-liquid separation, washing twice by using a sodium hydroxide solution with the pH value of 10.5 and the temperature of 55 ℃, and then washing twice by using deionized water. Drying the cleaned material at 120 deg.C for 24h, sieving with 200 mesh sieve to obtain Ni-Co-Al ternary precursor with full concentration gradient and chemical formula of Ni0.78Co0.19Al0.03(OH)2。
After the button cell prepared by the sample is charged and discharged for 50 times at 0.1 ℃, the capacity retention rate reaches 97.0 percent.
Claims (4)
1. A preparation method of a full concentration gradient nickel-cobalt-aluminum ternary precursor is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a nickel-cobalt mixed solution A with high nickel concentration, a nickel-cobalt mixed solution B with high cobalt concentration, an aluminum solution C and a mixed solution D of a complexing agent and a precipitator;
(2) adding the solution A into a reaction kettle, and simultaneously adding the solution B into the solution A; adding the solution C into a reaction kettle, and adding deionized water into the solution C at the same time; adding the solution D into a reaction kettle until the A, B, C three solutions are completely added, and aging for a certain time;
(3) after the reaction is finished, carrying out solid-liquid separation, washing and drying on the materials to obtain a full-concentration gradient nickel-cobalt-aluminum ternary precursor;
the complexing agent in the step (1) is ammonia water, and the precipitator is sodium hydroxide;
the concentration of total metals in the solution A in the step (1) is 1-2M; the concentration of total metals in the solution B is 1-2M; the concentration of the solution C is 0.5-1M; the concentration of ammonia water in the solution D is 1-3M; the concentration of sodium hydroxide is 3-6M;
the molar ratio of nickel to cobalt in the solution A in the step (1) is 10: 1-20: 1; the molar ratio of nickel to cobalt in the solution B is 1: 1-1: 3;
nickel in the reaction system in the step (2): cobalt: the molar ratio of aluminum is 0.55-0.80: 0.15-0.40: 0.02-0.06;
the addition rate of the A, B, C three solutions and the deionized water in the step (2) is carried out according to a mathematical equation;
the mathematical equation for the addition rate of A, B, C and deionized water in step (2) is y ═ a-bx, y denotes flow rate, x denotes time, 0< a <10, 0< b < 1.
2. The method of claim 1, wherein: preparing nickel sulfate and cobalt sulfate used by the solution A and the solution B in the step (1); the salt used for preparing the solution C is sodium metaaluminate.
3. The method of claim 1, wherein: the pH value of the system in the step (2) is 10.5-12; the temperature is 50-70 ℃, and the aging time is 6-24 h.
4. The method of claim 1, wherein: and (4) respectively putting the materials in the step (3) into hot alkali liquor and deionized water at the pH of 10.5-12 for washing.
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| CN110224123B (en) * | 2019-06-13 | 2020-09-15 | 广东邦普循环科技有限公司 | High-voltage lithium cobalt oxide cathode material and preparation method and application thereof |
| CN110683590A (en) * | 2019-09-27 | 2020-01-14 | 天津大学 | Preparation method of nickel-cobalt-aluminum hydroxide precursor based on aluminum element concentration gradient distribution |
| CN111302407A (en) * | 2020-02-28 | 2020-06-19 | 新奥石墨烯技术有限公司 | High-nickel quaternary positive electrode material precursor and preparation method thereof, high-nickel quaternary positive electrode material and preparation method thereof, and lithium ion battery |
| CN113060773A (en) * | 2021-03-17 | 2021-07-02 | 中国科学院过程工程研究所 | Preparation method and application of full-concentration-gradient high-nickel ternary material |
| CN113023795A (en) * | 2021-05-24 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Multi-element positive electrode precursor and preparation method and application thereof |
| CN115180657A (en) * | 2022-06-30 | 2022-10-14 | 金川集团股份有限公司 | Preparation method of aluminum-doped nickel-doped gradient cobalt carbonate material |
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| CN107359346B (en) * | 2017-06-19 | 2019-07-26 | 荆门市格林美新材料有限公司 | A kind of anode material of lithium battery modified multicomponent presoma and preparation method |
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