CN109539792B - Spray pyrolysis device for preparing ternary anode precursor and application method thereof - Google Patents

Spray pyrolysis device for preparing ternary anode precursor and application method thereof Download PDF

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CN109539792B
CN109539792B CN201811426834.3A CN201811426834A CN109539792B CN 109539792 B CN109539792 B CN 109539792B CN 201811426834 A CN201811426834 A CN 201811426834A CN 109539792 B CN109539792 B CN 109539792B
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spray pyrolysis
pyrolysis device
gas
cavity
ternary
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CN109539792A (en
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黄明
姚淦
张章明
龚金保
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Hengdian Group DMEGC Magnetics Co Ltd
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Hengdian Group DMEGC Magnetics Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B17/00—Furnaces of a kind not covered by any preceding group
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • 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
    • 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
    • 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

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  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
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Abstract

The invention provides a spray pyrolysis device for preparing a ternary anode precursor and a using method thereof. The method comprises the following steps: (1) spraying the ternary mixed salt solution into a first spray pyrolysis device to generate a pre-product; (2) and (3) feeding the pre-product into a second spray pyrolysis device through a conveying device, separating solid from gas, wherein the solid is the ternary anode precursor, and treating or recycling the gas after the gas is discharged. According to the invention, two groups of spray pyrolysis devices are communicated in a U shape, so that the designed diameter of the device is reduced, the sufficient pyrolysis time of materials in the furnace is ensured, and the chlorine content in the product is reduced. The device has similar pyrolysis effect with a large-scale spray pyrolysis device, and greatly reduces the occupied area of equipment.

Description

Spray pyrolysis device for preparing ternary anode precursor and application method thereof
Technical Field
The invention belongs to the field of lithium battery manufacturing, relates to a spray pyrolysis device and a using method thereof, and particularly relates to a spray pyrolysis device for preparing a ternary cathode precursor and a using method thereof.
Background
The lithium ion battery does not contain toxic substances such as lead, cadmium, mercury and the like, and has wide application in the fields of new energy automobiles, energy storage and consumer electronics. With the continuous expansion of the scale of lithium ion batteries, the price of related raw materials is higher and higher, and particularly, the price of related scarce resources, such as metal cobalt, is higher and lower. The rising price of raw materials leads to the rising cost of the lithium ion battery, and has adverse effects on the further application of the lithium ion battery. Since the positive electrode material has a high proportion in the overall battery cost, reducing the processing cost of the positive electrode material and the precursor is an important means for reducing the overall battery cost.
The prior ternary anode precursor is mainly synthesized by a coprecipitation method, the process flow is complex, the consumed time is long, and meanwhile, a large amount of ammonia nitrogen wastewater is generated in the production process and needs to be treated, so that the great environmental protection cost is generated. The process flow for preparing the ternary cathode precursor by the spray pyrolysis method is simple, the time consumption is short, the generated hydrogen chloride gas can be recycled by absorption treatment, and the processing cost of the material can be effectively reduced.
The preparation of the ternary anode precursor by the spray pyrolysis method is to uniformly mix three metal salt solutions of nickel, cobalt and manganese in proportion and spray the mixture into a high-temperature atmosphere in a mist form, and obtain the ternary oxide precursor with uniformly mixed components by the rapid evaporation of a solvent and the hydrolysis reaction of the metal salt.
CN106197025B discloses a spray pyrolysis furnace for preparing pure-phase cobaltosic oxide, comprising: the device comprises a pyrolysis furnace, two gas mixing and proportioning instruments, a spray gun gas adjusting and conveying device, a spray gun, a combustion air atmosphere adjusting device, a burner, a combustion section atmosphere adjusting and conveying device and a conveying section atmosphere adjusting device. Mixing compressed air and oxygen by a gas mixing proportioning instrument, and enabling the mixed air and the oxygen to enter a spray gun after passing through a spray gun gas regulating and conveying device; the mixed gas and the cobalt salt solution are contacted and atomized in the spray gun and then enter the pyrolysis furnace; simultaneously adjusting a combustion air atmosphere adjusting device, adjusting the oxygen content in the combustion air, and feeding the combustion air into the burner; in addition, the compressed air and oxygen are mixed by a gas mixing proportioning instrument and then enter a combustion section atmosphere adjusting and conveying device and are input into a pyrolysis furnace; and opening the atmosphere adjusting device of the conveying section. The spray pyrolysis furnace can thoroughly solve the problem that cobaltosic oxide produced by the conventional spray pyrolysis furnace contains cobaltous oxide.
However, since the raw material is sprayed from the top in the spray pyrolysis process, sufficient atomization requires a large pressure to form uniform droplets, and the droplets have a large initial velocity when entering the furnace body. Simultaneously, under the action of gravity, the fog drops are further accelerated and quickly pass through a heating area, so that the pyrolysis process is incomplete and the reaction is incomplete. In the conventional spray pyrolysis equipment, a certain negative pressure is formed at the top, waste gas generated by reaction is pumped out, an upward airflow is formed at the same time, the descending speed of fog drops is reduced, and the reaction time is prolonged. The whole process needs a large reaction space, so that the design diameter of a common spray pyrolysis furnace is more than two meters.
CN106587172A discloses a production process and a production device for ternary oxide of a power battery anode, wherein ternary mixed solution is sprayed into a pyrolysis furnace through a top nozzle, and the solution is hydrolyzed into the ternary oxide, hydrogen chloride and water vapor in the pyrolysis furnace through a fuel gas heating furnace body and the sprayed solution. The gas enters the absorption tower after being dedusted by the cyclone separator at the top of the furnace, and the ternary oxide is discharged from the discharging equipment at the bottom of the furnace through natural sedimentation. The hot gas generated by burning the gas at the furnace bottom is upward, so that the reaction time of liquid drops in the furnace can be effectively prolonged, and the reaction can be fully carried out. However, the design requirement for the diameter of the furnace body is very large, and more than 2 meters is generally required. When the diameter of the furnace body is smaller than 1 meter, a large amount of materials are stuck on the furnace wall due to the same design, a large amount of waste materials are generated, and the experiment is not facilitated. If the design is that the waste gas and the oxide enter and exit from the furnace bottom at the same time, the oxide and the waste gas react, the proportion of chloride in the oxide is greatly increased, the content of chlorine radicals in the product is seriously exceeded, and the time for sintering the oxide in the furnace is also greatly reduced.
In summary, the spray pyrolysis apparatus disclosed in the prior art still has large design diameter, equipment scale and occupied area, thereby causing large increase of raw materials and energy consumption required in the actual production process, being not beneficial to the development and adjustment of the process and being not beneficial to the integrated arrangement of the equipment. Therefore, there is a great need for improvement of the structure of the spray pyrolysis apparatus disclosed in the prior art to solve the problems existing at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a spray pyrolysis device for preparing a ternary anode precursor and a using method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a spray pyrolysis device, which comprises a first spray pyrolysis device 1 and a second spray pyrolysis device 2, wherein a discharge port of the first spray pyrolysis device 1 is connected with a conveying device, and an outlet of the conveying device is arranged in a cavity of the second spray pyrolysis device 2.
The spray pyrolysis device designed by the invention has a U-shaped two-section structure, materials are subjected to preliminary pyrolysis in the first spray pyrolysis device and then are conveyed to the second spray pyrolysis device through the conveying device to be continuously and deeply pyrolyzed.
As a preferable technical solution of the present invention, the conveying device includes a powder conveying valve 5 connected to a discharge port of the first spray pyrolysis device 1 for conveying a material, and a pipeline 13 connected to the powder conveying valve 5, and an outlet of the pipeline 13 is disposed in a cavity of the second spray pyrolysis device 2.
Preferably, the powder conveying valve 5 is a rotary valve, a butterfly valve or a gate valve.
Preferably, the powder conveying valve 5 is a rotary valve, a shell of the rotary valve is provided with a feed inlet, a first air inlet 8 and a discharge outlet, the feed inlet is connected with the discharge outlet of the first spray pyrolysis device 1, the first air inlet 8 is used for introducing gas to push the rotary valve to rotate, and the discharge outlet is connected with an inlet of the pipeline 13; the valve body of the rotary valve comprises a valve rod and rotary baffles distributed longitudinally along the valve rod. The blade of rotary valve can be promoted to the gas that 8 first air intakes let in, drives the blade and rotates, keeps the temperature of rotary valve and discharge gate simultaneously, and the granule of tentatively forming in the first spray pyrolysis device 1 is passed through the rotary valve and is conveyed the pipeline after, is driven to second spray pyrolysis device 2 by gas, carries out further drying and pyrolysis.
Preferably, the outlet of the pipeline 13 is positioned at 1/3-2/3 of the cavity of the second spray pyrolysis device 2. If the outlet of the duct 13 is too high, the preproduct sprayed into the second spray pyrolysis apparatus 2 via the duct 13 is too close to the outlet, so that the pyrolysis time of the preproduct in the second spray pyrolysis apparatus 2 is shortened, which is not favorable for deepening the reaction degree; and the outlet position of the pipeline 13 is too low, so that the pre-product entering the second spray pyrolysis device 2 is too close to the material collecting cavity at the bottom, the settling time of the pre-product in the second spray pyrolysis device 2 is too short, and the pyrolysis reaction is not thorough.
As a preferred technical solution of the present invention, the first spray pyrolysis apparatus 1 includes a first cavity and a nozzle 3 disposed at the top of the first cavity.
Preferably, the first spray pyrolysis apparatus 1 further comprises a first heating member 11 disposed on an outer wall of the first chamber.
Preferably, the nozzle 3 is a two-fluid aerosol nozzle or a pressure nozzle. The maximum injection angle of the nozzle 3 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 direct injection of the materials to the inner wall of the cavity caused by the overlarge injection angle is prevented, and the materials are adhered to the inner wall of the cavity to cause the loss of effective reaction materials. The selection can be made by the skilled person on the basis of expert knowledge, for example, the spray angle of the spray head is 60 degrees when the diameter is 1.2 m.
Preferably, the diameter of the first cavity is 0.5-1.8m, and may be, for example, 0.5m, 0.6m, 0.7m, 0.8m, 0.9m, 1.0m, 1.1m, 1.2m, 1.3m, 1.4m, 1.5m, 1.6m, 1.7m or 1.8 m. When the diameter of the cavity is less than 0.5m, a large amount of materials ejected by the spray head can be adhered to the furnace wall, a large amount of waste materials are generated, and the experiment is not facilitated. If the design is that the waste gas and the oxide enter and exit from the furnace bottom at the same time, the oxide and the waste gas react, the proportion of chloride in the oxide is greatly increased, the content of chlorine radicals in the product is seriously exceeded, and the time for sintering the oxide in the furnace is also greatly reduced.
As a preferable technical scheme of the invention, the second spray pyrolysis device 2 comprises a second cavity and a material collecting cavity 7 arranged at the bottom of the second cavity. The material collecting cavity 7 is used for receiving the settled ternary anode precursor.
Preferably, the second spray pyrolysis device 2 further comprises a second heating element 12 disposed on the outer wall of the second cavity. The heating means 12 is used to heat the second spray pyrolysis apparatus 2.
Preferably, the second spray pyrolysis device 2 further comprises a heating device 4 disposed at the bottom of the second cavity.
Preferably, the heating device 4 is arranged above the material collection chamber 7. The heating device 4 at the bottom of the second cavity supplies heat for the second spray pyrolysis device 2 and is matched with the second heating part 12, so that a pre-product entering the second spray pyrolysis device 2 can be thoroughly pyrolyzed, and finally, a fully pyrolyzed ternary anode precursor is prepared.
Preferably, the heating device 4 is a gas nozzle or an ignition burner.
Preferably, the bottom of the second cavity is provided with a second air inlet 9 for introducing air. One of the purposes of the present invention to provide the second air inlet 9 is to maintain the micro-positive pressure in the second spray pyrolysis device 2; the second purpose is to introduce high-temperature gas from the second air inlet 9 to maintain the reaction temperature in the second spray pyrolysis device 2, and simultaneously, the sprayed ascending gas flow generates a secondary dispersion effect on the settled pre-product, so that the reaction time of the pre-product in the second spray pyrolysis device 2 is prolonged.
Preferably, the diameter of the second cavity is 0.5-1.8m, and may be, for example, 0.5m, 0.6m, 0.7m, 0.8m, 0.9m, 1.0m, 1.1m, 1.2m, 1.3m, 1.4m, 1.5m, 1.6m, 1.7m or 1.8 m. The diameters of the first cavity and the second cavity are smaller than the design diameter of the existing large-scale spray pyrolysis device, the two small-scale spray pyrolysis devices are connected through the conveying device in the actual industrial production process, and compared with the large-scale spray pyrolysis device, the large-scale spray pyrolysis device has more flexible activity on the basis of ensuring the same pyrolysis effect, and can be flexibly arranged according to site construction conditions and plant layout.
As a preferable technical scheme of the invention, an air outlet and a feed back port are arranged at the upper part of the second spray pyrolysis device 2; the second spray pyrolysis device 2 further comprises a separation device 6, an inlet of the separation device 6 is connected with an air outlet of the second spray pyrolysis device 2, and an outlet of the separation device 6 is connected with a feed back port of the second spray pyrolysis device 2.
Preferably, the separation device 6 is a cyclone separator or a double cyclone separator. The separator 6 can recover the ternary positive electrode precursor in the exhaust gas again.
Preferably, the top of the separating device 6 is provided with an exhaust port 10 for discharging the exhaust gas or dust.
In a second aspect, the present invention provides a method of preparing a ternary positive electrode precursor, the method being carried out in an apparatus as described in the first aspect;
preferably, the method comprises:
(I) preheating the first spray pyrolysis device 1 and the second spray pyrolysis device 2, depressurizing the first spray pyrolysis device 1, and pressurizing the second spray pyrolysis device 2;
(II) spraying the ternary mixed salt solution into the first spray pyrolysis device 1 through a nozzle 3 to generate a pre-product;
(III) the pre-product obtained in the step (II) enters a second spray pyrolysis device 2 through a conveying device, solid and gas are separated, the solid is the ternary anode precursor, and the gas is discharged and then treated or recovered;
preferably, the method comprises:
(I) preheating the first spray pyrolysis device 1 and the second spray pyrolysis device 2, introducing gas into a first air inlet 8, reducing the pressure of the first spray pyrolysis device 1 by operating a powder delivery valve 5, and boosting the pressure of the second spray pyrolysis device 2 by connecting a second air inlet 9;
(II) spraying the ternary mixed salt solution into the first spray pyrolysis device 1 through a nozzle 3, and pyrolyzing to generate a pre-product;
(III) the pre-product obtained in the step (II) falls to a rotary valve, is conveyed to a second spray pyrolysis device 2 through a pipeline 13 to be pyrolyzed continuously, after the reaction is finished, the solid is collected to a material collecting cavity 7 to obtain a ternary anode precursor, and the gas enters a separating device 6;
preferably, the process of discharging the gas into the separation device 6 comprises the steps that the gas enters the separation device 6 through the gas outlet of the second spray pyrolysis device 2 to be subjected to solid-gas separation, the waste gas is treated or recycled, and the solid is recycled into the second spray pyrolysis device 2.
The ternary mixed salt solution is sprayed into the spray pyrolysis device provided by the invention through the nozzle 3, primary rapid hydrolysis and drying are carried out in the first spray pyrolysis device 1 to form spherical oxide particles, the spherical oxide particles and hydrogen chloride and water vapor generated by hydrolysis enter the second spray pyrolysis device 2 through the powder conveying valve 5 at the bottom of the first spray pyrolysis device, and the ternary oxide slowly settles while continuing to react in the second spray pyrolysis device 2, so that the primary separation of waste gas and the ternary oxide is completed. And after the waste gas is discharged from the second spray pyrolysis device 2, a small amount of ternary oxides in the waste gas are removed through a rotary separator and enter an absorption tower to be recovered, and a certain suction force needs to be provided for a gas outlet. The invention basically reduces the reaction environment of the large-scale spray pyrolysis device by adopting a U-shaped two-section design, reduces the design diameter of the furnace body, ensures the sufficient pyrolysis reaction time of the oxide in the furnace and reduces the chlorine content in the product.
As a preferable technical scheme of the invention, the ternary mixed salt is a chloride salt.
Preferably, the cations in the ternary mixed salt are nickel, cobalt and manganese respectively.
Preferably, the mass ratio of nickel, cobalt and manganese is expressed as x: y: z, the x: y: z is (0.33-0.9): (0.03-0.33): (0.03 to 0.33), wherein x + y + z is 1, for example, 0.5:0.2:0.3, 0.6:0.2:0.2, 0.7:0.2:0.1, or 0.8:0.1: 0.1.
Preferably, the total concentration of nickel, cobalt and manganese elements in the ternary mixed salt solution is 40-250 g/L, for example, 50g/L, 100g/L, 150g/L, 200g/L or 250g/L, preferably 100-200 g/L, and further preferably 150-180 g/L.
Preferably, the ternary mixed salt solution is further doped with any one or a combination of at least two of Al, Mg, Zr, Ti, Mn, La, Mo, W, Si, B and P.
As a preferable embodiment of the present invention, the preheating temperature of the first spray pyrolysis apparatus 1 is 600 to 1200 ℃, for example, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ or 1200 ℃, preferably 700 to 1100 ℃, and more preferably 850 to 950 ℃.
Preferably, the preheating temperature of the second spray pyrolysis device 2 is 500 to 1000 ℃, for example, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 1000 ℃, preferably 600 to 900 ℃, and more preferably 700 to 800 ℃.
Preferably, the first spray pyrolysis device 1 is depressurized to-500 to-100 Pa, for example, it may be-500 Pa, -450Pa, -400Pa, -350Pa, -300Pa, -250Pa, -200Pa, -150Pa or-100 Pa.
Preferably, the gauge pressure in the second spray pyrolysis apparatus 2 is 0 to 200Pa, and may be, for example, 0Pa, 50Pa, 100Pa, 150Pa, or 200 Pa.
In the preferred embodiment of the present invention, in step (i), the gas with a temperature of 300 to 800 ℃ is introduced into the first air inlet 8, and the temperature may be, for example, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃, preferably 500 to 700 ℃, and more preferably 550 to 650 ℃.
Preferably, in the step (iii), the gas with a temperature of 300 to 800 ℃ is introduced into the second air inlet 9, for example, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃, preferably 500 to 700 ℃, and more preferably 550 to 650 ℃.
In a third aspect, the invention provides a ternary cathode precursor, which is prepared by the method of the second aspect.
Preferably, the ternary positive electrode precursor has a chlorine content of < 0.8%, and may be, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, or 0.7%.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
the reaction environment of the large-scale spray pyrolysis furnace is basically reduced by adopting a U-shaped two-section design, the design diameter of a furnace body is reduced, the sufficient pyrolysis time of oxides in the furnace is ensured, and the chlorine content in the product is reduced.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus according to an embodiment of the present invention.
Wherein, 100-a spray pyrolysis device; 110-a first spray pyrolysis unit; 120-a second spray pyrolysis apparatus; 130-conveying means.
Fig. 2 is a schematic structural diagram of an apparatus according to an embodiment of the present invention.
Wherein, 1-a first spray pyrolysis device; 2-a second spray pyrolysis unit; 3-a nozzle; 4-a heating device; 5-powder conveying valve; 6-a separation device; 7-a material collection cavity; 8-a first air inlet; 9-a second air inlet; 10-an exhaust port; 11-a first heating member; 12-a second heating member; 13-pipeline.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In one embodiment, the present invention provides a spray pyrolysis apparatus 100 as shown in fig. 1, the spray pyrolysis apparatus 100 comprises a first spray pyrolysis apparatus 110 and a second spray pyrolysis apparatus 120, a discharge port of the first spray pyrolysis apparatus is connected to a conveying apparatus 130, and an outlet of the conveying apparatus 130 is disposed in a cavity of the second spray pyrolysis apparatus 120.
In another embodiment, the invention provides a spray pyrolysis apparatus, as shown in fig. 2, comprising a first spray pyrolysis apparatus 1 and a second spray pyrolysis apparatus 2, wherein a discharge port of the first spray pyrolysis apparatus 1 is connected with a conveying device, and an outlet of the conveying device is arranged in a cavity of the second spray pyrolysis apparatus 2.
The conveying device comprises a powder conveying valve 5 connected with a discharge port of the first spray pyrolysis device 1 and used for conveying materials and a pipeline 13 connected with the powder conveying valve 5, and an outlet of the pipeline 13 is formed in a cavity of the second spray pyrolysis device 2.
The first spray pyrolysis device 1 comprises a first cavity and a nozzle 3 arranged at the top of the first cavity, the diameter of the first cavity is 1.2m, and the outer wall of the first cavity is coated with a first heating component 11; the nozzle 3 may be a two-fluid aerosol nozzle or a pressure nozzle, the maximum spray angle of the nozzle 3 being 90 degrees.
The second spray pyrolysis device 2 comprises a second cavity and a material collecting cavity 7 arranged at the bottom of the second cavity, the diameter of the second cavity is 1.2m, and the outer wall of the second cavity is coated with a second heating component 12; a heating device 4 is arranged above the material collecting cavity 7, and the heating device 4 can be a gas nozzle or an ignition burner; the bottom of the cavity is also provided with a second air inlet 9 for introducing air.
The second spray pyrolysis device 2 further comprises a separation device 6, the upper part of the second spray pyrolysis device 2 is provided with an air outlet and a feed back port, the inlet of the separation device 6 is connected with the air outlet of the second spray pyrolysis device 2, the outlet of the separation device 6 is connected with the feed back port of the second spray pyrolysis device 2, and the top of the separation device is provided with an exhaust port 10 for discharging waste gas or dust; the separation device 6 may be a cyclone separator or a double cyclone separator.
The process flow of the spray pyrolysis device provided by the invention is as follows:
(I) preheating the first spray pyrolysis device 1 and the second spray pyrolysis device 2, opening the rotary valve 5, communicating the first air inlet 8 to reduce the pressure of the first spray pyrolysis device 1, and communicating the second air inlet 9 to increase the pressure of the second spray pyrolysis device 2;
(II) spraying the ternary mixed salt solution into the first spray pyrolysis device 1 through a nozzle 3 for preliminary pyrolysis to generate a pre-product;
(III) the pre-product obtained in the step (II) enters the second spray pyrolysis device 2 through the conveying device to continuously carry out pyrolysis reaction, after the reaction is finished, the reaction product is settled to the material collecting cavity 7, the ternary anode precursor is recycled, the rest components enter the separating device 6 through the gas outlet of the second spray pyrolysis device 2 to be further separated, the solid particles are recycled to the second spray pyrolysis device 2, and the waste gas is treated or recycled after being discharged from the top gas outlet 10 of the separating device 6.
Example 1
In this embodiment, a spray pyrolysis apparatus provided in the specific embodiment is used to prepare a ternary positive electrode precursor, and the method includes: preparing a ternary mixed salt solution, preheating a furnace body, performing spray pyrolysis and settling separation, and specifically comprising the following implementation steps of:
(1) preparing a ternary mixed salt solution: weighing a certain amount of nickel chloride, cobalt chloride and manganese chloride, preparing 50L of ternary mixed solution according to the mass ratio of 0.5:0.2:0.3, controlling the metal concentration at 150g/L, and adding aluminum chloride accounting for 0.5% of the total mass of nickel, cobalt and manganese.
(2) Preheating a furnace body: preheating the first spray pyrolysis device 1 to 1150 ℃ through the first heating part 11, introducing gas at 800 ℃ into the first air inlet 8, driving the powder conveying valve 5 to rotate, and controlling the negative pressure in the first spray pyrolysis device 1 to be-400 Pa; the second spray pyrolysis device 2 is preheated to 1000 ℃ through the second heating part 12 and the heating device 4, 800 ℃ gas is introduced into the second air inlet 9, the temperature in the cavity of the material collecting cavity 7 is controlled to be 800 ℃, and the cavity gauge pressure of the second spray pyrolysis device 2 is controlled to be 100 Pa.
(3) Spray pyrolysis: after the spray pyrolysis device operates stably, the prepared ternary mixed solution is sprayed into the first pyrolysis device 1 through the nozzle 3 at the speed of 5L/h for preliminary pyrolysis, and a pre-product generated by the reaction enters the second spray pyrolysis device 2 through the powder conveying valve 5 and the pipeline 13.
(4) Settling separation: fully pyrolyzing the pre-product in a second spray pyrolysis device 2 to obtain a ternary anode precursor, and secondarily dispersing solid particles under the action of ascending air flow introduced from a second air inlet 9; and gas obtained by reaction enters the separation device 6 through the gas outlet of the second spray pyrolysis device 2, solid particles in the gas are separated and recovered again through the separation device 6, waste gas is discharged through the gas outlet 10 at the top of the separation device 6 and then treated or recovered, air is continuously sprayed in after the solution is exhausted, the furnace is stopped after 15 minutes, gas is stopped from being introduced into the first air inlet 8 and the second air inlet 9, the temperature is reduced to the normal temperature, and after the solution is completely settled, the aluminum-doped 523 oxide precursor in the gas is recovered in the material collection cavity 7.
The obtained aluminum-doped 523 oxide precursor was tested for the content of chlorine using an XRF-ray fluorescence spectrometer, and the test results are shown in table 1.
Example 2
In this embodiment, a spray pyrolysis apparatus provided in the specific embodiment is used to prepare a ternary positive electrode precursor, and the method includes: preparing a ternary mixed salt solution, preheating a furnace body, performing spray pyrolysis and settling separation, and specifically comprising the following implementation steps of:
(1) preparing a ternary mixed salt solution: weighing a certain amount of nickel chloride, cobalt chloride and manganese chloride, preparing 40L of ternary mixed solution according to the mass ratio of 0.5:0.2:0.3, controlling the metal concentration at 180g/L, and adding aluminum chloride accounting for 0.5% of the total mass of nickel, cobalt and manganese.
(2) Preheating a furnace body: preheating the first spray pyrolysis device 1 to 1080 ℃ through the first heating part 11, introducing 700 ℃ gas into the first air inlet 8, driving the powder conveying valve 5 to rotate, and controlling the negative pressure in the first spray pyrolysis device 1 to-150 Pa; the second spray pyrolysis device 2 is preheated to 900 ℃ through the second heating part 12 and the heating device 4, 700 ℃ gas is introduced into the second air inlet 9, the temperature in the cavity of the material collecting cavity 7 is controlled to be 700 ℃, and the cavity gauge pressure of the second spray pyrolysis device 2 is controlled to be 150 Pa.
(3) Spray pyrolysis: after the spray pyrolysis device operates stably, the prepared ternary mixed solution is sprayed into the first pyrolysis device 1 through the nozzle 3 at the speed of 5L/h for preliminary pyrolysis, and a pre-product generated by the reaction enters the second spray pyrolysis device 2 through the powder conveying valve 5 and the pipeline 13.
(4) Settling separation: fully pyrolyzing the pre-product in a second spray pyrolysis device 2 to obtain a ternary anode precursor, and secondarily dispersing solid particles under the action of ascending air flow introduced from a second air inlet 9; and gas obtained by reaction enters the separation device 6 through the gas outlet of the second spray pyrolysis device 2, solid particles in the gas are separated and recovered again through the separation device 6, waste gas is discharged through the gas outlet 10 at the top of the separation device 6 and then treated or recovered, air is continuously sprayed in after the solution is exhausted, the furnace is stopped after 15 minutes, gas is stopped from being introduced into the first air inlet 8 and the second air inlet 9, the temperature is reduced to the normal temperature, and after the solution is completely settled, the aluminum-doped 523 oxide precursor in the gas is recovered in the material collection cavity 7.
The obtained aluminum-doped 523 oxide precursor was tested for the content of chlorine using an XRF-ray fluorescence spectrometer, and the test results are shown in table 1.
Example 3
In this embodiment, a spray pyrolysis apparatus provided in the specific embodiment is used to prepare a ternary positive electrode precursor, and the method includes: preparing a ternary mixed salt solution, preheating a furnace body, performing spray pyrolysis and settling separation, and specifically comprising the following implementation steps of:
(1) preparing a ternary mixed salt solution: weighing a certain amount of nickel chloride, cobalt chloride and manganese chloride, preparing 50L of ternary mixed solution according to the mass ratio of 0.6:0.2:0.2, controlling the metal concentration at 170g/L, and adding aluminum chloride accounting for 0.5 percent of the total mass of nickel, cobalt and manganese.
(2) Preheating a furnace body: preheating the first spray pyrolysis device 1 to 930 ℃ through the first heating part 11, introducing gas at 600 ℃ into the first air inlet 8, driving the powder conveying valve 5 to rotate, and controlling the negative pressure in the first spray pyrolysis device 1 to be-190 Pa; the second spray pyrolysis device 2 is preheated to 860 ℃ through the second heating part 12 and the heating device 4, gas with the temperature of 600 ℃ is introduced into the second air inlet 9, the temperature in the cavity of the material collecting cavity 7 is controlled to be 600 ℃, and the cavity gauge pressure of the second spray pyrolysis device 2 is controlled to be 130 Pa.
(3) Spray pyrolysis: after the spray pyrolysis device operates stably, the prepared ternary mixed solution is sprayed into the first pyrolysis device 1 through the nozzle 3 at the speed of 5L/h for preliminary pyrolysis, and a pre-product generated by the reaction enters the second spray pyrolysis device 2 through the powder conveying valve 5 and the pipeline 13.
(4) Settling separation: fully pyrolyzing the pre-product in a second spray pyrolysis device 2 to obtain a ternary anode precursor, and secondarily dispersing solid particles under the action of ascending air flow introduced from a second air inlet 9; and gas obtained by reaction enters the separation device 6 through the gas outlet of the second spray pyrolysis device 2, solid particles in the gas are separated and recovered again through the separation device 6, waste gas is discharged through the gas outlet 10 at the top of the separation device 6 and then treated or recovered, air is continuously sprayed in after the solution is exhausted, the furnace is stopped after 15 minutes, gas is stopped from being introduced into the first air inlet 8 and the second air inlet 9, the temperature is reduced to the normal temperature, and after the solution is completely settled, the aluminum-doped 622 oxide precursor in the material collection cavity 7 is recovered.
The obtained aluminum-doped 622 oxide precursor was tested for the chlorine content using an XRF-ray fluorescence spectrometer, and the results are shown in table 1.
Example 4
In this embodiment, a spray pyrolysis apparatus provided in the specific embodiment is used to prepare a ternary positive electrode precursor, and the method includes: preparing a ternary mixed salt solution, preheating a furnace body, performing spray pyrolysis and settling separation, and specifically comprising the following implementation steps of:
(1) preparing a ternary mixed salt solution: weighing a certain amount of nickel chloride, cobalt chloride and manganese chloride, preparing 50L of ternary mixed solution according to the mass ratio of 0.8:0.1:0.1, controlling the metal concentration at 170g/L, and adding aluminum chloride accounting for 0.3 percent of the total mass of nickel, cobalt and manganese.
(2) Preheating a furnace body: preheating the first spray pyrolysis device 1 to 860 ℃ through the first heating part 11, introducing 550 ℃ gas into the first air inlet 8, driving the powder conveying valve 5 to rotate, and controlling the negative pressure in the first spray pyrolysis device 1 to be-350 Pa; the second spray pyrolysis device 2 is preheated to 790 ℃ through the second heating part 12 and the heating device 4, 550 ℃ gas is introduced into the second air inlet 9, the temperature in the cavity of the material collecting cavity 7 is controlled to 550 ℃, and the cavity gauge pressure of the second spray pyrolysis device 2 is controlled to 100 Pa.
(3) Spray pyrolysis: after the spray pyrolysis device operates stably, the prepared ternary mixed solution is sprayed into the first pyrolysis device 1 through the nozzle 3 at the speed of 3L/h for preliminary pyrolysis, and a pre-product generated by the reaction enters the second spray pyrolysis device 2 through the powder conveying valve 5 and the pipeline 13.
(4) Settling separation: fully pyrolyzing the pre-product in a second spray pyrolysis device 2 to obtain a ternary anode precursor, and secondarily dispersing solid particles under the action of ascending air flow introduced from a second air inlet 9; and gas obtained by reaction enters the separation device 6 through the gas outlet of the second spray pyrolysis device 2, solid particles in the gas are separated and recovered again through the separation device 6, waste gas is discharged through the gas outlet 10 at the top of the separation device 6 and then treated or recovered, air is continuously sprayed in after the solution is exhausted, the furnace is stopped after 15 minutes, gas is stopped from being introduced into the first air inlet 8 and the second air inlet 9, the temperature is reduced to the normal temperature, and after the solution is completely settled, the aluminum-doped 811 oxide precursor in the material collection cavity 7 is recovered.
The obtained aluminum-doped 811 oxide precursor was tested for the chlorine content using an XRF-ray fluorescence spectrometer, and the results are shown in table 1.
Example 5
In this embodiment, a spray pyrolysis apparatus provided in the specific embodiment is used to prepare a ternary positive electrode precursor, and the method includes: preparing a ternary mixed salt solution, preheating a furnace body, performing spray pyrolysis and settling separation, and specifically comprising the following implementation steps of:
(1) preparing a ternary mixed salt solution: weighing a certain amount of nickel chloride, cobalt chloride and manganese chloride, preparing 50L of ternary mixed solution according to the mass ratio of 0.8:0.1:0.1, controlling the metal concentration at 170g/L, and adding aluminum chloride accounting for 0.3 percent of the total mass of nickel, cobalt and manganese.
(2) Preheating a furnace body: preheating the first spray pyrolysis device 1 to 700 ℃ through the first heating part 11, introducing gas at 450 ℃ into the first air inlet 8, driving the powder conveying valve 5 to rotate, and controlling the negative pressure in the first spray pyrolysis device 1 to be-200 Pa; the second spray pyrolysis device 2 is preheated to 600 ℃ through the second heating part 12 and the heating device 4, 450 ℃ gas is introduced into the second air inlet 9, the temperature in the cavity of the material collecting cavity 7 is controlled to be 450 ℃, and the cavity gauge pressure of the second spray pyrolysis device 2 is controlled to be 100 Pa.
(3) Spray pyrolysis: after the spray pyrolysis device operates stably, the prepared ternary mixed solution is sprayed into the first pyrolysis device 1 through the nozzle 3 at the speed of 3L/h for preliminary pyrolysis, and a pre-product generated by the reaction enters the second spray pyrolysis device 2 through the powder conveying valve 5 and the pipeline 13.
(4) Settling separation: fully pyrolyzing the pre-product in a second spray pyrolysis device 2 to obtain a ternary anode precursor, and secondarily dispersing solid particles under the action of ascending air flow introduced from a second air inlet 9; and gas obtained by reaction enters the separation device 6 through the gas outlet of the second spray pyrolysis device 2, solid particles in the gas are separated and recovered again through the separation device 6, waste gas is discharged through the gas outlet 10 at the top of the separation device 6 and then treated or recovered, air is continuously sprayed in after the solution is exhausted, the furnace is stopped after 15 minutes, gas is stopped from being introduced into the first air inlet 8 and the second air inlet 9, the temperature is reduced to the normal temperature, and after the solution is completely settled, the aluminum-doped 811 oxide precursor in the material collection cavity 7 is recovered.
The obtained aluminum-doped 811 oxide precursor was tested for the chlorine content using an XRF-ray fluorescence spectrometer, and the results are shown in table 1.
Example 6
In this embodiment, a spray pyrolysis apparatus provided in the specific embodiment is used to prepare a ternary positive electrode precursor, and the method includes: preparing a ternary mixed salt solution, preheating a furnace body, performing spray pyrolysis and settling separation, and specifically comprising the following implementation steps of:
(1) preparing a ternary mixed salt solution: weighing a certain amount of nickel chloride, cobalt chloride and manganese chloride, preparing 50L of ternary mixed solution according to the mass ratio of 0.8:0.1:0.1, controlling the metal concentration at 150g/L, and adding aluminum chloride accounting for 0.6 percent of the total mass of nickel, cobalt and manganese.
(2) Preheating a furnace body: preheating the first spray pyrolysis device 1 to 600 ℃ through the first heating part 11, introducing gas at 300 ℃ into the first air inlet 8, driving the powder conveying valve 5 to rotate, and controlling the negative pressure in the first spray pyrolysis device 1 to be-100 Pa; the second spray pyrolysis device 2 is preheated to 500 ℃ through the second heating part 12 and the heating device 4, 300 ℃ gas is introduced into the second air inlet 9, the temperature in the cavity of the material collecting cavity 7 is controlled to be 300 ℃, and the cavity gauge pressure of the second spray pyrolysis device 2 is controlled to be 50 Pa.
(3) Spray pyrolysis: after the spray pyrolysis device operates stably, the prepared ternary mixed solution is sprayed into the first pyrolysis device 1 through the nozzle 3 at the speed of 3L/h for preliminary pyrolysis, and a pre-product generated by the reaction enters the second spray pyrolysis device 2 through the powder conveying valve 5 and the pipeline 13.
(4) Settling separation: fully pyrolyzing the pre-product in a second spray pyrolysis device 2 to obtain a ternary anode precursor, and secondarily dispersing solid particles under the action of ascending air flow introduced from a second air inlet 9; and gas obtained by reaction enters the separation device 6 through the gas outlet of the second spray pyrolysis device 2, solid particles in the gas are separated and recovered again through the separation device 6, waste gas is discharged through the gas outlet 10 at the top of the separation device 6 and then treated or recovered, air is continuously sprayed in after the solution is exhausted, the furnace is stopped after 15 minutes, gas is stopped from being introduced into the first air inlet 8 and the second air inlet 9, the temperature is reduced to the normal temperature, and after the solution is completely settled, the aluminum-doped 811 oxide precursor in the material collection cavity 7 is recovered.
The obtained aluminum-doped 811 oxide precursor was tested for the chlorine content using an XRF-ray fluorescence spectrometer, and the results are shown in table 1.
Comparative example 1
A523 oxide precursor is prepared by using a small single-furnace-body spray pyrolysis device, the preparation method adopts a ternary mixed solution with the same proportion as that of the embodiment 1, the diameter of a furnace body of the spray pyrolysis device is 0.8m, the preheating temperature is 950 ℃, and the ternary mixed solution is sprayed into the spray pyrolysis device at the speed of 3L/h for pyrolysis reaction to prepare the 523 oxide precursor.
The obtained 523 oxide precursor was tested for the content of chlorine using an XRF-ray fluorescence spectrometer, and the test results are shown in table 1.
Comparative example 2
The 523 oxide precursor is prepared by a large spray pyrolysis device which is produced at 2000t every year. The preparation method adopts the ternary mixed solution with the same proportion as that of the embodiment 1, the diameter of a furnace body of the spray pyrolysis device is 4.8m, the preheating temperature is 960 ℃, and the ternary mixed solution is sprayed into the spray pyrolysis device at the speed of 500L/h for pyrolysis reaction to prepare 523 oxide precursor.
The obtained 523 oxide precursor was tested for the content of chlorine using an XRF-ray fluorescence spectrometer, and the test results are shown in table 1.
TABLE 1 content of chlorine element in ternary cathode precursor
Chlorine content (wt%)
Example 1 0.32
Example 2 0.38
Example 3 0.43
Example 4 0.48
Example 5 0.64
Example 6 0.79
Comparative example 1 8.57
Comparative example 2 0.39
Because the chlorine element in the finally prepared ternary positive electrode precursor comes from the ternary mixed salt solution which is not completely pyrolyzed, the content of the chlorine element can reflect the degree and the efficiency of the pyrolysis reaction laterally, if the content of the chlorine element in the precursor is higher, the pyrolysis reaction is incomplete, otherwise, the pyrolysis reaction is complete.
As can be seen from the test results of the chlorine content in example 1 and comparative example 1, the chlorine content in the ternary cathode precursor prepared in example 1 of the present invention is significantly reduced compared to comparative example 1, which indicates that the small single-furnace spray pyrolysis apparatus used in comparative example 1 cannot achieve sufficient pyrolysis reaction, because the spray pyrolysis apparatus used in comparative example 1 is a single-furnace spray pyrolysis apparatus with a diameter of 0.8m, the reaction time of the raw material liquid in the pyrolysis apparatus is insufficient, the reaction degree is insufficient, and the pyrolysis reaction is not complete.
From the test results of the chlorine content in the example 1 and the comparative example 2, it can be seen that the chlorine content in the ternary cathode precursor prepared in the example 1 is very close to that in the ternary cathode precursor prepared in the large-scale spray pyrolysis furnace with annual output of 2000t, which also indicates that the chlorine content in the ternary cathode precursor prepared in the example 1 is very close to that in the ternary cathode precursor prepared in the large-scale spray pyrolysis furnace with annual output of 2000t, and the pyrolysis reaction degree of the ternary cathode precursor and the ternary cathode precursor is also very close, but the invention has the advantages that the design diameter (0.5-1.8m) of the spray pyrolysis device provided by the invention is far smaller than that (4.8m) of the large-scale spray pyrolysis furnace with annual output of 2000t, so that in the actual industrial application process, compared with the large-scale spray pyrolysis furnace, the spray pyrolysis device provided by the invention has a smaller floor area, the investment, operation and maintenance costs are lower.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (40)

1. A spray pyrolysis device is characterized by comprising a first spray pyrolysis device (1) and a second spray pyrolysis device (2), wherein a discharge port of the first spray pyrolysis device (1) is connected with a conveying device, and an outlet of the conveying device is arranged in a cavity of the second spray pyrolysis device (2);
the first spray pyrolysis device (1) comprises a first cavity and a nozzle (3) arranged at the top of the first cavity; the diameter of the first cavity is 0.5-1.8 m;
the second spray pyrolysis device (2) comprises a second cavity and a material collecting cavity (7) arranged at the bottom of the second cavity; a second air inlet (9) for introducing air is formed in the bottom of the second cavity; the diameter of the second cavity is 0.5-1.8 m;
the conveying device comprises a powder conveying valve (5) connected with a discharge port of the first spray pyrolysis device (1) and used for conveying materials and a pipeline (13) connected with the powder conveying valve (5), and an outlet of the pipeline (13) is formed in a cavity of the second spray pyrolysis device (2).
2. The device according to claim 1, characterized in that the powder delivery valve (5) is a rotary valve, a butterfly valve or a gate valve.
3. The device according to claim 2, wherein the powder delivery valve (5) is a rotary valve, the housing of the rotary valve is provided with a feed inlet, a first air inlet (8) and a discharge outlet, the feed inlet is connected with the discharge outlet of the first spray pyrolysis device (1), the first air inlet (8) is used for introducing gas to drive the rotary valve to rotate, and the discharge outlet is connected with the inlet of the pipeline (13); the valve body of the rotary valve comprises a valve rod and rotary baffles distributed longitudinally along the valve rod.
4. The apparatus according to claim 1, characterized in that the outlet of the duct (13) is located 1/3-2/3 of the cavity of the second spray pyrolysis apparatus (2).
5. The apparatus according to claim 1, wherein the first spray pyrolysis apparatus (1) further comprises a first heating member (11) disposed at an outer wall of the first chamber.
6. Device according to claim 1, characterized in that the nozzle (3) is a two-fluid aerosol nozzle or a pressure nozzle.
7. The apparatus according to claim 1, wherein the second spray pyrolysis apparatus (2) further comprises a second heating member (12) disposed on an outer wall of the second chamber.
8. The apparatus according to claim 1, wherein the second spray pyrolysis apparatus (2) further comprises a heating apparatus (4) disposed at the bottom of the second chamber.
9. The device according to claim 8, characterized in that the heating device (4) is arranged above the material collecting chamber (7).
10. The device according to claim 9, characterized in that the heating device (4) is a gas nozzle or an ignition burner.
11. The apparatus according to claim 1, characterized in that the second spray pyrolysis apparatus (2) is provided with an air outlet and a feed back port at the upper part; the second spray pyrolysis device (2) further comprises a separation device (6), the inlet of the separation device (6) is connected with the gas outlet of the second spray pyrolysis device (2), and the outlet of the separation device (6) is connected with the feed back port of the second spray pyrolysis device (2).
12. The apparatus according to claim 11, characterized in that the separation device (6) is a cyclone or a double cyclone.
13. The apparatus according to claim 12, characterized in that the top of the separating device (6) is provided with an exhaust (10) for exhaust of flue gases or dust.
14. A method of preparing a ternary positive electrode precursor, wherein the method is carried out in an apparatus according to any one of claims 1 to 13.
15. The method of claim 14, wherein the method comprises:
(I) preheating a first spray pyrolysis device (1) and a second spray pyrolysis device (2), depressurizing the first spray pyrolysis device (1), and pressurizing the second spray pyrolysis device (2);
(II) spraying the ternary mixed salt solution into the first spray pyrolysis device (1) through a nozzle (3) to generate a pre-product;
and (III) feeding the pre-product obtained in the step (II) into a second spray pyrolysis device (2) through a conveying device, separating solid and gas, wherein the solid is the ternary anode precursor, and treating or recycling the gas after the gas is discharged.
16. The method of claim 15, wherein the method comprises:
(I) preheating a first spray pyrolysis device (1) and a second spray pyrolysis device (2), introducing gas into a first air inlet (8), reducing the pressure of the first spray pyrolysis device (1) by operating a powder conveying valve (5), and boosting the pressure of the second spray pyrolysis device (2) by switching on a second air inlet (9);
(II) spraying the ternary mixed salt solution into the first spray pyrolysis device (1) through a nozzle (3), and pyrolyzing to generate a pre-product;
(III) the pre-product obtained in the step (II) falls to a rotary valve, is conveyed to a second spray pyrolysis device (2) through a pipeline (13) to be pyrolyzed continuously, after the reaction is finished, the solid is collected to a material collecting cavity (7) to obtain the ternary anode precursor, and the gas enters a separating device (6).
17. The method according to claim 16, wherein the gas is discharged into the separation device (6) and the gas is introduced into the separation device (6) through the gas outlet of the second spray pyrolysis device (2) for solid-gas separation, the waste gas is treated or recycled, and the solid is recycled into the second spray pyrolysis device (2).
18. The method of claim 15, wherein the ternary mixed salt is a chloride salt.
19. The method of claim 18, wherein the cations in the ternary mixed salt are nickel, cobalt and manganese, respectively.
20. The method according to claim 19, wherein the mass ratio of nickel, cobalt and manganese is expressed as x: y: z, the x: y: z is (0.33-0.9): (0.03-0.33): (0.03-0.33), wherein x + y + z is 1.
21. The method as claimed in claim 20, wherein the total concentration of nickel, cobalt and manganese elements in the ternary mixed salt solution is 40-250 g/L.
22. The method as claimed in claim 21, wherein the total concentration of nickel, cobalt and manganese elements in the ternary mixed salt solution is 100-200 g/L.
23. The method as claimed in claim 22, wherein the total concentration of nickel, cobalt and manganese elements in the ternary mixed salt solution is 150-180 g/L.
24. The method of claim 23, wherein the ternary mixed salt solution is further doped with any one or a combination of at least two of Al, Mg, Zr, Ti, Mn, La, Mo, W, Si, B, and P.
25. The method according to claim 16, wherein the preheating temperature of the first spray pyrolysis device (1) is 600-1200 ℃.
26. The method according to claim 25, wherein the preheating temperature of the first spray pyrolysis device (1) is 700 to 1100 ℃.
27. The method according to claim 26, wherein the preheating temperature of the first spray pyrolysis device (1) is 850 to 950 ℃.
28. The method according to claim 16, characterized in that the preheating temperature of the second spray pyrolysis device (2) is 500-1000 ℃.
29. The method according to claim 28, wherein the preheating temperature of the second spray pyrolysis device (2) is 600 to 900 ℃.
30. The method according to claim 29, wherein the preheating temperature of the second spray pyrolysis device (2) is 700 to 800 ℃.
31. The method according to claim 16, characterized in that the first spray pyrolysis apparatus (1) is depressurized to a pressure of-500 to-100 Pa.
32. The method according to claim 16, wherein the gauge pressure in the second spray pyrolysis device (2) is 0 to 200 Pa.
33. The method as claimed in claim 16, wherein in step (i), the first air inlet (8) is supplied with air at a temperature of 300 to 800 ℃.
34. The method as claimed in claim 33, wherein in step (i), the first air inlet (8) is supplied with air at a temperature of 500 to 700 ℃.
35. The method as claimed in claim 34, wherein in step (i), the first air inlet (8) is supplied with air at a temperature of 550 to 650 ℃.
36. The method according to claim 16, wherein in the step (iii), the gas with the temperature of 300-800 ℃ is introduced into the second air inlet (9).
37. The method as claimed in claim 36, wherein in step (iii), gas with a temperature of 500-700 ℃ is introduced into the second air inlet (9).
38. The method according to claim 37, wherein in the step (iii), the gas with the temperature of 550-650 ℃ is introduced into the second air inlet (9).
39. A ternary positive electrode precursor, characterized in that it is prepared by a process according to any one of claims 14 to 38.
40. The ternary positive electrode precursor according to claim 39, wherein the ternary positive electrode precursor has a chlorine content of < 0.8%.
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