CN112993381A - Preparation method of high-rate lithium ion battery - Google Patents

Preparation method of high-rate lithium ion battery Download PDF

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Publication number
CN112993381A
CN112993381A CN202110165213.XA CN202110165213A CN112993381A CN 112993381 A CN112993381 A CN 112993381A CN 202110165213 A CN202110165213 A CN 202110165213A CN 112993381 A CN112993381 A CN 112993381A
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active material
voltage
natural graphite
lithium ion
positive electrode
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金妍
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Shandong Tianhan New Energy Technology Co ltd
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Suzhou Jingcheng Intelligent Technology Co ltd
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    • H—ELECTRICITY
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    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • 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
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • 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
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    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • 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
    • H01M4/364—Composites as mixtures
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    • 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
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    • 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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    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • 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
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a preparation method of a high-rate lithium ion battery, wherein a positive active material of the lithium ion battery only comprises a first active material and a second active material, the average particle size of the first active material is D50, the average particle size of the second active material is D50, and the mass ratio of the first active material to the second active material is as follows: second active material ═ m: 1; the cathode active material of the lithium ion battery is natural graphite, the average particle size of the natural graphite is natural graphite D50, the preparation method comprises the steps of preparing a cathode and an anode, assembling the cathode and the anode by clamping a diaphragm into a battery core, loading the battery core into a shell, injecting electrolyte, sealing after formation to obtain the high-rate lithium ion battery, and the battery prepared by the invention has the advantages of reduced capacity attenuation and long cycle life under high rate.

Description

Preparation method of high-rate lithium ion battery
Technical Field
The invention relates to a preparation method of a high-rate lithium ion battery.
Background
The high-rate lithium ion battery needs to work under a large current, wherein after the current is increased, the polarization effect of the battery is increased, the corresponding charging cut-off voltage needs to be increased, and the working temperature also needs to be increased, so that the battery needs to have good rate performance and good high-voltage and high-temperature resistance.
Disclosure of Invention
The invention provides a preparation method of a high-rate lithium ion battery, wherein a positive active material of the lithium ion battery only comprises a first active material and a second active material, the average particle size of the first active material is D50, the average particle size of the second active material is D50, and the mass ratio of the first active material to the second active material is as follows: second active material ═ m: 1; the cathode active material of the lithium ion battery is natural graphite, the average particle size of the natural graphite is natural graphite D50, and the natural graphite and the first active material D50 and the second active material D50 satisfy the following relational expression: the preparation method comprises the steps of preparing a positive electrode and a negative electrode, assembling the positive electrode and the negative electrode with a clamping diaphragm to form a battery core, putting the battery core into a shell, injecting an electrolyte, wherein the electrolyte contains 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate as additives, and sealing after formation to obtain the high-rate lithium ion battery.
The specific scheme is as follows:
a preparation method of a high-rate lithium ion battery comprises the following steps: :
1) providing a first active material and a second active material, wherein the average particle size of the first active material is D50, the average particle size of the second active material is D50, and the mass ratio of the first active material: second active material ═ m: 1;
2) mixing the first active material and the second active material according to a mass ratio to prepare positive electrode slurry, coating the positive electrode slurry on a current collector, and drying to obtain a positive electrode;
3) providing natural graphite having an average particle diameter of natural graphite D50, which satisfies the following relationship with the first active material D50 and the second active material D50: (first active material D50 × m + second active material D50)/(m +1) ═ r natural graphite D50;
4) preparing negative electrode slurry from the natural graphite, coating the negative electrode slurry on a current collector, and drying to obtain a negative electrode;
5) assembling a battery core assembled by clamping a diaphragm by a positive electrode and a negative electrode, putting the battery core into a shell, and injecting electrolyte, wherein the electrolyte contains 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate as additives, and the volume ratio of the 2, 4-difluoroanisole, the delta-nonalactone and the divinyl sulfate is 3:6: 2;
6) charging to a first preset voltage by a current constant current of 0.05-0.1C, then obtaining current constant current charging and discharging circulation for a plurality of times by adopting 0.01-0.02C between the first preset voltage and a second preset voltage, and then performing constant current charging and discharging circulation for a plurality of times by adopting a current of 0.05-0.1C between a charging cut-off voltage and a discharging cut-off voltage;
7) and sealing to obtain the high-rate lithium ion battery.
Further, the first active material is LiMn0.45Ni0.28Co0.25Ca0.01Al0.01O2The second active material is LiMn0.35Ni0.45Co0.18Mg0.01Zr0.01O2。
Further, the first active material D50 was 2.2 microns and the second active material D50 was 1.5 microns, wherein the mass ratio of first active material: the second active material was 2.67: 1.
Further, r is 0.74.
Further, in the electrolyte, the volume content of the 2, 4-difluoroanisole is 1.2%, the volume content of the delta-nonalactone is 2.4%, and the volume content of the divinyl sulfate is 0.8%.
Further, the first predetermined voltage is 3.85V; the second predetermined voltage is 3.92V.
Further, the charge cut-off voltage is 4.28V; the discharge cut-off voltage was 2.80V.
Further, the organic solvent of the electrolyte is a mixed solution of ethylene carbonate, propylene carbonate and diethyl carbonate in a volume ratio of 2:2: 3.
The invention has the following beneficial effects:
1) a combination of two specific active materials, i.e. the first active material is LiMn0.45Ni0.28Co0.25Ca0.0 1Al0.01O2The second active material is LiMn0.35Ni0.45Co0.18Mg0.01Zr0.01O2The first active material D50 was 2.2 microns and the second active material D50 was 1.5 microns, wherein the mass ratio of first active material: the second active material 2.67:1 can achieve excellent rate performance and cycle life;
2) when the natural graphite D50 and the first active material D50 and the second active material D50 satisfy the following relational expressions: (first active material D50 × m + second active material D50)/(m +1) ═ r natural graphite D50, the rate performance of the battery was greatly improved, and the cycle life was not decreased thereby; the reason may be that the specific surface area of the negative electrode active material and the specific surface area of the positive electrode active material reach a certain coordination relationship, and if too large, the cycle life is easily reduced, and if too small, the rate capacity attenuation is large;
3) the 2, 4-difluoroanisole, the delta-nonalactone and the divinyl sulfate are used as additives, wherein the volume ratio of the 2, 4-difluoroanisole to the delta-nonalactone to the divinyl sulfate is 3:6:2, so that the stability of the high-rate battery under high voltage and high temperature can be stabilized, and the cycle life of the battery can be prolonged;
4) the inventors have found that, when the small-current formation is performed in a predetermined voltage range, the internal resistance of the battery can be reduced, the rate performance of the battery can be improved, the generation of heat inside the battery can be avoided, the cycle life can be improved, the principle is not clear, the additive composition is preliminarily presumed to be related, and the film forming performance of the additive is better in the voltage range.
Detailed Description
The present invention will be described in more detail below with reference to specific examples, but the scope of the present invention is not limited to these examples. In the positive electrode active material used in the present invention, the first active material is LiMn0.45Ni0.28Co0.25Ca0.0 1Al0.01O2The second active material is LiMn0.35Ni0.45Co0.18Mg0.01Zr0.01O2. The organic solvent of the electrolyte is a mixed solution of ethylene carbonate, propylene carbonate and diethyl carbonate in a volume ratio of 2:2: 3.
Example 1
1) Providing a first active material and a second active material, the first active material D50 being 2.2 microns and the second active material D50 being 1.5 microns;
2) mixing a first active material and a second active material according to a mass ratio of 2.67:1 to prepare a positive electrode slurry, wherein the mass ratio of the active material: adhesive: the conductive agent is 100:4: 4; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a positive electrode;
3) providing natural graphite having an average particle size of natural graphite D50 ═ 2.72 micrometers, which satisfies the following relationships with the first active material D50 and the second active material D50: (first active material D50 × 2.67+ second active material D50)/(2.67+1) ═ 0.74 × natural graphite D50;
4) preparing the natural graphite into negative electrode slurry, wherein the active material: adhesive: the conductive agent is 100:4: 3; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a negative electrode;
5) assembling a battery core assembled by clamping a diaphragm into a positive electrode and a negative electrode, putting the battery core into a shell, and injecting an electrolyte, wherein the electrolyte contains 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate as additives, and the volume content of the electrolyte is 1.2% of the 2, 4-difluoroanisole, 2.4% of the delta-nonalactone and 0.8% of the divinyl sulfate;
6) charging to a first preset voltage of 3.85V by a constant current of 0.05C, then performing 3 times of constant current charging and discharging cycles by using 0.01C between the first preset voltage of 3.85V and a second preset voltage of 3.92V, and then performing 3 times of constant current charging and discharging cycles by using a current of 0.05C between a charging cut-off voltage of 4.28V and a discharging cut-off voltage of 2.80V;
7) and sealing to obtain the high-rate lithium ion battery.
Example 2
1) Providing a first active material and a second active material, the first active material D50 being 2.2 microns and the second active material D50 being 1.5 microns;
2) mixing a first active material and a second active material according to a mass ratio of 2.67:1 to prepare a positive electrode slurry, wherein the mass ratio of the active material: adhesive: the conductive agent is 100:4: 4; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a positive electrode;
3) providing natural graphite having an average particle size of natural graphite D50 ═ 2.72 micrometers, which satisfies the following relationships with the first active material D50 and the second active material D50: (first active material D50 × 2.67+ second active material D50)/(2.67+1) ═ 0.74 × natural graphite D50;
4) preparing the natural graphite into negative electrode slurry, wherein the active material: adhesive: the conductive agent is 100:4: 3; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a negative electrode;
5) assembling a battery core assembled by clamping a diaphragm into a positive electrode and a negative electrode, putting the battery core into a shell, and injecting an electrolyte, wherein the electrolyte contains 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate as additives, and the volume content of the electrolyte is 1.2% of the 2, 4-difluoroanisole, 2.4% of the delta-nonalactone and 0.8% of the divinyl sulfate;
6) charging to a first preset voltage of 3.85V by a constant current of 0.1C, then performing 3 times of constant current charging and discharging cycles by adopting 0.02C between the first preset voltage of 3.85V and a second preset voltage of 3.92V, and then performing 3 times of constant current charging and discharging cycles by adopting a current of 0.1C between a charging cut-off voltage of 4.28V and a discharging cut-off voltage of 2.80V;
7) and sealing to obtain the high-rate lithium ion battery.
Comparative example 1
1) Providing a first active material and a second active material, the first active material D50 being 2.2 microns and the second active material D50 being 1.5 microns;
2) mixing a first active material and a second active material according to a mass ratio of 2:1 to prepare positive electrode slurry, wherein the active material: adhesive: the conductive agent is 100:4: 4; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a positive electrode;
3) providing natural graphite, wherein the average particle size of the natural graphite is 2.72 microns (D50);
4) preparing the natural graphite into negative electrode slurry, wherein the active material: adhesive: the conductive agent is 100:4: 3; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a negative electrode;
5) assembling a battery core assembled by clamping a diaphragm into a positive electrode and a negative electrode, putting the battery core into a shell, and injecting an electrolyte, wherein the electrolyte contains 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate as additives, and the volume content of the electrolyte is 1.2% of the 2, 4-difluoroanisole, 2.4% of the delta-nonalactone and 0.8% of the divinyl sulfate;
6) charging to a first preset voltage of 3.85V by a constant current of 0.1C, then performing 3 times of constant current charging and discharging cycles by adopting 0.02C between the first preset voltage of 3.85V and a second preset voltage of 3.92V, and then performing 3 times of constant current charging and discharging cycles by adopting a current of 0.1C between a charging cut-off voltage of 4.28V and a discharging cut-off voltage of 2.80V;
7) and sealing to obtain the high-rate lithium ion battery.
Comparative example 2
1) Providing a first active material and a second active material, the first active material D50 being 2.2 microns and the second active material D50 being 1.5 microns;
2) mixing a first active material and a second active material according to a mass ratio of 2.67:1 to prepare a positive electrode slurry, wherein the mass ratio of the active material: adhesive: the conductive agent is 100:4: 4; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a positive electrode;
3) providing natural graphite, wherein the average particle size of the natural graphite is 2.2 microns (D50);
4) preparing the natural graphite into negative electrode slurry, wherein the active material: adhesive: the conductive agent is 100:4: 3; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a negative electrode;
5) assembling a battery core assembled by clamping a diaphragm into a positive electrode and a negative electrode, putting the battery core into a shell, and injecting an electrolyte, wherein the electrolyte contains 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate as additives, and the volume content of the electrolyte is 1.2% of the 2, 4-difluoroanisole, 2.4% of the delta-nonalactone and 0.8% of the divinyl sulfate;
6) charging to a first preset voltage of 3.85V by a constant current of 0.1C, then performing 3 times of constant current charging and discharging cycles by adopting 0.02C between the first preset voltage of 3.85V and a second preset voltage of 3.92V, and then performing 3 times of constant current charging and discharging cycles by adopting a current of 0.1C between a charging cut-off voltage of 4.28V and a discharging cut-off voltage of 2.80V;
7) and sealing to obtain the high-rate lithium ion battery.
Comparative example 3
1) Providing a first active material and a second active material, the first active material D50 being 2.2 microns and the second active material D50 being 1.5 microns;
2) mixing a first active material and a second active material according to a mass ratio of 2.67:1 to prepare a positive electrode slurry, wherein the mass ratio of the active material: adhesive: the conductive agent is 100:4: 4; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a positive electrode;
3) providing natural graphite, wherein the average particle size of the natural graphite is 3.2 microns (D50);
4) preparing the natural graphite into negative electrode slurry, wherein the active material: adhesive: the conductive agent is 100:4: 3; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a negative electrode;
5) assembling a battery core assembled by clamping a diaphragm into a positive electrode and a negative electrode, putting the battery core into a shell, and injecting an electrolyte, wherein the electrolyte contains 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate as additives, and the volume content of the electrolyte is 1.2% of the 2, 4-difluoroanisole, 2.4% of the delta-nonalactone and 0.8% of the divinyl sulfate;
6) charging to a first preset voltage of 3.85V by a constant current of 0.1C, then performing 3 times of constant current charging and discharging cycles by adopting 0.02C between the first preset voltage of 3.85V and a second preset voltage of 3.92V, and then performing 3 times of constant current charging and discharging cycles by adopting a current of 0.1C between a charging cut-off voltage of 4.28V and a discharging cut-off voltage of 2.80V;
7) and sealing to obtain the high-rate lithium ion battery.
Comparative example 4
1) Providing a first active material and a second active material, the first active material D50 being 2.2 microns and the second active material D50 being 1.5 microns;
2) mixing a first active material and a second active material according to a mass ratio of 2.67:1 to prepare a positive electrode slurry, wherein the mass ratio of the active material: adhesive: the conductive agent is 100:4: 4; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a positive electrode;
3) providing natural graphite, wherein the average particle size of the natural graphite is 2.72 microns (D50);
4) preparing the natural graphite into negative electrode slurry, wherein the active material: adhesive: the conductive agent is 100:4: 3; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a negative electrode;
5) assembling a battery core assembled by clamping a diaphragm into a positive electrode and a negative electrode, putting the battery core into a shell, and injecting an electrolyte, wherein the electrolyte contains 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate as additives, and the volume content of the electrolyte is 1.6% of the 2, 4-difluoroanisole, 1.6% of the delta-nonalactone and 1.2% of the divinyl sulfate;
6) charging to a first preset voltage of 3.85V by a constant current of 0.1C, then performing 3 times of constant current charging and discharging cycles by adopting 0.02C between the first preset voltage of 3.85V and a second preset voltage of 3.92V, and then performing 3 times of constant current charging and discharging cycles by adopting a current of 0.1C between a charging cut-off voltage of 4.28V and a discharging cut-off voltage of 2.80V;
7) and sealing to obtain the high-rate lithium ion battery.
Comparative example 5
1) Providing a first active material and a second active material, the first active material D50 being 2.2 microns and the second active material D50 being 1.5 microns;
2) mixing a first active material and a second active material according to a mass ratio of 2.67:1 to prepare a positive electrode slurry, wherein the mass ratio of the active material: adhesive: the conductive agent is 100:4: 4; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a positive electrode;
3) providing natural graphite, wherein the average particle size of the natural graphite is 2.72 microns (D50);
4) preparing the natural graphite into negative electrode slurry, wherein the active material: adhesive: the conductive agent is 100:4: 3; coating on a current collector, wherein the coating thickness is 60 microns, and drying to obtain a negative electrode;
5) assembling a battery core assembled by clamping a diaphragm into a positive electrode and a negative electrode, putting the battery core into a shell, and injecting an electrolyte, wherein the electrolyte contains 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate as additives, and the volume content of the electrolyte is 1.2% of the 2, 4-difluoroanisole, 2.4% of the delta-nonalactone and 0.8% of the divinyl sulfate;
6) charging to a first preset voltage of 3.65V by a constant current of 0.1C, then performing 3 times of constant current charging and discharging cycles by using 0.02C between the first preset voltage of 3.65V and a second preset voltage of 3.72V, and then performing 3 times of constant current charging and discharging cycles by using a current of 0.1C between a charging cut-off voltage of 4.28V and a discharging cut-off voltage of 2.80V;
7) and sealing to obtain the high-rate lithium ion battery.
Test and results
The batteries after formation of examples 1-2 and comparative examples 1-5 were tested, and the capacity retention rate of the battery was measured by charging and discharging the battery 300 times at a rate of 1C at 45 degrees celsius, and the results are shown in table 1, the first active material: the second active material 2.67:1 can achieve excellent rate performance and cycle life; when the natural graphite D50 and the first and second active materials D50 and D50 satisfy the following relations: when the first active material D50 × m + the second active material D50)/(m +1) ═ r natural graphite D50, the rate capability of the battery is greatly improved; 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate are used as additives, wherein the volume ratio of the 2, 4-difluoroanisole to the delta-nonalactone to the divinyl sulfate is 3:6:2, so that the stability of the high-rate battery under high voltage and high temperature can be stabilized, and the cycle life of the battery can be prolonged; the small current formation is carried out in a preset voltage interval, so that the internal resistance of the battery can be reduced, and the rate capability of the battery can be improved.
TABLE 1
Capacity retention (%)
Example 1 98.3
Example 2 98.1
Comparative example 1 95.4
Comparative example 2 94.5
Comparative example 3 94.9
Comparative example 4 95.2
Comparative example 5 96.3
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.

Claims (8)

1. A preparation method of a high-rate lithium ion battery comprises the following steps: :
1) providing a first active material and a second active material, wherein the average particle size of the first active material is D50, the average particle size of the second active material is D50, and the mass ratio of the first active material: second active material ═ m: 1;
2) mixing the first active material and the second active material according to a mass ratio to prepare positive electrode slurry, coating the positive electrode slurry on a current collector, and drying to obtain a positive electrode;
3) providing natural graphite having an average particle diameter of natural graphite D50, which satisfies the following relationship with the first active material D50 and the second active material D50: (first active material D50 × m + second active material D50)/(m +1) ═ r natural graphite D50;
4) preparing negative electrode slurry from the natural graphite, coating the negative electrode slurry on a current collector, and drying to obtain a negative electrode;
5) assembling a battery core assembled by clamping a diaphragm by a positive electrode and a negative electrode, putting the battery core into a shell, and injecting electrolyte, wherein the electrolyte contains 2, 4-difluoroanisole, delta-nonalactone and divinyl sulfate as additives, and the volume ratio of the 2, 4-difluoroanisole, the delta-nonalactone and the divinyl sulfate is 3:6: 2;
6) charging to a first preset voltage by a current constant current of 0.05-0.1C, then obtaining current constant current charging and discharging circulation for a plurality of times by adopting 0.01-0.02C between the first preset voltage and a second preset voltage, and then performing constant current charging and discharging circulation for a plurality of times by adopting a current of 0.05-0.1C between a charging cut-off voltage and a discharging cut-off voltage;
7) and sealing to obtain the high-rate lithium ion battery.
2. The method of the preceding claim, the first active material being LiMn0.45Ni0.28Co0.25Ca0.01Al0.01O2The second active material is LiMn0.35Ni0.45Co0.18Mg0.01Zr0.01O2。
3. The method of the preceding claim, the first active material D50 being 2.2 microns and the second active material D50 being 1.5 microns, wherein the mass ratio of first active material: second active material 2.67: 1.
4. the method of the preceding claim, wherein r is 0.74.
5. The method of the preceding claim, wherein the electrolyte comprises, by volume, 1.2% 2, 4-difluoroanisole, 2.4% δ -nonanolide, and 0.8% divinyl sulfate.
6. The method of the preceding claim, the first predetermined voltage being 3.85V; the second predetermined voltage is 3.92V.
7. The method of the preceding claim, the charge cutoff voltage is 4.28V; the discharge cut-off voltage was 2.80V.
8. The method of the preceding claim, wherein the organic solvent of the electrolyte is a mixed solution of ethylene carbonate, propylene carbonate, and diethyl carbonate in a volume ratio of 2:2: 3.
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