CN110921723B - Preparation method of hollow lithium ion battery anode material precursor - Google Patents
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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
- 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
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- H—ELECTRICITY
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- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a precursor of a hollow lithium ion battery anode material, belonging to the technical field of lithium ion battery materials. The invention provides a preparation method of a precursor of a hollow lithium ion battery anode material, which comprises the step of carrying out synthesis reaction in two stages in the process of synthesizing the precursor. According to the size requirement of the loose part in the precursor, determining the switching point of the first stage and the second stage, and adjusting the reaction conditions: the stirring linear speed of the second stage is higher than that of the first stage, and the total metal salt flow of the second stage is not more than that of the first stage; and inert gas is always introduced into the reaction kettle in the synthesis process. The method has simple process control, no new cost increase on the basis of the existing mainstream discontinuous process, wide process application range, good product crystallinity, low content of Na and S impurities and adjustable size of loose parts of the precursor, and is suitable for manganese-containing precursors and manganese-free precursors such as nickel, cobalt, aluminum and the like.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a preparation method of a precursor of a hollow lithium ion battery anode material.
Background
The energy crisis and the environmental pollution problem are becoming more serious, and the traditional fossil energy can not meet the future development requirements of human beings. In 1990, commercial lithium ion batteries were successfully developed by sony, and due to the advantages of small size, high energy density, environmental protection, high efficiency, no memory effect and the like, the technology of the lithium ion batteries is rapidly developed and widely applied to the fields of 3C products, electric tools, military and the like. With the development and the gradual maturity of lithium battery technology, the application of the lithium battery technology is gradually expanded to the field of electric automobiles, and the commercial lithium ion battery anode material mainly comprises lithium iron phosphate, lithium manganate and ternary materials at present. Among them, the ternary material has high energy density and high endurance, and has become a hot point for the research of the anode material of the current power battery. The power battery is required to have not only long cruising power and high safety but also high output and high cycle characteristics. The positive electrode active material lithium composite oxide is required to have a uniform particle diameter, a large specific surface area, and a stable structure. The hollow type anode material can well meet the requirements, the hollow type material prepared by the intermittent method is uniform in particle size distribution, large in specific surface area and provided with a large hollow part, the contact area of the material and electrolyte can be effectively increased, and therefore the output performance of the battery is improved.
The preparation of the hollow cathode material is very keyAnd (4) one step. There are two main methods for preparing the hollow cathode material precursor. The first method is a template method, wherein a template agent (such as carbon microspheres) is mixed with a coprecipitation reaction raw material to prepare a precursor with a core-shell structure (the core is the template agent), and the template agent is removed in a certain mode to finally obtain the cathode material with a hollow part, wherein the template agent is introduced in the preparation process of the precursor, so that the material cost and the later process difficulty are obviously increased, and the mass production is difficult; the second method is a kernel oxidation method, which comprises adopting an oxidizing atmosphere (such as air and oxygen) at the early stage of precursor preparation process, and switching to an inert gas atmosphere (such as nitrogen and helium) at the later stage, wherein Mn is added under the oxidizing atmosphere2+Is very easy to be oxidized into Mn3+The crystallinity of coprecipitation is reduced, so that primary particles are arranged loosely and have fine sizes, the primary particles are arranged tightly and have large sizes in the inert gas atmosphere, the precursor with the loose inner part and the dense outer part shrinks outwards in the subsequent lithium mixing sintering process, and a hollow structure is formed gradually.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of a precursor of a hollow lithium ion battery anode material, which does not need to introduce a template agent or adopt oxidizing atmosphere in the synthesis process, has low process difficulty and is easy for mass production.
The solution of the invention is realized by the following steps:
a preparation method of a precursor of a hollow lithium ion battery anode material comprises the following steps:
(1) preparing a metal salt solution with the total metal molar concentration of 1-2.5moL/L, wherein the metal salt is one or more of nickel, cobalt and manganese; preparing 1-10mol/L alkali solution; preparing an ammonia water solution with the ammonium ion concentration of 2-6 mol/L; selectively preparing an aluminum salt solution with the aluminum molar weight of 0.02-0.5 mol/L;
(2) adding pure water into a reaction kettle, controlling the reaction temperature to be 40-80 ℃, adjusting the pH value to 8.5-12.5 by using an alkali solution, adjusting the ammonium ion concentration to 1-50g/L by using ammonia water, and continuously introducing inert gas into the reaction kettle;
(3) on the basis of the step (2), introducing a metal salt solution, an alkali solution and an ammonia water solution into the reaction kettle through a metering pump, and selectively introducing an aluminum salt solution; the reaction process is divided into a first stage and a second stage, the switching point of the first stage and the second stage is determined according to the size requirement of the loose part in the precursor, and the reaction conditions are adjusted: the stirring linear speed of the second stage is higher than that of the first stage, and the total metal salt feeding flow of the second stage is not more than that of the first stage;
(4) and after the synthesis process of the precursor is finished, filtering, aging, washing and drying to synthesize the precursor.
Further, in the above-mentioned case,
and (4) discharging clear liquid in the reaction kettle while performing the step (3), and controlling the liquid level in the reaction kettle.
Further, in the above-mentioned case,
the metal salt solution is one or more of sulfate, nitrate, chloride and acetate.
The aluminum salt solution is one or more of aluminum sulfate and metaaluminate.
The alkali solution is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate.
The inert gas is one of nitrogen or helium.
Further, in the above-mentioned case,
the reaction conditions of the first stage are that the stirring linear speed is 2-8m/s, the temperature is controlled to be 40-80 ℃, the pH value is controlled to be 8.5-12.5, and the concentration of ammonium ions is controlled to be 1-50 g/L.
The reaction conditions of the second stage are that the stirring linear speed is 4-15m/s, the temperature is controlled to be 40-80 ℃, the pH value is controlled to be 8.5-12.5, and the concentration of ammonium ions is controlled to be 1-50 g/L.
The switching between the first stage and the second stage of the invention means that the stirring speed and the total metal salt feeding flow are directly adjusted to target values, and the reaction immediately enters the second stage from the first stage. The stirring linear velocity is low, the precursor grows more loosely, and primary particles are finer; the stirring linear velocity is high, the precursor grows more compactly, and the primary particles are thicker. The total metal salt feeding flow is large, the precursor grows fast, and the particles are loose; the total metal salt feeding flow is small, the precursor grows slowly, and the particles are compact.
The method utilizes the influence of the stirring linear velocity and the total metal salt flow on the particle morphology and the stacking porosity to prepare precursor particles with sparse inside and dense outside, has simple process control, has no new cost on the basis of the existing mainstream discontinuous process, has wide process application range, is suitable for manganese-containing precursors and manganese-free precursors such as nickel, cobalt and aluminum, has good product crystallinity, low content of Na and S impurities and adjustable size of the loose part of the precursor.
Drawings
FIG. 1 shows Ni in example 10.35Co0.35Mn0.30(OH)2Electron microscopy of the precursor;
FIG. 2 shows Ni in example 10.35Co0.35Mn0.30(OH)2A section electron microscope image of the precursor;
FIG. 3 shows Ni in example 20.5Co0.2Mn0.3(OH)2Electron microscopy of the precursor;
FIG. 4 shows Ni in example 20.5Co0.2Mn0.3(OH)2Sectional electron microscope images of the precursors.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way. Furthermore, features from embodiments in this document and from different embodiments may be combined accordingly by a person skilled in the art from the description in this document.
Example 1
Preparing a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution with the total metal concentration of 2mol/L, wherein the molar ratio of nickel to cobalt to manganese is 35:35:30, preparing a sodium hydroxide solution with the total metal concentration of 2mol/L, and preparing an ammonia water solution with the total metal concentration of 6mol/L as a complexing agent. Adding pure water into a reaction kettle with the volume of 300L, controlling the temperature at 60 ℃, adjusting the pH value to 12.0 by using alkali, adjusting the ammonium ion concentration to 20g/L by using ammonia water, and continuously introducing nitrogen into the reaction kettle.
In the first stage, the total metal salt feeding flow is controlled to be 120mL/min, the stirring linear speed is controlled to be 3m/s, the temperature is controlled to be 60 ℃, the pH value is controlled to be 10.0-12.0, the ammonium ion concentration is controlled to be 20g/L, after precursor particles grow to be 2.2 mu m, the reaction conditions are switched, and the second stage is carried out. The feeding flow of the total metal salt in the second stage is controlled to be 90mL/min, the stirring linear speed is controlled to be 6m/s, the temperature is controlled to be 60 ℃, the pH value is controlled to be 10.0-12.0, the concentration of ammonium ions is controlled to be 20g/L, and the reaction is stopped after the precursor grows to be 5.0 mu m. And (3) discharging clear liquid through a physical settling tank while carrying out the coprecipitation reaction. Filtering, aging, washing and drying the prepared slurry to obtain Ni with loose inside and compact outside0.35Co0.35Mn0.30(OH)2And (5) precursor products.
Example 2
Preparing a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution with the total metal concentration of 2mol/L, wherein the molar ratio of nickel to cobalt to manganese is 5:2:3, preparing a 2mol/L sodium hydroxide solution, and preparing a 6mol/L ammonia water solution as a complexing agent. Adding pure water into a reaction kettle with the volume of 300L, controlling the temperature to be 55 ℃, adjusting the pH value to 11.5 by using alkali, adjusting the ammonium ion concentration to 10g/L by using ammonia water, and continuously introducing nitrogen into the reaction kettle. In the first stage, the metal salt feeding flow is controlled to be 120mL/min, the stirring linear speed is controlled to be 5m/s, the temperature is controlled to be 55 ℃, the pH value is controlled to be 10.0-11.5, the ammonium ion concentration is controlled to be 10g/L, after precursor particles grow to be 3 mu m, the reaction conditions are switched, and the second stage is carried out. In the second stage, the metal salt feeding flow is controlled to be 120mL/min, the stirring linear speed is controlled to be 8m/s, the temperature is controlled to be 55 ℃, the pH value is controlled to be 10.0-11.5, the concentration of ammonium ions is controlled to be 10g/L, and the reaction is stopped after the precursor grows to be 5.0 mu m. And (3) discharging clear liquid by adopting a filtering concentrator while carrying out the coprecipitation reaction. Preparation ofFiltering, aging, washing and drying the obtained slurry to obtain Ni with loose inside and compact outside0.5Co0.2Mn0.3(OH)2And (5) precursor products.
As can be seen from FIGS. 1 to 4, the precursor prepared by the technical scheme of the invention has a very obvious structure with loose inside and dense outside.
In addition, as can be seen from table 1, the precursor prepared by the technical scheme of the invention has low content of impurities Na and S and low tap density.
TABLE 1 physicochemical Properties of precursors
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A preparation method of a precursor of a hollow lithium ion battery anode material comprises the following steps:
(1) preparing a metal salt solution with the total metal molar concentration of 1-2.5moL/L, wherein the metal salt is one or more of nickel, cobalt and manganese; preparing 1-10mol/L alkali solution; preparing an ammonia water solution with the ammonium ion concentration of 2-6 mol/L; selectively preparing an aluminum salt solution with the aluminum molar weight of 0.02-0.5 mol/L;
(2) adding pure water into a reaction kettle, controlling the reaction temperature to be 40-80 ℃, adjusting the pH value to 8.5-12.5 by using an alkali solution, adjusting the ammonium ion concentration to 1-50g/L by using ammonia water, and continuously introducing inert gas into the reaction kettle;
(3) on the basis of the step (2), introducing a metal salt solution, an alkali solution and an ammonia water solution into the reaction kettle through a metering pump, and selectively introducing an aluminum salt solution; the reaction process is divided into a first stage and a second stage, the switching point of the first stage and the second stage is determined according to the size requirement of the loose part in the precursor, and the reaction conditions are adjusted: the stirring linear speed of the second stage is higher than that of the first stage, and the total metal salt feeding flow of the second stage is not more than that of the first stage;
(4) and after the synthesis process of the precursor is finished, filtering, aging, washing and drying to synthesize the precursor.
2. The method according to claim 1, wherein step (3) is carried out while discharging a clear liquid from the reaction vessel to control the liquid level in the reaction vessel.
3. The method of claim 1, wherein the metal salt solution is one or more of a sulfate, a nitrate, a chloride, and an acetate.
4. The method according to claim 1, wherein the aluminum salt solution is one or more of aluminum sulfate and metaaluminate.
5. The method of claim 1, wherein the alkali solution is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, and ammonium bicarbonate.
6. The method of claim 1, wherein the inert gas is one of nitrogen or helium.
7. The production method according to any one of claims 1 to 6, wherein the reaction conditions in the first stage are a stirring linear velocity of 2 to 8m/s, a temperature of 40 to 80 ℃, a pH of 8.5 to 12.5, and an ammonium ion concentration of 1 to 50 g/L.
8. The production method according to any one of claims 1 to 6, wherein the reaction conditions in the second stage are a stirring linear velocity of 4 to 15m/s, a temperature of 40 to 80 ℃, a pH of 8.5 to 12.5, and an ammonium ion concentration of 1 to 50 g/L.
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| CN111600015B (en) * | 2020-07-27 | 2020-11-13 | 金驰能源材料有限公司 | Narrow-distribution small-granularity spherical nickel-cobalt-manganese hydroxide precursor and preparation method thereof |
| CN112357973A (en) * | 2020-09-30 | 2021-02-12 | 宜宾光原锂电材料有限公司 | Preparation method of positive electrode material precursor and prepared positive electrode material precursor |
| CN112357975B (en) * | 2020-09-30 | 2021-09-07 | 宜宾光原锂电材料有限公司 | Preparation method of hollow ternary cathode material precursor and prepared ternary cathode material precursor |
| CN112194203A (en) * | 2020-10-29 | 2021-01-08 | 格林爱科(荆门)新能源材料有限公司 | Preparation method of nickel-cobalt oxide material |
| CN112758992A (en) * | 2020-12-28 | 2021-05-07 | 宜宾光原锂电材料有限公司 | Multilayer coated cobalt-free precursor, cathode material and production method thereof |
| CN112830527B (en) * | 2021-04-22 | 2021-07-13 | 金驰能源材料有限公司 | Precursor of hollow cathode material and preparation method thereof |
| CN114772658B (en) * | 2022-04-24 | 2023-10-17 | 南通金通储能动力新材料有限公司 | Precursor of positive electrode material of power lithium ion battery and preparation method thereof |
| CN115959720B (en) * | 2023-03-17 | 2023-06-23 | 四川新能源汽车创新中心有限公司 | High-nickel precursor material, high-nickel positive electrode material and preparation method thereof |
| CN117234266B (en) * | 2023-11-13 | 2024-03-22 | 长沙矿冶研究院有限责任公司 | Ternary precursor reaction kettle reaction reverse selectivity control method and system |
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