CN113292115A - Low-cobalt cathode material and preparation method and application thereof - Google Patents

Low-cobalt cathode material and preparation method and application thereof Download PDF

Info

Publication number
CN113292115A
CN113292115A CN202110768017.1A CN202110768017A CN113292115A CN 113292115 A CN113292115 A CN 113292115A CN 202110768017 A CN202110768017 A CN 202110768017A CN 113292115 A CN113292115 A CN 113292115A
Authority
CN
China
Prior art keywords
cobalt
precursor
mol
molar concentration
low
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110768017.1A
Other languages
Chinese (zh)
Inventor
孙化雨
其他发明人请求不公开姓名
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
Original Assignee
Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Envision Power Technology Jiangsu Co Ltd, Envision Ruitai Power Technology Shanghai Co Ltd filed Critical Envision Power Technology Jiangsu Co Ltd
Priority to CN202110768017.1A priority Critical patent/CN113292115A/en
Publication of CN113292115A publication Critical patent/CN113292115A/en
Pending legal-status Critical Current

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
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

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

Abstract

The invention provides a low-cobalt cathode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: continuously adding a nickel precursor, a cobalt precursor, a manganese precursor, a precipitator and a complexing agent into a reaction kettle for reaction, so that the molar concentration of the nickel precursor in the reaction kettle is kept unchanged, the molar concentration of the cobalt precursor is continuously increased, and the molar concentration of the manganese precursor is continuously reduced, thereby obtaining ternary precursor particles; mixing the ternary precursor particles with a lithium precursor, and sintering to obtain a low-cobalt cathode material with gradually increased cobalt content from inside to outside; the low-cobalt cathode material has the advantage of low content and stable structure, and is beneficial to improving the electrical performance of the lithium ion battery.

Description

Low-cobalt cathode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a low-cobalt cathode material and a preparation method and application thereof.
Background
The low-cobalt material being lithium ionThe main solution of cost reduction is currently adopted in the cell, but the reduction of cobalt element brings the deterioration of electrochemical performance and processing performance, such as: the compaction is reduced, the capacity is reduced, the low-temperature performance is deteriorated, and the high-temperature cycle resistance is obviously increased; therefore, it is a difficult problem to ensure the performance while reducing the cost, and the NCM cobalt content in the industrial production is generally not less than 0.12 mol% (based on the transition metal) in order to satisfy the electrochemical performance and the processability of the project. The performance of the material is obviously influenced by the contents of three elements of Ni, Co and Mn, the high Co content is beneficial to increasing the orderliness of the material, and in addition, the low cobalt material can generate more serious Li during sintering preparation+/Ni2+And mixed drainage is adopted, the initial capacity exertion of the material is reduced, and meanwhile, the phase change of a bulk phase and the surface is further serious in the circulation process to form a rock salt phase, so that the circulation performance of the low-cobalt material is greatly deteriorated.
Therefore, a low cobalt material is required to solve a series of problems such as deterioration of kinetics, deterioration of resistance, and deterioration of cycle.
Many studies and reports have been made to solve this problem. CN112678883A discloses a preparation method of a surface cobalt-rich ternary low-cobalt cathode material with controllable component concentration. The invention adopts a microemulsion oil/water (o/w) system, regulates and controls the precipitation rate of metal salt by controlling the proportion of water phase and oil phase, further uniformly precipitates the cobalt-rich precursor on the surface of the prepared low-cobalt precursor, can obtain low-cobalt type cathode material precursors with different coating thicknesses, and simultaneously obtains the lithium battery cathode material with controllable components and concentration and the surface cobalt-rich ternary low-cobalt cathode material by adding a metal silver film between an inner core and an outer layer and then reacting with a lithium source. The preparation method is simple, and the prepared material has the advantages of uniform and controllable coating, low cost, excellent electrochemical performance and the like. CN111403728A discloses a preparation method of a high-nickel low-cobalt co-deposited magnesium anode material. The method comprises the following steps: dissolving nickel salt, cobalt salt and manganese salt into aqueous solution of hydrogen chloride, adding citric acid under stirring, and then adding alkali liquor to adjust the pH value to be alkaline, so as to obtain mixed liquor; heating and drying the mixed solution to obtain gel; soaking the obtained gel in ammonia water, and performing solvent replacement and aging to obtain an aged gel; further drying the obtained aged gel to obtain dry gel, and grinding to obtain gel powder; adding the gel powder into a magnesium salt solution, and carrying out microwave treatment on the gel powder to obtain magnesium intercalation powder; calcining the inserted magnesium powder to obtain the high-nickel low-cobalt co-deposited magnesium-coated anode material. The method can prepare the magnesium anode material with higher gram capacity; the prepared magnesium anode material has good cycle performance; can be universally used for lithium batteries and magnesium batteries, and has better use effect. CN108767239A discloses a high-nickel low-cobalt ternary positive electrode material and a preparation method thereof, wherein the chemical general formula of the material is Li [ NiCoMn ] MO, x is mole percent, x is more than or equal to 0.01 and less than or equal to 0.05, and M is one or a combination of more of Sc, Y, Zr, Ti, Mg or Al. The preparation method adopts a coprecipitation method to prepare the precursor, and then adopts a simple solid phase method to synthesize the cathode material containing excessive lithium and doped with M ions, so that the product cost is low, and the preparation method is simple and convenient to control; the raw materials have wide sources, the industrial production is easy, the prepared material has good crystallinity, no impurity phase, fine particles and uniform distribution, and simultaneously has high discharge specific capacity and excellent cycle performance.
However, the preparation method of the low cobalt material provided by the above patent is relatively complex, and the stability of the prepared low cobalt material is still to be improved.
Therefore, developing a preparation method of underestimated materials with simple preparation process to obtain underestimated materials with stable structure is a technical problem which needs to be solved urgently by the technical personnel in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-cobalt cathode material and a preparation method and application thereof; the preparation method comprises the following steps: continuously adding a nickel precursor, a cobalt precursor, a manganese precursor, a precipitator and a complexing agent into a reaction kettle for reaction, and after the nickel precursor, the cobalt precursor, the manganese precursor, the precipitator and the complexing agent are added into the reaction kettle, keeping the molar concentration of nickel in the reaction kettle unchanged, continuously increasing the molar concentration of cobalt and continuously reducing the molar concentration of manganese to obtain ternary precursor particles; mixing the obtained ternary precursor particles with a lithium precursor, and sintering to obtain the low-cobalt cathode material; the content of cobalt in the low-cobalt cathode material gradually increases from the inside to the outside of the particles in a gradient manner, so that the obtained low-cobalt cathode material is ensured to have a stable structure while the total content of cobalt in the low-cobalt cathode material is low, the problem that the surface of the low-cobalt material is easy to change phase is solved, and the low-cobalt cathode material has important research value.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a preparation method of a low-cobalt cathode material, including the following steps:
(1) continuously adding a nickel precursor, a cobalt precursor, a manganese precursor, a precipitator and a complexing agent into a reaction kettle for reaction to obtain ternary precursor particles;
(2) mixing the ternary precursor particles obtained in the step (1) with a lithium precursor, and sintering to obtain the low-cobalt cathode material;
after the nickel is added into the reaction kettle in the step (1), keeping the molar concentration of nickel in the reaction kettle unchanged; the molar concentration of the cobalt is increased from 0.04-0.05 mol/L (such as 0.041mol/L, 0.042mol/L, 0.043mol/L, 0.044mol/L, 0.045mol/L, 0.046mol/L, 0.047mol/L, 0.048mol/L or 0.049mol/L and the like) to 0.14-0.15 mol/L (such as 0.141mol/L, 0.142mol/L, 0.143mol/L, 0.144mol/L, 0.145mol/L, 0.146mol/L, 0.147mol/L, 0.148mol/L or 0.149mol/L and the like); the molar concentration of manganese is reduced from 0.36-0.45 mol/L (such as 0.37mol/L, 0.38mol/L, 0.39mol/L, 0.4mol/L, 0.41mol/L, 0.42mol/L, 0.43mol/L, 0.44mol/L or 0.45 and the like) to 0.26-0.35 mol/L (such as 0.27mol/L, 0.28mol/L, 0.29mol/L, 0.3mol/L, 0.31mol/L, 0.32mol/L, 0.33mol/L, 0.34mol/L or 0.35mol/L and the like).
The low cobalt in the low cobalt cathode material provided by the invention is represented by the general formula LinNixCoyMn1-x-yO2Y in the positive electrode material is less than or equal to 0.15.
According to the preparation method of the low-cobalt material, the nickel precursor, the cobalt precursor and the manganese precursor are continuously added into the reaction kettle, so that the molar concentration of nickel in the reaction kettle is unchanged, the molar concentration of cobalt is increased from 0.04-0.05 mol/L to 0.14-0.15 mol/L, and the molar concentration of manganese is reduced from 0.36-0.45 mol/L to 0.26-0.35 mol/L; and the total molar concentration of nickel, cobalt and manganese is ensured to be 1 mol/L; the molar ratio of cobalt to manganese in the reaction kettle is continuously adjusted, so that the obtained ternary precursor particles have different cobalt concentrations from the inside to the outside and are distributed in a gradient increasing manner; and further mixing the lithium ion battery anode material with a lithium precursor, and sintering to obtain the final anode material which has the advantages of low cobalt content (y is less than or equal to 0.15) and stable structure, so that the prepared lithium ion battery has excellent electrochemical performance.
The preparation method provided by the invention utilizes the characteristic of liquidity existing in a liquid phase environment, illustratively, the precipitation speed of a nickel precursor, a cobalt precursor, a manganese precursor, a precipitator and a complexing agent can be controlled by adjusting the speed of introducing the cobalt precursor and the manganese precursor into a reaction kettle in the process of continuously adding the nickel precursor, the cobalt precursor, the manganese precursor, the precipitator and the complexing agent into the reaction kettle; a cobalt precursor with low flow rate is adopted initially, so that the molar concentration of cobalt in the reaction kettle (the molar content of cobalt occupies the volume of all liquid) is low; a manganese precursor with high flow rate is adopted initially, so that the molar concentration of manganese (the molar content of manganese accounts for the volume of all liquid) in the reaction kettle is higher; and then gradually increasing the flow rate of the cobalt precursor and reducing the flow rate of the manganese precursor, thereby precipitating ternary precursor particles with the cobalt content in gradient increasing distribution.
Preferably, the nickel precursor of step (1) comprises nickel sulfate.
Preferably, the molar concentration of nickel in the reaction kettle in the step (1) is 0.5-0.6 mol/L, such as 0.51mol/L, 0.52mol/L, 0.53mol/L, 0.54mol/L, 0.55mol/L, 0.56mol/L, 0.57mol/L, 0.58mol/L or 0.59mol/L, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
In the present invention, since the sum of the molar ratios of the nickel precursor, the cobalt precursor, and the manganese precursor needs to be kept at 1, the molar concentration of the nickel precursor needs to be adjusted adaptively according to actual needs.
Preferably, the cobalt precursor of step (1) comprises cobalt sulfate.
Preferably, the manganese precursor of step (1) comprises manganese sulfate.
Preferably, the precipitant of step (1) comprises sodium hydroxide.
Preferably, the precipitant in step (1) has a molar concentration of 1-10 mol/L, such as 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
Preferably, the complexing agent of step (1) comprises ammonia.
Preferably, the complexing agent in step (1) has a molar concentration of 1-3 mol/L, such as 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, 2mol/L, 2.2mol/L, 2.4mol/L, 2.6mol/L or 2.8mol/L, and the specific values therebetween are not limited to space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the molar concentration of cobalt in the reaction kettle of step (1) increases at a rate of 0.00015 to 0.00025 mol/L.min, such as 0.00016 mol/L.min, 0.00017 mol/L.min, 0.00018 mol/L.min, 0.00019 mol/L.min, 0.0002mol/L.min, 0.00021 mol/L.min, 0.00022 mol/L.min, 0.00023 mol/L.min or 0.00024 mol/L.min, and the specific values therebetween are limited to space and are not exhaustive for the sake of brevity.
Preferably, the reduction rate of the manganese molar concentration in the reaction kettle in the step (1) is 0.00015-0.00025 mol/L.min, such as 0.00016 mol/L.min, 0.00017 mol/L.min, 0.00018 mol/L.min, 0.00019 mol/L.min, 0.0002mol/L.min, 0.00021 mol/L.min, 0.00022 mol/L.min, 0.00023 mol/L.min or 0.00024 mol/L.min, and the specific values between the above values are limited to space and the invention is not exhaustive for the specific values included in the range for the sake of brevity.
Both the "positive rate" and "reduced rate" are made to be variations in the original flow rate, not the final flow rate.
In the present invention, the rate of increase in the molar concentration of cobalt is 0.00015 to 0.00025 mol/L.min; the reduction rate of the molar concentration of manganese is 0.00015-0.00025 mol/L.min; and in order to maintain the total molar concentration of nickel, cobalt and manganese at 1mol/L, it is necessary that the changes in the molar concentrations of the cobalt precursor and the manganese precursor be performed simultaneously.
Preferably, the amount of the precipitant added in step (1) is 6-12L/h, such as 7L/h, 8L/h, 9L/h, 10L/h, 10.5L/h, 110.7L/h, 11L/h, 11.5L/h or 12L/h, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive list of the specific values included in the range.
Preferably, the complexing agent is added in the amount of 5-15L/h, such as 6L/h, 7L/h, 8L/h, 9L/h, 10L/h, 11L/h, 12L/h, 13L/h or 14L/h in step (1), and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
Preferably, the ammonia water content is 10-30% by mass, for example, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26% or 28%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, before the step (2), the method further comprises the steps of removing impurities, dehydrating, drying, screening and removing iron from the ternary precursor particles obtained in the step (1).
Preferably, the molar ratio of the ternary precursor to the lithium precursor in the step (2) is 1: 1.03-1.08, such as 1:1.042, 1:1.044, 1:1.046, 1:1.048, 1:1.05, 1:1.052, 1:1.054, 1:1.056 or 1: 1.058.
Preferably, the sintering temperature in step (2) is 900-1000 ℃, such as 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃ or 990 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the sintering time in step (2) is 7-9 h, such as 7.2h, 7.4h, 7.6h, 7.8h, 8h, 8.2h, 8.4h, 8.6h or 8.8h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the range.
Preferably, the preparation method comprises the following steps:
(1) continuously adding a nickel precursor, a cobalt precursor, a manganese precursor, a precipitator and a complexing agent into a reaction kettle for reaction to obtain ternary precursor particles; after the nickel is added into the reaction kettle, the molar concentration of nickel in the reaction kettle is 0.5-0.6 mol/L; the molar concentration of the cobalt is increased from 0.04-0.05 mol/L to 0.14-0.15 mol/L according to the speed of 0.00015-0.00025 mol/L.min; the molar concentration of manganese is reduced from 0.36-0.45 mol/L to 0.26-0.35 mol/L according to the speed of 0.00015-0.00025 mol/L.min;
(2) and (2) mixing the ternary precursor particles obtained in the step (1) with a lithium precursor according to a molar ratio of 1 (1.03-1.08), and sintering at 900-1000 ℃ for 7-9 h to obtain the low-cobalt cathode material.
In a second aspect, the present invention provides a low-cobalt cathode material obtained by the method for preparing the low-cobalt cathode material according to the first aspect.
In a third aspect, the present invention provides a lithium ion battery, wherein the lithium ion battery comprises the low cobalt cathode material according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the low-cobalt cathode material, firstly, a nickel precursor, a cobalt precursor, a manganese precursor, a precipitator and a complexing agent are continuously added into a reaction kettle for reaction, so that the molar concentration of nickel in the reaction kettle is kept unchanged, the molar concentration of cobalt is continuously increased, and the molar concentration of manganese is continuously reduced, and ternary precursor particles are obtained; (ii) a And mixing and sintering the ternary precursor particles and the lithium precursor, so that the obtained low-cobalt cathode material has different cobalt contents from the inside to the outside, the total cobalt content is lower (y is less than or equal to 0.15), the structure is stable, the multiplying power 3C/0.1C of the button battery obtained by the low-cobalt cathode material prepared by the preparation method provided by the invention is 81.4-86%, the resistance is 0.697-1.014 omega, and the electrochemical performance of the battery is excellent.
Drawings
Fig. 1 is a scanning electron microscope photograph of the low-cobalt positive electrode material obtained in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of a low-cobalt cathode material comprises the following steps:
(1) continuously adding nickel sulfate, cobalt sulfate, manganese sulfate, ammonia water and sodium hydroxide into a reaction kettle for reaction to obtain ternary precursor particles;
the adding amount of the sodium hydroxide in the reaction kettle is 15L/h; the adding amount of ammonia water is 10L/h; keeping the molar concentration of nickel in the reaction kettle to be 0.55mol/L unchanged, increasing the molar concentration of cobalt from 0.05mol/L to 0.15mol/L according to the increasing speed of 0.0002mol/L.min, reducing the molar concentration of manganese from 0.4mol/L to 0.3mol/L according to the reducing speed of 0.0002mol/L.min, wherein the molar concentration of ammonia water is 3mol/L, and the molar concentration of sodium hydroxide is 10 mol/L;
(2) and (2) mixing the ternary precursor particles obtained in the step (1) with a lithium precursor according to a molar ratio of 1:1.06, and sintering at 950 ℃ for 8h to obtain the low-cobalt cathode material.
Example 2
A preparation method of a low-cobalt cathode material comprises the following steps:
(1) adding nickel sulfate, cobalt sulfate, manganese sulfate/ammonia water and sodium hydroxide into a reaction kettle, and reacting to obtain ternary precursor particles;
the adding amount of the sodium hydroxide in the reaction kettle is 10L/h; the adding amount of ammonia water is 5L/h; keeping the molar concentration of nickel in the reaction kettle to be 0.6mol/L, increasing the molar concentration of cobalt from 0.04mol/L to 0.14mol/L according to the increasing speed of 0.0002mol/L.min, reducing the molar concentration of manganese from 0.36mol/L to 0.26mol/L according to the decreasing speed of 0.0002mol/L.min, wherein the molar concentration of ammonia water is 2mol/L, and the molar concentration of sodium hydroxide is 10 mol/L;
(2) and (2) mixing the ternary precursor particles obtained in the step (1) with a lithium precursor according to a molar ratio of 1:1.06, and sintering at 1000 ℃ for 7h to obtain the low-cobalt cathode material.
Example 3
A preparation method of a low-cobalt cathode material comprises the following steps:
(1) adding nickel sulfate, cobalt sulfate, manganese sulfate/ammonia water and sodium hydroxide into a reaction kettle, and reacting to obtain ternary precursor particles;
the adding amount of the sodium hydroxide in the reaction kettle is 20L/h; the adding amount of ammonia water is 15L/h; keeping the molar concentration of nickel in the reaction kettle to be 0.5mol/L unchanged, increasing the molar concentration of cobalt from 0.05mol/L to 0.14mol/L according to the increasing speed of 0.0002mol/L.min, reducing the molar concentration of manganese from 0.45mol/L to 0.36mol/L according to the decreasing speed of 0.0002mol/L.min, wherein the molar concentration of ammonia water is 3mol/L, and the molar concentration of sodium hydroxide is 10 mol/L;
(2) and (2) mixing the ternary precursor particles obtained in the step (1) with a lithium precursor according to a molar ratio of 1:1.06, and sintering at 900 ℃ for 9h to obtain the low-cobalt cathode material.
Comparative example 1
A preparation method of a low-cobalt cathode material comprises the following steps:
(1) adding nickel sulfate, cobalt sulfate, manganese sulfate, ammonia water and sodium hydroxide into a reaction kettle, and reacting to obtain ternary precursor particles;
the adding amount of nickel sulfate, cobalt sulfate and manganese sulfate is 50L/h in the process of adding into the reaction kettle; the addition amount of the sodium hydroxide is 15L/h; the adding amount of ammonia water is 10L/h; the molar concentration of nickel is 0.55mol/L, the molar concentration of cobalt is kept to be 0.05mol/L, the molar concentration of manganese is 0.4mol/L, the molar concentration of ammonia water is 2mol/L, and the molar concentration of sodium hydroxide is 10 mol/L;
(2) and (2) mixing the ternary precursor particles obtained in the step (1) with a lithium precursor according to a molar ratio of 1:1.06, and sintering at 950 ℃ for 8h to obtain the low-cobalt cathode material.
Comparative example 2
A preparation method of a low-cobalt cathode material comprises the following steps:
(1) adding nickel sulfate, cobalt sulfate, manganese sulfate, ammonia water and sodium hydroxide into a reaction kettle, and reacting to obtain ternary precursor particles;
the adding amount of nickel sulfate, cobalt sulfate and manganese sulfate is 50L/h in the process of adding into the reaction kettle; the addition amount of the sodium hydroxide is 15L/h; the adding amount of ammonia water is 10L/h; keeping the molar concentration of nickel constant at 0.55mol/L, the molar concentration of cobalt at 0.15mol/L, the molar concentration of manganese at 0.3mol/L, the molar concentration of ammonia water at 2mol/L, and the molar concentration of sodium hydroxide at 10 mol/L;
(2) and (2) mixing the ternary precursor particles obtained in the step (1) with a lithium precursor according to a molar ratio of 1:1.06, and sintering at 950 ℃ for 8h to obtain the low-cobalt cathode material.
Application examples 1 to 3
A button cell with low cobalt content comprises the low cobalt positive electrode materials obtained in the embodiments 1-3 respectively;
the preparation process comprises the following steps:
(1) respectively mixing the low-cobalt positive electrode material obtained in the embodiments 1-3 and the nickel cobalt lithium manganate ternary positive electrode material according to the mass ratio of 1:10, wherein the mixing mode is ball milling for 2 hours, and the rotating speed is 500rpm, so as to obtain a positive electrode active substance mixture;
(2) mixing the positive active material mixture obtained in the step (1) with conductive carbon black and PVDF according to the mass ratio of 8:1:1, adding a solvent NMP, and stirring to obtain positive slurry;
(3) coating the anode slurry obtained in the step (2) on an aluminum foil, and drying in a vacuum drying oven at 110 ℃ for 6h to obtain an anode plate;
(4) placing the positive plate obtained in the step (3) in a glove box Mikeluona according to the formula: stirring materials with NCM (carbon fiber), CNT (carbon fiber), PVDF (polyvinylidene fluoride) 97.2:1.0:0.8:1.0, homogenizing, and then preparing a button cell, wherein the button cell is provided with the following electricity button types: 2016. the compaction is 3.2 to 3.6 g/cc. Then drying the pole piece, wherein the drying conditions are as follows: and (5) performing electricity fastening and standing for 12h at the temperature of 110 ℃/6h after manufacturing.
Comparative application examples 1 to 2
A button cell with low cobalt content comprises the positive electrode materials obtained in comparative examples 1-2;
the preparation process is the same as in application example 1.
And (3) performance testing:
(1) and (3) observing the appearance: observing the cathode material obtained in the example 1 by using a scanning electron microscope; the scanning electron microscope topography of the cathode material obtained in example 1 is shown in fig. 1, and it can be seen from fig. 1 that: the low-cobalt cathode material obtained in the embodiment 1 has a smooth surface, the surface is uniformly covered by a coating, and particles are in a single crystal shape;
(2) rate capability: setting a flow on a Xinwei tester, and testing current: 0.1C, constant current and constant voltage charging, 0.1C constant current discharging, and the cut-off condition of the constant voltage section: 50 μ a, voltage: 2.8-4.25V; reading the charge-discharge capacity and the first effect, and then using the conditions of 0.1C, constant current and constant voltage charge, 3C constant current discharge and constant voltage section cutoff: 50 μ a, voltage: 2.8-4.25V; record 3C/0.1C capacity.
(3) Resistance: EIS of the button cell was tested at low temperature-20 ℃ and the value of Rct + Rs was calculated.
The button batteries obtained in the application examples 1-3 and the comparative application examples 1-2 are tested according to the test method, and the test results are shown in table 1:
TABLE 1
Figure BDA0003152665550000121
As can be seen from the data in table 1:
by controlling the molar concentrations of the cobalt precursor and the dream precursor in the reaction kettle, the invention can form low-cobalt high-manganese interior with lower cobalt deposition and more manganese deposition in the early stage, and then gradually form high-cobalt low-manganese ternary precursor particles with more cobalt deposition and lower manganese deposition.
The multiplying power 3C/0.1C of the button battery prepared from the low-cobalt cathode material prepared by the preparation method provided by the embodiments 1-3 is 81.4-86%, and the resistance is 0.697-1.014 omega; the button cell of the cathode material prepared by the preparation method provided by the comparative examples 1-2 has the battery multiplying power of 75.3-77.9% and the resistance of 1.316-1.906 omega, which is because the Li on the outer layer of the low-cobalt cathode material particles provided by the invention+The amount of extraction is large, so that the outer Co-rich layer can optimize Li at low temperature+Diffusion rate, reduced polarization and improved battery rate performance.
The applicant states that the present invention is illustrated by the above examples to a low cobalt cathode material and its preparation method and application, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (10)

1. The preparation method of the low-cobalt cathode material is characterized by comprising the following steps of:
(1) continuously adding a nickel precursor, a cobalt precursor, a manganese precursor, a precipitator and a complexing agent into a reaction kettle for reaction to obtain ternary precursor particles;
(2) mixing the ternary precursor particles obtained in the step (1) with a lithium precursor, and sintering to obtain the low-cobalt cathode material;
keeping the molar concentration of nickel in the reaction kettle in the step (1) unchanged; the molar concentration of the cobalt is gradually increased from 0.04-0.05 mol/L to 0.14-0.15 mol/L, and the molar concentration of the manganese is gradually decreased from 0.36-0.45 mol/L to 0.26-0.35 mol/L.
2. The production method according to claim 1, wherein the nickel precursor of step (1) comprises nickel sulfate;
preferably, the molar concentration of nickel in the reaction kettle in the step (1) is 0.5-2.5 mol/L;
preferably, the cobalt precursor of step (1) comprises cobalt sulfate;
preferably, the manganese precursor of step (1) comprises manganese sulfate.
3. The method according to claim 1 or 2, wherein the precipitant of step (1) comprises sodium hydroxide;
preferably, the molar concentration of the precipitant in the step (1) is 6-12 mol/L;
preferably, the complexing agent of step (1) comprises aqueous ammonia;
preferably, the mass percentage of the ammonia water is 10-30%;
preferably, the molar concentration of the complexing agent in the step (1) is 1-3 mol/L.
4. The method according to any one of claims 1 to 3, wherein the molar concentration of cobalt in the reaction vessel in the step (1) increases at a rate of 0.00015 to 0.00025 mol/L-min;
preferably, the reduction rate of the molar concentration of manganese in the reaction kettle in the step (1) is 0.00015-0.00025 mol/L.min.
5. The preparation method according to any one of claims 1 to 4, wherein the amount of the precipitant added in step (1) is 10 to 20L/h;
preferably, the addition amount of the complexing agent in the step (1) is 5-15L/h.
6. The preparation method according to any one of claims 1 to 5, characterized by further comprising the steps of removing impurities, dehydrating, drying, screening and removing iron from the ternary precursor particles obtained in step (1) before step (2).
7. The preparation method according to any one of claims 1 to 6, wherein the molar ratio of the ternary precursor to the lithium precursor in the step (2) is 1 (1.03 to 1.08);
preferably, the sintering temperature in the step (2) is 900-1000 ℃;
preferably, the sintering time in the step (2) is 7-9 h.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) continuously adding a nickel precursor, a cobalt precursor, a manganese precursor, a precipitator and a complexing agent into a reaction kettle for reaction to obtain ternary precursor particles; after the nickel is added into the reaction kettle, the molar concentration of nickel in the reaction kettle is 0.5-0.6 mol/L; the molar concentration of the cobalt is increased from 0.04-0.05 mol/L to 0.14-0.15 mol/L according to the speed of 0.00015-0.00025 mol/L.min; the molar concentration of manganese is reduced from 0.36-0.45 mol/L to 0.26-0.35 mol/L according to the speed of 0.00015-0.00025 mol/L.min;
(2) and (2) mixing the ternary precursor particles obtained in the step (1) with a lithium precursor according to a molar ratio of 1 (1.03-1.08), and sintering at 900-1000 ℃ for 7-9 h to obtain the low-cobalt cathode material.
9. A low-cobalt positive electrode material, which is obtained by the method for producing a low-cobalt positive electrode material according to any one of claims 1 to 8.
10. A lithium ion battery comprising the low cobalt positive electrode material of claim 9.
CN202110768017.1A 2021-07-07 2021-07-07 Low-cobalt cathode material and preparation method and application thereof Pending CN113292115A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110768017.1A CN113292115A (en) 2021-07-07 2021-07-07 Low-cobalt cathode material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110768017.1A CN113292115A (en) 2021-07-07 2021-07-07 Low-cobalt cathode material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN113292115A true CN113292115A (en) 2021-08-24

Family

ID=77330714

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110768017.1A Pending CN113292115A (en) 2021-07-07 2021-07-07 Low-cobalt cathode material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113292115A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114583102A (en) * 2022-02-21 2022-06-03 远景动力技术(江苏)有限公司 Positive electrode active material, electrochemical device, and electronic device
CN114583141A (en) * 2022-05-09 2022-06-03 浙江帕瓦新能源股份有限公司 Precursor material with three-layer structure, preparation method thereof and anode material
CN114835174A (en) * 2022-05-30 2022-08-02 远景动力技术(江苏)有限公司 Low-cobalt positive electrode active material, method for producing same, electrochemical device, and electronic device
CN115259244A (en) * 2022-08-31 2022-11-01 宁波容百新能源科技股份有限公司 Cobalt gradient high-nickel ternary cathode material, preparation method thereof and lithium ion battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103000876A (en) * 2012-12-11 2013-03-27 奇瑞汽车股份有限公司 Lithium nickel manganese oxide material precursor and preparation method thereof, lithium nickel manganese oxide material and preparation method thereof, and lithium ion battery
CN103078109A (en) * 2013-01-16 2013-05-01 中南大学 Gradient coated LiNiO2 material and preparation method
CN104201369A (en) * 2014-07-01 2014-12-10 宁波金和新材料股份有限公司 Lithium-ion-battery gradient cathode-material precursor and preparation method thereof
CN108793268A (en) * 2018-06-19 2018-11-13 中南大学 Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103000876A (en) * 2012-12-11 2013-03-27 奇瑞汽车股份有限公司 Lithium nickel manganese oxide material precursor and preparation method thereof, lithium nickel manganese oxide material and preparation method thereof, and lithium ion battery
CN103078109A (en) * 2013-01-16 2013-05-01 中南大学 Gradient coated LiNiO2 material and preparation method
CN104201369A (en) * 2014-07-01 2014-12-10 宁波金和新材料股份有限公司 Lithium-ion-battery gradient cathode-material precursor and preparation method thereof
CN108793268A (en) * 2018-06-19 2018-11-13 中南大学 Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
YAN LI ET AL.: "An Ostward ripening route towards Ni-rich layered cathod material with cobalt-rich surface for lithium ion battery", 《SCIENCE CHINA MATERIALS》, vol. 61, pages 719 - 727 *
张春芳等: "锂离子电池镍钴锰/铝三元浓度梯度正极材料的研究进展", 《电化学》, no. 1, pages 76 - 86 *
杜柯等: "梯度包覆镍酸锂材料Li[Ni(0.92)Co(0.04)Mn(0.04)]O2的合成与研究", 《无机化学学报》, no. 5, pages 154 - 159 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114583102A (en) * 2022-02-21 2022-06-03 远景动力技术(江苏)有限公司 Positive electrode active material, electrochemical device, and electronic device
CN114583102B (en) * 2022-02-21 2023-08-15 远景动力技术(江苏)有限公司 Positive electrode active material, electrochemical device, and electronic device
CN114583141A (en) * 2022-05-09 2022-06-03 浙江帕瓦新能源股份有限公司 Precursor material with three-layer structure, preparation method thereof and anode material
CN114835174A (en) * 2022-05-30 2022-08-02 远景动力技术(江苏)有限公司 Low-cobalt positive electrode active material, method for producing same, electrochemical device, and electronic device
CN114835174B (en) * 2022-05-30 2024-02-02 远景动力技术(江苏)有限公司 Low-cobalt positive electrode active material, method for producing same, electrochemical device, and electronic device
CN115259244A (en) * 2022-08-31 2022-11-01 宁波容百新能源科技股份有限公司 Cobalt gradient high-nickel ternary cathode material, preparation method thereof and lithium ion battery
CN115259244B (en) * 2022-08-31 2023-10-17 宁波容百新能源科技股份有限公司 Cobalt gradient high-nickel ternary positive electrode material, preparation method thereof and lithium ion battery

Similar Documents

Publication Publication Date Title
CN113292115A (en) Low-cobalt cathode material and preparation method and application thereof
CN112599781B (en) Double-concentration gradient doped lithium ion battery anode material and preparation method thereof
CN111916687B (en) Positive electrode material, preparation method thereof and lithium ion battery
CN110518219A (en) The nickelic gradient nickel cobalt manganese aluminium quaternary positive electrode of core-shell structure and preparation method
CN115196691A (en) Nickel-iron-manganese ternary precursor for sodium ion battery and preparation method and application thereof
CN113644272B (en) Cerium-bismuth composite oxide doped lithium ion battery positive electrode material and preparation method thereof
CN110890541A (en) Preparation method of surface-modified lithium-rich manganese-based positive electrode material and lithium ion battery
CN108550822A (en) A kind of lanthanum, the nickelic ternary anode material of lithium battery of magnesium codope and preparation method
CN108767216A (en) Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope
CN114477312B (en) Method for preparing ternary positive electrode material precursor by layered doping
CN113603153B (en) Tungsten doped high nickel cobalt-free precursor and preparation method thereof
WO2024040908A1 (en) Porous spherical ternary precursor and preparation method therefor, ternary positive electrode material, positive electrode plate and battery
CN111477866B (en) Ternary cathode material nickel-cobalt-aluminum for lithium ion battery and preparation method thereof
EP4383373A1 (en) Multilayer annular hole nickel-cobalt-aluminum precursor, preparation method for precursor and positive electrode material
CN116534918A (en) Layered positive electrode material, preparation method thereof and application of layered positive electrode material in sodium ion battery
CN115172756A (en) Single crystal coated polycrystalline anode material with concentration gradient and preparation method thereof
CN113387401B (en) Preparation method of scandium-tungsten doped anode material precursor
CN114715957A (en) Niobium-coated nickel-cobalt-manganese ternary precursor, and preparation method and application thereof
CN112599736B (en) Boron-doped lithium phosphate coated lithium ion battery positive electrode material and preparation method thereof
CN112551598A (en) Preparation method and application of lithium ion battery precursor
CN112054183A (en) Method for preparing material with component gradient characteristic and application of material in battery
CN114937779B (en) High-nickel monocrystal ternary positive electrode material for lithium ion battery and preparation method thereof
CN108832111B (en) LiNi0.8Co0.15Al0.05O2Positive electrode material and preparation method thereof
CN115140783B (en) Ternary positive electrode material precursor, and preparation method and application thereof
CN113437266A (en) Cathode compositions for lithium ion batteries

Legal Events

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

Application publication date: 20210824