CN107834064B - High-nickel small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof - Google Patents
High-nickel small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof Download PDFInfo
- Publication number
- CN107834064B CN107834064B CN201711260819.1A CN201711260819A CN107834064B CN 107834064 B CN107834064 B CN 107834064B CN 201711260819 A CN201711260819 A CN 201711260819A CN 107834064 B CN107834064 B CN 107834064B
- Authority
- CN
- China
- Prior art keywords
- nickel
- cobalt
- reaction kettle
- particle
- reaction
- 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.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a high-nickel small-particle-size nickel-cobalt-manganese hydroxide and a preparation method thereof, wherein the preparation method comprises the following steps: (1) continuously introducing a nickel-cobalt-manganese mixed metal solution, a precipitator and a complexing agent for nucleation under the conditions of more mother liquor and high complexing agent concentration, and highly dispersing crystal nuclei through high-speed stirring to enter a crystal nucleus growth stage; (2) when the reaction is started until the material can be precipitated, when D50 is 1.3-1.5 mu m, extracting feed liquid with the effective volume of 1/6-1/3 from the upper part of the reaction kettle, pouring out supernatant liquid when the feed liquid is completely precipitated, and returning the precipitate to the reaction kettle for continuous reaction; (3) the procedure was repeated to introduce new seeds and increase the solids content, and the reaction was stopped until D50 ═ 3 μm. The method adopts nucleation crystallization/new seed crystal introduction to prepare the nickel-cobalt-manganese hydroxide, can avoid artificial balling, does not need to modify the existing reaction kettle, is simple and convenient to operate, and can enlarge production; the prepared nickel-cobalt-manganese hydroxide has uniform and concentrated particle size distribution, no agglomeration, high tap density and good sphericity.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to high-nickel small-particle-size nickel-cobalt-manganese hydroxide and a preparation method thereof.
Background
Since the lithium ion battery was first developed and succeeded by Sony corporation in 1990, the lithium ion battery has wide application prospects and potential huge economic benefits in the aspects of portable electronic equipment, electric automobiles, national defense technologies, space technologies and the like because of the main advantages of high voltage and high capacity and the remarkable characteristics of long cycle life and good safety performance, and quickly becomes a research hotspot which is widely concerned at present. In the structural combination of lithium ion materials, the high nickel positive electrode material has been paid attention to due to its high capacity, and has become the focus of the current research, especially the high nickel positive electrode small particles with high energy, high multiplying power and high safety performance are most concerned.
The key to the preparation of the high-nickel anode small particles lies in the preparation of a small-particle-size nickel-cobalt-manganese hydroxide precursor; the precursor has good sphericity, uniform particle size dispersion, no agglomeration and high tap density, and can be used as a matrix to prepare the high-nickel anode small-particle material with good performance.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the technical defects of the background technology and provides a high-nickel small-particle-size nickel-cobalt-manganese hydroxide and a preparation method thereof. In the invention, under the conditions of high ammonia water concentration and high rotating speed, artificial ball hitting can be avoided by nucleating crystallization/introducing new seed crystals and increasing solid content; the preparation method of the invention does not need to modify the existing reaction kettle, is simple and convenient to operate and can enlarge the production; the high-nickel small-particle-size nickel-cobalt-manganese hydroxide prepared by the method has uniform particle size distribution, concentration, no agglomeration, high tap density and good sphericity; the high-nickel small-particle-size nickel cobalt manganese hydroxide D50 is 1.5-3 mu m, the particle size distribution is 1-10 mu m, and the tap density is 1.6-2.4 g/cm 3; the lithium ion battery anode material prepared from the high-nickel small-particle-size nickel-cobalt-manganese hydroxide has high capacity, high tap density, centralized particle size distribution and good single crystal morphology.
The technical means adopted by the invention for solving the technical problems is as follows:
a preparation method of high-nickel small-particle-size nickel-cobalt-manganese hydroxide comprises the following steps:
(1) the nickel-cobalt-manganese soluble salt is prepared according to the mol ratio of nickel-cobalt-manganese in the hydroxide, namely according to the general formula Ni1-x- yCoxMny(OH)2Wherein x is more than or equal to 0.09 and less than or equal to 0.12, and y is more than or equal to 0.03 and less than or equal to 0.05, and preparing a first mixed metal salt solution containing Ni ions, Co ions and Mn ions; preparing a second mixed solution consisting of a precipitator; preparing a third mixed solution consisting of complexing agents;
(2) adding pure water with the effective volume of 80% into the reaction kettle under the stirring condition, introducing the second mixed solution and the third mixed solution in the step (1) to prepare mother liquor, and continuously introducing inert gas as protection;
(3) enabling the first mixed metal salt solution, the second mixed solution and the third mixed solution in the step (1) to flow in parallel, continuously introducing into a high-speed stirring reaction kettle, and carrying out coprecipitation reaction under the action of the second mixed solution and the third mixed solution, wherein crystal nuclei are continuously formed and grown; when the granularity reaches 1.3-1.5 mu m, feeding continuously, pumping the feed liquid from the upper part of the reaction kettle, pouring out the supernatant after the feed liquid is precipitated, pouring the precipitate back to the reaction kettle, then adopting the same method when the reaction kettle is full, introducing new seed crystals, increasing the solid content, slowing down the growth rate of particles, avoiding the adverse conditions of small particle agglomeration and the like caused by artificial balling, stopping feeding when the granularity D50 reaches 2.5-3 mu m, and finishing the reaction;
(4) and (4) sequentially aging the reaction products obtained in the step (3), carrying out alkaline washing centrifugation on the aged slurry, and then drying, crushing, sieving and removing iron to obtain the high-nickel small-particle-size nickel-cobalt-manganese hydroxide.
In the technical scheme, the materials are continuously discharged and fed back in the reaction process, so that new seed crystals are introduced and the solid content is increased, and the adverse conditions of small particle agglomeration and the like caused by artificial balling can be avoided.
In the technical scheme, the feed liquid is continuously introduced in the reaction process, the continuous production is realized, and the productivity is not reduced.
Preferably, in the step (1), the concentration of the first mixed metal salt solution is 1.5-2 mol/L.
Preferably, in the step (1), the precipitant is KOH, LiOH, NaOH, Na2CO3Further preferably NaOH.
Preferably, in the step (1), the concentration of the second mixed solution is 2-6 mol/L.
Preferably, in the step (1), the complexing agent is any one or more of ammonia water, disodium ethylene diamine tetraacetate, sulfosalicylic acid and glycine, and further preferably ammonia water.
Preferably, in the step (1), the concentration of the third mixed solution is 7-14 mol/L.
Preferably, in the step (2), the mother liquor accounts for more than 80% of the effective volume of the reaction kettle, wherein the pH value is 12.0-12.4, the ammonia value is 10-12 g/L, and the temperature is 40-65 ℃.
Preferably, in the step (2), the value of the third mixed solution in the reaction kettle system is 8-14 g/L.
Preferably, in the step (2), the inert gas is one or both of nitrogen and argon.
Preferably, in the step (3), the coprecipitation reaction temperature is 40-65 ℃.
Preferably, in the step (3), the pH of the coprecipitation reaction is 11.0-12.6.
Preferably, in the step (3), the rotation speed during the coprecipitation reaction is 700-1200 rpm.
Preferably, in the step (3), the volume of the feed liquid extracted from the upper part of the reaction kettle accounts for 1/6-1/3 of the effective volume of the reaction kettle.
More preferably, in the step (3), the volume of the feed liquid extracted from the upper part of the reaction kettle accounts for 1/4 of the effective volume of the reaction kettle.
Preferably, in the step (4), the aging time is 45-85 min.
Preferably, in the step (4), the temperature of the alkaline washing is 50-85 ℃.
Preferably, in the step (4), the drying temperature is 100-150 ℃.
Preferably, in the step (4), the high-nickel small-particle-size nickel cobalt manganese hydroxide D50 is 1.5-3 μm.
Preferably, in the step (4), the particle size distribution of the high-nickel small-particle-size nickel-cobalt-manganese hydroxide is 1-10 μm, and the tap density is 1.6-2.4 g/cm 3.
The high-nickel small-particle-size nickel-cobalt-manganese hydroxide is prepared by the method, wherein the high-nickel small-particle-size nickel-cobalt-manganese hydroxide D50 is 1.5-3 mu m, the particle size distribution is 1-10 mu m, and the tap density is 1.6-2.4 g/cm 3; the high-nickel small-particle-size nickel-cobalt-manganese hydroxide has the advantages of good sphericity, uniform particle size distribution, no agglomeration and high tap density.
And sintering the high-nickel small-particle-size nickel cobalt manganese hydroxide at 700-1000 ℃ for 24-27 h to obtain the lithium ion battery anode material.
The lithium ion battery anode material has high capacity, high tap density, concentrated particle size distribution and good single crystal morphology.
The basic principle of the invention is as follows:
the invention adopts nucleation crystallization/new seed crystal introduction to prepare the high nickel small particle size hydroxide:
(1) continuously introducing a nickel-cobalt-manganese mixed metal solution, a precipitator and a complexing agent for nucleation under the conditions of more mother liquor and high complexing agent concentration, and highly dispersing crystal nuclei through high-speed stirring to enter a crystal nucleus growth stage;
(2) when the reaction is started until the materials can be precipitated, and D50 is 1.3-1.5 mu m, extracting feed liquid with the effective volume of 1/4 from the upper part of the reaction kettle, pouring out supernatant liquid when the feed liquid is completely precipitated, and returning the precipitate to the reaction kettle for continuous reaction;
(3) the procedure was repeated to introduce new seeds and increase the solids content, and the reaction was stopped until D50 ═ 3 μm.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) in the invention, under the conditions of high ammonia water concentration and high rotating speed, artificial ball hitting can be avoided by nucleating crystallization/introducing new seed crystals and increasing solid content;
(2) the preparation method of the invention does not need to modify the existing reaction kettle, is simple and convenient to operate and can enlarge the production;
(3) the high-nickel small-particle-size nickel-cobalt-manganese hydroxide prepared by the method has uniform particle size distribution, concentration, no agglomeration, high tap density and good sphericity;
(4) the high-nickel small-particle-size nickel-cobalt-manganese hydroxide D50 prepared by the method is 1.5-3 mu m, the particle size distribution is 1-10 mu m, and the tap density is 1.6-2.4 g/cm 3;
(5) the lithium ion battery anode material prepared from the high-nickel small-particle-size nickel-cobalt-manganese hydroxide has high capacity, high tap density, centralized particle size distribution and good single crystal morphology.
Drawings
FIG. 1 is an SEM image of high-nickel small-particle-size nickel cobalt manganese hydroxide prepared in example 1 of the present invention;
FIG. 2 is a photograph showing the particle size distribution of the high nickel small particle size nickel cobalt manganese hydroxide prepared in example 1 of the present invention;
FIG. 3 is an SEM image of high-nickel small-particle-size nickel cobalt manganese hydroxide prepared in example 2 of the present invention;
FIG. 4 is a photograph of the particle size distribution of the high nickel small particle size nickel cobalt manganese hydroxide prepared in example 2 of the present invention;
fig. 5 is an SEM image of a lithium ion battery positive electrode material prepared using the high nickel small particle size nickel cobalt manganese hydroxide prepared in example 1 of the present invention as a base material.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It is to be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. Moreover, it should be understood that the invention is not limited to the above-described embodiments, but is capable of various modifications and changes within the scope of the invention.
The invention provides a preparation process of high-nickel small-particle-size nickel-cobalt-manganese hydroxide, which comprises the following steps of:
(1) the nickel-cobalt-manganese soluble salt is prepared according to the mol ratio of nickel-cobalt-manganese in the hydroxide, namely according to the general formula Ni1-x- yCoxMny(OH)2Wherein x is more than or equal to 0.09 and less than or equal to 0.12, and y is more than or equal to 0.03 and less than or equal to 0.1, and a first mixed metal salt solution with the total concentration of Ni, Co and Mn ions of 1.5-2.0 mol/L is prepared;
preparing a second mixed solution with the concentration of 2-6 mol/L of a sodium hydroxide precipitator;
preparing a third mixed solution with the concentration of the ammonia water complexing agent being 7-14 mol/L;
(2) adding pure water with the effective volume of 80% into a reaction kettle under the stirring condition, introducing a complexing agent and a precipitating agent to prepare a mother solution, and continuously introducing certain nitrogen as protection;
(3) and (3) continuously introducing the prepared three solutions into a reaction kettle in a parallel flow manner, and carrying out coprecipitation reaction under the action of sodium hydroxide and ammonia water. Feeding continuously when the particle size reaches 1.5 mu m, pumping 1/4 feed liquid from the upper part of the reaction kettle, pouring out supernatant after precipitation, pouring the material back to the reaction kettle, then adopting the same method when the reaction kettle is full, introducing new seed crystal by the method, increasing the solid content of the system in the kettle, slowly increasing the particle size, avoiding artificial balling, stopping feeding when the particle size D50 reaches 2.5-3 mu m, and finishing the reaction;
the coprecipitation reaction temperature is 40-65 ℃;
the pH value of the coprecipitation reaction is 11.0-12.6;
the co-precipitation rotating speed is 700-1200 rpm;
the inert gas is one or two of nitrogen or argon;
the initial reaction mother liquor accounts for more than 80% of the effective volume of the kettle body, wherein the pH value is 12.0-12.4, the ammonia value is 10-12 g/L, and the temperature is 40-65 ℃;
(4) sequentially aging, washing and drying the obtained reaction product to obtain high-nickel small-particle-size nickel-cobalt-manganese hydroxide;
the aging time is 45-85 min;
the washing temperature is 50-85 ℃;
the drying temperature is 100-150 ℃.
Example 1
Dissolving nickel sulfate, cobalt sulfate and manganese sulfate with water to prepare a sulfate aqueous solution with the total concentration of three ions of Ni, Co and Mn being 1.5mol/L, wherein the ratio of nickel, cobalt and manganese is Ni, Co and Mn being 0.83, 0.12 and 0.05; preparing a second mixed solution with the concentration of sodium hydroxide of 4 mol/L; preparing a third mixed solution with the ammonia water concentration of 9 mol/L;
40L of deionized water is added into a 50L reaction kettle, and a sodium hydroxide solution and ammonia water are introduced to prepare a mother solution with the pH value of 12.4, the ammonia value of 10g/L and the temperature of 50 ℃. Adjusting the rotating speed of the reaction kettle to 900r/min, starting stirring, introducing nitrogen into the reaction kettle for atmosphere protection, and continuously introducing nitrogen in the whole reaction process;
continuously introducing the prepared three solutions into a reaction kettle through a precisely-metered peristaltic pump at the same time to perform a nucleation growth reaction, controlling the pH value of the system to be 12.2-12.3, controlling the ammonia value to be 10-11 g/L, and controlling the reaction time to be 10 h; after the feeding reaction is carried out for a period of time, when the feed liquid discharged into the beaker can be completely precipitated, the pH value is gradually reduced to about 12.2;
continuously reacting until the granularity D50 of the material in the kettle is 1.3-1.5 mu m, beginning to extract 1/4 feed liquid from the upper part of the reaction kettle, pouring out supernatant after precipitation, pouring the material back to the reaction kettle, and then adopting the same method every two hours to introduce new seed crystals, so that the solid content in the kettle is increased, the granularity is slowly increased, and meanwhile, artificial ball hitting can be avoided; when the granularity grows to 2.0 mu m, adjusting the rotating speed to 1200r/min, adjusting the pH value of the system to 12.1-12.2 and the ammonia value to 11-11.5 g/L, continuing to react until the granularity D50 reaches about 2.5 mu m, stopping feeding, continuing to stir for 1h, discharging, washing and drying;
aging the slurry obtained after coprecipitation for 1h, performing solid-liquid separation, putting the cake-shaped solid into a washing kettle with the temperature of 60 ℃ and the volume of 1m3, simultaneously adding 10mol/L of caustic soda into the washing kettle, washing, centrifuging, and drying in a forced air drying oven at the temperature of 130 ℃ for 20h until the moisture meets the requirement;
scanning electron microscope detection is carried out on the high-nickel small-particle-size nickel-cobalt-manganese hydroxide obtained in the embodiment 1 of the invention, and the detection result is shown in fig. 1, so that the high-nickel small-particle-size nickel-cobalt-manganese hydroxide prepared in the embodiment 1 of the invention has the advantages of good sphericity, uniform particle size distribution and no agglomeration;
the particle size test of the high nickel small particle size nickel cobalt manganese hydroxide obtained in the embodiment 1 of the present invention is performed, and the detection result is shown in fig. 2, which shows that the particle size distribution of the high nickel small particle size nickel cobalt manganese hydroxide obtained in the embodiment 1 of the present invention is concentrated without agglomeration, and D50 is 2.79 μm;
tap density test is carried out on the high-nickel small-particle-size nickel-cobalt-manganese hydroxide obtained in the embodiment 1 of the invention, and the detection result shows that the tap density of the prepared high-nickel small-particle-size nickel-cobalt-manganese hydroxide is 2.24g/cm3, and the specific surface area is 4.5976m2/g；
Example 2
Dissolving nickel sulfate, cobalt sulfate and manganese sulfate with water to prepare a sulfate aqueous solution with the total concentration of Ni, Co and Mn being 2.0mol/L, wherein the ratio of nickel, cobalt and manganese is Ni, Co and Mn being 0.88, 0.09 and 0.03; preparing a second mixed solution with the concentration of 6mol/L of sodium hydroxide; preparing a third mixed solution with the ammonia water concentration of 12 mol/L;
150L of deionized water is added into a 200L reaction kettle, and a sodium hydroxide solution and ammonia water are introduced to prepare a mother solution with the pH value of 12.5, the ammonia value of 9g/L and the temperature of 50 ℃. Adjusting the rotating speed of the reaction kettle to 700r/min, starting stirring, introducing nitrogen into the reaction kettle for atmosphere protection, and continuously introducing nitrogen in the whole reaction process;
continuously introducing the prepared three solutions into a reaction kettle through a precisely-metered peristaltic pump at the same time to perform a nucleation growth reaction, controlling the pH value of the system to be 12.1-12.2, controlling the ammonia value to be 10-11 g/L, and controlling the reaction time to be 10 h; after the feeding reaction is carried out for a period of time, when the feed liquid discharged into the beaker can be completely precipitated, the pH value is gradually reduced to about 12.1;
continuously reacting until the granularity D50 of the material in the kettle is 1.3-1.5 mu m, beginning to extract 1/4 feed liquid from the upper part of the reaction kettle, pouring out supernatant after precipitation, pouring the material back to the reaction kettle, and then adopting the same method every two hours to introduce new seed crystals, so that the solid content in the kettle is increased, the granularity is slowly increased, and meanwhile, artificial ball hitting can be avoided; when the granularity grows to 2.0 mu m, adjusting the rotating speed to 900r/min, adjusting the pH value of the system to 12.0-12.1 and the ammonia value to 11-11.5 g/L, continuing to react until the granularity D50 reaches about 2.5 mu m, stopping feeding, continuing to stir for 1h, discharging, washing and drying;
aging the slurry obtained after coprecipitation for 1h, performing solid-liquid separation, putting the cake-shaped solid into a washing kettle with the temperature of 60 ℃ and the volume of 1m3, simultaneously adding 10mol/L of caustic soda into the washing kettle, washing, centrifuging, and drying in a forced air drying oven at the temperature of 130 ℃ for 20h until the moisture meets the requirement;
scanning electron microscope detection is carried out on the high-nickel small-particle-size nickel-cobalt-manganese hydroxide obtained in the embodiment 2 of the invention, and the detection result is shown in fig. 3, so that the high-nickel small-particle-size nickel-cobalt-manganese hydroxide prepared in the embodiment 2 of the invention has good sphericity, uniform particle size distribution and no agglomeration;
the particle size test of the high nickel small particle size nickel cobalt manganese hydroxide obtained in the embodiment 2 of the present invention is performed, and the detection result is shown in fig. 4, which shows that the particle size distribution of the high nickel small particle size nickel cobalt manganese hydroxide obtained in the embodiment 2 of the present invention is concentrated without agglomeration, and D50 is 2.82 μm;
tap density test is carried out on the high-nickel small-particle-size nickel-cobalt-manganese hydroxide obtained in the embodiment 2 of the invention, and the detection result shows that the tap density of the prepared high-nickel small-particle-size nickel-cobalt-manganese hydroxide is 1.91g/cm3Specific surface area of 6.4874m2/g；
According to the embodiment, the invention provides a preparation method of high-nickel small-particle-size nickel-cobalt-manganese hydroxide, under the conditions of more mother liquor, high ammonia water concentration and high rotation speed, nickel-cobalt-manganese mixed metal solution, sodium hydroxide and ammonia water are continuously introduced for nucleation, after nucleation, crystal nuclei are highly dispersed through high-speed stirring, the crystal nuclei enter a crystal nucleus growth stage, in the initial growth stage, a part of feed liquid is discharged from a reaction kettle, supernatant liquid is removed, and precipitates are poured back to the reaction kettle, so that the solid content is increased, new seed crystals are introduced, the phenomenon of particle agglomeration caused by excessive small particles due to artificial balling is avoided, and finally small hydroxide particles with uniform particle size distribution, no agglomeration, good sphericity and high tap density D50 of 1.5-3 μm are obtained. The preparation method of the high-nickel small-particle-size single crystal nickel cobalt manganese hydroxide provided by the invention has the advantages that the solid content is increased, new seed crystals are introduced, the high-nickel small particles with concentrated particle size distribution, no agglomeration, high tap density and good sphericity are formed under the conditions of high ammonia water concentration and high rotating speed, the existing reaction kettle is not required to be modified, the operation is simple and convenient, and the production can be enlarged.
The invention also provides a method for preparing the lithium ion battery anode material by using the high-nickel small-particle-size nickel-cobalt-manganese hydroxide prepared by the technical scheme of the embodiment 1 as the base material. The lithium source used for preparing the cathode material is battery-grade lithium hydroxide; the sintering temperature of the lithium ion battery anode material is 700-1000 ℃, and the sintering time is 24-27 h; the lithiation ratio of the lithium ion battery anode material, namely Li (Ni + Co + Mn) is 1.05; the 0.1C and 4.3V half-capacitance of the lithium ion battery anode material is 215.3 mAh/g;
fig. 5 is an SEM photograph of the above lithium ion battery positive electrode material.
The above description is not intended to limit the invention, nor is the invention limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the spirit of the invention.
Claims (5)
1. A preparation method of high-nickel small-particle-size nickel-cobalt-manganese hydroxide is characterized by comprising the following steps of:
(1) the nickel-cobalt-manganese soluble salt is prepared according to the mol ratio of nickel-cobalt-manganese in the hydroxide, namely according to the general formula Ni1-x-yCoxMny(OH)2Wherein x is more than or equal to 0.09 and less than or equal to 0.12, and y is more than or equal to 0.03 and less than or equal to 0.05, and preparing a first mixed metal salt solution containing Ni ions, Co ions and Mn ions; preparing a second mixed solution consisting of a precipitator; preparing a third mixed solution consisting of complexing agents;
(2) adding pure water with the effective volume of 80% into the reaction kettle under the stirring condition, introducing the second mixed solution and the third mixed solution in the step (1) to prepare mother liquor, and continuously introducing inert gas as protection;
(3) enabling the first mixed metal salt solution, the second mixed solution and the third mixed solution in the step (1) to flow in parallel, continuously introducing into a high-speed stirring reaction kettle, and carrying out coprecipitation reaction under the action of the second mixed solution and the third mixed solution; continuing feeding when the particle size reaches 1.3-1.5 mu m, pumping the feed liquid from the upper part of the reaction kettle, pouring out the supernatant after the feed liquid is precipitated, pouring the precipitate back to the reaction kettle, then adopting the same method when the reaction kettle is full, introducing new seed crystals, stopping feeding when the particle size D50 reaches 2.5-3 mu m, and finishing the reaction;
(4) sequentially aging the reaction products obtained in the step (3), carrying out alkaline washing centrifugation on the aged slurry, and then drying, crushing, sieving and removing iron to obtain high-nickel small-particle-size nickel-cobalt-manganese hydroxide;
in the step (1), the concentration of the first mixed metal salt solution is 1.5-2 mol/L, the concentration of the second mixed solution is 2-6 mol/L, and the concentration of the third mixed solution is 7-14 mol/L;
in the step (2), the value of the third mixed solution in the reaction kettle system is 8-14 g/L;
in the step (2), the mother liquor accounts for more than 80% of the effective volume of the reaction kettle, wherein the pH value is 12.0-12.4, the ammonia value is 10-12 g/L, and the temperature is 40-65 ℃;
in the step (3), the temperature of the coprecipitation reaction is 40-65 ℃, the pH value of the coprecipitation reaction is 11.0-12.6, and the rotating speed of the coprecipitation reaction is 700-1200 rpm;
in the step (3), the volume of the feed liquid extracted from the upper part of the reaction kettle accounts for 1/6-1/3 of the effective volume of the reaction kettle.
2. The method for preparing nickel cobalt manganese hydroxide with high nickel content and small particle size as claimed in claim 1, wherein in the step (1), the complexing agent is any one or more of ammonia water, disodium ethylene diamine tetraacetate, sulfosalicylic acid and glycine.
3. The method for preparing nickel cobalt manganese hydroxide with high nickel content and small particle size as claimed in claim 1, wherein in the step (4), the aging time is 45-85 min, the alkali washing temperature is 50-85 ℃, and the drying temperature is 100-150 ℃.
4. A high-nickel small-particle-size nickel-cobalt-manganese hydroxide, which is characterized by being prepared by the method of any one of claims 1 to 3.
5. The high-nickel small-particle-size nickel-cobalt-manganese hydroxide as claimed in claim 4, wherein the high-nickel small-particle-size nickel-cobalt-manganese hydroxide D50 is 1.5-3 μm, the particle size distribution is 1-10 μm, and the tap density is 1.6-2.4 g/cm3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711260819.1A CN107834064B (en) | 2017-12-04 | 2017-12-04 | High-nickel small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711260819.1A CN107834064B (en) | 2017-12-04 | 2017-12-04 | High-nickel small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107834064A CN107834064A (en) | 2018-03-23 |
| CN107834064B true CN107834064B (en) | 2021-09-17 |
Family
ID=61641292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711260819.1A Active CN107834064B (en) | 2017-12-04 | 2017-12-04 | High-nickel small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107834064B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108525674A (en) * | 2018-03-27 | 2018-09-14 | 上海倍绿环保科技有限公司 | Couple the cobalt manganese O composite metallic oxide catalyst and preparation method thereof of electrostatic field collaboration removal low-concentration methane gas |
| CN108598441B (en) * | 2018-05-29 | 2021-02-26 | 东莞理工学院 | Different-granularity narrow-distribution ternary precursor and preparation method thereof |
| CN108946827B (en) * | 2018-07-03 | 2020-09-29 | 华友新能源科技（衢州）有限公司 | Ultra-small particle size nickel-cobalt-manganese hydroxide and preparation method thereof |
| CN110739447A (en) * | 2018-07-20 | 2020-01-31 | 河南科隆新能源股份有限公司 | Preparation method capable of controlling particle size distribution of lithium ion battery precursors |
| CN108807968A (en) * | 2018-08-09 | 2018-11-13 | 中国恩菲工程技术有限公司 | Nickel-cobalt-manganese ternary persursor material and its synthetic method |
| CN109860581B (en) * | 2018-12-25 | 2022-05-17 | 河南科隆新能源股份有限公司 | Preparation method of spherical nickel cobalt manganese hydroxide precursor with narrow particle size distribution |
| CN109888242A (en) * | 2019-03-12 | 2019-06-14 | 四川纳创时代新能源科技有限公司 | A kind of high-tap density cobalt nickel lithium manganate ternary material and preparation method thereof |
| CN109950535B (en) * | 2019-03-20 | 2022-04-29 | 兰州金川新材料科技股份有限公司 | Method for continuously synthesizing precursor by washing filter material with hydroxide and secondary crystallization |
| CN110931776B (en) * | 2019-12-24 | 2021-02-02 | 中南大学 | Preparation method of nickel-cobalt-manganese ternary positive electrode material precursor with multi-level distribution of particle sizes |
| CN113130886A (en) * | 2019-12-30 | 2021-07-16 | 荆门市格林美新材料有限公司 | Preparation method and application of superfine high-nickel ternary precursor |
| CN111547779B (en) * | 2020-05-12 | 2022-04-05 | 宁波容百新能源科技股份有限公司 | A kind of preparation method of narrow particle size distribution ternary precursor |
| CN112694139B (en) * | 2020-12-29 | 2022-12-06 | 福建常青新能源科技有限公司 | Preparation method of single crystal NCM ternary cathode material precursor |
| CN114804223B (en) * | 2021-01-21 | 2023-11-10 | 中国石油化工股份有限公司 | A continuous and stable preparation method of ternary precursor for lithium-ion batteries |
| CN115771914A (en) * | 2021-09-07 | 2023-03-10 | 浙江海创锂电科技有限公司 | A kind of preparation method of doping type small particle size high-nickel precursor |
| CN113800577B (en) * | 2021-09-28 | 2023-08-15 | 南通金通储能动力新材料有限公司 | A method for preparing a small particle size ternary precursor |
| CN114645329B (en) * | 2022-03-30 | 2023-08-01 | 宁波容百新能源科技股份有限公司 | Nickel-cobalt-manganese hydroxide with high nickel and low cobalt fine whisker and preparation method thereof |
| CN115012036B (en) * | 2022-05-31 | 2023-10-03 | 宁波容百新能源科技股份有限公司 | Fine whisker small-particle-size nickel cobalt manganese hydroxide and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102869613A (en) * | 2009-12-02 | 2013-01-09 | 住友金属矿山株式会社 | Nickel complex hydroxide particles and nonaqueous electrolyte secondary battery |
| CN103943847A (en) * | 2014-04-21 | 2014-07-23 | 中信国安盟固利电源技术有限公司 | Method for preparing nickel-cobalt-manganese ternary material precursor |
| KR20160099876A (en) * | 2015-02-13 | 2016-08-23 | 주식회사 이엔드디 | Manufacturing method for Ni-Co-Mn composite precursor |
| CN107342417A (en) * | 2016-12-28 | 2017-11-10 | 杉杉能源（宁夏）有限公司 | A kind of high ni-type precursor of nickel-cobalt-lithium-manganese-oxide with specific morphology and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5638232B2 (en) * | 2009-12-02 | 2014-12-10 | 住友金属鉱山株式会社 | Non-aqueous electrolyte secondary battery positive electrode active material nickel cobalt manganese composite hydroxide particles and production method thereof, non-aqueous electrolyte secondary battery positive electrode active material and production method thereof, and non-aqueous electrolyte secondary battery |
| JP6094591B2 (en) * | 2012-09-28 | 2017-03-15 | 住友金属鉱山株式会社 | Nickel-cobalt composite hydroxide and its production method and production apparatus, positive electrode active material for non-aqueous electrolyte secondary battery, its production method, and non-aqueous electrolyte secondary battery |
-
2017
- 2017-12-04 CN CN201711260819.1A patent/CN107834064B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102869613A (en) * | 2009-12-02 | 2013-01-09 | 住友金属矿山株式会社 | Nickel complex hydroxide particles and nonaqueous electrolyte secondary battery |
| CN103943847A (en) * | 2014-04-21 | 2014-07-23 | 中信国安盟固利电源技术有限公司 | Method for preparing nickel-cobalt-manganese ternary material precursor |
| KR20160099876A (en) * | 2015-02-13 | 2016-08-23 | 주식회사 이엔드디 | Manufacturing method for Ni-Co-Mn composite precursor |
| CN107342417A (en) * | 2016-12-28 | 2017-11-10 | 杉杉能源（宁夏）有限公司 | A kind of high ni-type precursor of nickel-cobalt-lithium-manganese-oxide with specific morphology and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107834064A (en) | 2018-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107834064B (en) | High-nickel small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof | |
| CN110048118B (en) | High-nickel cobalt lithium manganate single crystal precursor, preparation method thereof and high-nickel cobalt lithium manganate single crystal positive electrode material | |
| KR20200041978A (en) | High voltage lithium nickel cobalt manganese oxide precursor, manufacturing method thereof, and high voltage lithium nickel cobalt manganese oxide cathode material | |
| CN112531158B (en) | High-nickel ternary single crystal material and preparation method thereof | |
| CN112582605A (en) | Preparation method of nickel-cobalt-manganese ternary precursor for reducing sulfur content in continuous production process | |
| CN114394630B (en) | A preparation method for controlling the morphology of ternary precursor material | |
| CN107265520A (en) | The preparation method and product of a kind of spherical nickel cobalt manganese persursor material | |
| CN110808369B (en) | Preparation method of low-sodium-sulfur nickel-cobalt-aluminum ternary precursor | |
| CN108502937A (en) | A kind of polynary persursor material of ball-shaped lithium-ion battery anode and its preparation method and application | |
| CN114349068B (en) | Preparation method of large-particle-size nickel-cobalt-aluminum ternary positive electrode material precursor | |
| CN108987740B (en) | Nickel-cobalt lithium aluminate anode material, preparation method thereof and battery applying nickel-cobalt lithium aluminate anode material | |
| CN110092421B (en) | A kind of production method of spherical basic cobalt carbonate with controllable particle size | |
| CN111661879B (en) | Nickel cobalt tungsten oxide, its preparation method and lithium ion battery | |
| CN110817976B (en) | Positive electrode material precursor and preparation method and application thereof | |
| CN113206242A (en) | Nickel-cobalt-manganese-aluminum quaternary precursor, positive electrode material and preparation method | |
| CN113582234A (en) | Preparation method of battery-grade spheroidal manganese carbonate | |
| CN116199274A (en) | Porous hollow ternary precursor and preparation method thereof | |
| CN109346718B (en) | A kind of single crystal nickel cobalt lithium manganate precursor and its preparation method and application | |
| CN116002648A (en) | High-compaction low-temperature lithium iron phosphate positive electrode material, and preparation method and application thereof | |
| CN114988495B (en) | A kind of preparation method and precursor of multi-generation co-agglomeration precursor for lithium battery | |
| CN110350162B (en) | Multiplying power type nickel-cobalt-aluminum positive electrode material and preparation method and application thereof | |
| CN110282665B (en) | Lithium battery positive electrode material precursor with mesoscopic structure and preparation method thereof | |
| CN114645329B (en) | Nickel-cobalt-manganese hydroxide with high nickel and low cobalt fine whisker and preparation method thereof | |
| CN115012036B (en) | Fine whisker small-particle-size nickel cobalt manganese hydroxide and preparation method thereof | |
| CN117794864A (en) | Nanometer cobalt hydroxide and preparation method and application 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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: Yuyao xiaocao'e town Zhejiang city Ningbo province Caoejiang village 315400 Applicant after: Ningbo new energy Polytron Technologies Inc Address before: Yuyao xiaocao'e town Zhejiang city Ningbo province Caoejiang village 315400 Applicant before: Ningbo 100 lithium material Co. Ltd. |
|
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: Jia Ling Road 315400 Yuyao City, Zhejiang province Ningbo City No. 39 Applicant after: Ningbo new energy Polytron Technologies Inc Address before: 315400 Cao'e Village, Xiaocao'e Town, Yuyao City, Ningbo City, Zhejiang Province Applicant before: Ningbo new energy Polytron Technologies Inc |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220607 Address after: 315400 No. 39, Tan Jialing East Road, Yuyao, Ningbo, Zhejiang Patentee after: NINGBO RONBAY NEW ENERGY TECHNOLOGY CO.,LTD. Patentee after: Ningbo rongbai Material Technology Co., Ltd Address before: 315400 No. 39, Tan Jialing East Road, Yuyao, Ningbo, Zhejiang Patentee before: NINGBO RONBAY NEW ENERGY TECHNOLOGY CO.,LTD. |