CN110783562A - Precursor for lithium ion battery anode material and preparation method thereof - Google Patents

Precursor for lithium ion battery anode material and preparation method thereof Download PDF

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CN110783562A
CN110783562A CN201910900214.7A CN201910900214A CN110783562A CN 110783562 A CN110783562 A CN 110783562A CN 201910900214 A CN201910900214 A CN 201910900214A CN 110783562 A CN110783562 A CN 110783562A
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precursor
concentration
lithium ion
ion battery
equal
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陈龙
雷天起
夏昕
杨茂萍
李道聪
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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 discloses a preparation method of a precursor for a lithium ion battery anode material, which is characterized by comprising the following steps of: mixing the metal mixed salt solution, alkali liquor and ammonia water solution, and reacting under the condition that the ammonia concentration is adjusted to be 6-12g/L, pH to be 12-13 to prepare precursor seed material; adjusting the ammonia concentration to 10-18g/L, pH to 11-12 in the previous step, and continuing the reaction to obtain precursor slurry; and carrying out post-treatment on the precursor slurry to obtain a precursor. The method has the advantages of simple process, controllable yield of the prepared precursor, controllable reaction time, compact and non-porous section of the precursor, high sphericity and high tap density, and is suitable for large-scale industrial production.

Description

Precursor for lithium ion battery anode material and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a precursor for a Li-shaped lithium ion battery anode material and a preparation method thereof.
Background
The high requirement of electric automobiles on endurance mileage makes Li (Ni) based on ternary layered cathode material xCo yMn 1-x-y)O 2(0<x<1，0<y<1) The lithium ion battery technology is rapidly developed and becomes the mainstream anode material of a battery system of a passenger vehicle power automobile. The ternary precursor is one of main raw materials for producing the ternary cathode material, and occupies more than 60 percent of the core technology of the ternary cathode material. In order to achieve higher capacity and design space in a battery system, the ternary precursor is generally required to have high tap density and good sphericity and particle size distribution. In addition, the compressive strength of the precursor is also receiving increasing attention, and the precursor with high compactness is the basis for keeping the particles of the positive electrode material stable and unbroken in the processes of rolling the electrode plate and releasing lithium in a battery system.
The coprecipitation production technology of ternary precursors is mature in the industry, but the main concerns in the patents related to the published coprecipitation production technology are as follows: the method comprises the following steps of regulating the distribution uniformity of elements doped in precursor particles (such as Chinese patents with publication numbers of CN103553152A and CN 107968201A), regulating the distribution of main elements of nickel, cobalt and manganese in the particles (such as Chinese patents with publication numbers of CN103872302A and CN 106935797A, CN 10555236A, CN 107785543A, CN 107799729A, CN 107968198A), regulating the particle size distribution of precursors (such as Chinese patents with publication numbers of CN105680030A and CN 108264097A), preventing oxidation and improving crystallinity in the production and synthesis process (such as Chinese patents with publication numbers of CN104332622A and CN 107742720A), removing impurities in a washing section after the precursors are produced (such as Chinese patents with publication numbers of CN 106830106A), and recycling and regenerating the precursors from waste batteries (such as Chinese patents with publication numbers of CN 107768764A, CN108172923A, CN107959076A and CN 108285977A). The section compactness of the precursor particles is an important factor for determining the tap density and the particle stability of the precursor, and the analysis shows that the improvement aiming at the section compactness is rarely related in the prior art.
Disclosure of Invention
In view of the above, the present invention needs to provide a precursor for a lithium ion battery positive electrode material and a preparation method thereof, which improves the section compactness of the precursor by optimizing the preparation process and adopting segmented regulation, and obtains a precursor with a compact section and no gap, so that the positive electrode material obtained by using the precursor has high tap density.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a precursor for a lithium ion battery anode material comprises the following steps:
s1, mixing the metal mixed salt solution, the alkali liquor and the ammonia water solution, and reacting under the condition that the ammonia concentration is 6-12g/L, pH is 12-13 to prepare precursor seed materials; in this step, the feeding speed of the metal mixed salt solution is calculated according to the total reaction time and the total required target yield, for example, with a target 10kg material, 2mol/L salt solution, the total reaction time being 60h, and the target precursor relative molecular mass being about 92g/mol, the feeding speed is calculated as follows:
10×1000g/(92g/mol×2mol/L×60×60min)＝0.0151L/min＝15.1mL/min。
s2, adjusting the ammonia concentration in the step S1 to 10-18g/L, pH to 11-12, and continuing to react to obtain precursor slurry; in this step, when the precursor slurry of the precursor seed material growing to the target particle size value, a laser particle size analyzer can be used for testing and monitoring, and the reaction is stopped.
And S3, carrying out post-treatment on the precursor slurry to obtain a precursor.
Further, in the step S1, the concentration of metal ions in the metal mixed salt solution is 1.5-2.5 mol/L, the concentration of the alkali liquor is 4-6 mol/L, and the concentration of the ammonia water solution is 6-14 mol/L.
Further, the metal mixed salt solution is Ni xCo yM 1-x-ySO 4Wherein x is more than 0.5 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.2, and M is at least one of Mn, Al, Zr and Ti; the alkali liquor is at least one of sodium hydroxide or potassium hydroxide.
Further, the process parameters in step S1 are: the temperature is 50-55 ℃, the stirring speed is 800-; the process parameters in step S2 are: the temperature is 50-55 ℃, and the stirring speed is 700-.
Further, the total reaction time of the steps S1 and S2 is 20-60h, and the ratio of the reaction time in the step S1 to the reaction time in the step S2 is controlled to be 6-120. Wherein the actual reaction time in step S2 can be increased or decreased as appropriate according to the particle size test value.
Further, the reactions of step S1 and step S2 are performed in a nitrogen or argon atmosphere.
Further, in step S2, the precursor slurry has a particle size D50 of 3-18 μm.
Further, in step S3, the post-treatment step includes filter pressing, washing, drying, sieving, and demagnetizing.
The invention also provides a precursor for the lithium ion battery anode material, which is prepared by adopting the preparation method.
Further, the chemical general formula of the precursor for the lithium ion battery anode material is as follows: ni xCo yM 1-x-y(OH) 2Wherein x is more than 0.5 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.2, and M is at least one of Mn, Al, Zr and Ti.
Compared with the prior art, the method has the advantages that the parameters are less, and the staged regulation and control are simpler and more convenient, so that the prepared precursor has high section compactness and low porosity, and the tap density of the anode material is improved. Meanwhile, the yield of the precursor strength distributor prepared by the method can be flexibly designed.
Drawings
FIG. 1 is a scanning electron microscope image of a cross section of a precursor prepared only in step S2 in example 1;
fig. 2 is a scanning electron microscope image of a cross section of the precursor prepared in example 1.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention discloses a preparation method of a precursor for a lithium ion battery anode material, which comprises the following steps:
a preparation stage: setting target yield, total reaction time and target particle size value (based on D50 measured by laser particle size tester) according to Ni xCo yM 1-x-ySO 4(wherein x is more than 0.5 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.2, M is one or more of Mn, Al, Zr and Ti) a molar ratio is configured, the concentration of total metal ions is 1.5-2.5 mol/L, the concentration of configured sodium hydroxide lye is 4-6 mol/L, the concentration of configured ammonia complexing agent solution is 6-14 mol/L, the feeding flow rate of the metal mixed salt is calculated, for example, the target 10kg material, 2mol/L saline solution and the total reaction time is 60h, the relative molecular mass of the target precursor is about 92g/mol, the feeding flow rate is calculated in a mode of 10 × 1000g/(92g/mol × 2mol/L × 60 × 60min), 0.0151L/min is 15.1mL/min, and the ratio of T1/T2 is set to be 6-120;
s1, adding three materials, namely a metal mixed salt solution, a sodium hydroxide alkali solution and an ammonia complexing agent solution, into a reaction kettle with the process parameters of ammonia water concentration of 7-12g/L, pH of 12-13, temperature of 50-55 ℃, stirring speed of 700-1000rpm, and reaction time recorded as T1 to prepare an initial precursor seed material, introducing nitrogen for protection in the reaction process, and simultaneously controlling the concentration and clear liquid discharge rate to be consistent with the total feeding flow rate;
s2, adjusting the process parameters in the reaction kettle to ensure that the concentration of ammonia water is 10-18g/L, the pH is 11-12, the temperature is 50-55 ℃, the stirring speed is 700-1000rpm, continuing the reaction for a period of time to be recorded as T2, introducing nitrogen for protection in the reaction process when the seed material grows to the precursor slurry with the target particle size value, and simultaneously controlling the concentration and clear liquid discharge rate to be consistent with the total feeding flow rate;
and S3, performing filter pressing, washing, drying, screening and demagnetizing on the precursor slurry to obtain the precursor with high compactness.
The following examples were carried out according to the above procedure, with the following specific steps:
example 1
A preparation stage: in this example, the target yield was set to 10. + -.1 kg, the total reaction time was set to 60 hours and the target particle size D50 was set to 17.5. + -. 0.2. mu.m, in terms of Ni 0.85Co 0.1Mn 0.05SO 4Preparing a metal mixed salt solution containing nickel, cobalt and manganese according to a molar ratio, wherein the concentration of total metal ions is 2mol/L, the concentration of a prepared sodium hydroxide alkali liquor is 4.5mol/L, the concentration of a prepared ammonia water solution is 11mol/L, the feeding flow rate of the metal mixed salt is calculated to be about 15mL/min, and the ratio of T1/T2 is set to be 120;
s1, mixing and adding three materials, namely a metal mixed salt solution, a sodium hydroxide alkali solution and an ammonia water solution, into a reaction kettle, adjusting parameters to ensure that the ammonia concentration is 10g/L, the pH value is 12.5, the temperature is 52 ℃, the stirring speed is 900rpm, reacting for 0.5h in the reaction kettle to prepare precursor seeds, introducing nitrogen for protection in the reaction process, and simultaneously ensuring that the concentration and clear liquid discharging speed is consistent with the total feeding flow rate;
s2, adjusting parameters in the reaction kettle to be that the ammonia concentration is 15g/L, the pH value is 11.6, the temperature is 52 ℃, the stirring speed is 1000rpm, continuing the reaction for 59.5h (the actual time can be properly increased or shortened according to the particle size test value), stopping the reaction when the seed material grows to precursor slurry with the target particle size value D50 of 17.5 +/-0.2 mu m, introducing nitrogen for protection in the reaction process, and simultaneously, the concentration and clear liquid discharge rate is consistent with the total feeding flow rate;
and S3, performing filter pressing, washing, drying, screening and demagnetizing on the precursor slurry to obtain the precursor with high compactness.
The electron microscope pictures of the precursor in this example are shown in fig. 1 and 2, and the tap density and the cross-sectional porosity data are shown in table 1. It can be seen from fig. 2 that the precursor prepared by the present process has a dense cross-section without microcracks, and from fig. 1 it can be seen that the cross-section of the comparative sample prepared by only step S2 has holes. The section porosity of the sample of the embodiment is lower than that of the comparison sample (namely, the section compactness is high) and the tap density is higher than that of the comparison sample, which is beneficial to the pressure resistance strength and the structural stability of the anode material after post sintering.
Example 2
A preparation stage: the target yield was set to 4. + -.1 kg, the total reaction time was 24h and the target particle size D50 was set to 4. + -. 0.3. mu.m, in terms of Ni 0.6Co 0.2Mn 0.2SO 4Preparing a mixed salt solution containing nickel, cobalt and manganese metals according to a molar ratio, wherein the concentration of total metal ions is 2mol/L, the concentration of a prepared sodium hydroxide alkali liquor is 4.2mol/L, the concentration of a prepared ammonia water solution is 8mol/L, the feeding flow rate of the metal mixed salt is calculated to be about 15mL/min, and the ratio of T1/T2 is set to be 7;
s1, adding three materials, namely a metal mixed salt solution, a sodium hydroxide alkali solution and an ammonia water solution, into a reaction kettle, adjusting parameters to ensure that the ammonia concentration is 6g/L, the pH value is 12, the temperature is 50 ℃, and the stirring speed is 1000rpm, reacting for 3 hours to prepare precursor seed materials, introducing nitrogen for protection in the reaction process, and simultaneously controlling the concentration and clear liquid discharge rate to be consistent with the total feeding flow rate;
s2, adjusting the process parameters in the reaction kettle to ensure that the ammonia concentration is 10g/L, the pH value is 11.8, the temperature is 50 ℃, the stirring speed is 900rpm, continuing the reaction for 21h (the actual time can be properly increased or shortened according to the particle size test value), introducing nitrogen for protection in the reaction process when the seed material grows to a precursor slurry with a target particle size value D50 of 4 +/-0.3 mu m, and simultaneously controlling the concentration and clear liquid discharge rate to be consistent with the total feeding flow rate;
and S3, performing filter pressing, washing, drying, screening and demagnetizing on the precursor slurry to obtain the precursor with high compactness.
Example 3
A preparation stage: the target yield was 6. + -.1 kg, the total reaction time was 40h and the target particle size D50 was 9.5. + -. 0.2. mu.m, in terms of Ni 0.65Co 0.20Mn 0.10Zr 0.03Ti 0.02SO 4Preparing a mixed salt solution containing nickel, cobalt, manganese, zirconium and titanium metal according to a molar ratio, wherein the concentration of total metal ions is 1.6mol/L, the concentration of a prepared sodium hydroxide alkali solution is 4.1mol/L, the concentration of a prepared ammonia water solution is 7mol/L, calculating the feeding flow rate of the metal mixed salt to be 17mL/min, and setting the ratio of T1/T2 to be 30;
s1, adding three materials, namely a metal mixed salt solution, a sodium hydroxide alkali solution and an ammonia water solution, into a reaction kettle, adjusting the process parameters to ensure that the ammonia concentration is 9g/L, the pH value is 12.2, the temperature is 51 ℃, the stirring speed is 800rpm, and the reaction time is 1.3h to prepare precursor seeds;
s2, adjusting the process conditions in the reaction kettle to ensure that the ammonia concentration is 12g/L, the pH is 11.4, the temperature is 50-55 ℃, the stirring speed is 700rpm), continuing the reaction for 28.7h (the actual time is properly increased or shortened according to the particle size test value), growing the seed material into the precursor slurry with the target particle size value, introducing nitrogen for protection in the reaction process, and simultaneously controlling the concentration and clear liquid discharge rate to be consistent with the total feeding flow rate;
and S3, performing filter pressing, washing, drying, screening and demagnetizing on the precursor slurry to obtain the precursor with high compactness.
Example 4
A preparation stage: setting the target yield of 8 + -1 kg, the total reaction time of 30h and the target particle size D50 to 9.0 + -0.2 according to Ni 0.9Co 0.07Al 0.03SO 4Preparing a mixed salt solution containing nickel, cobalt and aluminum metals according to a molar ratio, wherein the concentration of total metal ions is 2.4mol/L, the concentration of a prepared sodium hydroxide alkali liquor is 5.8mol/L, the concentration of a prepared ammonia water solution is 13mol/L, calculating the feeding flow rate of the metal mixed salt to be 20mL/min, and setting the ratio of T1/T2 to be 20;
s1, adding three materials, namely a metal mixed salt solution, a sodium hydroxide alkali solution and an ammonia water solution, into a reaction kettle, adjusting the process conditions to ensure that the ammonia concentration is 12g/L, the pH is 12.8, the temperature is 55 ℃, the stirring speed is 800rpm, reacting in the reaction kettle for 1.4h to prepare a precursor seed material, introducing nitrogen for protection in the reaction process, and simultaneously controlling the concentration and clear liquid discharge speed to be consistent with the total feeding flow rate;
s2, adjusting parameters in the reaction kettle to be that the ammonia concentration is 18g/L, the pH value is 11.8, the temperature is 55 ℃, the stirring speed is 800rpm, continuing the reaction for 28.6h (the actual time can be properly increased or shortened according to the particle size test value), when the seed material grows to be precursor slurry with a target particle size value, introducing nitrogen for protection in the reaction process, and simultaneously controlling the concentration and clear liquid discharge rate to be consistent with the total feeding flow rate;
and S3, performing filter pressing, washing, drying, screening and demagnetizing on the precursor slurry to obtain the precursor with high compactness.
Table 1 shows the tap density and cross-sectional porosity of the precursors of examples 1-4.
TABLE 1
Figure BDA0002211580360000061
Figure BDA0002211580360000071
Note: the comparative samples in table 1 are precursors prepared using only step S2 in the corresponding example;
the tap density is measured according to a measuring method of GB/T5162-2006 metal powder tap density, and the section porosity measuring method is characterized in that the proportion of the hole area to the total particle section area is counted by adopting picture software in a section SEM.
As can be seen from Table 1, the precursor prepared by the preparation method provided by the invention has higher tap density and lower section porosity, and is beneficial to structural stability of the sintered material.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of a precursor for a lithium ion battery anode material is characterized by comprising the following steps:
s1, mixing the metal mixed salt solution, the alkali liquor and the ammonia water solution, and reacting under the condition that the ammonia concentration is 6-12g/L, pH is 12-13 to prepare precursor seed materials;
s2, adjusting the ammonia concentration in the step S1 to 10-18g/L, pH to 11-12, and continuing to react to obtain precursor slurry;
and S3, carrying out post-treatment on the precursor slurry to obtain a precursor.
2. The method according to claim 1, wherein in step S1, the metal ion concentration in the metal mixed salt solution is 1.5-2.5 mol/L, the alkali solution concentration is 4-6 mol/L, and the ammonia solution concentration is 6-14 mol/L.
3. The method of claim 1, wherein the metal mixed salt solution is Ni xCo yM 1-x-ySO 4Wherein x is more than 0.5 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.2, M is at least one of Mn, Al, Zr and Ti, and the alkali liquor is at least one of sodium hydroxide or potassium hydroxide.
4. The method according to claim 1, wherein the process parameters in step S1 are: the temperature is 50-55 ℃, the stirring speed is 800-; the process parameters in step S2 are: the temperature is 50-55 ℃, and the stirring speed is 700-.
5. The method of claim 1, wherein the total reaction time of the steps S1 and S2 is 20 to 60 hours, and the ratio of the reaction time of the step S1 to the reaction time of the step S2 is controlled to 6 to 120.
6. The method of claim 1, wherein the reactions of step S1 and step S2 are performed in a nitrogen or argon atmosphere.
7. The method of claim 1, wherein in step S2, the precursor slurry has a particle size value D50 of 3 to 18 μm.
8. The method according to claim 1, wherein in step S3, the post-treatment step comprises filter pressing, washing, drying, sieving, and demagnetizing.
9. A precursor for a positive electrode material of a lithium ion battery, characterized by being produced by the production method according to any one of claims 1 to 8.
10. The precursor for a positive electrode material for a lithium ion battery according to claim 9, wherein the precursor for a positive electrode material for a lithium ion battery has a chemical formula of: ni xCo yM 1-x-y(OH) 2Wherein x is more than 0.5 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.2, and M is at least one of Mn, Al, Zr and Ti.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111276688A (en) * 2020-02-13 2020-06-12 荆门市格林美新材料有限公司 Cerium-zirconium co-doped porous structure cathode material and preparation method thereof
CN112279310A (en) * 2020-10-26 2021-01-29 合肥国轩高科动力能源有限公司 Preparation method of ternary cathode material precursor

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CN107611383A (en) * 2017-08-25 2018-01-19 浙江华友钴业股份有限公司 A kind of preparation method of the nickel-cobalt-manganese ternary presoma of low-sulfur high-tap density
CN107640792A (en) * 2017-11-16 2018-01-30 中南大学 A kind of high compact small particle nickel cobalt manganese hydroxide and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107611383A (en) * 2017-08-25 2018-01-19 浙江华友钴业股份有限公司 A kind of preparation method of the nickel-cobalt-manganese ternary presoma of low-sulfur high-tap density
CN107640792A (en) * 2017-11-16 2018-01-30 中南大学 A kind of high compact small particle nickel cobalt manganese hydroxide and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111276688A (en) * 2020-02-13 2020-06-12 荆门市格林美新材料有限公司 Cerium-zirconium co-doped porous structure cathode material and preparation method thereof
CN111276688B (en) * 2020-02-13 2021-02-19 荆门市格林美新材料有限公司 Cerium-zirconium co-doped porous structure cathode material and preparation method thereof
CN112279310A (en) * 2020-10-26 2021-01-29 合肥国轩高科动力能源有限公司 Preparation method of ternary cathode material precursor

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