CN111153447B - Grid-shaped porous precursor material, preparation method thereof and anode material - Google Patents
Grid-shaped porous precursor material, preparation method thereof and anode material Download PDFInfo
- Publication number
- CN111153447B CN111153447B CN202010253246.5A CN202010253246A CN111153447B CN 111153447 B CN111153447 B CN 111153447B CN 202010253246 A CN202010253246 A CN 202010253246A CN 111153447 B CN111153447 B CN 111153447B
- Authority
- CN
- China
- Prior art keywords
- precursor material
- latticed
- solution
- equal
- controlled
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- 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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Abstract
The invention provides a latticed porous precursor material for a lithium ion battery anode material, a preparation method of the latticed porous precursor material and an anode material prepared from the precursor material. The invention prepares the latticed porous precursor material by adding nickel, cobalt, manganese and other solutions, a complexing agent, a precipitating agent and a pore-forming agent into a reactor with certain base solution together in a certain gas atmosphere in a parallel flow manner for continuous coprecipitation reaction, wherein the cross section of the material is latticed, primary particles are in a fine needle shape, and are arranged in a tiled manner or a vertical manner or are arranged in a mixed manner, and secondary particles have good dispersibility and high sphericity. And the positive electrode material prepared from the latticed porous precursor material has high rate performance, high activation rate of the energy storage material and improved capacity.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a latticed porous precursor material for a lithium ion battery anode material, a preparation method of the latticed porous precursor material and an anode material prepared from the precursor material.
Background
Along with the attention of people to environmental protection, the traditional fuel automobile is gradually replaced by a power electric automobile, and along with the maturity of the electric automobile industry technology and the improvement of the environmental protection consciousness of people in recent years, the production and sale scale of the electric automobile is gradually increased. The lithium ion secondary battery of the power type electric automobile has higher requirements on energy density, rate capability, cycle performance, charge-discharge efficiency, safety performance and the like, and the positive electrode material for the power type lithium ion secondary battery is researched and prepared, so that the lithium ion secondary battery has wide application prospect.
The traditional lithium ion battery has the defects of insufficient energy density, cycle performance, rate performance and safety performance. In order to solve the problems, the anode material is prepared into a porous shape, the diffusion path of ions is effectively shortened, the transmission of lithium ions can be effectively improved, the rate capability is obviously improved, meanwhile, the electrolyte is fully immersed, the energy storage material is activated, the capacity is improved, and in addition, the cycle performance, the thermal stability and the safety performance are also effectively improved.
The patent with the application number of CN201910960146.3 provides a preparation method of a high-nickel ternary cathode material with a layered porous structure, which comprises the following steps: preparing cobalt salt, manganese salt and carbonate into a cobalt manganese carbonate precursor by adopting a coprecipitation method, roasting the cobalt manganese carbonate precursor to obtain a cobalt manganese oxide, introducing nickel ions and lithium ions into the cobalt manganese oxide by adopting an impregnation method, and finally roasting to obtain the layered porous high-nickel ternary positive electrode material. The particle size and the shape of the porous anode material prepared by the roasting method are not easy to control.
The patent with the application number of CN201910230383.4 provides a preparation method of a high-capacity single-crystal ternary cathode material, wherein a nickel-cobalt-manganese hydroxide precursor with a core-shell structure is prepared by adopting a coprecipitation method, a loose and porous core is prepared by intermittently introducing quantitative bicarbonate at the initial stage of nucleation, the nucleation is finished, a loose flaky shell is prepared by greatly reducing the rotating speed and improving the pH value, and meanwhile, in the phase of core-shell conversion, a dispersing agent is added to effectively prevent the aggregation between the shells caused by the reduction of the rotating speed. The method has long process flow, increases production burden and has low production efficiency.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: a latticed spheroidal porous precursor material is provided.
In addition, based on the general inventive concept, aiming at the technical problems in the prior art, the invention provides the preparation method of the latticed spherical-like porous precursor material, which has the advantages of simple process flow, continuous and efficient production and stable product quality.
The solution of the invention is realized by the following steps:
a latticed sphere-like porous precursor material is characterized in that the chemical molecular formula of the precursor materialIs (1-n) NixCoyMn1-x-y(OH)2nM (OH) z, where x is greater than 0.3 and less than or equal to 0.8, y is greater than 0 and less than or equal to 0.4, n is greater than or equal to 0 and less than or equal to 0.02, and z is greater than or equal to 2 and less than or equal to 4; when n is not equal to 0, M is any one or more of Al, Zn, Fe, Zr, Yb, Mg and Ti. The cross section of the precursor is in a grid shape, the primary particles are in a fine needle shape and are arranged in a flat mode or a vertical mode or a mixed mode of the primary particles and the vertical mode, the dispersibility of the secondary particles is good, and the sphericity is high.
In addition, the tap density of the latticed sphere-like porous precursor material is 0.5-1.5g/cm, the specific surface area is 15-70 m/g, and the median particle size is 1.5-15 μm.
Based on the general inventive concept, the present invention provides a method for preparing the aforementioned latticed spheroidal porous precursor material, comprising the steps of:
dissolving nickel, cobalt and manganese soluble salts in water according to a certain proportion, and fully dissolving to form a uniform mixed solution, wherein the concentration of the mixed solution is 1-4 mol/L;
dissolving a certain amount of salt of the doping element M in water to obtain a solution A; adding the solution A into the mixed solution in the step (1), and uniformly mixing to obtain a solution B;
step (3), when n =0, adding the mixed solution, the complexing agent, the precipitating agent and the pore-forming agent in the step (1) into a reactor with a certain base solution together in a gas K atmosphere in a concurrent flow manner to carry out continuous coprecipitation reaction; when n is not equal to 0, adding the solution B, the complexing agent, the precipitating agent and the pore-forming agent in the step (2) into a reactor with certain bottom liquid in a gas K atmosphere in a concurrent flow manner for continuous coprecipitation reaction;
and (4) storing the slurry after the granularity of the reaction product of the coprecipitation reaction is stable, carrying out solid-liquid separation on the slurry continuously discharged from the reactor, and aging, washing, drying and screening the solid product to obtain the latticed spheroidal porous precursor material.
Further, the nickel, cobalt and manganese soluble salts in the step (1) are all sulfates, and the total amount of metal ions in the mixed solution in the step (1) is controlled to be 1-4 mol/L.
Further, in the step (2), when n ≠ 0, the doping element is one or more of Al, Zn, Fe, Zr, Yb, Mg and Ti, and the content of M ions in the solution A is controlled to be 20000ppm or less.
Further, the complexing agent in the step (3) is one or two selected from urea, ammonia water, citric acid and ethylenediamine tetraacetic acid.
Further, the precipitating agent in step (3) is selected from one or more of sodium hydroxide, potassium hydroxide, ammonia water, sodium oxalate, sodium carbonate, sodium bicarbonate, ammonium bicarbonate or other soluble carbonate.
Further, the pore-forming agent in step (3) is one or more selected from glycerol, polyethylene glycol, oxygen and air.
Further, the gas K in step (3) is selected from one or more of nitrogen, argon, air and oxygen, and the gas K may be replaced by one or more selected from the above gases according to the reaction time period, wherein nitrogen and argon are preferred in the initial stage of the reaction, and air and oxygen are preferred in the growth stage.
Further, the base solution in the reactor in the step (3) is a mixed solution of sodium hydroxide and ammonia water. The initial temperature of the base solution is controlled to be 40-90 ℃, and the initial concentration of ammonia water is 1-30 g/l; the alkalinity of the system is controlled between 1g/l and 30g/l in the reaction process, and the solid matter content of the system is controlled between 50 g/l and 400g/l in the reaction process. The initial pH value of the base solution is controlled to be between 11.0 and 12.0, the pH value of a system is controlled to be between 11.0 and 12.0 in the reaction process, the temperature of the system is controlled to be between 40 and 90 ℃ in the reaction process, and the retention time of materials in the reactor is between 9 and 50 hours. The stirring speed of the coprecipitation reaction is controlled to be 250r/min-700 r/min.
Further, the aging in the step (4) is to age the solid material by using 5-15wt% of liquid caustic soda, wherein the temperature of the liquid caustic soda is 45-80 ℃, and the time for aging is 30-240 min.
Further, the drying in the step (4) is controlled at a drying temperature of 100 ℃ and 140 ℃ and the drying time of 12h-24 h.
The precursor material prepared by the preparation method has uniform fine needle-shaped primary particles, and is arranged in a flat mode or a vertical mode or a mixed mode of the two modes. The secondary particles have good dispersibility and high sphericity, and the cross section of the secondary particles is of a latticed porous structure.
In addition, based on the general inventive concept, the invention also provides a nickel cobalt lithium manganate positive electrode material, which is characterized in that the preparation raw material of the positive electrode material comprises the latticed spheroidal porous precursor material.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention adopts a continuous feeding mode to carry out coprecipitation reaction, provides a preparation method of the latticed spheroidal porous precursor material with simple process flow, continuous and efficient production and stable product quality, and has wide application market and bright application prospect.
2. The product prepared by the invention has a higher specific surface area and a uniformly distributed grid hole structure, and the prepared anode material has high rate performance, high activation rate of the energy storage material and improved capacity.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention and are not to be considered as limiting the invention.
Fig. 1 is a cross-sectional Scanning Electron Microscope (SEM) image of the latticed spheroidal porous precursor material prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of the latticed spheroidal porous precursor material prepared in example 1 of the present invention.
Fig. 3 is a cross-sectional Scanning Electron Microscope (SEM) image of the latticed spheroidal porous precursor material prepared in example 2 of the present invention.
Fig. 4 is an XRD pattern of the latticed spheroidal porous precursor material prepared in example 2 of the present invention.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way. Furthermore, those skilled in the art can combine features from the embodiments of this document and from different embodiments accordingly based on the description of this document.
Example 1:
preparing a mixed solution with a total ion concentration of 2 mol/L from nickel, cobalt and manganese according to a metal ion molar ratio of 1:1:1, adding deionized water into a reaction kettle, controlling the stirring speed at 400r/min, heating to 50 ℃, adding ammonia water, adjusting the ammonia water concentration to 16g/l, adding a sodium hydroxide solution, adjusting the pH value to 11.6, continuously introducing nitrogen gas into the reaction kettle in the initial stage of the reaction, introducing air into the reaction kettle in the growth stage, simultaneously introducing the mixed solution, the precipitant and the complexing agent into the reaction kettle in a parallel flow manner at a flow rate of 50ml/min, keeping the pH value of the coprecipitation reaction between 11.00 and 12.00, starting overflow, and continuously preparing the latticed spherical porous precursor Ni material with the required metal ion molar ratio of 1:1: 1:1 by controlling the solid matter content to 200g/l to obtain the latticed spherical porous precursor Ni1/ 3Co1/3Mn1/3(OH)2。
FIG. 1 shows a synthesized latticed spheroidal porous precursor material Ni1/3Co1/3Mn1/3(OH)2FIG. 2 is a cross-sectional scanning electron microscope image of the synthesized latticed spheroidal porous precursor material Ni1/3Co1/3Mn1/3(OH)2XRD pattern of (a).
As can be seen from FIG. 1, the precursor material Ni is prepared1/3Co1/3Mn1/3(OH)2The primary particles are fine needle-shaped, the secondary particles have good dispersibility, the holes are uniformly distributed in a grid shape, and the sphericity is high. As can be seen from FIG. 2, the precursor material Ni obtained by the preparation method1/3Co1/3Mn1/3(OH)2The crystal form (A) is complete and has no any impurity peak. Through detection, the precursor material Ni1/3Co1/3Mn1/3(OH)2BET of 38.9326m2(g), TD is 1.02g/m3D50 is 5.18. mu.m.
Further, the method can be used for preparing a novel materialThe precursor material Ni prepared by the method is1/3Co1/3Mn1/3(OH)2The anode material was prepared, and the electrochemical properties of the anode material were measured, with the results shown in table 1. The positive electrode material has high rate performance, high activation rate of the energy storage material and improved capacity.
TABLE 1 electrochemical Properties of cathode materials
Example 2:
preparing a mixed solution with a total ion concentration of 2 mol/L by nickel, cobalt and manganese according to a metal ion molar ratio of 5:2:3, dissolving zirconium sulfate doped with element zirconium, adding the dissolved zirconium sulfate into the mixed solution of nickel-cobalt-manganese salt, controlling the concentration of Zr within 2000ppm to form a solution A, adding the solution A into the mixed solution of nickel-cobalt-manganese salt to form a solution B, adding a precipitator which is a sodium hydroxide solution with a molar concentration of 2 mol/L and a complexing agent which is an ammonia water solution with a concentration of 20 g/L into a reaction kettle, adding deionized water into the reaction kettle, stirring at a stirring speed of 400r/min, heating to 50 ℃, adding ammonia water, adjusting the concentration of the ammonia water to 24g/l, adding a sodium hydroxide solution, adjusting the pH value to 11.70, continuously introducing nitrogen gas into the reaction initial stage, introducing air into the growth stage, simultaneously introducing a liquid pore-making agent glycerol into the reaction kettle at a flow rate of 10ml/min, simultaneously introducing the solution B, the precipitator, the complexing agent and the pore-making agent into the reaction kettle, keeping the reaction pH value at 12.00, continuously introducing the pore-making coprecipitation content, controlling the overflow content of Ni-nickel-cobalt precursor to be a continuous porous material with a metal ion molar ratio of 0.50.5Co0.2Mn0.3(OH)2·0.002Zr (OH)4。
FIG. 3 shows the precursor material 0.998Ni0.5Co0.2Mn0.3(OH)2·0.002Zr (OH)4FIG. 4 is a cross-sectional scanning electron microscope image of the precursor material 0.998Ni0.5Co0.2Mn0.3(OH)2·0.002Zr (OH)4XRD pattern of (a).
From the figure3 it can be seen that the precursor material is 0.998Ni0.5Co0.2Mn0.3(OH)2·0.002Zr (OH)4The primary particles are fine needle-shaped, the secondary particles have good dispersibility, the holes are uniformly distributed in a grid shape, and the sphericity is high. From the XRD pattern of FIG. 4, it can be seen that the precursor material 0.998Ni0.5Co0.2Mn0.3(OH)2·0.002Zr (OH)4The crystal form (A) is complete and has no any impurity peak. The BET of the precursor material is detected to be 41.0694m2(g), TD is 1.09g/m3D50 is 4.99. mu.m.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A latticed sphere-like porous precursor material is characterized in that the chemical molecular formula of the precursor material is (1-n) NixCoyMn1-x-y(OH)2nM (OH) z, where x is greater than 0.3 and less than or equal to 0.8, y is greater than 0 and less than or equal to 0.4, n is greater than or equal to 0 and less than or equal to 0.02, and z is greater than or equal to 2 and less than or equal to 4; when n is not equal to 0, M is any one or more of Al, Zn, Fe, Zr, Yb, Mg and Ti; the cross section of the precursor material is of a latticed porous structure, and primary particles are in a fine needle shape and are arranged in a flat and vertical mixed manner; tap density of the precursor material is 0.5-1.5g/cm thin powder, specific surface area is 15-41.0694 m/g, median particle size is 1.5-5.18 μm.
2. A method for preparing a latticed spheroidal porous precursor material according to claim 1, comprising the steps of:
dissolving nickel, cobalt and manganese soluble salts in water according to a certain proportion, and fully dissolving to form a uniform mixed solution, wherein the concentration of the mixed solution is 1-4 mol/L;
step (2), when n is not equal to 0, dissolving a certain amount of salt of the doping element M in water to obtain a solution A; adding the solution A into the mixed solution in the step (1), and uniformly mixing to obtain a solution B;
step (3), when n =0, adding the mixed solution, the complexing agent, the precipitating agent and the pore-forming agent in the step (1) into a reactor with a certain base solution together in a gas K atmosphere in a concurrent flow manner to carry out continuous coprecipitation reaction; when n is not equal to 0, adding the solution B, the complexing agent, the precipitating agent and the pore-forming agent in the step (2) into a reactor with certain bottom liquid in a gas K atmosphere in a concurrent flow manner for continuous coprecipitation reaction; in the coprecipitation reaction process, the alkalinity is controlled to be 1g/l-30g/l, the solid matter content is controlled to be 50-400 g/l, the pH value is controlled to be 11.0-12.0, and the temperature is controlled to be 40-90 ℃;
step (4), storing slurry after the particle size of the reaction product of the coprecipitation reaction in the step (3) is stable, performing solid-liquid separation on the slurry, and aging, washing, drying and screening the solid product to obtain the latticed spheroidal porous precursor material in the claim 1;
the gas K at the initial stage of the reaction is nitrogen or argon, and the gas K at the growth stage is air or oxygen.
3. The method according to claim 2, wherein the soluble salts of nickel, cobalt and manganese in step (1) are all sulfates, and the total amount of metal ions in the mixed solution is controlled to be 1-4 mol/L.
4. The method according to claim 2, wherein in the step (2), the content of M ion in the solution A is controlled to be 20000ppm or less.
5. The preparation method of claim 2, wherein the complexing agent in step (3) is selected from one or more of urea, ammonia water, citric acid and ethylenediamine tetraacetic acid; the precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, ammonia water, sodium oxalate, sodium carbonate, sodium bicarbonate, ammonium bicarbonate or other soluble carbonates; the pore-making agent is selected from one or more of glycerol, polyethylene glycol, oxygen and air.
6. The method according to claim 2, wherein the base solution in the step (3) is a mixed solution of sodium hydroxide and ammonia water; the initial temperature of the base solution is controlled to be 40-90 ℃, the initial concentration of ammonia water is 1-30 g/l, and the pH value is controlled to be 11.0-12.0.
7. A nickel cobalt lithium manganate positive electrode material, characterized in that, the preparation raw material of the positive electrode material comprises the latticed spheroidal porous precursor material of claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010253246.5A CN111153447B (en) | 2020-04-02 | 2020-04-02 | Grid-shaped porous precursor material, preparation method thereof and anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010253246.5A CN111153447B (en) | 2020-04-02 | 2020-04-02 | Grid-shaped porous precursor material, preparation method thereof and anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111153447A CN111153447A (en) | 2020-05-15 |
| CN111153447B true CN111153447B (en) | 2020-07-10 |
Family
ID=70567769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010253246.5A Active CN111153447B (en) | 2020-04-02 | 2020-04-02 | Grid-shaped porous precursor material, preparation method thereof and anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111153447B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111717941A (en) * | 2020-06-22 | 2020-09-29 | 华友新能源科技（衢州）有限公司 | Nickel-cobalt-manganese hydroxide of needle-shaped whisker and preparation method thereof |
| CN114804234A (en) * | 2022-05-18 | 2022-07-29 | 宁夏中化锂电池材料有限公司 | NCM/NCA core-shell structure ternary precursor material and preparation method thereof |
| CN115353153A (en) * | 2022-07-29 | 2022-11-18 | 宁夏中色金辉新能源有限公司 | High-specific-surface-area nickel-cobalt-manganese ternary precursor and preparation method thereof |
-
2020
- 2020-04-02 CN CN202010253246.5A patent/CN111153447B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111153447A (en) | 2020-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110931772B (en) | Preparation method of high-power type positive electrode material for lithium ion battery | |
| CN109455772B (en) | Modified precursor and anode material for lithium ion battery and preparation methods of precursor and anode material | |
| CN107482213B (en) | A kind of nickel aluminium codope mangano-manganic oxide and preparation method thereof | |
| CN111153447B (en) | Grid-shaped porous precursor material, preparation method thereof and anode material | |
| CN111509214B (en) | High-nickel layered composite material and lithium ion battery anode material prepared from same | |
| CN107123792B (en) | Ternary cathode material with double-layer composite structure and preparation method thereof | |
| CN109817955A (en) | Non-aqueous electrolyte secondary battery nickelic positive electrode and preparation method thereof | |
| CN108767216B (en) | Lithium ion battery anode material with variable slope and full concentration gradient and synthesis method thereof | |
| CN109461891B (en) | High-voltage lithium cobalt oxide cathode material and preparation method thereof | |
| CN109273688B (en) | High-nickel cathode material with surface rich in rock salt phase and preparation method and application thereof | |
| CN111293305B (en) | Hexagonal flaky nickel cobalt lithium manganate precursor and preparation method thereof | |
| WO2023071409A1 (en) | Single-crystal ternary positive electrode material, preparation method therefor, and application thereof | |
| CN111129463A (en) | Preparation method of MOF-coated single crystal ternary cathode material and precursor thereof | |
| CN108134064B (en) | Positive electrode material precursor, preparation method thereof and positive electrode material | |
| CN110391417B (en) | Preparation method of mono-like crystal lithium-rich manganese-based positive electrode material | |
| CN109962234B (en) | Concentration gradient single crystal anode material and preparation method thereof | |
| CN113023794A (en) | Cobalt-free high-nickel cathode material, preparation method thereof, lithium ion battery cathode and lithium ion battery | |
| CN112952085B (en) | Gradient high-nickel single crystal ternary material, preparation method thereof and battery using material | |
| CN111592053A (en) | Nickel-based layered lithium ion battery positive electrode material and preparation method and application thereof | |
| CN111769277A (en) | Gradient single crystal high-nickel cathode material and preparation method thereof | |
| CN111170369B (en) | Lithium manganate or lithium nickel manganese material and preparation method and application thereof | |
| CN112582587A (en) | Core-shell structure high-nickel cathode material with single crystal as core and preparation method thereof | |
| CN112952056B (en) | Lithium-rich manganese-based composite cathode material and preparation method and application thereof | |
| CN112758995A (en) | Ternary positive electrode precursor and preparation method and application thereof | |
| CN117133906A (en) | Coated oxygen-site doped modified sodium ion battery positive electrode material 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |