CN113130846A - Secondary battery anode material and battery thereof - Google Patents
Secondary battery anode material and battery thereof Download PDFInfo
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- CN113130846A CN113130846A CN202110454891.8A CN202110454891A CN113130846A CN 113130846 A CN113130846 A CN 113130846A CN 202110454891 A CN202110454891 A CN 202110454891A CN 113130846 A CN113130846 A CN 113130846A
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- secondary battery
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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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- 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
Abstract
The invention discloses a secondary battery anode material and a battery thereof, wherein the anode material is prepared by the following method: s1, mixing the lithium cobalt oxide, the lithium nickel oxide and the lithium manganese oxide, and then grinding to obtain mixed powder A; s2, putting the mixed powder A into a tablet machine, and tabletting to prepare a sheet with the diameter of 20mm for later use; s3, ultrasonically dispersing the silicon dioxide aerogel in deionized water to form a silicon dioxide aerogel suspension; s4, adding a proper amount of graphene into the silicon dioxide aerogel suspension liquid under the ultrasonic dispersion treatment state, and drying until the water content is 8% after complete adsorption to obtain a spraying liquid B; and S5, uniformly spraying the spraying liquid B on two surfaces of the sheet, drying, heating to 350-450 ℃, sintering for 3-5 h, and grinding the mixture to obtain the coating. The anode material of the secondary battery has the characteristics of high electric capacity, high charge-discharge rate, long cycle life and high safety.
Description
Technical Field
The invention relates to the field of secondary battery materials, in particular to a secondary battery anode material and a battery thereof.
Background
The lithium ion secondary battery has the advantages of high working voltage, large specific energy, long cycle life, small pollution and the like, is widely applied to the field of 3C electronic products such as mobile phones, notebook computers and the like at present, and is also a main choice of power batteries for electric automobiles and electric tools. In each component of the lithium ion secondary battery, the performance of the positive electrode material determines the advantages of the overall performance of the battery, and is a key factor influencing the energy density, cycle life and safety of the lithium ion secondary battery.
In order to improve the comprehensive performance of the anode material of the lithium ion secondary battery, researchers widely adopt a surface coating method to avoid direct contact between the anode material and electrolyte at present, and obtain good effects on improving the cycle life and the safety of the battery. However, the coating layer adopted at present is usually a simple substance and a compound with good chemical stability, including a metal simple substance (such as Au, Ag, etc.), a metal oxide (such as Al)2O3、TiO2、ZnO、SiO2Etc.), phosphates (e.g., AlPO)4Etc.) and other compounds (e.g., BiOF and AlF)3Etc.). However, the lithium battery anode material coated by the sprayed metal simple substance not only hinders the diffusion of lithium ions, but also reduces the activity of the surface of the material due to corrosion in the reduction process; the compounds such as metal oxide, phosphate and fluoride are electrochemical inert substances, the coating materials are mostly insulators or semiconductor materials, the electronic conductivity and/or the ionic conductivity are poor, and after the lithium battery anode material is coated, the resistance between the material and an electrolyte is increased, and the lithium ion is prevented from being inserted and extracted. In addition, although the coating material prevents the lithium battery positive electrode material from directly contacting with the electrolyte, the coating material has the problems of corroding the surface of the material, increasing the impedance, reducing the specific capacity and the like.
Disclosure of Invention
In order to solve the problems, the invention provides a secondary battery anode material and a secondary battery, wherein the secondary battery anode material has the characteristics of high electric capacity, high charge and discharge rate, long cycle life and high safety.
In order to achieve the purpose, the invention adopts the technical scheme that:
a secondary battery positive electrode material is prepared by the following method:
s1, mixing the lithium cobalt oxide, the lithium nickel oxide and the lithium manganese oxide, and then grinding to obtain mixed powder A;
s2, putting the mixed powder A into a tablet machine, and tabletting to prepare a sheet with the diameter of 20mm for later use;
s3, ultrasonically dispersing the silicon dioxide aerogel in deionized water to form a silicon dioxide aerogel suspension;
s4, adding a proper amount of graphene into the silicon dioxide aerogel suspension liquid under the ultrasonic dispersion treatment state, completely adsorbing, and drying until the water content is about 8% to obtain a spraying liquid B;
and S5, uniformly spraying the spraying liquid B on two surfaces of the sheet, drying, heating to 350-450 ℃, sintering for 3-5 h, and grinding the mixture to obtain the coating.
Further, the mass ratio of the lithium cobalt oxide, the lithium nickel oxide and the lithium manganese oxide is 1:1: 2.
Further, in the step S2, the thickness of the sheet is 100 to 200 μm.
Further, in the step S3, the power of ultrasonic dispersion is 900-1000W, and the mass of the deionized water is 6 times of that of the silica aerogel.
Further, in the step S4, the power of ultrasonic dispersion is 800-900W.
Further, the silica aerogel is hydrophilic silica aerogel.
Further, the mass ratio of the silica aerogel to the graphene is 5: 1.
further, the dosage of the graphene is 0.1% -8% of that of the mixed powder A.
The invention also provides a battery, and the secondary battery positive electrode material.
The invention has the following beneficial effects:
the anode material has larger specific surface area and abundant internal pore structures, and can effectively relieve the volume expansion effect of the anode material in the charge-discharge cycle process, so that the anode material has better electrochemical performance. The graphene is uniformly dispersed based on the silicon dioxide aerogel, the continuity of a lithium ion diffusion channel is guaranteed, meanwhile, the coating effect of the graphene and the silicon dioxide aerogel can also reduce the side reaction between electrolyte and the anode material, the structural attenuation of the anode material of the lithium ion battery and the formation of an SEI (solid electrolyte interphase) film are inhibited, and the cycle performance of the anode material is improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
A secondary battery positive electrode material is prepared by the following method:
s1, mixing the lithium cobalt oxide, the lithium nickel oxide and the lithium manganese oxide, and then grinding to obtain mixed powder A;
s2, putting the mixed powder A into a tablet machine, and tabletting to prepare a sheet with the diameter of 20mm for later use;
s3, ultrasonically dispersing the silicon dioxide aerogel in deionized water to form a silicon dioxide aerogel suspension;
s4, adding a proper amount of graphene into the silicon dioxide aerogel suspension liquid under the ultrasonic dispersion treatment state, completely adsorbing, and drying until the water content is about 8% to obtain a spraying liquid B;
and S5, uniformly spraying the spraying liquid B on two surfaces of the sheet, drying, heating to 350-450 ℃, sintering for 3-5 h, and grinding the mixture to obtain the coating.
In this embodiment, the mass ratio of the lithium cobalt oxide, the lithium nickel oxide, and the lithium manganese oxide is 1:1: 2.
In this embodiment, in step S2, the thickness of the sheet is 100 μm. In the step S3, the power of ultrasonic dispersion is 900W, and the mass of the deionized water is 6 times of that of the silica aerogel. In the step S4, the power of ultrasonic dispersion is 800W; the silicon dioxide aerogel is hydrophilic silicon dioxide aerogel; the mass ratio of the silicon dioxide aerogel to the graphene is 5: 1; the dosage of the graphene is 0.1% of that of the mixed powder A.
Example 2
A secondary battery positive electrode material is prepared by the following method:
s1, mixing the lithium cobalt oxide, the lithium nickel oxide and the lithium manganese oxide, and then grinding to obtain mixed powder A;
s2, putting the mixed powder A into a tablet machine, and tabletting to prepare a sheet with the diameter of 20mm for later use;
s3, ultrasonically dispersing the silicon dioxide aerogel in deionized water to form a silicon dioxide aerogel suspension;
s4, adding a proper amount of graphene into the silicon dioxide aerogel suspension liquid under the ultrasonic dispersion treatment state, completely adsorbing, and drying until the water content is about 8% to obtain a spraying liquid B;
and S5, uniformly spraying the spraying liquid B on two surfaces of the sheet, drying, heating to 350-450 ℃, sintering for 3-5 h, and grinding the mixture to obtain the coating.
In this embodiment, the mass ratio of the lithium cobalt oxide, the lithium nickel oxide, and the lithium manganese oxide is 1:1: 2.
In this embodiment, in the step S2, the thickness of the sheet is 100 to 200 μm. In the step S3, the power of ultrasonic dispersion is 1000W, and the mass of the deionized water is 6 times of that of the silica aerogel. In the step S4, the power of ultrasonic dispersion is 900W; the silicon dioxide aerogel is hydrophilic silicon dioxide aerogel; the mass ratio of the silicon dioxide aerogel to the graphene is 5: 1; the dosage of the graphene is 8% of that of the mixed powder A.
Example 3
A secondary battery positive electrode material is prepared by the following method:
s1, mixing the lithium cobalt oxide, the lithium nickel oxide and the lithium manganese oxide, and then grinding to obtain mixed powder A;
s2, putting the mixed powder A into a tablet machine, and tabletting to prepare a sheet with the diameter of 20mm for later use;
s3, ultrasonically dispersing the silicon dioxide aerogel in deionized water to form a silicon dioxide aerogel suspension;
s4, adding a proper amount of graphene into the silicon dioxide aerogel suspension liquid under the ultrasonic dispersion treatment state, completely adsorbing, and drying until the water content is about 8% to obtain a spraying liquid B;
and S5, uniformly spraying the spraying liquid B on two surfaces of the sheet, drying, heating to 350-450 ℃, sintering for 3-5 h, and grinding the mixture to obtain the coating.
In this embodiment, the mass ratio of the lithium cobalt oxide, the lithium nickel oxide, and the lithium manganese oxide is 1:1: 2.
In this embodiment, in step S2, the thickness of the sheet is 150 μm. In the step S3, the power of ultrasonic dispersion is 950W, and the mass of the deionized water is 6 times of that of the silica aerogel. In the step S4, the power of ultrasonic dispersion is 850W; the silicon dioxide aerogel is hydrophilic silicon dioxide aerogel; the mass ratio of the silicon dioxide aerogel to the graphene is 5: 1; the dosage of the graphene is 4% of that of the mixed powder A.
And (3) performance detection:
assembling the positive electrode materials obtained in example 1, example 2 and example 3 into a CR2032 button cell for electrochemical test; specifically, the positive electrode material, carbon black and polyvinylidene fluoride are mixed according to a specific gravity of 8:1:1, a proper amount of N-methyl pyrrolidone is added as a solvent, the mixture is ground for 45min and then coated on an aluminum sheet with the thickness of 1mm, the aluminum sheet is subjected to vacuum drying at 130 ℃ for 12 hours and then subjected to punching sheet pressing, the electrode sheet is compacted by adopting the pressure of 10MPa, and the pressure is maintained for 20s, so that the positive electrode sheet is prepared. Lithium metal sheet is used as a negative electrode material, Celgard2400 polypropylene is used as a diaphragm, and LiPF6Dissolution in EC: the 1M mixed solution of DMC (1: 1) is used as electrolyte, and the assembly of each component of the CR2032 button cell is completed in a glove box.
And (3) test results: the obtained positive electrode material is a core-shell composite material, under the condition of a current density of 200mA/g, the initial cycle discharge specific capacity is up to 1799.7mAh/g (example 1), 1867.9mAh/g (example 2) and 1859.7mAh/g (example 3), the charge specific capacity is up to 1397.6 mAh/g (example 1), 1431.7mAh/g (example 2) and 1417.9 mAh/g (example 3), the reversible specific capacity of the material can still be maintained at 1039 mAh/g (example 1), 1051mAh/g (example 2) and 1043mAh/g (example 3) after 100-cycle circulation, and the positive electrode material shows better charge-discharge cycle performance.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (9)
1. A secondary battery positive electrode material, characterized in that: the preparation method comprises the following steps:
s1, mixing the lithium cobalt oxide, the lithium nickel oxide and the lithium manganese oxide, and then grinding to obtain mixed powder A;
s2, putting the mixed powder A into a tablet machine, and tabletting to prepare a sheet with the diameter of 20mm for later use;
s3, ultrasonically dispersing the silicon dioxide aerogel in deionized water to form a silicon dioxide aerogel suspension;
s4, adding a proper amount of graphene into the silicon dioxide aerogel suspension liquid under the ultrasonic dispersion treatment state, and drying until the water content is 8% after complete adsorption to obtain a spraying liquid B;
and S5, uniformly spraying the spraying liquid B on two surfaces of the sheet, drying, heating to 350-450 ℃, sintering for 3-5 h, and grinding the mixture to obtain the coating.
2. A positive electrode material for a secondary battery according to claim 1, wherein: the mass ratio of the lithium cobalt oxide, the lithium nickel oxide and the lithium manganese oxide is 1:1: 2.
3. A positive electrode material for a secondary battery according to claim 1, wherein: in the step S2, the thickness of the sheet is 100 to 200 μm.
4. A positive electrode material for a secondary battery according to claim 1, wherein: in the step S3, the power of ultrasonic dispersion is 900-1000W, and the mass of the deionized water is 6 times of that of the silicon dioxide aerogel.
5. A positive electrode material for a secondary battery according to claim 1, wherein: in the step S4, the power of ultrasonic dispersion is 800-900W.
6. A positive electrode material for a secondary battery according to claim 1, wherein: the silica aerogel is hydrophilic silica aerogel.
7. A positive electrode material for a secondary battery according to claim 1, wherein: the mass ratio of the silicon dioxide aerogel to the graphene is 5: 1.
8. a positive electrode material for a secondary battery according to claim 1, wherein: the dosage of the graphene is 0.1% -8% of that of the mixed powder A.
9. A battery, characterized by: which comprises the positive electrode material for secondary batteries according to any one of claims 1 to 8.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114583148A (en) * | 2022-03-05 | 2022-06-03 | 青岛泰达华润新能源科技有限公司 | Preparation method of silicon oxide-based graphite composite negative electrode material for lithium ion battery |
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