CN112968150A - Positive electrode material and preparation method thereof - Google Patents

Positive electrode material and preparation method thereof Download PDF

Info

Publication number
CN112968150A
CN112968150A CN201911275235.0A CN201911275235A CN112968150A CN 112968150 A CN112968150 A CN 112968150A CN 201911275235 A CN201911275235 A CN 201911275235A CN 112968150 A CN112968150 A CN 112968150A
Authority
CN
China
Prior art keywords
positive electrode
particles
active material
wrapping
raw material
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.)
Granted
Application number
CN201911275235.0A
Other languages
Chinese (zh)
Other versions
CN112968150B (en
Inventor
阮泽文
陈娜
郝嵘
潘仪
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.)
BYD Co Ltd
Original Assignee
BYD 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 BYD Co Ltd filed Critical BYD Co Ltd
Priority to CN201911275235.0A priority Critical patent/CN112968150B/en
Publication of CN112968150A publication Critical patent/CN112968150A/en
Application granted granted Critical
Publication of CN112968150B publication Critical patent/CN112968150B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present disclosure relates to an array structure layer coated positive electrode material, which includes positive electrode active material particles and coating particles combined on the surfaces of the positive electrode active material particles; the particle size of the positive electrode active material particles is 1.0-10.0 μm; the coated particles are arranged in an array at intervals; the particle size of the coated particles is within the range of 20-300 nm. The positive electrode material can improve the combination effect of the positive electrode surface material, the binder and the conductive agent, and reduce the reject ratio caused by pole piece powder falling.

Description

Positive electrode material and preparation method thereof
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to an array structure layer coated positive electrode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high working voltage, large capacity, small volume, light weight, long cycle life and the like, and has wide application in the fields of portable electronic products, electric bicycles, electric automobiles, energy storage and the like. The positive electrode material has attracted attention in recent years and is rapidly developed as a key factor influencing the performance and application of the lithium ion battery, but the positive electrode material still has the defects of poor structural stability, poor rate performance, poor high-temperature performance and the like. The coating is used as a common method for material surface modification, has positive effects on stabilizing the structure of the anode material, improving the electrochemical stability and the like, and is often used as one of effective means for modifying the anode material.
At present, the coating modification of the anode material is mainly to uniformly mix the coating raw material and the anode material by a solid-phase or liquid-phase method and then sinter the mixture at high temperature to obtain uniform coating layers on the surfaces of anode particles, the binding capacity of the coating layers, a binder and a conductive agent is poor, a large amount of binder is needed to effectively bond the anode active substance and a current collector, otherwise, the active substance is easy to fall off from a pole piece and cannot be normally used.
Therefore, a method for coating and modifying the positive electrode material and a positive electrode material coating and modifying structure are urgently needed to be found for improving the stability of the positive electrode material structure of the lithium ion battery.
Disclosure of Invention
The purpose of the present disclosure is to improve the bonding effect of the positive electrode surface material, the binder and the conductive agent, reduce the fraction defective caused by the powder falling of the electrode sheet, and provide a positive electrode material coated with an array structure layer.
In order to achieve the above object, the present disclosure provides an array structure layer coated positive electrode material, which includes positive electrode active material particles and coating particles bonded to surfaces of the positive electrode active material particles; the particle size of the positive electrode active material particles is 1.0-10.0 μm; the coated particles are arranged in an array at intervals; the particle size of the coated particles is within the range of 20-300 nm.
Optionally, the particle size of the coated particles is 50-240nm, and the median particle size D50 is in the range of 100-200 nm; the coating particles are arranged in a point array, a linear array or a polygonal array; the ratio of the number of the positive electrode active material particles to the number of the coated particles is 1: 100-500.
Optionally, the material of the coated particles is Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of; the material of the positive electrode active material particles is at least one of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium manganese oxide.
Optionally, the surface of the positive electrode active material particle is also provided with a wrapping layer; the thickness of the wrapping layer is 2-20 nm; the wrapping layer is made of Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of (1).
The present disclosure also provides a method for preparing an array structure layer coated positive electrode material, including the steps of:
s1, mixing and dispersing the wrapping raw material B and an organic solvent to obtain a material C; the particle size of the wrapping raw material B is within the range of 100-500 nm;
s2, mixing and dispersing the material C and the positive active material particles, and evaporating to remove the organic solvent to obtain an active material D; the particle size of the positive electrode active material particles is 1.0-10.0 μm;
s3, sintering the active material D and then crushing the active material D; the sintering conditions are such that the raw wrapping material B is and only partially melted.
Optionally, in step S1, the addition amount of the coating raw material B is 0.5 to 3.0 mass% based on the mass of the positive electrode active material particles; preferably, the amount of the wrapping material B added is 0.5 to 1.0 mass%.
Optionally, in step S1The organic solvent is ethanol, methanol or acetone, and the wrapping raw material B is selected from Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of; the material of the positive electrode active material particles is at least one of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium manganese oxide.
Optionally, a wrapping raw material A is also added in the process of mixing and dispersing the wrapping raw material B and the organic solvent; the particle size of the wrapping raw material A is within the range of 10-300nm, and the particle size of the wrapping raw material A is smaller than that of the wrapping raw material B; the sintering condition is that the wrapping raw material A is completely melted; the wrapping raw material A is selected from Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of (1).
The disclosure also provides an array structure layer coated positive electrode material prepared by the method.
The present disclosure also provides a battery including a positive active layer including an active material wrapped by an array-structured layer, and a current collector.
Through the technical scheme, the array structure layer coated positive electrode material is provided, the nano-sized array structure coating is attached to the surface of positive electrode particles, the roughness of the surface of the positive electrode active material is obviously increased, so that the positive electrode active material is combined with a binder and a conductive agent more firmly, the adhesion between the active particles and a current collector is effectively realized, the peel strength of a pole piece is improved to a great extent, and the reject ratio caused by powder falling of the pole piece is reduced.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
Fig. 1 is SEM photographs of comparative example 1 (left) and example 7 (right) in a specific embodiment of the present disclosure.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The positive electrode material comprises positive electrode active material particles and coating particles combined on the surfaces of the positive electrode active material particles; the particle size of the positive electrode active material particles is 1.0-10.0 μm; the coated particles are arranged in an array at intervals; the particle size of the coated particles is within the range of 20-300 nm.
Through the technical scheme, the positive electrode material coated by the array structure layer can stabilize the interface of the positive electrode material and electrolyte, inhibit the occurrence of side reactions, protect the positive electrode material and improve the cycling stability of the material; on the other hand, the nano-sized coating particles are attached to the surface of the anode particles to form nano-array protrusions, so that the surface roughness of the active material is obviously increased, and compared with the active material particles with smooth surfaces, the nano-array protrusions on the surface of the active material can play a role of rivets, so that the active particles with array structures are combined with the binder more firmly.
According to the disclosure, the particle size of the coated particles is 50-240nm, and the median particle size D50 is in the range of 100-200 nm; the ratio of the number of the positive electrode active material particles to the number of the coated particles is 1: 100-500.
According to the present disclosure, the coated particles exhibit a dot-matrix structure on the surface of the positive active material, and when the dot-matrix structure is accumulated to a certain extent, a linear matrix structure or a polygonal matrix structure may be exhibited.
According to the present disclosure, the array structure layer may be directly coated on the surface of the positive active material; or coating the surface of the particle with one or more other coating substances; or coating other one or more substances on the surface of the particles, and then coating the array structure to form a double-layer or multi-layer coating layer.
According to the present disclosure, the material encapsulating the particles is Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of; the micro-morphology of the positive electrode material particles can be sheet, rod and secondary ball, and can also be single crystal and single-like crystal, the positive electrode active material can be lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium manganese oxide with a sheet structure, and can also be spinel type lithium manganese oxide material, and can also be at least one of other lithium-rich materials and derivatives thereof.
According to the present disclosure, the surface of the positive electrode active material particle further has a wrapping layer; the thickness of the wrapping layer is 2-20 nm; the wrapping layer is made of Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of (1).
In another aspect, the present disclosure also provides a method for preparing an array structure layer coated positive electrode material, including the following steps:
s1, mixing and dispersing the wrapping raw material B and an organic solvent to obtain a material C; the particle size of the wrapping raw material B is within the range of 100-500 nm;
s2, mixing and dispersing the material C and the positive active material particles, and evaporating to remove the organic solvent to obtain an active material D; the particle size of the positive electrode active material particles is 1.0-10.0 μm;
s3, sintering the active material D and then crushing the active material D; the sintering conditions are such that the raw wrapping material B is and only partially melted.
Preferably, the particles with the particle size larger than 300nm in the coating raw material B account for at least 50% of the total number of the particles of the coating raw material B.
Preferably, in the step S1, the addition amount of the coating raw material B is 0.5 to 3.0 mass% based on the mass of the positive electrode active material particles; preferably, the amount of the wrapping raw material B added is 0.5 to 1.0 mass%.
Preferably, in step S1, the organic solvent is ethanol, methanol or acetone, and the wrapping raw material B is selected from Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of; the material of the positive electrode active material particles is at least one of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium manganese oxide.
According to the disclosure, a wrapping raw material A is also added in the process of mixing and dispersing the wrapping raw material B and the organic solvent; the particle size of the wrapping raw material A is within the range of 10-300nm, and the particle size of the wrapping raw material A is smaller than that of the wrapping raw material B; the sintering condition is that the wrapping raw material A is completely melted; the wrapping raw material A is selected from Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of (1).
According to the present disclosure, the completely melted portions of the wrapping raw material a and the wrapping raw material B together form the wrapping layer, and the portions of the wrapping raw material B that are not melted form the wrapped particles.
According to the present disclosure, the wrapping raw material may be uniformly dispersed in the organic solvent using a planetary mixer. In the process of uniformly dispersing the wrapping raw material B in the organic solvent by using the planetary mixer, the wrapping raw material B can be uniformly dispersed in the organic solvent, and then the active particles are added into the organic solvent for mixing; the solvent can be heated in the mixing process to promote the volatilization of the solvent, and the mixed material is obtained, so that the mixing efficiency is improved, and the mechanical damage of the mixing equipment to the special shape of the coating raw material is avoided.
According to the present disclosure, the temperature during the dispersion process is 60-110 ℃ in steps S1 and S2; in step S3, the sintering conditions include: the sintering temperature is 200-500 ℃, the heating rate is 1-2 ℃/min, the sintering time is 4-10h, and the sintering atmosphere is oxygen or air.
In another aspect, the present disclosure further provides an array structure layer coated positive electrode material prepared by the above method.
In still another aspect, the present disclosure also provides a battery including a positive active layer including an active material surrounded by the above array structure layer, and a current collector.
Preferably, the peel strength between the positive active layer and the current collector is greater than 0.0125N/40 mm. The method for measuring the peeling strength is carried out by referring to a method for testing the tension of the pole piece by a Meister MTS-CMT2503 electronic tension machine.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The materials, reagents, instruments and equipment used in the examples of the present disclosure are commercially available, unless otherwise specified.
Example 1
Taking the mass of the nickel cobalt lithium manganate as a reference, weighing Al with the mass percent of 2.0%, the particle size of 100-500nm and the D50-220 nm2O3Mixing the raw materials with ethanol water solution, dispersing uniformly at 80 deg.C with planetary mixer, adding nickel cobalt lithium manganate with particle diameter of 1.0-10.0 μm and D50 ═ 3.2 μm, dispersing at 80 deg.C until the material is dried, sintering the dried material in oxygen atmosphere furnace at 450 deg.C for 8h, crushingAfter crushing, the dotted Al of the example was obtained2O3A coated active material.
Example 2
This example prepared a coated active material according to the method of example 1. Except that, in this example, only 2.0% by mass of Al with a particle size of 400-485 nm, D50-500 nm was used2O3The raw material is used as a wrapping raw material.
Example 3
This example prepared a coated active material according to the method of example 1. Except that, in this example, 2.0 mass% of Al having a particle size in the range of 220-355nm and D50-285 nm was used2O3The raw material is used as a wrapping raw material.
Example 4
This example prepared a coated active material according to the method of example 1. Except that, in this example, 2.0 mass% of Al was used, the particle size was in the range of 305-460nm, and D50-405 nm2O3The raw material is used as a wrapping raw material.
Example 5
This example prepared a coated active material according to the method of example 1. Except that, in this example, 0.6 mass% of Al was used, the particle size was in the range of 305-460nm, and D50-405 nm2O3The raw material is used as a wrapping raw material.
Example 6
This example prepared a coated active material according to the method of example 1. Except that, in this example, 2.8% by mass of Al was used, the particle size was in the range of 305-460nm, and D50-405 nm2O3The raw material is used as a wrapping raw material.
Example 7
This example prepared a coated active material according to the method of example 1. Except that, in this example, 1.0 mass% of Al was used, the particle size was in the range of 305-460nm, and D50-405 nm2O3The raw material is used as a wrapping raw material.
Example 8
This example prepared a coated active material according to the method of example 1. Except that, in this example, 2.0 mass% of Al was used, the particle size was in the range of 305-460nm, and D50-405 nm2O33.0 percent of raw material and Al with the grain diameter of 10-200nm and D50-80 nm2O3Raw materials.
Example 9
This example prepared a coated active material according to the method of example 1. Except that TiO with the mass percentage of 1.5%, the particle size of 365-2The nanowire raw material is used as a wrapping raw material to finally obtain the linear TiO of the embodiment2A coated active material.
Example 10
Based on the mass of the nickel cobalt lithium manganate, weighing B with the mass percentage of 1.0 percent, the particle size of 320-375nm and the particle size of D50-350 nm2O3Mixing the raw materials, lithium hydroxide and ethanol water, and uniformly dispersing at the temperature of 70 ℃ by using a planetary mixer to obtain a material with uniformly dispersed inclusions. Continuously dispersing nickel cobalt lithium manganate with the particle size of the material being within the range of 1.0-10.0 mu m and D50 being 4.0 mu m at 70 ℃ until the material is dried, sintering the dried material in an oxygen atmosphere furnace at 300 ℃ for 4h, and crushing to obtain the point-like Li of the embodiment2BO3A coated active material.
Comparative example 1
Adding nickel cobalt lithium manganate with the particle size of 1.0-10.0 mu m and the D50 being 3.4 mu m into an ethanol water solution, uniformly dispersing by using a planetary mixer, dispersing at 80 ℃ until the material is dried, sintering the dried material in an oxygen atmosphere furnace at 450 ℃ for 8h, and crushing and dissociating to obtain the active material of the comparative example.
Comparative example 2
Taking the mass of the nickel cobalt lithium manganate as a reference, weighing Al with the mass percent of 3.0%, the particle size of 10-200nm and D50-80 nm2O3Dissolving the raw materials in ethanol water solution, and uniformly dispersing at 80 deg.C by using planetary mixer to obtain uniformly dispersed coatingAnd (4) homogenizing the solution. Adding nickel cobalt lithium manganate with particle size of 1.0-10.0 μm and D50 ═ 3.4 μm into the solution after the coating is dispersed uniformly, continuing to disperse at 80 ℃ until the material is dried, sintering the dried material in an oxygen atmosphere furnace at 450 ℃ for 8h, and crushing and dissociating to obtain the Al of the comparative example2O3A uniformly coated active material.
Test example 1
The active materials prepared in examples 1-10 and comparative examples 1-2 were tested separately by the following methods: the laser particle size distribution (PSA) and Transmission Electron Microscopy (TEM) measurements are shown in Table 1.
Figure BDA0002315379630000091
Figure BDA0002315379630000101
Test example 1
The active materials prepared in the examples 1-10 and the comparative examples 1-2 are respectively mixed with PVDF and carbon nanotubes according to the mass ratio of 100:2.0:3.0 to obtain slurry, then the slurry is coated on an aluminum foil to obtain a positive pole piece, and then the prepared 12 groups of positive pole pieces are subjected to peel strength test (refer to a method for testing the pole piece tensile force by a Mester MTS-CMT2503 electronic tensile machine), and specific results are shown in Table 2.
Test example 2
The preparation method of the positive pole piece in the test example is the same as that in the test example 1, the artificial graphite and SBR are mixed to obtain slurry, the slurry is coated on copper foil to prepare a negative electrode material, the positive and negative pole pieces and the diaphragm are prepared into a battery core in a winding mode, then the battery core is placed into a battery shell, baked, injected with electrolyte, welded and sealed, and subjected to formation and aging to obtain the battery. The battery is subjected to 1C/1C cycle test at 45 ℃, the voltage range is 2.5-4.25V, the battery is charged at constant current of 1C to 4.25V and then at constant voltage, and the cut-off current is 0.2C. The specific results of the capacity retention after 500 weeks of 12-pack batteries are shown in table 2.
TABLE 2 results of performance test of examples and comparative examples
Figure BDA0002315379630000102
Figure BDA0002315379630000111
The data in table 2 show that the peel strength of the positive electrode plate prepared from the active material coated in an array manner is more than 0.015N/40mm, which is significantly higher than that of the active material which is not coated and is only uniformly coated, and meanwhile, the capacity retention rate after 500 cycles is also obviously improved to more than 90%. Therefore, the positive electrode material coated by the array structure layer can effectively improve the adhesion effect and increase the peeling strength between the positive electrode active layer and the current collector; and the cycle performance of the battery prepared by using the positive electrode material coated by the array structure layer is obviously improved.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (10)

1. The positive electrode material coated by the array structure layer is characterized by comprising positive electrode active material particles and coating particles combined on the surfaces of the positive electrode active material particles; the particle size of the positive electrode active material particles is 1.0-10.0 μm; the coated particles are arranged in an array at intervals; the particle size of the coated particles is within the range of 20-300 nm.
2. The cathode material as claimed in claim 1, wherein the coated particles have a particle size of 50-240nm, and a median particle size D50 within a range of 100-200 nm; the coating particles are arranged in a point array, a linear array or a polygonal array; the ratio of the number of the positive electrode active material particles to the number of the coated particles is 1: 100-500.
3. The positive electrode material according to claim 1, wherein the material of the coating particle is Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of; the material of the positive electrode active material particles is at least one of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium manganese oxide.
4. The positive electrode material according to claim 1, wherein the surface of the positive electrode active material particles further has a coating layer; the thickness of the wrapping layer is 2-20 nm; the wrapping layer is made of Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of (1).
5. A method for preparing the positive electrode material coated by the array structure layer as claimed in any one of claims 1 to 4, wherein the method comprises the following steps:
s1, mixing and dispersing the wrapping raw material B and an organic solvent to obtain a material C; the particle size of the wrapping raw material B is within the range of 100-500 nm;
s2, mixing and dispersing the material C and the positive active material particles, and evaporating to remove the organic solvent to obtain an active material D; the particle size of the positive electrode active material particles is 1.0-10.0 μm;
s3, sintering the active material D and then crushing the active material D; the sintering conditions are such that the raw wrapping material B is and only partially melted.
6. The method according to claim 5, wherein in step S1, the coating raw material B is added in an amount of 0.5 to 3.0 mass% based on the mass of the positive electrode active material particles; preferably, the amount of the wrapping material B added is 0.5 to 1.0 mass%.
7. The method according to claim 5, wherein the organic solvent is ethanol, methanol or acetone, and the wrapping raw material B is selected from Al in step S12O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of; the material of the positive electrode active material particles is at least one of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium manganese oxide.
8. The method according to claim 5, wherein the wrapping raw material A is further added during the mixing and dispersing process of the wrapping raw material B and the organic solvent; the particle size of the wrapping raw material A is within the range of 10-300nm, and the particle size of the wrapping raw material A is smaller than that of the wrapping raw material B; the sintering condition is that the wrapping raw material A is completely melted; the wrapping raw material A is selected from Al2O3、ZrO2、TiO2、MnO2、CeO2、V2O5、SiO2、Li2TiO3、Li2ZrO3、Li2BO3And LiAlO2At least one of (1).
9. An array-structured-layer-coated positive electrode material, which is prepared by the method of any one of claims 5 to 8.
10. A battery comprising a positive active layer and a current collector, wherein the positive active layer comprises an active material surrounded by an array structure layer according to claims 1-4 and claim 9.
CN201911275235.0A 2019-12-12 2019-12-12 Positive electrode material and preparation method thereof Active CN112968150B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911275235.0A CN112968150B (en) 2019-12-12 2019-12-12 Positive electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911275235.0A CN112968150B (en) 2019-12-12 2019-12-12 Positive electrode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112968150A true CN112968150A (en) 2021-06-15
CN112968150B CN112968150B (en) 2023-02-10

Family

ID=76270766

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911275235.0A Active CN112968150B (en) 2019-12-12 2019-12-12 Positive electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112968150B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113823786A (en) * 2021-09-30 2021-12-21 中国矿业大学(北京) Modified lithium-rich manganese-based positive electrode material and preparation method thereof
WO2024216447A1 (en) * 2023-04-17 2024-10-24 北京当升材料科技股份有限公司 Multi-element positive electrode material and preparation method therefor, and lithium ion battery

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050130042A1 (en) * 2003-12-11 2005-06-16 Byd America Corporation Materials for positive electrodes of lithium ion batteries and their methods of fabrication
JP2007165061A (en) * 2004-12-10 2007-06-28 Canon Inc Electrode structure for lithium secondary battery and secondary battery having such electrode structure
US20150364798A1 (en) * 2013-01-23 2015-12-17 Kabushiki Kaisha Toyota Jidoshokki Positive electrode for lithium-ion secondary battery and production process for the same, and lithium-ion secondary battery
CN105185974A (en) * 2015-07-15 2015-12-23 湖南杉杉能源科技股份有限公司 Cathode material for lithium ion batteries and preparation method thereof
CN105226256A (en) * 2015-10-26 2016-01-06 河南师范大学 For modified cathode material and the lithium titanate battery of lithium titanate battery
CN106602009A (en) * 2016-12-09 2017-04-26 江南大学 Lithium-rich positive electrode modified material of lithium ion battery and preparation method of lithium-rich positive electrode modified material
US20170324084A1 (en) * 2014-12-05 2017-11-09 Lg Chem, Ltd. Positive electrode active material, method for preparing the same and lithium secondary battery including the same
CN109830654A (en) * 2018-12-29 2019-05-31 深圳市卓能新能源股份有限公司 Anode coating, battery anode slice and lithium ion battery
CN110233259A (en) * 2018-12-29 2019-09-13 宁德时代新能源科技股份有限公司 Positive active material, positive pole piece and electrochemical energy storage device

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050130042A1 (en) * 2003-12-11 2005-06-16 Byd America Corporation Materials for positive electrodes of lithium ion batteries and their methods of fabrication
JP2007165061A (en) * 2004-12-10 2007-06-28 Canon Inc Electrode structure for lithium secondary battery and secondary battery having such electrode structure
US20150364798A1 (en) * 2013-01-23 2015-12-17 Kabushiki Kaisha Toyota Jidoshokki Positive electrode for lithium-ion secondary battery and production process for the same, and lithium-ion secondary battery
US20170324084A1 (en) * 2014-12-05 2017-11-09 Lg Chem, Ltd. Positive electrode active material, method for preparing the same and lithium secondary battery including the same
CN105185974A (en) * 2015-07-15 2015-12-23 湖南杉杉能源科技股份有限公司 Cathode material for lithium ion batteries and preparation method thereof
CN105226256A (en) * 2015-10-26 2016-01-06 河南师范大学 For modified cathode material and the lithium titanate battery of lithium titanate battery
CN106602009A (en) * 2016-12-09 2017-04-26 江南大学 Lithium-rich positive electrode modified material of lithium ion battery and preparation method of lithium-rich positive electrode modified material
CN109830654A (en) * 2018-12-29 2019-05-31 深圳市卓能新能源股份有限公司 Anode coating, battery anode slice and lithium ion battery
CN110233259A (en) * 2018-12-29 2019-09-13 宁德时代新能源科技股份有限公司 Positive active material, positive pole piece and electrochemical energy storage device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113823786A (en) * 2021-09-30 2021-12-21 中国矿业大学(北京) Modified lithium-rich manganese-based positive electrode material and preparation method thereof
WO2024216447A1 (en) * 2023-04-17 2024-10-24 北京当升材料科技股份有限公司 Multi-element positive electrode material and preparation method therefor, and lithium ion battery

Also Published As

Publication number Publication date
CN112968150B (en) 2023-02-10

Similar Documents

Publication Publication Date Title
CN107546379B (en) Lithium iron manganese phosphate-ternary material composite cathode material and preparation method thereof
EP3526844B1 (en) Cathode slurry for lithium ion battery
US10727489B2 (en) Anode slurry for lithium ion battery
CN114245940B (en) Lithium ion battery, positive electrode plate for lithium ion battery and device
CN105161693B (en) A kind of high circulation lithium electricity polynary positive pole material NCM and preparation method thereof
CN111403806A (en) Carbon-coated solid electrolyte material and preparation method and application thereof
CN116097468A (en) Positive electrode material, positive electrode sheet, lithium secondary battery, battery module, battery pack and device
WO2023226372A1 (en) High-tap-density lithium iron phosphate positive electrode material, and preparation method therefor and use thereof
CN114843472B (en) Cobalt-free layered cathode material and preparation method and application thereof
CN110943206A (en) Positive active material, method for preparing same, and battery comprising same
CN109698334A (en) Positive plate, lithium titanate battery and preparation method thereof
CN112968150B (en) Positive electrode material and preparation method thereof
CN115832224B (en) Positive plate and preparation method thereof, electrode assembly, energy storage device and electric equipment
CN114865225A (en) Composite diaphragm, preparation method thereof and lithium ion battery
CN114497773A (en) Positive plate, preparation method thereof and battery
CN114361395A (en) Oxide positive electrode material coated with conducting polymer by ball milling, preparation method and application
CN114249357A (en) Surface modified high-nickel ternary cathode material and dry preparation process thereof
CN114497440B (en) Negative plate and battery comprising same
CN114695851B (en) Composite anode material, anode, battery and preparation method thereof
CN114975961A (en) Composite coated modified lithium ion battery anode material and preparation method and application thereof
CN113675381A (en) Lithium ion battery positive electrode material, positive electrode plate and lithium ion battery
CN112133900A (en) Positive electrode active material and lithium ion battery containing the same
CN113937276A (en) Lithium ion battery positive electrode material and preparation method and application thereof
CN109860523B (en) Preparation method of electrode for enhancing cycle performance of electrode material
CN116705987B (en) Negative plate, electrochemical device and preparation method of electrochemical device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant