CN110589903A - Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof - Google Patents

Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof Download PDF

Info

Publication number
CN110589903A
CN110589903A CN201910669368.XA CN201910669368A CN110589903A CN 110589903 A CN110589903 A CN 110589903A CN 201910669368 A CN201910669368 A CN 201910669368A CN 110589903 A CN110589903 A CN 110589903A
Authority
CN
China
Prior art keywords
cobalt
nickel
solution
reaction
equal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910669368.XA
Other languages
Chinese (zh)
Inventor
顾春芳
王梁梁
朱用
张振兴
叶庆龄
朱涛
赵亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nantong Jintong Energy Storage Power New Materials Co Ltd
Original Assignee
Nantong Jintong Energy Storage Power New Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nantong Jintong Energy Storage Power New Materials Co Ltd filed Critical Nantong Jintong Energy Storage Power New Materials Co Ltd
Priority to CN201910669368.XA priority Critical patent/CN110589903A/en
Publication of CN110589903A publication Critical patent/CN110589903A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A process for preparing the large-particle Ni-Co-Mn hydroxide includes such steps as adding pure water and complexing agent as basic liquid to reaction system, introducing nitrogen gas continuously, stirring at 40 ~ deg.C, adding Ni-Co-Mn salt solution, alkali solution and ammonia water, controlling pH value to 11.0 ~.0, stopping reaction until the particle size reaches 12.0 microns, adding alkali solution to regulate pH value to 13.0, adding bicarbonate solution, ageing for 2 ~ hr, adding Ni-Co-Mn salt solution, alkali solution and ammonia water, controlling pH value to 11.0 ~.0, and finishing reaction when the particle size in reaction system reaches target one.

Description

Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to large-particle nickel-cobalt-manganese hydroxide and a preparation method thereof.
Background
With the development of new energy industry, lithium ion batteries are receiving attention as a new generation of green energy. The anode material, as one of the key core technologies of the lithium ion battery, occupies one third of the production cost of the whole lithium ion battery, and the performance of the anode material directly affects the capacity, the cycle, the safety performance and the like of the lithium ion battery.
The lithium ion battery materials which have been successfully commercialized at present mainly comprise lithium cobaltate, lithium iron phosphate and nickel cobalt manganese ternary positive electrode materials. Wherein, lithium cobaltate is used as the earliest successfully commercialized anode material, the pole piece compaction density of the lithium cobaltate is the highest of all anode materials and can reach 4.0g/cm3. Therefore, lithium cobaltate materials still dominate the 3C market in pursuit of light and thin, but the high cost and toxicity of lithium cobaltate require more suitable materials for replacement.
The nickel-cobalt-manganese ternary material integrates the synergistic effect of three elements of nickel, cobalt and manganese, and nickel and manganese substitute for part of cobalt, so that the material has the advantages of higher capacity, low cost, excellent cycle performance and the like, and the nickel-cobalt-manganese ternary material gradually replaces a lithium cobaltate material at each application end. However, the pole piece compaction density of the conventional ternary cathode material is only 3.5g/cm3Therefore, the ternary cathode material replaces lithium cobaltate to sacrifice the volume energy density of the material, so that the ternary lithium ion battery has high application value in further improving the volume energy density.
The pole piece compaction density of the ternary positive electrode material can be effectively improved by blending the large and small particles under different grading, the optimal pole piece of the ternary positive electrode material is prepared by blending and combining the large and small particles, and the compaction density can reach 3.8 ~ 3.9.9 g/cm3And the pole piece compaction density of lithium cobaltate is approximate. The process has the requirement that the granularity of large particles is D50 more than 18.0 mu m, however, when the ternary precursor is prepared by coprecipitation, when the reaction granularity in the system grows to 12.0 mu m (deleted), the material amount in the reaction system is increased, the particles become smoother under the action of stirring shearing force and inter-particle collision, newly-formed crystal nuclei are difficult to attach to the surfaces of the large particles for growth, so that the growth speed of the granularity in the system is reduced, the granularity is difficult to grow to more than 18.0 mu m, and meanwhile, the stirring shearing and the inter-particle collision easily cause the large particles to be easy to crack. Therefore, how to effectively increase the growth rate of the large-particle precursor and maintain the integrity of the particles, and to realize the simplification of the production process and the high productivity becomes a problem to be solved urgently.
Chinese patent CN201611266605 discloses a preparation method of a large particle precursor for a lithium ion battery anode material, which comprises adding a metal mixed salt solution, a precipitant and a complexing agent into a reactor 1 in parallel for continuous reaction 1, adding an overflow solution into a reaction system 2, and adding the metal mixed salt solution, the precipitant and the complexing agent into the reactor 2 in parallel for continuous reaction 2. The precursor prepared by the method has large particle size and narrow particle size distribution, the serial connection of the reactors has high requirement on the air tightness of reaction equipment and pipelines, and the treatment process is relatively complicated by continuously converting materials.
Chinese patent CN20170407336 discloses a method for preparing a nickel-rich precursor material capable of preventing particle fracture, which comprises preparing reaction slurry, and setting a target particle size D50= D of the precursor; during the preparation reaction, the real-time particle size D50 of the generated reactant is monitored and recorded as D1; when the actually measured d1 value is obviously smaller than the d value, the particle size distribution Span value of the reactant is adjusted to be low by changing the process conditions, and when the actually measured d1 value is detected to be close to d subsequently, the process conditions are changed again to increase the particle size distribution Span value of the reactant so as to control the Span value within a certain range; and continuing the subsequent preparation reaction until the particle size of the produced reactant is as large as the d value while keeping the Span value in a control range. The precursor material prepared by the patent has high sphericity and complete particles, but has wide particle size distribution and smaller D50.
Therefore, how to solve the above-mentioned deficiencies of the prior art is a problem to be solved by the present invention.
Disclosure of Invention
The invention aims to provide a large-particle nickel-cobalt-manganese hydroxide and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the large-particle nickel-cobalt-manganese hydroxide has the general formula of NixCoyMnz(OH)2Wherein x is more than or equal to 0.4 and less than 1.0, and x + y + z = 1; the average particle size of the nickel-cobalt-manganese hydroxide is more than or equal to 18 mu m, the particle size distribution Span value is less than or equal to 0.70, and the TD is more than or equal to 2.0g/cm3。
The relevant content in the above technical solution is explained as follows:
1. in the scheme, the Span value is a radial distance and represents a particle size distribution distance; and TD is tap density.
In order to achieve the purpose, the invention adopts another technical scheme that:
a preparation method of large-particle nickel-cobalt-manganese hydroxide; the method comprises the following steps:
step one, adding pure water and a complexing agent into a reaction system to serve as a base solution, continuously introducing nitrogen, controlling the reaction temperature to be 40 ~ 60 ℃, then starting stirring, adding a nickel-cobalt-manganese salt solution, an alkali solution and ammonia water into the reaction system, and adding the alkali solution to control the pH of the reaction solution to be 11.0 ~ 12.0.0;
step two, when the reaction granularity in the step one reaches 12.0 mu m, stopping the reaction, adding an alkali solution into the reaction system to adjust the pH value, controlling the pH value of the reaction system to be more than or equal to 13.0, and adding a bicarbonate solution and aging for 2 ~ 4 hours after the pH value is adjusted;
and step three, after the aging of the step two is finished, continuously adding the salt solution of nickel, cobalt and manganese, the alkali solution and ammonia water into the reaction system, adding the alkali solution to control the pH value of the reaction solution to be 11.0 ~ 12.0.0, and finishing the reaction when the granularity in the reaction system grows to the target granularity.
The relevant content in the above technical solution is explained as follows:
1. in the scheme, the nickel-cobalt-manganese salt solution in the first step and the third step is at least one of sulfate, nitrate and chloride of nickel-cobalt-manganese, and the concentration of the salt solution is 2 ~ 4 mol/L;
the concentration of the alkali solution in the first step and the third step is 20 ~ 50%, and the concentration of the ammonia water is 2 ~ 5 mol/L.
2. In the scheme, the bicarbonate solution in the step two is at least one of ammonium bicarbonate, potassium bicarbonate, sodium bicarbonate, calcium bicarbonate and magnesium bicarbonate, wherein the concentration of the bicarbonate solution is 1 ~ 4mol/L, and the input amount is 1 ~ 5% of the mass percentage of the materials in the reaction system.
3. In the scheme, the general formula of the nickel-cobalt-manganese hydroxide prepared in the third step is NixCoyMnz (OH)2Wherein x is more than or equal to 0.4 and less than 1.0, and x + y + z = 1; the average particle size of the nickel-cobalt-manganese hydroxide is more than or equal to 18.0 mu m, the particle size distribution Span value is less than or equal to 0.70, and the TD is more than or equal to 2.0g/cm3。
The working principle and the advantages of the invention are as follows:
the invention provides a large-particle nickel-cobalt-manganese hydroxide and a preparation method thereof, the method can prepare the nickel-cobalt-manganese hydroxide with the particle size D50 of more than or equal to 18.0 mu m, high sphericity and no cracking, and the preparation method has simple production flow and high productivity and is suitable for large-scale industrial production.
Compared with the prior art, the preparation method has the following characteristics:
firstly, the invention releases a small amount of CO by using a specific amount of bicarbonate to react in an alkaline solution in the stage of grain size growth to be slow2The surface of the particle is changed from smooth to loose, the specific surface area of the particle is increased, and a concave-convex surface required by the growth of crystal nucleus is manufactured, so that the newly generated crystal nucleus is better attached to the surface of the particle for growth;
in the coprecipitation reaction, the growth speed of particles is slowed down along with the increase of the amount of products in a system, and part of materials are required to be rotated out through more reaction containers or the rotating speed is reduced so that the particles are agglomerated; the invention does not need to additionally use a new reaction vessel or transfer materials, has simple production process and high productivity; meanwhile, the rotating speed is kept unchanged, no agglomeration occurs among particles along with the reaction time, and the sphericity is high.
Drawings
FIG. 1 is an SEM photograph of nickel cobalt manganese hydroxide D50 reaching 12.0 μm according to an embodiment of the present invention;
FIG. 2 is a particle size distribution diagram of 12.0 μm obtained by D50;
FIG. 3 is an SEM photograph of nickel cobalt manganese hydroxide D50 prepared according to an embodiment of the present invention after being charged with bicarbonate to reach 12.0 μm;
FIG. 4 is a graph showing the particle size distribution of nickel cobalt manganese hydroxide D50 after being added with bicarbonate after reaching 12.0 μm according to an example of the present invention;
FIG. 5 is an SEM photograph of the nickel cobalt manganese hydroxide D50 prepared according to the example of the invention after reaching 19.5 μm;
FIG. 6 is a particle size distribution curve of nickel cobalt manganese hydroxide D50 prepared according to an example of the present invention after reaching 19.5 μm.
Detailed Description
The invention is further described with reference to the following figures and examples:
example (b): the present disclosure will be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the disclosure may be shown and described, and which, when modified and varied by the techniques taught herein, can be made by those skilled in the art without departing from the spirit and scope of the disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The singular forms "a", "an", "the" and "the", as used herein, also include the plural forms.
As used herein, the terms "comprising," "including," "having," and the like are open-ended terms that mean including, but not limited to.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
Referring to FIG. 1 ~ 6, a large particle Ni-Co-Mn hydroxide of the general formula NixCoyMnz(OH)2Wherein x is more than or equal to 0.4 and less than 1.0, and x + y + z = 1; the average particle size (D50) of the nickel-cobalt-manganese hydroxide is not less than 18 mu m, the particle size distribution Span value is not more than 0.70, and the TD is not less than 2.0g/cm3。
The preparation method of the large-particle nickel-cobalt-manganese hydroxide comprises the following steps:
step one, adding pure water and a complexing agent into a reaction system to serve as a base solution, continuously introducing nitrogen, controlling the reaction temperature to be 40 ~ 60 ℃, then starting stirring, pumping a nickel-cobalt-manganese salt solution, an alkali solution and ammonia water into the reaction system through a metering pump, and adding the alkali solution to control the pH of the reaction solution to be 11.0 ~ 12.0.0;
step two, when the reaction granularity in the step one reaches 12.0 mu m, suspending the reaction, adding an alkali solution into the reaction system to adjust the pH value, controlling the pH value of the reaction system to be more than or equal to 13.0, and improving the OH content in the solution-Ion concentration, inhibition of HCO3-Ion hydrolysis to form trace amount of H2CO3Adding bicarbonate solution and aging for 2 ~ 4 hours after the pH is adjusted;
and step three, after the aging of the step two is finished, continuously pumping a nickel-cobalt-manganese salt solution, an alkali solution and ammonia water into the reaction system through a metering pump, adding the alkali solution to control the pH of the reaction solution to be 11.0 ~ 12.0.0, wherein the condition is relatively suitable for the growth of large-particle products, the precipitation of nickel-cobalt-manganese metal ions is incomplete when the pH is too low, the growth rate of crystals is too slow when the pH is too high, the growth of large-particle products is not facilitated, and the reaction is finished when the particle size grows to the target particle size (D50 is more than or equal to 18.0 microns) in.
Wherein, the nickel-cobalt-manganese salt solution in the first step and the third step is at least one of sulfate, nitrate and chloride of nickel-cobalt-manganese, and the concentration of the salt solution is 2 ~ 4 mol/L;
the concentration of the alkali solution in the first step and the third step is 20 ~ 50%, and the concentration of the ammonia water is 2 ~ 5 mol/L.
Wherein the bicarbonate solution in the step two is at least one of ammonium bicarbonate, potassium bicarbonate, sodium bicarbonate, calcium bicarbonate and magnesium bicarbonate, the concentration of the bicarbonate solution is 1 ~ 4mol/L, and the input amount is 1 ~ 5% of the mass percentage of the materials in the reaction system.
Wherein the general formula of the nickel-cobalt-manganese hydroxide prepared in the third step is NixCoyMnz (OH)2Wherein x is more than or equal to 0.4 and less than 1.0, and x + y + z = 1; d50 is more than or equal to 18.0 mu m, and the particle size distribution Span value is less than or equal to 0.70.
The preparation method of the large-particle nickel-cobalt-manganese hydroxide can be carried out according to the following steps in a specific experiment:
step (1), adding 2500L of pure water into a reaction system for carrying out 10m ethanol planting, then respectively opening the liquid adding of 2mol/L of nickel-cobalt-manganese mixed flow rate salt solution and 3mol/L of ammonia water solution in a metering pump uniform speed parallel flow mode, wherein the molar coefficient ratio of metal nickel, cobalt and manganese in the raw materials is 60: 20: 20; simultaneously supplying 4mol/L sodium hydroxide solution to control the pH value of the process to be 11.5 +/-0.1; nitrogen (or other inert gases) is introduced for protection in the feeding process, the ammonia concentration in the reaction liquid is controlled to be 1.0 +/-0.2 mol/L, the stirring speed is 150 rpm, and the temperature of the reaction system is controlled to be 50 +/-4 ℃.
And (2) monitoring the change of the granularity in the reaction process in real time, stopping the reaction when the granularity grows to 12.0 mu m, adding an alkali solution to ensure that the pH value in the reaction system is 13.0, and then adding 300L of 2mol/L ammonium bicarbonate solution into the reaction system for aging for 4 hours.
And (3) after aging is finished, respectively starting liquid adding of 2mol/L nickel-cobalt-manganese mixed flow rate salt solution and 3mol/L ammonia water solution in a metering pump uniform speed parallel flow mode, simultaneously supplying 4mol/L sodium hydroxide solution, controlling the pH value in the process to be 11.5 +/-0.1, continuing to react until the granularity grows to the target granularity D50 larger than 18.0 microns, and finishing the reaction.
And (4) aging the product obtained in the step (3) for 2h, centrifugally washing until the material is neutral, and finally completely drying at 150 ℃ to obtain a final sample, namely a nickel-cobalt-manganese ternary precursor Ni0.6Co0.2Mn0.2(OH)2。
As can be seen from the combination of FIG. 1 and FIG. 2, after the reaction particle size is increased to 12.0 μm, the surface of the particles is smooth, and after aging in ammonium bicarbonate solution, the roughness of the surface of the particles is increased without decreasing the sphericity. Meanwhile, as can be seen from fig. 3 and 4, the particle size in the system is not changed after the ammonium bicarbonate solution is aged.
As can be seen from FIG. 5, the product after the reaction has smooth surface, high sphericity of the particles and no cracking. As can be seen from FIG. 6, the product has a narrow particle size distribution and a high degree of uniformity of particle size.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (5)

1. A large-particle nickel cobalt manganese hydroxide is characterized in that: the general formula of the nickel-cobalt-manganese hydroxide is NixCoyMnz(OH)2Wherein x is more than or equal to 0.4 and less than 1.0, and x + y + z = 1; the average particle size of the nickel-cobalt-manganese hydroxide is more than or equal to 18 mu m, the particle size distribution Span value is less than or equal to 0.70, and the TD is more than or equal to 2.0g/cm3。
2. A preparation method of large-particle nickel-cobalt-manganese hydroxide; the method is characterized in that:
the method comprises the following steps:
step one, adding pure water and a complexing agent into a reaction system to serve as a base solution, continuously introducing nitrogen, controlling the reaction temperature to be 40 ~ 60 ℃, then starting stirring, adding a nickel-cobalt-manganese salt solution, an alkali solution and ammonia water into the reaction system, and adding the alkali solution to control the pH of the reaction solution to be 11.0 ~ 12.0.0;
step two, when the reaction granularity in the step one reaches 12.0 mu m, stopping the reaction, adding an alkali solution into the reaction system to adjust the pH value, controlling the pH value of the reaction system to be more than or equal to 13.0, and adding a bicarbonate solution and aging for 2 ~ 4 hours after the pH value is adjusted;
and step three, after the aging of the step two is finished, continuously adding the salt solution of nickel, cobalt and manganese, the alkali solution and ammonia water into the reaction system, adding the alkali solution to control the pH value of the reaction solution to be 11.0 ~ 12.0.0, and finishing the reaction when the granularity in the reaction system grows to the target granularity.
3. The method according to claim 2, wherein the nickel cobalt manganese salt solution in the first step and the third step is at least one of sulfate, nitrate and chloride of nickel cobalt manganese, and the concentration of the salt solution is 2 ~ 4 mol/L;
the concentration of the alkali solution in the first step and the third step is 20 ~ 50%, and the concentration of the ammonia water is 2 ~ 5 mol/L.
4. The preparation method according to claim 2, wherein the bicarbonate solution in the second step is at least one of ammonium bicarbonate, potassium bicarbonate, sodium bicarbonate, calcium bicarbonate and magnesium bicarbonate, wherein the concentration of the bicarbonate solution is 1 ~ 4mol/L, and the input amount is 1 ~ 5% of the mass percentage of the materials in the reaction system.
5. The method of claim 2, wherein: the general formula of the nickel-cobalt-manganese hydroxide prepared in the third step is NixCoyMnz (OH)2Wherein x is more than or equal to 0.4 and less than 1.0, and x + y + z = 1; the average particle size of the nickel-cobalt-manganese hydroxide is more than or equal to 18.0 mu m, the particle size distribution Span value is less than or equal to 0.70, and the TD is more than or equal to 2.0g/cm 3.
CN201910669368.XA 2019-07-24 2019-07-24 Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof Pending CN110589903A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910669368.XA CN110589903A (en) 2019-07-24 2019-07-24 Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910669368.XA CN110589903A (en) 2019-07-24 2019-07-24 Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110589903A true CN110589903A (en) 2019-12-20

Family

ID=68853179

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910669368.XA Pending CN110589903A (en) 2019-07-24 2019-07-24 Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110589903A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112299494A (en) * 2020-10-29 2021-02-02 格林爱科(荆门)新能源材料有限公司 Preparation method of nickel-cobalt hydroxide material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109273701A (en) * 2018-11-23 2019-01-25 中南大学 High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material and preparation method thereof
CN110002515A (en) * 2019-03-26 2019-07-12 南通金通储能动力新材料有限公司 A kind of high capacity monocrystalline type tertiary cathode material preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109273701A (en) * 2018-11-23 2019-01-25 中南大学 High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material and preparation method thereof
CN110002515A (en) * 2019-03-26 2019-07-12 南通金通储能动力新材料有限公司 A kind of high capacity monocrystalline type tertiary cathode material preparation method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112299494A (en) * 2020-10-29 2021-02-02 格林爱科(荆门)新能源材料有限公司 Preparation method of nickel-cobalt hydroxide material

Similar Documents

Publication Publication Date Title
CN107265520B (en) A kind of preparation method and product of spherical nickel cobalt manganese persursor material
CN110817975B (en) Method for reducing sulfur content of ternary precursor
EP4086229A1 (en) Preparation method for high nickel ternary precursor capable of preferential growth of crystal planes by adjusting and controlling addition amount of seed crystals
CN108258235B (en) Method for preparing nickel-cobalt-manganese ternary precursor material through hierarchical reaction
CN114394630B (en) Preparation method for controlling morphology of ternary precursor material
CN109422297B (en) Method for regulating and controlling nucleation in crystallization process of nickel-cobalt-manganese precursor
CN108987682B (en) Preparation method of nickel-rich precursor material capable of preventing particle fracture
CN104269548B (en) A kind of method optimizing size distribution in nickel cobalt manganese persursor material preparation process
CN101269848A (en) High-density spherical cobaltic-cobaltous oxide and method for preparing the same
CN110817976B (en) Positive electrode material precursor and preparation method and application thereof
CN112537807B (en) High-performance nano rod-shaped nickel-manganese binary precursor and preparation method thereof
CN114084914A (en) Ternary precursor and preparation method and application thereof
CN113735190A (en) Small-particle ternary precursor and preparation method thereof
EP4023609A1 (en) Aluminum-coated precursor, preparation method therefor, and use thereof
CN111977705A (en) Preparation method of nickel-cobalt-manganese composite hydroxide
CN111072075A (en) Preparation method of lithium ion battery anode material
CN114620777B (en) Ultrahigh nickel ternary precursor and preparation method thereof
CN111600010A (en) Preparation method of single crystal large particles of ternary material
CN114645329B (en) Nickel-cobalt-manganese hydroxide with high nickel and low cobalt fine whisker and preparation method thereof
CN110282665B (en) Lithium battery positive electrode material precursor with mesoscopic structure and preparation method thereof
CN112850802A (en) Production process and production device of wide-distribution cobaltosic oxide
CN116354409A (en) Ultrahigh BET high-nickel ternary precursor and continuous preparation method thereof
CN114195204A (en) High-sphericity manganese-rich carbonate precursor and preparation method and application thereof
CN116588993B (en) Ternary precursor, preparation method thereof, lithium battery positive electrode material and lithium battery
CN110589903A (en) Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20191220

RJ01 Rejection of invention patent application after publication