CN115763745A - Coated nickel cobalt lithium manganate positive electrode material, preparation method thereof and battery - Google Patents
Coated nickel cobalt lithium manganate positive electrode material, preparation method thereof and battery Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 238000000034 method Methods 0.000 claims description 14
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 11
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 11
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- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- 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
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Abstract
The invention relates to the technical field of batteries, in particular to a coated nickel cobalt lithium manganate positive electrode material, a preparation method thereof and a battery; the preparation method of the coated nickel cobalt lithium manganate cathode material comprises the following steps: mixing a substrate with an inorganic coating agent to obtain a prefabricated substrate, wherein the substrate comprises secondary spherical nickel cobalt lithium manganate; mixing and dissolving polyamide and a first solvent, and mixing the polyamide and a second solvent to obtain a polyamide solution, wherein the solubility of the polyamide in the first solvent is greater than that of the polyamide in the second solvent; and spraying the polyamide solution on the surface of the prefabricated substrate, removing the solvent, washing, centrifuging and drying to obtain the coated nickel cobalt lithium manganate cathode material. The coated nickel cobalt lithium manganate positive electrode material disclosed by the invention is good in structural stability and good in cycle performance.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a coated lithium nickel cobalt manganese oxide positive electrode material, a preparation method thereof and a battery.
Background
Lithium nickel cobalt manganese (LiNi) x Co y Mn z O 2 Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1, x + y + z = 1) is a lithium ion battery anode material with excellent electrochemical performance, and the lithium ion battery prepared by using the material has the advantages of high specific capacity, high energy density, small self-discharge, no memory effect, strong cycling stability and the like.
However, the nickel cobalt lithium manganate material still has certain problems, such as that the electrolyte has certain corrosion effect on the electrode material, so that the capacity of the material is attenuated, and the cycling stability of the material is influenced. Therefore, modification of the positive electrode material becomes an important means for improving the electrochemical performance of the material, and among them, coating is the simplest and most effective method. The existence of the coating layer can maintain the stability of the surface structure of the coating layer, avoid the direct contact between the active substance and the electrolyte, and inhibit the dissolution of the transition metal element of the material under the high potential condition, thereby improving the capacity retention rate of the cathode material.
However, due to the existence of the coating layer, the interface stability is poor, the electronic conductivity is low, and the cycle performance of the prepared battery is still poor.
Disclosure of Invention
The invention aims to provide a coated nickel cobalt lithium manganate positive electrode material, a preparation method thereof and a battery.
The invention is realized in the following way:
in a first aspect, the invention provides a preparation method of a coated lithium nickel cobalt manganese oxide positive electrode material, which comprises the following steps:
mixing a matrix with an inorganic coating agent to obtain a prefabricated matrix, wherein the matrix comprises secondary spherical nickel cobalt lithium manganate;
mixing and dissolving polyamide and a first solvent, and mixing the polyamide and a second solvent to obtain a polyamide solution, wherein the solubility of the polyamide in the first solvent is greater than that of the polyamide in the second solvent;
and spraying the polyamide solution on the surface of the prefabricated substrate, removing the solvent, washing, centrifuging and drying to obtain the coated nickel cobalt lithium manganate cathode material.
In alternative embodiments, at least one of the first solvent and the second solvent is selected from at least one of formamide, glycerol, and ethylene glycol.
In an alternative embodiment, the ratio of the mass of polyamide to the total mass of first and second solvents is 1% to 5%; the mass ratio of the first solvent to the second solvent is (3-8) to (4-6).
In an alternative embodiment, removing the solvent comprises a heat treatment, and the temperature of the heat treatment is 120-180 ℃.
In an alternative embodiment, the inorganic capping agent is a nanoparticle having conductive properties; the nano-particles with conductive characteristics comprise silane modified conductive zinc oxide whiskers.
In an alternative embodiment, the inorganic coating agent comprises 1% to 10% by weight of the matrix.
In an alternative embodiment, the polyamide is a polyamide oligomer and the weight average molecular weight Mw ranges from 1000 to 50000g/mol.
In an alternative embodiment, the mass ratio of polyamide solution to preformed matrix is 2 (2-4).
In a second aspect, the invention provides a cathode material prepared by the method for preparing the coated nickel cobalt lithium manganate cathode material according to any one of the previous embodiments.
In a third aspect, the present invention provides a battery comprising the positive electrode material of the previous embodiment.
The invention has the following beneficial effects:
according to the preparation method of the coated nickel cobalt lithium manganate positive electrode material, provided by the embodiment of the invention, the polyamide is precipitated to form the porous film attached to the surface of the nickel cobalt lithium manganate matrix after the solvent is volatilized, so that the polyamide porous film coated nickel cobalt lithium manganate matrix can be formed, the cycle performance of the prepared positive electrode material under high voltage is improved, the structural stability of the positive electrode material is improved, and the positive electrode material can resist electrolyte corrosion under high voltage. In addition, during preparation, the inorganic coating agent is added to improve certain conductivity, and the inorganic coating agent and the polyamide coating layer cooperate to further improve the conductivity of the material.
The positive electrode material provided by the embodiment of the invention is prepared by the preparation method of the coated nickel cobalt lithium manganate positive electrode material, the organic-inorganic coating layer is formed on the surface of the positive electrode material, the cycle performance of the material under high voltage is improved, the formed polyamide porous membrane is used for coating a nickel cobalt lithium manganate matrix, the polyamide porous membrane can resist electrolyte corrosion under the high voltage condition, the positive electrode material is prevented from being directly contacted with the electrolyte, and the repeated extraction and insertion of lithium are facilitated.
The battery provided by the embodiment of the invention comprises the positive electrode material, the cycle performance of the battery is enhanced under high voltage, the positive electrode material is resistant to electrolyte corrosion under the high voltage condition, the direct contact between the positive electrode material and the electrolyte is avoided, and the repeated extraction and insertion of lithium are facilitated.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an SEM image of a lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The lithium nickel cobalt manganese oxide material has the performances of high voltage platform, high discharge capacity and the like, and is widely applied to the field of lithium batteries.
Lithium nickel cobalt manganese (LiNi) x Co y Mn z O 2 Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1, x + y + z = 1) is a lithium ion battery anode material with excellent electrochemical performance, and the lithium ion battery prepared by using the material has the advantages of high specific capacity, high energy density, small self-discharge, no memory effect, strong cycling stability and the like. However, the lithium nickel cobalt manganese oxide positive electrode material has fast cycle capacity attenuation and poor structural stability under the high-voltage condition.
In the related technology, the ternary anode material for high voltage is usually made into a monocrystal or monocrystal-like shape similar to the shape of lithium cobaltate to improve the problems, but the process difficulty is high, the resilience is serious after the pole piece is made, and the capacity and rate capability are low; in addition, the secondary spherical ternary material provided by the related technology has poor cycle performance under high voltage due to low electrolyte corrosion resistance and weak stress corrosion resistance under high voltage. For example, in some embodiments, the porous conductive polyimide material containing an imidazole structure is composited with a lithium ion positive electrode material, a pore-foaming agent and a conductive filler are uniformly dispersed in an organic solvent, a diamine monomer containing the imidazole structure is dissolved in the organic solvent under the protection of an inert atmosphere, a dianhydride monomer is added in batches to uniformly mix the solution and perform a polymerization reaction to obtain a porous conductive polyamide acid (PAA) dispersion liquid containing the imidazole structure, and then the porous conductive polyamide acid dispersion liquid is composited with the lithium ion positive electrode material to form the positive electrode material; however, the formation of a porous structure in polyimide by using an organic porogen has the problems of uneven dispersion of the organic porogen, incapability of effectively removing the porogen and the like, and the process is complicated.
The invention provides a preparation method of a coated nickel cobalt lithium manganate positive electrode material, which comprises the following steps:
mixing a substrate with an inorganic coating agent to obtain a prefabricated substrate, wherein the substrate comprises secondary spherical nickel cobalt lithium manganate;
mixing polyamide with a first solvent, swelling and dissolving, and mixing with a second solvent to obtain a polyamide solution, wherein the solubility of the polyamide in the first solvent is greater than that in the second solvent;
and atomizing and spraying the polyamide solution on the prefabricated matrix, removing the solvent, washing, centrifuging and drying to obtain the coated nickel cobalt lithium manganate cathode material.
Mixing a substrate with an inorganic coating agent to obtain a prefabricated substrate, wherein the substrate comprises secondary spherical nickel cobalt lithium manganate; mixing polyamide with a first solvent, swelling and dissolving, and then mixing with a second solvent to obtain a polyamide solution; atomizing and spraying the polyamide solution on a prefabricated matrix, removing the solvent, washing, centrifuging and drying. Through volatilizing the solvent, polyamide is precipitated to form a porous membrane to be attached to the surface of a nickel cobalt lithium manganate matrix, so that the polyamide porous membrane can be formed to coat the nickel cobalt lithium manganate matrix, the cycle performance of the prepared cathode material under high voltage is improved, the structural stability of the prepared cathode material can be improved, and the cathode material can resist electrolyte corrosion under high voltage. In addition, the preparation method can uniformly disperse the solvent, ensure that the solvent can be reliably removed, and has simple and easily controlled process.
The surface of the anode material prepared by the preparation method of the invention is provided with the organic-inorganic coating layer, so that the cycle performance of the material under high voltage is improved, the formed polyamide porous membrane is coated on the nickel cobalt lithium manganate matrix, the anode material can resist electrolyte corrosion under the high voltage condition, the direct contact between the anode material and the electrolyte is avoided, and the repeated extraction and the insertion of lithium are facilitated.
Optionally, the secondary spherical nickel cobalt lithium manganate ternary material as the matrix can also be doped with aluminum (Al), yttrium (Y), indium (In), and the like.
In a preferred embodiment, the inorganic capping agent is a nanoparticle having conductive properties.
Further, the nanoparticles having conductive properties include silane-modified conductive zinc oxide whiskers.
Alternatively, 3-aminopropyltriethoxysilane or the like can be used as the silane in the silane modification.
The conductive zinc oxide whiskers modified by silane are embedded into the matrix and the polyurethane coating film, so that the toughness and strength of the material can be enhanced, the positive plate made of the positive material has better bending resistance, the problem of serious rebound of the positive plate is solved, and the preparation process is simple and easy to operate.
In a preferred embodiment, the inorganic coating agent comprises 1% to 10% by weight of the matrix, for example: 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., and is not particularly limited herein.
In the present invention, the first solvent is at least one selected from the group consisting of formamide, glycerol, and ethylene glycol.
In the present invention, the second solvent is at least one selected from the group consisting of formamide, glycerol, and ethylene glycol.
The solubility of the polyamide in the first solvent is greater than the solubility of the polyamide in the second solvent; since the solubility of formamide, glycerol and ethylene glycol decreases in this order, the first and second solvents should be selected according to the requirements mentioned above, for example: when the first solvent is formamide, the second solvent at least comprises one of glycerol and glycol; when the first solvent is glycerol, the second solvent at least comprises glycol; and is not particularly limited herein.
In a preferred embodiment, the ratio of the mass of polyamide to the total mass of first and second solvents is between 1% and 5%, for example: 1%, 2%, 3%, 4%, 5%, etc.
Further, the mass ratio of the first solvent to the second solvent is (3-8) to (4-6), for example: 3, 4.
In a preferred embodiment, the polyamide is a polyamide oligomer having a weight-average molecular weight Mw of from 1000 to 50000g/mol, for example: 1000g/mol, 5000g/mol, 10000g/mol, 20000g/mol, 25000g/mol, 30000g/mol, 40000g/mol, 50000g/mol, and the like.
Further, the mass ratio of the polyamide solution to the preformed substrate is 2 (2-4), for example: 1, 2.
In a preferred embodiment, the method of removing the solvent comprises a heat treatment at a temperature of 120 ℃ to 180 ℃, for example: 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, etc.
In the heat treatment process, due to the difference of solvents, the solubility of polyamide in a first solvent is better than that of polyamide in a second solvent, the volatilization of the solvents and the solubility of the polyamide are controlled at different temperatures, and the polyamide is separated out after the solvents are volatilized to form a porous membrane attached to the surface of a substrate; meanwhile, the amine end groups of the polyamide and silane bonds in the silane-modified conductive zinc oxide whiskers form intermolecular acting force and hydrogen bridge bonds, and are bonded to form a net structure, so that the bonding force between the polyamide film and the matrix is enhanced, and the structural stability and the conductivity of the positive electrode material are enhanced.
In some embodiments, the temperature for drying the coated lithium nickel cobalt manganese oxide cathode material can be 120-150 ℃.
The present invention will be described in further detail with reference to examples.
Example 1
S1: 10g of secondary spherical nickel cobalt lithium manganate ternary material LiNi 0.9 Co 0.05 Mn 0.05 O 2 And (3) putting the substrate and 1g of silane modified zinc oxide whiskers into a mixing device, and uniformly mixing to obtain the prefabricated substrate.
S2: adding polyamide into formamide solvent, stirring for swelling and dissolving, adding solvent glycerol, and stirring for fully mixing for 30min to obtain polyamide solution; wherein the mass ratio of formamide to glycerol is 3.
S3: spraying the polyamide solution into a mixing device in a rotary atomizing manner, then uniformly mixing the polyamide solution with a prefabricated substrate, sequentially carrying out heat treatment at 120 ℃ and 180 ℃, removing a solvent, forming a polyamide porous membrane and coating the polyamide porous membrane on the surface of the substrate, washing, centrifuging, and then drying at 120 ℃ to form a coated nickel cobalt lithium manganate positive electrode material; the SEM is shown in FIG. 1.
As can be seen from FIG. 1, the preparation method of the invention can prepare the polyamide porous membrane coated lithium nickel cobalt manganese oxide matrix.
Example 2
S1: liNi which is a secondary spherical nickel cobalt lithium manganate ternary material 0.9 Co 0.05 Mn 0.05 O 2 Putting the substrate and the silane modified zinc oxide whisker into a mixing device and uniformly mixing to prepare a prefabricated substrate; the silane modified zinc oxide whisker accounts for 1 percent of the weight of the matrix.
S2: adding polyamide into a glycerol solvent, stirring for swelling and dissolving, adding a mixed solvent of a solvent formamide and ethylene glycol, and stirring for fully mixing for 30min to obtain a polyamide solution; wherein the ratio of the polyamide to the total mass of the glycerol, the formamide and the ethylene glycol is 3%, and the ratio of the glycerol to the total mass of the formamide and the ethylene glycol is 4.
S3: and (2) spraying the polyamide solution into a mixing device in a rotary atomizing manner, then uniformly mixing the polyamide solution with a prefabricated substrate, sequentially carrying out heat treatment at 130 ℃ and 160 ℃, removing a solvent, forming a polyamide porous membrane, coating the polyamide porous membrane on the surface of the substrate, washing, centrifuging, and then drying at 120 ℃ to form the coated nickel cobalt lithium manganate positive electrode material.
Example 3
S1: liNi which is a secondary spherical nickel cobalt lithium manganate ternary material 0.9 Co 0.05 Mn 0.05 O 2 Putting the substrate and the silane modified zinc oxide whisker into a mixing device and uniformly mixing to prepare a prefabricated substrate; the silane modified zinc oxide whisker accounts for 5 percent of the matrix.
S2: adding polyamide into a mixed solvent of formamide and glycerol, stirring for swelling and dissolving, adding a solvent of ethylene glycol, and stirring and fully mixing for 30min to obtain a polyamide solution; wherein the ratio of the polyamide to the total mass of the glycerol, the formamide and the ethylene glycol is 1%, and the mass ratio of the total mass of the formamide and the glycerol to the ethylene glycol is 1.
S3: and (2) spraying the polyamide solution into a mixing device in a rotary atomizing manner, then uniformly mixing the polyamide solution with a prefabricated substrate, sequentially carrying out heat treatment at 140 ℃ and 150 ℃, removing a solvent, forming a polyamide porous membrane, coating the polyamide porous membrane on the surface of the substrate, washing, centrifuging, and then drying at 120 ℃ to form the coated nickel cobalt lithium manganate positive electrode material.
Example 4
S1: liNi which is a secondary spherical nickel cobalt lithium manganate ternary material 0.9 Co 0.05 Mn 0.05 O 2 Putting the substrate and the silane modified zinc oxide whisker into a mixing device, and uniformly mixing to prepare a prefabricated substrate; the silane modified zinc oxide whisker accounts for 3 percent of the matrix.
S2: adding polyamide into a formamide solvent, stirring for swelling and dissolving, adding ethylene glycol, and stirring for fully mixing for 30min to obtain a polyamide solution; wherein the mass ratio of the polyamide to the total mass of the formamide and the ethylene glycol is 2%, and the mass ratio of the formamide to the ethylene glycol is 2.
S3: and carrying out rotary atomization on the polyamide solution, spraying the polyamide solution into a mixing device, then uniformly mixing the polyamide solution with a prefabricated substrate, sequentially carrying out heat treatment at 120 ℃ and 150 ℃, removing a solvent, forming a polyamide porous membrane, coating the polyamide porous membrane on the surface of the substrate, washing, centrifuging, and then drying at 120 ℃ to form the coated nickel cobalt lithium manganate positive electrode material.
Comparative example 1
Comparative example 1 differs from example 1 in that: in the step S1, only secondary spherical nickel cobalt lithium manganate ternary material LiNi is used 0.9 Co 0.05 Mn 0.05 O 2 The substrate is not added with silane modified zinc oxide whiskers, namely, no inorganic coating agent is added, and only polyamide forms a porous membrane to coat the surface of the nickel cobalt lithium manganate substrate.
The material prepared in comparative example 1 was poor in conductivity and stability.
Comparative example 2
Comparative example 2 differs from example 1 in that: liNi prepared from secondary spherical nickel cobalt lithium manganate ternary material 0.9 Co 0.05 Mn 0.05 O 2 As a positive electrode material, any coating of example 1 was not performedAnd (6) processing.
The material prepared in comparative example 2 was poor in conductivity and stability.
Comparative example 3
Comparative example 3 differs from example 1 in that: liNi which is a secondary spherical nickel cobalt lithium manganate ternary material 0.9 Co 0.05 Mn 0.05 O 2 The silicon-modified zinc oxide whisker inorganic coating agent is added as a matrix, and a porous membrane is formed without using polyamide to coat the surface of the nickel cobalt lithium manganate matrix.
The material prepared in comparative example 3 had poor conductivity and stability.
Detecting the resistivity of the anode materials obtained in the examples and the comparative examples by a four-probe method under 12 Mpa; the results are shown in Table 1.
TABLE 1
| Resistivity (omega. M) | |
| Example 1 | 1368 |
| Example 2 | 1443 |
| Example 3 | 1621 |
| Comparative example 1 | 6883 |
| Comparative example 2 | 7211 |
| Comparative example 3 | 6880 |
Test examples
The anode materials prepared in the embodiment 1 and the comparative examples 1 and 2 are prepared into button cells to be tested for the electrochemical performance of the lithium ion battery, and the method comprises the following specific steps: the method comprises the steps of taking N-methyl pyrrolidone as a solvent, uniformly mixing a positive electrode material, acetylene black and PVDF according to the mass ratio of 9.2: 0.5: 0.3, coating the mixture on an aluminum foil, carrying out forced air drying at 80 ℃ for 8 hours, and carrying out vacuum drying at 120 ℃ for 12 hours. Assembling a battery in an argon-protected glove box, wherein a negative electrode is a metal lithium sheet, a diaphragm is a polypropylene film, and electrolyte is 1M LiPF 6 EC/DMC (1: 1, V/V), assembling the button cell by adopting a 2032 type button cell case in an argon-protected glove box, and then carrying out electrochemical performance test at 25 ℃ at 3.0-4.2V. The results are shown in Table 2.
TABLE 2
According to the results in the table, the positive electrode material prepared by the method provided by the invention has better cycle performance after being prepared into a battery.
In conclusion, the preparation material of the coated nickel cobalt lithium manganate positive electrode material disclosed by the invention has the advantages that the nickel cobalt lithium manganate positive electrode material coated by the polyamide porous film is resistant to electrolyte corrosion under a high-voltage condition, so that the positive electrode material is prevented from being in direct contact with the electrolyte, and the repeated extraction and insertion of lithium are facilitated.
During the heat treatment process, due to the difference of solvents, namely the solubility of polyamide in the first solvent is better than that of polyamide in the second solvent, the volatilization of the solvents and the solubility of the polyamide are controlled at different temperatures, and the polyamide is separated out after the solvents are volatilized to form a porous membrane to be attached to the surface of the substrate; meanwhile, the amine end groups of the polyamide and silane bonds in the silane-modified conductive zinc oxide whiskers form intermolecular acting force and hydrogen bridge bonds, and are bonded to form a net structure, so that the bonding force between the polyamide film and the matrix is enhanced, and the structural stability and the conductivity of the positive electrode material are enhanced.
According to the invention, the organic-inorganic coating layer is formed on the surface of the anode material, so that the cycle performance of the material under high voltage is improved, the silane-modified conductive zinc oxide whiskers are embedded into the matrix and the polyurethane coating film, so that the toughness and strength of the material are enhanced, the anode plate made of the anode material has better bending resistance, the problem of serious resilience of the anode plate can be solved, and the preparation process is simple.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a coated nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps:
mixing a substrate with an inorganic coating agent to obtain a prefabricated substrate, wherein the substrate comprises secondary spherical nickel cobalt lithium manganate;
mixing and dissolving polyamide and a first solvent, and then mixing the polyamide and a second solvent to obtain a polyamide solution, wherein the solubility of the polyamide in the first solvent is greater than that of the polyamide in the second solvent;
and spraying the polyamide solution on the surface of the prefabricated substrate, removing the solvent, washing, centrifuging and drying to obtain the coated nickel cobalt lithium manganate cathode material.
2. The method for preparing the coated lithium nickel cobalt manganese oxide cathode material according to claim 1, wherein at least one of the first solvent and the second solvent is at least one selected from formamide, glycerol and glycol.
3. The preparation method of the coated lithium nickel cobalt manganese oxide cathode material according to claim 2, wherein the ratio of the mass of the polyamide to the total mass of the first solvent and the second solvent is 1% -5%; the mass ratio of the first solvent to the second solvent is (3-8) to (4-6).
4. The preparation method of the coated lithium nickel cobalt manganese oxide cathode material according to any one of claims 1 to 3, wherein the solvent removal comprises heat treatment, and the temperature of the heat treatment is 120-180 ℃.
5. The preparation method of the coated nickel cobalt lithium manganate positive electrode material of claim 1, wherein the inorganic coating agent is conductive nanoparticles; the nanoparticles with conductivity comprise silane modified conductive zinc oxide whiskers.
6. The preparation method of the coated nickel cobalt lithium manganate positive electrode material as set forth in claim 1 or 5, wherein said inorganic coating agent is 1% -10% of the weight of said matrix.
7. The preparation method of the coated nickel cobalt lithium manganate positive electrode material of claim 1, wherein the polyamide is polyamide oligomer, and the weight average molecular weight Mw is 1000-50000g/mol.
8. The preparation method of the coated lithium nickel cobalt manganese oxide cathode material according to claim 1 or 7, wherein the mass ratio of the polyamide solution to the prefabricated substrate is 2 (2-4).
9. A positive electrode material prepared by the method for preparing the coated nickel cobalt lithium manganate positive electrode material as set forth in any one of claims 1 to 8.
10. A battery comprising the positive electrode material according to claim 9.
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| PCT/CN2023/081399 WO2024108821A1 (en) | 2022-11-23 | 2023-03-14 | Coated nickel cobalt lithium manganate positive electrode material and preparation method therefor, and battery |
| FR2312712A FR3142296A1 (en) | 2022-11-23 | 2023-11-20 | LITHIUM-NICKEL-COBALT-MANGANESE OXIDE-COATED CATHODE MATERIAL AND PREPARATION METHOD THEREFOR, AND BATTERY |
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| CN103078081B (en) * | 2013-01-15 | 2016-04-06 | 宁德新能源科技有限公司 | Surface coated anode active material of lithium ion battery particle and preparation method thereof |
| CN110556538B (en) * | 2018-06-01 | 2021-05-04 | 宁德时代新能源科技股份有限公司 | Positive plate and lithium ion battery |
| CN115763745A (en) * | 2022-11-23 | 2023-03-07 | 广东邦普循环科技有限公司 | Coated nickel cobalt lithium manganate positive electrode material, preparation method thereof and battery |
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