KR101271669B1 - 폐배터리의 유가금속 재활용방법 - Google Patents
폐배터리의 유가금속 재활용방법 Download PDFInfo
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- KR101271669B1 KR101271669B1 KR20110036628A KR20110036628A KR101271669B1 KR 101271669 B1 KR101271669 B1 KR 101271669B1 KR 20110036628 A KR20110036628 A KR 20110036628A KR 20110036628 A KR20110036628 A KR 20110036628A KR 101271669 B1 KR101271669 B1 KR 101271669B1
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- hydroxide
- leaching
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000002386 leaching Methods 0.000 claims abstract description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011572 manganese Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 29
- 239000010926 waste battery Substances 0.000 claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- 239000006182 cathode active material Substances 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 12
- 229910013716 LiNi Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 abstract description 15
- 239000000243 solution Substances 0.000 description 49
- 230000008569 process Effects 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000008859 change Effects 0.000 description 12
- 238000000975 co-precipitation Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910020632 Co Mn Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910017705 Ni Mn Co Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000027326 copulation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 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
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- 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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60Y—INDEXING SCHEME RELATING TO ASPECTS CROSS-CUTTING VEHICLE TECHNOLOGY
- B60Y2200/00—Type of vehicle
- B60Y2200/90—Vehicles comprising electric prime movers
- B60Y2200/92—Hybrid vehicles
-
- 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
- C01P2006/40—Electric properties
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
-
- 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
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
Description
도 2는 본 발명에 따른 양극활물질 제조의 다른 방법을 나타낸 공정도이고,
도 3은 본 발명에 따른 유가금속회수방법을 나타낸 공정도이고,
도 4는 폐 배터리팩에서 배터리모듈을 분리하는 모습을 나타낸 것이고,
도 5는 폐 배터리팩에서 배터리모듈의 전기적 연결을 설명한 것이고,
도 6은 배터리모듈에서 배터리셀을 분리하는 모습을 나타낸 것이고,
도 7은 배터리모듈에서 분리한 기판을 나타낸 것이고,
도 8은 배터리모듈에서 분리한 프레임을 나타낸 것이고,
도 9는 배터리모듈에서 분리한 배터리셀을 나타낸 것이고,
도 10은 배터리셀 방전 중의 모습을 나타낸 것이고,
도 11은 배터리셀 방전 후 방전용액을 나타낸 것이고,
도 12는 방전용액을 보충하지 않은 경우 배터리셀의 방전과정에서의 전압변화를 나타낸 것이고,
도 13은 방전용액을 보충하는 경우 배터리셀의 방전과정에서의 전압변화를 나타낸 것이고,
도 14는 방전된 배터리셀을 탈수 후 건조할 경우 건조율을 나타낸 것이고,
도 15는 방전된 배터리셀을 탈수 없이 건조할 경우 건조율을 나타낸 것이고,
도 16은 방전 및 건조된 배터리셀을 나타낸 것이고,
도 17은 방전 및 건조된 배터리셀에서 분리한 음극구조체의 모습이고,
도 18은 방전 및 건조된 배터리셀에서 분리한 양극구조체의 모습이고,
도 19는 양극구조체의 분쇄시간 및 입도별 농축율을 나타낸 것이고,
도 20은 -8mesh로 분리한 경우 분쇄시간 별 각 유가금속의 농축율을 나타낸 것이고,
도 21은 -18mesh로 분리한 경우 분쇄시간 별 각 유가금속의 농축율을 나타낸 것이고,
도 22는 -40mesh로 분리한 경우 분쇄시간 별 각 유가금속의 농축율을 나타낸 것이고,
도 23은 -65mesh로 분리한 경우 분쇄시간 별 각 유가금속의 농축율을 나타낸 것이고,
도 24는 황산 농도에 따른 유가금속 분말의 침출거동을 나타낸 것이고,
도 25는 황산 농도에 따른 유가금속 분말의 침출거동을 나타낸 것이고,
도 26은 침출온도에 따른 유가금속 분말의 침출거동을 나타낸 것이고,
도 27은 pH에 따른 불순물 제거 과정에서의 침전율을 나타낸 것이고,
도 28은 pH에 따른 공침 거동을 나타낸 것이고,
도 29는 실험에서 얻어진 삼성분계 수산화물의 XRD 결과를 나타낸 것이고,
도 30은 실험에서 얻어진 삼성분계 수산화물의 SEM 이미지를 나타낸 것이고,
도 31은 실험에서 얻어진 리튬탄산염의 XRD 결과를 나타낸 것이다.
Co | Mn | Ni | Li | Al | Cu | Fe | |
1 | 4.9 | 11.9 | 12.5 | 2.3 | 7.2 | 13.0 | 0.04 |
2 | 4.9 | 12.0 | 12.1 | 2.2 | 7.2 | 12.7 | 0.04 |
3 | 5.0 | 11.7 | 12.3 | 2.2 | 7.1 | 12.8 | 0.04 |
4 | 4.7 | 11.1 | 11.4 | 2.1 | 6.8 | 12.2 | 0.04 |
5 | 5.7 | 13.2 | 13.4 | 2.5 | 8.1 | 14.5 | 0.04 |
Ave. | 5.1 | 12.0 | 12.3 | 2.3 | 7.3 | 13.1 | 0.04 |
LiNixMnyCozO2 | Li | Ni | Mn | Co |
원자량 | 6.94 | 58.70 | 54.94 | 58.93 |
함량 (%) | 2.26 | 12.34 | 11.97 | 5.05 |
몰비 | 0.33 | 0.21 | 0.22 | 0.09 |
비율 | 1 | 0.6 | 0.7 | 0.3 |
성분 | Co | Mn | Ni | Li |
농도(g/L) | 10.39 | 14.47 | 16.07 | 12.25 |
침출 효율(%) | 98.4 | 98.9 | 98.8 | 98.6 |
성분 | Co | Mn | Ni | Li |
실험대상 추출액 | 17930 | 19270 | 17950 | 5570 |
pH 9 | 2386.4 | 2302.9 | 1779.1 | 4893.6 |
pH 10 | 15.3 | 553.8 | 2.5 | 4375.4 |
pH 11 | 0.3 | 0.0 | 0.5 | 4225.8 |
pH 12 | 0.3 | 0.0 | 0.5 | 4100.0 |
Co | Mn | Ni | Li | Al | Cu | |
공침 후 여액 | 0.1 | - | - | 5360.0 | 1.7 | 0.3 |
Li2CO3 침전 후 여액 | 1.45 | - | - | 416.8 | 0.04 | 0.33 |
Claims (20)
- 폐배터리의 유가금속 재활용 방법에 있어서,
폐배터리로부터 리튬, 니켈, 코발트 및 망간을 포함하는 유가금속 분말을 얻는 단계와;
상기 유가금속 분말을 환원분위기에서 산침출하여 침출용액을 얻는 단계와;
상기 침출용액으로부터 니켈, 코발트 및 망간의 수산화물과 리튬탄산염(Li2CO3)을 얻는 단계를 포함하며,
상기 침출용액을 얻은 후,
pH를 조절하여 구리, 알루미늄 및 철 중 적어도 하나의 불순물을 제거하는 단계를 더 포함하며,
상기 수산화물을 얻는 단계의 pH는 상기 불순물 제거 단계의 pH보다 높은 방법. - 제1항에 있어서,
상기 수산화물과 상기 리튬탄산염을 혼합 및 열처리하여 LiNixCoyMnzO2형태의 양극활물질을 얻는 단계를 더 포함하는 방법. - 제1항 및 제2항 중 어느 한 항에 있어서,
상기 침출용액은,
1.5M 내지 4M의 황산 및 4.5vol% 내지 10vol%의 과산화수소를 동시에 사용하여 50℃ 내지 80℃에서 얻어지는 것을 특징으로 하는 방법. - 삭제
- 삭제
- 제1항에 있어서,
상기 수산화물을 얻는 단계의 pH는 10 내지 13이며, 상기 불순물 제거 단계의 pH는 5.5 내지 6.5인 것을 특징으로 하는 방법. - 제1항 및 제2항 중 어느 한 항에 있어서,
상기 리튬탄산염은 상기 수산화물을 회수하고 남은 여액으로부터 리튬을 탄산화하여 얻어지는 것을 특징으로 하는 방법. - 제1항 및 제2항 중 어느 한 항에 있어서,
상기 침출용액을 얻은 후,
상기 침출용액 내의 니켈, 망간 및 코발트 각각의 농도를 조절하는 단계를 더 포함하는 것을 특징으로 하는 방법. - 제1항 및 제2항 중 어느 한 항에 있어서,
상기 폐배터리는 전기적으로 연결된 복수의 배터리모듈을 포함하고, 상기 배터리모듈은 전기적으로 연결된 복수의 배터리셀을 포함하며, 상기 배터리셀은 양극활물질로 LiNixCoyMnzO2를 사용하는 리튬이온전지타입이며,
상기 유가금속 분말을 얻는 단계는;
상기 폐배터리를 분해하여 상기 배터리셀을 얻는 단계와;
상기 배터리셀을 방전시키는 단계와;
상기 배터리셀 중 적어도 일부를 분쇄하고 입도분리하여 상기 유가금속 분말을 회수하는 단계를 포함하는 것을 특징으로 하는 방법. - 제9항에 있어서,
상기 방전은 방전용액 내에서 이루어지며,
상기 방전 후, 상기 배터리셀을 탈수하고 건조하는 단계를 더 포함하는 것을 특징으로 하는 방법. - 제10항에 있어서,
상기 방전 후,
상기 배터리셀을 양극구조체, 음극구조체 및 분리막으로 분리하는 단계를 더 포함하며,
상기 분쇄 및 입도분리는 상기 양극구조체를 대상으로 수행되는 것을 특징으로 하는 방법. - 제11항에 있어서,
상기 양극구조체는,
알루미늄 호일과;
상기 알루미늄 호일에 고정되어 있는 상기 양극활물질을 포함하는 것을 특징으로 하는 방법. - 제12항에 있어서,
상기 분쇄 및 입도분리는,
리튬, 니켈, 코발트 및 망간은 95%이상 회수되고, 알루미늄은 15%이하 회수되도록 수행되는 것을 특징으로 하는 방법. - 제1항에 있어서,
상기 폐배터리는,
하이브리드 전기자동차에서 얻어지는 것을 특징으로 하는 방법. - 삭제
- 삭제
- 삭제
- 삭제
- 삭제
- 삭제
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