CN108767245B - Mixed type anode material and manufacturing method thereof - Google Patents
Mixed type anode material and manufacturing method thereof Download PDFInfo
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- CN108767245B CN108767245B CN201810666780.1A CN201810666780A CN108767245B CN 108767245 B CN108767245 B CN 108767245B CN 201810666780 A CN201810666780 A CN 201810666780A CN 108767245 B CN108767245 B CN 108767245B
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/364—Composites as mixtures
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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
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Abstract
The invention discloses a mixed type anode material and a preparation method thereof, wherein the mixed type anode material comprises 73-85% of an active material, 3-18% of a conductive agent, 5-7% of an oxide and 5-12% of a binder; the active material comprises lithium cobaltate and lithium iron phosphate, the compacted density of the anode material is effectively improved after reasonably grinding and optimizing the oxide and the active material, the electrical conductivity, the thermal conductivity, the high-temperature storage performance, the cycle performance and the safety performance of the battery are obviously improved by adding a plurality of oxides, the service life of the anode material is greatly prolonged, and the cycle performance, the high-temperature storage and the safety performance under high voltage are solved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a mixed type cathode material and a manufacturing method thereof.
Background
At present, lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium iron phosphate are mainly used as the anode material of the lithium ion battery, wherein the lithium cobaltate is still the mainstream in the market, but the defects of limited cobalt resource, high price, toxic cobalt, poor safety and the like limit the large-scale application of the lithium cobaltate in the future. Lithium nickelate has higher actual capacity than lithium cobaltate, and nickel has lower price than cobalt, but lithium nickelate is difficult to prepare and has poor thermal stability. The lithium manganate has the advantages of rich raw materials, low price, environmental friendliness and good thermal stability, but has low capacity and poor cycle performance; lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate have high energy density but poor thermal stability; lithium iron phosphate is low in price, rich in resources, good in cycle performance, excellent in thermal stability and environment-friendly, but the materials are poor in conductivity and low in density, cannot meet the use requirements of people and restrict further application of the lithium iron phosphate in the field of lithium ion battery anode materials.
Disclosure of Invention
Aiming at the defects of the prior art, the capacity, the high-temperature storage performance, the cycle performance and the safety performance of the battery are improved, and the invention aims to provide a mixed type cathode material and a manufacturing method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the mixed type anode material comprises 73-85% of active material, 3-18% of conductive agent, 5-7% of oxide and 5-12% of binder; the active material comprises lithium cobaltate and lithium iron phosphate, and the molar ratio of the lithium cobaltate to the lithium iron phosphate is (1-11): (2-9).
The conductive agent comprises the following raw materials of 60-75 parts of graphene, 30-35 parts of activated carbon, 2-5 parts of monoethanolamine, 4-5 parts of polyvinylpyrrolidone, 8-10 parts of xanthan gum and 35-40 parts of styrene; the preparation method comprises the following steps: firstly, mixing xanthan gum and styrene, and uniformly mixing at the temperature of 40-45 ℃ to obtain an organic carrier; then adding other residual raw materials, heating to 50-55 deg.C, adjusting ph to neutral, and mechanically stirring; then mixing the mixture on a three-roll grinder, and grinding the slurry to 10-15 microns in granularity to obtain the finished product.
The oxide is a mixture of manganese oxide, ruthenium dioxide and gallium sesquioxide, and the mixing ratio of manganese oxide, ruthenium dioxide and gallium sesquioxide is 6-9:2-3: 4-6.
The binder is prepared by mixing sodium carboxymethylcellulose and sodium alginate according to a ratio of 8-10: 1.
The preparation method of the mixed type cathode material comprises the following steps:
(1) preparing an oxide: weighing each oxide according to the mixing proportion of manganese oxide, ruthenium dioxide and gallium sesquioxide, feeding the oxides into a rotary furnace for presintering, heating to 700-800 ℃ at room temperature for 1-2 hours, and preserving heat and mixing materials for 2-3 hours; taking out and cooling, then grinding for 8-10 hours by adopting a grinding medium as an acetone solution, and controlling the grain diameter of the mixture to be 50-100 mu m;
(2) preparation of active material: weighing raw materials according to the molar ratio of lithium cobaltate to lithium iron phosphate, and putting the weighed materials into a ball milling tank for ball milling for 1-2 hours at the ball milling rotation speed of 100-120 rpm;
(3) pouring the oxide obtained in the step (1) into the active material obtained in the step (2), uniformly stirring, pouring a conductive agent and a binder, and continuously stirring or ball-milling for at least 1.5h to prepare slurry;
(4) and (4) spraying or sputtering the slurry prepared in the step (3) on a current collector, and drying at the temperature of 80-105 ℃ to obtain the anode material.
And (3) adopting an absolute ethyl alcohol solution for ball milling in the step (2), and adding ferrocene which is 5-10% of the mass of the absolute ethyl alcohol into the absolute ethyl alcohol solution.
And after the slurry is prepared, sending the slurry into ultrasonic waves for dispersion treatment for 10-15min, wherein the power of the ultrasonic waves is 280-350W.
The invention has the beneficial effects that:
compared with the prior art, the invention has at least the following advantages: according to the invention, after the oxide and the active material are reasonably ground and optimized, the compaction density of the anode material is effectively improved, and by adding a plurality of oxides, the electrical conductivity, the thermal conductivity, the high-temperature storage performance, the cycle performance and the safety performance of the battery are obviously improved, the service life of the anode material is greatly prolonged, and the cycle performance, the high-temperature storage and the safety performance under high voltage are solved.
According to the invention, the graphene and the activated carbon are introduced into the conductive agent, and the excellent conductivity of the graphene and the activated carbon is utilized, so that the capacity of an electrode material is improved, the internal resistance of the battery is reduced, the conductivity of the conductive agent is improved, and meanwhile, the cycle life of the battery is also prolonged.
Detailed Description
Example 1: the mixed type anode material comprises 76% of active material, 10% of conductive agent, 6% of oxide and 8% of binder; the active material comprises lithium cobaltate and lithium iron phosphate, and the molar ratio of the lithium cobaltate to the lithium iron phosphate is 5: 8.
the conductive agent comprises the following raw materials of 65g of graphene, 32g of activated carbon, 3g of monoethanolamine, 5g of polyvinylpyrrolidone, 8g of xanthan gum and 35g of styrene; the preparation method comprises the following steps: firstly, mixing xanthan gum and styrene, and uniformly mixing at the temperature of 40-45 ℃ to obtain an organic carrier; then adding other residual raw materials, heating to 50-55 deg.C, adjusting ph to neutral, and mechanically stirring; then mixing the materials on a three-roll grinder, and grinding the slurry to 15 microns in granularity to obtain the finished product.
The oxide is a mixture of manganese oxide, ruthenium dioxide and gallium sesquioxide, and the mixing ratio of manganese oxide, ruthenium dioxide and gallium sesquioxide is 7:2: 5.
The binder is prepared by mixing sodium carboxymethylcellulose and sodium alginate according to a ratio of 10: 1.
The preparation method of the mixed type cathode material comprises the following steps:
(1) preparing an oxide: weighing each oxide according to the mixing proportion of manganese oxide, ruthenium dioxide and gallium sesquioxide, feeding the oxides into a rotary furnace for presintering, heating to 750 ℃ at room temperature for 1.5 hours, and mixing the materials for 2-3 hours under heat preservation; taking out and cooling, then grinding for 10 hours by using a grinding medium as an acetone solution, and controlling the grain diameter of the mixture to be 100 mu m;
(2) preparation of active material: weighing raw materials according to the molar ratio of lithium cobaltate to lithium iron phosphate, putting the weighed materials into a ball milling tank for ball milling for 1.5 hours, wherein the ball milling rotating speed is 100rpm, and the ball milling adopts absolute ethyl alcohol solution, and ferrocene with the mass equivalent to 8% of the absolute ethyl alcohol is added into the absolute ethyl alcohol solution;
(3) pouring the oxide obtained in the step (1) into the active material obtained in the step (2), uniformly stirring, then pouring a conductive agent and a binder, continuously stirring or ball-milling for at least 1.5h to prepare slurry, and then sending the slurry into ultrasonic waves for dispersion treatment for 12min, wherein the power of the ultrasonic waves is 300W;
(4) and (4) spraying or sputtering the slurry prepared in the step (3) on a current collector, and drying at the temperature of 100 ℃ to obtain the cathode material.
Example 2: in this example, except for the positive electrode active material, lithium cobaltate and lithium iron phosphate are used in a molar ratio of 1: except for 9, the contents are the same as those of example 1.
Example 3: in this example, except that the positive electrode active material used was lithium cobaltate and lithium iron phosphate at a molar ratio of 11: except for 2, the contents are the same as those of example 1.
The test of this example 1 compares with the traditional battery:
when the working voltage is high (2.75V-4.2V), the conductivity and the high-temperature storage performance of the cathode material are superior to those of the traditional battery; the compacted density of the cathode material is between 2.5 and 3.2g/cc, and the safety of the cathode material takes the characteristics of the traditional battery, especially the overcharge resistance.
Claims (5)
1. The preparation method of the mixed type anode material is characterized in that the mixed type anode material comprises 73-85% of active material, 3-18% of conductive agent, 5-7% of oxide and 5-12% of binder; the active material comprises lithium cobaltate and lithium iron phosphate, and the molar ratio of the lithium cobaltate to the lithium iron phosphate is (1-11): (2-9);
the conductive agent comprises the following raw materials of 60-75 parts of graphene, 30-35 parts of activated carbon, 2-5 parts of monoethanolamine, 4-5 parts of polyvinylpyrrolidone, 8-10 parts of xanthan gum and 35-40 parts of styrene; the preparation method comprises the following steps: firstly, mixing xanthan gum and styrene, and uniformly mixing at the temperature of 40-45 ℃ to obtain an organic carrier; then adding other residual raw materials, heating to 50-55 deg.C, adjusting ph to neutral, and mechanically stirring; then mixing the materials on a three-roll grinder, and grinding the slurry to 10-15 microns in granularity to obtain a finished product;
the manufacturing method comprises the following steps:
(1) preparing an oxide: weighing each oxide according to the mixing proportion of manganese oxide, ruthenium dioxide and gallium sesquioxide, and feeding the oxides into a rotary furnace for presintering, wherein the presintering is to heat up to 700-; taking out and cooling, then grinding for 8-10 hours by adopting a grinding medium as an acetone solution, and controlling the grain diameter of the mixture to be 50-100 mu m;
(2) preparation of active material: weighing raw materials according to the molar ratio of lithium cobaltate to lithium iron phosphate, and putting the weighed materials into a ball milling tank for ball milling for 1-2 hours at the ball milling rotation speed of 100-120 rpm;
(3) pouring the oxide obtained in the step (1) into the active material obtained in the step (2), uniformly stirring, pouring a conductive agent and a binder, and continuously stirring or ball-milling for at least 1.5h to prepare slurry;
(4) and (4) spraying or sputtering the slurry prepared in the step (3) on a current collector, and drying at the temperature of 80-105 ℃ to obtain the anode material.
2. The method for manufacturing the mixed type cathode material according to claim 1, wherein the ball milling in the step (2) adopts an absolute ethyl alcohol solution, and ferrocene with the mass equivalent to 5% -10% of that of the absolute ethyl alcohol is added into the absolute ethyl alcohol solution.
3. The method as claimed in claim 1, wherein the slurry is prepared and then dispersed in ultrasonic wave for 10-15min, and the power of the ultrasonic wave is 280-350W.
4. The method for manufacturing the hybrid cathode material as claimed in claim 1, wherein the oxide is a mixture of manganese oxide, ruthenium dioxide and gallium sesquioxide, and the mixing ratio of manganese oxide, ruthenium dioxide and gallium sesquioxide is 6-9:2-3: 4-6.
5. The method for preparing the hybrid cathode material as claimed in claim 1, wherein the binder is prepared by mixing sodium carboxymethylcellulose and sodium alginate according to a ratio of 8-10: 1.
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| CN108767245B true CN108767245B (en) | 2021-07-02 |
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| US20130252105A1 (en) * | 2012-03-23 | 2013-09-26 | Samsung Corning Precision Materials Co., Ltd. | Positive electrode active material, method of preparing positive electrode active material, and lithium secondary battery using positive electrode active material |
| CN105390700A (en) * | 2015-11-16 | 2016-03-09 | 哈尔滨工业大学 | Method for modifying positive electrode of lithium ion battery by adding metal oxide/carbon composite material |
| CN106340640A (en) * | 2016-11-01 | 2017-01-18 | 上海电力学院 | Method for improving high temperature electrochemical property of lithium manganate anode material |
| CN107528054A (en) * | 2017-08-27 | 2017-12-29 | 长沙小新新能源科技有限公司 | A kind of graphene high power lithium battery anode composite slurry and preparation method thereof |
| CN107611402A (en) * | 2017-09-13 | 2018-01-19 | 天津理工大学 | Compound lithium-rich positive electrode and preparation method thereof |
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