WO2021261697A1 - 양극 스크랩을 이용한 활물질 재사용 방법 - Google Patents
양극 스크랩을 이용한 활물질 재사용 방법 Download PDFInfo
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- WO2021261697A1 WO2021261697A1 PCT/KR2021/000558 KR2021000558W WO2021261697A1 WO 2021261697 A1 WO2021261697 A1 WO 2021261697A1 KR 2021000558 W KR2021000558 W KR 2021000558W WO 2021261697 A1 WO2021261697 A1 WO 2021261697A1
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- WIPO (PCT)
- Prior art keywords
- active material
- lithium
- precursor
- lithium precursor
- aqueous solution
- Prior art date
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- 239000011149 active material Substances 0.000 title claims abstract description 247
- 238000000034 method Methods 0.000 title claims abstract description 104
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 180
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 179
- 239000002243 precursor Substances 0.000 claims abstract description 76
- 239000011230 binding agent Substances 0.000 claims abstract description 37
- 238000000137 annealing Methods 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 30
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000004020 conductor Substances 0.000 claims abstract description 22
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 22
- 239000006182 cathode active material Substances 0.000 claims abstract description 18
- 238000010298 pulverizing process Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 96
- 238000010438 heat treatment Methods 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 239000007774 positive electrode material Substances 0.000 claims description 33
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 150000002739 metals Chemical class 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 238000001694 spray drying Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000011164 primary particle Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- -1 Li 2 CO 3 Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000011163 secondary particle Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 229910013553 LiNO Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 47
- 230000008569 process Effects 0.000 description 43
- 238000009826 distribution Methods 0.000 description 24
- 239000010410 layer Substances 0.000 description 21
- 238000012986 modification Methods 0.000 description 18
- 230000004048 modification Effects 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000011241 protective layer Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 229910001512 metal fluoride Inorganic materials 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 108700028369 Alleles Proteins 0.000 description 2
- 239000004412 Bulk moulding compound Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000000670 limiting effect Effects 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
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101000856236 Clostridium acetobutylicum (strain ATCC 824 / DSM 792 / JCM 1419 / LMG 5710 / VKM B-1787) Butyrate-acetoacetate CoA-transferase subunit B Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001803 electron scattering Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- 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
- C22B7/001—Dry processes
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- 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
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/02—Electrodes composed of, or comprising, active material
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- H—ELECTRICITY
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- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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
- 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
Definitions
- the present invention relates to a method of recycling resources when manufacturing a lithium secondary battery.
- the present invention particularly relates to a method of recovering and reusing positive electrode scraps generated in a lithium secondary battery manufacturing process or a positive electrode active material of a lithium secondary battery that is discarded after use.
- This application is a priority claim application for Korean Patent Application No. 10-2020-0076728 filed on June 23, 2020, and all contents disclosed in the specification and drawings of the application are incorporated herein by reference.
- Lithium secondary batteries that can be repeatedly charged and discharged are in the spotlight as an alternative to fossil energy.
- Lithium secondary batteries have been mainly used in traditional hand-held devices such as cell phones, video cameras, and power tools.
- electric vehicles EVs, HEVs, PHEVs
- ESSs large-capacity power storage devices
- UPS uninterruptible power supply systems
- a lithium secondary battery includes an electrode assembly in which unit cells having a structure in which a positive electrode plate and a negative electrode plate coated with an active material are coated on a current collector with a separator interposed therebetween, and a casing for sealing and housing the electrode assembly together with an electrolyte, that is, a battery case to provide
- the cathode active material of the lithium secondary battery mainly uses a lithium-based oxide, and the anode active material uses a carbon material.
- the lithium-based oxide contains a metal such as cobalt, nickel, or manganese.
- cobalt, nickel, and manganese are very expensive precious metals, and among them, cobalt is a strategic metal, and each country in the world has a special interest in supply and demand. is known If there is an imbalance in the supply and demand of raw materials for strategic metals, raw material prices are highly likely to rise.
- waste batteries lithium secondary batteries
- resources can be recovered from wastes discarded after the positive electrode plate is punched or from the positive electrode having defects in the process.
- a positive electrode active material layer 20 when manufacturing a lithium secondary battery, as shown in FIG. 1 , a positive electrode active material layer 20 ) by forming the positive electrode sheet 30, and then punching out the positive electrode plate 40 to a predetermined size. The part remaining after punching is discarded as anode scrap (scrap, 50). If it is possible to recover the cathode active material from the cathode scrap 50 and reuse it, it would be very desirable from an industrial-economic point of view and an environmental point of view.
- the method of recovering the cathode active material is mostly to dissolve the cathode in hydrochloric acid, sulfuric acid, nitric acid, etc., extract active material elements such as cobalt, nickel, and manganese, and then use it again as a raw material for the cathode active material synthesis.
- the method of extracting the active material element using an acid has the disadvantage that the process for recovering the pure raw material is not environmentally friendly, and the neutralization process and the wastewater treatment process are required, which increases the process cost.
- it has a disadvantage that lithium, which is one of the main elements of the cathode active material, cannot be recovered.
- a method that can be directly reused without dissolving the positive electrode active material and extracting the active material in elemental form is required.
- the positive electrode sheet 30 is usually subjected to a rolling step. Therefore, in the case of anode scrap made of electrodes, particles on the surface are pressed and broken by the rolling process. In the case of a fresh active material that has never been used, there is no particle breakage, but in the case of a reusable active material obtained from a rolled electrode, the more the particles broken by rolling, the more the specific surface area of the active material increases. Problems that may affect adhesion and electrode performance may occur. Therefore, there is also a need for a solution for this.
- the problem to be solved by the present invention is to provide a method for recovering and reusing an active material from a cathode scrap.
- the cathode active material reuse method of the present invention is (a) heat-treating a cathode scrap including a lithium composite transition metal oxide cathode active material layer on a current collector in air to thermally decompose a binder and a conductive material in the active material layer by doing so, separating the current collector from the active material layer and recovering the active material in the active material layer; (b-1) washing the recovered active material with an aqueous solution of a lithium compound showing basicity in an aqueous solution and drying; (b-2) pulverizing the dried active material; (b-3) adding a lithium precursor to the pulverized active material; and (c) annealing the active material to which the lithium precursor is added to obtain a reusable active material.
- (d) may further include the step of surface coating on the annealed active material.
- the lithium composite transition metal oxide includes primary particles having a size of several tens to hundreds of nanometers to form secondary particles, and the pulverizing is to reduce the size of the dried active material to the primary particle size. It may include the step of reducing the particle size to a larger size.
- the lithium composite transition metal oxide may include nickel, cobalt and manganese.
- the heat treatment may be performed at 300 to 650 °C.
- the heat treatment may be performed at 550° C. for 30 minutes at a temperature increase rate of 5° C./min.
- the lithium compound aqueous solution is prepared to contain more than 0% and 15% or less of the lithium compound, and preferably LiOH is used.
- the washing may be performed within 1 hour.
- the washing may be performed by stirring the recovered active material simultaneously with the impregnation of the lithium compound aqueous solution.
- the grinding step may be performed using a ball mill, a planetary mill, a grinder, a 3-roll mill, or a jet mill.
- the step of adding the lithium precursor to the pulverized active material may be added in the form of a solid or liquid.
- the step of adding the lithium precursor to the pulverized active material is preferably a step of obtaining a particle-controlled active material by mixing the pulverized active material with a lithium precursor solution and spray-drying.
- the lithium precursor may be any one or more of LiOH, Li 2 CO 3 , LiNO 3 and Li 2 O.
- the lithium precursor may be added in an amount capable of adding as much as the ratio of lithium lost compared to the ratio of lithium and other metals in the raw material active material used for the active material layer.
- the lithium precursor may be added in an amount in which lithium is added in a molar ratio of 0.001 to 0.4.
- the lithium precursor is preferably added in an amount capable of further adding lithium in a molar ratio of 0.0001 to 0.1 molar ratio based on a molar ratio of lithium: other metals of 1:1.
- the annealing may be performed at 400 to 1000° C. in air.
- the temperature of the annealing step may be a temperature exceeding the melting point of the lithium precursor.
- the active material in the active material layer may be recovered in the form of a powder, and a carbon component generated by carbonization of the binder or the conductive material may not remain on the surface.
- the step of coating the surface may be one or more of a metal, an organic metal, and a carbon component, coated on the surface in a solid or liquid manner, and then heat-treated at 100 ⁇ 1200 °C.
- the reusable active material may be represented by the following formula (1).
- the reusable active material may have a fluorine (F) content of 100 ppm or less.
- the waste positive electrode active material such as positive electrode scrap generated during the lithium secondary battery manufacturing process can be reused without using an acid, so it is eco-friendly.
- the method according to the present invention does not require a neutralization process or a wastewater treatment process, so it is possible to alleviate environmental issues and reduce process costs.
- the present invention it is possible to recover the positive electrode active material without a metal element that cannot be recovered. Since the current collector is not dissolved, the current collector can also be recovered. It is economical because it is a method that can directly reuse the active material recovered in powder form rather than extracting the active material element and using it again as a raw material for synthesizing the cathode active material.
- the present invention it is safe because it does not use toxic and explosive solvents such as NMP, DMC, acetone, and methanol, and because simple processes such as heat treatment, washing, and annealing are used, process management is easy and suitable for mass production.
- toxic and explosive solvents such as NMP, DMC, acetone, and methanol
- the electrochemical performance of the recovered active material is not deteriorated, and excellent resistance characteristics and capacity characteristics can be realized.
- the active material pulverization step it is possible to reduce the particles split during rolling in the previous process. Since small particles can be re-granulated by adjusting the particle size again in the stage after pulverization, it is possible to improve the particle size and specific surface area.
- the lithium precursor supplementation can be carried out simultaneously while re-granulating, thereby simplifying the process for obtaining the lithium precursor and particle-controlled active material.
- 1 is a view showing positive electrode scrap discarded after the positive electrode plate is punched from the positive electrode sheet.
- FIG. 2 is a flowchart of an active material reuse method according to the present invention.
- FIG. 3 is a schematic diagram illustrating a lithium precursor addition step by spray drying among the lithium precursor addition step of FIG. 2 .
- 5 and 6 are scanning electron microscope (SEM) pictures of the sample active material.
- 11 is a particle size distribution graph of the active materials of Examples and Comparative Examples.
- the present invention is a lithium secondary battery There is a difference in that the active material is also recovered from the cathode scrap generated during the manufacturing process.
- the present invention relates to a method of directly reusing the cathode active material without dissolving it.
- a method for removing the current collector from the positive electrode is required.
- To remove the current collector from the positive electrode it is possible to remove the binder through high-temperature heat treatment, to melt the binder using a solvent, to completely melt the current collector, and to select the active material through dry grinding and sieving. do.
- the stability of the solvent is important in dissolving the binder using the solvent.
- NMP is probably the most efficient solvent, but it has the disadvantages of toxicity and high price.
- a solvent recovery process such as reprocessing the waste solvent is required. Melting the current collector will be cheaper than using a solvent.
- there is a risk of explosion because it is difficult to remove foreign substances from the surface of the reusable active material and hydrogen gas is generated during the current collector removal process. It is difficult to completely separate the current collector and the active material by dry grinding and sieving. During the pulverization process, the particle size distribution of the active material is changed and it is difficult to remove the binder, so there is a disadvantage in that the characteristics of the reused battery deteriorate.
- the active material and the current collector are separated using high-temperature heat treatment.
- heat treatment is carried out in air, it is advantageous for mass production and commercialization because it is a relatively simple process that does not require a special device configuration and only needs to be heated.
- foreign substances should not remain on the surface of the reusable active material. In the present invention, even the step of removing foreign substances from the surface of the reusable active material is proposed.
- FIG. 2 is a flowchart of an active material reuse method according to the present invention.
- a cathode scrap to be discarded is prepared (step S10).
- the positive electrode scrap may be a portion left after manufacturing a positive electrode sheet including a lithium composite transition metal oxide positive electrode active material layer on a current collector and punching out.
- anode scrap by collecting anodes having defects during the process.
- positive electrode scrap may be prepared by separating the positive electrode from the discarded lithium secondary battery after use.
- an active material that is a lithium composite transition metal oxide (hereinafter simply referred to as 'NCM-based lithium composite transition metal oxide') containing nickel (Ni), cobalt (Co) and manganese (Mn), a carbon-based carbon as a conductive material
- 'NCM-based lithium composite transition metal oxide' containing nickel (Ni), cobalt (Co) and manganese (Mn), a carbon-based carbon as a conductive material
- NMP N-methyl pyrrolidone
- PVdF polyvinylidene fluoride
- a lithium composite transition metal oxide is used as a cathode active material for a lithium secondary battery.
- lithium cobalt oxide of LiCoO 2 lithium manganese oxide (LiMnO 2 or LiMn 2 O 4 etc.), lithium iron phosphate compound (LiFePO 4 etc.) Or lithium nickel oxide (LiNiO 2, etc.) is mainly used.
- An NCM-based lithium composite transition metal oxide is used as a method for improving low thermal stability while maintaining the excellent reversible capacity of LiNiO 2 .
- An NCM-based lithium composite transition metal oxide is used.
- the reuse of an NCM-based lithium composite transition metal oxide active material is
- the positive electrode scrap has an active material layer on a current collector of a metal foil such as aluminum foil.
- the active material layer is formed by coating a slurry in which an active material, a conductive material, a binder, a solvent, etc. are mixed, and has a structure in which the binder connects the active material and the conductive material after the solvent is volatilized. Therefore, if the binder is removed, the active material may be separated from the current collector.
- step S20 the anode scrap is crushed to an appropriate size.
- Shredding refers to the cutting or shredding of anode scrap into pieces of suitable, easy-to-handle size. After crushing, the anode scrap is cut into small pieces, for example 1 cm x 1 cm.
- various dry crushing equipment such as hand-mill, pin-mill, disk-mill, cutting-mill, hammer-mill may be used, or a high-speed cutter may be used.
- Crushing can be carried out in consideration of the characteristics required in the equipment used in the handling of the anode scrap and subsequent processes. For example, in the case of using equipment that requires continuous processing in loading and unloading anode scrap, the fluidity of the anode scrap must be good, so that too large anode scrap must be crushed.
- the anode scrap is heat-treated in air (step S30).
- the heat treatment is performed to thermally decompose the binder in the active material layer.
- Heat treatment can be performed at 300 ⁇ 650 °C, so it can be called high temperature heat treatment.
- At a temperature of less than 300 °C it is difficult to remove the binder, so that the current collector cannot be separated.
- the current collector melts (Al melting point: 660 °C), and the current collector cannot be separated.
- the heat treatment time is maintained so that the binder can be sufficiently thermally decomposed. For example, around 30 minutes. Preferably it is set as 30 minutes or more. The longer the heat treatment time, the longer the time for thermal decomposition of the binder to occur. Preferably, the heat treatment time is 30 minutes or more and less than 5 hours.
- the heat treatment equipment may be various types of furnaces.
- it may be a box-type furnace or a rotary kiln capable of continuous processing in consideration of productivity.
- the heat treatment may be performed at 550° C. for 30 minutes at a temperature increase rate of 5° C./min.
- the temperature rise rate is, for example, a degree that can be implemented without excessive force in a box-type furnace and can be heated without generating a thermal shock or the like to the anode scrap.
- 550°C is to allow the thermal decomposition of the binder to occur well while considering the melting point of the Al current collector. At this temperature, heat treatment for less than 10 minutes is insufficient for thermal decomposition, so heat treatment should be carried out for more than 10 minutes, and heat treatment should be performed for more than 30 minutes if possible.
- the binder and conductive material in the active material layer are thermally decomposed through heat treatment in air, they become CO 2 and H 2 O and are removed. Since the binder is removed, the active material is separated from the current collector, and the active material to be recovered may be selected in powder form. Therefore, only in step S30, the current collector can be separated from the active material layer and the active material in the active material layer can be recovered.
- step S30 it is important that the heat treatment in step S30 be performed in air. If the heat treatment is performed in a reducing gas or inert gas atmosphere, the binder and the conductive material are not thermally decomposed but only carbonized. When carbonization is performed, the carbon component remains on the surface of the active material, thereby degrading the performance of the reusable active material. When heat treatment is performed in air, carbon material in the binder or conductive material reacts with oxygen and is burned and removed as CO and CO 2 gas, so that almost all of the binder and conductive material are removed without remaining.
- the active material is recovered in the form of a powder, and the carbon component generated by carbonization of the binder or the conductive material may not remain on the surface.
- the recovered active material is washed and dried (step S40).
- This lithium compound aqueous solution is prepared to contain more than 0% and 15% or less of the lithium compound and preferably uses LiOH.
- the amount of LiOH is preferably 15% or less.
- the use of excess LiOH may leave excess LiOH on the surface of the active material even after washing, which may affect future annealing processes. In order to clean the surface of the active material in the pre-annealing step as much as possible, the addition of excess LiOH is not good for the process, so it is limited to 15% or less.
- Washing may be performed by immersing the recovered active material in the lithium compound aqueous solution. After immersion, washing may be performed within a week, preferably within one day, and still more preferably within one hour. When washing for more than a week, there is a risk of capacity degradation due to excessive lithium elution. Therefore, it is preferable to carry out within 1 hour. Washing includes immersing the active material in an aqueous lithium compound solution showing basicity in an aqueous solution state, stirring the immersion state, and the like. It is recommended to use agitation as much as possible. If the lithium compound is immersed in an aqueous solution without stirring, the washing process is slow and may cause lithium leaching.
- the stirring be performed simultaneously with the impregnation of the lithium compound aqueous solution. Drying may be performed in air in an oven (convection type) after filtration.
- Step S30 of the heat treatment as long material binder and conductive in the active material layer are removed is vaporized as a CO 2 and H 2 O
- CO 2 and H 2 O is the active material the lithium and reaction of the surface of Li 2 CO 3
- LiOH is also formed
- fluorine (F) present in a binder such as PVdF reacts with a metal element constituting the positive electrode active material to form LiF or metal fluoride. If LiF or metal fluoride remains, battery characteristics deteriorate when the active material is reused.
- a washing step as in step S40 to remove reactants that may have been generated on the surface of the reused active material during the heat treatment step (S30), foreign substances are not left on the surface of the recycled active material.
- step S40 it is important to wash with a lithium compound aqueous solution showing basicity in an aqueous solution state. If an aqueous solution of sulfuric acid or hydrochloric acid is used rather than an aqueous solution of a lithium compound showing basicity in an aqueous solution, it is possible to wash F on the surface of the active material, but it elutes transition metals (Co, Mg) present in the active material, thereby reducing the performance of the reused cathode active material.
- transition metals Co, Mg
- the lithium compound aqueous solution showing basicity in the aqueous solution state used in the present invention can remove the binder that may remain in a trace amount even after thermal decomposition in step S30, and does not elute the transition metal present in the active material, and in the washing process It is very desirable because it can also serve to supplement the amount of lithium that can be eluted.
- step S40 in the present invention, it is possible to adjust the LiF content on the surface of the recovered active material to less than 500 ppm, and through this, the capacity improvement effect can be seen.
- the F content may be 100 ppm or less. More preferably, the F content may be 30 ppm or less.
- LiF or lithium metal compound formed by decomposition of the binder may be removed to improve electrical resistance characteristics.
- the dried active material is ground (step S42).
- the lithium composite transition metal oxide includes primary particles having a size of several tens to hundreds of nm gathered to form secondary particles. It may include a step.
- the grinding step ( S42 ) may be performed using a ball mill, a planetary mill, a grinder, a 3-roll mill, or a jet mill.
- Ball mills and planetary mills are well-known equipment used for powder mixing and grinding.
- the 3-roll mill is an equipment that disperses and pulverizes the paste sample fed by rotating three rollers at different rotation ratios.
- Jet mill is a fine pulverizer that blows compressed air or water vapor over several atmospheres from a special nozzle, sucks the pulverized raw material into this high-speed jet, accelerates it sufficiently, and then collides the particles with each other or collides the accelerated particles with a colliding plate to pulverize them. say It is used when using products of several nm in dry type, and in particular, there is little heat generation due to pulverization. Structurally, there is a classifier attached to the grinder, so it is possible to obtain a pulverized product of a desired size.
- the particles on the surface may be pressed and cracked or broken by the rolling process.
- the NCM-based active material has greater particle splitting due to rolling during electrode formation, so compared to the raw material active material used for the active material layer (that is, a fresh active material that has never been used), the recovered active material contains a lot of small particles. There is a problem of particle non-uniformity. In order for the active material to be at a reusable level, it is desirable that the particle size distribution should not be different from that of the fresh active material.
- the NCM-based active material uses a mixture of primary particles having a size of several tens to hundreds of nm and includes secondary particles of alleles. Secondary particles are split and formed into primary particles or smaller particles than large particles. Since the specific surface area of the active material increases as the number of particles broken by rolling increases, in the case of a reusable active material obtained from a rolled electrode, there may be problems that may affect slurry properties, electrode adhesion, and electrode performance when reused. Therefore, the present invention tries to solve this through the grinding step S42.
- the particles divided during rolling in the previous process may be made small.
- Small particle size is to pulverize the active material to a size greater than or equal to the primary particle size. Thereafter, particle size and specific surface area can be improved because the particle size can be adjusted again in a subsequent process such as a lithium precursor addition step or annealing to enable re-granulation.
- a lithium precursor is added to the pulverized active material (step S44).
- step S44 Loss of lithium in the active material may occur during the preceding steps S30 and S40.
- step S44 such lithium loss is compensated.
- the step of adding the lithium precursor to the pulverized active material (S44) may be added in a solid or liquid form.
- the lithium precursor may be any one or more of LiOH, Li 2 CO 3 , LiNO 3 and Li 2 O.
- the solid lithium precursor may be added by a powder mixing or milling process. While the solid lithium precursor is added, the previously pulverized active material may be re-particulated.
- the lithium precursor is added in an amount capable of adding as much as the ratio of lithium lost compared to the ratio of lithium and other metals in the raw material active material (ie, fresh active material) used in the active material layer.
- a lithium precursor in an amount capable of adding lithium in a molar ratio of 0.001 to 0.4 may be added.
- lithium in a molar ratio of 0.01 to 0.2 is added.
- the lithium precursor is preferably added in an amount capable of further adding lithium in a molar ratio of 0.0001 to 0.1 based on a molar ratio of lithium: other metals of 1:1.
- the reason for adding the excess lithium as described above is to form a surface protection layer by surface coating on the active material, which will be further described below. In the case of manufacturing a secondary battery using such an active material, it is possible to maintain a lifespan characteristic while suppressing a side reaction caused by an electrolyte.
- the lithium precursor to the pulverized active material may be added in a liquid form.
- the lithium precursor solution uses a lithium compound soluble in an aqueous solution or an organic solvent, and the temperature of the spray-drying step is preferably 80° C. or higher, because when it is 80° C. or less, a problem in which the solution is not completely dried may occur. More preferably, the temperature of the spray drying step may be 100 ⁇ 300 °C.
- Spray drying may have an advantage in that there is no agglomeration of particles due to drying, and thus it is produced in the form of a powder rather than a lump.
- the lithium precursor component is coated or contacted on the surface of the active material as the lithium precursor solution is dried immediately after spraying. .
- the spray drying proposed here can recover the particles made into small particles in the previous pulverization step into large particles, it can solve the particle non-uniformity and make the particle size close to the initial characteristics of the fresh active material. Therefore, it can be expected that the battery characteristics using the active material recovered by the method according to the present invention will be at a level similar to those of the battery using the fresh active material.
- the lithium precursor can be refilled while re-granulating, so that the lithium precursor is added and the particle-controlled active material can be obtained.
- the advantage is that the lithium precursor coating, drying and granulation (particle readjustment) are performed simultaneously in one step.
- the lithium precursor is coated on the surface of the active material, and the active material is obtained by controlling the particles. Since the lithium precursor addition, re-granulation, and drying are performed in one step, there is an effect of simplifying the process. In addition, spray drying is special in that it is not a means for simply obtaining the active material, but a means for re-granulating the previously pulverized active material into small particles.
- FIG. 3 is a schematic diagram illustrating a lithium precursor addition step by spray drying among the lithium precursor addition step of FIG. 2 .
- a lithium precursor aqueous solution 100 is prepared by dissolving LiOH in distilled water, and a mixed solution 120 in which the active material 110 that has been pulverized in step S42 is mixed and dispersed is shown.
- the pulverized active material 110 is pulverized to a size greater than or equal to the primary particle size, so that the pulverized active material 110 has uniform sizes.
- the mixed solution 120 may be kept in a stirred state.
- the particle size of the spray-dried active material 120" can be adjusted by adjusting the density of the mixed solution 120, the temperature in the heating container 140, the size of the micro-droplets 120', and the like. Accordingly, an annealing process to be described later
- the reusable active material obtained according to the present invention can have a particle size distribution similar to that of the fresh active material. We define that the distributions are similar.
- step S50 the active material to which the lithium precursor is added, obtained in the previous step S44, is annealed.
- step S50 the crystal structure of the active material is restored through annealing to restore or improve the properties of the reused active material to the level of a fresh active material that has never been used.
- a deformed structure may appear on the surface of the active material.
- the active material that is an NCM-based lithium composite transition metal oxide in step S40, Ni is rock salted by moisture [NiCO 3 ⁇ 2Ni(OH) 2 )H 2 0] to form a spinel structure. . If the battery is manufactured as it is, battery characteristics such as capacity reduction may deteriorate.
- the crystal structure is restored through step S50.
- the active material, which is an NCM-based lithium composite transition metal oxide is restored to a hexagonal structure. Accordingly, it is possible to restore or improve the initial properties to a level similar to that of the fresh active material.
- Annealing may be performed at 400 to 1000° C. in air.
- the annealing temperature may be 600-900°C. This temperature should be changed within a limited range depending on the type of the lithium precursor. It is preferable to set the annealing time to 1 hour or more. Preferably, it is about 5 hours. If the annealing time is long, the crystal structure can be sufficiently recovered, but even if it is used for a long time, the performance is not significantly affected. Annealing time is made into 15 hours or less, for example.
- the annealing equipment may use the same or similar equipment as in the heat treatment step S30.
- the annealing temperature is preferably between 700 and 900° C., more preferably between 710 and 780° C. This is because the melting point of Li 2 CO 3 is 723°C. Most preferably, it is carried out at 750°C.
- the annealing temperature is preferably 400 to 600°C, more preferably 450 to 480°C. This is because the melting point of LiOH is 462°C.
- the annealing temperature is preferably a temperature exceeding the melting point of the lithium precursor. However, at a temperature exceeding 1000°C, thermal decomposition of the positive electrode active material occurs and the performance of the active material is deteriorated, so it should not exceed 1000°C.
- step S50 As the lithium precursor is melted through this step S50, aggregation of the active material particles may be induced, and re-particulation may be performed in this process. In this way, according to step S50, a reusable active material can be obtained.
- step S60 may be further performed.
- a surface coating is applied to the active material annealed in step S50.
- the step of coating the surface may be one or more of a metal, an organic metal, and a carbon component, coated on the surface in a solid or liquid manner, and then heat-treated at 100 to 1200°C.
- a metal, an organic metal, and a carbon component coated on the surface in a solid or liquid manner, and then heat-treated at 100 to 1200°C.
- the heat treatment is performed at a temperature exceeding 1200° C., there is a risk that performance may be deteriorated due to thermal decomposition of the positive electrode active material.
- coating on the surface in a solid or liquid manner may use methods such as mixing, milling, spray drying, and grinding.
- a surface protection layer is formed by a dissimilar metal through the surface coating.
- the molar ratio of lithium: other metals in the positive active material is 1:1, lithium in the active material reacts with the surface coating material and the lithium: other metal in the positive active material decreases to less than 1:1, the capacity expression can be reduced by 100%. can't Therefore, the insufficient lithium is added in the previous step S44 so that the molar ratio of lithium to other metals in the positive electrode active material is 1:1, and an excess is added so that 0.0001 to 0.1 mole ratio of lithium is more contained in the positive active material compared to other metals in the positive electrode active material. . Then, when the surface is coated, the molar ratio of lithium: other metals in the positive electrode active material becomes 1:1, and a surface protective layer can be formed.
- a metal oxide such as B, W, B-W is coated on an active material and then heat treated, a lithium borooxide layer can be formed on the surface of the active material, which serves as a surface protective layer.
- a lithium borooxide layer can be formed on the surface of the active material, which serves as a surface protective layer.
- step S44 more lithium added in a molar ratio of 0.0001 to 0.1 reacts with metal oxides such as B, W, and BW in step S60, and the lithium: other metal molar ratio in the positive electrode active material does not decrease to less than 1:1, so that the capacity decrease is not none.
- the reusable active material obtained by the above-described method may be represented by the following formula (1).
- the reusable active material may have an F content of 100 ppm or less. According to the present invention, since it is possible to recover an active material having a reduced F content, if it is reused as an active material, excellent resistance characteristics and capacity characteristics can be realized.
- LiF or metal fluoride is removed in step S40 of washing. Removal of particle non-uniformity through addition of a lithium precursor and particle control is performed in pulverization and lithium precursor addition steps (S42 and S44).
- the washing and drying steps using a lithium compound aqueous solution showing basicity in an aqueous solution are safe and inexpensive, but can remove LiF or metal fluoride without loss of other elements, and do not affect the anode structure because it prevents the elution of transition metals, etc. Not only that, but also has the advantage of supplementing the lithium loss that occurs during the process.
- the lithium precursor addition step (S44) is performed using spray drying, the lithium precursor can be added in a simple way, and it helps to have a particle size similar to that of the fresh active material.
- the annealing step is also safe and inexpensive, it has the advantage of recovering the cell characteristics of the reused active material by improving the crystal structure recovery, that is, crystallinity.
- the reusable active material obtained according to the present invention may have a particle size distribution similar to that of the fresh active material, and thus a separate treatment for controlling the particle size distribution may not be required. Since the carbon component generated by carbonization of the binder or the conductive material does not remain on the surface, a step or the like for removing the carbon component is not required. Accordingly, the active material obtained through the method of FIG. 2 may be reused as it is without additional treatment and used to manufacture the positive electrode.
- the positive active material was prepared by the following method and then evaluated.
- the experiment was mainly performed in two categories. The first is an experiment related to pulverization as in step S42, and the second is verification of the effectiveness of the method according to the present invention on the NCM active material.
- the small particle experiment by pulverization in step S42 is carried out by mixing zirconia balls (1-5 mm) in 15 g of the positive active material from which the binder and conductive material are removed through step S30 according to the present invention in a 1: 4 ratio and performing ball milling.
- a powder shaker equipment was used, and the zirconia balls were put in and proceeded for 1 hour to 3 hours.
- grinding equipment a planetary mill may be used in addition to the powder shaker equipment which is a ball mill equipment, and a grinder, a 3-roll mill, a jet mill, etc. may be used.
- Sample #1 is a fresh cathode active material.
- Sample #2 is a cathode active material from which a binder and a conductive material are removed through step S30 according to the present invention. Sample #2 was obtained by thermally decomposing the binder and the conductive material by applying heat to the anode scrap at 550° C. for 30 minutes.
- Sample #3 is a positive electrode active material obtained by ball milling Sample #2 for 1 hour by the method presented above.
- Sample #4 is a positive electrode active material obtained by ball milling Sample #2 for 3 hours by the method presented above.
- Sample #5 was annealed at 750° C. for 5 hours after adding Li 2 CO 3 as a lithium precursor to Sample #4. That is, steps S44 and S50 of the method of the present invention are further performed. Li 2 CO 3 was added in a solid phase by mixing using a mortar mixer.
- 4 is a particle size distribution graph of sample active materials.
- 5 and 6 are scanning electron microscope (SEM) pictures of the sample active material. The SEM picture was taken with a general SEM device that is well used in the laboratory. For example, you can take pictures using HITACHI's s-4200. However, there is no deviation depending on the measuring device or method.
- Sample #2 the active materials of Sample #1 are split into sub-micron particles (less than 1 micrometer) and micronized by pressure in the electrode process.
- Sample #3 in which these fines were ball milled, during the ball milling process, these fines were agglomerated into small particles, and the large particles tended to become smaller.
- Sample #4 which had a longer milling time compared to Sample #3, the distribution of differentials was further reduced and the distribution of alleles was also reduced. That is, it can be seen that as the milling time increases, the opposite particles are minimized and the particles become elementary particles, and the fine particles tend to become elementary particles.
- sample #5 has a particle size distribution opposite to that of sample #1.
- the same particle size distribution as sample #5 was obtained by adding a lithium precursor in a solid state. Accordingly, it can be re-granulated and a particle size distribution similar to Sample #1 can be obtained.
- the lithium precursor can be re-particulated by mixing or dissolving the lithium precursor in a particulated powder form and then mixing the pulverized active material. For example, in the case of spray drying, a lithium compound is dissolved in a solvent (aqueous solution or organic solvent), mixed with the positive active material, and the particle size can be variously adjusted by changing conditions.
- Example 1 A reused active material was collected according to the active material reuse method of the present invention as described above.
- the positive electrode scrap to be discarded after punching the NCM-based lithium composite transition metal oxide as an active material was prepared, and the heat treatment in step S30 was performed at 550° C. for 30 minutes.
- the washing in step S40 was performed for 10 minutes using LiOH.
- Step S42 was performed by performing ball milling for 3 hours as in Sample #4 of the previous category experiment.
- Step S44 was performed by adding Li 2 CO 3 using an induction mixer as in Sample #5 of the previous category experiment.
- a lithium precursor Li 2 CO 3 in an amount capable of further adding lithium at a molar ratio of 0.09 during the process is added. Annealed according to S50 at 750° C. for 15 hours.
- the molar ratio of lithium to other metals is 1:1, but the average error of the ICP equipment that confirms this is ⁇ 0.05, preferably ⁇ 0.02, so lithium of the raw material active material through ICP measurement: mole of different metal The ratio may be 1 ⁇ 0.05:1.
- a lithium precursor was added based on the analysis ratio through ICP analysis.
- Example 2 In addition to Example 1, the active material surface protective layer recovery process of step S60 was also performed.
- Comparative Example 1 A fresh NCM-based lithium composite transition metal oxide, not a reused active material, was used.
- Comparative Example 2 Only the heat treatment of step S30 of the active material reuse method of the present invention as described above was performed to remove the binder, the conductive material, and the Al current collector, and the NCM-based lithium composite transition metal oxide active material was collected. Step S30 was performed under the same conditions as in Example 1. Steps after step S40 of the active material reuse method of the present invention were not carried out.
- Comparative Example 3 Further, in Comparative Example 2, the active material was collected by carrying out the surface modification of step S40 of the active material reuse method of the present invention as described above. That is, the surface modification was performed, but steps after step S42 of the active material reuse method of the present invention were not performed. Step S40 was performed under the same conditions as in Example 1.
- Comparative Example 4 Further from Comparative Example 2, as described above, in the active material reuse method of the present invention, the surface modification of step S40 was not performed and only the crystal structure recovery of step S50 was performed without steps S42 and S44, so that NCM-based lithium composite transition metal The oxide active material was collected. Note that even if annealing for crystal structure recovery was performed, it was carried out without addition of a lithium precursor.
- Comparative Example 5 In the same manner as in Example 1, only steps S30, S40 and S50 were performed. Note that even if annealing for crystal structure recovery was performed, it was carried out without addition of a lithium precursor.
- ICP analysis was performed on the positive active materials recovered or prepared in Examples and Comparative Examples, respectively, to analyze the amount of remaining LiF, the ratio of lithium and other metals in the active material, and the amount of specific elements such as B or W.
- ND means measured 30 ppm or less.
- Comparative Example 2 is about 0.2 to 0.5 compared to Comparative Example 1
- Comparative Example 3 is about 0.2 to 0.5 compared to Comparative Example 2 while washing and drying S40. It can be seen that the ratio of /other metals decreases.
- the NCM-based lithium composite transition metal oxide has a relatively large particle specific surface area and appears to have a large decrease in the lithium ratio compared to other metals due to the change to the spinel structure. Therefore, it can be seen that the insufficient lithium must be supplemented.
- Table 2 shows the values measured by the ICP analysis, and as mentioned above, the ICP analysis has an error value of about ⁇ 0.02. Therefore, even in Comparative Example 1, which is a fresh active material, the ratio between lithium and other metals may be less than 1. Therefore, the amount of lithium precursor added to compensate for the loss of lithium is the amount of lithium that is reduced based on the ratio of lithium to other metals (molar ratio analyzed by ICP) in the raw material active material (ie, fresh active material) used in the active material layer. Let the content be added.
- FIGS. 7 and 8 are results of cell evaluation using the active materials of Examples and Comparative Examples. At different currents, the rate performance was examined by evaluating the capacity according to the number of cycle repetitions.
- the equipment used for evaluation is a general charging/discharging test device that is well used in the laboratory. There is no deviation depending on the measuring device or method.
- the horizontal axis indicates the number of cycles and the vertical axis indicates capacity.
- the voltage was set to 3 ⁇ 4.3V, and initial formation charge and discharge was performed at 0.1C/0.1C.
- Example 1 compared to Comparative Example 5
- pulverization and addition of a lithium precursor were performed to control the particle size distribution. It can be seen that by adding the lithium precursor in this way, the capacity is improved by supplementing the lithium lost in the previous steps.
- the loss of lithium through heat treatment and washing has been described with reference to Table 2.
- the active material can be recovered from the cathode scrap to a level that can be directly reused. It is safe because it does not use toxic and explosive solvents such as NMP, DMC, acetone, and methanol, and it is suitable for mass production because it uses simple and safe methods such as heat treatment, washing and drying, and annealing.
- toxic and explosive solvents such as NMP, DMC, acetone, and methanol
- Figure 9 (e) is an SEM photograph of Comparative Example 2
- (f) is an enlarged photograph of (e).
- no binder or conductive material is observed in the recovered active material. That is, it can be confirmed that they are removed during the high-temperature heat treatment process. Therefore, it can be seen that the active material is separated from the current collector only by heat treatment in air, and almost no binder or conductive material remains on the surface of the active material.
- 11 is a particle size distribution graph of the active materials of Examples and Comparative Examples.
- the particle size distribution can be obtained with a general particle size analyzer well used in the laboratory. For example, it can be measured using a Horiba LA 950V2 particle size analyzer. However, there is no deviation depending on the measuring device or method. 11 , the horizontal axis represents particle size (um) and the vertical axis represents volume %.
- the particle size distribution graph results of FIG. 11 are consistent with the SEM results of FIGS. 9 and 10 .
- the NCM-based active material has large particle splitting due to rolling during electrode formation, so it can be seen that a large number of small particles are formed in the particle size distribution of Comparative Example 2 after the primary heat treatment, and the small particle distribution is relatively large even in Comparative Example 3 after surface modification can confirm.
- agglomeration of particles is increased, so that Comparative Example 5 or Example 1 has a similar particle size distribution to Comparative Example 1, which is a fresh active material.
- Example 1 is more similar to the particle size distribution of Comparative Example 1 because it undergoes a step of reducing the particles to a size greater than or equal to the primary particles by performing pulverization.
- the particle size branching is defined as similar.
- the fresh active material used in this experiment further contained B and W.
- B and W the content of B and W decreased during the heat treatment, and looking at the remaining results, it can be seen that almost all of B is removed in subsequent processes.
- W it can be seen that a large amount is removed during the surface modification process through washing as in Comparative Example 3.
- the annealing step as in Example 1
- the surface coating step is to coat B and W in the case of this experimental example.
- the surface coating may act as a surface protective layer of the positive electrode active material.
- Surface coating can also be a process that replenishes a certain element that is lacking while at the same time rebuilds the surface protective layer in the fresh active material.
- the surface protective layer is made of BW, and the amount of lithium lost during the process is not 1:1 in the ratio of other metals to lithium in the active material itself (Lithium of the active material + lithium formed on the surface protective layer): other metals
- the meaning is interpreted as a ratio. Therefore, in the above experiment, the 0.09 molar ratio lost as in Comparative Example 3 can be interpreted as the amount of lithium combined with lithium in the positive active material and lithium for forming a surface protective layer, and in Examples, the amount of lithium that can be supplemented A lithium precursor is added.
- the surface coating step is subjected to a heat treatment process after the solid or liquid phase reaction.
- the surface coating heat treatment may be performed at a temperature of 200 to 500 ° C, and other components are also metal components at a temperature within 100 to 1200 ° C. , it can be coated with carbon components and organometallic components.
- the cathode scrap can be reused using a simple, eco-friendly, and economical method, and even if a lithium secondary battery is manufactured by reusing the NCM-based lithium composite transition metal oxide cathode active material prepared in this way as it is, the battery There is no problem with the performance of
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Abstract
Description
Claims (20)
- (a)집전체 상에 리튬 복합 전이금속 산화물 양극 활물질층을 포함하는 양극 스크랩을 공기 중 열처리하여 상기 활물질층 안의 바인더와 도전재를 열분해함으로써, 상기 집전체를 상기 활물질층으로부터 분리하고 상기 활물질층 안의 활물질을 회수하는 단계;(b-1)회수된 활물질을 수용액 상태에서 염기성을 보이는 리튬 화합물 수용액으로 세척하고 건조하는 단계;(b-2)상기 건조된 활물질을 분쇄하는 단계;(b-3)상기 분쇄된 활물질에 리튬 전구체를 첨가하는 단계; 및(c)상기 리튬 전구체가 첨가된 활물질을 어닐링하여 재사용 가능한 활물질을 얻는 단계를 포함하는 양극 활물질 재사용 방법.
- 제1항에 있어서, (d)어닐링된 활물질에 표면 코팅하는 단계를 더 포함하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 리튬 복합 전이금속 산화물은 수십~수백 nm 크기를 가지는 1차 입자들이 모여 2차 입자화된 대립자를 포함하는 것이며, 상기 분쇄하는 단계는 상기 건조된 활물질을 상기 1차 입자 크기 이상의 크기로 소립자화시키는 단계를 포함하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제3항에 있어서, 상기 리튬 복합 전이금속 산화물은 니켈, 코발트 및 망간을 포함하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 열처리는 300 ~ 650℃에서 수행하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 리튬 화합물 수용액은 0% 초과 15% 이하의 리튬 화합물을 함유하도록 제조되고, 상기 세척은 1 시간 이내로 수행하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 세척은 상기 회수된 활물질을 상기 리튬 화합물 수용액 함침과 동시에 교반하여 수행하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 분쇄하는 단계는 볼 밀, 플래너터리 밀, 그라인더(grinder), 3-롤 밀(3-roll mill) 또는 제트 밀(jet mill)을 이용해 수행하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 분쇄된 활물질에 리튬 전구체를 첨가하는 단계는 고상 또는 액상의 형태로 첨가하는 것임을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 분쇄된 활물질에 리튬 전구체를 첨가하는 단계는 상기 분쇄된 활물질을 리튬 전구체 용액에 혼합하고 분무 건조함으로써 입자 조절된 활물질을 얻는 단계임을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 리튬 전구체는 LiOH, Li 2CO 3, LiNO 3 및 Li 2O 중 어느 하나 이상인 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 리튬 전구체는 상기 활물질층에 사용된 원재료 활물질 안의 리튬과 다른 금속의 비율 대비해서 손실된 리튬 비율 만큼을 첨가할 수 있는 양으로 첨가하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제12항에 있어서, 상기 리튬 전구체는 리튬을 0.001 ~ 0.4 몰 비로 첨가하는 양을 첨가하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제12항에 있어서, 상기 리튬 전구체는 리튬 : 다른 금속 몰 비 1 : 1을 기준으로 하여 리튬을 0.0001 ~ 0.1 몰 비 더 첨가할 수 있는 양으로 첨가하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 어닐링은 400 ~ 1000℃, 공기 중에서 수행하는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 어닐링하는 단계의 온도는 상기 리튬 전구체의 녹는점을 초과하는 온도인 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 활물질층 안의 활물질은 분말 형태로 회수되며 상기 바인더나 도전재의 탄화로 생기는 탄소 성분이 표면에 남아 있지 않는 것을 특징으로 하는 양극 활물질 재사용 방법.
- 제2항에 있어서, 상기 표면 코팅하는 단계는 금속, 유기 금속 및 탄소성분 중 1종 이상을 고상 또는 액상 방식으로 표면에 코팅 후 100 ~ 1200℃에서 열처리하는 것임을 특징으로 하는 양극 활물질 재사용 방법.
- 제1항에 있어서, 상기 재사용 가능한 활물질은 하기 화학식 1로 표시되는 것을 특징으로 하는 양극 활물질 재사용 방법.[화학식 1]Li aNi xMn yCo zM wO 2+δ(상기 화학식 1에서, M은 B, W, Al, Ti 및 Mg로 이루어진 군에서 선택되는 1종 이상을 포함하고, 1<a≤1.1, 0<x<0.95, 0<y<0.8, 0<z<1.0, 0≤w≤0.1, -0.02≤δ≤0.02, x+y+z+w=1이다.)
- 제1항에 있어서, 상기 재사용 가능한 활물질은 플루오린(F)의 함량이 100ppm 이하인 것을 특징으로 하는 양극 활물질 재사용 방법.
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US17/792,865 US20230063543A1 (en) | 2020-06-23 | 2021-01-14 | Method for reusing active material by using positive electrode scrap |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN115513549A (zh) * | 2022-09-15 | 2022-12-23 | 厦门海辰储能科技股份有限公司 | 一种电极极片的回收方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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KR102675713B1 (ko) * | 2022-07-06 | 2024-06-19 | 주식회사 엘지에너지솔루션 | 재생 양극 활물질, 이의 재생 방법 및 이를 포함하는 이차 전지 |
US20240145801A1 (en) * | 2022-10-26 | 2024-05-02 | Battelle Memorial Institute | Direct recycling and converting cathode materials into high-performance single crystal cathode materials |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20030070469A (ko) * | 2002-02-25 | 2003-08-30 | 한국지질자원연구원 | 폐리튬이온전지로부터 코발트를 회수하는 방법 |
KR20050112487A (ko) * | 2004-05-25 | 2005-11-30 | (주)지케이엠 | 폐리튬 이차전지로부터 유가금속의 고효율 회수 방법 |
JP2012186150A (ja) * | 2011-02-15 | 2012-09-27 | Sumitomo Chemical Co Ltd | 電池廃材からの活物質の回収方法 |
KR20160008040A (ko) * | 2014-07-11 | 2016-01-21 | 주식회사 포스코 | 폐연료전지의 재활용 방법 |
KR20170033787A (ko) * | 2015-09-17 | 2017-03-27 | 주식회사 에코프로비엠 | 폐양극활물질을 재활용한 양극활물질 전구체의 제조 방법, 이에 의하여 제조된 양극활물질 전구체, 및 이를 이용한 양극활물질의 제조 방법, 이에 의하여 제조된 양극활물질 |
KR20200076728A (ko) | 2017-11-02 | 2020-06-29 | 이록 오와이 | 자기장 힘을 활용하는 전기기계식 잠금장치 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5675452B2 (ja) | 2011-03-15 | 2015-02-25 | 三井金属鉱業株式会社 | 再生材料の製造方法 |
JP5269228B1 (ja) | 2012-03-30 | 2013-08-21 | Jx日鉱日石金属株式会社 | リチウムイオン電池用正極材から正極活物質を分離回収する方法 |
CN110676533B (zh) | 2014-08-06 | 2023-02-17 | 史蒂文·E·斯卢普 | 处理锂离子电池的正极材料的方法 |
JP6312576B2 (ja) | 2014-10-29 | 2018-04-18 | 信越化学工業株式会社 | リチウム複合酸化物の再生方法、電気化学デバイスの製造方法、並びに、リチウムイオン二次電池の製造方法 |
CN104538696B (zh) * | 2015-01-08 | 2017-04-05 | 兰州理工大学 | 从镍钴锰酸锂正极材料的废锂离子电池中回收金属的方法 |
CN110165324B (zh) * | 2019-06-24 | 2021-07-16 | 中国科学院青海盐湖研究所 | 一种从废旧锂电池中回收正极并再生修复的方法及系统 |
CN110842006A (zh) * | 2019-11-15 | 2020-02-28 | 武汉瑞杰特材料有限责任公司 | 锂电池正极回收材料的干法纯化分离与再生方法及得到的锂电池正极回收材料 |
-
2020
- 2020-06-23 KR KR1020200076728A patent/KR20210158233A/ko unknown
-
2021
- 2021-01-14 JP JP2022543004A patent/JP7357799B2/ja active Active
- 2021-01-14 EP EP21828438.8A patent/EP4142015A4/en active Pending
- 2021-01-14 US US17/792,865 patent/US20230063543A1/en active Pending
- 2021-01-14 CN CN202180014616.2A patent/CN115104214A/zh active Pending
- 2021-01-14 WO PCT/KR2021/000558 patent/WO2021261697A1/ko active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20030070469A (ko) * | 2002-02-25 | 2003-08-30 | 한국지질자원연구원 | 폐리튬이온전지로부터 코발트를 회수하는 방법 |
KR20050112487A (ko) * | 2004-05-25 | 2005-11-30 | (주)지케이엠 | 폐리튬 이차전지로부터 유가금속의 고효율 회수 방법 |
JP2012186150A (ja) * | 2011-02-15 | 2012-09-27 | Sumitomo Chemical Co Ltd | 電池廃材からの活物質の回収方法 |
KR20160008040A (ko) * | 2014-07-11 | 2016-01-21 | 주식회사 포스코 | 폐연료전지의 재활용 방법 |
KR20170033787A (ko) * | 2015-09-17 | 2017-03-27 | 주식회사 에코프로비엠 | 폐양극활물질을 재활용한 양극활물질 전구체의 제조 방법, 이에 의하여 제조된 양극활물질 전구체, 및 이를 이용한 양극활물질의 제조 방법, 이에 의하여 제조된 양극활물질 |
KR20200076728A (ko) | 2017-11-02 | 2020-06-29 | 이록 오와이 | 자기장 힘을 활용하는 전기기계식 잠금장치 |
Non-Patent Citations (1)
Title |
---|
See also references of EP4142015A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115513549A (zh) * | 2022-09-15 | 2022-12-23 | 厦门海辰储能科技股份有限公司 | 一种电极极片的回收方法 |
CN115513549B (zh) * | 2022-09-15 | 2024-01-26 | 厦门海辰储能科技股份有限公司 | 一种电极极片的回收方法 |
Also Published As
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EP4142015A4 (en) | 2023-12-13 |
JP2023510563A (ja) | 2023-03-14 |
KR20210158233A (ko) | 2021-12-30 |
JP7357799B2 (ja) | 2023-10-06 |
EP4142015A1 (en) | 2023-03-01 |
CN115104214A (zh) | 2022-09-23 |
US20230063543A1 (en) | 2023-03-02 |
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