CN112441625A - Method and equipment for preparing lithium battery anode material precursor by step-by-step nucleation method - Google Patents

Method and equipment for preparing lithium battery anode material precursor by step-by-step nucleation method Download PDF

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CN112441625A
CN112441625A CN202011176418.XA CN202011176418A CN112441625A CN 112441625 A CN112441625 A CN 112441625A CN 202011176418 A CN202011176418 A CN 202011176418A CN 112441625 A CN112441625 A CN 112441625A
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pipeline
preparing
storage tank
tank
salt solution
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李少龙
康梅
刘纪迎
米玺学
孙磊
吴靖
王耀玺
郭淑珍
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Ningxia Zhongse Jinhui New Energy Co Ltd
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Ningxia Zhongse Jinhui New Energy Co Ltd
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a method for preparing a precursor of a lithium battery anode material by a step-by-step nucleation method, which comprises the steps of preparing a metal salt solution, preparing a complexing agent, preparing a precipitator and synthesizing the precursor, wherein in the coprecipitation reaction process, small-core precipitates generated by the reaction are firstly discharged and secondly returned to a reaction kettle to continue to grow up, and the intermediate tank is arranged, and then the intermediate precipitates are secondarily added into the reaction kettle as mother cores to continue to grow up, so that a leading product of D50 in the final precipitates is controlled.

Description

Method and equipment for preparing lithium battery anode material precursor by step-by-step nucleation method
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a method and equipment for preparing a precursor of a lithium battery positive electrode material by a step-by-step nucleation method.
Background
In the existing preparation method of the lithium ion battery cathode material, a nickel-cobalt-manganese mixed salt solution in a reaction kettle, a precipitator and a complexing agent are all fed by adopting a precise flow metering pump, so that the production cost is high, and certain economic burden is caused to enterprises. For example, chinese patent CN 109250765A discloses a feeding method using a metering pump, which has the problems of high equipment cost and high maintenance cost.
Disclosure of Invention
It is necessary to provide a method and a device for preparing a lithium battery anode material precursor by a step-by-step nucleation method.
A method for preparing a lithium battery anode material precursor by a step-by-step nucleation method comprises the following steps:
preparing a metal salt solution: according to the formula NixCoyMnz (OH)2Wherein x + y + z =1, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1, at least one of soluble nickel salt, cobalt salt and manganese salt is dissolved in pure water according to the molar ratio of x, y, z to prepare a metal salt solution, and the metal salt solution is fully stirred to be uniform;
preparing a complexing agent;
preparing a precipitator;
synthesizing a precursor: adding the base solution into a reaction kettle, introducing inert gas, respectively driving the metal salt solution, the complexing agent and the precipitating agent into the reaction kettle while stirring, carrying out coprecipitation reaction, discharging and storing a small-core precipitate generated by the reaction as a seed crystal, continuously carrying out the reaction, simultaneously accurately metering the seed crystal, continuously or intermittently returning the seed crystal to the reaction kettle, carrying out secondary growth on the seed crystal and the residual materials in the kettle, returning the seed crystal to the reaction kettle for secondary growth, continuously growing the seed crystal, and after the reaction is finished, sequentially carrying out alkali washing, pure water washing, dewatering, drying, demagnetizing and packaging on the obtained precipitate to obtain a precursor product; wherein the metal salt solution is fed into the reaction kettle under the control of gravity self-overflow provided by a stable liquid reflux device.
The utility model provides a step-by-step nucleation prepares lithium cell cathode material precursor equipment which characterized in that: the device comprises a first storage tank, a stable liquid reflux device, a reaction kettle, a second storage tank, a third storage tank and an intermediate tank, wherein the first storage tank is used for containing a prepared metal salt solution, the side wall of the reaction kettle is provided with an intermediate material outlet to be connected with the intermediate tank, the intermediate tank is also provided with an intermediate material reflux pipeline to reflux the small nuclear sediments into the reaction kettle, the stable liquid reflux device comprises a stable liquid tank, a liquid supplementing pipeline, a feeding pipeline and a reflux pipeline, the stable liquid tank is arranged above the reaction kettle and the first storage tank to form height difference between the stable liquid tank and the reaction kettle and between the stable liquid tank and the first storage tank, the liquid supplementing pipeline is connected between the stable liquid tank and the first storage tank, a circulating pump is further arranged on the liquid supplementing pipeline to pump the metal salt solution in the first storage tank at a lower position into the stable liquid tank, the upper part of the stable liquid tank is provided with a feeding port and a reflux port, the feeding pipeline is connected between the feeding port of, still set up flowmeter and control valve on the material loading pipeline for the volume of the metal salt solution that monitoring and control got into reation kettle, backflow pipeline connect between the backward flow mouth of stationary flow jar and first storage tank, in order to flow back unnecessary metal salt solution in the stationary flow jar to first storage tank in, and then have the metal salt solution to flow in all the time in making the material loading pipeline, the second storage tank is used for storing the complexing agent, and the third storage tank is used for storing the precipitant, and second storage tank and third storage tank are connected with reation kettle.
Drawings
FIG. 1 is a schematic view of an apparatus used in the present production method.
Fig. 2 is a schematic view of another embodiment of the apparatus.
Fig. 3, 4 and 5 are effect diagrams of examples 1, 2 and 3.
In the figure: the device comprises a first storage tank 10, a flow stabilizing tank 21, a partition plate 211, a flow stabilizing chamber 212, an overflow chamber 213, a communication channel 214, a liquid supplementing pipeline 22, a feeding pipeline 23, a flow meter 231, a control valve 232, a return pipeline 24, a reaction kettle 30, a second storage tank 40, a third storage tank 50, an adjusting tank 60, a circulating pipeline 61 and an intermediate tank 70.
Detailed Description
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
The embodiment of the invention provides a method for preparing a precursor of a lithium battery positive electrode material by a step-by-step nucleation method, which comprises the following steps:
preparing a metal salt solution: according to the formula NixCoyMnz (OH)2Wherein x + y + z =1, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1, at least one of soluble nickel salt, cobalt salt and manganese salt is dissolved in pure water according to the molar ratio of x, y, z to prepare a metal salt solution, and the metal salt solution is fully stirred to be uniform;
preparing a complexing agent;
preparing a precipitator;
synthesizing a precursor: adding the base solution into a reaction kettle 30, introducing inert gas, respectively driving the metal salt solution, the complexing agent and the precipitant into the reaction kettle 30 while stirring, carrying out coprecipitation reaction, discharging and storing a small-core precipitate generated by the reaction in advance to be used as a seed crystal, continuously carrying out the reaction, accurately metering the seed crystal, continuously (when the reaction kettle adopts continuous production) or intermittently (when the reaction kettle adopts intermittent production) returning the seed crystal to the reaction kettle and the residual materials in the kettle for secondary growth, and after the reaction is finished, sequentially carrying out alkali washing, pure water washing, dehydration, drying, demagnetization and packaging on the obtained precipitate to obtain a precursor product; wherein the metal salt solution is fed into the reaction kettle 30 by gravity self-overflow control provided by a stable liquid reflux device.
Further, the complexing agent is one or more of ammonia water and soluble ammonium salt.
Further, the precipitator is one or more of sodium hydroxide and potassium hydroxide.
Further, the inert gas is one of nitrogen, argon or helium.
Further, the base solution is an ammonia solution.
Referring to fig. 1 and 2, the invention further provides equipment for preparing a lithium battery anode material precursor by a step-by-step nucleation method, which comprises a first storage tank 10, a liquid stabilizing backflow device, a reaction kettle 30, a second storage tank 40, a third storage tank 50 and an intermediate tank 70, wherein the first storage tank 10 is used for containing a configured metal salt solution, an intermediate material discharge port is formed in the side wall of the reaction kettle and is connected with the intermediate tank 70, the intermediate tank 70 is further provided with an intermediate material backflow pipeline for refluxing the small nuclear precipitates into the reaction kettle 30, the first storage tank 10 is used for containing the configured metal salt solution, the liquid stabilizing backflow device comprises a steady flow tank 21, a liquid supplementing pipeline 22, a feeding pipeline 23 and a backflow pipeline 24, the steady flow tank 21 is arranged above the reaction kettle 30 and the first storage tank 10 so as to form a height difference between the steady flow tank 21 and the reaction kettle 30 as well as between the first storage tank 10, the liquid supplementing pipeline 22 is connected between the steady flow tank 21 and the first storage tank, still set up the circulating pump on fluid infusion pipeline 22, in order to squeeze into stationary flow jar 21 with the metal salt solution in the first storage tank 10 of lower position, offer material loading mouth and backward flow mouth on stationary flow jar 21 upper portion, material loading pipeline 23 is connected between stationary flow jar 21's material loading mouth and reation kettle 30, still set up flowmeter 231 and control valve 232 on material loading pipeline 23, a quantity for monitoring and control get into reation kettle 30's metal salt solution, backward flow pipeline 24 is connected between stationary flow jar 21's backward flow mouth and first storage tank 10, in order to flow back to first storage tank 10 with the surplus metal salt solution in stationary flow jar 21, and then make the metal salt solution flow in the material loading pipeline 23 all the time, second storage tank 40 is used for storing the complexing agent, third storage tank 50 is used for storing the precipitant, second storage tank 40 and third storage tank 50 are connected with reation kettle 30.
In the scheme, the intermediate tank is arranged, precipitates with certain granularity can be discharged in advance according to process requirements, then the intermediate precipitates are used as mother nuclei to be added into the reaction kettle for the second time to enable the mother nuclei to grow continuously, the precursor produced by the two-step method has two remarkable particle size characteristics, namely the precursor precipitate grown from the original reaction kettle to the end of the reaction has a larger particle size, the seed crystal after the second reflux has a smaller particle size, but the particle size uniformity is good, and the precursor precipitate can be used as a leading product of D50 in the final precipitate. The scheme can control the particle size distribution of the final product through the guidance of the intermediate tank.
As a preferable scheme, a liquid stabilizing reflux device may be respectively disposed above the second storage tank 40 and the third storage tank 50, instead of a precision metering pump, so that the complexing agent and the precipitating agent are automatically fed into the reaction kettle 30 under the action of gravity.
In the scheme, the steady flow tank 21 is firstly arranged at a high position to form a gravity difference with the reaction kettle 30, so that the salt solution in the steady flow tank 21 automatically flows into the reaction kettle 30 by virtue of the gravity, and meanwhile, the flow meter 231 and the control valve 232 are arranged on the feeding pipe to control the flow of the salt solution entering the reaction kettle 30. In this scheme, at first form the power that the salt solution got into reation kettle 30 from the mode of overflow, flowmeter 231 and control valve 232 all adopt conventional work piece, can realize flow detection and control can, salt solution liquid level height remains throughout to be higher than the height of material loading mouth in the steady flow jar 21 of high-order, guarantee from the overflow, and steady flow jar 21 continuously stable the beating into of salt solution through the circulating pump, the circulating pump here also only need adopt conventional work piece, promote the salt solution to in steady flow jar 21 can. The scheme replaces the prior art with a precise metering pump, the precise metering pump is equipment with the functions of metering liquid flow, flow rate and on-off control, belongs to precise control equipment, is high in cost, requires tens of thousands yuan for imported equipment and tens of thousands yuan for domestic equipment, is easy to cause the problem of inaccurate metering of the precise equipment, needs to replace new equipment frequently, and increases the operation cost undoubtedly. In the scheme, the function of pumping liquid is realized only by adopting a common circulating pump, and a conventional liquid flow meter 231 and a control valve 232 are matched, so that the conventional parts belong to the conventional parts, the purchase cost is lower than 1/2 of a metering pump, and the conventional parts can be replaced independently, so that the replacement cost of spare parts is reduced.
The invention adopts a high-level self-overflow mode, and a mode of pumping liquid into the steady flow tank 21 by a circulating pump, so that the problems of impact and turbulence when the liquid enters the steady flow tank 21 exist, which can cause the problems of being not beneficial to the stability of the liquid and easy to be involved in air in the liquid, but the invention adopts the high-level stable overflow mode, so that the liquid in the steady flow tank 21 can automatically overflow into the feeding pipeline 23 through the feeding port, and the self-overflow mode can ensure that the flow velocity of the liquid entering the feeding pipeline 23 is stable, no turbulence exists, no air exists, and the flow monitored by the flow meter 231 is more accurate.
Further, stationary flow jar 21 is a hollow tank body, still sets up division board 211 in stationary flow jar 21, and division board 211 is divided into two cavities of stationary flow room 212 and overflow room 213 in with stationary flow jar 21, material loading mouth and backward flow mouth are connected with overflow room 213 and stationary flow room 212 respectively, division board 211 highly is higher than the height of material loading mouth, and the entry and the overflow room 213 intercommunication of material loading pipeline 23, the entry and the stationary flow room 212 intercommunication of fluid infusion pipeline 22, the top and the lateral wall of division board 211 and the top and the lateral wall sealing connection of stationary flow jar 21, bottom and sealed can 21 bottom contactless to form intercommunication passageway 214. The scheme makes the liquid entering from the liquid supplementing pipeline 22 directly enter the flow stabilizing chamber 212, so that the liquid enters the space of the chamber and is stabilized and slowly flowed for one time, the liquid is prevented from being impacted by the liquid plume and carried into the gas, then the liquid in the chamber flows to the overflow chamber 213 from the communicating channel 214, the arrangement of the partition plate 211 ensures that liquid firstly enters the flow stabilization chamber 212 to be stabilized, the liquid flows from the bottom to the overflow chamber 213, the liquid at the bottom of the flow stabilization tank 21 has better stability compared with the liquid pumped from the upper part close to the inlet of the liquid supplementing pipeline 22, the liquid overflows from the bottom to the overflow chamber 213 and then enters the feeding pipeline 23 from the feeding port, generally, in order to ensure the sufficient overflow of the feeding pipeline 23, the height of the liquid level in the overflow chamber 213 is higher than that of the feeding port, the liquid overflowing from the bottom to the top can drive the entrained and residual gas in the liquid to the liquid surface, and thus the gas can not enter the feeding pipeline 23; similarly, the bottom communicating channel provides the only path for the liquid in the plenum chamber 212 to flow into the overflow chamber 212, and this location is at the bottom of the two chambers, which also promotes the gas in the plenum chamber 212 to float above the liquid and not enter the overflow chamber 212 along the communicating channel 214. Thereby ensuring that the liquid entering the feeding pipeline 23 has no entrainment gas, and the flowmeter 231 has accurate measurement and no error.
In order to ensure that the gas in the steady flow tank 21 is discharged in time, the top of the steady flow tank 21 is provided with a gas valve so as to discharge the indoor gas in time, and avoid secondary dissolution and liquid in the case of more enriched gas and higher gas pressure.
Furthermore, a liquid level meter is arranged at the return port and used for detecting the liquid level of the return port, so that liquid always flows back through the return port. When the liquid level of the return port is low, the liquid level meter sends a signal to the controller or the outside, and the controller controls the circulating pump to increase the flow or artificially controls the circulating pump to increase the flow. Therefore, the liquid level in the steady flow cavity is always high, the liquid is always continuously overflowed into the overflow chamber 213, and the liquid level in the overflow chamber 213 is ensured to be as high as the separation plate 211.
Further, a heat-insulating sleeve is arranged on the outer wall of the return pipeline 24, and a constant-temperature medium circularly flows inside the heat-insulating sleeve so as to keep the constant temperature of the return pipeline 24. Backflow pipeline 24 flows back unnecessary liquid to first storage tank 10 in, realizes the circulation, and this backward flow process makes the salt solution be in the circulation flow state all the time, and this circulation process is the cooling of liquid with higher speed easily, perhaps causes the evaporation of solvent water easily, and these two kinds of circumstances all can reduce the solubility, make the salt go out, can lead to metal ion content in the salt solution to be less than the technological requirement, so this scheme sets up the heat preservation sleeve pipe for backflow pipeline 24, makes its constancy of temperature, and the solubility is invariable, and salt ion does not appear. In the same way, a heat-insulating sleeve is also arranged on the feeding pipeline 23. This scheme is designed for the demand that cooperates stationary flow jar 21 to flow back repeatedly, compares in prior art, if do not have many times, relapse from the overflow backward flow, then the salt solution in first storage tank 10 is directly squeezed into reation kettle 30 by accurate measuring pump, and quick circulation in the pipeline does not have the problem that pipeline moisture evaporation leads to solvent reduction or temperature reduction to lead to the solubility to reduce.
Referring to fig. 2, as another embodiment, the apparatus further includes an adjusting tank 60, the backflow pipeline 22 is connected between a backflow port of the steady flow tank and the adjusting tank 60 to backflow the excess metal salt solution in the steady flow tank 21 into the adjusting tank 60, a circulation pipeline 61 is further disposed between the adjusting tank 60 and the fluid infusion pipeline 24, a circulation control valve and a fluid infusion control valve are further disposed on the circulation pipeline 61 and the fluid infusion pipeline 22, respectively, and a concentration detector is further disposed inside the adjusting tank for monitoring the concentration of the metal ions in the liquid in the adjusting tank in real time.
Because the liquid flowing back to the first storage tank along the return pipeline may have the condition of reduced solubility or lower metal ion concentration, and directly flows back to the first storage tank to be pumped into the steady flow tank again for direct use, and the problem that the metal ion content of the salt solution entering the reaction kettle cannot be monitored is likely to occur, in the improvement scheme, the liquid overflowing from the steady flow tank enters the adjusting tank to be independently collected, and a metering tool for monitoring the concentration in real time is added, when the metal ion concentration meets the process requirement, the circulation control valve is opened, the liquid flowing back according with the requirement is merged into the liquid supplementing pipeline 22 to be secondarily used, but the requirement is not met, the circulation control valve is closed, the metal ion content of the liquid in the adjusting tank is independently adjusted, and the liquid is secondarily used when the metal ion content meets the requirement.
Example 1
Preparing a metal salt solution: according to the chemical formula Ni4Co3Mn3(OH)2Dissolving three soluble nickel salt, cobalt salt and manganese salt in pure water according to a molar ratio of 4:3:3 to prepare a metal salt solution, and fully stirring the metal salt solution until the metal salt solution is uniform;
preparing an ammonia water solution with the mass fraction of 20%;
preparing a sodium hydroxide solution with the mass fraction of 20%;
synthesizing a precursor: adding 20% ammonia water solution into a reaction kettle 30 filled with pure water, introducing nitrogen, respectively pumping the metal salt solution, the complexing agent and the precipitating agent into the reaction kettle 30 while stirring, controlling the temperature to be 30-50 ℃, and the pH value: 9.5-13.0, stirring speed of 100-; wherein the metal salt solution is fed into the reaction kettle 30 by gravity self-overflow control provided by a stable liquid reflux device.
Example 2
Preparing a metal salt solution: according to the chemical formula Ni6Co3Mn1(OH)2Dissolving soluble nickel salt, cobalt salt and manganese salt in pure water according to a molar ratio of 6:3:1 to prepare a metal salt solution, and fully stirring the metal salt solution until the metal salt solution is uniform;
preparing an ammonia water solution with the mass fraction of 25%;
preparing a sodium hydroxide solution with the mass fraction of 25%;
synthesizing a precursor: adding 25% ammonia water solution into a reaction kettle 30 filled with pure water, introducing argon, respectively pumping the metal salt solution, the complexing agent and the precipitating agent into the reaction kettle 30 while stirring, controlling the temperature to be 35-55 ℃, and controlling the pH value to be: 9.5-12.0, stirring speed of 100-; wherein the metal salt solution is fed into the reaction kettle 30 by gravity self-overflow control provided by a stable liquid reflux device.
Example 3
Preparing a metal salt solution: according to the chemical formula Ni6Co2Mn2(OH)2Dissolving three soluble nickel salt, cobalt salt and manganese salt in pure water according to a molar ratio of 6:2:2 to prepare a metal salt solution, and fully stirring the metal salt solution until the metal salt solution is uniform;
preparing an ammonia water solution with the mass fraction of 25%;
preparing a sodium hydroxide solution with the mass fraction of 20%;
synthesizing a precursor: adding 25% ammonia water solution into a reaction kettle 30 filled with pure water, introducing nitrogen, respectively pumping the metal salt solution, the complexing agent and the precipitating agent into the reaction kettle 30 while stirring, controlling the temperature to be 35-50 ℃, and controlling the pH value: 10-12.0, stirring at a rotating speed of 100-; wherein the metal salt solution is fed into the reaction kettle 30 by gravity self-overflow control provided by a stable liquid reflux device.
The precursors prepared in examples 1, 2 and 3 were examined and their internal particle size distributions were determined as shown in FIGS. 3, 4 and 5, respectively. Therefore, the particle size D50 of the prepared precursor is =9.5 to 10.5, and the requirement of the designed particle size is met.
The modules or units in the device of the embodiment of the invention can be combined, divided and deleted according to actual needs.
The above disclosure is only illustrative of the preferred embodiments of the present invention, which should not be taken as limiting the scope of the invention, but rather the invention can be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It will be understood by those skilled in the art that all or a portion of the above-described embodiments may be practiced and equivalents thereof may be resorted to as falling within the scope of the invention as claimed. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (10)

1. A method for preparing a precursor of a lithium battery positive electrode material by a step-by-step nucleation method is characterized by comprising the following steps:
preparing a metal salt solution: according to the formula NixCoyMnz (OH)2Wherein x + y + z =1, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1, at least one of soluble nickel salt, cobalt salt and manganese salt is dissolved in pure water according to the molar ratio of x, y, z to prepare a metal salt solution, and the metal salt solution is fully stirred to be uniform;
preparing a complexing agent;
preparing a precipitator;
synthesizing a precursor: adding the base solution into a reaction kettle, introducing inert gas, respectively driving the metal salt solution, the complexing agent and the precipitating agent into the reaction kettle while stirring, carrying out coprecipitation reaction, discharging and storing a small-core precipitate generated by the reaction as a seed crystal, continuously carrying out the reaction, simultaneously accurately metering the seed crystal, continuously or intermittently returning the seed crystal to the reaction kettle, carrying out secondary growth on the seed crystal and the residual materials in the kettle, returning the seed crystal to the reaction kettle for secondary growth, continuously growing the seed crystal, and after the reaction is finished, sequentially carrying out alkali washing, pure water washing, dewatering, drying, demagnetizing and packaging on the obtained precipitate to obtain a precursor product; wherein the metal salt solution is fed into the reaction kettle under the control of gravity self-overflow provided by a stable liquid reflux device.
2. The method for preparing the precursor of the lithium battery positive electrode material by the fractional nucleation method according to claim 1, wherein: the complexing agent is one or more of ammonia water and soluble ammonium salt.
3. The method for preparing the precursor of the lithium battery positive electrode material by the fractional nucleation method according to claim 1, wherein: the precipitator is one or more of sodium hydroxide and potassium hydroxide.
4. The method for preparing the precursor of the lithium battery positive electrode material by the fractional nucleation method according to claim 1, wherein: the inert gas is one of nitrogen, argon or helium.
5. The method for preparing the precursor of the lithium battery positive electrode material by the fractional nucleation method according to claim 1, wherein: the base solution is ammonia solution.
6. The utility model provides a step-by-step nucleation prepares lithium cell cathode material precursor equipment which characterized in that: the device comprises a first storage tank, a stable liquid reflux device, a reaction kettle, a second storage tank, a third storage tank and an intermediate tank, wherein the first storage tank is used for containing a prepared metal salt solution, the side wall of the reaction kettle is provided with an intermediate material outlet to be connected with the intermediate tank, the intermediate tank is also provided with an intermediate material reflux pipeline to reflux the small nuclear sediments into the reaction kettle, the stable liquid reflux device comprises a stable liquid tank, a liquid supplementing pipeline, a feeding pipeline and a reflux pipeline, the stable liquid tank is arranged above the reaction kettle and the first storage tank to form height difference between the stable liquid tank and the reaction kettle and between the stable liquid tank and the first storage tank, the liquid supplementing pipeline is connected between the stable liquid tank and the first storage tank, a circulating pump is further arranged on the liquid supplementing pipeline to pump the metal salt solution in the first storage tank at a lower position into the stable liquid tank, the upper part of the stable liquid tank is provided with a feeding port and a reflux port, the feeding pipeline is connected between the feeding port of, still set up flowmeter and control valve on the material loading pipeline for the volume of the metal salt solution that monitoring and control got into reation kettle, backflow pipeline connect between the backward flow mouth of stationary flow jar and first storage tank, in order to flow back unnecessary metal salt solution in the stationary flow jar to first storage tank in, and then have the metal salt solution to flow in all the time in making the material loading pipeline, the second storage tank is used for storing the complexing agent, and the third storage tank is used for storing the precipitant, and second storage tank and third storage tank are connected with reation kettle.
7. The apparatus for preparing a precursor of a positive electrode material for a lithium battery according to claim 6, wherein: the stationary flow jar is a hollow tank body, still sets up the division board in the stationary flow jar, and the division board is divided into two cavities of stationary flow room and overflow room in with the stationary flow jar, material loading mouth and backward flow mouth are connected with overflow room and stationary flow room respectively, the height that highly is higher than the material loading mouth of division board, the entry and the overflow room intercommunication of material loading pipeline, the entry and the stationary flow room intercommunication of fluid infusion pipeline, the top and the lateral wall of division board and the top and the lateral wall sealing connection of stationary flow jar, bottom and sealing tank bottom contactless to form intercommunication passageway.
8. The apparatus for preparing a precursor of a positive electrode material for a lithium battery according to claim 6, wherein: and a liquid level meter is arranged at the return port and used for detecting the liquid level of the return port so that liquid always flows back from the return port.
9. The apparatus for preparing a precursor of a positive electrode material for a lithium battery according to claim 6, wherein: and a heat-insulating sleeve is arranged on the outer wall of the return pipeline, and a constant-temperature medium circularly flows in the heat-insulating sleeve so as to keep the constant temperature of the return pipeline.
10. The apparatus for preparing a precursor of a positive electrode material for a lithium battery according to claim 6, wherein: still including adjusting the jar, return line connects between the backward flow mouth and the adjustment jar of stationary flow jar to with in the stationary flow jar unnecessary metal salt solution flows back to the adjustment jar, still set up circulating line between adjustment jar and fluid infusion pipeline, still set up circulation control valve and fluid infusion control valve respectively on circulating line and fluid infusion pipeline, still set up the concentration detection monitor inside the adjustment jar for the metal ion's of liquid concentration in the real-time supervision adjustment jar.
CN202011176418.XA 2020-10-29 2020-10-29 Method and equipment for preparing lithium battery anode material precursor by step-by-step nucleation method Withdrawn CN112441625A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113683127A (en) * 2021-08-18 2021-11-23 中国科学院成都有机化学有限公司 Lithium-rich manganese-based precursor and preparation method thereof, lithium-rich manganese-based positive electrode material and preparation method thereof
WO2024011625A1 (en) * 2022-07-15 2024-01-18 宁德时代新能源科技股份有限公司 Continuous reaction system, manganese iron oxalate precursor, lithium manganese iron phosphate, preparation method, and secondary battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113683127A (en) * 2021-08-18 2021-11-23 中国科学院成都有机化学有限公司 Lithium-rich manganese-based precursor and preparation method thereof, lithium-rich manganese-based positive electrode material and preparation method thereof
WO2024011625A1 (en) * 2022-07-15 2024-01-18 宁德时代新能源科技股份有限公司 Continuous reaction system, manganese iron oxalate precursor, lithium manganese iron phosphate, preparation method, and secondary battery

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