CN1361061A - Preparation method of cobalt lithium oxide material - Google Patents
Preparation method of cobalt lithium oxide material Download PDFInfo
- Publication number
- CN1361061A CN1361061A CN00136974A CN00136974A CN1361061A CN 1361061 A CN1361061 A CN 1361061A CN 00136974 A CN00136974 A CN 00136974A CN 00136974 A CN00136974 A CN 00136974A CN 1361061 A CN1361061 A CN 1361061A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- lithium
- micron
- lithium oxide
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 30
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 26
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 3
- 238000005469 granulation Methods 0.000 claims description 16
- 230000003179 granulation Effects 0.000 claims description 16
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 7
- 235000011613 Pinus brutia Nutrition 0.000 claims description 7
- 241000018646 Pinus brutia Species 0.000 claims description 7
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 5
- 239000013256 coordination polymer Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 238000010671 solid-state reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 abstract 1
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 230000005587 bubbling Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a process for preparing lithium cobalt oxide material, which comprises mixing lithium carbonate, lithium hydroxide or any one of cobaltosic oxide, cobaltous oxide and cobalt carbonate or their mixture, wherein the molar ratio of the former and the latter is 0.95-1.15: 1, loosely packing and piling the mixture, the thickness is less than 30 mm, tabletting and granulating, carrying out high temperature solid phase reaction on the granulated raw material, cooling and disintegrating. The tap density of the product prepared by the preparation method is obviously superior to that of the non-granulated cobalt lithium oxide material, the tap density of the product reaches 2.4-2.75 g/cubic centimeter, and the product is suitable for manufacturing the anode of the lithium ion battery.
Description
The invention relates to the manufacture method of cobalt-lithium oxide.
Cobalt-lithium oxide is a kind of important materials of making lithium-ions battery.Cobalt-lithium oxide reaches safety performance owing to have higher specific storage and excellent cycle performance, now is widely used in the preparation of lithium ion cell positive.
At present, be engaged in the producer of battery material research more in the world, cobalt-lithium oxide material production technique optimizing carried out unremitting effort always, and proposing technologies such as sol-gel method, oxalic acid precipitation chemical complexometry, high temperature solid phase synthesis.The cobalt-lithium oxide material of existing high temperature solid phase synthesis manufacturing exists the drawback of material requirements harshness.
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of technology simple and can effectively improve the manufacture method of tap density cobalt-lithium oxide.
Technical scheme of the present invention is summarized as follows:
The preparation method of cobalt-lithium oxide material of the present invention, it comprises the following steps: any or its mixture in any or its mixture in Quilonum Retard, the lithium hydroxide and tricobalt tetroxide, cobalt sesquioxide, the cobaltous carbonate is mixed mutually, wherein the mole ratio of the former with the latter add-on is 0.95-1.15: 1, described Quilonum Retard or lithium hydroxide are the above rank of CP level, and its main content is greater than 99.5%; Lithium hydroxide also is the above rank of CP level, mean particle size 1.0-20.5 micron, and described tricobalt tetroxide, cobalt sesquioxide, cobaltous carbonate X-ray diffraction analysis should not have assorted peak, mean particle size 0.75-8.5 micron; Its size-grade distribution D
50=1.0-14.5 micron; Above-mentioned mixed raw pine dress is piled up, and its thickness is less than or equal to 30 millimeters, carries out the compressing tablet granulation on press, the pressure 0.5-30Mpa of press; Raw material after the compressing tablet granulation is handled carries out high temperature solid state reaction again; Be ground into D after the cooling
50The cobalt-lithium oxide powder of=5.0-20.0 micron can obtain the used positive electrode material of lithium-ions battery.
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
Quilonum Retard 377.5 grams are mixed mutually with tricobalt tetroxide 820.1 grams, described Quilonum Retard main content 99.6%, 11.2 microns of averageparticle, described tricobalt tetroxide X-ray diffraction analysis thing does not have assorted peak mutually, 4.8 microns of mean particle sizes; Its size-grade distribution D
50=8.2 microns; Above-mentioned mixed raw pine dress is piled up, and 6 millimeters of its thickness carry out the compressing tablet granulation on press, the pressure 10Mpa of press; Raw material after the compressing tablet granulation is handled was calcined 8 hours down at 900 ℃, 12 ℃/minute of heat-up rates, 2 cubic metres/hour of bubbling air amounts; Speed with 5 ℃/minute is lowered the temperature gradually, during to room temperature, product is pulverized powder size D
50=10-15 micron.This moment these powder tap density 2.56 gram/cubic centimetres, specific surface area 0.3 meters squared per gram.
Embodiment 2
Quilonum Retard 383.2 grams are mixed mutually with tricobalt tetroxide 820.1 grams, described Quilonum Retard main content 99.5%, 1.5 microns of mean particle sizes, described tricobalt tetroxide does not have assorted peak mutually through the X-ray diffraction analysis thing, 1.2 microns of mean particle sizes; Its size-grade distribution D
50=3.2 microns; Above-mentioned mixed raw pine dress is piled up, and 8 millimeters of its thickness carry out the compressing tablet granulation on press, the pressure 16Mpa of press; Raw material after the compressing tablet granulation is handled was calcined 7 hours down at 980 ℃, 8 ℃/minute of heat-up rates, 3 cubic metres/hour of bubbling air amounts; Speed with 5 ℃/minute is lowered the temperature gradually, during to room temperature, product is ground into powder, granularity D
50=10-15 micron.This moment these powder tap density 2.61 gram/cubic centimetres, specific surface area 0.28 meters squared per gram.
Embodiment 3
Lithium hydroxide (LiOH.H2O content 90%) 480.9 grams are mixed mutually with cobalt sesquioxide 847.4 grams, and described cobalt sesquioxide does not have assorted peak through X-ray diffraction analysis, 2.6 microns of mean particle sizes; Its size-grade distribution D
50=6.3 microns; Above-mentioned mixed raw pine dress is piled up, and 8 millimeters of its thickness carry out the compressing tablet granulation on press, the pressure 5Mpa of press; Raw material after the compressing tablet granulation is handled was calcined 8 hours down at 925 ℃, 5 ℃/minute of heat-up rates, and 0.1 cubic metre/hour of bubbling air amount is lowered the temperature gradually with 7 ℃/minute speed, during to room temperature, product is pulverized powder size D
50=10-15 micron.This moment these powder tap density 2.64 gram/cubic centimetres, specific surface area 0.25 meters squared per gram.
Embodiment 4
Quilonum Retard 199.2 grams, lithium hydroxide (LiOH.H2O content 90%) 250.0 grams and tricobalt tetroxide 410.0 grams, three cobalt oxides, 423.7 grams are mixed mutually, described Quilonum Retard main content 99.5%, 11.2 microns of averageparticle, described tricobalt tetroxide X-ray diffraction analysis thing does not have assorted peak mutually, 4.8 microns of mean particle sizes; Its size-grade distribution D
50=8.2 microns; Described cobalt sesquioxide X-ray diffraction analysis thing does not have assorted peak mutually, 2.6 microns of mean particle sizes, its size-grade distribution D
50=6.3 microns, above-mentioned mixed raw pine dress to be piled up, 8 millimeters of its thickness carry out the compressing tablet granulation on press, the pressure 16Mpa of press; Raw material after the compressing tablet granulation is handled was calcined 8 hours down at 950 ℃, 5 ℃/minute of heat-up rates, 3 cubic metres/hour of bubbling air amounts; Speed with 7 ℃/minute is lowered the temperature gradually, during to room temperature, product is pulverized its size-grade distribution of powder D
50=10-15 micron, these powder tap density 2.70 gram/square centimeters, specific surface area 0.27 meters squared per gram.
Embodiment 5
Quilonum Retard 239.0 grams, lithium hydroxide (LiOH.H2O content 90%) 200.0 grams and tricobalt tetroxide 246.0 grams, three cobalt oxides, 254.2 grams, cobaltous carbonate (C.P level) 496.0 grams are mixed described Quilonum Retard main content 99.6%, 11.2 microns of averageparticle mutually; Described tricobalt tetroxide X-ray diffraction analysis thing does not have assorted peak mutually, 4.8 microns of mean particle sizes; Its size-grade distribution D
50=8.2 microns; Described cobalt sesquioxide X-ray diffraction analysis thing does not have assorted peak mutually, 2.6 microns of mean particle sizes; Its size-grade distribution D
50=6.3 microns; Above-mentioned mixed raw pine dress is piled up, and 8 millimeters of its thickness carry out the compressing tablet granulation on press, the pressure 16Mpa of press.Raw material after the compressing tablet granulation is handled was calcined 8 hours down at 950 ℃, 5 ℃/minute of heat-up rates, 3 cubic metres/hour of bubbling air amounts; Speed with 7 ℃/minute is lowered the temperature gradually, during to room temperature, product is pulverized powder size distribution D
50=10-15 micron; These powder tap density 2.68 gram/cubic centimetres, specific surface area 0.28 meters squared per gram.
Cobalt-lithium oxide manufacture method of the present invention is owing to increased granulation process, not harsh to employed raw-material requirement, and the tap density that makes product obviously is better than the cobalt-lithium oxide material without granulation, (the current material tap density is less than 2.2 gram/cubic centimetres), the cobalt-lithium oxide tap density of manufacturing of the present invention reaches 2.4-2.75 gram/cubic centimetre, and the other technologies index all reaches the desired index of Postive electrode material of li-ion accumulator.
Claims (1)
1. the preparation method of a cobalt-lithium oxide material, it is characterized in that, it comprises the following steps: any or its mixture in any or its mixture in Quilonum Retard, the lithium hydroxide and tricobalt tetroxide, cobalt sesquioxide, the cobaltous carbonate is mixed mutually, wherein the mole ratio of the former with the latter add-on is 0.95-1.15: 1, described Quilonum Retard or lithium hydroxide are the above rank of CP level, and its main content is greater than 99.5%; Lithium hydroxide also is the above rank of CP level, mean particle size 1.0-20.5 micron, and described tricobalt tetroxide, cobalt sesquioxide, cobaltous carbonate X-ray diffraction analysis should not have assorted peak, mean particle size 0.75-8.5 micron; Its size-grade distribution D
50=1.0-14.5 micron; Above-mentioned mixed raw pine dress is piled up, and its thickness is less than or equal to 30 millimeters, carries out the compressing tablet granulation on press, the pressure 0.5-30Mpa of press; Raw material after the compressing tablet granulation is handled carries out high temperature solid state reaction again; Be ground into D after the cooling
50The cobalt-lithium oxide powder of=5.0-20.0 micron can obtain the used positive electrode material of lithium-ions battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001369741A CN1189396C (en) | 2000-12-26 | 2000-12-26 | Preparation method of cobalt lithium oxide material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001369741A CN1189396C (en) | 2000-12-26 | 2000-12-26 | Preparation method of cobalt lithium oxide material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1361061A true CN1361061A (en) | 2002-07-31 |
| CN1189396C CN1189396C (en) | 2005-02-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001369741A Expired - Fee Related CN1189396C (en) | 2000-12-26 | 2000-12-26 | Preparation method of cobalt lithium oxide material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1189396C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845927A (en) * | 2016-03-25 | 2016-08-10 | 奇瑞汽车股份有限公司 | Preparation method of lithium ion battery cathode material lithium cobalt oxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109994729B (en) | 2019-03-19 | 2021-03-05 | 宁德新能源科技有限公司 | Positive electrode material and electrochemical device using same |
-
2000
- 2000-12-26 CN CNB001369741A patent/CN1189396C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845927A (en) * | 2016-03-25 | 2016-08-10 | 奇瑞汽车股份有限公司 | Preparation method of lithium ion battery cathode material lithium cobalt oxide |
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| Publication number | Publication date |
|---|---|
| CN1189396C (en) | 2005-02-16 |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050216 Termination date: 20101226 |