CN110534717B - Positive electrode material and preparation method thereof - Google Patents
Positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN110534717B CN110534717B CN201910831610.9A CN201910831610A CN110534717B CN 110534717 B CN110534717 B CN 110534717B CN 201910831610 A CN201910831610 A CN 201910831610A CN 110534717 B CN110534717 B CN 110534717B
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive electrode
- electrode material
- nickel
- manganese oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a cathode material, wherein the chemical formula of the cathode material is Li1.01～1.12NixCoyMn(1‑x‑y)M0.001～ 0.008B0.001～0.015O2Wherein, 0.45<x<0.75，0.15<y<0.35，0<x+y<1, M is one or more of Al, Ti, Sn and Nb, the anode material comprises a lithium nickel cobalt manganese oxide matrix and LiMO coated on the lithium nickel cobalt manganese oxide matrix2‑B2O3A glassy composite coating layer. The invention also provides a preparation method of the cathode material. The preparation method has low equipment requirement, simple preparation process, pure dry process and easy industrial popularization and application.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to an anode material with a glassy conductor coating layer and a preparation method thereof.
Background
The lithium ion battery is used as a novel green energy source and is widely applied to a driving power supply of a portable electric appliance, a power supply of an electric automobile and an energy storage power supply of solar renewable energy. Currently, the limiting factor of lithium ion batteries is the capacity fade that accompanies their cycling and, thus, poor cycle life. The reason for the capacity fading is that, on one hand, the intrinsic structure of the nickel-cobalt-manganese oxide active material is gradually irreversibly changed along with the circulation, and on the other hand, when the nickel-cobalt-manganese oxide active material is delithiated, the oxidation property is enhanced, and the nickel-cobalt-manganese oxide active material is easily subjected to side reaction with the organic electrolyte, so that the nickel-cobalt-manganese oxide active material is lost, and the capacity fading is caused. Therefore, the key to improve the cycle life of the lithium ion battery is to study how to inhibit the malignant interaction between the lithium nickel cobalt manganese oxide and the electrolyte and improve the stability of the nickel cobalt manganese oxide active material in the battery cycle.
In order to solve the above problems, it is necessary to modify the lithium nickel cobalt manganese oxide by doping or surface modification, wherein the surface coating is a relatively mild and effective modification means. Li2O-2B2O is a surface coating modified material with great research potential, and has great forbidden bandwidth and strong B-O, so that the material has excellent chemical stability under acidic conditions. Second Li2O-2B2O is a glassy material having a three-dimensional network structure that allows the passage of ions. This feature makes it a very important material for the solid electrolyte or as an additive to increase ionic conductivity. It is also an extremely potential surface modification material to solve the problem of high voltage lithium nickel cobalt manganese oxide due to its large energy band width, high chemical stability and three-dimensional ion transport channel.
Chinese patent application CN108878861A proposes a method for repairing the surface of lithium nickel cobalt manganese oxide and the lithium nickel cobalt manganese oxide thereof, which is to coat a mesoporous boron aluminum phosphate layer with a high-speed lithium ion channel on the surface of a lithium nickel cobalt manganese oxide substrate by a simple aqueous phase coating-high temperature tempering process, thereby obtaining the surface-repaired lithium nickel cobalt manganese oxide. The lithium nickel cobalt manganese oxide obtained by the method has good high-voltage cycling stability and higher energy utilization rate. In the related patent application, the coating means is wet coating, and although the uniformity of the coating layer can be ensured, the cost is increased in the actual industrial production, and the process is more complicated and is not beneficial to the industrial application.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a preparation method which can obtain a positive electrode material with high rate capability and cycle performance and is easy for industrial application, and a positive electrode material with high rate capability and cycle performance.
The invention provides a cathode material, wherein the chemical formula of the cathode material is Li1.01～1.12NixCoyMn(1-x-y)M0.001～0.008B0.001～0.015O2Wherein, 0.45<x<0.75，0.15<y<0.35，0<x+y<1, M is one or more of Al, Ti, Sn and Nb, the anode material comprises a lithium nickel cobalt manganese oxide matrix and LiMO coated on the lithium nickel cobalt manganese oxide matrix2-B2O3A glassy composite coating layer.
The invention also provides a preparation method of the cathode material, which comprises the following steps: uniformly mixing a lithium salt and a nickel-cobalt-manganese hydroxide precursor, and sintering at a high temperature to obtain a lithium-nickel-cobalt-manganese oxide matrix; putting the lithium nickel cobalt manganese oxide matrix and a metal compound containing M into a ball milling tank, carrying out ball milling and mixing for 1-3 h, and carrying out first heat treatment to obtain a lithium nickel cobalt manganese oxide coated matrix coated with a metal oxide film, wherein M is one or more of Al, Ti, Sn and Nb; uniformly mixing the lithium nickel cobalt manganese oxide coated matrix coated with the metal oxide film and a boron-containing compound in a high-speed mixer for 5-15 min, and performing secondary heat treatment to obtain the product with LiMO2-B2O3The positive electrode material of the glassy composite coating film.
The preparation method of the cathode material provided by the invention has the advantages of cheap and easily-obtained materials, low equipment requirement, simple preparation process, pure dry process and easy industrial popularization and application. The LiMO prepared by the preparation method2-B2O3The ratio of discharge specific capacity of 3C/0.1C of the positive electrode material of the glassy composite coating reaches 94%, the ratio of the capacity retention of 50-cycle circulation still reaches 96%, and the cycle performance is excellent.
Drawings
Fig. 1 is an SEM image of the positive electrode material of example 1 of the present invention.
Fig. 2 is an SEM image of the positive electrode material of example 2 of the present invention.
Fig. 3 is an SEM image of the positive electrode material of comparative example 1 of the present invention.
FIG. 4 is a cycling diagram of button cell batteries made of the positive electrode materials of example 1 and comparative examples 1 and 2 of the present invention at 3.0-4.3V.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the embodiments in the drawings, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The embodiments described below and the features of the embodiments can be combined with each other without conflict.
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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a preparation method of a positive electrode material, which comprises the following steps:
s1: and uniformly mixing the lithium salt and the nickel-cobalt-manganese hydroxide precursor, and sintering at a high temperature to obtain the lithium-nickel-cobalt-manganese oxide matrix.
The molar ratio of the lithium salt to the nickel-cobalt-manganese hydroxide precursor is 1.01-1.12: 1. The lithium salt is selected from one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate. The chemical formula of the nickel-cobalt-manganese hydroxide precursor is NixCoyMn(1-x-y)(OH)2Wherein, 0.45<x<0.75，0.15<y<0.35，0<x+y<1. The average particle size D50 of the nickel-cobalt-manganese hydroxide precursor is 2-5 um, and the BET ratio of the nickel-cobalt-manganese hydroxide precursorThe surface area is 5 to 20m2/g。
Preferably, the lithium salt and the nickel-cobalt-manganese hydroxide precursor are added into a high-speed mixer to be uniformly mixed, so as to obtain powder. The rotating speed of the high-speed mixer is 900-1200 rpm/min, and the mixing time is 10-30 min.
The specific process of high-temperature sintering is as follows: and putting the powder into a sintering furnace, heating to 650-750 ℃ at a speed of 1-8 ℃/min in the air or oxygen atmosphere of the sintering furnace, then heating to 850-950 ℃ at a speed of 1-3 ℃/min, then preserving heat for 5-15 h, and finally cooling to room temperature at a speed of 60-120 ℃/h.
It is understood that step S1 further includes the following steps: and cooling, dissociating and crushing the powder after high-temperature sintering to obtain the lithium nickel cobalt manganese oxide matrix.
S2: and putting the lithium nickel cobalt manganese oxide matrix and a metal compound containing M into a ball milling tank for ball milling, and performing first heat treatment to obtain the lithium nickel cobalt manganese oxide coated matrix coated with the metal oxide film, wherein M is at least one or more of Al, Ti, Sn and Nb.
The M-containing metal compound is one or more of aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum oxyhydroxide, titanium dioxide, titanium hydroxide, tin oxide and niobium pentoxide. The molar ratio of the metal compound to the lithium nickel cobalt manganese oxide matrix is 0.001-0.008: 1. the ball milling time is 1-3 h. The ball-to-feed ratio was 1.3: 1. The first heat treatment temperature is 600-900 ℃, and the first heat treatment time is 8-16 h.
One or more M metal compounds are coated on the surface of the nickel-cobalt-manganese oxide matrix through dry blending, and a metal oxide coating film is generated on the surface of the nickel-cobalt-manganese oxide matrix after heat treatment to obtain the lithium-nickel-cobalt-manganese oxide coated matrix, so that the side reaction caused by HF in electrolyte is reduced, and the cycling stability of the cathode material at normal temperature is improved.
It is understood that step S2 further includes the following steps: and cooling and sieving the substrate after the first heat treatment to obtain the lithium nickel cobalt manganese oxide coated substrate coated with the metal oxide film.
S3: and uniformly mixing the lithium nickel cobalt manganese oxide coated matrix coated with the metal oxide film and a boron-containing compound in a high-speed mixer, and carrying out secondary heat treatment to obtain the cathode material.
The boron-containing compound is boric acid, metaboric acid, pyroboric acid (H)2B4O7) And boron oxide. The molar ratio of the boron-containing compound to the lithium nickel cobalt manganese oxide coated matrix is 0.001-0.015: 1. The mixing time is 5-15 min. The temperature of the second heat treatment is 300-600 ℃, and the time of the second heat treatment is 4-12 h.
Performing secondary dry blending coating on the lithium nickel cobalt manganese oxide coated matrix and a boron-containing compound, and performing heat treatment to form Li2O-2B2O3The coating, this coating has higher ion conductivity, and the melting point is low, and viscosity is lower when the melting, and the positive electrode material surface of formation is comparatively smooth, can contact well with the conducting agent, does benefit to lithium ion's transmission, effectively improves positive electrode material's multiplying power performance, cyclicity performance, storage performance and security performance.
The preparation method of the anode material provided by the invention forms LiMO together by two times of dry coating on the surface of the material2-B2O3The glassy composite coating layer can reduce the direct contact area of the anode material and the electrolyte, reduce the corrosion of HF in the electrolyte to the anode material, improve the electronic conductivity of the anode material and improve the rate capability; and the internal resistance can be reduced, the polarization loss is reduced, and the cycle performance of the anode material is further improved. In addition, the materials selected in the whole flow are cheap and easy to obtain, the equipment requirement is low, the preparation process is simple, and the method is a pure dry process and is easy to industrially popularize and apply.
The invention provides a positive electrode material prepared by the preparation method. The positive electrode material comprises a lithium nickel cobalt manganese oxide matrix and LiMO coated on the lithium nickel cobalt manganese oxide matrix2-B2O3A glassy composite coating layer. The chemical formula of the cathode material is Li1.01～1.12NixCoyMn(1-x-y)M0.001～0.008B0.001～0.015O2Wherein, 0.45<x<0.75，0.15<y<0.35，0<x+y<1, M is one or more of Al, Ti, Sn and Nb. The LiMO2-B2O3The thickness of the glassy state composite coating layer is 30-80 nm.
At the contact part of the anode material and the electrolyte, the LiMO2-B2O3The glassy composite coating layer can act as a protective layer, and the oxidative decomposition of the electrolyte under high voltage and the dissolution of active substances are relieved. LiMO as a coating layer during the first few cycles due to electrochemical stress2-B2O3Has a three-dimensional open network framework structure which can accommodate some moving Li+And further forms a more chemically resistant and ion conductive LiMO during cycling2-B2O3The interface, which is the main component of the solid electrolyte membrane (SEI), correspondingly promotes Li at the solid-liquid interface during the subsequent charge-discharge cycles+Diffusion and transport. Due to LiMO2-B2O3Under the action of the coating layer, the multiplying power performance and the cycle performance of the lithium nickel cobalt manganese oxide after composite coating can be obviously improved and transmitted.
The present invention will be specifically described below by way of examples and comparative examples.
Example 1
Lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.60Co0.20Mn0.20(OH)2) According to a molar ratio of 1.08: 1, adding the precursor into a high-speed mixer, wherein the average particle size D50 of the precursor is 2-5 um, and the BET specific surface area of the precursor is 5-20 m2(ii) in terms of/g. Heating the powder obtained after mixing for 20min at the rotating speed of 900rpm/min to 730 ℃ at the speed of 4 ℃/min in the air atmosphere of a sintering furnace, then heating to 950 ℃ at the speed of 3 ℃/min, preserving heat for 12h, finally cooling to room temperature at the speed of 100 ℃/h, dissociating and crushing to obtain the Li-Ni-Co-Mn oxide matrix1.08Ni0.6Co0.2Mn0.2O2. Mixing a lithium nickel cobalt manganese oxide matrix and aluminum oxyhydroxide (AlOOH) according to a molar ratio of 1: 0.001 is put into a ball milling tank, and the weight ratio of the ball to the material is 1.3:1 adding polyurethane balls, performing ball milling and mixing for 2h, then preserving heat for 12h at 700 ℃, cooling and sieving to obtain Li-Ni-Co-Mn oxide coated matrix Li1.08Ni0.6Co0.2Mn0.2Al0.001O2. Coating a matrix with lithium nickel cobalt manganese oxide and white metaboric acid (HBO)2) According to a molar ratio of 1: 0.002 and 10min, and the obtained powder mixture is black gray consistent with the color of lithium nickel cobalt manganese oxide. Then keeping the temperature at 450 ℃ for 8h, cooling and sieving to obtain the lithium nickel cobalt manganese oxide Li coated with the glassy state conductor1.08Ni0.6Co0.2Mn0.2Al0.001B0.002O2。
Example 2
Lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.60Co0.20Mn0.20(OH)2) According to a molar ratio of 1.08: 1 into a high-speed mixer with the rotation speed of 1200rpm/min, heating the powder obtained after mixing for 20min to 730 ℃ at the speed of 3.5 ℃/min under the air atmosphere of a sintering furnace, then heating to 945 ℃ at the speed of 3 ℃/min, then preserving the temperature for 12h, finally cooling to room temperature at the speed of 100 ℃/h, dissociating and crushing to obtain the Li-Ni-Co-Mn oxide matrix Li1.08Ni0.6Co0.2Mn0.2O2. Mixing a lithium nickel cobalt manganese oxide matrix and aluminum hydroxide according to a molar ratio of 1: 0.0015 is put into a ball milling tank, and the weight ratio of the materials is 1.3:1 adding polyurethane balls, performing ball milling and mixing for 2h, then preserving heat for 10h at 650 ℃, cooling and sieving to obtain black gray lithium nickel cobalt manganese oxide coated matrix Li1.08Ni0.6Co0.2Mn0.2Al0.0015O2. Coating the substrate with black gray lithium nickel cobalt manganese oxide and pyroboric acid (H)2B4O7) According to a molar ratio of 1: 0.4 is evenly mixed in a high-speed mixer for 10min, then is kept at 460 ℃ for 8h, is cooled and is sieved to obtain the lithium nickel cobalt manganese oxide Li coated with the glassy conductor1.08Ni0.6Co0.2Mn0.2Al0.0015B0.003O2。
Example 3
Lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.60Co0.20Mn0.20(OH)2) According to a molar ratio of 1.08: 1, adding the mixture into a high-speed mixer with the rotating speed of 1000rpm/min, heating the powder obtained after mixing for 20min to 730 ℃ at the speed of 3 ℃/min under the air atmosphere of a sintering furnace, then heating to 935 ℃ at the speed of 3 ℃/min, then preserving the temperature for 12h, finally cooling to room temperature at the speed of 100 ℃/h, dissociating and crushing to obtain the Li-Ni-Co-Mn oxide matrix1.08Ni0.6Co0.2Mn0.2O2. Mixing a lithium nickel cobalt manganese oxide matrix and titanium dioxide according to a molar ratio of 1: 0.0023, putting into a ball milling tank, and mixing according to a ball material ratio of 1.3:1 adding polyurethane balls, performing ball milling and mixing for 2h, then preserving heat for 12h at 600 ℃, cooling and sieving to obtain Li-Ni-Co-Mn oxide coated matrix Li1.08Ni0.6Co0.2Mn0.2Ti0.0023O2. Coating a lithium nickel cobalt manganese oxide coating matrix with boron oxide according to a molar ratio of 1: 0.0035 are evenly mixed in a high-speed mixer for 10min, then the mixture is kept at 440 ℃ for 8h, and the lithium nickel cobalt manganese oxide Li coated by the glassy state conductor can be obtained after cooling and sieving1.08Ni0.6Co0.2Mn0.2Ti0.0023B0.0035O2。
Example 4
Lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.60Co0.20Mn0.20(OH)2) According to a molar ratio of 1.08: 1 into a high-speed mixer with the rotation speed of 950rpm/min, heating the powder obtained after mixing for 20min to 730 ℃ at the speed of 3 ℃/min under the air atmosphere of a sintering furnace, then heating to 930 ℃ at the speed of 3 ℃/min, then preserving the temperature for 12h, finally cooling to room temperature at the speed of 100 ℃/h, dissociating and crushing to obtain the Li-Ni-Co-Mn oxide matrix1.08Ni0.6Co0.2Mn0.2O2. Mixing the lithium nickel cobalt manganese oxide matrix with tin oxide according to the mole ratioThe molar ratio is 1: 0.004, putting into a ball milling tank, and mixing according to a ball material ratio of 1.3:1 adding polyurethane balls, performing ball milling and mixing for 2h, then preserving heat for 12h at 700 ℃, cooling and sieving to obtain Li-Ni-Co-Mn oxide coated matrix Li1.08Ni0.6Co0.2Mn0.2Sn0.004O2. Coating a lithium nickel cobalt manganese oxide coating matrix with metaboric acid according to a molar ratio of 1: 0.004, uniformly mixing in a high-speed mixer for 10min, then preserving the heat for 8h at 420 ℃, cooling and sieving to obtain the lithium nickel cobalt manganese oxide Li coated with the glassy conductor1.08Ni0.6Co0.2Mn0.2Sn0.004B0.004O2。
Example 5
Lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.60Co0.20Mn0.20(OH)2) According to a molar ratio of 1.08: 1 is added into a high-speed mixer with the rotating speed of 1100rpm/min, the powder obtained after 20min of mixing is heated to 730 ℃ at the speed of 3 ℃/min in the air atmosphere of a sintering furnace, then heated to 925 ℃ at the speed of 3 ℃/min and then is kept for 10h, finally the lithium nickel cobalt manganese oxide matrix Li is obtained after the temperature is cooled to room temperature at the speed of 100 ℃/h and is dissociated and crushed1.08Ni0.6Co0.2Mn0.2O2. Mixing a lithium nickel cobalt manganese oxide matrix and aluminum acetate according to a molar ratio of 1: 0.0043 is put into a ball milling tank, and the weight ratio of the ball to the material is 1.3:1 adding polyurethane balls, performing ball milling and mixing for 2h, then preserving heat for 12h at 580 ℃, cooling and sieving to obtain Li-Ni-Co-Mn oxide coated matrix Li1.08Ni0.6Co0.2Mn0.2Al0.0043O2. Coating a lithium nickel cobalt manganese oxide coating matrix with boron oxide according to a molar ratio of 1: 0.005 evenly mixing in a high-speed mixer for 10min, then preserving the heat for 8h at 400 ℃, cooling and sieving to obtain the lithium nickel cobalt manganese oxide Li coated with the glassy conductor1.08Ni0.6Co0.2Mn0.2Al0.0043B0.005O2。
Comparative example 1
Lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.60Co0.20Mn0.20(OH)2) According to a molar ratio of 1.08: 1 into a high-speed mixer with the rotation speed of 1200rpm/min, heating the powder obtained after mixing for 20min to 730 ℃ at the speed of 3 ℃/min under the air atmosphere of a sintering furnace, then heating to 940 ℃ at the speed of 3 ℃/min, preserving the temperature for 12h, finally cooling to room temperature at the speed of 100 ℃/h, dissociating and crushing to obtain the lithium nickel cobalt manganese oxide Li without surface modification1.08Ni0.60Co0.20Mn0.20O2。
Comparative example 2
Lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.60Co0.20Mn0.20(OH)2) According to a molar ratio of 1.08: 1 into a high-speed mixer with the rotation speed of 1200rpm/min, heating the powder obtained after mixing for 20min to 730 ℃ at the speed of 3 ℃/min under the air atmosphere of a sintering furnace, then heating to 940 ℃ at the speed of 3 ℃/min, preserving the temperature for 12h, finally cooling to room temperature at the speed of 100 ℃/h, dissociating and crushing to obtain the Li-Ni-Co-Mn oxide matrix1.08Ni0.6Co0.2Mn0.2O2. Mixing a lithium nickel cobalt manganese oxide matrix and aluminum oxyhydroxide according to a molar ratio of 1: 0.002 is put into a ball milling tank, and the weight ratio of the ball to the material is 1.3:1 adding polyurethane balls, performing ball milling and mixing for 2h, then preserving heat for 12h at 700 ℃, cooling and sieving to obtain the lithium nickel cobalt manganese oxide Li which is only subjected to primary surface coating1.08Ni0.6Co0.2Mn0.2Al0.002O2。
Fig. 1 to 3 are Scanning Electron Micrographs (SEM) of the positive electrode materials obtained in examples 1 and 2 and comparative example 1. The primary crystal grain sizes in the graphs were measured by imageJ software, and 30 points were measured for each graph, and it was found that the average primary crystal grain of the positive electrode material of example 1 was 2.77um, the average primary crystal grain of the positive electrode material of example 2 was 2.83um, and the average primary crystal grain of the positive electrode material of comparative example 1 was 2.80 um. The crystal grain size of the anode material is controllable, and the surface appearance of the anode material with coating and without coating is different. The coated positive electrode materials of the embodiments 1 and 2 have some extra substances on the surfaces, so that the surfaces of the positive electrode materials have some blurs, which is caused by the existence of the coating layer on the surface of the positive electrode material, and the coating substances are distributed on the surface of the positive electrode material and in gaps among crystal groups; while the surface of the cathode material of comparative example 1 without coating exhibited a clearer and smoother surface profile.
After the positive electrode materials obtained in examples 1-5 and comparative examples 1-2 were made into batteries, the electrochemical properties related to the batteries were tested by a button cell tester. Table 1 shows the test results of the electrochemical performance of the battery made of the positive electrode materials obtained in examples 1 to 5 and comparative examples 1 to 2, namely the first discharge specific capacity at 0.1C, the discharge capacity retention rate at 3C/0.1C rate, and the 3C cycle capacity retention rate at 50 weeks. FIG. 4 is a cycle chart of a button cell at 3.0-4.3V for a cell made of the positive electrode material obtained in example 1 and comparative examples 1 and 2.
TABLE 1 first charge-discharge capacity, rate and cycle performance
From the test results, it can be seen that examples 1 to 5 of the present invention pass through LiMO2-B2O3Compared with a proportional material, the coated lithium nickel cobalt manganese oxide has better processing performance, cycling stability and rate capability, the powder flowability is improved, the first discharge specific capacity is obviously improved, the 3C/0.1C rate discharge specific capacity retention rate reaches 94%, the 50-cycle capacity retention rate still reaches 96%, and the cycling performance is superior. The comparative example 1 is not coated with any substance, the powder flowability is poor, the first discharge capacity is low, and the multiplying power and the cycle performance are poor and are only 90 percent and 88 percent respectively; in the comparative example 2, aluminum oxyhydroxide (AlOOH) is added for coating, the powder fluidity is slightly improved, the cycle performance is improved and is close to 92%, but the first discharge specific capacity and the rate capability are not obviously improved.
In addition, other modifications within the spirit of the invention will occur to those skilled in the art, and it is understood that such modifications are included within the scope of the invention as claimed.
Claims (8)
1. A preparation method of a positive electrode material comprises the following steps:
uniformly mixing a lithium salt and a nickel-cobalt-manganese hydroxide precursor, and sintering at a high temperature to obtain a lithium-nickel-cobalt-manganese oxide matrix, wherein the chemical formula of the nickel-cobalt-manganese hydroxide precursor is NixCoyMn(1-x-y)(OH)2Wherein, 0.45<x<0.75，0.15<y<0.35，0<x+y<1, the average particle size D50 of the nickel-cobalt-manganese hydroxide precursor is 2-5 um, and the BET specific surface area of the nickel-cobalt-manganese hydroxide precursor is 5-20 m2The high-temperature sintering is that the temperature is raised to 650-750 ℃ at the speed of 1-8 ℃/min under the air or oxygen atmosphere of a sintering furnace, then the temperature is raised to 850-950 ℃ at the speed of 1-3 ℃/min, the temperature is kept for 5-15 h, and finally the temperature is lowered to the room temperature at the speed of 60-120 ℃/h;
putting the lithium nickel cobalt manganese oxide matrix and a metal compound containing M into a ball milling tank, carrying out ball milling and mixing for 1-3 h, carrying out first heat treatment to obtain a lithium nickel cobalt manganese oxide coated matrix coated with a metal oxide film, wherein M is one or more of Al, Ti, Sn and Nb, the first heat treatment temperature is 600-900 ℃, and the first heat treatment time is 8-16 h;
uniformly mixing the lithium nickel cobalt manganese oxide coated matrix coated with the metal oxide film and a boron-containing compound in a high-speed mixer for 5-15 min, and performing secondary heat treatment to obtain the product with LiMO2-B2O3The positive electrode material of the glassy composite coating film has the second heat treatment temperature of 300-600 ℃ and the second heat treatment time of 4-12 hours.
2. The method for preparing a positive electrode material according to claim 1, wherein the lithium salt is one or more selected from the group consisting of lithium carbonate, lithium hydroxide, lithium acetate, and lithium nitrate.
3. The method for preparing the positive electrode material according to claim 1, wherein the M-containing metal compound is one or more of aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum oxyhydroxide, titanium dioxide, titanium hydroxide, tin oxide, and niobium pentoxide.
4. The method for producing a positive electrode material according to claim 1, wherein the boron-containing compound is one of boric acid, metaboric acid, pyroboric acid, and boron oxide.
5. The method for preparing a positive electrode material according to claim 1, wherein the molar ratio of the lithium salt to the nickel-cobalt-manganese hydroxide precursor is 1.01 to 1.12:1, and the molar ratio of the metal compound to the lithium-nickel-cobalt-manganese oxide matrix is 0.001 to 0.008: 1.
6. the method of preparing a positive electrode material of claim 1, wherein uniformly mixing a lithium salt with a nickel cobalt manganese hydroxide precursor comprises: and adding the lithium salt and the nickel-cobalt-manganese hydroxide precursor into a high-speed mixer for uniform mixing, wherein the rotating speed of the high-speed mixer is 900-1200 rpm/min, and the mixing time is 10-30 min.
7. A positive electrode material, characterized by being produced by the method for producing a positive electrode material according to any one of claims 1 to 6, the positive electrode material having a chemical formula of Li1.01～1.12NixCoyMn(1-x-y)M0.001～0.008B0.001～0.015O2Wherein, 0.45<x<0.75，0.15<y<0.35，0<x+y<1, M is one or more of Al, Ti, Sn and Nb, the anode material comprises a lithium nickel cobalt manganese oxide matrix and LiMO coated on the lithium nickel cobalt manganese oxide matrix2-B2O3A glassy composite coating layer.
8. The positive electrode material according to claim 7, wherein the Li is1.01～1.12NixCoyMn(1-x-y)M0.001～ 0.008B0.001～0.015O2Comprising Li1.08Ni0.6Co0.2Mn0.2Al0.001B0.002O2、Li1.08Ni0.6Co0.2Mn0.2Al0.0015B0.003O2、Li1.08Ni0.6Co0.2Mn0.2Ti0.0023B0.0035O2、Li1.08Ni0.6Co0.2Mn0.2Sn0.004B0.004O2、Li1.08Ni0.6Co0.2Mn0.2Al0.0043B0.005O2Any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910831610.9A CN110534717B (en) | 2019-09-04 | 2019-09-04 | Positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910831610.9A CN110534717B (en) | 2019-09-04 | 2019-09-04 | Positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110534717A CN110534717A (en) | 2019-12-03 |
| CN110534717B true CN110534717B (en) | 2021-10-01 |
Family
ID=68666718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910831610.9A Active CN110534717B (en) | 2019-09-04 | 2019-09-04 | Positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110534717B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102207997B1 (en) * | 2020-06-18 | 2021-01-25 | 에스케이이노베이션 주식회사 | Cathode active material for lithium secondary battery, lithium secondary battery and method of manufacturing the same |
| CN111646523A (en) * | 2020-06-29 | 2020-09-11 | 蜂巢能源科技有限公司 | High-safety double-doped high-nickel ternary cathode material, preparation method thereof and lithium ion battery |
| CN112614988B (en) * | 2020-12-15 | 2021-10-19 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| CN113697823A (en) * | 2021-08-11 | 2021-11-26 | 格林美股份有限公司 | Quaternary positive electrode material and preparation method and application thereof |
| CN117894971B (en) * | 2024-03-18 | 2024-06-04 | 中南大学 | Glassy metal organic framework material modified ternary positive electrode material, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107910534A (en) * | 2017-11-22 | 2018-04-13 | 淮安新能源材料技术研究院 | A kind of nickelic tertiary cathode material preparation method of NCM811 types |
| CN108390039A (en) * | 2018-02-23 | 2018-08-10 | 成都新柯力化工科技有限公司 | A kind of nickelic anode material of lithium battery that double oxide coats altogether and preparation method |
| CN108807926A (en) * | 2018-06-22 | 2018-11-13 | 格林美（无锡）能源材料有限公司 | A kind of Co/B coats nickel cobalt manganese lithium ion anode material and preparation method thereof altogether |
| CN109461928A (en) * | 2018-09-19 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of high-energy density polynary positive pole material and preparation method thereof |
| CN109686932A (en) * | 2018-12-12 | 2019-04-26 | 无锡晶石新型能源股份有限公司 | A kind of preparation method by the nickelic tertiary cathode material of polynary coating modification |
| CN109830651A (en) * | 2017-11-23 | 2019-05-31 | 天津国安盟固利新材料科技股份有限公司 | A kind of tertiary cathode high-nickel material and preparation method thereof that double-coating is modified |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867949B (en) * | 2011-07-04 | 2015-09-30 | 微宏动力***（湖州）有限公司 | Lithium ion secondary battery anode material and preparation method thereof |
| KR101564131B1 (en) * | 2012-08-21 | 2015-11-04 | 주식회사 엘지화학 | Cathode active material for lithium secondary battery and manufacturing method thereof |
| JP6377997B2 (en) * | 2014-08-08 | 2018-08-22 | トヨタ自動車株式会社 | Positive electrode composite material and sulfide all solid state battery using the same |
| CN107394170A (en) * | 2017-07-27 | 2017-11-24 | 苏州思创源博电子科技有限公司 | A kind of preparation method of the sulphur lithium anode material of metal oxide cladding |
| CN107425188A (en) * | 2017-07-30 | 2017-12-01 | 苏州思创源博电子科技有限公司 | A kind of preparation method of oxide cladding lithium cobaltate cathode material |
| CN110148712B (en) * | 2018-02-11 | 2021-05-25 | 湖南杉杉能源科技股份有限公司 | Composite coating modified lithium-manganese-rich cathode material and preparation method thereof |
| CN109888225A (en) * | 2019-02-27 | 2019-06-14 | 桑顿新能源科技有限公司 | Positive electrode and preparation method thereof and lithium ion battery |
| CN110120505B (en) * | 2019-05-07 | 2020-12-11 | 厦门厦钨新能源材料股份有限公司 | Lithium ion battery positive electrode material, preparation method and lithium ion battery |
-
2019
- 2019-09-04 CN CN201910831610.9A patent/CN110534717B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107910534A (en) * | 2017-11-22 | 2018-04-13 | 淮安新能源材料技术研究院 | A kind of nickelic tertiary cathode material preparation method of NCM811 types |
| CN109830651A (en) * | 2017-11-23 | 2019-05-31 | 天津国安盟固利新材料科技股份有限公司 | A kind of tertiary cathode high-nickel material and preparation method thereof that double-coating is modified |
| CN108390039A (en) * | 2018-02-23 | 2018-08-10 | 成都新柯力化工科技有限公司 | A kind of nickelic anode material of lithium battery that double oxide coats altogether and preparation method |
| CN108807926A (en) * | 2018-06-22 | 2018-11-13 | 格林美（无锡）能源材料有限公司 | A kind of Co/B coats nickel cobalt manganese lithium ion anode material and preparation method thereof altogether |
| CN109461928A (en) * | 2018-09-19 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of high-energy density polynary positive pole material and preparation method thereof |
| CN109686932A (en) * | 2018-12-12 | 2019-04-26 | 无锡晶石新型能源股份有限公司 | A kind of preparation method by the nickelic tertiary cathode material of polynary coating modification |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110534717A (en) | 2019-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110534717B (en) | Positive electrode material and preparation method thereof | |
| KR102283734B1 (en) | Composite, its manufacturing method and use in lithium ion secondary battery | |
| CN111200120B (en) | Ternary cathode material, preparation method thereof and lithium ion battery | |
| CN109659542B (en) | High-voltage lithium cobalt oxide cathode material with core-shell structure and preparation method thereof | |
| CN107403913B (en) | Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof | |
| CN109065858B (en) | Surface modified ternary positive electrode material, preparation method thereof and battery prepared from surface modified ternary positive electrode material | |
| CN111646523A (en) | High-safety double-doped high-nickel ternary cathode material, preparation method thereof and lithium ion battery | |
| CN111762768B (en) | Spinel type lithium manganate-phosphate composite cathode material and preparation method thereof | |
| KR20220150938A (en) | Composite cathode material for lithium ion battery, manufacturing method and use thereof | |
| CN112864385A (en) | Ternary cathode material, preparation method thereof and lithium ion battery | |
| CN103682266A (en) | Li and Mn codoped manganese phosphate/carbon composite material and preparation method thereof | |
| CN112897586A (en) | Spinel lithium-rich lithium manganate and preparation method and application thereof | |
| WO2023221625A1 (en) | Large-particle-size single-crystal ternary positive electrode material, and preparation method therefor and use thereof | |
| CN104733714B (en) | Modification method of lithium ion battery cathode material | |
| CN116314704B (en) | Coated modified sodium ion layered cathode material and preparation method thereof | |
| CN112038609A (en) | Lithium iron phosphate surface-modified spinel type lithium nickel manganese oxide positive electrode material and preparation method thereof | |
| CN115498171A (en) | High-nickel ternary cathode material and preparation method and application thereof | |
| CN113023790B (en) | Positive electrode material and preparation method and application thereof | |
| CN110148712A (en) | A kind of rich lithium manganese anode material and preparation method thereof that compound coating is modified | |
| CN111129462A (en) | Quick-charging lithium battery positive electrode material and preparation method thereof | |
| CN114400316A (en) | High-nickel lithium ion battery positive electrode material with thermal safety and preparation method thereof | |
| CN114094080A (en) | Single crystal type lithium-rich layered-spinel composite cathode material and preparation method thereof | |
| CN117525403A (en) | High-voltage high-capacity medium-high nickel monocrystal ternary positive electrode material, preparation method thereof and battery | |
| CN113247966A (en) | Lithium-rich manganese-based precursor, positive electrode material and preparation method thereof | |
| CN113013389A (en) | Ternary positive electrode material coated with manganese oxide compound 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 | ||
| CB02 | Change of applicant information |
Address after: 361026, Fujian, Xiamen, China (Fujian) free trade experimentation area, Xiamen area, Ke Tong society, No. 300 Applicant after: Xiamen xiaw new energy materials Co., Ltd Address before: 361026, Fujian, Xiamen, China (Fujian) free trade experimentation area, Xiamen area, Ke Tong society, No. 300 Applicant before: XTC NEW ENERGY MATERIALS(XIAMEN) Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |