CN104701533A - Preparation method of 523 ternary material blending modified positive material - Google Patents
Preparation method of 523 ternary material blending modified positive material Download PDFInfo
- Publication number
- CN104701533A CN104701533A CN201510074136.1A CN201510074136A CN104701533A CN 104701533 A CN104701533 A CN 104701533A CN 201510074136 A CN201510074136 A CN 201510074136A CN 104701533 A CN104701533 A CN 104701533A
- Authority
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- China
- Prior art keywords
- ternary
- preparation
- mixed
- positive material
- positive electrode
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Classifications
-
- 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
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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 relates to a preparation method of positive material for lithium ion batteries, and in particular relates to a preparation method of 523 ternary material blending modified positive material. The preparation method of the 523 ternary material blending modified positive material comprises the following steps: a. preparing conventional ternary positive material LiNi0.5Co0.2Mn0.3O2; b. preparing ternary positive material LiNi0.5Co0.2Mn0.3O2 by a molten salt medium method; and c. mixing the conventional ternary positive material and the ternary positive material prepared by the molten salt medium method in a three-dimensional cone mixer according to the mass ratio of 7:3. According to the preparation method, the conventional 523 ternary material and the 523 ternary material prepared by the molten salt medium method are blended with each other for modification, so that the 523 ternary material blending modified positive material is high in compaction density and has high gram volume and good high-and-low temperature performance.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, specifically a kind of preparation method of 523 ternary material blending and modifying positive electrodes.
Background technology
The advantages such as lithium rechargeable battery has that specific capacity is high, operating voltage is high, operating temperature range is wide, self-discharge rate is low, has extended cycle life, memory-less effect, pollution-free, lightweight, security performance is good, are thus widely used in the mobile devices such as mobile phone, digital camera, notebook computer.Along with the development of science and technology, it is very fast that the digital product of various employing lithium ion battery upgrades updating speed, and product is mostly tending towards portability, economization, and this just requires that lithium ion battery product will to high-energy-density future development, in recent years with expensive LiCoO
2positive electrode is that main lithium battery producer has been difficult to reduce costs, the positive electrode that therefore a kind of energy density of necessary searching is high, electrical property well has low cost simultaneously.
High Energy Density Materials, compacted density and capacity mainly by improving material realize.Current LiCoO
2positive electrode develops product the most ripe the earliest, has compacting high, the feature that processing characteristics is good, but shortage of resources, expensive, can cause the decline of other electrical properties especially cycle performance while improving its compacted density, the space of improving energy density is further very little.Ni-based/that ternary material has capacity is high, stable cycle performance, the advantages such as low price, but to compare with cobalt acid lithium material, its major defect is that compacted density is low, constrains the application of this material on lithium ion battery with high energy density greatly.The mode of usual employing bulky grain secondary ball and monocrystalline grating improves ternary material compacted density.But for monocrystalline prepared by common process, its inside still may exist blind bore gap, limit the further raising of material compacted density.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of compacted density that can improve 523 ternary materials, and then can improve the preparation method of 523 ternary material blending and modifying positive electrodes of the electrical properties such as lithium ion battery energy density.
The preparation method of 523 ternary material blending and modifying positive electrodes of the present invention comprises the following steps:
A. conventional three-way positive electrode LiNi is prepared
0.5co
0.2mn
0.3o
2, concrete steps are:
A1. according to required mol ratio by 523 ternary precursor Ni
0.5co
0.2mn
0.3(OH)
2with battery-level lithium carbonate respectively at after porphyrize in agate mortar, put into the mixed machine of three-dimensional cone and mix, dry in 90-100 DEG C of vacuum drying chamber; Ground again;
A2. the material after grinding is put into Muffle furnace to sinter, first 480-500 DEG C of pre-burning; After at 700-740 DEG C of sintering; Again at 800-850 DEG C of sintering; Naturally cool with stove afterwards, fragmentation obtains conventional three-way positive electrode LiNi
0.5co
0.2mn
0.3o
2;
B. adopt fused-salt medium legal system for tertiary cathode material LiNi
0.5co
0.2mn
0.3o
2, concrete steps are:
B1. by LiOH and 523 ternary precursors with Li/M=1.10 ratio respectively at after porphyrize in agate mortar, put into the mixed machine of three-dimensional cone and mix, dry 12-15h in 90-100 DEG C of vacuum drying chamber; Ground again;
B2. the mixture in b1 is mixed at three-dimensional blender tank with NaCl with the ratio of 1:3;
B3. by the mixture in b2, sinter at 800-1000 degree; Omnipotent disintegrating machine is used to carry out fragmentation after cooling;
B4. with the NaCl in distilled water washing b3, filter; To filter products obtained therefrom to dry, then double sintering is also broken at 750 DEG C;
C. the mass ratio of tertiary cathode material standby with adopting fused-salt medium legal system for conventional three-way positive electrode according to 7:3 is mixed in the mixed machine of three-dimensional cone.
The present invention is by conventional 523 ternary materials and the standby 523 ternary material blending and modifyings of fused-salt medium legal system, fused-salt medium method can provide liquid phase environment for reaction, particle can fully be grown, form well-grown primary particle, thus reduce the space of inside particles, improve particle real density, it can not only obtain the positive electrode of high compacted density, also has higher gram volume and good high temperature performance.
Embodiment
The embodiment of the present invention is as follows:
A. conventional three-way positive electrode LiNi is prepared
0.5co
0.2mn
0.3o
2, concrete steps are:
A1. according to required mol ratio by 523 ternary precursor Ni
0.5co
0.2mn
0.3(OH)
2with battery-level lithium carbonate respectively at after porphyrize in agate mortar, put into the mixed machine of three-dimensional cone and mix, dry 14h in 95 DEG C of vacuum drying chambers; Ground 4h again;
A2. the material after grinding is put into Muffle furnace to sinter, first at 500 DEG C of pre-burning 2h; After 720 DEG C sintering 5h; At 840 DEG C of sintering 7h; Naturally cool with stove afterwards, fragmentation obtains conventional three-way positive electrode LiNi
0.5co
0.2mn
0.3o
2;
B. adopt fused-salt medium legal system for tertiary cathode material LiNi
0.5co
0.2mn
0.3o
2, concrete steps are:
B1. by LiOH and 523 ternary precursors with Li/M=1.10 ratio respectively at after porphyrize in agate mortar, put into the mixed machine of three-dimensional cone and mix, dry 14h in 95 DEG C of vacuum drying chambers; Ground 4h again;
B2. by the mixture in b1 with the ratio of 1:3 with NaCl at three-dimensional blender tank mixing 4h;
B3. by the mixture in b2, sinter at 950 DEG C, throughput is 40L/min; Omnipotent disintegrating machine is used to carry out fragmentation after cooling;
B4. with the NaCl in distilled water washing b3, filter, in triplicate; To filter products obtained therefrom to dry at 120 DEG C, then double sintering is also broken at 750 DEG C.
C. prepare by conventional 523 tertiary cathode materials with by fused-salt medium legal system the tertiary cathode material that the mass ratio of 523 standby tertiary cathode materials according to 7:3 is mixed to get modification in the mixed machine of three-dimensional cone.
Indices is as follows after testing for the obtained material of example of executing of reality of the present invention:
Table 1 embodiment of the present invention sample physical and chemical indexes
The roller diameter that test compacted density uses is 800mm;
Inventive samples be D50 at about 13.93 μm, pH is less, and limit compacted density is 3.92.
Table 2 embodiment of the present invention sample gram volume and high rate performance
Table 3 embodiment of the present invention sample is high-temperature behavior data after 85 degree of 4H bakings
Table 4 embodiment of the present invention sample cryogenic property data
The high temperature performance of inventive samples all reaches industry standard.
Claims (1)
1. a preparation method for 523 ternary material blending and modifying positive electrodes, is characterized in that: comprise the following steps,
A. conventional three-way positive electrode LiNi is prepared
0.5co
0.2mn
0.3o
2, concrete steps are:
A1. according to required mol ratio by 523 ternary precursor Ni
0.5co
0.2mn
0.3(OH)
2with battery-level lithium carbonate respectively at after porphyrize in agate mortar, put into the mixed machine of three-dimensional cone and mix, dry in 90-100 DEG C of vacuum drying chamber; Ground again;
A2. the material after grinding is put into Muffle furnace to sinter, first 480-500 DEG C of pre-burning; After at 700-740 DEG C of sintering; Again at 800-850 DEG C of sintering; Naturally cool with stove afterwards, fragmentation obtains conventional three-way positive electrode LiNi
0.5co
0.2mn
0.3o
2;
B. adopt fused-salt medium legal system for tertiary cathode material LiNi
0.5co
0.2mn
0.3o
2, concrete steps are:
B1. by LiOH and 523 ternary precursors with Li/M=1.10 ratio respectively at after porphyrize in agate mortar, put into the mixed machine of three-dimensional cone and mix, dry 12-15 h in 90-100 DEG C of vacuum drying chamber; Ground again;
B2. the mixture in b1 is mixed at three-dimensional blender tank with NaCl with the ratio of 1:3;
B3. by the mixture in b2, sinter at 800-1000 degree; Omnipotent disintegrating machine is used to carry out fragmentation after cooling;
B4. with the NaCl in distilled water washing b3, filter; To filter products obtained therefrom to dry, then double sintering is also broken at 750 DEG C;
C. the mass ratio of tertiary cathode material standby with adopting fused-salt medium legal system for conventional three-way positive electrode according to 7:3 is mixed in the mixed machine of three-dimensional cone.
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|---|---|---|---|
| CN201510074136.1A CN104701533A (en) | 2015-02-11 | 2015-02-11 | Preparation method of 523 ternary material blending modified positive material |
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| CN201510074136.1A CN104701533A (en) | 2015-02-11 | 2015-02-11 | Preparation method of 523 ternary material blending modified positive material |
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| Publication Number | Publication Date |
|---|---|
| CN104701533A true CN104701533A (en) | 2015-06-10 |
Family
ID=53348436
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470499A (en) * | 2015-12-04 | 2016-04-06 | 江苏海四达电源股份有限公司 | Preparation method for improving compaction density of NCA cathode material for lithium-ion battery |
| CN106328921A (en) * | 2015-06-25 | 2017-01-11 | 湖南桑顿新能源有限公司 | Preparation method of highly compacted positive electrode material NCM622 of lithium battery |
| CN108011144A (en) * | 2017-10-31 | 2018-05-08 | 合肥国轩高科动力能源有限公司 | A kind of recovery processing technique of ternary cathode material of lithium ion battery |
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|---|---|---|---|---|
| CN102683645A (en) * | 2011-03-17 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery |
| CN102738453A (en) * | 2012-07-11 | 2012-10-17 | 中国第一汽车股份有限公司 | High-tap-density lithium-enriched material prepared by using hydroxyl coprecipitation-fused salt method |
| CN103000873A (en) * | 2012-10-09 | 2013-03-27 | 江苏科捷锂电池有限公司 | Method for preparing lithium manganese oxide spinel anode material through molten-salt growth method |
| KR20130122279A (en) * | 2012-04-30 | 2013-11-07 | 주식회사 엘지화학 | Mixed positive-electrode material with improved output property and lithium secondary battery comprising the same |
| CN103700817A (en) * | 2013-12-18 | 2014-04-02 | 江苏科捷锂电池有限公司 | Preparation method of LiV3O8 and LiNi0.4Co0.2Mn0.4O2 blended modified lithium battery cathode material |
-
2015
- 2015-02-11 CN CN201510074136.1A patent/CN104701533A/en active Pending
Patent Citations (5)
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|---|---|---|---|---|
| CN102683645A (en) * | 2011-03-17 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery |
| KR20130122279A (en) * | 2012-04-30 | 2013-11-07 | 주식회사 엘지화학 | Mixed positive-electrode material with improved output property and lithium secondary battery comprising the same |
| CN102738453A (en) * | 2012-07-11 | 2012-10-17 | 中国第一汽车股份有限公司 | High-tap-density lithium-enriched material prepared by using hydroxyl coprecipitation-fused salt method |
| CN103000873A (en) * | 2012-10-09 | 2013-03-27 | 江苏科捷锂电池有限公司 | Method for preparing lithium manganese oxide spinel anode material through molten-salt growth method |
| CN103700817A (en) * | 2013-12-18 | 2014-04-02 | 江苏科捷锂电池有限公司 | Preparation method of LiV3O8 and LiNi0.4Co0.2Mn0.4O2 blended modified lithium battery cathode material |
Non-Patent Citations (1)
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| 俞会根等: ""三元正极材料 Li[Ni-Co-Mn]O2的研究进展"", 《电源技术》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328921A (en) * | 2015-06-25 | 2017-01-11 | 湖南桑顿新能源有限公司 | Preparation method of highly compacted positive electrode material NCM622 of lithium battery |
| CN105470499A (en) * | 2015-12-04 | 2016-04-06 | 江苏海四达电源股份有限公司 | Preparation method for improving compaction density of NCA cathode material for lithium-ion battery |
| CN108011144A (en) * | 2017-10-31 | 2018-05-08 | 合肥国轩高科动力能源有限公司 | A kind of recovery processing technique of ternary cathode material of lithium ion battery |
| CN108011144B (en) * | 2017-10-31 | 2019-09-13 | 合肥国轩高科动力能源有限公司 | A kind of recovery processing technique of ternary cathode material of lithium ion battery |
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| PB01 | Publication | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20151117 Address after: 753000, room 323, Xinghai town office building, Dawukou District, the Ningxia Hui Autonomous Region, Shizuishan Applicant after: JIANGSU KING LITHIUM CELL CO., LTD. Address before: Jinyang Jingkou Industrial Park Road 212006 Zhenjiang City, Jiangsu province Jingkou District No. 9 Applicant before: Jiangsu King Lithium Cell Co.,Ltd. |
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Application publication date: 20150610 |