CN108400309B - Method for preparing modified high-voltage single crystal ternary positive electrode material by composite coating - Google Patents
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Abstract
The invention discloses a method for preparing a modified high-voltage single crystal ternary cathode material by composite coating, and belongs to the technical field of electrochemistry. The problems of poor coating uniformity, poor conductivity and electrical property in the prior art are solved, and the method comprises the following steps: adding lithium salt and hydroxide precursor into a ball mill, mixing for 5-8h, and sintering to obtain a single crystal coated substrate; adding the single crystal coated substrate and deionized water into a stirring tank, adding soluble phosphate and soluble aluminum salt into the stirring tank, dissolving lithium hydroxide in the deionized water, adding the solution into the stirring tank, stirring for 1-2h, and performing suction filtration and dehydration to obtain an initially coated high-voltage single crystal ternary cathode material; and (3) carrying out heat treatment on the initially coated high-voltage single crystal ternary positive electrode material at the temperature of 500-850 ℃ for 4-10h to obtain the composite coated high-voltage single crystal ternary positive electrode material. The invention can be used for coating and preparing the high-voltage single crystal ternary anode material.
Description
Technical Field
The invention relates to a method for preparing a modified high-voltage single crystal ternary cathode material by composite coating, belonging to the technical field of electrochemistry.
Background
At present, the energy density of the mainstream high-voltage ternary cathode material is improved mainly by preparing a single-crystal ternary material and combining a coating process, but most of the materials are coated with oxides (Al2O3, ZrO2, TiO2 and the like) by a dry method or a wet method, and the defects that the coating is not uniform and the oxides containing Li cannot be generated by all the coating materials are influenced; and the conventional wet coating process can generate sewage which can be discharged after reaching the standard after sewage treatment, thereby increasing the manufacturing cost of materials.
Disclosure of Invention
The invention aims to provide a method for preparing a modified high-voltage single crystal ternary cathode material by composite coating, and the prepared high-voltage single crystal ternary cathode material has long cycle life and high rate capability.
The method for preparing the modified high-voltage single crystal ternary cathode material by composite coating comprises the following steps:
(1) adding lithium salt and hydroxide precursor into a ball mill according to the mol ratio of 1.02-1.18:1, adding polyurethane balls, mixing for 5-8h, and sintering to obtain monocrystal coated matrix LiαNi1-xCoxMnyO2；
(2) According to the mass ratio of 1: 1-15 ratio coating single crystal with matrix LiαNi1-xCoxMnyO2Adding deionized water into a stirring tank, adding soluble phosphate and soluble aluminum salt into the stirring tank, dissolving lithium hydroxide by the deionized water, adding the solution into the stirring tank, stirring for 1-2h, and performing suction filtration and dehydration to obtain an initially-coated high-voltage single crystal ternary cathode material;
(3) the initially coated high-voltage single crystal ternary anode material is subjected to heat treatment for 4-10h at the temperature of 500-850 ℃ to obtain the composite coated high-voltage single crystal ternary anode materialLiαNi1-xCoxMnyO2/Mz。
Further, the sintering process in the step (1) comprises the following specific steps:
heating to 650 ℃ at the speed of 2-10 ℃/min, heating to 800 ℃ at the speed of 1-2 ℃/min, then preserving heat for 5-10h, heating to 1050 ℃ at 950 ℃ for 1-12h, and finally cooling to room temperature at the speed of 100 ℃/h.
Further, the single crystal coated matrix Li of the step (1)αNi1-xCoxMnyO2Wherein alpha is more than or equal to 1.02 and less than or equal to 1.08, x is more than or equal to 0.1 and less than or equal to 0.35, and y is more than or equal to 0.1 and less than or equal to 0.35.
Further, the lithium salt in the step (1) is one or more of lithium hydroxide, lithium carbonate and lithium nitrate.
Further, the total amount of the soluble phosphate and the soluble aluminum salt added in the step (2) is the same as that of the single-crystal-coated base LiαNi1-xCoxMnyO2The molar ratio of (A) to (B) is 0.0001-0.1: 1.
Further, the molar ratio of the added amount of the lithium hydroxide to the total amount of the soluble phosphate and the soluble aluminum salt in the step (2) is 1-13: 1.
Further, the soluble phosphate in the step (2) is one or more of aluminum dihydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate and potassium phosphate; the soluble aluminum salt is one or more of aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum dihydrogen phosphate and aluminum phosphate.
Further, the soluble aluminum salt in the step (2) is aluminum phosphate, zirconium balls with the diameter of 0.1-0.4mm are used for sanding for 1-2h at the rotating speed of 2000-3000r/min, and the granularity of the aluminum phosphate is sanded to D50 of 10-100 nm.
Further, the coating substance of the initially coated high-voltage single crystal ternary cathode material in the step (2) is Al (OH)3And Li3PO4A mixture of (a).
Further, the surface coating substance of the composite coated high-voltage single crystal ternary cathode material in the step (3) is LiAlO2、Li3PO4And LiAlP2O7。
Compared with the prior art, the invention has the beneficial effects that:
the high-voltage single crystal ternary cathode material prepared by the method disclosed by the invention is more uniform in surface coating, does not generate wastewater, is pollution-free and can realize zero emission. The final cladding material of the high-voltage single crystal ternary anode material for the lithium ion battery provided by the invention is LiAlO2、Li3PO4、LiAlP2O7The coating not only avoids the corrosion of electrolyte to the coating matrix and reduces the side reaction of HF and materials, but also has the synergistic effect of the surface coating which is a plurality of oxides containing Li, thereby effectively improving the Li of the material interface+The diffusion property, thereby improving the cycling stability and rate capability of the material under high voltage.
Drawings
FIG. 1 is a scanning electron micrograph of a single crystal type ternary positive electrode material prepared according to example 1 of the present invention;
FIG. 2-1 is a scanning electron microscope image of the composite coated single crystal ternary positive electrode material prepared in example 1 of the present invention;
FIG. 2-2 is a scanning electron microscope image of the composite coated single crystal ternary positive electrode material prepared in example 1 of the present invention;
FIG. 3 is a graph of the cycle performance of a composite coated single crystal ternary positive electrode material prepared in example 1 of the present invention;
FIG. 4 is a graph of rate capability of composite coated single crystal ternary positive electrode material prepared in example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The method for preparing the modified high-voltage single crystal ternary cathode material by composite coating comprises the following steps:
(1) lithium carbonate, lithium nitrate and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.5Co0.2Mn0.3(OH)2) Adding the mixture according to a molar ratio of 1.15:1To a ball mill and adding polyurethane balls, wherein m (mixing balls): m (to be mixed) is 2:1, after mixing for 6h, the temperature is raised to 650 ℃ at the speed of 5 ℃/min, then the temperature is raised to 780 ℃ at the speed of 2 ℃/min, the temperature is kept for 8h, then the temperature is raised to 1050 ℃ and the temperature is kept for 8h, finally the temperature is lowered to room temperature at the speed of 100 ℃/h, and the sintered material block is crushed and sieved to obtain the monocrystal coated substrate LiαNi1-xCoxMnyO2Wherein alpha is more than or equal to 1.02 and less than or equal to 1.08, x is more than or equal to 0.1 and less than or equal to 0.35, and y is more than or equal to 0.1 and less than or equal to 0.35;
(2) according to the mass ratio of 1: 1-15 ratio coating single crystal with matrix LiαNi1-xCoxMnyO2And deionized water to a stirred tank, and Al (H) to the stirred tank2PO4)3，Al(H2PO4)3In an amount corresponding to the amount of the single crystal-coated base LiαNi1- xCoxMnyO2The molar ratio of the lithium hydroxide to the sodium hydroxide is 0.0034:1, the lithium hydroxide is dissolved by deionized water, added into a stirring tank and stirred for 2 hours, and is filtered and dehydrated to obtain a coating substance Al (OH)3And Li3PO4The initial coated high voltage single crystal ternary positive electrode material of (1), wherein the added amount of lithium hydroxide and Al (H)2PO4)3Is 9: 1;
(3) drying the initially coated high-voltage single crystal ternary positive electrode material, then carrying out heat treatment at 850 ℃ for 7h, cooling and sieving to obtain a surface coating substance LiAlO2、Li3PO4And LiAlP2O7The composite coated high-voltage single crystal ternary positive electrode material LiαNi1-xCoxMnyO2/Mz。
Comparative example 1
(1) Lithium carbonate, lithium nitrate and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.5Co0.2Mn0.3(OH)2) Adding into a ball mill according to a molar ratio of 1.15:1, and adding polyurethane balls, wherein m (mixing balls): m (to be mixed) is 2:1, after mixing for 6h, the temperature is raised to 650 ℃ at the speed of 5 ℃/min, then the temperature is raised to 780 ℃ at the speed of 2 ℃/min, the temperature is kept for 8h, and the temperature is raised to 780 DEG CKeeping the temperature at 1050 ℃ for 8h, finally cooling to room temperature at the speed of 100 ℃/h, and crushing and sieving a sintered material block to obtain a single crystal coated substrate;
according to the mass ratio of 1: 1-15 ratio coating single crystal with matrix LiαNi1-xCoxMnyO2And deionized water is added into a stirring tank, nano alumina powder is added into the stirring tank, and the molar ratio n (Al) of the added nano alumina powder to the monocrystal coated matrix2O3) N (single crystal ternary) is 0.0017: 1; finally stirring for 1 h; removing the filtrate water by using a filter flask; and drying in a blast drying oven at 120 ℃; sintering the dried material in a roller kiln, and keeping the temperature at 850 ℃ for 7 h; and cooling and sieving to obtain the ternary cathode material coated with the aluminum oxide.
The materials in example 1 and comparative example 1 were subjected to powder resistivity test, rate capability test and high temperature cycle performance test.
The powder resistance was measured using a four-electrode powder resistance meter, and the powder resistivity was measured at different pressures as shown in table 1, and the experiment demonstrated that the powder resistivity was significantly reduced after composite coating.
TABLE 1
Cycle performance (fig. 3) and rate performance (fig. 4) tests a 2032-type power-down test was used, in which the proportions of the positive electrode material were: active substance: and (2) performing composite coating on the SP (polyvinylidene fluoride) with the ratio of 90:5:5 by adopting a ceramic diaphragm and a metal lithium sheet as a negative electrode, wherein the charge-discharge voltage is 3.0-4.5V, so that the cycle performance is obviously improved, and the rate performance is improved.
Example 2
The method for preparing the modified high-voltage single crystal ternary cathode material by composite coating comprises the following steps:
(1) lithium carbonate, lithium nitrate and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.5Co0.2Mn0.3(OH)2) Adding the mixture into a ball mill according to the mol ratio of 1.10:1, and adding polyurethane balls, wherein m (mixing balls)): m (to be mixed) is 2:1, after mixing for 7h, the temperature is raised to 650 ℃ at the speed of 6 ℃/min, then the temperature is raised to 770 ℃ at the speed of 1.5 ℃/min, the temperature is kept for 8h, then the temperature is raised to 1000 ℃ and the temperature is kept for 5h, finally the temperature is lowered to room temperature at the speed of 100 ℃/h, and the sintered material block is crushed and sieved to obtain the single crystal coated substrate LiαNi1-xCoxMnyO2Wherein alpha is more than or equal to 1.02 and less than or equal to 1.08, x is more than or equal to 0.1 and less than or equal to 0.35, and y is more than or equal to 0.1 and less than or equal to 0.35;
(2) according to the mass ratio of 1: 1-15 ratio coating single crystal with matrix LiαNi1-xCoxMnyO2And deionized water is added into a stirring tank, ammonium dihydrogen phosphate and aluminum nitrate are added into the stirring tank, and the total adding amount of soluble phosphate and soluble aluminum salt and the monocrystal coated matrix LiαNi1-xCoxMnyO2Is 0.0136: 1, dissolving lithium hydroxide by using deionized water, adding the solution into a stirring tank, stirring for 1.5h, and carrying out suction filtration and dehydration to obtain a coating substance Al (OH)3And Li3PO4The initially coated high voltage single crystal ternary positive electrode material of (1), wherein the molar ratio of the added amount of lithium hydroxide to the total amount of soluble phosphate and soluble aluminum salt is 3: 1;
(3) drying the initially coated high-voltage single crystal ternary positive electrode material, then carrying out heat treatment at 700 ℃ for 6h, cooling and sieving to obtain a surface coating substance LiAlO2、Li3PO4And LiAlP2O7The composite coated high-voltage single crystal ternary positive electrode material LiαNi1-xCoxMnyO2/Mz。
Example 3
The method for preparing the modified high-voltage single crystal ternary cathode material by composite coating comprises the following steps:
(1) lithium hydroxide, lithium nitrate and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.5Co0.2Mn0.3(OH)2) Adding into a ball mill according to a molar ratio of 1.02:1, and adding polyurethane balls, wherein m (mixing balls): m (to be mixed) is 2:1, after mixing for 5h, the temperature is raised to 650 ℃ at the speed of 2 ℃/min, and then the temperature is raised to 1 DEG CHeating to 750 deg.C at a speed of/min, maintaining the temperature for 5h, heating to 950 deg.C, maintaining the temperature for 1h, cooling to room temperature at a speed of 100 deg.C/h, pulverizing sintered material block, and sieving to obtain single crystal coated matrix LiαNi1-xCoxMnyO2Wherein alpha is more than or equal to 1.02 and less than or equal to 1.08, x is more than or equal to 0.1 and less than or equal to 0.35, and y is more than or equal to 0.1 and less than or equal to 0.35;
(2) according to the mass ratio of 1:1 ratio coating single crystal with matrix LiαNi1-xCoxMnyO2And deionized water is added into a stirring tank, ammonium dihydrogen phosphate, potassium phosphate and aluminum nitrate are added into the stirring tank, and the total adding amount of soluble phosphate and soluble aluminum salt and the monocrystal coated matrix LiαNi1-xCoxMnyO2The molar ratio of the lithium hydroxide is 0.0102:1, the lithium hydroxide is dissolved by deionized water and then added into a stirring tank to be stirred for 1h, and the coating substance Al (OH) is obtained after suction filtration and dehydration3And Li3PO4The initially coated high voltage single crystal ternary positive electrode material of (1), wherein the molar ratio of the added amount of lithium hydroxide to the total amount of the soluble phosphate and the soluble aluminum salt is 2: 1;
(3) drying the initially coated high-voltage single crystal ternary positive electrode material, then carrying out heat treatment at 500 ℃ for 4h, cooling and sieving to obtain a surface coating substance LiAlO2、Li3PO4And LiAlP2O7The composite coated high-voltage single crystal ternary positive electrode material LiαNi1-xCoxMnyO2/Mz。
Example 4
The method for preparing the modified high-voltage single crystal ternary cathode material by composite coating comprises the following steps:
(1) lithium nitrate and nickel cobalt manganese hydroxide precursor (chemical formula Ni)0.5Co0.2Mn0.3(OH)2) Adding into a ball mill according to a molar ratio of 1.18:1, and adding polyurethane balls, wherein m (mixing balls): m (to be mixed) is 2:1, after mixing for 8h, the temperature is raised to 650 ℃ at the speed of 10 ℃/min, then the temperature is raised to 800 ℃ at the speed of 2 ℃/min, the temperature is kept for 10h, then the temperature is raised to 1050 ℃ and the temperature is kept for 12h, and finally the speed of 100 ℃/h is usedCooling to room temperature, crushing and sieving the sintered material block to obtain the monocrystal coated matrix LiαNi1-xCoxMnyO2Wherein alpha is more than or equal to 1.02 and less than or equal to 1.08, x is more than or equal to 0.1 and less than or equal to 0.35, and y is more than or equal to 0.1 and less than or equal to 0.35;
(2) according to the mass ratio of 1: 15 ratio of coating single crystal with matrix LiαNi1-xCoxMnyO2And deionized water is added into the stirring tank, and sodium phosphate, potassium phosphate and aluminum nitrate are added into the stirring tank, and the total amount of the soluble phosphate and the soluble aluminum salt is added with the monocrystal coated matrix LiαNi1-xCoxMnyO2The molar ratio of the lithium hydroxide to the sodium hydroxide is 0.0068:1, the lithium hydroxide is dissolved by deionized water, added into a stirring tank and stirred for 2 hours, and is filtered and dehydrated to obtain a coating substance Al (OH)3And Li3PO4The initially coated high voltage single crystal ternary positive electrode material of (1), wherein the molar ratio of the added amount of lithium hydroxide to the total amount of soluble phosphate and soluble aluminum salt is 3: 1; before using the aluminum phosphate, sanding for 1-2h by using a zirconium ball with the diameter of 0.1-0.4mm at the rotating speed of 2000-3000r/min until the granularity of the aluminum phosphate is sanded to D50 of 10-100 nm;
(3) drying the initially coated high-voltage single crystal ternary positive electrode material, then carrying out heat treatment for 10h at 850 ℃, cooling and sieving to obtain a surface coating substance LiAlO2、Li3PO4And LiAlP2O7The composite coated high-voltage single crystal ternary positive electrode material LiαNi1-xCoxMnyO2/Mz。
Claims (8)
1. A method for preparing a modified high-voltage single crystal ternary cathode material by composite coating is characterized by comprising the following steps:
(1) adding lithium salt and hydroxide precursor into a ball mill according to the mol ratio of 1.02-1.18:1, adding polyurethane balls, mixing for 5-8h, and sintering to obtain monocrystal coated matrix LiαNi1-xCoxMnyO2Wherein alpha is more than or equal to 1.02 and less than or equal to 1.08, x is more than or equal to 0.1 and less than or equal to 0.35, and y is more than or equal to 0.1 and less than or equal to 0.35;
(2) according to the mass ratio of 1: 1-15 ratio coating single crystal with matrix LiαNi1-xCoxMnyO2Adding deionized water into a stirring tank, adding soluble phosphate and soluble aluminum salt into the stirring tank, dissolving lithium hydroxide by the deionized water, adding the solution into the stirring tank, stirring for 1-2h, and performing suction filtration and dehydration to obtain an initially-coated high-voltage single crystal ternary cathode material;
(3) the initially coated high-voltage single-crystal ternary positive electrode material is subjected to heat treatment at the temperature of 500-850 ℃ for 4-10h to obtain a composite coated high-voltage single-crystal ternary positive electrode material, wherein the surface coating substance of the composite coated high-voltage single-crystal ternary positive electrode material is LiAlO2、Li3PO4And LiAlP2O7。
2. The method for preparing the modified high-voltage single-crystal ternary cathode material by composite coating according to claim 1, wherein the sintering process in the step (1) comprises the following specific steps:
heating to 650 ℃ at the speed of 2-10 ℃/min, heating to 800 ℃ at the speed of 1-2 ℃/min, then preserving heat for 5-10h, heating to 1050 ℃ at 950 ℃ for 1-12h, and finally cooling to room temperature at the speed of 100 ℃/h.
3. The method for preparing the modified high-voltage single-crystal ternary cathode material by composite coating according to claim 2, wherein the method comprises the following steps: the lithium salt in the step (1) is one or more of lithium hydroxide, lithium carbonate and lithium nitrate.
4. The method for preparing the modified high-voltage single-crystal ternary cathode material by composite coating according to claim 3, wherein the method comprises the following steps: the total amount of the soluble phosphate and the soluble aluminum salt added in the step (2) and the single crystal coated matrix LiαNi1- xCoxMnyO2The molar ratio of (A) to (B) is 0.0001-0.1: 1.
5. The method for preparing the modified high-voltage single-crystal ternary cathode material by composite coating according to claim 4, wherein the method comprises the following steps: the molar ratio of the addition amount of the lithium hydroxide to the total amount of the soluble phosphate and the soluble aluminum salt in the step (2) is 1-13: 1.
6. The method for preparing the modified high-voltage single-crystal ternary cathode material by composite coating according to claim 5, wherein the method comprises the following steps: the soluble phosphate in the step (2) is one or more of aluminum dihydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate and potassium phosphate; the soluble aluminum salt is one or more of aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum dihydrogen phosphate and aluminum phosphate.
7. The method for preparing the modified high-voltage single-crystal ternary cathode material by composite coating according to claim 6, wherein the method comprises the following steps: and (2) sanding the soluble aluminum salt which is aluminum phosphate for 1-2h by using zirconium balls with the diameter of 0.1-0.4mm at the rotating speed of 2000-3000r/min until the granularity of the aluminum phosphate is 10-100 nm by sanding D50.
8. The method for preparing the modified high-voltage single-crystal ternary cathode material by composite coating according to claim 7, wherein the method comprises the following steps: the coating substance of the initially coated high-voltage single crystal ternary positive electrode material in the step (2) is Al (OH)3And Li3PO4A mixture of (a).
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| CN111773791B (en) * | 2020-07-03 | 2021-08-24 | 蜂巢能源科技有限公司 | Filtering device, filtering method, preparation method of nickel-cobalt-manganese ternary positive electrode material with low surface residual alkali and lithium ion battery |
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| CN114122552A (en) * | 2021-11-23 | 2022-03-01 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | LiAlO prepared by recycling retired lithium ion battery2Method for coating single crystal anode material |
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