CN112742325A - Precursor preparation system and preparation method - Google Patents
Precursor preparation system and preparation method Download PDFInfo
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- CN112742325A CN112742325A CN202011495588.4A CN202011495588A CN112742325A CN 112742325 A CN112742325 A CN 112742325A CN 202011495588 A CN202011495588 A CN 202011495588A CN 112742325 A CN112742325 A CN 112742325A
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- 239000002243 precursor Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 201
- 239000002245 particle Substances 0.000 claims abstract description 58
- 239000002002 slurry Substances 0.000 claims abstract description 56
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000004891 communication Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 6
- 230000001276 controlling effect Effects 0.000 description 27
- 150000003839 salts Chemical class 0.000 description 15
- 239000008139 complexing agent Substances 0.000 description 14
- 239000012716 precipitator Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 238000011437 continuous method Methods 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229940053662 nickel sulfate Drugs 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 3
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 1
- BRMXSFRLQQTALQ-UHFFFAOYSA-J cobalt(2+);manganese(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2] BRMXSFRLQQTALQ-UHFFFAOYSA-J 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 discloses a precursor preparation system and a preparation method, wherein the precursor preparation system comprises a first reaction kettle, a second reaction kettle, a conveying mechanism and a control mechanism; the conveying mechanism is configured to continuously convey the small-particle crystal nuclei in the first kettle body into the second kettle body in the whole process of preparing the precursor; the pH value in the first reaction chamber of the first reaction kettle is greater than the pH value in the second reaction chamber of the second reaction kettle; the first feeding assembly provides the flow of slurry to the first reaction chamber and is a, the second feeding assembly provides the flow of slurry to the second reaction chamber and is b, the flow of conveying mechanism conveying small particle crystal nucleus is c, the flow a is 0.01-0.3 times of the flow b, and the flow c is equal to the flow a. The precursor preparation system can keep the pH value in the reaction process stable, ensures that the sphericity of all particle size particles is better, is easier to control the particle size of the precursor, and is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a precursor preparation system and a preparation method.
Background
The anode material is the most costly part of the lithium ion battery, and the performance of the anode material plays a decisive role in the lithium ion battery. The positive electrode material is generally subjected to secondary sintering by adopting a precursor and a lithium source, and various physical and chemical indexes of the precursor have a supporting effect on the physical and chemical indexes of the positive electrode material and influence the processing performance and the electrical performance of the positive electrode material.
The production method of the precursor of the lithium ion battery anode material commonly used in industry is a coprecipitation method, and the coprecipitation method is divided into a batch method and a continuous method. The batch method is characterized in that a small amount of base solution is added into a kettle, materials in the kettle are completely discharged when the kettle is full of materials and the granularity is large enough to meet the requirement, and the base solution is added again for reaction. The continuous method is characterized in that feeding and overflowing are carried out during the reaction process, and when the reaction is stable, the product is continuously produced, so that the product has good reproducibility and high stability.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a precursor preparation system and a preparation method, wherein the precursor preparation system can keep the pH value in the reaction process stable, ensure that the sphericity of all particles with the particle size is better, and the particle size of the precursor is easier to control, so that the precursor preparation system is suitable for large-scale production.
In order to achieve the above object, the present invention provides a precursor preparation system, which includes a first reaction vessel, a second reaction vessel, a conveying mechanism, and a control mechanism; the first reaction kettle comprises a first kettle body, a first feeding assembly and a first stirring assembly; the first kettle body is provided with a first reaction chamber, the first feeding assembly is configured to provide slurry into the first reaction chamber, and the first stirring assembly is configured to stir the slurry in the first reaction chamber; the second reaction kettle comprises a second kettle body, a second feeding assembly and a second stirring assembly; the second kettle body is provided with a second reaction chamber and an overflow port communicated with the second reaction chamber, the overflow port is used for discharging precursors, the second feeding assembly is configured to be capable of providing slurry into the second reaction chamber, and the second stirring assembly is configured to be capable of stirring the slurry in the second reaction chamber; the conveying mechanism is configured to continuously convey the small particle crystal nuclei in the first kettle body into the second kettle body in the whole process of preparing the precursor; wherein the pH in the first reaction chamber is greater than the pH in the second reaction chamber; the first feeding assembly provides the slurry to the first reaction chamber at a flow rate a, the second feeding assembly provides the slurry to the second reaction chamber at a flow rate b, the conveying mechanism conveys small-particle crystal nuclei at a flow rate c, and the control mechanism is configured to control the first feeding assembly and the second feeding assembly so that: the flow rate a is 0.01-0.3 times of the flow rate b, and the flow rate c is equal to the flow rate a.
Optionally, the first reaction kettle comprises a first baffle plate, and the first baffle plate is arranged on the inner wall of the first kettle body; and/or the second reaction kettle comprises a second baffle plate, and the second baffle plate is arranged on the inner wall of the second kettle body.
Optionally, the bottom of the first kettle body is provided with a first liquid discharge port communicated with the first reaction chamber, and/or the bottom of the second kettle body is provided with a second liquid discharge port communicated with the second reaction chamber.
Optionally, the first feed assembly comprises a first gas inlet in communication with the first reaction chamber for providing nitrogen to the first reaction chamber, and/or the second feed assembly comprises a second gas inlet in communication with the second reaction chamber for providing nitrogen to the second reaction chamber.
Optionally, the first reaction kettle comprises a first jacket covering the outer wall of the first kettle body, and/or the second reaction kettle comprises a second jacket covering the outer wall of the second kettle body.
According to the technical scheme, the slurry is supplied into the first reaction chamber through the first feeding assembly and is stirred through the first stirring assembly, so that the slurry in the first reaction chamber forms small particle crystal nuclei with good sphericity and compactness under the influence of the pH value in the first reaction chamber, the small particle crystal nuclei are continuously conveyed into the second reaction chamber through the conveying mechanism, meanwhile, the second feeding assembly also continuously supplies the slurry into the second reaction chamber, the slurry and the small particle crystal nuclei are stirred together to control the particle size in the second reaction chamber, and through setting the flow rate a, the flow rate b and the flow rate c, when the flow rate a is 0.01-0.3 times of the flow rate b and the flow rate c is equal to the flow rate a, the sphericity of all the particles can be ensured to be good, and through adjusting the flow rate a, the flow rate b and the flow rate c, The flow rates b and c also make it easier to control the particle size of the finally formed precursor. In addition, in the preparation process, the particle size in the second reaction chamber is adjusted by adopting the small particle crystal nucleus added into the first reaction chamber, so that the particle size in the second reaction chamber is not controlled by the pH value in the whole reaction process, the reaction process of the second reaction chamber is kept at a relatively stable pH value, the small particle crystal nucleus with better sphericity and compactness is prepared in the first reaction chamber, and the precursor finally produced from the second reaction chamber is ensured to have better sphericity. In addition, the precursor preparation system provided by the invention adopts a continuous method to prepare the precursor, namely, the first feeding assembly, the second feeding assembly and the conveying mechanism continuously convey the slurry, so that the production efficiency can be greatly improved on the premise of ensuring the good sphericity of the final precursor, and the precursor preparation system is suitable for large-scale production.
The invention also provides a precursor preparation method, which comprises the following steps: s1, continuously adding the slurry into the first reaction chamber at the flow rate a and stirring; s2, continuously adding the slurry into the second reaction chamber at a flow rate b and stirring, and simultaneously, continuously conveying the small particle nuclei formed in the first reaction chamber into the second reaction chamber at a flow rate c; s3, performing filter pressing, washing and drying on the slurry in the second reaction chamber to obtain a precursor; and step S1 is performed simultaneously with step S2, the pH value in the first reaction chamber is greater than that in the second reaction chamber, the flow rate a is 0.01-0.3 times of the flow rate b, and the flow rate c is equal to the flow rate a.
Optionally, in step S1 and step S2, nitrogen gas is continuously introduced into the first reaction chamber and the second reaction chamber, respectively, and the flow rate of the nitrogen gas is 20 to 200L/h.
Optionally, in step S1, the stirring speed is 120-250 rpm; in step S2, the stirring speed is 50 to 250 rpm.
Optionally, in the step S1 and the step S2, the reaction temperature is 40-80 ℃.
Optionally, in step S1, the reaction residence time is 20-200 h; in step S2, the reaction residence time is 5-50 h.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a schematic view of one embodiment of a precursor preparation system of the present invention;
FIG. 2 is a scanning electron micrograph of nickel cobalt manganese hydroxide prepared by the precursor preparation system of the present invention;
FIG. 3 is a scanning electron micrograph of nickel cobalt manganese hydroxide prepared according to a comparative example.
Description of the reference numerals
110-a first kettle body, 111-a first reaction chamber, 112-a first liquid discharge port, 120-a first feeding assembly, 130-a first stirring assembly, 140-a first baffle plate, 150-a first jacket, 210-a second kettle body, 211-a second reaction chamber, 212-a second liquid discharge port, 213-an overflow port, 220-a second feeding assembly, 230-a second stirring assembly, 240-a second baffle plate, 250-a second jacket and 300-a conveying mechanism
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
As shown in fig. 1, the precursor preparation system of the present invention includes a first reaction vessel, a second reaction vessel, a conveying mechanism 300 and a control mechanism; the first reaction kettle comprises a first kettle body 110, a first feeding assembly 120 and a first stirring assembly 130; the first kettle body 110 is provided with a first reaction chamber 111, the first feeding assembly 120 is configured to be capable of providing slurry into the first reaction chamber 111, and the first stirring assembly 130 is configured to be capable of stirring the slurry in the first reaction chamber 111; the second reaction kettle comprises a second kettle body 210, a second feeding assembly 220 and a second stirring assembly 230; the second kettle body 210 has a second reaction chamber 211 and an overflow port 213 communicated with the second reaction chamber 211, the overflow port 213 is used for discharging the precursor, the second feeding assembly 220 is configured to be capable of providing the slurry into the second reaction chamber 211, and the second stirring assembly 230 is configured to be capable of stirring the slurry in the second reaction chamber 211; the conveying mechanism 300 is configured to be able to continuously convey the small particle nuclei in the first kettle body 110 into the second kettle body 210 throughout the process of preparing the precursor; wherein the pH in the first reaction chamber 111 is greater than the pH in the second reaction chamber 211; the first feeding assembly 120 supplies the slurry to the first reaction chamber 111 at a flow rate a, the second feeding assembly 220 supplies the slurry to the second reaction chamber 211 at a flow rate b, the conveying mechanism 300 conveys the small particle nuclei at a flow rate c, and the control mechanism is configured to control the first feeding assembly 120 and the second feeding assembly 220 such that: the flow rate a is 0.01-0.3 times of the flow rate b, and the flow rate c is equal to the flow rate a.
The slurry is provided into the first reaction chamber 111 through the first feeding assembly 120 and is stirred through the first stirring assembly 130, so that the slurry in the first reaction chamber 111 forms small particle crystal nuclei with better sphericity and compactness under the influence of the pH value in the first reaction chamber 111, these small particle nuclei are continuously transferred into the second reaction chamber 211 by the transfer mechanism 300, meanwhile, the second feeding assembly 220 also continuously supplies the slurry into the second reaction chamber 211, these slurries are stirred together with the small particle nuclei to control the particle size in the second reaction chamber 211, and by setting the flow rate a, the flow rate b and the flow rate c, when the flow rate a is 0.01-0.3 times of the flow rate b and the flow rate c is equal to the flow rate a, the sphericity of all the particles with the particle diameter can be ensured to be good, and the particle size of the finally formed precursor can be more easily controlled by adjusting the flow rate a, the flow rate b and the flow rate c. In addition, in the preparation process, the particle size in the second reaction chamber 211 is adjusted by using the small particle crystal nuclei added into the first reaction chamber, so that the particle size in the second reaction chamber 211 is not controlled by the pH in the whole reaction process, the reaction process of the second reaction chamber 211 is kept at a relatively stable pH value, and then the small particle crystal nuclei with better sphericity and compactness are prepared in the first reaction chamber 111, and the sphericity of the precursor finally produced from the second reaction chamber 211 is ensured to be better. In addition, because the precursor preparation system of the present invention adopts a continuous method to prepare the precursor, i.e., the first feeding assembly 120, the second feeding assembly 220 and the conveying mechanism 300 continuously convey the slurry, the production efficiency can be greatly improved on the premise of ensuring the good sphericity of the final precursor, and the present invention is suitable for large-scale production.
In order to improve the stirring effect as much as possible, in one embodiment of the present invention, the first reaction tank includes a first baffle plate 140 having a flat plate shape, the first baffle plate 140 is disposed on an inner wall of the first tank 110, the second reaction tank includes a second baffle plate 240 having a flat plate shape, and the second baffle plate 240 is disposed on an inner wall of the second tank 210. The first baffle 140 and the second baffle 240 can provide certain resistance to the slurry during stirring, and disturb the flowing direction and the flowing state of the slurry, thereby improving the stirring effect.
In order to facilitate the cleaning of the inside of the first and second tanks 110 and 210, in one embodiment of the present invention, a first drain port 112 communicating with the first reaction chamber 111 is provided at the bottom of the first tank 110, and a second drain port 212 communicating with the second reaction chamber 211 is provided at the bottom of the second tank 210. When the preparation work is completed, the first drain port 112 and the second drain port 212 may be opened to drain the residual slurry in the first reaction chamber 111 and the second reaction chamber 211, respectively.
Further, the first feeding assembly 120 comprises a first gas inlet communicated with the first reaction chamber 111 for providing nitrogen gas to the first reaction chamber 111, and the second feeding assembly 220 comprises a second gas inlet communicated with the second reaction chamber 211 for providing nitrogen gas to the second reaction chamber 211, wherein the flow rate of the nitrogen gas is 20-200L/h.
In order to stabilize the reaction state of the first and second kettle bodies 110 and 210, in an embodiment of the present invention, the first reaction kettle includes a first jacket 150 covering the outer wall of the first kettle body 110, and the second reaction kettle includes a second jacket 250 covering the outer wall of the second kettle body 210, and the temperature in the first and second reaction chambers 111 and 211 can be stabilized by the heat preservation effect of the first and second jackets 150 and 250, so that the reaction state can be stabilized.
Through the embodiment, the precursor preparation system can keep the pH value in the reaction process stable, ensures that the sphericity of all particle size particles is better, is easier to control the particle size of the precursor, and is suitable for large-scale production.
The invention also provides a precursor preparation method, which comprises the following steps:
s1, continuously adding the slurry into the first reaction chamber 111 at the flow rate a and stirring;
s2, continuously adding the slurry into the second reaction chamber 211 at a flow rate b and stirring, and simultaneously, continuously transporting the small particle nuclei formed in the first reaction chamber 111 into the second reaction chamber 211 at a flow rate c;
s3, performing filter pressing, washing and drying on the slurry in the second reaction chamber 211 to obtain a precursor;
wherein, the step S1 is performed simultaneously with the step S2, the pH value in the first reaction chamber 111 is greater than the pH value in the second reaction chamber 211, and the flow rate a is 0.01-0.3 times of the flow rate b, and the flow rate c is equal to the flow rate a.
In the above preparation process, since the step S1 is performed simultaneously with the step S2, the slurry in the first reaction chamber 111 forms small particle nuclei having good sphericity and compactness under the influence of the pH value in the first reaction chamber 111, the small particle nuclei are continuously transferred to the second reaction chamber 211, and simultaneously, the slurry is continuously supplied into the second reaction chamber 211, the slurry is stirred together with the small particle nuclei to control the particle size in the second reaction chamber 211, by setting the flow rate a, the flow rate b, and the flow rate c, when the flow rate a is 0.01 to 0.3 times of the flow rate b and the flow rate c is equal to the flow rate a, the sphericity of all the particle size particles can be ensured to be good, and the particle size of the finally formed precursor can be more easily controlled by adjusting the flow rate a, the flow rate b, and the flow rate c.
In addition, in the precursor preparation process, since the first reaction chamber 111 is used for preparing small-particle-size crystal nuclei, a higher pH value needs to be adjusted to control the growth of particle size; the particle size of the second reaction chamber 211 is controlled by the small particle size overflowing from the first reaction chamber 111, so that a lower pH suitable for particle size growth can be selected, and the pH is not adjusted during the reaction process, thereby ensuring a stable pH value. During the precursor preparation process, the pH of the first reaction chamber 111 is greater than the pH of the second reaction chamber 111.
The precursor preparation method adopts a continuous method to prepare the precursor, namely, the step S1 and the step S2 are carried out simultaneously and continuously conveying slurry, and the particle size of the second reaction chamber 211 is regulated and controlled through small-particle slurry on the one hand, and on the other hand, the small-particle slurry can be used as crystal nuclei to continue to grow, so that the production efficiency can be greatly improved on the premise of ensuring better sphericity of the final precursor, and the method is suitable for large-scale production.
Further, in step S1 and step S2, nitrogen gas is continuously introduced into the first reaction chamber 111 and the second reaction chamber 211, respectively, at a flow rate of 20 to 200L/h.
Further, in step S1, the stirring speed is 120-250 rpm; in step S2, the stirring speed is 50 to 250 rpm.
Further, in the step S1 and the step S2, the reaction temperature is 40-80 ℃.
Further, in the step S1, the reaction residence time is 20-200 h; in step S2, the reaction residence time is 5-50 h.
The precursor preparation method of the present invention is illustrated by the following comparison of three examples and one comparative example. The slurry comprises mixed salt, a precipitator and a complexing agent, wherein the mixed salt is prepared by adding nickel sulfate, cobalt sulfate and manganese sulfate into water together according to a certain proportion.
Example 1
Adding nickel sulfate, cobalt sulfate and manganese sulfate into water together according to the molar ratio of 8:1:1 to prepare 2.0mol/L mixed salt, preparing 32% liquid alkali into 10mol/L alkali liquor serving as a precipitator and 25% ammonia water serving as a complexing agent.
In the first kettle body 110D50The average particle size is 4.0 +/-0.3 um, the stirring speed is controlled to be 140rpm, the reaction pH value is 12.2 +/-0.1, the reaction ammonia content is 3.0 +/-0.3 g/L, the nitrogen flow rate is 50L/h, the reaction temperature is 50.0 +/-1.0 ℃, and the reaction residence time is 200 h. In the second kettle body 210D5010.0 +/-0.5 um, controlling the stirring speed to be 120rpm, controlling the reaction pH value to be 11.8 +/-0.1, controlling the reaction ammonia content to be 12.0 +/-1.0 g/L, controlling the nitrogen flow rate to be 50L/h, controlling the reaction temperature to be 50.0 +/-1.0 ℃ and controlling the reaction residence time to be 10 h.
The total inlet flow a of the mixed salt, the precipitator and the complexing agent of the first kettle body 110 is 0.2 times of the total inlet flow b of the mixed salt, the precipitator and the complexing agent of the second kettle body 210; the flow rate c of the slurry added into the second kettle 210 from the first kettle 110 is 0.2 times of the total inlet flow rate b of the mixed salt, the precipitator and the complexing agent of the second kettle 210.
The slurry prepared by the second kettle body 210 is subjected to filter pressing, washing and drying for 8 hours at 100 ℃, and D with good sphericity is finally obtained50Ni-Co-Mn hydroxide of 10.5. + -. 0.5. mu.m0.8Co0.1Mn0.1(OH)2As shown in fig. 2.
Example 2
Adding nickel sulfate, cobalt sulfate and manganese sulfate into water together according to the molar ratio of 6:2:2 to prepare 1.5mol/L mixed salt, preparing 32% liquid alkali into 8mol/L alkali liquor serving as a precipitator and 20% ammonia water serving as a complexing agent.
In the first kettle body 110D503.0 +/-0.3 um, controlling the stirring speed to be 170rpm, controlling the reaction pH value to be 12.4 +/-0.1, controlling the reaction ammonia content to be 2.0 +/-0.3 g/L, controlling the nitrogen flow rate to be 100L/h, controlling the reaction temperature to be 55.0 +/-1.0 ℃ and controlling the reaction residence time to be 100 h. In the second kettle body 210D5014.0 +/-0.5 um, controlling the stirring speed to be 80rpm, controlling the reaction pH value to be 11.3 +/-0.1, controlling the reaction ammonia content to be 8.0 +/-1.0 g/L, controlling the nitrogen flow rate to be 100L/h, controlling the reaction temperature to be 55.0 +/-1.0 ℃ and controlling the reaction residence time to be 10 h.
The total inlet flow of the mixed salt, the precipitator and the complexing agent of the first kettle body 110 is 0.1 time of the total inlet flow of the mixed salt, the precipitator and the complexing agent of the second kettle body 210; the flow rate of the slurry added into the second kettle 210 from the first kettle 110 is 0.1 times of the total inlet flow rate of the mixed salt, the precipitator and the complexing agent of the second kettle 210.
Carrying out filter pressing and washing on the slurry prepared by the second kettle body 210, and drying for 6h at 120 ℃ to finally obtain D50Ni-Co-Mn hydroxide of 14.0. + -. 0.5. mu.m0.6Co0.2Mn0.2(OH)2。
Example 3
Adding nickel sulfate, cobalt sulfate and manganese sulfate into water together according to a molar ratio of 5:2:3 to prepare 1.0mol/L mixed salt, preparing 32 mass percent of liquid alkali into 5mol/L alkali liquor serving as a precipitator, and taking 15 percent of ammonia water as a complexing agent.
In the first kettle body 110D502.0 +/-0.3 um, controlling the stirring speed to be 200rpm, controlling the reaction pH value to be 12.8 +/-0.1, and reacting ammoniaThe content is 1.5 +/-0.3 g/L, the nitrogen flow rate is 150L/h, the reaction temperature is 60.0 +/-1.0 ℃, and the reaction retention time is 100 h. In the second kettle body 210D5018.0 +/-0.5 um, controlling the stirring speed to be 65rpm, controlling the reaction pH value to be 10.8 +/-0.1, controlling the reaction ammonia content to be 6.0 +/-1.0 g/L, controlling the nitrogen flow rate to be 150L/h, controlling the reaction temperature to be 60.0 +/-1.0 ℃ and controlling the reaction residence time to be 5 h.
The total inlet flow of the mixed salt, the precipitator and the complexing agent of the first kettle body 110 is 0.05 times of the total inlet flow of the mixed salt, the precipitator and the complexing agent of the second kettle body 210; the flow rate of the slurry added into the second kettle 210 from the first kettle 110 is 0.05 times of the total inlet flow rate of the mixed salt, the precipitator and the complexing agent of the second kettle 210.
Carrying out filter pressing, washing and drying on the slurry prepared by the second kettle body 210 at 140 ℃ for 3 hours to finally obtain D50Ni cobalt manganese hydroxide of 18.0 + -0.5 μm0.5Co0.2Mn0.3(OH)2。
Comparative example 1
Adding nickel sulfate, cobalt sulfate and manganese sulfate into water together according to the molar ratio of 8:1:1 to prepare 2.0mol/L mixed salt, preparing 32% liquid alkali into 10mol/L alkali liquor serving as a precipitator and 25% ammonia water serving as a complexing agent.
Adopting a conventional reaction kettle only having a second kettle body, controlling the stirring speed to be 120rpm, the reaction ammonia content to be 12.0 +/-1.0 g/L, the nitrogen flow rate to be 50L/h, the reaction temperature to be 50.0 +/-1.0 ℃, the reaction residence time to be 10h, and keeping D by adjusting the reaction pH to be 12.2-12.550Is 10.0 +/-0.5 um.
Carrying out filter pressing, washing and drying on the slurry prepared by the reaction kettle for 8 hours at 100 ℃ to finally obtain D with good sphericity50Ni-Co-Mn hydroxide of 10.5. + -. 0.5. mu.m0.8Co0.1Mn0.1(OH)2As shown in FIG. 3, compared with the inventive method of this patent, the particle size of the precursor is not easy to control, and the number of small particles is large, and the sphericity and compactness are poor.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications may be made to the technical solution of the invention, and in order to avoid unnecessary repetition, various possible combinations of the invention will not be described further. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (10)
1. A precursor preparation system is characterized by comprising a first reaction kettle, a second reaction kettle, a conveying mechanism (300) and a control mechanism;
the first reaction kettle comprises a first kettle body (110), a first feeding assembly (120) and a first stirring assembly (130); the first kettle body (110) is provided with a first reaction chamber (111), the first feeding assembly (120) is configured to provide slurry into the first reaction chamber (111), and the first stirring assembly (130) is configured to stir the slurry in the first reaction chamber (111);
the second reaction kettle comprises a second kettle body (210), a second feeding assembly (220) and a second stirring assembly (230); the second kettle body (210) is provided with a second reaction chamber (211) and an overflow port (213) communicated with the second reaction chamber (211), the overflow port (213) is used for discharging a precursor, the second feeding assembly (220) is configured to be capable of providing slurry into the second reaction chamber (211), and the second stirring assembly (230) is configured to be capable of stirring the slurry in the second reaction chamber (211);
the conveying mechanism (300) is configured to continuously convey the small particle crystal nuclei in the first kettle body (110) into the second kettle body (210) in the whole process of preparing the precursor;
wherein the pH in the first reaction chamber (111) is greater than the pH in the second reaction chamber (211); the first feeding assembly (120) provides the slurry to the first reaction chamber (111) at a flow rate a, the second feeding assembly (220) provides the slurry to the second reaction chamber (211) at a flow rate b, the conveying mechanism (300) conveys small-particle crystal nuclei at a flow rate c, and the control mechanism is configured to control the first feeding assembly (120) and the second feeding assembly (220) such that: the flow rate a is 0.01-0.3 times of the flow rate b, and the flow rate c is equal to the flow rate a.
2. Precursor preparation system according to claim 1, wherein the first reaction vessel comprises-a first baffle (140), the first baffle (140) being arranged on an inner wall of the first vessel body (110); and/or the second reaction kettle comprises a second baffle plate (240), and the second baffle plate (240) is arranged on the inner wall of the second kettle body (210).
3. Precursor preparation system according to claim 1, wherein the bottom of the first tank (110) is provided with a first drain (112) communicating with the first reaction chamber (111) and/or the bottom of the second tank (210) is provided with a second drain (212) communicating with the second reaction chamber (211).
4. Precursor preparation system according to claim 1, wherein a first feed assembly (120) comprises a first gas inlet in communication with the first reaction chamber (111) for providing nitrogen to the first reaction chamber (111) and/or a second feed assembly (220) comprises a second gas inlet in communication with the second reaction chamber (211) for providing nitrogen to the second reaction chamber (211).
5. The precursor preparation system according to any one of claims 1-4, wherein the first reaction vessel comprises a first jacket (150) covering an outer wall of the first vessel body (110), and/or wherein the second reaction vessel comprises a second jacket (250) covering an outer wall of the second vessel body (210).
6. A precursor preparation method, characterized by comprising the steps of:
s1, continuously adding the slurry into the first reaction chamber (111) at a flow rate a and stirring;
s2, continuously adding the slurry into the second reaction chamber (211) at the flow rate b and stirring, and simultaneously, continuously delivering the small particle nuclei formed in the first reaction chamber (111) into the second reaction chamber (211) at the flow rate c;
s3, performing filter pressing, washing and drying on the slurry in the second reaction chamber (211) to obtain a precursor;
wherein, the step S1 is performed simultaneously with the step S2, the pH value in the first reaction chamber (111) is greater than the pH value in the second reaction chamber (211), the flow rate a is 0.01-0.3 times of the flow rate b, and the flow rate c is equal to the flow rate a.
7. The precursor preparation method according to claim 6, wherein nitrogen gas is continuously introduced into the first reaction chamber (111) and the second reaction chamber (211) in steps S1 and S2, respectively, at a flow rate of 20-200L/h.
8. The precursor preparation method according to claim 6, wherein in step S1, the stirring speed is 120-250 rpm; in step S2, the stirring speed is 50 to 250 rpm.
9. The precursor preparation method according to claim 6, wherein the reaction temperature in steps S1 and S2 is 40-80 ℃.
10. The precursor preparation method according to any one of claims 6 to 9, wherein in step S1, the reaction residence time is 20 to 200 hours; in step S2, the reaction residence time is 5-50 h.
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| CN113426398A (en) * | 2021-08-26 | 2021-09-24 | 广东芳源环保股份有限公司 | Production device and method of wide-distribution micro-powder-free ternary precursor |
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