CN117466344A - Micro-powder-free positive electrode material precursor and preparation method thereof - Google Patents

Micro-powder-free positive electrode material precursor and preparation method thereof Download PDF

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Publication number
CN117466344A
CN117466344A CN202311819577.0A CN202311819577A CN117466344A CN 117466344 A CN117466344 A CN 117466344A CN 202311819577 A CN202311819577 A CN 202311819577A CN 117466344 A CN117466344 A CN 117466344A
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reaction
reaction kettle
positive electrode
concentration
electrode material
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张庆
王明彩
张忠伟
吴慧玥
李梦云
马啸宇
王贺鹏
尹正中
徐云军
程迪
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Henan Kelong New Energy Co ltd
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Henan Kelong New Energy Co ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a cathode material precursor without micro powder and a preparation method thereof. The product has higher tap density and low micro powder content, so that when the subsequently prepared positive electrode material is applied to a lithium battery, side reactions and micro short circuits in the battery are avoided, and the lithium ion battery has higher safety performance, cycle performance and higher specific capacity.

Description

Micro-powder-free positive electrode material precursor and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery anode material precursors, and particularly relates to a micro-powder-free anode material precursor and a preparation method thereof.
Background
Since the commercial production of the lithium ion battery in the 90 th century, the lithium ion battery has the advantages of higher specific energy, no pollution, no memory effect, long cycle life and the like, and is an ideal power supply source for portable electronic products such as mobile phones, notebook computers, cameras and the like, and is also a power source for future electric tools and military power supply equipment, so a series of researches on the lithium ion battery have become a hot spot for the research of the battery world in recent years.
The control of the micro powder is a process that each battery factory needs to strictly take care in the manufacturing process of the battery, the micro powder can be derived from raw materials, dust in the environment and mechanical dust in the process, the storage life of the battery is directly determined by the content of the micro powder, and more serious, the internal short circuit of the battery is possibly caused by the existence of the micro powder, the battery generates heat in the charging and discharging processes, and finally the explosion of the battery is possibly caused.
The presence of the micro powder affects the self-discharge of the battery from two aspects, namely, side reaction and micro short circuit in the battery are increased, and the influence is more serious along with the increase of the micro powder, in addition, the presence of the micro powder can deteriorate the high-temperature storage performance of the battery, so that the capacity of the battery is attenuated in the storage process, the internal resistance is increased, and the phenomena such as expanding gas and the like are accompanied, therefore, in actual production, the particle distribution of materials is required to be strictly controlled, and the particle size Dmin is prevented from being too small.
The positive electrode material is used as one of the 4-large core materials of the battery, so that the comprehensive performance of the battery is restricted. The positive electrode material can bear the shape and structural characteristics of the precursor, so that the structure and the preparation process of the precursor have a critical influence on the performance of the positive electrode material. The common precursor synthesis processes at present mainly comprise a continuous process and a batch process. The precursor prepared by the continuous process often has a relatively wide particle size distribution (K90 > 1.2), and excessive tiny particles (or called 'micropowders') often exist in the product, and the existence of the micro powder severely restricts the comprehensive performance of the battery. On one hand, the precursor has micro powder, which is easy to cause the problems of particle agglomeration, overburning and the like in a high-temperature sintering section, and influences the comprehensive performance of the material, and finally, the battery capacity is lower and the circulation is poor; on the other hand, the fine powder present in the precursor is extremely likely to adhere to the surface of large particles, resulting in a lower compacted density of the positive electrode material and a decrease in the energy density of the battery. While batch processes produce precursors, while reducing the presence of fines, undoubtedly increase investment and cost, and batch processes cannot be used for production of specific widely distributed products.
Based on the method, a cathode material precursor without micro powder and a preparation method thereof are developed, and the cathode material precursor has very important commercial application value.
Disclosure of Invention
Aiming at the problems that a large amount of micro powder is generated in the process of preparing a precursor by current coprecipitation and the performance of a battery which is prepared subsequently is seriously affected, the invention provides a precursor of a cathode material without micro powder and a preparation method thereof.
The first object of the present invention is to provide a positive electrode material precursor without micro powder, which has the characteristics of stabilizing the structure of the positive electrode material and ensuring the sufficient release of the capacity of the positive electrode material.
Positive electrode material without micro powderA material precursor, wherein the chemical formula of the positive electrode material precursor is Ni 0.5 Mn 0.15 Co 0.25 OH 2 The particle size of the precursor of the cathode material without micro powder is 5.03-6.08 mu m.
The second object of the present invention is to provide a method for preparing a positive electrode material precursor without micro powder, comprising the steps of:
continuously introducing a mixed solution containing soluble nickel salt, soluble manganese salt and soluble cobalt salt, a precipitant solution and a complexing agent solution into a reaction kettle for reaction, circularly reacting a reaction solution in three tanks of the reaction kettle, a concentration tank and a middle tank before the particle size of solid particles in the reaction kettle is less than 1.59-1.70 mu m, closing the material circulation among the three tanks when the particle size of solid particles in the reaction solution is 1.59-1.70 mu m, pumping the materials of the middle tank and the concentration tank into the reaction kettle, opening a valve from the reaction kettle to a storage tank, continuing the reaction, stopping the reaction when the particle size of solid particles in the reaction solution is up to the target particle size, fully stirring the materials of the reaction kettle into the storage tank, and obtaining the precursor of the cathode material without micro powder.
Further, when the particle diameter of the solid particles in the reaction liquid of the reaction vessel is 8.08 to 9.33. Mu.m, the reaction is stopped.
Further, in the reaction process, the pH of the reaction solution is 11.28-11.43, and the reaction temperature is 42-57 ℃.
Further, in the mixed solution containing the soluble nickel salt, the soluble manganese salt and the soluble cobalt salt, the total concentration of Ni, mn and Co is 1.23-3.24 mol/L.
Further, in the precipitant solution, the concentration of the precipitant is 4-15 mol/L.
Further, in the complexing agent solution, the concentration of the complexing agent is 3-8.7 mol/L.
Further, the method specifically comprises the following steps:
step 1, selecting nickel cobalt manganese soluble salt as a raw material according to the molar ratio of nickel cobalt manganese elements in a required positive electrode material precursor;
step 2, preparing the nickel, cobalt and manganese soluble salts selected in the step 1 and pure water into mixed salt solution with the total concentration of metal ions of 1.23-3.24 mol/L;
step 3, preparing sodium hydroxide solution with the concentration of 4-15 mol/L;
step 4, preparing ammonia water with the concentration of 3-13.7mol/L as a complexing agent;
step 5, opening a jacket of the reaction kettle to feed water and return water, starting the reaction kettle to stir, and introducing nitrogen into the reaction kettle for protection;
step 6, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a base solution for starting up the reaction;
step 7, stirring is started, the mixed metal salt solution prepared in the step 2, the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, and the reaction temperature, the pH and the ammonia concentration are controlled;
step 8, continuously feeding according to the step 7, and enabling materials in the reaction kettle to enter the middle groove through the overflow pipe;
step 9, pumping the materials in the middle tank into a concentration tank through a diaphragm pump, pressurizing and refluxing the materials in the concentration tank to a reaction kettle through gravity and the concentration tank, and circulating the materials in the reaction kettle, the middle tank and the concentration tank;
and 10, when the particle size of solid particles in reaction liquid of the reaction kettle reaches 1.59-1.70 mu m, material circulation among three tank bodies is closed, materials of the intermediate tank and the concentration tank are pumped into the reaction kettle, a valve from the reaction kettle to a storage tank is opened, the reaction temperature, the pH value and the ammonia concentration are controlled to continue to react, when the particle size of the solid particles in the reaction liquid of the reaction kettle is 8.08-9.33 mu m, the reaction is stopped, the materials of the reaction kettle are pumped into the storage tank, and then the materials of the reaction kettle are fully stirred, aged, washed, dried, screened and demagnetized to obtain a positive electrode material precursor with the particle size of 5.03-6.08 mu m without micropowder.
The invention has the beneficial effects that: the preparation method of the cathode material precursor without micro powder solves the problem that a large amount of micro powder is generated in the current process of preparing the precursor by coprecipitation, and the performance of a battery prepared subsequently is seriously affected. The precursor particles prepared by the method effectively control the content of the whole micro powder, and the product has higher tap density, so that when the subsequently prepared positive electrode material is applied to a lithium battery, side reactions and micro short circuits in the battery are avoided, and the lithium ion battery has higher safety performance, cycle performance and higher specific capacity. Compared with the prior art, the method controls the growth and quantity of the micro powder through the cyclic production of the middle groove of the reaction kettle thickener and the specific ammonia-alkali range in the crystallization reaction process, avoids the post-processing procedure of selectively removing small particles through the grading system after the precursor is obtained, saves the production cost, improves the production efficiency, and improves the consistency of product distribution.
The key point of the invention is that after crystallization reaction is started, the reaction liquid needs to be circulated in a reaction kettle, a middle tank and a concentrator, and the particle diameter Dmin level and the D50 level are monitored in time, and the Dmin level directly influences the micro powder condition of the final product, so that before the reaction kettle is opened to a storage tank valve, the Din is required to be ensured to be more than 1 mu m, the D50 level when the Dmin is more than 1 mu m is recorded, and after the reaction kettle is opened to the storage tank valve, the stability of the growth environment is required to be ensured by adjusting the flow of sodium hydroxide solution and ammonia water entering the reaction kettle. The intermediate tank of the reaction kettle and the concentrator in the early stage of the reaction are subjected to cyclic reaction to ensure that Dmin is more than 1 mu m, and the flow of sodium hydroxide solution and ammonia water entering the reaction kettle is regulated to ensure the stability of the growth environment, so that the condition that the final product has no micropowder is indispensable.
Drawings
Fig. 1 is an SEM image of the positive electrode material precursor prepared in example 1.
Detailed Description
The following examples will enable those skilled in the art to more fully understand the present invention and are not intended to limit the same in any way.
The preparation method of the cathode material precursor without micro powder comprises the following steps:
step 1, according to the mole ratio of nickel, cobalt and manganese elements in the required positive electrode material precursor, selecting the nickel, cobalt and manganese to be soluble
The sexual salt is used as a raw material. The proportion of the mixed solution in the example is that the molar ratio of nickel to cobalt to manganese is as follows: 50%:20 percent to 30 percent;
step 2, preparing the nickel, cobalt and manganese soluble salts selected in the step 1 and pure water into a mixed salt solution with the total concentration of metal ions of 1.87 mol/L;
step 3, preparing sodium hydroxide solution with the concentration of 8.4 mol/L;
step 4, preparing ammonia water with the concentration of 9.5mol/L as a complexing agent;
step 5, opening a jacket of the reaction kettle to feed water and return water, starting the reaction kettle to stir, and introducing nitrogen with the flow rate of 1 m/h into the reaction kettle for protection;
step 6, adding pure water to the reaction kettle until the pure water overflows the bottom stirring paddle to about 3000L of water, and then adding 8KG of the sodium hydroxide solution prepared in the step 3 and 20KG of the ammonia water prepared in the step 4 to form a base solution for starting up the reaction;
step 7, stirring is started, the mixed metal salt solution prepared in the step 2, the sodium hydroxide solution prepared in the step 3 (flow 1.25L/min) and the ammonia water prepared in the step 4 (0.34L/min) are added into a reaction kettle in parallel flow for reaction, and the reaction temperature (50+/-1 ℃), ph (12.1+/-0.1) and the ammonia concentration of 4.3g/L are controlled;
and 8, continuously feeding according to the step 7, enabling materials in the reaction kettle to enter the middle tank through the overflow pipe, pumping the materials in the middle tank into the concentration tank through the diaphragm pump, enabling the materials in the concentration tank to flow back to the reaction kettle through gravity and the pressurization of the concentration tank, and circulating the materials in the reaction kettle, the middle tank and the concentration tank.
And 9, when the particle diameter D50 of solid particles in the reaction liquid of the reaction kettle reaches 1.65-1.67 mu m, D10 is 1.05-1.09 mu m, material circulation among three tanks is closed, materials of the intermediate tank and the concentration tank are pumped into the reaction kettle, a valve from the reaction kettle to the storage tank is opened, the reaction temperature (50+/-1 ℃) is controlled, the pH value (12.1+/-0.1) and the ammonia concentration (4.3+/-0.1 g/L) are controlled to continuously react, when the particle diameter of the solid particles in the reaction liquid of the reaction kettle is 8.95 mu m, the reaction is stopped, the materials of the reaction kettle are pumped into the storage tank, fully stirred, and then the precursor of the cathode material with the particle diameter of 5.55 mu m without micro powder can be obtained through ageing, washing, drying, sieving and demagnetizing. From the figure, no small particles can be seen.

Claims (8)

1. A positive electrode material precursor without micro powder is characterized in that the chemical formula of the positive electrode material precursor is Ni 0.5 Mn 0.15 Co 0.25 OH 2 The particle size of the precursor of the cathode material without micro powder is 5.03-6.08 mu m.
2. The method for preparing a positive electrode material precursor without fine powder according to claim 1, comprising the steps of:
continuously introducing a mixed solution containing soluble nickel salt, soluble manganese salt and soluble cobalt salt, a precipitant solution and a complexing agent solution into a reaction kettle for reaction, circularly reacting a reaction solution in three tanks of the reaction kettle, a concentration tank and a middle tank before the particle size of solid particles in the reaction kettle is less than 1.59-1.70 mu m, closing the material circulation among the three tanks when the particle size of solid particles in the reaction solution is 1.59-1.70 mu m, pumping the materials of the middle tank and the concentration tank into the reaction kettle, opening a valve from the reaction kettle to a storage tank, continuing the reaction, stopping the reaction when the particle size of solid particles in the reaction solution is up to the target particle size, fully stirring the materials of the reaction kettle into the storage tank, and obtaining the precursor of the cathode material without micro powder.
3. The method for producing a positive electrode material precursor without fine powder according to claim 2, wherein the reaction is stopped when the particle diameter of solid particles in the reaction liquid of the reaction vessel is 8.08 to 9.33 μm.
4. The method for producing a positive electrode material precursor without fine powder according to claim 2, wherein the pH of the reaction solution is 11.28 to 11.43 and the reaction temperature is 42 to 57 ℃.
5. The method for producing a positive electrode material precursor without fine powder according to claim 2, wherein the total concentration of Ni, mn and Co in the mixed solution containing the soluble nickel salt, the soluble manganese salt and the soluble cobalt salt is 1.23 to 3.24mol/L.
6. The method for producing a positive electrode material precursor without fine powder according to claim 2, wherein the concentration of the precipitant in the precipitant solution is 4 to 15mol/L.
7. The method for producing a positive electrode material precursor without fine powder according to claim 2, wherein the concentration of the complexing agent in the complexing agent solution is 3 to 13.7mol/L.
8. The method for preparing a positive electrode material precursor without micropowder according to claim 2, characterized by comprising the following steps:
step 1, selecting nickel cobalt manganese soluble salt as a raw material according to the molar ratio of nickel cobalt manganese elements in a required positive electrode material precursor;
step 2, preparing the nickel, cobalt and manganese soluble salts selected in the step 1 and pure water into mixed salt solution with the total concentration of metal ions of 1.23-3.24 mol/L;
step 3, preparing sodium hydroxide solution with the concentration of 4-15 mol/L;
step 4, preparing ammonia water with the concentration of 3-13.7mol/L as a complexing agent;
step 5, opening a jacket of the reaction kettle to feed water and return water, starting the reaction kettle to stir, and introducing nitrogen into the reaction kettle for protection;
step 6, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a base solution for starting up the reaction;
step 7, stirring is started, the mixed metal salt solution prepared in the step 2, the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, and the reaction temperature, the pH and the ammonia concentration are controlled;
step 8, continuously feeding according to the step 7, and enabling materials in the reaction kettle to enter the middle groove through the overflow pipe;
step 9, pumping the materials in the middle tank into a concentration tank through a diaphragm pump, pressurizing and refluxing the materials in the concentration tank to a reaction kettle through gravity and the concentration tank, and circulating the materials in the reaction kettle, the middle tank and the concentration tank;
and 10, when the particle size of solid particles in reaction liquid of the reaction kettle reaches 1.59-1.70 mu m, material circulation among three tank bodies is closed, materials of the intermediate tank and the concentration tank are pumped into the reaction kettle, a valve from the reaction kettle to a storage tank is opened, the reaction temperature, the pH value and the ammonia concentration are controlled to continue to react, when the particle size of the solid particles in the reaction liquid of the reaction kettle is 8.08-9.33 mu m, the reaction is stopped, the materials of the reaction kettle are pumped into the storage tank, and then the materials of the reaction kettle are fully stirred, aged, washed, dried, screened and demagnetized to obtain a positive electrode material precursor with the particle size of 5.03-6.08 mu m without micropowder.
CN202311819577.0A 2023-12-27 2023-12-27 Micro-powder-free positive electrode material precursor and preparation method thereof Pending CN117466344A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112174226A (en) * 2020-09-29 2021-01-05 荆门市格林美新材料有限公司 Method for continuously preparing nickel-cobalt-manganese ternary precursor with ultrahigh metal yield
CN113104906A (en) * 2021-05-12 2021-07-13 罗钢 Intermittent nickel-cobalt-manganese ternary precursor preparation process
CN114394630A (en) * 2021-12-31 2022-04-26 宜宾光原锂电材料有限公司 Preparation method for controlling morphology of ternary precursor material
WO2023029897A1 (en) * 2021-09-02 2023-03-09 荆门市格林美新材料有限公司 Preparation method and preparation apparatus for high tap density ternary precursor material
CN115893519A (en) * 2022-11-15 2023-04-04 泾河新城陕煤技术研究院新能源材料有限公司 Preparation method of nickel-cobalt-manganese hydroxide with wide particle size distribution and high peak intensity ratio

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112174226A (en) * 2020-09-29 2021-01-05 荆门市格林美新材料有限公司 Method for continuously preparing nickel-cobalt-manganese ternary precursor with ultrahigh metal yield
CN113104906A (en) * 2021-05-12 2021-07-13 罗钢 Intermittent nickel-cobalt-manganese ternary precursor preparation process
WO2023029897A1 (en) * 2021-09-02 2023-03-09 荆门市格林美新材料有限公司 Preparation method and preparation apparatus for high tap density ternary precursor material
CN114394630A (en) * 2021-12-31 2022-04-26 宜宾光原锂电材料有限公司 Preparation method for controlling morphology of ternary precursor material
CN115893519A (en) * 2022-11-15 2023-04-04 泾河新城陕煤技术研究院新能源材料有限公司 Preparation method of nickel-cobalt-manganese hydroxide with wide particle size distribution and high peak intensity ratio

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