CN115571925B - 一种废旧锂电池回收制备碳酸锂和三元前驱体的方法 - Google Patents
一种废旧锂电池回收制备碳酸锂和三元前驱体的方法 Download PDFInfo
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- CN115571925B CN115571925B CN202210946041.4A CN202210946041A CN115571925B CN 115571925 B CN115571925 B CN 115571925B CN 202210946041 A CN202210946041 A CN 202210946041A CN 115571925 B CN115571925 B CN 115571925B
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- Prior art keywords
- ammonia
- lithium
- leaching
- reaction
- ternary
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 52
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 38
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 38
- 239000002243 precursor Substances 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 104
- 238000002386 leaching Methods 0.000 claims abstract description 89
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 39
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 37
- 238000000975 co-precipitation Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 238000000926 separation method Methods 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Chemical class 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052748 manganese Chemical class 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 11
- 238000004537 pulping Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000003518 caustics Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002912 waste gas Substances 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 22
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 19
- 238000013329 compounding Methods 0.000 abstract description 7
- 239000010926 waste battery Substances 0.000 abstract description 4
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229940073644 nickel Drugs 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
项目 | 实施例1 | 实施例2 | 实施例3 | 对比例 |
钴回收率/% | 91.7 | 95.6 | 99.5 | 91.2 |
镍回收率/% | 93.5 | 95.9 | 99.5 | 91.6 |
锰回收率/% | 91.4 | 94.6 | 98.3 | 89.1 |
锂回收率/% | 91.5 | 97.6 | 97.9 | 89.5 |
碳酸锂纯度/% | 92.5 | 95.2 | 99.5 | 90.8 |
Claims (6)
Priority Applications (1)
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CN202210946041.4A CN115571925B (zh) | 2022-08-08 | 2022-08-08 | 一种废旧锂电池回收制备碳酸锂和三元前驱体的方法 |
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CN202210946041.4A CN115571925B (zh) | 2022-08-08 | 2022-08-08 | 一种废旧锂电池回收制备碳酸锂和三元前驱体的方法 |
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CN115571925A CN115571925A (zh) | 2023-01-06 |
CN115571925B true CN115571925B (zh) | 2023-12-29 |
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CN109193057A (zh) * | 2018-09-07 | 2019-01-11 | 昆明理工大学 | 一种利用废旧三元锂电池制备正极材料前驱体的方法 |
CN109935922A (zh) * | 2019-03-14 | 2019-06-25 | 北京矿冶科技集团有限公司 | 一种从废旧锂离子电池材料中回收有价金属的方法 |
CN110028111A (zh) * | 2019-03-25 | 2019-07-19 | 中南大学 | 三元正极材料前驱体及碳酸锂的制备方法 |
CN111252814A (zh) * | 2020-01-19 | 2020-06-09 | 广西师范大学 | 一种废旧三元锂离子电池正极材料的回收方法 |
CN111463475A (zh) * | 2020-03-11 | 2020-07-28 | 长沙有色冶金设计研究院有限公司 | 一种选择性回收废旧动力锂电池正极材料的方法 |
CN111690812A (zh) * | 2020-06-15 | 2020-09-22 | 南方科技大学 | 一种废旧三元锂电池的回收方法 |
CN112646974A (zh) * | 2020-11-12 | 2021-04-13 | 四川顺应动力电池材料有限公司 | 一种从废旧三元锂电池正极材料中回收有价金属的方法 |
CN113258158A (zh) * | 2021-04-27 | 2021-08-13 | 湖北金泉新材料有限公司 | 一种废旧锂离子电池资源化的处理方法 |
-
2022
- 2022-08-08 CN CN202210946041.4A patent/CN115571925B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109193057A (zh) * | 2018-09-07 | 2019-01-11 | 昆明理工大学 | 一种利用废旧三元锂电池制备正极材料前驱体的方法 |
CN109935922A (zh) * | 2019-03-14 | 2019-06-25 | 北京矿冶科技集团有限公司 | 一种从废旧锂离子电池材料中回收有价金属的方法 |
CN110028111A (zh) * | 2019-03-25 | 2019-07-19 | 中南大学 | 三元正极材料前驱体及碳酸锂的制备方法 |
CN111252814A (zh) * | 2020-01-19 | 2020-06-09 | 广西师范大学 | 一种废旧三元锂离子电池正极材料的回收方法 |
CN111463475A (zh) * | 2020-03-11 | 2020-07-28 | 长沙有色冶金设计研究院有限公司 | 一种选择性回收废旧动力锂电池正极材料的方法 |
CN111690812A (zh) * | 2020-06-15 | 2020-09-22 | 南方科技大学 | 一种废旧三元锂电池的回收方法 |
CN112646974A (zh) * | 2020-11-12 | 2021-04-13 | 四川顺应动力电池材料有限公司 | 一种从废旧三元锂电池正极材料中回收有价金属的方法 |
CN113258158A (zh) * | 2021-04-27 | 2021-08-13 | 湖北金泉新材料有限公司 | 一种废旧锂离子电池资源化的处理方法 |
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Denomination of invention: A method for recycling and preparing lithium carbonate and ternary precursor from waste lithium batteries Granted publication date: 20231229 Pledgee: China Construction Bank Corporation Nanning New City Branch Pledgor: Anhui Boshike Environmental Protection Technology Co.,Ltd.|Guangxi Boshike Environmental Technology Co.,Ltd. Registration number: Y2024450000051 |