CN116253368A - Preparation method and equipment of positive electrode material precursor - Google Patents
Preparation method and equipment of positive electrode material precursor Download PDFInfo
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- CN116253368A CN116253368A CN202310120069.7A CN202310120069A CN116253368A CN 116253368 A CN116253368 A CN 116253368A CN 202310120069 A CN202310120069 A CN 202310120069A CN 116253368 A CN116253368 A CN 116253368A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 239000000243 solution Substances 0.000 claims abstract description 150
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
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- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
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- 239000011656 manganese carbonate Substances 0.000 description 1
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/08—Apparatus therefor
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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
- B01J19/0053—Details of the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/14—Production of inert gas mixtures; Use of inert gases in general
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- 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
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Abstract
The application relates to the technical field of positive electrode material precursors, and provides a preparation method of a positive electrode material precursor, which comprises the following steps: providing a mixed metal salt solution, a precipitant solution, a complexing agent solution and a base solution; adding a metal salt solution, a precipitator solution and a complexing agent solution into a base solution at a certain flow rate to carry out coprecipitation reaction; when the coprecipitation reaction starts to produce primary particles having a particle diameter of 1 to 5 μm, the following cyclic process is performed: performing tangential flow filtration on intermediate reaction liquid generated by the coprecipitation reaction to obtain trapped liquid with trapped particle size larger than preset particle size, and then mixing the trapped liquid with mixed metal salt solution, precipitant solution and complexing agent solution which are added into base liquid to continue the coprecipitation reaction; and ending the coprecipitation reaction when precursor particles generated by the coprecipitation reaction in the circulation process reach the target particle size to obtain a final reaction liquid, and then carrying out solid-liquid separation on the final reaction liquid to obtain the positive electrode material precursor. The preparation method can rapidly increase the solid content of the reaction liquid.
Description
Technical Field
The application belongs to the technical field of positive electrode material precursors, and particularly relates to a preparation method and equipment of a positive electrode material precursor.
Background
The industrial production of the ternary precursor mainly adopts a coprecipitation method, but the ternary precursor with high sphericity is difficult to prepare by adopting the traditional coprecipitation method, and the morphology structure of the ternary positive electrode material is completely inherited to the ternary precursor, so that the performance exertion of the positive electrode material is directly influenced. Aiming at the sphericity problem, in many improved methods, the improvement of the solid content of the reaction liquid is the key for preparing the precursor with high sphericity.
At present, the effective method for regulating and controlling the solid content of the reaction liquid mainly comprises the methods of externally adding hard solid microspheres, natural sedimentation concentration, microporous filtration concentration, evaporation concentration and the like. However, the addition of hard solid microspheres to the reaction solution facilitates the introduction of impurities into the hot, strongly basic reaction environment. The natural sedimentation concentration method is simple, but is difficult to accurately control, and the solid content of a reaction system is easy to greatly fluctuate in a short time, so that the sphericity and the particle size distribution of a precursor product are influenced. Although the microporous filtration concentration technology can continuously concentrate, the component is complex, the structure is complicated, and in the use process, high-pressure air flow is required to be introduced to sweep the surface of the filter medium to prevent scale deposition, and the introduction of the high-pressure air flow can disturb the flow field of a reaction system, so that reaction non-uniformity is easy to cause; in practical application, the fault rate is high, and potential safety hazards which are difficult to eliminate exist. The evaporation concentration method is easy to cause obvious disturbance to the concentration of the precipitant and the complexing agent in the reaction system, thereby influencing the proportion of precursor elements and the morphology of particles.
Therefore, it is necessary to develop a method and apparatus for preparing a positive electrode material precursor having a high sphericity.
Disclosure of Invention
The invention aims to provide a preparation method and equipment of a positive electrode material precursor, and aims to solve the problem that the existing preparation method and equipment of the positive electrode material precursor cannot continuously and accurately control the solid content of a reaction system, so that the positive electrode material precursor with high sphericity is difficult to prepare.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a positive electrode material precursor, including:
providing a mixed metal salt solution, a precipitant solution, a complexing agent solution and a base solution;
adding the mixed metal salt solution, the precipitator solution and the complexing agent solution into the base solution at a certain flow rate to carry out coprecipitation reaction;
when the coprecipitation reaction starts to produce primary particles having a particle diameter of 1 to 5 μm, the following cyclic process is performed: performing tangential flow filtration on intermediate reaction liquid generated by the coprecipitation reaction to obtain trapped liquid with trapped particle size larger than preset particle size, and then mixing the trapped liquid with mixed metal salt solution, precipitant solution and complexing agent solution which are added into base liquid to continue the coprecipitation reaction;
and ending the coprecipitation reaction when precursor particles generated by the coprecipitation reaction in the circulation process reach the target particle size to obtain a final reaction liquid, and then carrying out solid-liquid separation on the final reaction liquid to obtain the positive electrode material precursor.
In a second aspect, the present application provides a device for implementing a method for preparing a positive electrode material precursor provided in the present application, including:
the reaction device comprises a reaction container and a reaction unit, wherein the reaction container is used for containing mixed metal salt solution, precipitant solution and complexing agent solution and reacting to generate a positive electrode material precursor;
the tangential filtration device is used for carrying out tangential flow filtration treatment on intermediate reaction liquid which generates a precursor of the positive electrode material in the reaction container to obtain trapped liquid and filtrate;
and the first conveying device is used for conveying the intermediate reaction liquid to the tangential filtering device, conveying the trapped liquid to the reaction container and continuously reacting with the mixed metal salt solution, the precipitant solution and the complexing agent solution.
Compared with the prior art, the application has the following beneficial effects:
according to the preparation method of the positive electrode material precursor, the mixed metal salt solution, the precipitant solution and the complexing agent solution are added into the base solution at a certain flow rate to carry out the coprecipitation reaction, when the coprecipitation reaction generates initial particles with the particle size of 1-5 mu m, the intermediate reaction solution generated by the coprecipitation reaction is subjected to tangential flow filtration treatment to obtain the trapped solution, and then the trapped solution is mixed with the mixed metal salt solution, the precipitant solution and the complexing agent solution which are being added to continue the circulation process of the coprecipitation reaction, so that the solid content of the intermediate reaction solution can be quickly and accurately controlled.
According to the equipment for preparing the positive electrode material precursor, provided by the second aspect, the preparation method of the positive electrode material precursor can be realized, the intermediate reaction liquid for generating the positive electrode material precursor in the reaction container is conveyed to the tangential filtering device through the first conveying device to be subjected to tangential flow filtering treatment, the obtained trapped liquid is conveyed back to the reaction container and continuously reacts with the mixed metal salt solution, the precipitant solution and the complexing agent solution which are being added, and meanwhile, the filtrate is discharged, so that continuous quantitative concentration of the intermediate reaction liquid can be realized. Through adopting tangential filter equipment to realize carrying out tangential flow filtration to intermediate reaction liquid, let the flow direction and the filtration direction of intermediate reaction liquid perpendicular to carry out circulation flow under first conveyor's drive, not only filter effectually, through constantly "washing out" filter media in the filtration process moreover, can prevent that big granule from blockking up filter media, thereby need not to additionally add external blowback equipment and clean filter media surface, equipment cost is lower.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a process flow diagram of a method for preparing a precursor of a positive electrode material according to an embodiment of the present application;
fig. 2 is a schematic structural diagram of an apparatus for preparing a precursor of a positive electrode material according to an embodiment of the present application;
FIG. 3 is a scanning electron microscope image of a positive electrode material precursor prepared by the method for preparing a positive electrode material precursor provided in example 1 of the present application;
fig. 4 is a scanning electron microscope image of the positive electrode material precursor prepared by the preparation method of the positive electrode material precursor provided in example 2 of the present application;
FIG. 5 is a scanning electron microscope image of a positive electrode material precursor prepared by the positive electrode material precursor preparation method provided in comparative example 1 of the present application;
wherein, each reference sign in the figure:
1-reaction device, 11-reaction vessel, 12-intermediate reaction liquid outlet, 13-trapped liquid inlet, 14-raw material inlet, 15-product outlet, 2-tangential filter, 21-intermediate reaction liquid inlet, 22-trapped liquid outlet, 23-filtrate outlet, 3-first conveyer and 4-second conveyer.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
A first aspect of the present application provides a method for preparing a precursor of a cathode material, as shown in fig. 1, including:
s01: providing a mixed metal salt solution, a precipitant solution, a complexing agent solution and a base solution;
s02: adding the mixed metal salt solution, the precipitator solution and the complexing agent solution into the base solution at a certain flow rate to carry out coprecipitation reaction;
s03: when the coprecipitation reaction starts to produce primary particles having a particle diameter of 1 to 5 μm, the following cyclic process is performed: performing tangential flow filtration on intermediate reaction liquid generated by the coprecipitation reaction to obtain trapped liquid with trapped particle size larger than preset particle size, and then mixing the trapped liquid with mixed metal salt solution, precipitant solution and complexing agent solution which are added into base liquid to continue the coprecipitation reaction;
s04: and ending the coprecipitation reaction when precursor particles generated by the coprecipitation reaction in the circulation process reach the target particle size to obtain a final reaction liquid, and then carrying out solid-liquid separation on the final reaction liquid to obtain the positive electrode material precursor.
According to the preparation method of the positive electrode material precursor, the mixed metal salt solution, the precipitant solution and the complexing agent solution are added into the base solution at a certain flow rate to carry out the coprecipitation reaction, when the coprecipitation reaction generates initial particles with the particle size of 1-5 mu m, the intermediate reaction solution generated by the coprecipitation reaction is subjected to tangential flow filtration treatment to obtain the trapped solution, and then the trapped solution is mixed with the mixed metal salt solution, the precipitant solution and the complexing agent solution which are being added to continue the circulation process of the coprecipitation reaction, so that the solid content of the intermediate reaction solution can be quickly and accurately controlled.
In the above step S01, the mixed metal salt solution contains at least Ni element and Mn element, and for example, the mixed metal salt solution may be a nickel-manganese mixed salt solution, a nickel-cobalt-manganese mixed salt solution, or the like, or a nickel-manganese mixed salt solution containing Mg, al, ti, or the like, or a nickel-cobalt-manganese mixed salt solution containing Mg, al, ti, or the like. The specific nickel-cobalt-manganese mixed salt solution can be prepared by mixing nickel salt, cobalt salt and manganese salt, wherein the nickel salt can be nickel sulfate, nickel carbonate, nickel nitrate and the like, the manganese salt can be manganese sulfate, manganese carbonate, manganese nitrate and the like, and the cobalt salt can be cobalt sulfate, cobalt carbonate, cobalt nitrate and the like. The precipitant includes at least one of sodium hydroxide and potassium hydroxide, for example, the precipitant is sodium hydroxide. The complexing agent comprises at least one of ammonia water, ammonium sulfate and ammonium chloride, for example, the complexing agent is ammonia water. The base solution comprises pure water, sodium hydroxide solution and ammonia water solution, and specifically, the base solution can be formed by adding a proper amount of pure water, naOH solution and ammonia water solution into a reaction container and mixing. The pH of the base solution is 10 to 13, preferably 11 to 12.
In the step S02, three peristaltic pumps may be used to add the mixed metal salt solution, the precipitant solution, and the complexing agent solution into the base solution of the reaction vessel at a certain flow rate, respectively, to perform the coprecipitation reaction. The flow rate of the metal salt solution is 150-400 mL/h, such as 150mL/h, 200mL/h, 250mL/h, 300mL/h, 350mL/h, 400mL/h, etc., the flow rate of the precipitant solution can be automatically regulated by a main control system according to the pH value of the reaction system, and the flow rate of the complexing agent solution can be regulated according to the ammonia concentration of the reaction system. The conditions for the coprecipitation reaction include: the temperature is 45-60 ℃, the stirring rotation speed is 800-1500 rpm/min, the pH value is 10.5-12, for example, the temperature can be 45 ℃, 50 ℃, 55 ℃, 60 ℃, the rotation speed can be 800rpm/min, 1000rpm/min, 1200rpm/min, 1500rpm/min, and the like, and the pH value can be 10.5, 10.6, 10.7, 10.8, 10.9, 12, and the like. The conditions for the coprecipitation reaction also include an ammonia concentration of 3 to 5g/L, for example, 3g/L, 4g/L, 5g/L, etc.
In the above step S03, the intermediate reaction solution is a reaction solution which is being fed and is produced by the coprecipitation reaction. When the coprecipitation reaction starts to produce primary particles having a particle diameter of 1 to 5. Mu.m, the solid content of the intermediate reaction liquid at this time is 50 to 100g/L. After at least one cycle of the cycle process, the method further comprises the following steps: and (3) measuring the solid content of the intermediate reaction liquid generated by the coprecipitation reaction, and adjusting the flow rate of the intermediate reaction liquid subjected to tangential flow filtration treatment when the solid content of the intermediate reaction liquid reaches the preset solid content so as to maintain the solid content of the intermediate reaction liquid within the preset solid content range. The preset solid content of the intermediate reaction liquid can be set according to the actual production conditions or requirements, and the specific preset solid content of the intermediate reaction liquid can be 200-700 g/L. And (3) carrying out solid content measurement on the intermediate reaction liquid after at least one cycle of the circulating process so as to determine whether the solid content of the intermediate reaction liquid reaches the preset solid content, thereby adjusting the flow rate of the intermediate reaction liquid subjected to tangential flow filtration treatment, stabilizing the solid content of the intermediate reaction liquid within the preset solid content range, and continuing the circulating process of the step S03.
In the embodiment, the flow rate of the intermediate reaction liquid subjected to the tangential flow filtration treatment is 2000-4000L/h, and the tangential flow filtration treatment is performed on the intermediate reaction liquid within the flow rate range, so that the solid content of the intermediate reaction liquid can be ensured to be increased to the preset solid content in a short time.
In the embodiment, the preset particle size is 0.5 mu m, and the intermediate reaction liquid generated by the coprecipitation reaction is subjected to tangential flow filtration treatment to obtain the trapped liquid with the trapped particle size larger than the preset particle size.
In step S04, the final reaction solution is a reaction solution after the completion or stop of the coprecipitation reaction, and the solid-liquid separation is for the purpose of separating the positive electrode material precursor from the solvent, and thus, any separation method capable of separating the precursor and the solvent is within the scope disclosed in the present embodiment, and may be, for example, filtration, centrifugation, or other methods. The target particle size of the precursor of the positive electrode material is 3-8 mu m.
In an embodiment, the step of solid-liquid separating the final reaction liquid further comprises a step of aging the final reaction liquid. The aging treatment is to stabilize the precursor particles of the positive electrode material so that the precursor particles are easier to wash. After the final reaction liquid is aged, the solid product is washed, and the washing treatment is used for purifying the positive electrode material precursor so as to improve the purity of the positive electrode material precursor.
In the embodiment, after the step of solid-liquid separating the final reaction liquid, the positive electrode material precursor after the solid-liquid separation may be subjected to a treatment such as drying, to remove moisture, thereby further improving the purity of the positive electrode material precursor.
A second aspect of the embodiments of the present application provides an apparatus for preparing a precursor of a positive electrode material, as shown in fig. 2, where the apparatus is configured to implement a method for preparing a precursor of a positive electrode material provided herein, including:
the reaction device 1 comprises a reaction container 11 for containing a mixed metal salt solution, a precipitant solution and a complexing agent solution and reacting to generate a positive electrode material precursor;
the tangential filtration device 2 is used for carrying out tangential flow filtration treatment on the intermediate reaction liquid which generates the precursor of the positive electrode material in the reaction container 11 to obtain trapped liquid and filtrate;
a first conveying device 3 for conveying the intermediate reaction liquid into the tangential filtration device 2 and conveying the trapped liquid into the reaction vessel 11 and continuing the reaction with the mixed metal salt solution, the precipitant solution and the complexing agent solution.
In the embodiment, the reaction device 1 included in the apparatus for preparing a precursor of a positive electrode material of the embodiment of the present application includes a reaction vessel 11, an intermediate reaction liquid discharge port 12 for discharging an intermediate reaction liquid in the reaction vessel 11, and a retentate liquid feed port 13 for adding a retentate liquid into the reaction vessel, and both the intermediate reaction liquid discharge port 12 and the retentate liquid feed port 13 are in communication with the reaction vessel 11. Or the reaction vessel 11 contained in the reaction device 1 is directly provided with an intermediate reaction liquid discharge port 12 for discharging the intermediate reaction liquid in the reaction vessel 11 and a trapped liquid feed port 13 for adding the trapped liquid into the reaction vessel 11, the intermediate reaction liquid discharge port 12 of the reaction vessel 11 is communicated with the liquid feed port of the first conveying device 3 so as to convey the intermediate reaction liquid of the reaction vessel 11 into the tangential filtration device 2, specifically into the tangential filtration device 2 and perform tangential flow filtration treatment, and the trapped liquid feed port 13 of the reaction vessel 11 is communicated with the trapped liquid discharge port 22 of the tangential filtration device 2 so as to convey the trapped liquid obtained by the tangential flow filtration of the tangential filtration device 2 into the reaction vessel 11 and continuously react with the mixed metal salt solution, the precipitant solution and the complexing agent solution. In the embodiment, the reaction vessel 11 included in the reaction apparatus 1 is further provided with a raw material feed port 14 for feeding a mixed metal salt solution, a precipitant solution and a complexing agent solution into the reaction vessel 11 and a product discharge port 15 for discharging a positive electrode material precursor.
In the embodiment, the tangential filtration device 2 included in the apparatus for producing a cathode material precursor of the embodiment of the present application is provided with an intermediate reaction liquid feed port 21 for adding an intermediate reaction liquid into the tangential filtration device 2, a retentate liquid discharge port 22 for discharging retentate liquid of the tangential filtration device 2, and a filtrate liquid discharge port 23 for discharging filtrate liquid of the tangential filtration device 2. The intermediate reaction liquid feed port 21 of the tangential filtration device 2 is communicated with the liquid outlet of the first conveying device 3 so as to convey the intermediate reaction liquid of the reaction vessel 11 into the tangential filtration device 2, in particular to convey the intermediate reaction liquid into the tangential filtration device 2 for tangential flow filtration treatment, the trapped liquid discharge port 22 of the tangential filtration device 2 is communicated with the trapped liquid feed port 13 of the reaction vessel 1 so as to convey the trapped liquid obtained by the tangential filtration device 2 for tangential flow filtration back into the reaction vessel 11, and the trapped liquid is communicated with the liquid inlet of the second conveying device 4 so as to discharge the filtrate obtained by the tangential flow filtration of the tangential filtration device 2, and the mixed metal salt solution, the precipitant solution and the complexing agent solution for continuous reaction. In the embodiment, the tangential filtration device 2 is provided with a filter membrane with a pore diameter of 50-500 nm so as to facilitate the filtration and discharge of the alkaline waste liquid in the intermediate reaction liquid, and obtain the trapped liquid with a particle diameter of more than 0.5 μm.
In an embodiment, the first conveying device 3 included in the apparatus for preparing a precursor of a cathode material according to the embodiment of the present application includes a first pump, where the first pump is provided with a liquid inlet and a liquid outlet for conveying an intermediate reaction liquid, the liquid inlet of the first pump is communicated with the intermediate reaction liquid outlet 12 of the reaction vessel 11, and the liquid outlet of the first pump is communicated with the intermediate reaction liquid inlet 21 of the tangential filtration device 2, so as to convey the intermediate reaction liquid of the reaction vessel 11 into the tangential filtration device 2, specifically into the tangential filtration device 2, and perform tangential flow filtration treatment.
In an embodiment, the apparatus for preparing a precursor of a positive electrode material according to the embodiment of the present application is further provided with a second transporting device 4 for discharging the filtrate. The second conveying device 4 comprises a second pump provided with a liquid inlet and a liquid outlet for conveying out filtrate obtained by tangential flow filtration of the tangential filter device 2, the liquid inlet of the second pump being in communication with the filtrate outlet 23 of the tangential filter device 2, and the liquid outlet of the second pump being in communication with the waste liquid inlet so as to facilitate discharge of filtrate obtained by tangential flow filtration of the tangential filter device.
In an embodiment, the apparatus for preparing a precursor of a cathode material according to the embodiment of the present application is further provided with a particle size detection device for detecting the particle size of the particles contained in the intermediate reaction liquid, so as to determine whether the particle size of the particles reaches 1 to 5 μm.
Therefore, based on the device included in the apparatus for preparing a precursor of a cathode material according to the above-mentioned application embodiment, the apparatus for preparing a precursor of a cathode material according to the embodiment of the present application can implement a method for preparing a precursor of a cathode material, and the intermediate reaction liquid for generating a precursor of a cathode material in the reaction vessel 11 is conveyed to the tangential filtration device 2 by the first conveying device 3 to perform tangential flow filtration treatment, and the obtained trapped liquid is conveyed back to the reaction vessel 11 and continuously reacts with the mixed metal salt solution, the precipitant solution and the complexing agent solution, and the filtrate is discharged by the second conveying device 4, so that continuous quantitative concentration of the intermediate reaction liquid can be implemented. Therefore, the tangential flow filtration is carried out on the intermediate reaction liquid by adopting the tangential filtration device 2, so that the flow direction of the intermediate reaction liquid is vertical to the filtration direction, and the intermediate reaction liquid circularly flows under the drive of the first conveying device 3, so that the filtration effect is good, and large particles can be prevented from blocking the filtration medium by continuously flushing the filtration medium in the filtration process, so that external back flushing equipment is not required to be additionally arranged to clean the surface of the filtration medium, and the equipment cost is lower.
The following description is made with reference to specific embodiments.
Example 1
The embodiment of the application provides a preparation method of a positive electrode material precursor, which comprises the following steps:
s11: coSO is carried out 4 ·7H 2 O、MnSO 4 ·4H 2 O and NiSO 4 ·6H 2 Mixing O to prepare nickel-cobalt-manganese mixed salt solution (the molar ratio of Ni, co and Mn is 92:4:4), preparing NaOH solution with the molar concentration of 5-11 mol/L, preparing ammonia water solution with the mass fraction of 10% -28%, and adding proper amounts of pure water, the NaOH solution and the ammonia water solution into a continuously stirred reaction container (5L) to prepare base solution;
s12: introducing nitrogen into the reaction vessel as a protective atmosphere, regulating the rotating speed of a stirring paddle to 800rpm/min, introducing a nickel-cobalt-manganese mixed salt solution, a NaOH solution and an ammonia water solution into a base solution of the reaction vessel at a certain flow rate (the flow rate of the nickel-cobalt-manganese mixed salt solution is 150 mL/h), controlling the pH value of the reaction system to be 10.5, the ammonia concentration to be 3g/L and the jacket temperature to be 45 ℃, and performing coprecipitation reaction;
s13: in the continuous feeding, when the particle size of the initial particles in the reaction vessel is 1-2 mu m, the solid content of the intermediate reaction liquid is 60g/L at the moment, a tangential filtration device is started, a filtrate outlet is opened, filtrate is continuously discharged, the pump speed of a first pump (a metering pump) is regulated to ensure that the flow rate of the intermediate reaction liquid subjected to the tangential flow filtration treatment is 2000L/h, and the circulation is carried out for 1h, so that the solid content in the reaction vessel is rapidly increased and reaches 260g/L;
s14: controlling the pump speed of the first pump and the second pump to ensure that the feeding amount of the nickel-cobalt-manganese mixed salt solution, the NaOH solution and the ammonia water solution and the discharge amount of the filtrate are in relative balance speed, keeping the liquid level in the reaction vessel constant, continuing the coprecipitation reaction, stopping feeding after the reaction is performed for a plurality of hours, closing the tangential filtering device and the first pump, and entering an aging stage; and (3) after aging for a certain time, collecting materials at the bottom of the reaction container, and then washing, filtering, drying and the like to obtain the anode material precursor.
Example 2
The embodiment of the application provides a preparation method of a positive electrode material precursor, which comprises the following steps:
s21: coSO is carried out 4 ·7H 2 O、MnSO 4 ·4H 2 O and NiSO 4 ·6H 2 Mixing O to prepare nickel-cobalt-manganese mixed salt solution (the molar ratio of Ni, co and Mn is 92:4:4), preparing NaOH solution with the molar concentration of 5-11 mol/L, preparing ammonia water solution with the mass fraction of 10% -28%, and adding proper amounts of pure water, the NaOH solution and the ammonia water solution into a continuously stirred reaction container (5L) to prepare base solution;
s22: introducing nitrogen into the reaction vessel as a protective atmosphere, regulating the rotating speed of a stirring paddle to 1000rpm/min, introducing a nickel-cobalt-manganese mixed salt solution, a NaOH solution and an ammonia water solution into a base solution of the reaction vessel at a certain flow rate (the flow rate of the nickel-cobalt-manganese mixed salt solution is 200 mL/h), controlling the pH value of the reaction system to be 11, the ammonia concentration to be 3.5g/L, and the jacket temperature to be 50 ℃ to carry out coprecipitation reaction;
s23: in the continuous feeding, when the particle size of the initial particles in the reaction vessel is 3-5 mu m, the solid content of the intermediate reaction liquid is 60g/L at the moment, a tangential filtration device is started, a filtrate outlet is opened, filtrate is continuously discharged, the pump speed of a first pump is regulated to enable the flow rate of the intermediate reaction liquid subjected to tangential flow filtration treatment to be 4000L/h, and the circulation is carried out for 1h, so that the solid content in the reaction vessel is rapidly increased and reaches 310g/L;
s24: controlling the pump speed of the first pump and the second pump to ensure that the feeding amount of the nickel-cobalt-manganese mixed salt solution, the NaOH solution and the ammonia water solution and the discharge amount of the filtrate are in relative balance speed, keeping the liquid level in the reactor constant, continuing the coprecipitation reaction, stopping feeding after the reaction is performed for a plurality of hours, closing the tangential filtering device and the first pump, and entering an aging stage; and (3) after aging for a certain time, collecting materials at the bottom of the reaction container, and then washing, filtering, drying and the like to obtain the anode material precursor.
Example 3
The embodiment of the application provides a preparation method of a positive electrode material precursor, which comprises the following steps:
s31: coSO is carried out 4 ·7H 2 O、MnSO 4 ·4H 2 O and NiSO 4 ·6H 2 Mixing O to prepare nickel-cobalt-manganese mixed salt solution (the molar ratio of Ni, co and Mn is 92:4:4), preparing NaOH solution with the molar concentration of 5-11 mol/L, preparing ammonia water solution with the mass fraction of 10% -28%, and adding proper amounts of pure water, the NaOH solution and the ammonia water solution into a continuously stirred reaction container (5L) to prepare base solution;
s32: introducing nitrogen into the reaction vessel as a protective atmosphere, regulating the rotating speed of a stirring paddle to 800rpm/min, introducing a nickel-cobalt-manganese mixed salt solution, a NaOH solution and an ammonia water solution into a base solution of the reaction vessel at a certain flow rate (the flow rate of the nickel-cobalt-manganese mixed salt solution is 300 mL/h), controlling the pH value of the reaction system to be 11, the ammonia concentration to be 4g/L, and the jacket temperature to be 50 ℃ to carry out coprecipitation reaction;
s33: in the continuous feeding, when the particle size of the initial particles in the reaction vessel is 1-2 mu m, the solid content of the intermediate reaction liquid is 60g/L, a tangential filtration device is started, a filtrate outlet is opened, filtrate is continuously discharged, the pump speed of a first pump is regulated to ensure that the flow rate of the intermediate reaction liquid subjected to tangential flow filtration treatment is 3000L/h, and the circulation is carried out for 1h, so that the solid content in the reaction vessel is rapidly increased and reaches 340g/L;
s34: controlling the pump speed of the first pump and the second pump to ensure that the feeding amount of the nickel-cobalt-manganese mixed salt solution, the NaOH solution and the ammonia water solution and the discharge amount of the filtrate are in relative balance speed, keeping the liquid level in the reactor constant, continuing the coprecipitation reaction, stopping feeding after the reaction is performed for a plurality of hours, closing the tangential filtering device and the first pump, and entering an aging stage; and (3) after aging for a certain time, collecting materials at the bottom of the reaction container, and then washing, filtering, drying and the like to obtain the anode material precursor.
Example 4
The embodiment of the application provides a preparation method of a positive electrode material precursor, which comprises the following steps:
s41: coSO is carried out 4 ·7H 2 O、MnSO 4 ·4H 2 O、NiSO 4 ·6H 2 Mixing O and MgSO4.7H2O to prepare a magnesium-doped nickel-cobalt-manganese mixed salt solution (the molar ratio of Ni, co, mn and Mg is 92:4:3.8:0.2), preparing a NaOH solution with the molar concentration of 5-11 mol/L, preparing an ammonia solution with the mass fraction of 10% -28%, and adding proper amounts of pure water, the NaOH solution and the ammonia solution into a continuously stirred reaction vessel (5L) to prepare a base solution;
s42: introducing nitrogen into the reaction vessel as a protective atmosphere, regulating the rotating speed of a stirring paddle to 1500rpm/min, introducing a magnesium-doped nickel-cobalt-manganese mixed salt solution, a NaOH solution and an ammonia water solution into a base solution of the reaction vessel at a certain flow rate (the flow rate of the magnesium-doped nickel-cobalt-manganese mixed salt solution is 400 mL/h), controlling the pH value of the reaction system to be 12, the ammonia concentration to be 5g/L, and the jacket temperature to be 60 ℃ to perform coprecipitation reaction;
s43: in the continuous feeding, when the particle size of the initial particles in the reaction vessel is 3-5 mu m, the solid content of the intermediate reaction liquid is 60g/L at the moment, a tangential filtration device is started, a filtrate outlet is opened, filtrate is continuously discharged, the pump speed of a first pump is regulated to enable the flow rate of the intermediate reaction liquid subjected to tangential flow filtration treatment to be 4000L/h, and the circulation is carried out for 1h, so that the solid content in the reaction vessel is rapidly increased and reaches 430g/L;
s44: controlling the pump speed of the first pump and the second pump, so that the feeding amount of the magnesium-doped nickel-cobalt-manganese mixed salt solution, the NaOH solution and the ammonia water solution and the discharge amount of the filtrate are in relatively balanced speed, the liquid level in the reactor is kept constant, the coprecipitation reaction is continuously carried out, after the reaction is carried out for a plurality of hours, the feeding is stopped, the tangential filtering device and the first pump are closed, and the ageing stage is carried out; and (3) after aging for a certain time, collecting materials at the bottom of the reaction container, and then washing, filtering, drying and the like to obtain the anode material precursor.
Comparative example 1
The comparative example provides a method for preparing a positive electrode material precursor, comprising the following steps:
s1: coSO is carried out 4 ·7H 2 O、MnSO 4 ·4H 2 O and NiSO 4 ·6H 2 Mixing O to prepare nickel-cobalt-manganese mixed salt solution (the molar ratio of Ni, co and Mn is 92:4:4), preparing NaOH solution with the molar concentration of 5-11 mol/L, preparing ammonia water solution with the mass fraction of 10% -28%, and adding proper amounts of pure water, the NaOH solution and the ammonia water solution into a continuously stirred reaction container (5L) to prepare base solution;
s2: introducing nitrogen into the reaction vessel as a protective atmosphere, regulating the rotating speed of a stirring paddle to 1500rpm/min, introducing a nickel-cobalt-manganese mixed salt solution, a NaOH solution and an ammonia water solution into a base solution of the reaction vessel at a certain flow rate (the flow rate of the nickel-cobalt-manganese mixed salt solution is 400 mL/h), controlling the pH value of a reaction system to be 12, the ammonia concentration to be 5g/L and the jacket temperature to be 60 ℃, performing coprecipitation reaction, stopping feeding after reacting for a plurality of hours, and entering an aging stage; and (3) after aging for a certain time, collecting materials at the bottom of the reaction container, and then washing, filtering, drying and the like to obtain the anode material precursor.
Correlation performance test analysis:
the microscopic morphologies of the positive electrode material precursors prepared in examples 1 to 2 and comparative example 1 were observed by using a scanning electron microscope, and the test results are shown in fig. 3 to 5. Fig. 3 is a scanning electron microscope image of the positive electrode material precursor prepared in example 1, fig. 4 is a scanning electron microscope image of the positive electrode material precursor prepared in example 2, and fig. 5 is a scanning electron microscope image of the positive electrode material precursor prepared in comparative example 1.
As can be seen from fig. 3 to 5, the positive electrode material precursor particles in fig. 3 and 4 have good uniformity, regular morphology and high sphericity, however, the positive electrode material precursor particles in fig. 5 have very uneven size and low sphericity, which illustrates that in the embodiment of the present application, the intermediate reaction solution generated by the coprecipitation reaction is subjected to tangential flow filtration to obtain a trapped solution, and then the trapped solution is mixed with the mixed metal salt solution, the precipitant solution and the complexing agent solution which are being added to continue the circulation process of the coprecipitation reaction, so that concentration of the intermediate reaction solution can be achieved, and the solid content of the intermediate reaction solution can be rapidly increased and precisely controlled; in the dynamic continuous coprecipitation reaction process, the quantitative increase of the solid content is helpful to increase the collision probability among particles, so that small seed crystals generated in the coprecipitation reaction are effectively dispersed under the condition of high collision probability, the phenomenon of agglomeration of the small seed crystals can be avoided, and each small seed crystal can independently grow; and under the action of strong stirring, the seed crystal is repeatedly collided to carry out surface polishing, so that the prepared positive electrode material precursor has good particle size uniformity, regular morphology and high sphericity.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (10)
1. The preparation method of the positive electrode material precursor is characterized by comprising the following steps:
providing a mixed metal salt solution, a precipitant solution, a complexing agent solution and a base solution;
adding the mixed metal salt solution, the precipitator solution and the complexing agent solution into the base solution at a certain flow rate to perform coprecipitation reaction;
when the coprecipitation reaction starts to produce primary particles having a particle diameter of 1 to 5 μm, the following cycle is performed: performing tangential flow filtration treatment on the intermediate reaction liquid generated by the coprecipitation reaction to obtain trapped liquid with trapped particle size larger than a preset particle size, and then mixing the trapped liquid with the mixed metal salt solution, the precipitant solution and the complexing agent solution which are added into the base liquid to continue the coprecipitation reaction;
ending the coprecipitation reaction to obtain a final reaction liquid when precursor particles generated by the coprecipitation reaction in the circulation process reach the target particle size, and then carrying out solid-liquid separation on the final reaction liquid to obtain a positive electrode material precursor.
2. The method of claim 1, wherein after at least one cycle of the cycling process, further comprising:
and (3) measuring the solid content of the intermediate reaction liquid generated by the coprecipitation reaction, and when the solid content of the intermediate reaction liquid reaches a preset solid content, regulating the flow rate of the intermediate reaction liquid subjected to the tangential flow filtration treatment so as to maintain the solid content of the intermediate reaction liquid within the preset solid content range.
3. The method of manufacturing of claim 2, wherein at least one of the following conditions is satisfied:
the preset particle size is 0.5 mu m;
the preset solid content of the intermediate reaction liquid is 200-700 g/L;
the flow rate of the intermediate reaction liquid for the tangential flow filtration treatment is 2000-4000L/h.
4. The method according to claim 1, wherein in the step of adding the mixed metal salt solution, the precipitant solution and the complexing agent solution to the base solution at a flow rate to perform a coprecipitation reaction, the flow rate of the mixed metal salt solution is 150 to 400mL/h; and/or
The target particle diameter is 3-8 mu m.
5. The method according to any one of claims 1 to 4, wherein the conditions for the coprecipitation reaction include: the temperature is 45-60 ℃, the stirring speed is 800-1500 rpm/min, and the pH value is 10.5-12.
6. The method according to any one of claims 1 to 4, wherein at least one of the following conditions is satisfied:
the mixed metal salt solution at least comprises Ni element and Mn element;
the precipitant comprises at least one of sodium hydroxide and potassium hydroxide;
the complexing agent comprises at least one of ammonia water, ammonium sulfate and ammonium chloride.
7. The process according to any one of claims 1 to 4, further comprising aging the final reaction solution before solid-liquid separation of the final reaction solution.
8. An apparatus for preparing a positive electrode material precursor, characterized in that the apparatus is used to realize the preparation method of a positive electrode material precursor according to any one of claims 1 to 7, comprising:
the reaction device comprises a reaction container and a reaction unit, wherein the reaction container is used for containing mixed metal salt solution, precipitant solution and complexing agent solution and reacting to generate a positive electrode material precursor;
the tangential filtration device is used for carrying out tangential flow filtration treatment on the intermediate reaction liquid for generating the precursor of the positive electrode material in the reaction container to obtain trapped liquid and filtrate;
and the first conveying device is used for conveying the intermediate reaction liquid into the tangential filtering device, conveying the trapped liquid into the reaction container and continuously reacting with the mixed metal salt solution, the precipitant solution and the complexing agent solution.
9. The apparatus of claim 8, wherein at least one of the following conditions is satisfied:
the reaction container is provided with an intermediate reaction liquid outlet and a trapped liquid inlet;
the first conveying device comprises a first pump, and a liquid inlet of the first pump is communicated with the intermediate reaction liquid outlet;
the tangential filtration device is provided with an intermediate reaction liquid feed inlet, a trapped liquid discharge outlet and a filtrate discharge outlet; wherein the intermediate reaction liquid feed inlet is communicated with the liquid outlet of the first pump, and the trapped liquid discharge outlet is communicated with the trapped liquid feed inlet;
the device is also provided with a second conveying device for discharging the filtrate;
the equipment is also provided with a particle size detection device for detecting the particle size of the particles contained in the intermediate reaction liquid.
10. The apparatus of claim 9, wherein at least one of the following conditions is satisfied:
the reaction container is also provided with a raw material feeding port for adding the mixed metal salt solution, the precipitator solution and the complexing agent solution and a product discharge port for discharging the positive electrode material precursor;
the tangential filtration device is provided with a filter membrane, and the aperture of the filter membrane is 50-500 nm;
the second conveying device comprises a second pump, a liquid inlet of the second pump is communicated with the filtrate outlet, and a liquid outlet of the second pump is communicated with the waste liquid inlet.
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