CN112919552A - High tap density multi-element oxide precursor and preparation method and preparation system thereof - Google Patents
High tap density multi-element oxide precursor and preparation method and preparation system thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000000197 pyrolysis Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 22
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- 239000012530 fluid Substances 0.000 claims abstract description 15
- 238000002844 melting Methods 0.000 claims abstract description 15
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052748 manganese Chemical class 0.000 claims description 5
- 239000011572 manganese Chemical class 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Chemical class 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 238000000889 atomisation Methods 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000005118 spray pyrolysis Methods 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
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- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
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- 230000001737 promoting effect Effects 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 229910013478 LiNixCoyMzO2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 high viscosity Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
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- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/008—Pyrolysis reactions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of powder material preparation methods, in particular to a high-tap-density multi-element oxide precursor, a preparation method and a preparation system thereof. The preparation method comprises the following steps: s1, adding metal salt containing crystal water into a liquid conveying device according to the stoichiometric ratio of each metal element in the multi-element oxide, stirring, heating and melting to obtain sub-molten salt liquid; s2, atomizing the sub-molten salt liquid through a two-fluid atomizer to form atomized liquid drops, and bringing the atomized liquid drops into a fluidized bed pyrolysis furnace by utilizing compressed gas for pyrolysis; and S3, collecting the pyrolysis product obtained in the step S2 through a dust collector to obtain the high tap density multi-element oxide precursor material. The method combines sub-molten salt liquid, two-fluid atomization and fluidized bed pyrolysis, realizes the high-efficiency preparation of the high-tap-density multi-element oxide precursor, and the precursor has the advantages of uniform element distribution, uniform particle size, high purity and good spherical morphology.
Description
Technical Field
The invention relates to the technical field of powder material preparation methods, in particular to a high-tap-density multi-element oxide precursor, a preparation method and a preparation system thereof.
Background
With the increase of greenhouse effect and the exhaustion of fossil energy, the development of new energy is becoming a focus of attention. The lithium ion battery has a series of advantages of high energy density, long cycle life, good safety performance and the like, so that the lithium ion battery is widely applied to the fields of portable electronic products, energy storage devices, new energy automobiles and the like. However, in order to meet the requirement of the mileage of a new energy automobile, a lithium ion battery is required to have a higher energy density. The nickel-based multi-element cathode material with the layered structure (LiNixCoyMzO2, M is Mn, Al, x is more than 0.6) has the advantages of high specific capacity, low cost and the like, and is considered to be one of the most potential cathode materials for the lithium ion power battery.
At present, the preparation method of the commercialized nickel-based multi-component material precursor is mainly a hydroxide coprecipitation method. Although the method can prepare the multi-element oxide precursor with controllable morphology and good mechanical property, the coprecipitation process has the disadvantages of long flow, complex operation, harsher synthesis conditions, poor material component uniformity and high production cost, and the defects hinder the application of the precursor in the aspect of large-scale production. Compared with the traditional anode material synthesis method, the spray pyrolysis method has the advantages of short flow, strong adaptability to raw materials, simple working procedures, high productivity, high production efficiency and the like, and is beneficial to industrial production. Chinese patent document CN 106784780a discloses a method for preparing an oxide precursor of a ternary cathode material for a lithium ion battery, which uses a metal chloride solution as a raw material to rapidly prepare the oxide precursor of the ternary cathode material for the lithium ion battery with good sphericity by ultrasonic spray pyrolysis. However, with the development of the times and the popularization of new energy automobiles and intelligent electronic devices, the demand of the energy density and the power density of the lithium ion battery is higher and higher. Spray pyrolysis is a rapid heterogeneous reaction process, and in the pyrolysis process, the rapid evaporation of a solvent can impact primary particles, so that the prepared material is often in a porous or hollow structure, the primary particles are fine, the tap density of the material is low, and the requirement of high energy density of a lithium ion battery is difficult to meet. Therefore, how to avoid the precursor from forming a porous or hollow structure in the spray pyrolysis process and increase the primary particles of the material is the key point for preparing the precursor of the high-tap-density nickel-based positive electrode material by the spray pyrolysis process.
Disclosure of Invention
Aiming at the problems in the prior art, according to the reason that the nickel-based material with high tap density cannot be obtained, the invention adopts metal salt containing crystal water to obtain sub-molten salt liquid, namely high-concentration precursor solution, then utilizes compressed gas to atomize the sub-molten salt liquid through a double-flow atomizer, and carries out pyrolysis to obtain the multi-element oxide precursor with high tap density.
In order to achieve the above object, the present invention provides a method for preparing a high tap density multi-component oxide precursor, which specifically comprises:
s1, adding metal salt containing crystal water into a liquid conveying device according to the stoichiometric ratio of each metal element in the multi-element oxide, stirring, heating and melting to obtain sub-molten salt liquid;
s2, atomizing the sub-molten salt liquid through a two-fluid atomizer to form atomized liquid drops, and bringing the atomized liquid drops into a fluidized bed pyrolysis furnace by utilizing compressed gas for pyrolysis;
and S3, collecting the pyrolysis product obtained in the step S2 through a dust collector to obtain the high tap density multi-element oxide precursor material.
Further, the metal salts include nitrates or/and chlorides of nickel, cobalt and manganese/aluminum; the stoichiometric ratio of nickel, cobalt and manganese/aluminum is x: y: z, and the x: y: z is (0.33-1) to (0-0.33): (0 to 0.33); the sub-molten salt liquid can be doped with one or more of Al, Mg, Zr, Ti, Mo, W, B and P; the doped elements in the multi-element oxide precursor are not more than 5%.
Further, the heating melting temperature is 60-250 ℃, and preferably 80-180 ℃. The water content of the molten salt is 1-50%.
Furthermore, the particle size of the atomized liquid drops is 1-50 μm.
Further, the compressed gas is one of oxygen or air.
Further, the pyrolysis process conditions of the fluidized bed pyrolysis furnace are as follows: the temperature is 650 ℃ and 950 ℃, and the time is 10-50 min.
Based on the same invention concept, the invention provides a preparation system of a high-tap-density multi-component oxide precursor, which specifically comprises a dust collector, a fluidized bed, a double-flow atomizer, a heater, a filter, a blower, a liquid feeding device and an exhaust fan;
a fluidizing gas inlet is formed in the bottom of the fluidized bed and is sequentially connected with a heater, a filter and a blower; the top of the fluidized bed is provided with a dust collector which is used for collecting pyrolysis products and is connected with an exhaust fan;
the double-fluid atomizer is arranged at the center of the cavity of the fluidized bed, the atomizer is connected with compressed gas through an air pipe, and the liquid conveying device is connected with the double-fluid atomizer through a peristaltic pump.
Furthermore, the nozzle caliber of the atomizing nozzle of the double-flow atomizer is 0.5-2.0mm, and preferably 0.7-1.0 mm. The maximum spray angle of the atomizing spray head is properly adjusted according to the diameter of the cavity, so that the uniform dispersion of the materials in the whole cavity is ensured, and the loss of effective reaction materials caused by the direct injection of the materials onto the inner wall of the cavity due to the overlarge spray angle is prevented.
Furthermore, the preparation system also comprises a tail gas treatment device, wherein the tail gas treatment device is connected with an exhaust fan and is used for removing waste gas generated in the pyrolysis process.
Further, the dust collector is a bag type dust collector or an electrostatic collector. The diameter of the cavity of the fluidized bed 2 is 0.1-5.0m, preferably 1.0-5.0; when the diameter of the cavity is too small, a large amount of materials sprayed by the spray head can be adhered to the furnace wall, a large amount of waste materials are generated, and production is not facilitated; the power of the blower 7 is 0.75-15 Kw; the liquid feeding device 8 is provided with a microwave heating temperature control device; the compressed gas 9 is oxygen or air, preferably oxygen; the gas pressure is 0.4-0.7 MPa.
Based on the same inventive concept, the invention provides a high tap density multi-component oxide precursor, which is prepared by the preparation method.
Has the advantages that:
(1) according to the invention, the two-fluid atomization and fluidized bed pyrolysis are combined, so that the multi-element metal oxide precursor is efficiently prepared by spray pyrolysis of the sub-molten salt, and the problem of low tap density of the powder material prepared by the traditional spray pyrolysis method is effectively solved. The principle may be: based on the principle of preparing the powder material by spray pyrolysis, the number of primary particles in atomized liquid drops is increased, and the particle size and the density of the prepared powder material can be effectively improved, so that the tap density of the powder material is improved. The sub-molten salt adopted by the invention is an unconventional medium between the aqueous solution and the molten salt, and the high-concentration medium such as the sub-molten salt is used as a spray pyrolysis raw material, so that the number of crystal cores in atomized liquid drops can be obviously increased, the volatilization amount of a solvent is reduced, the impact on primary particles is relieved, and the formation of large-particle-size solid particles is facilitated.
(2) The fluidized bed is adopted to pyrolyze the atomized liquid drops, so that the residence time of reactants in the pyrolysis furnace can be effectively prolonged, the crystal growth is promoted, and the tap density of the powder material is improved. Meanwhile, the longer pyrolysis time can ensure that the metal salt hydrolysis reaction is more fully carried out, and impurity ions (Cl) are effectively removed-,HNO3-Etc.) so that the prepared material has a higher purity. Compared with the traditional atomization modes (such as ultrasonic atomization, electrostatic atomization and the like), the two-fluid atomization mode adopted by the invention has strong adaptability to raw materials, can realize the atomization of various fluids such as high viscosity, colloid, suspension and the like, and has good effect. The multi-element precursor material with uniform element distribution, uniform particle size, high purity and good spherical morphology can be prepared.
(3) The invention adopts the double-fluid atomizer to realize the high-efficiency atomization of the solution, and the fluidized bed pyrolysis furnace can provide larger reaction space and pyrolyze a large amount of solid particles. Compared with the traditional spray pyrolysis method, the method has higher yield, can realize the rapid preparation of the nickel-based multi-component oxide precursor, and is favorable for promoting the large-scale production and application of the nickel-based multi-component anode material.
(4) The metal salts selected by the invention are all hydrates, have low melting point and high concentration, can realize melting at a lower temperature to form the required sub-molten salt, are beneficial to saving energy consumption and are suitable for industrial application.
Drawings
Fig. 1 is a schematic diagram of a system for preparing a high tap density multi-component oxide precursor according to an embodiment of the present invention.
[ description of reference ]
1. A dust collector; 2. a fluidized bed; 3. an atomizer; 4. a fluidizing gas inlet; 5. a heater; 6. a filter; 7. a blower; 8. a liquid feeding device; 9. compressing the gas; 10. an exhaust fan.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to specific embodiments, but the scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The preparation system of the high tap density multi-component oxide precursor provided by the invention has the following process flow of preparing the precursor:
step 1, preheating a furnace body: the heater 5 is turned on to raise the temperature to 650 ℃ and 950 ℃, then the blower 7 is turned on to preheat the cavity of the fluidized bed 2 through the fluidizing gas inlet 4 after the air is filtered by the filter 6;
step 4, dust collection: the precursor of the multi-component oxide is collected by a dust collector 1 and exhausted by an exhaust fan 10 for tail gas treatment or recovery.
Example 1
In this embodiment, a preparation system shown in fig. 1 is used to prepare an NCM ternary positive electrode precursor, and specifically includes the following steps:
step 1, preheating a furnace body: turning on a heater 5 to raise the temperature to 800 ℃, then turning on a blower 7 to filter air through a filter 6 and preheat the cavity of the fluidized bed 2 through a fluidizing gas inlet 4, and controlling the temperature in the cavity of the fluidized bed 2 to be 800 ℃;
Step 4, dust collection: and (3) collecting the pyrolysis product obtained in the third step through a bag dust collector 1, discharging tail gas through an exhaust fan 10, treating or recycling, continuously spraying air after the molten salt liquid is used up, shutting down the furnace after 15min, and taking down the dust collector to recycle after the temperature is reduced to normal temperature to obtain the required high-tap-density NCM precursor material. The tap density values of the precursor materials obtained are detailed in table 1.
Table 1 tap density of the precursor material obtained in example 1
Example 2
In this embodiment, a preparation system shown in fig. 1 is used to prepare an NCM622 ternary positive electrode precursor, and specifically includes the following steps:
step 1, preheating a furnace body: the heater 5 is turned on to raise the temperature to 650-;
Step 4, dust collection: and (3) collecting the pyrolysis product obtained in the third step through a bag dust collector 1, discharging tail gas through an exhaust fan 10, treating or recycling, continuously spraying air after the molten salt liquid is used up, shutting down the furnace after 15min, and taking down the dust collector to recycle after the temperature is reduced to normal temperature to obtain the required high-tap-density ternary doped precursor material. The tap density of the precursor material obtained is detailed in table 2.
Table 2 tap density of the precursor material obtained in example 2
Example 3
In this embodiment, a preparation system shown in fig. 1 is used to prepare an Al-doped NCM811 ternary positive electrode precursor, and specifically includes the following steps:
step 1, preheating a furnace body: turning on a heater 5 to raise the temperature to 850 ℃, then turning on a blower 7 to filter air through a filter 6 and preheat the cavity of the fluidized bed 2 through a fluidizing gas inlet 4, and controlling the temperature in the cavity of the fluidized bed 2 to be 850 ℃;
Step 4, dust collection: collecting the pyrolysis product obtained in the third step through a bag dust collector 1, discharging tail gas through an exhaust fan 10, treating or recycling, continuously spraying air after the molten salt liquid is exhausted, stopping the furnace after 15min, cooling to normal temperature, taking down the dust collector for recycling to obtain the required high-tap-density ternary doped precursor material, wherein the tap density of the precursor material is 2.41g/cm3。
According to the embodiment and the tap density of the precursor material obtained by the embodiment, the tap density can reach 2.42g/cm at most3The preparation method disclosed by the invention has the advantages that the obtained multi-component oxide precursor has high tap density, can meet the requirements of the lithium battery cathode material, is simple, can realize the rapid preparation of the nickel-based multi-component oxide precursor, and is beneficial to promoting the large-scale production and application of the nickel-based multi-component cathode material.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications of the technical solutions and concepts of the present invention should be covered by the scope of the present invention.
Claims (10)
1. A preparation method of a high tap density multi-component oxide precursor is characterized by specifically comprising the following steps:
s1, adding metal salt containing crystal water into a liquid conveying device according to the stoichiometric ratio of each metal element in the multi-element oxide, stirring, heating and melting to obtain sub-molten salt liquid;
s2, atomizing the sub-molten salt liquid through a two-fluid atomizer to form atomized liquid drops, and bringing the atomized liquid drops into a fluidized bed pyrolysis furnace by utilizing compressed gas for pyrolysis;
and S3, collecting the pyrolysis product obtained in the step S2 through a dust collector to obtain the high tap density multi-element oxide precursor material.
2. The method for preparing a high tap density multi-component oxide precursor according to claim 1, wherein the metal salt comprises nitrate or/and chloride salts of nickel, cobalt and manganese/aluminum; the stoichiometric ratio of nickel, cobalt and manganese/aluminum is x: y: z, and the x: y: z is (0.33-1) to (0-0.33): (0 to 0.33); the sub-molten salt liquid can be doped with one or more of Al, Mg, Zr, Ti, Mo, W, B and P; the doping element of the multi-element oxide precursor is not more than 5%.
3. The method according to claim 1, wherein the heating melting temperature is 60 to 250 ℃.
4. The method according to claim 1, wherein the atomized droplets have a particle size of 1 to 50 μm.
5. The method of claim 1, wherein the compressed gas is one of oxygen or air.
6. The method for preparing a high tap density polyoxide precursor as claimed in claim 1, wherein the process conditions for pyrolysis in the fluidized bed pyrolysis furnace are: the temperature is 650 ℃ and 950 ℃, and the time is 10-50 min.
7. The preparation system of the high tap density multi-component oxide precursor is characterized by comprising a dust collector, a fluidized bed, a double-flow atomizer, a heater, a filter, a blower, a liquid feeding device and an exhaust fan;
a fluidizing gas inlet is formed in the bottom of the fluidized bed and is sequentially connected with a heater, a filter and a blower; the top of the fluidized bed is provided with a dust collector which is used for collecting pyrolysis products and is connected with an exhaust fan;
the double-fluid atomizer is arranged at the center of the cavity of the fluidized bed, the atomizer is connected with compressed gas through an air pipe, and the liquid conveying device is connected with the double-fluid atomizer through a peristaltic pump.
8. The system for preparing a high tap density multiple oxide precursor as claimed in claim 7, wherein the nozzle bore of the atomizer head of the two-flow atomizer is 0.5-2.0 mm.
9. The system for preparing a high tap density multiple oxide precursor according to claim 7, further comprising an exhaust gas treatment device connected to the exhaust fan for removing the exhaust gas generated in the pyrolysis process.
10. A high tap density multi-component oxide precursor, wherein the high tap density multi-component oxide precursor is prepared by the preparation method of any of claims 1 to 6 or by the preparation system of any of claims 7 to 9 and by the preparation method of any of claims 1 to 6.
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