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CN118993177B - Preparation method and precursor for improving the consistency of primary particles of positive electrode material precursor - Google Patents

Preparation method and precursor for improving the consistency of primary particles of positive electrode material precursor Download PDF

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Publication number
CN118993177B
CN118993177B CN202411479460.7A CN202411479460A CN118993177B CN 118993177 B CN118993177 B CN 118993177B CN 202411479460 A CN202411479460 A CN 202411479460A CN 118993177 B CN118993177 B CN 118993177B
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primary particles
solution
precursor
positive electrode
preparation
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CN118993177A (en
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宋方亨
邢王燕
闵佳玉
杜先锋
王硕
左美华
张彬
王政强
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Yibin Guangyuan Lithium Battery Co ltd
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Yibin Guangyuan Lithium Battery Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/40Complex oxides containing nickel and at least one other metal element
    • C01G53/42Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/40Complex oxides containing nickel and at least one other metal element
    • C01G53/42Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

本发明公开了一种提升正极材料前驱体一次颗粒一致性的制备方法及前驱体。本发明提供的提升正极材料前驱体一次颗粒一致性的制备方法,其包括:采用共沉淀法制备正极材料前驱体时,当溶液中出现一次颗粒大小不一的情况时,暂停所有进料,通过提升生长期转速抑制一次颗粒的异常生长,随后通入低浓度盐溶液、过氧化氢溶液引导一次颗粒往同一方向进行生长,减少成核位点,确保颗粒的一致性。采用本发明提供的方案可制备一次颗粒均一的前驱体,规避因工艺调整或产品自身特性带来的一次颗粒差异,稳定正极材料电性能。

The present invention discloses a preparation method and precursor for improving the consistency of primary particles of a positive electrode material precursor. The preparation method for improving the consistency of primary particles of a positive electrode material precursor provided by the present invention comprises: when the positive electrode material precursor is prepared by a coprecipitation method, when primary particles of different sizes appear in the solution, all feeds are suspended, the abnormal growth of primary particles is suppressed by increasing the rotation speed during the growth period, and then a low-concentration salt solution and a hydrogen peroxide solution are introduced to guide the primary particles to grow in the same direction, reduce nucleation sites, and ensure the consistency of particles. The scheme provided by the present invention can be used to prepare a precursor with uniform primary particles, avoid the difference in primary particles caused by process adjustment or the characteristics of the product itself, and stabilize the electrical properties of the positive electrode material.

Description

Preparation method for improving consistency of primary particles of positive electrode material precursor and precursor
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a preparation method for improving the consistency of primary particles of a positive electrode material precursor and the precursor.
Background
The ternary lithium battery has become one of the main application materials in the lithium battery market due to the factors of high capacity, long service life, excellent high-low temperature circulation and the like. The electrical property of the ternary material battery is mainly determined by ternary precursors, the ternary precursors are usually coprecipitated by adopting mixed salt, a precipitator and a complexing agent at a certain temperature and pH, and the ternary precursors are prepared by washing, drying, screening and other procedures, and the prepared precursors have certain differences in morphology and structure according to different series, indexes and sizes, wherein the primary particle stacking mode, the diameter width and the diameter length have great influence on the electrical property.
In the precursor preparation process, the process difference or the reaction system is regulated frequently, the primary particle diameter is wide, the diameter and the length are easy to change obviously, and the method is particularly characterized in that in the same particle, the primary particle diameter difference is more than 100nm, and the diameter and the length difference is more than 200nm. The morphology structure is obvious in primary particle difference, the primary particles are easy to burn in the sintering process, and the electrical properties of each point of the prepared positive electrode material particles are different, so that the consistency of the materials is poor, and the overall performance is further influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method for improving the consistency of primary particles of a positive electrode material precursor and the precursor.
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a preparation method for improving the consistency of primary particles of a precursor of a positive electrode material, which comprises the steps of suspending all feeding when the primary particles in a solution are different in size when the precursor of the positive electrode material is prepared by adopting a coprecipitation method, then improving the rotating speed to inhibit the abnormal growth of the primary particles, and then introducing a low-concentration salt solution and a hydrogen peroxide solution to guide the primary particles to grow in the same direction, so that nucleation sites are reduced, and the consistency of the primary particles of the precursor of the positive electrode material is improved.
The invention provides a positive electrode material precursor, which is prepared by adopting the method.
The invention has the following beneficial effects:
The invention provides a preparation method for improving the consistency of primary particles of a positive electrode material precursor and the precursor. The invention provides a preparation method for improving the consistency of primary particles of a precursor of a positive electrode material, which comprises the steps of suspending all feeding when the primary particles in a solution are different in size when the precursor of the positive electrode material is prepared by adopting a coprecipitation method, inhibiting the abnormal growth of the primary particles by improving the rotating speed of a growing period, and then introducing a low-concentration salt solution and a hydrogen peroxide solution to guide the primary particles to grow in the same direction, so that nucleation sites are reduced, and the consistency of the particles is ensured. The scheme provided by the invention can be used for preparing the precursor with uniform primary particles, so that the primary particle difference caused by process adjustment or product self-characteristics is avoided, and the electrical property of the positive electrode material is stabilized.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the product obtained in example 1;
FIG. 2 is an SEM image of the product obtained in example 2;
fig. 3 is an SEM image of the product obtained in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following specifically describes a preparation method for improving the consistency of primary particles of a positive electrode material precursor and the precursor.
In a first aspect, the embodiment of the invention provides a preparation method for improving the consistency of primary particles of a precursor of a positive electrode material, which comprises the steps of suspending all feeding when the primary particles in a solution are different in size when the precursor of the positive electrode material is prepared by adopting a coprecipitation method, then increasing the rotating speed to inhibit the abnormal growth of the primary particles, and then introducing a low-concentration salt solution and a hydrogen peroxide solution to guide the primary particles to grow in the same direction, so that nucleation sites are reduced, and the consistency of the primary particles of the precursor of the positive electrode material is improved.
In the process of preparing the precursor, primary particles with inconsistent sizes are easy to form when the pH of the reaction system is adjusted or inert gas with high flow rate is introduced due to the characteristics of the reaction system or the product, obvious difference can be seen from a scanning electron microscope, the primary particle diameter width difference is larger than 100nm, the diameter length difference is larger than 200nm, and the performance of the positive electrode material or the battery is further reduced due to the poor consistency of the primary particles.
Therefore, the embodiment of the invention provides the preparation method for improving the consistency of the primary particles of the precursor of the positive electrode material, which can avoid the problem of poor consistency of the primary particles caused by adjustment of process conditions, and can reduce the number of nucleation sites on the surface of the secondary sphere under each process condition, so that the primary particle diameter wide difference of the precursor is less than 20nm, the diameter length difference is less than 50nm, the uniformity and consistency of the particles of the product are ensured, and the electrical performance of the product is stabilized. The method is completed through physical adjustment and a proper amount of additives, does not need to increase equipment, is simple, and is suitable for preparing the full-series precursor with the problems.
In an alternative embodiment, the method comprises the following steps of introducing mixed salt solution, precipitant solution and complexing agent solution into base solution in parallel under the protection of inert gas, reducing the pH value of a system to perform primary particle growth after crystal nucleus generation, suspending all feeding when the primary particle sizes are different in the solution, then increasing the rotating speed to inhibit the abnormal growth of the primary particles, maintaining the rotating speed to stir, introducing low-concentration salt solution and hydrogen peroxide solution with the same molar ratio to guide the primary particles to grow in the same direction when the precipitation tends to be suspended, reducing nucleation sites, improving the consistency of the primary particles of a precursor of a positive electrode material, and restoring the primary particles to the original feeding mode when the diameter width and diameter length difference value after re-feeding meet the design requirement until the materialization index of the primary particles is qualified.
In an alternative embodiment, the pH value of the reaction system is controlled to be 10.0-12.5, the pH value is lower than the lower limit, the growth rate is too fast, the growth and the size of precursor particles of the positive electrode material cannot be controlled, micro powder particles are easy to appear when the pH value exceeds the upper limit, the reaction cannot be normally carried out, the ammonia value is 2-20 g/L, ammonia is regulated along with the pH change and presents positive correlation, the ammonia value mismatch influences the coprecipitation efficiency, the temperature is 40-80 ℃, the mass transfer rate of the system is easy to be reduced when the temperature is lower than the lower limit, the particle crystallization is influenced, the precursor oxidation is caused when the upper limit is exceeded, the precursor performance is influenced, the rotating speed is 100-1000 rpm, the particles cannot be effectively dispersed and are seriously agglomerated when the lower than the lower limit, the electrical property of the precursor is reduced, the particles in the system cannot normally precipitate and crystallize, and the precursor cannot be synthesized when the upper limit is exceeded.
In an alternative embodiment, the pH value of the system is reduced after the crystal nucleus is generated, the feeding is stopped after the reaction is continued for 5-10 hours, if the feeding is stopped for less than the preset time, the state of the reaction system is inconsistent due to uneven mixing, and if the feeding is stopped for more than the preset time, the particles grow due to continuous feeding, so that the original crystal nucleus particle size is increased, and the regulation and control of the structure are affected.
In an alternative embodiment, the mixed salt solution has a concentration of 1.0mol/L to 2.5mol/L, the precipitant solution has a mass concentration of 20% to 25%, and the complexing agent solution has a mass concentration of 7% to 30%. And liquid alkali (sodium hydroxide solution) is used as a precipitator, and ammonia water is used as a complexing agent.
In an alternative embodiment, the rotational speed is increased to 1.2-2 times the original rotational speed, abnormal particle growth is restrained by increasing the rotational speed, the particle size growth rate is slowed down, the particle size range of the affected particles is weakened, the crystallization state of the system is changed by using high-rotational-speed stirring, and the pause time is maintained for 0.5-10 hours, so that the crystallization state is adjusted, the particle growth continuity is influenced by the time-out range, and the independent nucleation of the system is easily caused.
In an alternative embodiment, the low concentration salt solution concentration is 0.3 to 0.8 times that of the original mixed salt solution concentration, and the growth rate of the low concentration salt solution can be slowed down by the flow rate of the low concentration salt solution, so that the particles can be recrystallized in a uniform manner under a growth system.
In an alternative embodiment, the hydrogen peroxide solution has a mass fraction of 5% to 40%.
In an alternative embodiment, the method further comprises the steps of ageing the materials qualified in reaction, filtering, slurrying a filter cake obtained by filtering with dilute alkali, filtering and washing until the pH value of the filtrate is less than 9, and drying, screening and demagnetizing to obtain a precursor product with uniform primary particles.
In a second aspect, an embodiment of the present invention provides a positive electrode material precursor, where the positive electrode material precursor is prepared by using the method described above.
The above is apparent that the embodiment of the invention provides a preparation method for improving the consistency of primary particles of a positive electrode material precursor, which has the following characteristics and advantages:
(1) By adopting the scheme provided by the embodiment of the invention, the ternary precursor with uniform primary particles can be prepared, the primary particle difference caused by process adjustment or product self-characteristics can be avoided, and the electrical property of the positive electrode material is stabilized.
(2) The scheme provided by the embodiment of the invention is simple, convenient and effective, no new element is introduced, and the method is suitable for preparing the NCM (lithium nickel cobalt manganese oxide, liNiCoMnO 2) and NCA (lithium nickel cobalt aluminum oxide, liNiCoAlO 2) full-series precursors.
(3) The scheme provided by the embodiment of the invention can be applied to each stage of the precursor, the problem of particle consistency is solved in a targeted manner, no application taboo exists, and the scheme can be expanded to quaternary precursor equivalent type products.
(4) The scheme provided by the embodiment of the invention has low application cost and excellent reaction control, and the existing equipment is not required to be modified.
The invention is further described below with reference to examples.
Example 1
Preparing a reaction kettle base solution, wherein the temperature is 50 ℃, the ammonia value is 14g/L, the pH value is 11.4, simultaneously introducing nickel cobalt manganese sulfate solution, ammonia water and sodium hydroxide into the reaction kettle, introducing nitrogen for protection, setting the stirring rotating speed of the reaction kettle to be 550rpm, wherein the molar ratio of nickel to cobalt manganese in the mixed salt solution is 6:1:3, the concentration of the mixed salt solution is 1.6mol/L, the mass percentage concentration of the sodium hydroxide solution is 22%, and the mass percentage concentration of the ammonia water is 15%.
After the preparation of the crystal nucleus is finished, the pH value of a reaction system is adjusted to 10.9, particles are in a growth state, feeding is stopped after the reaction is continued for 8 hours, the rotating speed is increased to 750rpm, the current process is kept for 5 hours, then 0.8mol/L saline solution with the same proportion is introduced, 30% hydrogen peroxide solution by mass fraction is introduced, electron microscopy monitoring is continuously carried out during the process, when the diameter width and the diameter length difference value meet the design requirements after the feeding is carried out again for 10 hours, the feeding process before stopping is resumed until the materialization index is qualified.
Placing the kettle material in an ageing kettle for ageing, filtering, adding dilute alkali with a certain concentration into a filter cake for pulping, filtering and washing until the pH value of the filtrate is less than 9, and drying, screening and demagnetizing to obtain a precursor material with uniform primary particles. The SEM of the precursor materials is shown in fig. 1, and it can be seen that the precursor primary particles are uniform and have good consistency.
Example 2
Preparing a reaction kettle base solution, wherein the temperature is 45 ℃, the ammonia value is 6.5g/L, the pH value is 11.1, simultaneously introducing nickel cobalt manganese sulfate solution, ammonia water and sodium hydroxide into the reaction kettle, introducing nitrogen for protection, setting the stirring rotating speed of the reaction kettle to 360rpm, wherein the molar ratio of nickel to cobalt manganese in the mixed salt solution is 5:2:3, the concentration of the mixed salt solution is 1.6mol/L, the mass percentage concentration of the sodium hydroxide solution is 22%, and the mass percentage concentration of the ammonia water is 15%.
After the preparation of the crystal nucleus is finished, the pH value of a reaction system is adjusted to 10.8, particles are in a growth state, feeding is stopped after the reaction is continued for 6 hours, the rotating speed is increased to 504rpm, the current process is kept for 8 hours, then 0.8mol/L saline solution with the same proportion is introduced, 30% hydrogen peroxide solution by mass fraction is introduced, electron microscopy monitoring is continuously carried out during the process, when the diameter width and the diameter length difference value meet the design requirements after the feeding is carried out again for 6 hours, the feeding process before stopping is resumed until the materialization index is qualified.
Placing the kettle material in an ageing kettle for ageing, filtering, adding dilute alkali with a certain concentration into a filter cake for pulping, filtering and washing until the pH value of the filtrate is less than 9, and drying, screening and demagnetizing to obtain a precursor material with uniform primary particles. The SEM of the precursor materials is shown in fig. 2, and it can be seen that the precursor primary particles are uniform and have better consistency.
Comparative example 1 (comparative example 1, no rotation speed adjustment, no pause in feeding, no low concentration salt solution, no hydrogen peroxide solution)
Preparing a reaction kettle base solution, wherein the temperature is 50 ℃, the ammonia value is 14g/L, the pH value is 11.4, simultaneously introducing nickel cobalt manganese sulfate solution, ammonia water and sodium hydroxide into the reaction kettle, introducing nitrogen for protection, setting the stirring rotating speed of the reaction kettle to be 550rpm, wherein the molar ratio of nickel to cobalt manganese in the mixed salt solution is 6:1:3, the concentration of the mixed salt solution is 1.6mol/L, the mass percentage concentration of the sodium hydroxide solution is 22%, and the mass percentage concentration of the ammonia water is 15%.
After the preparation of the crystal nucleus is finished, the pH value of a reaction system is adjusted to 10.9, particles are in a growth state, the current process is kept to continuously feed, and the morphology change of an electron microscope is monitored in the process until the physical and chemical indexes are qualified.
Placing the kettle material in an ageing kettle for ageing, filtering, adding dilute alkali with a certain concentration into a filter cake for pulping, filtering and washing until the pH value of the filtrate is less than 9, and drying, screening and demagnetizing to obtain a precursor material, wherein SEM (scanning electron microscope) of the precursor material is shown in figure 3, and the primary particle size of the prepared precursor is large in width-diameter-length difference and does not meet the design requirement.
Comparative example 2 (comparative example was free of rotational speed adjustment compared to example 1)
Preparing a reaction kettle base solution, wherein the temperature is 50 ℃, the ammonia value is 14g/L, the pH value is 11.4, simultaneously introducing nickel cobalt manganese sulfate solution, ammonia water and sodium hydroxide into the reaction kettle, introducing nitrogen for protection, setting the stirring rotating speed of the reaction kettle to be 550rpm, wherein the molar ratio of nickel to cobalt manganese in the mixed salt solution is 6:1:3, the concentration of the mixed salt solution is 1.6mol/L, the mass percentage concentration of the sodium hydroxide solution is 22%, and the mass percentage concentration of the ammonia water is 15%.
After the preparation of the crystal nucleus is finished, the pH value of a reaction system is adjusted to 10.9, particles are in a growth state, feeding is stopped after the reaction is continued for 8 hours, the rotating speed is not improved, then 0.8mol/L saline solution with the same proportion is introduced, 30% hydrogen peroxide solution with mass fraction is introduced, and electron microscope monitoring is continuously carried out during the process, and the feeding process is resumed before stopping after the feeding is resumed for 10 hours until the physical and chemical indexes are qualified.
Placing the kettle material in an ageing kettle for ageing, filtering, adding dilute alkali with a certain concentration into a filter cake for pulping, filtering and washing until the pH value of the filtrate is less than 9, drying, screening and demagnetizing to obtain a precursor material, wherein the crystallization state is not obviously changed when primary particles with different sizes appear, and the uniformity of all particles in a system is not sufficiently changed when a low-concentration salt solution and a hydrogen peroxide solution are further used, so that the primary particle size width-diameter-length difference of the prepared precursor is larger and does not meet the design requirement.
Comparative example 3 (compared with example 1, there is no hold time after the rotational speed is raised in this comparative example)
Preparing a reaction kettle base solution, wherein the temperature is 50 ℃, the ammonia value is 14g/L, the pH value is 11.4, simultaneously introducing nickel cobalt manganese sulfate solution, ammonia water and sodium hydroxide into the reaction kettle, introducing nitrogen for protection, setting the stirring rotating speed of the reaction kettle to be 550rpm, wherein the molar ratio of nickel to cobalt manganese in the mixed salt solution is 6:1:3, the concentration of the mixed salt solution is 1.6mol/L, the mass percentage concentration of the sodium hydroxide solution is 22%, and the mass percentage concentration of the ammonia water is 15%.
After the preparation of the crystal nucleus is finished, the pH value of a reaction system is adjusted to 10.9, particles are in a growth state, feeding is stopped after the reaction is continued for 8 hours, the rotating speed is increased to 750rpm, no holding time is required, then 0.8mol/L saline solution with the same proportion is introduced, 30% hydrogen peroxide solution by mass fraction is introduced, electron microscope monitoring is continuously carried out during the process, and when feeding is resumed for 10 hours until the feeding process is stopped, the physicochemical index is qualified.
Placing the kettle material in an ageing kettle for ageing, filtering, adding dilute alkali with a certain concentration into a filter cake for pulping, filtering and washing until the pH value of the filtrate is less than 9, drying, screening and demagnetizing to obtain a precursor material, wherein the crystallization state is not changed due to no holding time after the rotation speed is increased, the subsequent process is insufficient to enable primary particles to uniformly grow, and the primary particle diameter of the prepared precursor is large in width-diameter-length difference and does not meet the design requirement.
Comparative example 4 (compared with example 1, the concentration of the mixed salt solution in this comparative example was not adjusted)
Preparing a reaction kettle base solution, wherein the temperature is 50 ℃, the ammonia value is 14g/L, the pH value is 11.4, simultaneously introducing nickel cobalt manganese sulfate solution, ammonia water and sodium hydroxide into the reaction kettle, introducing nitrogen for protection, setting the stirring rotating speed of the reaction kettle to be 550rpm, wherein the molar ratio of nickel to cobalt manganese in the mixed salt solution is 6:1:3, the concentration of the mixed salt solution is 1.6mol/L, the mass percentage concentration of the sodium hydroxide solution is 22%, and the mass percentage concentration of the ammonia water is 15%.
After the preparation of the crystal nucleus is finished, the pH value of a reaction system is adjusted to 10.9, particles are in a growth state, the feeding is stopped after the reaction is continued for 8 hours, the rotating speed is increased to 750rpm, the current process is kept for 5 hours, then 1.6mol/L of salt solution with the same proportion is introduced, 30% of hydrogen peroxide solution by mass fraction is introduced, the electron microscope monitoring is continuously carried out during the period, the width and the length of the primary particle diameter are not improved, and by contrast, the low-concentration salt solution plays a role of continuously reducing the growth power of the reaction system in the crystal form adjusting stage, and meanwhile, the raw materials and the time required by the crystal form conversion of the system are given. After the rotating speed is increased, if the original concentration mixed salt solution is adopted, the growth power is maintained at a higher level, the growth rate cannot be effectively reduced, abnormal particles continue to grow abnormally due to the power, and the diameter-width difference value of the finally prepared product is larger than 20nm and does not meet the design requirement.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1.一种提升正极材料前驱体一次颗粒一致性的制备方法,其特征在于,其包括:采用共沉淀法制备正极材料前驱体时,当溶液中出现一次颗粒大小不一的情况时,暂停所有进料,再提升转速抑制一次颗粒的异常生长,随后通入低浓度盐溶液、过氧化氢溶液引导一次颗粒向同一方向进行生长,减少成核位点,提升正极材料前驱体一次颗粒一致性,其中:所述低浓度盐溶液浓度为原有混合盐溶液浓度的0.3倍-0.8倍,所述提升转速是将转速提升至原有转速的1.2倍-2倍,维持暂停时间为0.5h-10h。1. A preparation method for improving the consistency of primary particles of a positive electrode material precursor, characterized in that it includes: when the positive electrode material precursor is prepared by a coprecipitation method, when the primary particles of different sizes appear in the solution, all feedings are suspended, and the rotation speed is increased to suppress the abnormal growth of the primary particles, and then a low-concentration salt solution and a hydrogen peroxide solution are introduced to guide the primary particles to grow in the same direction, reduce nucleation sites, and improve the consistency of the primary particles of the positive electrode material precursor, wherein: the concentration of the low-concentration salt solution is 0.3 times to 0.8 times the concentration of the original mixed salt solution, and the speed increase is to increase the speed to 1.2 times to 2 times the original speed, and the pause time is maintained for 0.5h-10h. 2.根据权利要求1所述的制备方法,其特征在于,包括以下步骤:惰性气体保护下,向底液中并流通入混合盐溶液、沉淀剂溶液和络合剂溶液,生成晶核后降低体系的pH进行一次颗粒的生长,当溶液中出现一次颗粒大小不一的情况时,暂停所有进料,再提升转速抑制一次颗粒的异常生长,维持转速搅拌,当沉淀趋于暂停时,通入相同摩尔比的低浓度盐溶液、过氧化氢溶液引导一次颗粒向同一方向进行生长,减少成核位点,提升正极材料前驱体一次颗粒一致性,当重新进料后径宽、径长差值符合设计要求,恢复为原有进料方式,直至一次颗粒的物化指标合格。2. The preparation method according to claim 1 is characterized in that it comprises the following steps: under the protection of inert gas, a mixed salt solution, a precipitant solution and a complexing agent solution are introduced into the bottom liquid in parallel, and after the crystal nucleus is generated, the pH of the system is lowered to grow the primary particles; when the primary particles of different sizes appear in the solution, all feedings are suspended, and the rotation speed is increased to suppress the abnormal growth of the primary particles, and the rotation speed is maintained to stir; when the precipitation tends to be suspended, a low-concentration salt solution and a hydrogen peroxide solution of the same molar ratio are introduced to guide the primary particles to grow in the same direction, reduce the nucleation sites, and improve the consistency of the primary particles of the positive electrode material precursor; when the diameter width and the diameter length difference meet the design requirements after re-feeding, the original feeding method is restored until the physical and chemical indicators of the primary particles are qualified. 3.根据权利要求2所述的制备方法,其特征在于,控制反应体系的pH值为10.0-12.5,氨值2g/L-20g/L,温度40℃-80℃,转速为100rpm-1000rpm。3. The preparation method according to claim 2 is characterized in that the pH value of the reaction system is controlled to be 10.0-12.5, the ammonia value is 2g/L-20g/L, the temperature is 40°C-80°C, and the rotation speed is 100rpm-1000rpm. 4.根据权利要求2所述的制备方法,其特征在于,生成晶核后降低体系的pH,继续反应5h-10h后暂停进料。4. The preparation method according to claim 2 is characterized in that the pH of the system is lowered after the crystal nucleus is generated, and the feeding is suspended after continuing the reaction for 5h-10h. 5.根据权利要求2所述的制备方法,其特征在于,所述混合盐溶液的浓度为1.0 mol/L-2.5mol/L,所述沉淀剂溶液的质量浓度为20%-25%,所述络合剂溶液的质量浓度为7%-30%。5. The preparation method according to claim 2, characterized in that the concentration of the mixed salt solution is 1.0 mol/L-2.5 mol/L, the mass concentration of the precipitant solution is 20%-25%, and the mass concentration of the complexing agent solution is 7%-30%. 6.根据权利要求2所述的制备方法,其特征在于,所述过氧化氢溶液的质量分数为5%-40%。6. The preparation method according to claim 2, characterized in that the mass fraction of the hydrogen peroxide solution is 5%-40%. 7.根据权利要求2所述的制备方法,其特征在于,还包括:将反应合格的物料陈化,过滤,将过滤得到的滤饼用稀碱进行浆化,再过滤洗涤至滤液pH值小于9,经干燥、筛分、除磁得到一次颗粒均一的前驱体产品。7. The preparation method according to claim 2 is characterized in that it also includes: aging and filtering the qualified reaction materials, slurrying the filter cake obtained by filtration with dilute alkali, filtering and washing until the pH value of the filtrate is less than 9, and obtaining a precursor product with uniform primary particles through drying, screening and demagnetization. 8.一种正极材料前驱体,其特征在于,所述正极材料前驱体采用权利要求1-7中任一项所述的方法制备得到。8. A cathode material precursor, characterized in that the cathode material precursor is prepared by the method according to any one of claims 1 to 7.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116062803A (en) * 2022-12-07 2023-05-05 宜宾光原锂电材料有限公司 Ternary positive electrode material precursor and preparation method thereof
CN116588993A (en) * 2023-07-17 2023-08-15 宜宾光原锂电材料有限公司 Ternary precursor and preparation method thereof, lithium battery cathode material and lithium battery

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200051931A (en) * 2018-11-06 2020-05-14 주식회사 포스코 Lithium compound, nickel-based positive active material, method of preparing lithium oxide, mehtod of preparing nickel-based positive active material, and secondary battery using the same
KR20240027110A (en) * 2022-07-15 2024-02-29 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 Continuous reaction system, ferromanganese phosphate precursor, lithium iron manganese phosphate, and method for producing the same and secondary battery
CN116617979A (en) * 2023-04-19 2023-08-22 宜宾光原锂电材料有限公司 A kind of ternary precursor preparation reaction kettle and preparation method
CN116854152B (en) * 2023-08-14 2024-06-14 金驰能源材料有限公司 Sodium ion battery positive electrode material precursor, preparation method thereof, positive electrode material and sodium ion battery
CN118495604A (en) * 2024-04-01 2024-08-16 华友新能源科技(衢州)有限公司 Positive electrode precursor material, and preparation method and application thereof
CN118598213A (en) * 2024-05-31 2024-09-06 兰州金通储能动力新材料有限公司 A high-compactness small-particle sodium electrode precursor and its preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116062803A (en) * 2022-12-07 2023-05-05 宜宾光原锂电材料有限公司 Ternary positive electrode material precursor and preparation method thereof
CN116588993A (en) * 2023-07-17 2023-08-15 宜宾光原锂电材料有限公司 Ternary precursor and preparation method thereof, lithium battery cathode material and lithium battery

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