CN109192961B - Preparation method of positive electrode material - Google Patents
Preparation method of positive electrode material Download PDFInfo
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Abstract
The application provides a preparation method of a positive electrode material, the positive electrode material comprises a core material and a metal oxide coating the core material, and the preparation method comprises the following steps in sequence: (1) mixing a simple substance of corresponding metal in the metal oxide with acid to prepare a solution; (2) adding the core material to obtain a coating intermediate; (3) and placing the anode material in a high-pressure oxidation atmosphere, and carrying out combustion treatment by using combustible gas as carrier gas to obtain the anode material of the metal oxide coated core material. The metal simple substance and the acid are directly used for preparing a solution, the heat generated when the combustible gas is burnt in the high-pressure oxygen atmosphere decomposes the solvent acid or salt in the solution and vaporizes water, the metal simple substance or the metal ions form corresponding oxides under the action of high temperature and oxygen to be coated on the active surface of the core material in situ, and the coated material has excellent electrochemical performance; the acid and the combustible gas used in the method are mixed and are degraded into pollution-free gas after oxygen-enriched combustion, and no additional pollutant treatment process is needed.
Description
Technical Field
The application relates to the field of cathode materials, in particular to a preparation method of a cathode 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 materials to a great extent, in order to improve the performance of the anode materials, the surface of the core material of the anode materials is coated and modified at present, the coating layer mainly serves to stabilize the surface of the core layer and prevent the surface structure of the core layer from being damaged, such as in LiNi0.5Mn1.5O4The surface of the metal oxide can be coated to improve the structural stability under high voltage, such as LiFePO4The surface is coated with a carbon layer to improve the conductivity.
However, the methods for coating the core material surface of the cathode material in the prior art generally include solid-solid phase mixing and solid-liquid phase mixing.
The solid-solid phase mixing is to crush the core layer material and the cladding layer material or prepare the core layer material and the cladding layer material into nano-scale materials, then mix the materials in a solid phase, then perform tabletting to increase the contact force between the core layer material and the cladding layer material, and then perform sintering and crushing to obtain the cladding material. The method has the problems that the core layer material and the cladding layer material are difficult to be uniformly mixed, and the bonding force between the sintered cladding layer and the core layer is not tight enough due to small contact force between solid and solid phases, so that the cladding is not uniform and discontinuous, and the consistency of the materials is poor.
Solid-liquid phase mixing is to put the core layer material into the precursor solution of the cladding layer material, then add the precipitant to deposit the cladding layer material on the surface of the core layer material, and obtain the cladding material after drying, sintering and crushing. The disadvantage of this process is that it requires the consumption of large amounts of solvent and a large amount of energy in the drying process.
Therefore, the coating method of the cathode material with excellent performance and less environmental pollution is still a difficult problem to be overcome by research and development personnel.
Content of application
The present application is directed to a positive electrode material and a method for preparing the same, wherein the positive electrode material comprises a core material and a surface metal oxide coating layer, wherein the surface of the core material is uniformly coated with the metal oxide coating layer.
In order to achieve the above object, the present application also provides a method for preparing a positive electrode material comprising a core material and a metal oxide coating the core material, comprising the following steps in order:
(1) mixing a simple substance of corresponding metal in the metal oxide with acid to prepare a solution;
(2) adding to the core material to obtain a coated intermediate;
(3) and placing the anode material in a high-pressure oxidation atmosphere, and carrying out combustion treatment by using combustible gas as carrier gas to obtain the anode material of the metal oxide coated core material.
According to the preparation method, a metal simple substance and an acid are directly used for preparing a solution, combustible gas is used as carrier gas, the heat generated when the combustible gas is combusted in a high-pressure oxidation atmosphere decomposes solvent acid and salt in the solution, water is vaporized, the metal simple substance or metal ions form corresponding oxides under the action of high temperature and oxygen, and the oxides are coated on the surface of a core material in situ, so that the core material can be uniformly coated by a coating layer, the core material is tightly contacted with the coating layer material, and the prepared anode material has excellent performance; because only acid is used as a solvent and no other organic solvent is contained, the solvent amount is relatively less, and the environmental pollution is less; during combustion, the liquid phase constituents of combustible gases and solutions can be decomposed into NOx、SOx、CO2And H2O is volatilized, and thus an additional pollutant treating process is not required. If the traditional drying or calcining method is adopted to replace the combustion method of the application, the temperature rise process is slow through direct heating of drying or calcining, long-time heating is needed for reaching the vaporization temperature of solvent acid and salt, the acidity is improved along with gradual vaporization of the solvent in the heating process, the anode material is corroded, meanwhile, segregation is caused by slow dissolution of metal simple substances, the oxidation speed is slow and incomplete, and therefore the performance of the obtained anode material coated with the metal oxide is poor.
Drawings
Fig. 1 is an SEM characterization of the cathode material prepared in example 1 of the present application.
Fig. 2 is an SEM characterization image of the cathode material prepared in comparative example 1 of the present application.
FIG. 3 is a graph showing the comparison of the cycle performance of the positive electrode materials prepared in examples 1 to 3 of the present application and comparative example 1.
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 positive electrode material, the positive electrode material comprises a core material and a metal oxide coating the core material, and the preparation method comprises the following steps in sequence:
(1) mixing a simple substance of corresponding metal in the metal oxide with acid to prepare a solution;
(2) adding the core material to obtain a coating intermediate;
(3) and placing the anode material in a high-pressure oxidation atmosphere, and carrying out combustion treatment by using combustible gas as carrier gas to obtain the anode material of the metal oxide coated core material.
Specifically, the core material may be LiCoO2、LiNiO2、LiNi0.5Mn1.5O4、LiMn2O4、LiFePO4And Li(1+a)NixCoyM(1-x-y)O2+bWherein-0.10 is more than or equal to a is more than or equal to 0.50, and 0.3 is more than or equal to x<0.9, 0.1-0.4, 0.05-0.10, M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V and Cu. The metal oxide being Al2O3、MgO、Fe2O3、SiO2And TiO2One or more of (a).
Specifically, the acid in step (1) is organic acid or inorganic acid with anion decomposable at 600 deg.C, and the acid can be one of nitric acid, dilute sulfuric acid, hydrochloric acid, acetic acid, citric acid and oxalic acid. In the metal oxide, some metal simple substances react with acid at normal temperature to generate salt, for example, the simple substances of aluminum, magnesium and iron react with nitric acid, dilute sulfuric acid, hydrochloric acid, acetic acid, citric acid and oxalic acid at normal temperature to generate salt; some metal simple substances can react with acid at high temperature to generate salt, for example, titanium simple substances can react with nitric acid, dilute sulfuric acid and hydrochloric acid at high temperature; some metals need to be dissolved in acid at high temperature, for example, elemental silicon needs to be heated to be dissolved in organic acid and inorganic acid. Therefore, the solution prepared by mixing the simple substance of the metal and the acid may be the whole simple substance of the metal and the solvent acid, may be the whole simple substance of the metal, the solvent acid and the salt, and may be the whole salt.
Further, the simple substance of the metal in the step (1) is mixed with acid, then ammonia water is slowly added for dilution, and the pH value is adjusted to 5-6 to prepare a solution. The pH value is adjusted to be 5-6, so that the impure phase generated by dissolution of transition metal due to strong acidity in the combustion reaction can be reduced or even eliminated, and the ammonia water can be completely decomposed at high temperature, so that the ammonia water is adopted for pH value adjustment, and impurity residues are avoided.
Specifically, the step (2) of adding the core material to obtain the coating intermediate is to spray the core material by using a solution, the core material can be placed in a high-speed mixer to be vacuumized, and the metal solution can be sprayed by an atomizing device at the top of the high-speed mixer. The core material is sprayed with the solution, so that the solution is uniformly adsorbed on the surface of the core material, and a coating layer is formed in situ during combustion. The step (2) can be specifically that after the core material is vacuumized to the vacuum degree of 1atm, nitrogen is introduced while high-speed stirring is carried out, the core material is sprayed by adopting a solution, spraying and high-speed stirring are stopped when the vacuum degree reaches 0, vacuumizing is carried out to the vacuum degree of 1atm, the mesoporous effect existing in the anode material powder can be eliminated by vacuumizing and spraying, the solution is uniformly adsorbed on the surface of the core material, and the nitrogen is introduced to cool heat generated by high-speed stirring and prevent segregation. Preferably, the solution is divided into multiple times of spraying, the carrier gas is introduced while the high-speed stirring is carried out, the solution is adopted to spray the core material, the spraying and the high-speed stirring are stopped when the vacuum degree reaches 0, and the operation of vacuumizing to the vacuum degree of 1atm is carried out repeatedly, so that the mesoporous effect existing in the anode material powder can be effectively eliminated, and the solution is uniformly adsorbed on the surface of the core material.
Specifically, in the step (2), the solution is added into the core material to obtain the coating intermediate, wherein the solid content of the coating intermediate is 90-99%, that is, the solid content of the core material and the solution is 90-99%, and the content of the solution of the coating layer is low.
Further, the step (3) is to place the coating intermediate in a high-pressure oxidation atmosphere, and to perform combustion treatment by using combustible gas as carrier gas to obtain the positive electrode material of the metal oxide coating core material, wherein the high-pressure oxidation atmosphere is an atmosphere with 200 to 500kPa and oxygen concentration of more than 99%, and the combustible gas is hydrogen or C1-C6 low-paraffin hydrocarbon, preferably propane or natural gas. The conditions of the combustion treatment were: the burning time is 10-30 s, the burning temperature is 800-1200 ℃, and the preferable burning temperature is 900-1000 ℃. The particle size of the metal oxide particles formed by combustion is less than 20nm, the particles are uniformly coated on the surface of the anode material, after the combustion is finished, the anode material is still in a dry state, the fluidity is good, and an additional solid-liquid separation or drying process is not needed.
The following provides a detailed description of the method for producing the positive electrode material of the present application with reference to examples.
Example 1
Al2O3Coated high nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2.005The preparation method comprises the following steps:
(1) mixing simple substance Al with nitric acid to react to generate Al (NO)3)3Then mixing the two solutions, slowly adding ammonia water for dilution, and adjusting the pH value to 6 to prepare a solution;
(2) mixing core material Li1.01Ni0.8Co0.1Mn0.1O2.005Adding into a high-speed mixer, slowly vacuumizing to make vacuum degree reach 1atm, stirring, and spraying the solution onto Li core material by using an atomizing device at the top of the high-speed mixer1.01Ni0.8Co0.1Mn0.1O2.005And using nitrogen as carrier gas, stopping spraying the solution when the vacuum degree is 0, stopping stirring, repeatedly vacuumizing until the vacuum degree reaches 1atm, repeatedly starting stirring, and spraying the solution to Li by using an atomization device at the top of the high-speed mixer1.01Ni0.8Co0.1Mn0.1O2.005Surface of core material, andtaking nitrogen as carrier gas, stopping spraying the solution when the vacuum degree is 0, stopping stirring, and repeating the operation of vacuumizing until the vacuum degree reaches 1atm "to obtain a coated intermediate with the solid content of 96 percent;
(3) placing the coated intermediate in high-pressure combustion coating equipment with the pressure of 400kPa and the oxygen content of 99 percent, and combusting for 20s at 1000 ℃ by taking propane as carrier gas to obtain Al2O3Coated Li1.01Ni0.8Co0.1Mn0.1O2.005The particle diameter of the metal oxide particles formed by combustion<20nm, and uniformly coating the surface of the positive electrode material.
On combustion of propane, water in solution vaporizes, Al (NO)3)3Al upon decomposition3+Combined with oxygen atoms at high temperature and oxygen to form Al2O3Coated with Li1.01Ni0.8Co0.1Mn0.1O2.005Of (2) is provided. For Al2O3Coated Li1.01Ni0.8Co0.1Mn0.1O2.005SEM characterization was performed, and the results are shown in FIG. 1, Al2O3Coating layer is uniform, and the obtained Al2O3Coated Li1.01Ni0.8Co0.1Mn0.1O2.005The anode material is subjected to cycle performance test according to a key material performance test specification for a lithium ion power storage battery in 2010, which is a major project of energy conservation and new energy automobiles in the '863 plan', and the capacity retention rate after 20 cycles is 98.1% (shown in figure 3).
Example 2
MgO and SiO2Coated Li1.01Ni0.8Co0.1Mn0.1O2.005The preparation method comprises the following steps:
(1) respectively mixing simple substance Mg and simple substance Si with nitric acid, and reacting the simple substance Mg with the nitric acid to generate Mg (NO)3)2Heating and dissolving the simple substance Si in nitric acid, mixing the simple substance Si and the nitric acid, slowly adding ammonia water for dilution, and adjusting the pH value to 6 to prepare a solution;
(2) mixing core material Li1.01Ni0.8Co0.1Mn0.1O2.005Adding into a high-speed mixer, slowly vacuumizing to make vacuum degree reach 1atm, stirring, and spraying the solution onto Li core material by using an atomizing device at the top of the high-speed mixer1.01Ni0.8Co0.1Mn0.1O2.005And using nitrogen as carrier gas, stopping spraying the solution when the vacuum degree is 0, stopping stirring, repeatedly vacuumizing until the vacuum degree reaches 1atm, repeatedly starting stirring, and spraying the solution to Li by using an atomization device at the top of the high-speed mixer1.01Ni0.8Co0.1Mn0.1O2.005Taking nitrogen as carrier gas on the surface of the core material, stopping spraying the solution when the vacuum degree is 0, stopping stirring, and repeatedly vacuumizing until the vacuum degree reaches 1 atm' to obtain a coated intermediate with the solid content of 96%;
(3) placing the coated intermediate in high-pressure combustion coating equipment with the pressure of 400kPa and the oxygen content of 99 percent, and combusting for 20s at 1000 ℃ by taking propane as carrier gas to obtain MgO and SiO2Coated Li1.01Ni0.8Co0.1Mn0.1O2.005The particle diameter of the metal oxide particles formed by combustion<20nm, and uniformly coating the surface of the positive electrode material.
On combustion of propane, water in solution vaporizes, Mg (NO)3)2And Mg in nitric acid decomposition2+Combines with oxygen atoms at high temperature and under the action of oxygen to form MgO to cover Li1.01Ni0.8Co0.1Mn0.1O2.005Si is oxidized at high temperature and oxygen to form SiO2Coated with Li1.01Ni0.8Co0.1Mn0.1O2.005Of (2) is provided. The obtained MgO and SiO2Coated Li1.01Ni0.8Co0.1Mn0.1O2.005The anode material is subjected to cycle performance test according to a key material performance test specification for a lithium ion power storage battery in 2010, which is a major project of energy conservation and new energy automobiles in the '863 plan', and the capacity retention rate of the anode material after 20 cycles98.0% (as shown in fig. 3).
Example 3
SiO2Coated Li1.01Ni0.6Co0.2Mn0.2O2.005The preparation method comprises the following steps:
(1) heating and dissolving simple substance Si in oxalic acid, slowly adding ammonia water for dilution, and adjusting the pH value to 5 to prepare a solution;
(2) mixing core material Li1.01Ni0.6Co0.2Mn0.2O2.005Adding into a high-speed mixer, slowly vacuumizing to make vacuum degree reach 1atm, stirring, and spraying the solution onto Li core material by using an atomizing device at the top of the high-speed mixer1.01Ni0.6Co0.2Mn0.2O2.005And using nitrogen as carrier gas, stopping spraying the solution when the vacuum degree is 0, stopping stirring, repeatedly vacuumizing until the vacuum degree reaches 1atm, repeatedly starting stirring, and spraying the solution to Li by using an atomization device at the top of the high-speed mixer1.01Ni0.6Co0.2Mn0.2O2.005Taking nitrogen as carrier gas on the surface of the core material, stopping spraying the solution when the vacuum degree is 0, stopping stirring, and repeatedly vacuumizing until the vacuum degree reaches 1 atm' to obtain a coated intermediate with the solid content of 99%;
(3) placing the coated intermediate in high-pressure combustion coating equipment with the pressure of 400kPa and the oxygen content of 99 percent, and combusting for 30s at 1200 ℃ by taking natural gas as carrier gas to obtain SiO2Coated Li1.01Ni0.6Co0.2Mn0.2O2.005The particle diameter of the metal oxide particles formed by combustion<20nm, and uniformly coating the surface of the positive electrode material.
When natural gas is burnt, water in the solution is vaporized, and Si is oxidized to form SiO under the action of high temperature and oxygen when oxalic acid is decomposed2Coated with Li1.01Ni0.6Co0.2Mn0.2O2.005Of (2) is provided. The obtained SiO2Coated Li1.01Ni0.6Co0.2Mn0.2O2.005The anode material is subjected to cycle performance test according to a key material performance test specification for a lithium ion power storage battery in 2010, which is a major project of energy conservation and new energy automobiles in the '863 plan', and the capacity retention rate after 20 cycles is 96.2% (shown in figure 3).
Comparative example 1
Al2O3Coated high nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2.005The preparation method comprises the following steps:
(1) mixing simple substance Al with nitric acid to react to generate Al (NO)3)3Slowly adding ammonia water to dilute and adjusting the pH value to 6 to prepare a solution;
(2) mixing core material Li1.01Ni0.8Co0.1Mn0.1O2.005Adding into a high-speed mixer, slowly vacuumizing to make vacuum degree reach 1atm, stirring, and spraying the solution onto Li core material by using an atomizing device at the top of the high-speed mixer1.01Ni0.8Co0.1Mn0.1O2.005And using nitrogen as carrier gas, stopping spraying the solution when the vacuum degree is 0, stopping stirring, repeatedly vacuumizing until the vacuum degree reaches 1atm, repeatedly starting stirring, and spraying the solution to Li by using an atomization device at the top of the high-speed mixer1.01Ni0.8Co0.1Mn0.1O2.005Taking nitrogen as carrier gas on the surface of the core material, stopping spraying the solution when the vacuum degree is 0, stopping stirring, and repeatedly vacuumizing until the vacuum degree reaches 1 atm' to obtain a coated intermediate with the solid content of 96%;
(3) placing the coated intermediate in a high-pressure calcining furnace with the pressure of 400kPa and the oxygen content of 99 percent, calcining at 1000 ℃ for 10min to obtain Al2O3Coated Li1.01Ni0.8Co0.1Mn0.1O2.005The positive electrode material of (1). For Al2O3Coated Li1.01Ni0.8Co0.1Mn0.1O2.005SEM characterization was performed, the results are as followsShown in FIG. 2, Al2O3Coating layer is not uniform, and Al is obtained2O3Coated Li1.01Ni0.8Co0.1Mn0.1O2.005The anode material is subjected to cycle performance test according to a key material performance test specification for a lithium ion power storage battery in 2010, which is a major project of energy conservation and new energy automobiles in the '863 plan', and the capacity retention rate after 20 cycles is 95% (as shown in fig. 3).
Referring to fig. 3, it can be seen from the comparison between examples 1 to 3 and comparative example 1 that in examples 1 to 3 of the present application, a metal simple substance and an acid are directly used to prepare a solution, a combustible gas is used as a carrier gas, heat generated when the combustible gas is combusted in a high-pressure oxidation atmosphere decomposes a solvent acid or a salt in the solution, and water is vaporized, the metal simple substance or a metal ion forms a corresponding oxide under the action of high temperature and oxygen, and the oxide is coated on the surface of the core material in situ, so as to obtain a uniformly coated positive electrode material, and the temperature can be controlled near the sintering temperature of the positive electrode material when the carrier gas is combusted, so as to eliminate a impure phase generated by dissolution of a transition metal generated by contact with an acidic solvent on the surface of the material, and thus the cycle. While comparative example 1 employs ordinary calcination, not combustion, in which direct heating of calcination does not reach the decomposition temperature for a long time, but only Al (NO)3)3The evaporation temperature and the acidity in the heating process are increased, the anode material is corroded, the oxidation speed is slow and incomplete, and the obtained coating is not uniform, so that the performance of the obtained anode material coated with the metal oxide is poor, and the capacity retention rate after the anode material is cycled for 20 times is only 95%.
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 (7)
1. A method for preparing a positive electrode material, wherein the positive electrode material comprises a core material and a metal oxide coating the core material, and is characterized by comprising the following steps in sequence:
(1) mixing a simple substance of corresponding metal in the metal oxide with acid to prepare a solution;
(2) adding to the core material to obtain a coated intermediate;
(3) placing the coating intermediate in a high-pressure oxidation atmosphere, carrying out combustion treatment in combustion coating equipment by taking combustible gas as carrier gas to obtain the anode material of the metal oxide coating core material,
wherein, the solution is added into the core material to obtain a coating intermediate, the solution is adopted to spray the core material, the core material is vacuumized until the vacuum degree is 1atm, nitrogen is introduced while high-speed stirring is carried out, the solution is adopted to spray the core material, the spraying and the high-speed stirring are stopped when the vacuum degree reaches 0, and the vacuum degree is 1atm,
the conditions of the combustion treatment are as follows: the burning time is 10-30 s, and the burning temperature is 800-1200 ℃.
2. The method for producing a positive electrode material according to claim 1, wherein the acid is an organic acid or an inorganic acid that is anion-decomposable at 600 ℃.
3. The method for producing a positive electrode material according to claim 2, wherein the acid is one of nitric acid, dilute sulfuric acid, hydrochloric acid, acetic acid, citric acid, and oxalic acid.
4. The method for preparing the positive electrode material according to claim 1, wherein the simple substance of the metal is mixed with an acid, and then ammonia water is slowly added to dilute the mixture, and the pH value is adjusted to 5-6 to prepare a solution.
5. The method for producing a positive electrode material according to claim 1, wherein the solution is divided into a plurality of showers, and the operations of "stirring at a high speed while introducing a carrier gas and spraying the core material with the solution are repeated, and the showering and the high-speed stirring are stopped when a vacuum degree reaches 0, and the vacuum is applied until the vacuum degree reaches 1 atm".
6. The method for preparing a positive electrode material according to claim 1, wherein the solid content of the coating intermediate is 90 to 99%.
7. The method for producing a positive electrode material according to claim 1, wherein the combustible gas is hydrogen or a C1-C6 low paraffin.
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| CN114335488B (en) * | 2022-01-06 | 2023-03-10 | 中国科学技术大学 | Coating modified lithium-rich manganese-based cathode material and preparation method thereof |
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| CN106602021A (en) * | 2016-12-22 | 2017-04-26 | 金瑞新材料科技股份有限公司 | Coated positive electrode material of lithium-ion battery and preparation method of positive electrode material |
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