CN104724763A - Preparation method of high-compaction ternary cathode material - Google Patents
Preparation method of high-compaction ternary cathode material Download PDFInfo
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- CN104724763A CN104724763A CN201510072339.7A CN201510072339A CN104724763A CN 104724763 A CN104724763 A CN 104724763A CN 201510072339 A CN201510072339 A CN 201510072339A CN 104724763 A CN104724763 A CN 104724763A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to manufacturing of anode materials for lithium ion batteries, and in particular relates to a preparation method of a high-compaction ternary cathode material. The method comprises the following steps that two ternary precursors in large and small particle sizes are mixed uniformly; a ternary precursor mixture is mixed with Li2CO3 uniformly, and heated and sintered in a large muffle furnace; the ternary precursor meeting the conditions that the particle size D50 is less than or equal to 12 micrometers and greater than or equal to 10 micrometers is mixed with Li2CO3, ground, dried, sintered and crushed to form a small-particle monocrystalline ternary material; and the materials prepared by the two times of sintering are mixed uniformly to form the finished high-compaction ternary cathode material, wherein the large particle size meets the conditions that D50 is less than or equal to 15 micrometers and greater than or equal to 10 micrometers, the small particle size meets the conditions that D50 is less than or equal to 7 micrometers and greater than or equal to 4 micrometers, and a mass ratio of the large particles to the small particles is between 6:4 and 8:2. By the preparation method, the compaction density of the ternary cathode material is improved, and the energy density is enabled to be higher.
Description
Technical field
The present invention relates to a kind of manufacture of anode material for lithium-ion batteries, specifically a kind of preparation method of high-pressure solid tertiary cathode material.
Background technology
Developed comparatively ripe at present, the anode material of lithium battery for market widespread use is cobalt acid lithium, but the price of cobalt costliness, the capacity density of limitation, and lower safety performance limits its development.By comparison, the price that ternary material is moderate, the advantage of capacity makes it just cause increasing concern.But, due to the defect in existing preparation technology, the advantage of ternary material is not fully played, wherein the capacity density of material is on the low side is one of factor limiting its performance boost, and the capacity density promoting ternary material is mainly considered from three angles: promote sparking voltage, promote compacting and promote gram volume.
Summary of the invention
Technical problem to be solved by this invention is to provide one can effectively promote tertiary cathode material compactness, and then improves the preparation method of high-pressure solid tertiary cathode material of its capacity density.
The preparation method of high-pressure solid tertiary cathode material of the present invention comprises the following steps:
Step one, by the ternary precursor Ni of large and small two kinds of variable grain granularities
0.5co
0.2mn
0.3(OH)
2, mix in the mixed machine of three-dimensional cone, wherein oarse-grained particle diameter meets 10 μm≤D50≤15 μm, and short grained particle diameter meets 4 μm≤D50≤7 μm, and the mass ratio of large and small grain particles is between 6:4 to 8:2;
Step 2, the ternary precursor mixture after step one is mixed and Li
2cO
3mix in the mixed machine of large three-dimensional cone, wherein the mol ratio of Li and Mn is 1.1:1 ~ 1.2:1;
Step 3, by ternary precursor and Li
2cO
3mixture to heat up in large retort furnace sintering, sintering temperature 900-950 DEG C; With stove naturally cooling after sintering, broken; Concrete heating step is: be first warmed up to 600 DEG C, then slows down heat-up rate speed and is warmed up to final target temperature, and under target temperature constant temperature for some time;
Step 4, prepares small-particle monocrystalline ternary material, particle diameter is met the ternary precursor Ni of 10 μm≤D50≤12 μm
0.5co
0.2mn
0.3(OH)
2with Li
2cO
3mixing, wherein the mol ratio of Li and Mn is 1.1:1 ~ 1.2:1, and mixture extra-fine grinding equipment grinds, post-drying, sintering, and broken, obtain small-particle monocrystalline ternary material, the particle diameter of small-particle monocrystalline is between 1 μm ~ 4 μm;
Step 5, the material prepared in material step 3 prepared and step 4 carries out mixing obtaining finished product in the mixed machine of large three-dimensional cone, and the mass ratio of the former with the latter is 8:2 ~ 8.2:2.
Preferably, in step one, the particle diameter of macrobead ternary precursor meets D50 is 12 μm, and it is 6 μm that the particle diameter of small-particle ternary precursor meets D50; In step 4, the particle diameter of ternary precursor meets D50 is 12 μm.
Preferably, in step 5, the mixing quality ratio of the former with the latter is 8:2.
The present invention is by carrying out the grating of different-grain diameter to tertiary cathode material, be doped with particle diameter particle less by comparison in Large stone material after, gap between macrobead just can fill by little particle, space is fully utilized, improve compacted density, make energy density higher.
Embodiment
The embodiment of the present invention comprises the following steps:
(1) by the ternary precursor Ni of varigrained size particles
0.5co
0.2mn
0.3(OH)
2mix in the mixed machine of three-dimensional cone.Wherein oarse-grained particle diameter meets D50 is 12 μm, and it is 6 μm that short grained particle diameter meets D50, and the mass ratio of large and small grain particles is between 6:4 to 8:2;
(2) by the ternary precursor mixture after mixed and Li
2cO
3mix in the mixed machine of large three-dimensional cone.Wherein the mol ratio of Li and Mn is 1.1:1;
(3) by ternary precursor and Li
2cO
3mixture sinter in large retort furnace, step is: be first warmed up to 600 DEG C with the heat-up rate of 5 DEG C/min, then is warmed up to target temperature 900 DEG C with the heat-up rate of 1 DEG C/min, with stove naturally cooling after constant temperature 6 ~ 10h, broken.
(4) separately particle diameter is met the Ni that D50 is 12 μm
0.5co
0.2mn
0.3(OH)
2ternary precursor and Li
2cO
3mixing, wherein the mol ratio of Li and Mn is 1.1:1, and mixture extra-fine grinding equipment grinds, post-drying, sintering, and broken, obtain small-particle monocrystalline ternary material, the particle diameter of small-particle monocrystalline is between 1 μm ~ 4 μm.
(5) the small-particle monocrystalline material of preparation in (3) and extra-fine grinding equipment in (4) ground out carries out mixing 1-4h large three-dimensional cone in mixed machine according to the mass ratio of 8:2, obtains finished product.
Claims (4)
1. a preparation method for high-pressure solid tertiary cathode material, is characterized in that: comprise the following steps,
Step one, by the ternary precursor Ni of large and small two kinds of variable grain granularities
0.5co
0.2mn
0.3(OH)
2, mix in the mixed machine of three-dimensional cone, wherein oarse-grained particle diameter meets 10 μm≤D50≤15 μm, and short grained particle diameter meets 4 μm≤D50≤7 μm, and the mass ratio of large and small grain particles is between 6:4 to 8:2;
Step 2, the ternary precursor mixture after step one is mixed and Li
2cO
3mix in the mixed machine of large three-dimensional cone, wherein the mol ratio of Li and Mn is 1.1:1 ~ 1.2:1;
Step 3, by ternary precursor and Li
2cO
3mixture to heat up in large retort furnace sintering, sintering temperature 900-950 DEG C; With stove naturally cooling after sintering, broken;
Step 4, prepares small-particle monocrystalline ternary material, particle diameter is met the ternary precursor Ni of 10 μm≤D50≤12 μm
0.5co
0.2mn
0.3(OH)
2with Li
2cO
3mixing, wherein the mol ratio of Li and Mn is 1.1:1 ~ 1.2:1, and mixture extra-fine grinding equipment grinds, post-drying, sintering, and broken, obtain small-particle monocrystalline ternary material, the particle diameter of small-particle monocrystalline is between 1 μm ~ 4 μm;
Step 5, the material prepared in material step 3 prepared and step 4 carries out mixing obtaining finished product in the mixed machine of large three-dimensional cone, and the mass ratio of the former with the latter is 8:2 ~ 8.2:2.
2. the preparation method of high-pressure solid tertiary cathode material according to claim 1, is characterized in that: concrete heating step is: be first warmed up to 600 DEG C, then slow down heat-up rate speed and be warmed up to final target temperature.
3. the preparation method of high-pressure solid tertiary cathode material according to claim 1, is characterized in that: in step one, the particle diameter of macrobead ternary precursor meets D50 is 12 μm, and it is 6 μm that the particle diameter of small-particle ternary precursor meets D50; In step 4, the particle diameter of ternary precursor meets D50 is 12 μm.
4. the preparation method of high-pressure solid tertiary cathode material according to claim 1, is characterized in that: in step 5, the mixing quality of the former with the latter is than being 8:2.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489881A (en) * | 2016-01-12 | 2016-04-13 | 哈尔滨工业大学 | Method for improving tap density of ternary nickel-cobalt-manganese cathode material for lithium-ion battery |
| CN105529457A (en) * | 2016-02-24 | 2016-04-27 | 无锡凯力克能源材料有限公司 | Industrial production method for highly compacted 3.7 g/cm3 lithium nickel cobalt manganese oxide NCM523 ternary cathode material |
| CN106784784A (en) * | 2015-11-20 | 2017-05-31 | 中国科学院宁波材料技术与工程研究所 | A kind of nickel cobalt manganese presoma and preparation method thereof |
| CN107123799A (en) * | 2017-05-18 | 2017-09-01 | 格林美（无锡）能源材料有限公司 | The preparation method of lithium secondary cell with high capacity positive active material and its presoma |
| CN107195858A (en) * | 2017-04-17 | 2017-09-22 | 深圳市比克动力电池有限公司 | Lithium ion battery, anode sizing agent, anode pole piece and preparation method |
| CN107256968A (en) * | 2017-06-19 | 2017-10-17 | 贝特瑞（天津）纳米材料制造有限公司 | A kind of high compacted density LiFePO4 and preparation method thereof |
| CN107665989A (en) * | 2016-07-28 | 2018-02-06 | 无锡晶石新型能源有限公司 | A kind of preparation method of high-pressure solid, high magnification nickel cobalt aluminium lithium material |
| CN107706373A (en) * | 2017-09-19 | 2018-02-16 | 合肥国轩高科动力能源有限公司 | High-nickel ternary material for lithium ion battery and preparation method thereof |
| CN108649216A (en) * | 2018-04-25 | 2018-10-12 | 三明厦钨新能源材料有限公司 | A kind of preparation method and saggar of nickel-cobalt lithium manganate cathode material |
| CN109461929A (en) * | 2018-09-21 | 2019-03-12 | 深圳市卓能新能源股份有限公司 | A kind of lithium ion battery and preparation method thereof |
| CN109665508A (en) * | 2017-10-16 | 2019-04-23 | 中天新兴材料有限公司 | Positive electrode material lithium iron phosphate and preparation method thereof |
| CN110010889A (en) * | 2019-04-17 | 2019-07-12 | 宁波容百新能源科技股份有限公司 | A kind of nickelic positive electrode of high-pressure solid high stability and preparation method thereof and a kind of lithium ion battery |
| CN111370685A (en) * | 2020-02-28 | 2020-07-03 | 江门市科恒实业股份有限公司 | High-compaction-density single crystal ternary cathode material and preparation method thereof |
| JP2021507497A (en) * | 2018-02-01 | 2021-02-22 | エルジー・ケム・リミテッド | Positive electrode active material for secondary batteries, their manufacturing methods, and lithium secondary batteries containing them |
| CN113921782A (en) * | 2021-09-26 | 2022-01-11 | 宁波容百新能源科技股份有限公司 | Ultrahigh nickel ternary cathode material with high compaction and high energy density |
| WO2024259622A1 (en) * | 2023-06-21 | 2024-12-26 | 广东邦普循环科技有限公司 | Ternary positive electrode material and preparation method therefor |
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| CN106784784A (en) * | 2015-11-20 | 2017-05-31 | 中国科学院宁波材料技术与工程研究所 | A kind of nickel cobalt manganese presoma and preparation method thereof |
| CN105489881A (en) * | 2016-01-12 | 2016-04-13 | 哈尔滨工业大学 | Method for improving tap density of ternary nickel-cobalt-manganese cathode material for lithium-ion battery |
| CN105529457A (en) * | 2016-02-24 | 2016-04-27 | 无锡凯力克能源材料有限公司 | Industrial production method for highly compacted 3.7 g/cm3 lithium nickel cobalt manganese oxide NCM523 ternary cathode material |
| CN107665989A (en) * | 2016-07-28 | 2018-02-06 | 无锡晶石新型能源有限公司 | A kind of preparation method of high-pressure solid, high magnification nickel cobalt aluminium lithium material |
| CN107195858A (en) * | 2017-04-17 | 2017-09-22 | 深圳市比克动力电池有限公司 | Lithium ion battery, anode sizing agent, anode pole piece and preparation method |
| CN107123799A (en) * | 2017-05-18 | 2017-09-01 | 格林美（无锡）能源材料有限公司 | The preparation method of lithium secondary cell with high capacity positive active material and its presoma |
| CN107256968A (en) * | 2017-06-19 | 2017-10-17 | 贝特瑞（天津）纳米材料制造有限公司 | A kind of high compacted density LiFePO4 and preparation method thereof |
| CN107706373A (en) * | 2017-09-19 | 2018-02-16 | 合肥国轩高科动力能源有限公司 | High-nickel ternary material for lithium ion battery and preparation method thereof |
| CN107706373B (en) * | 2017-09-19 | 2020-05-22 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery high nickel ternary material and preparation method thereof |
| CN109665508A (en) * | 2017-10-16 | 2019-04-23 | 中天新兴材料有限公司 | Positive electrode material lithium iron phosphate and preparation method thereof |
| JP2021507497A (en) * | 2018-02-01 | 2021-02-22 | エルジー・ケム・リミテッド | Positive electrode active material for secondary batteries, their manufacturing methods, and lithium secondary batteries containing them |
| JP7062173B2 (en) | 2018-02-01 | 2022-05-06 | エルジー エナジー ソリューション リミテッド | Positive electrode active material for secondary batteries, their manufacturing methods, and lithium secondary batteries containing them. |
| CN108649216A (en) * | 2018-04-25 | 2018-10-12 | 三明厦钨新能源材料有限公司 | A kind of preparation method and saggar of nickel-cobalt lithium manganate cathode material |
| CN108649216B (en) * | 2018-04-25 | 2021-02-26 | 三明厦钨新能源材料有限公司 | Preparation method of nickel cobalt lithium manganate positive electrode material and sagger |
| CN109461929A (en) * | 2018-09-21 | 2019-03-12 | 深圳市卓能新能源股份有限公司 | A kind of lithium ion battery and preparation method thereof |
| CN110010889A (en) * | 2019-04-17 | 2019-07-12 | 宁波容百新能源科技股份有限公司 | A kind of nickelic positive electrode of high-pressure solid high stability and preparation method thereof and a kind of lithium ion battery |
| CN110010889B (en) * | 2019-04-17 | 2021-09-07 | 贵州容百锂电材料有限公司 | High-compaction high-stability high-nickel cathode material, preparation method thereof and lithium ion battery |
| CN111370685A (en) * | 2020-02-28 | 2020-07-03 | 江门市科恒实业股份有限公司 | High-compaction-density single crystal ternary cathode material and preparation method thereof |
| CN113921782A (en) * | 2021-09-26 | 2022-01-11 | 宁波容百新能源科技股份有限公司 | Ultrahigh nickel ternary cathode material with high compaction and high energy density |
| WO2024259622A1 (en) * | 2023-06-21 | 2024-12-26 | 广东邦普循环科技有限公司 | Ternary positive electrode material and preparation method therefor |
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