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CN116666592A - Preparation method of high-safety modified high-nickel positive electrode material - Google Patents

Preparation method of high-safety modified high-nickel positive electrode material Download PDF

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CN116666592A
CN116666592A CN202310726435.3A CN202310726435A CN116666592A CN 116666592 A CN116666592 A CN 116666592A CN 202310726435 A CN202310726435 A CN 202310726435A CN 116666592 A CN116666592 A CN 116666592A
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nickel
anode material
positive electrode
preparation
electrode material
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何东红
田勇
王同军
李斌斌
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Gansu Dx Energy Technology Co ltd
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Gansu Dx Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62C—FIRE-FIGHTING
    • A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
    • A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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

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Abstract

The invention discloses a preparation method of a high-safety modified high-nickel anode material, which comprises an anode material and a polymer coating layer coated on the anode material, wherein the preparation method comprises the following steps of: dispersing the anode material in a solvent, carrying out ultrasonic treatment, adding diisocyanate, heating to 50-90 ℃, stirring for reaction, and drying to obtain an isocyanate modified high-nickel anode material; preparation of the coating layer: dissolving polyethylene glycol diamine in a solvent, dropwise adding diisocyanate, stirring for reaction, adding a flame retardant, continuing stirring for reaction, and then adding the high-nickel anode material obtained in the step (1), stirring for reaction to obtain the modified high-nickel anode material with the coating layer. The preparation method disclosed by the invention is simple to operate and is beneficial to realizing scale industrialization.

Description

Preparation method of high-safety modified high-nickel positive electrode material
Technical Field
The invention relates to the technical field of preparation of cathode materials, in particular to a preparation method of a modified high-nickel cathode material with high safety.
Background
The lithium ion battery becomes an important component of the new energy electric automobile battery due to the advantages of high specific energy, long cycle life and the like. However, the side reaction between the anode material and the electrolyte is severe, so that the structure of the anode material and the cathode material is unstable, and the battery of the new energy electric automobile has the problems of high temperature flammability, rapid cycle attenuation and the like. At present, the positive electrode materials for the lithium ion power battery mainly comprise lithium iron phosphate, lithium manganate, lithium nickel cobalt aluminate and the like, but the requirements of 300wh/kg of specific energy of the power battery can not be met due to low capacities of the lithium iron phosphate, the lithium manganate and the conventional lithium nickel cobalt manganate batteries, so that the high-nickel ternary positive electrode material becomes the positive electrode material of the power battery which is the hottest in the current research.
The high nickel type ternary positive electrode material has high specific capacity, but has the problems of storage and safety performance. Therefore, the development of the high-nickel ternary positive electrode material with high safety is of particular importance.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a high-safety modified high-nickel positive electrode material, which is simple to operate and can be produced in a large scale, aiming at the defects of the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the high-safety modified high-nickel positive electrode material comprises the steps of:
(1) Modification of the positive electrode material: dispersing the anode material in a solvent, carrying out ultrasonic treatment, adding diisocyanate, heating to 50-90 ℃, stirring for reaction, and drying to obtain an isocyanate modified high-nickel anode material;
(2) Preparation of the coating layer: dissolving polyethylene glycol diamine in a solvent, dropwise adding diisocyanate, stirring for reaction, adding a flame retardant, continuing stirring for reaction, adding the high-nickel anode material obtained in the step (1), and stirring for reaction to obtain the modified high-nickel anode material with the polymer coating layer.
Preferably, the general formula of the positive electrode material is LiNi x Co y M z O 2 M is one or more of Mn or Al, wherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.2, and z is more than or equal to 0 and less than or equal to 0.2.
Preferably, the structural formula of the polymer coating layer is shown as formula I,
wherein R2 is isocyanate modified high nickel anode material, R1 has a structural formula shown in formula II,
wherein, the structural formula of R is shown in a formula III,
preferably, the molecular weight of the polyethylene glycol diamine is 1000-10000.
Preferably, the flame retardant is diethyl N, N-bis (2-hydroxyethyl) amino methylene phosphonate, the structural formula of which is shown in formula IV,
preferably, the polymer coating layer accounts for 1-5% of the total mass of the positive electrode material.
The beneficial effects of the invention are as follows:
according to the invention, a thin polymer coating layer is synthesized on the surface of the high-nickel positive electrode material in situ, so that side reaction between the positive electrode material and electrolyte can be effectively prevented, and thus, the cycle stability of the battery is improved, meanwhile, a flame retardant chain segment is introduced into a molecular chain of the coating layer, the surface of the high-nickel positive electrode material is firmly coated, the thermal stability and the safety performance of the high-nickel positive electrode material are obviously improved, and in addition, the molecular chain of the polymer coating layer has a certain ionic conductivity, and the rate capability of the positive electrode material can be improved.
The invention has simple operation and is beneficial to realizing scale industrialization.
Detailed Description
The invention is further described below with reference to examples.
Example 1
The preparation method of the modified high-nickel positive electrode material with high safety comprises the following steps of:
(1) Modification of the positive electrode material: 100g of LiNi 0.8 Co 0.1 M 0.1 O 2 Dispersing the positive electrode material in N, N-dimethylacetamide, performing ultrasonic treatment for 30min, adding 3g of dimethylbenzene alkyl diisocyanate, and heating to 80 DEG C
Stirring and reacting for 3 hours, and drying to obtain the isocyanate modified high-nickel anode material;
(2) Preparation of the coating layer: 2g of polyethylene glycol diamine with molecular weight of 5000 is dissolved in N, N-dimethylacetamide, 0.55g of dimethylbenzene alkane diisocyanate is added dropwise, stirring reaction is carried out for 2h, 0.102g of flame retardant N, N-bis (2-hydroxyethyl) amino methylene phosphonic acid diethyl ester is added, stirring reaction is continued for 3h, then the high-nickel cathode material obtained in the step (1) is added, stirring reaction is carried out for 1h, and the high-nickel cathode material with a modified coating layer of a polymer coating layer is obtained.
The structural formula of the obtained polymer coating layer is shown as a formula I,
wherein R2 is isocyanate modified high nickel anode material, R1 has a structural formula shown in formula II,
wherein, the structural formula of R is shown in a formula III,
example 2:
the preparation method of the modified high-nickel positive electrode material with high safety comprises the following steps:
(1) Modification of the positive electrode material: 100g of LiNi 0.8 Co 0.1 M 0.1 O 2 Dispersing the anode material in N, N-dimethylacetamide, carrying out ultrasonic treatment for 30min, adding 1g of dimethylbenzene alkyl diisocyanate, heating to 80 ℃, stirring for reaction for 3h, and drying to obtain the high-nickel anode material modified by isocyanate;
(2) Preparation of the coating layer: dissolving 2g of polyethylene glycol diamine in N, N-dimethylacetamide, dropwise adding 0.55g of dimethylbenzene alkane diisocyanate, stirring and reacting for 2 hours, then adding 0.102g of flame retardant N, N-bis (2-hydroxyethyl) amino methylene phosphonic acid diethyl ester, continuously stirring and reacting for 3 hours, adding the isocyanate modified high-nickel anode material prepared in the step (1), stirring and reacting for 1 hour, and obtaining the modified high-nickel anode material with a polymer coating layer.
Example 3:
the preparation method of the modified high-nickel positive electrode material with high safety comprises the following steps:
(1) Modification of the positive electrode material: 100g of LiNi 0.8 Co 0.1 M 0.1 O 2 Dispersing the anode material in N, N-dimethylacetamide, carrying out ultrasonic treatment for 30min, adding 5g of dimethylbenzene alkyl diisocyanate, heating to 80 ℃, stirring for reaction for 3h, and drying to obtain the high-nickel anode material modified by isocyanate;
(2) Preparation of the coating layer: dissolving 2g of polyethylene glycol diamine in N, N-dimethylacetamide, dropwise adding 0.55g of dimethylbenzene alkane diisocyanate, stirring and reacting for 2 hours, then adding 0.102g of flame retardant N, N-bis (2-hydroxyethyl) amino methylene phosphonic acid diethyl ester, continuously stirring and reacting for 3 hours, adding the isocyanate modified high-nickel anode material prepared in the step (1), stirring and reacting for 1 hour, and obtaining the modified high-nickel anode material with a polymer coating layer.
Example 4:
the preparation method of the modified high-nickel positive electrode material with high safety comprises the following steps:
(1) Modification of the positive electrode material: 100g of LiNi 0.8 Co 0.1 M 0.1 O 2 Dispersing the anode material in N, N-dimethylacetamide, carrying out ultrasonic treatment for 30min, adding 3g of dimethylbenzene alkyl diisocyanate, heating to 80 ℃, stirring for reaction for 3h, and drying to obtain the high-nickel anode material modified by isocyanate;
(2) Preparation of the coating layer: dissolving 2g of polyethylene glycol diamine in N, N-dimethylacetamide, dropwise adding 0.55g of dimethylbenzene alkane diisocyanate, stirring and reacting for 2 hours, then adding 0.255g of flame retardant N, N-bis (2-hydroxyethyl) amino methylene phosphonic acid diethyl ester, continuously stirring and reacting for 3 hours, adding the isocyanate modified high nickel anode material prepared in the step (1), stirring and reacting for 1 hour, and obtaining the modified high nickel anode material with a polymer coating layer.
Example 5:
the preparation method of the modified high-nickel positive electrode material with high safety comprises the following steps:
(1) Modification of the positive electrode material: 100g of LiNi 0.8 Co 0.1 M 0.1 O 2 Dispersing the anode material in N, N-dimethylacetamide, carrying out ultrasonic treatment for 30min, adding 3g of dimethylbenzene alkyl diisocyanate, heating to 80 ℃, stirring for reaction for 3h, and drying to obtain the high-nickel anode material modified by isocyanate;
(2) Dissolving 2g of polyethylene glycol diamine in N, N-dimethylacetamide, dropwise adding 0.55g of dimethylbenzene alkane diisocyanate, stirring and reacting for 2 hours, then adding 0.051g of flame retardant N, N-bis (2-hydroxyethyl) amino methylene phosphonic acid diethyl ester, continuously stirring and reacting for 3 hours, adding the isocyanate modified high nickel anode material prepared in the step (1), stirring and reacting for 1 hour, and obtaining the modified high nickel anode material with a polymer coating layer.
Comparative example 1:
comparative example 1 is unmodified LiNi 0.8 Co 0.1 M 0.1 O 2 And a positive electrode material.
The positive electrode active materials prepared in examples 1 to 5 and comparative example 1 were respectively homogenized and mixed with PVDF, CNT, SP in a ratio of 95:2:2:1, coated, punched to obtain positive electrodes, and negative electrode sheets were prepared from graphite: SP: CMC: sbr=95:1:1.5:2.5, and a negative electrode was obtained by homogenizing, mixing, coating, and punching, and a commercial ceramic separator was used as a separator with LiPF6/ec+dec+dmc as an electrolyte (volume ratio of 1:1:1), and a soft pack battery was assembled, and the following experiment was performed, and the experimental results are shown in table 1.
Table 1 experimental results
As can be seen from the table above, the positive electrode material prepared by the invention has better thermal stability.
Finally, it is noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention, and that other modifications and equivalents thereof by those skilled in the art should be included in the scope of the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (6)

1. The preparation method of the modified high-nickel cathode material with high safety is characterized by comprising the following steps of:
(1) Modification of the positive electrode material: dispersing the anode material in a solvent, carrying out ultrasonic treatment, adding diisocyanate, heating to 50-90 ℃, stirring for reaction, and drying to obtain an isocyanate modified high-nickel anode material;
(2) Preparation of the coating layer: dissolving polyethylene glycol diamine in a solvent, dropwise adding diisocyanate, stirring for reaction, adding a flame retardant, continuing stirring for reaction, adding the high-nickel anode material obtained in the step (1), and stirring for reaction to obtain the modified high-nickel anode material with the polymer coating layer.
2. The method for preparing a high-safety modified high-nickel positive electrode material according to claim 1, wherein the positive electrode material has a general formula of LiNi x Co y M z O 2 M is one or more of Mn or Al, wherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.2, and z is more than or equal to 0 and less than or equal to 0.2.
3. The preparation method of the high-safety modified high-nickel anode material according to claim 1, wherein the structural formula of the polymer coating layer is shown as formula I,
wherein R2 is isocyanate modified high nickel anode material, R1 has a structural formula shown in formula II,
wherein R has the structural formula I
4. The method for producing a high-safety modified high-nickel positive electrode material according to claim 1, wherein the molecular weight of the polyethylene glycol diamine is 1000 to 10000.
5. The preparation method of the high-safety modified high-nickel cathode material according to claim 1, wherein the flame retardant is diethyl N, N-bis (2-hydroxyethyl) aminomethylene phosphonate, the structural formula of which is shown in formula IV,
6. the method for producing a high-safety modified high-nickel positive electrode material according to claim 1, wherein the polymer coating layer is 1 to 5% of the total mass of the positive electrode material.
CN202310726435.3A 2023-06-19 2023-06-19 Preparation method of high-safety modified high-nickel positive electrode material Pending CN116666592A (en)

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CN202310726435.3A CN116666592A (en) 2023-06-19 2023-06-19 Preparation method of high-safety modified high-nickel positive electrode material

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CN202310726435.3A CN116666592A (en) 2023-06-19 2023-06-19 Preparation method of high-safety modified high-nickel positive electrode material

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