CN103715421A - Preparation method of high voltage lithium cobalt oxide anode material - Google Patents
Preparation method of high voltage lithium cobalt oxide anode material Download PDFInfo
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- CN103715421A CN103715421A CN201310695699.3A CN201310695699A CN103715421A CN 103715421 A CN103715421 A CN 103715421A CN 201310695699 A CN201310695699 A CN 201310695699A CN 103715421 A CN103715421 A CN 103715421A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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 relates to a preparation method of a high voltage lithium cobalt oxide anode material. The method comprises the following steps of a, mixing and sintering battery-level cobaltosic oxide, lithium carbonate and nanometer magnesia according to the mole ratio Li/Co=1.07 and Mg/Co=0.026, and preparing a primary intermediate product A; b, mixing and sintering the battery-level cobaltosic oxide, the lithium carbonate and nanometer magnesia according to the mole ratio Li/Co=1.002, Mg/Co=0.026, and Zn/Co=0.005, and preparing a primary intermediate product B; c, mixing the intermediate products A and B, mixing and sintering a mixed product and nanometer titania, and preparing a secondary intermediate product; d, preparing a suspension liquid from the secondary intermediate product, adding a magnesium acetate alcoholic solution into the suspension liquid, adding an aluminium isopropoxide methylbenzene solution into the suspension liquid, and drying the mixture to prepare a three-time intermediate product; and e, sintering the three-time intermediate product to obtain the final product. The preparation method provided by the invention has the advantages that a special technology is utilized to coat with a lithium cobalt oxide material, the compatibility of the material on electrolyte is improved, and the battery capacity and the cycling property of the lithium cobalt oxide material are effectively improved.
Description
Technical field
The present invention relates to the manufacturing technology of anode material of lithium battery, specifically a kind of preparation method of high voltage lithium cobaltate cathode material.
Background technology
Cobalt acid lithium material is conventionally only for the lithium battery below 4.35V traditionally, if overtension,, because the compatibility of electrode and electrolyte is bad, electrolyte decomposition is serious, causes the defects such as circulating battery is poor.
Summary of the invention
Technical problem to be solved by this invention is, provide a kind of 4.45V of can be used in lithium battery, with the preparation method of the high voltage lithium cobaltate cathode material that compatibility of electrolyte is good, battery capacity is high, cyclicity is good.
The preparation method of high voltage lithium cobaltate cathode material of the present invention comprises the following steps:
A. product A in the middle of preparing once;
By battery-grade cobaltosic oxide, lithium carbonate, nano magnesia, Li/Co=1.07, Mg/Co=0.026 ratio are mixed in molar ratio; Mixed material is placed in air atmosphere sintering furnace, first at 550-600 ℃ of pre-burning 4-5h, lower the temperature with stove after burning 10-20h at 900-1000 ℃; Sintered product is pulverized, made once middle product A;
B. product B in the middle of preparing once; By battery-grade cobaltosic oxide, lithium carbonate, nano magnesia, Li/Co=1.002, Mg/Co=0.026, Zn/Co=0.005 ratio are mixed in molar ratio; Mixed material is placed in air atmosphere sintering furnace, first at 550-600 ℃ of pre-burning 4-5h, lower the temperature with stove after burning 10-20h at 900-980 ℃; Sintered product is pulverized, made once middle product B;
C. prepare the middle product of secondary; By middle product A and B in mass ratio 1:1～9:1 mix, by melange and nano titanium oxide in molar ratio the ratio of 1:0.005 mix; The material mixing is placed in air atmosphere sintering furnace, between 700-1000 ℃, after insulation 5-10h, with stove, lowers the temperature; Sintered product is pulverized, made the middle product of secondary;
D. three middle product preparations; By product in the middle of secondary with the alcohol of mass concentration 95% in mass ratio for the proportional arrangement of 1:1 becomes suspension; Under the state constantly stirring, the magnesium acetate alcoholic solution that is 10% by mass concentration joins in above-mentioned suspension; At 45-50 ℃, stir after 1-1.5h, the aluminium isopropoxide toluene solution that is 0.1mol/L by concentration joins in this suspension, mixes after 1-1.5h, and mixture dry 10-12h at 110-120 ℃ is made to middle product three times;
E. finished product sintering; Three middle product are placed in air atmosphere sintering furnace and are incubated 5-6h at 580-600 ℃, obtain end product.
The present invention, by special process is coated cobalt acid lithium material, has improved the compatibility of material to electrolyte, has effectively improved battery capacity and the cycle performance of cobalt acid lithium material.
Embodiment
The method of the embodiment of the present invention comprises the following steps:
A. product A in the middle of preparing once;
By battery-grade cobaltosic oxide, lithium carbonate, nano magnesia in molar ratio Li/Co=1.07, Mg/Co=0.026 ratio through three-dimensional mixer, mix, hybrid frequency is that 35Hz, incorporation time are 3-6h; Mixed material is placed in air atmosphere sintering furnace, first at 600 ℃ of pre-burning 5h, lower the temperature with stove after burning 15h at 1000 ℃; Sintered product is pulverized, crossed 200 mesh sieves and make once middle product A;
B. product B in the middle of preparing once; By battery-grade cobaltosic oxide, lithium carbonate, nano magnesia in molar ratio Li/Co=1.002, Mg/Co=0.026, Zn/Co=0.005 ratio through three-dimensional mixer, mix, hybrid frequency is that 35Hz, incorporation time are 5h; Mixed material is placed in air atmosphere sintering furnace, first at 600 ℃ of pre-burning 5h, lower the temperature with stove after burning 20h at 980 ℃; Sintered product is pulverized, crossed 200 mesh sieves and make once middle product B;
C. prepare the middle product of secondary; By middle product A and B in mass ratio 1:1～9:1 mix, by melange and nano titanium oxide in molar ratio the ratio of 1:0.005 through three-dimensional mixer, mix, hybrid frequency is that 35Hz, incorporation time are 5h; The material mixing is placed in air atmosphere sintering furnace, between 700-1000 ℃, after insulation 10h, with stove, lowers the temperature; Sintered product is pulverized, crossed 200 mesh sieves and make the middle product of secondary;
D. three middle product preparations; By product in the middle of secondary with the alcohol of mass concentration 95% in mass ratio for the proportional arrangement of 1:1 becomes suspension; Under the state constantly stirring, the magnesium acetate alcoholic solution that is 10% by mass concentration joins in above-mentioned suspension; At 50 ℃, stir after 1h, the aluminium isopropoxide toluene solution that is 0.1mol/L by concentration joins in this suspension, mixes after 1h, and mixture dry 10h at 120 ℃ is made to middle product three times;
E. finished product sintering; Three middle product are placed in air atmosphere sintering furnace and are incubated 5h at 600 ℃, obtain end product.The amount that in end product, in coating layer, the amount of Mg is 0.5～3%, Al is 0.25～2%.
The testing result of the end product that the embodiment of the present invention makes is as follows:
The full battery high-temperature test data of table 1
The full battery high-temperature test data of table 2
The full circulating battery test data of table 3
Claims (1)
1. a preparation method for high voltage lithium cobaltate cathode material, is characterized in that: comprises the following steps,
A. product A in the middle of preparing once;
By battery-grade cobaltosic oxide, lithium carbonate, nano magnesia, Li/Co=1.07, Mg/Co=0.026 ratio are mixed in molar ratio; Mixed material is placed in air atmosphere sintering furnace, first at 550-600 ℃ of pre-burning 4-5h, lower the temperature with stove after burning 10-20h at 900-1000 ℃; Sintered product is pulverized, made once middle product A;
B. product B in the middle of preparing once; By battery-grade cobaltosic oxide, lithium carbonate, nano magnesia, Li/Co=1.002, Mg/Co=0.026, Zn/Co=0.005 ratio are mixed in molar ratio; Mixed material is placed in air atmosphere sintering furnace, first at 550-600 ℃ of pre-burning 4-5h, lower the temperature with stove after burning 10-20h at 900-980 ℃; Sintered product is pulverized, made once middle product B;
C. prepare the middle product of secondary; By middle product A and B in mass ratio 1:1 ~ 9:1 mix, by melange and nano titanium oxide in molar ratio the ratio of 1:0.005 mix; The material mixing is placed in air atmosphere sintering furnace, between 700-1000 ℃, after insulation 5-10h, with stove, lowers the temperature; Sintered product is pulverized, made the middle product of secondary;
D. three middle product preparations; By product in the middle of secondary with the alcohol of mass concentration 95% in mass ratio for the proportional arrangement of 1:1 becomes suspension; Under the state constantly stirring, the magnesium acetate alcoholic solution that is 10% by mass concentration joins in above-mentioned suspension; At 45-50 ℃, stir after 1-1.5h, the aluminium isopropoxide toluene solution that is 0.1mol/L by concentration joins in this suspension, mixes after 1-1.5h, and mixture dry 10-12h at 110-120 ℃ is made to middle product three times;
E. finished product sintering; Three middle product are placed in air atmosphere sintering furnace and are incubated 5-6h at 580-600 ℃, obtain end product.
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| CN201310695699.3A CN103715421A (en) | 2013-12-18 | 2013-12-18 | Preparation method of high voltage lithium cobalt oxide anode material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319418A (en) * | 2014-10-24 | 2015-01-28 | 东莞锂威能源科技有限公司 | High capacity lithium ion battery |
| CN105449264A (en) * | 2015-03-24 | 2016-03-30 | 万向A一二三系统有限公司 | High-voltage lithium cobalt oxide/lithium titanate battery and preparation method thereof |
| CN106505194A (en) * | 2016-12-19 | 2017-03-15 | 惠州Tcl金能电池有限公司 | Modified cobalt acid lithium and preparation method thereof, lithium ion battery and its chemical synthesizing method |
| CN109994711A (en) * | 2017-12-29 | 2019-07-09 | 格林美（无锡）能源材料有限公司 | A kind of preparation method of doping and the lithium cobaltate cathode material coated |
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| US20070224506A1 (en) * | 2006-03-24 | 2007-09-27 | Sony Corporation | Cathode active material, method of manufacturing the same, and battery |
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| CN106505194A (en) * | 2016-12-19 | 2017-03-15 | 惠州Tcl金能电池有限公司 | Modified cobalt acid lithium and preparation method thereof, lithium ion battery and its chemical synthesizing method |
| CN109994711A (en) * | 2017-12-29 | 2019-07-09 | 格林美（无锡）能源材料有限公司 | A kind of preparation method of doping and the lithium cobaltate cathode material coated |
| CN109994711B (en) * | 2017-12-29 | 2021-03-23 | 格林美（江苏）钴业股份有限公司 | Preparation method of doped and coated lithium cobaltate positive electrode material |
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