CN114107673B - Recycling method of waste lithium battery anode material and recycled material - Google Patents
Recycling method of waste lithium battery anode material and recycled material Download PDFInfo
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- CN114107673B CN114107673B CN202111428187.1A CN202111428187A CN114107673B CN 114107673 B CN114107673 B CN 114107673B CN 202111428187 A CN202111428187 A CN 202111428187A CN 114107673 B CN114107673 B CN 114107673B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 74
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims description 19
- 238000004064 recycling Methods 0.000 title claims description 11
- 239000007788 liquid Substances 0.000 claims abstract description 89
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000706 filtrate Substances 0.000 claims abstract description 45
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 238000002386 leaching Methods 0.000 claims abstract description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 12
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 11
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 10
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 75
- 238000000605 extraction Methods 0.000 claims description 36
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000007774 positive electrode material Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 11
- 150000002923 oximes Chemical class 0.000 claims description 11
- MJUVQSGLWOGIOB-UHFFFAOYSA-N 2-[(Z)-hydroxyiminomethyl]-4-nonylphenol Chemical compound OC1=C(C=N/O)C=C(C=C1)CCCCCCCCC MJUVQSGLWOGIOB-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- IHLDEDLAZNFOJB-UHFFFAOYSA-N 6-octoxy-6-oxohexanoic acid Chemical compound CCCCCCCCOC(=O)CCCCC(O)=O IHLDEDLAZNFOJB-UHFFFAOYSA-N 0.000 claims description 8
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 claims description 8
- 229940005667 ethyl salicylate Drugs 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229940094933 n-dodecane Drugs 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 57
- 238000011084 recovery Methods 0.000 abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 abstract description 30
- 239000010941 cobalt Substances 0.000 abstract description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 30
- 239000010949 copper Substances 0.000 abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052802 copper Inorganic materials 0.000 abstract description 29
- 229910052759 nickel Inorganic materials 0.000 abstract description 28
- 238000004448 titration Methods 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000012086 standard solution Substances 0.000 description 9
- 229910001429 cobalt ion Inorganic materials 0.000 description 8
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229910001453 nickel ion Inorganic materials 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- 239000012490 blank solution Substances 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229960003540 oxyquinoline Drugs 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical group C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
-
- 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
Abstract
The application relates to the technical field of lithium battery anode material recovery, and particularly discloses a method for recovering waste lithium battery anode materials, which comprises the following operations: disassembling and crushing the anode material, adding the crushed anode material into the leaching solution, soaking and filtering the leaching solution, and collecting filtrate A; adding an extractant A into the filtrate A, collecting an upper layer liquid A and a lower layer liquid A, and adding dilute sulfuric acid into the upper layer liquid A to obtain a copper sulfate liquid; adding light calcium carbonate into the lower layer liquid A, collecting filtrate B, adding fluoride into the filtrate B, collecting filtrate C and filter residue C, press-filtering the filter residue C, adding the filter residue C into a calcium carbonate solution, and collecting filter residue D to obtain lithium carbonate; adding an extractant B into the filtrate C, collecting an upper layer liquid C and a lower layer liquid C, adding dilute sulfuric acid into the upper layer liquid C, and uniformly mixing to obtain a cobalt sulfate solution; adding extractant C into the lower layer liquid C, collecting upper layer liquid D, adding dilute sulfuric acid into the upper layer liquid D, and mixing uniformly to obtain nickel sulfate solution. The recovery rate of copper, lithium, cobalt and nickel recovered by the recovery method is higher than 90 percent.
Description
Technical Field
The application relates to the technical field of waste lithium battery anode material recovery, in particular to a waste lithium battery anode material recovery method and a recovered material.
Background
The lithium battery is a battery using lithium metal or lithium alloy as a positive electrode material and nonaqueous electrolyte solution, and has the advantages of light weight, high energy storage density, long service life and low self-discharge rate, and the service life of the battery can reach more than 6 years. The lithium battery has wide application, and does not generate toxic and harmful heavy metal elements and substances such as lead, mercury, cadmium and the like after recovery, and the lithium battery gradually replaces the traditional nickel-cadmium battery and nickel-hydrogen battery.
In the use process of the lithium battery, when the battery capacity is reduced to 80% of the initial capacity, the service life is reached, and the battery is scrapped. In order to reduce resource waste, waste lithium batteries are recycled, and the lithium batteries mainly comprise anode materials, cathode materials, electrolyte, diaphragms and the like, and precious metal resources in the lithium batteries are mainly concentrated on the anode materials. The positive electrode material is an intercalation compound with reversible intercalation and deintercalation capability, occupies a large proportion in a lithium battery, and mainly contains metal resources such as cobalt, nickel, copper, lithium and the like. At present, the recovery flow of the waste lithium battery anode material is generally to mechanically treat the battery monomer first and then to treat the anode plate by a wet method to obtain valuable metals.
However, as the metal elements in the positive plate are more in variety and different metal elements mutually interfere, more metal ions such as cobalt, nickel, lithium and the like still remain in the waste lithium battery positive electrode material after the waste lithium battery positive electrode material is recovered, so that the recovery rate of metal resources of the lithium battery positive electrode material is lower.
Disclosure of Invention
The application provides a method for recycling waste lithium battery anode materials and recycled materials in order to improve the recovery rate of metal resources in the recycled lithium battery anode materials.
In a first aspect, a method for recycling a positive electrode material of a waste lithium battery includes the following steps:
s1, disassembling and crushing a waste lithium battery anode material, adding the crushed material into the leaching solution for soaking, adding 40-50mL of the leaching solution into 1g of waste, reacting, filtering, and collecting filtrate A;
s2, adding 65% of dilute sulfuric acid into the filtrate A, regulating the pH value of the filtrate A to be 2-3, adding an extractant A into the filtrate A, oscillating, standing, layering, and separating to obtain an upper layer liquid A and a lower layer liquid A; adding dilute sulfuric acid with the mass fraction of 65% which is equal to that of the filtrate A into the upper layer liquid A, uniformly mixing, standing, layering, and collecting the lower layer liquid B to obtain a copper sulfate solution;
s3, adding calcium carbonate into the lower layer liquid A, adjusting the pH value of the lower layer liquid A to 3-5, stirring and filtering, and collecting filtrate B; adding fluoride into the filtrate B, stirring and filtering, and collecting filtrate C and filter residue C; filter-pressing the filter residue C, adding the filter residue C into a calcium carbonate solution, adjusting the temperature to 85-95 ℃ and the pH value to 10-13, filtering, and collecting the filter residue D to obtain lithium carbonate;
s4, adding an extractant B into the filtrate C, oscillating uniformly at 60-80 ℃, standing, layering, and collecting an upper layer liquid C and a lower layer liquid C; adding dilute sulfuric acid with the mass fraction of 65% which is equal to that of the filtrate C into the upper layer liquid C, uniformly mixing, standing, layering, and collecting the lower layer liquid D to obtain a cobalt sulfate solution;
s5, adding an extractant C into the lower layer liquid C, oscillating for 1-2min, standing, layering, and collecting an upper layer liquid D; adding dilute sulfuric acid with the mass fraction of 65% which is equal to that of the lower layer liquid C into the upper layer liquid D, uniformly mixing, standing, layering, and collecting the lower layer liquid E to obtain a nickel sulfate solution.
According to the technical scheme, metal ions in the anode material of the waste lithium battery are transferred from solid powder to an acid solution by using an organic acid or inorganic acid leaching solution dissolution method, then an extractant A is added into the acid solution containing the metal ions to extract copper ions, the copper ions enter an upper layer solution A, dilute sulfuric acid is added into the upper layer solution A to release the copper ions, and finally the copper ions and sulfate ions coexist in the solution to obtain a copper sulfate solution. Adding light calcium carbonate into the lower layer liquid A to adjust the acidity of the lower layer liquid A, adjusting the acidity of the lower layer liquid A to be weak, precipitating iron ions in the lower layer liquid A, filtering, and collecting filtrate B to achieve the effect of removing iron.
And adding fluoride into the filtrate B, reacting calcium ions, magnesium ions and fluoride ions to form calcium fluoride and magnesium fluoride, wherein the solubility product of the calcium fluoride and the magnesium fluoride is smaller, the calcium fluoride and the magnesium fluoride become precipitate, the solubility product of cobalt fluoride generated by the reaction of cobalt ions and fluoride ions is larger, the cobalt ions still exist in the filtrate C, the cobalt ions can be extracted by using the extractant B, the cobalt ions exist in the upper layer liquid B, and the cobalt ions are released by adding dilute sulfuric acid into the upper layer liquid B for back extraction, so that the cobalt sulfate solution containing cobalt ions and sulfate ions is obtained.
Because the calcium-magnesium slag contains lithium ions, the calcium-magnesium slag is subjected to filter pressing, residual liquid in the calcium-magnesium slag is discharged, then calcium carbonate is added for neutralization, and carbonate reacts with lithium ions to obtain the lithium carbonate. And (3) adding an extractant C into the lower layer liquid B to extract nickel ions, wherein the nickel ions exist in the upper layer liquid C, and adding dilute sulfuric acid into the upper layer liquid C to release the nickel ions, so as to obtain a solution containing nickel ions and sulfate radicals, namely a nickel sulfate solution.
The lithium carbonate obtained by the method is used as a main raw material of a power lithium battery, and the copper sulfate solution, the nickel sulfate solution and the cobalt sulfate solution can be used as ingredients of the positive electrode material of the lithium battery, so that the recovery of various metal materials in the positive electrode material of the waste lithium battery is realized.
As preferable: the extractant A is 260# extractant, the extractant B is a mixture of P507 extractant and 260# extractant with the volume ratio of (1-2), and the extractant C is a mixture of P204 extractant and 260# extractant with the volume ratio of (1-2).
By adopting the technical scheme, the 260# extractant can form chelate with copper ions, so that the copper ions are enriched into an organic phase and stably exist in the supernatant A. The P507 extractant and the 260# extractant can form chelate with cobalt ions, so that the cobalt ions are enriched and enter the upper layer liquid B. The P507 extractant and the 260# extractant can form chelate with nickel ions, so that the nickel ions are enriched and enter the upper layer liquid C.
As preferable: extraction auxiliary agents are added into the extractant A, the extractant B and the extractant C; the weight ratio of the extraction auxiliary agent to the extractant A, the extractant B and the extractant C is 1 (19-21), and the extraction auxiliary agent is prepared from the following raw materials in parts by weight: 40-48 parts of 5-nonylsalicylaldoxime, 35-45 parts of 2-hydroxy-5-tert-octylacetophenone oxime, 12-20 parts of ethyl salicylate, 17-25 parts of diluent and 4-6 parts of dispersing agent.
By adopting the technical scheme, the 5-nonylsalicylaldoxime and the 2-hydroxy-5-tert-octylacetophenone oxime have a composite effect, the 5-nonylsalicylaldoxime is formed by condensing hydroxy aldehyde and hydroxylamine, the 2-hydroxy-5-tert-octylacetophenone oxime is a product of condensing hydroxy ketone and hydroxylamine, the two have different structures, the 5-nonylsalicylaldoxime has strong extraction capacity and high extraction speed, the recovery rate of metal ions is relatively high, but the back extraction is difficult, and the 2-hydroxy-5-tert-octylacetophenone oxime has excellent phase separation performance, has high extraction recovery rate, is easy to back extract, has slower extraction speed, and can achieve the synergistic extraction effect by compounding the two. The addition of the ethyl salicylate ensures that the upper layer liquid A, the upper layer B and the upper layer liquid C are more stable, and has the function of a modifier. The addition of the diluent reduces the viscosity of the extractant, improves the phase separation performance of the extractant, and can improve the extraction efficiency, shorten the phase separation time, reduce the entrainment loss of the water phase and reduce the volatilization loss of the air oxidation organic phase. The addition of the dispersing agent can enhance the fluidity of the extraction auxiliary agent, so that various raw materials of the extraction auxiliary agent are distributed more uniformly in the system.
As preferable: the dispersing agent is a mixed solution of octyl adipate and polyethylene glycol, and the weight ratio of the octyl adipate to the polyethylene glycol is 1: (1-3).
By adopting the technical scheme, the octyl adipate and the polyethylene glycol can prevent particles in the solution from settling and gathering, can reduce interfacial tension between the raw materials, and simultaneously has higher wettability, so that the whole system is more uniform.
As preferable: the diluent is selected from any one of cyclohexane, n-dodecane and anhydrous kerosene.
By adopting the technical scheme, cyclohexane, n-dodecane and anhydrous kerosene are relatively stable to acid and alkali, the viscosity of the extracting agent is relatively low, and the viscosity of the extracting agent can be reduced, so that the flow property of the extracting auxiliary agent is improved.
As preferable: uniformly mixing 5-nonylsalicylaldoxime and 2-hydroxy-5-tert-octylacetophenone oxime, adding a diluent, uniformly stirring, adding ethyl salicylate and a dispersing agent, and uniformly stirring to obtain an extraction auxiliary.
By adopting the technical scheme, the addition of the ethylene, the diluent and the dispersing agent is separately mixed with the 5-nonylsalicylaldoxime and the 2-hydroxy-5-tert-octylacetophenone oxime, so that the preparation of the extraction auxiliary agent is more uniform, all the raw materials are uniformly dispersed in the system, and the extraction effect of the extracting agent is improved.
As preferable: the leaching solution is 65% of dilute sulfuric acid by mass fraction.
As preferable: the leaching solution is a mixed solution of 65% of dilute sulfuric acid and 28% of hydrogen peroxide in a volume ratio of 1 (8-10).
By adopting the technical scheme, the addition of the oxidant can promote the leaching of metal ions such as copper, lithium, cobalt, nickel and the like in the filtrate A. Meanwhile, hydrogen peroxide can react with ferrous iron to generate ferric iron, so that the subsequent iron removal effect can be improved.
In the second aspect, the material obtained by recycling the positive electrode material of the waste lithium battery is recycled.
By adopting the technical scheme, the waste lithium battery anode material is successfully recovered, the waste of waste battery resources is reduced, and the recovery rate of each metal material is very high.
In summary, the present application includes at least one of the following beneficial technical effects:
(1) The recovery rates of copper, lithium, cobalt and nickel obtained by the recovery method of the waste lithium battery anode material are above 90%, and the recovery rates of copper, lithium, cobalt and nickel are respectively as high as 99.4%, 99.2%, 98.8% and 90.0%.
(2) The application selects the leaching solution mixed by dilute sulfuric acid and hydrogen peroxide, extracts the extractant selected by copper, cobalt and nickel, and the recovery rate of copper, lithium, cobalt and nickel is obviously improved by adding the extraction auxiliary agent into the extractant.
Detailed Description
The present application will be described in further detail with reference to specific examples.
The following raw materials in the application are all commercial products, and specifically: the No. 260 extractant, the P204 extractant and the P507 extractant are all selected from Shandong Seikovia chemical industry Co., ltd, and the content of effective substances is 95%; the polyethylene glycol is selected from the model ZD-400 of Jinan Zhiding commercial limited company.
The following is a preparation example of the extraction aid in the present application:
the extraction auxiliary agent is prepared from the following raw materials in parts by weight: 40-48 parts of 5-nonylsalicylaldoxime, 35-45 parts of 2-hydroxy-5-tert-octylacetophenone oxime, 12-20 parts of ethyl salicylate, 17-25 parts of diluent and 4-6 parts of dispersing agent; the diluent is selected from any one of cyclohexane, n-dodecane and anhydrous kerosene.
Preparation example 1
The specific preparation operation of the extraction auxiliary agent in the application comprises the following steps:
according to the mixing amount of the table 1, the 5-nonylsalicylaldoxime and the 2-hydroxy-5-tert-octylacetophenone oxime are uniformly mixed, the diluent is added for dilution, and after uniform stirring, the ethyl salicylate and the dispersing agent are added to obtain the extraction auxiliary agent.
Preparation examples 2 to 10
The extraction auxiliary agents of preparation examples 2 to 10 are identical to the preparation method of preparation example 1, except that the blending amounts of the respective raw materials are different, and the details are shown in Table 1.
TABLE 1 amounts of raw materials of extraction auxiliaries of preparation examples 1 to 10 (unit: g)
Preparation examples 11 to 15
The extraction auxiliary agents of preparation examples 11 to 15 are identical to the preparation method of preparation example 1, except that the blending amounts of the respective raw materials are different, and the details are shown in Table 2.
TABLE 2 amounts of raw materials of extraction auxiliaries of preparation examples 11 to 15 (unit: g)
Example 1
The recovery method of the waste lithium battery anode material is prepared by the following operation steps:
s1, disassembling a waste lithium battery anode material, crushing, sieving with a 70-mesh sieve, and taking a screen lower material for standby, wherein the mass percent of copper in the waste lithium battery anode material is 18%, the mass percent of lithium is 13%, the mass percent of cobalt is 15%, and the mass percent of nickel is 8%; taking 250mL of dilute sulfuric acid with the mass fraction of 65% as a leaching solution, weighing 5g of undersize materials, adding the undersize materials into the leaching solution for soaking, fully stirring until the undersize materials are completely dissolved, filtering, and collecting filtrate A;
s2, adding 65% of dilute sulfuric acid into the filtrate A, regulating the pH of the filtrate A to 2.5, adding 200mL of 260# extractant into 200mL of filtrate A, oscillating and standing, collecting an upper layer liquid A and a lower layer liquid A after the liquid is layered, adding 200mL of 65% of dilute sulfuric acid into the upper layer liquid A, uniformly mixing, standing and layering, and collecting a lower layer liquid B to obtain a copper sulfate solution;
s3, adding light calcium carbonate into the lower layer liquid A, adjusting the pH of the lower layer liquid A to 5.8, stirring and filtering, collecting filtrate B, adding 50g of fluoride into the filtrate B, stirring and filtering, collecting filtrate C and filter residue C, press-filtering the filter residue C, controlling the temperature to 90 ℃, adding the filter residue C into a calcium carbonate solution, adjusting the pH to 12, filtering, collecting filter residue D, washing and drying to obtain lithium carbonate;
s4, adding 75mL of P507 extractant and 75mL of 260# extractant into 150mL of filtrate C, controlling the temperature at 70 ℃, oscillating for 3min, standing, collecting an upper layer liquid C and a lower layer liquid C after layering the liquid, adding 150mL of dilute sulfuric acid with the mass fraction of 65% into the upper layer liquid C, uniformly mixing, and collecting a lower layer liquid D to obtain a cobalt sulfate solution;
s5, measuring 100mL of lower layer liquid C, adding 50mL of P204 extractant and 50mL of 260# extractant, oscillating for 2min, standing, collecting upper layer liquid D after layering the liquid, adding 100mL of dilute sulfuric acid with the mass fraction of 65% into the upper layer liquid D, uniformly mixing, standing and layering, and collecting lower layer liquid E to obtain nickel sulfate solution.
Example 2
The recovery method of the waste lithium battery anode material is prepared by the following operation steps:
s1, disassembling a waste lithium battery anode material, crushing, sieving with a 70-mesh sieve, and taking a screen lower material for later use; uniformly mixing 27.8mL of hydrogen peroxide and 222.2mL of 65% dilute sulfuric acid as a leaching solution, weighing 5g of undersize materials, adding the undersize materials into the leaching solution for soaking, fully stirring until the undersize materials are completely dissolved, filtering, and collecting filtrate A;
s2, regulating the pH value of the filtrate A to be 2.5, adding 300mL of 260# extractant into 200mL of filtrate A, standing after shaking, collecting upper layer liquid A and lower layer liquid A after layering liquid, adding 200mL of dilute sulfuric acid with the mass fraction of 65% into the upper layer liquid A, uniformly mixing, and collecting lower layer liquid B after standing and layering to obtain a copper sulfate solution;
s3, adding light calcium carbonate into the lower layer liquid A, adjusting the pH value of the lower layer liquid A to 5.8, stirring and filtering, collecting filtrate B, adding 50g of calcium fluoride into the filtrate B, stirring and filtering, collecting filtrate C and filter residue C, press-filtering the filter residue C, controlling the temperature at 90 ℃, adding calcium carbonate solution for neutralization, adjusting the pH value to 12, filtering, collecting filter residue D, washing and drying to obtain lithium carbonate; s4, adding 112.5mL of P507 extractant and 112.5mL of 260# extractant into 150mL of filtrate C, controlling the temperature at 70 ℃, oscillating for 3min, standing, collecting upper layer liquid C and lower layer liquid C after liquid layering, adding 150mL of dilute sulfuric acid with the mass fraction of 65% into the upper layer liquid C, uniformly mixing, standing and layering, and collecting lower layer liquid D to obtain cobalt sulfate solution;
s5, 100mL of P204 extractant and 100mL of 260# extractant are added into 100mL of lower layer liquid C, the mixture is kept stand after shaking for 2min, upper layer liquid D is collected after layering of the liquid, 100mL of dilute sulfuric acid with the mass fraction of 65% is added into the upper layer liquid D for uniform mixing, and lower layer liquid E is collected after standing layering, so as to obtain nickel sulfate solution.
Example 3
Example 3 is identical to the method for recycling the positive electrode material of the waste lithium battery of example 2, except that: 400mL of the No. 260 extractant was added in step S2, and 10mL of the extraction aid prepared in preparation example 1 was added to the No. 260 extractant; 7.5mL of the extraction auxiliary agent prepared in preparation example 1 is added into the P507 extractant and the 260# extractant in the step S4; 150mL of the P204 extractant and 150mL of the 260# extractant were added in step S5, and 2mL of the extraction aid prepared in preparation example 1 was added to the P204 extractant and the 260# extractant, and the remaining raw materials and the blending amount were the same as in example 8.
Examples 4 to 17
Examples 4-17 are identical to the method for recycling the positive electrode material of the waste lithium battery of example 3, except that: the extraction auxiliary agent prepared in preparation examples 2-15 is selected, and the rest raw materials and the mixing amount are the same as in example 3.
Example 18
Example 18 is identical to the method for recycling the positive electrode material of the waste lithium battery of example 14, except that: in the step S1, the consumption of the hydrogen peroxide and the dilute sulfuric acid is 25mL and 225mL respectively, and the rest raw materials and the doping amount are the same as those in the example 14.
Example 19
Example 19 is identical to the method for recycling the positive electrode material of the waste lithium battery of example 14, except that: in the step S1, the consumption of the hydrogen peroxide and the dilute sulfuric acid is respectively 22.7mL and 227.3mL, and the rest raw materials and the doping amount are the same as those in the example 14.
Comparative example 1
The recovery method of the waste lithium battery cathode material of comparative example 1 is exactly the same as that of example 1, except that: the 260# extractant in step S2 was replaced with 8-hydroxyquinoline, and the remaining raw materials and blending amounts were the same as in example 1.
Comparative example 2
The recovery method of the waste lithium battery cathode material of comparative example 2 is exactly the same as that of example 1, except that: in step S4, no No. 260 extractant was added to the extractant B, and the other materials and amounts were the same as in example 1.
Comparative example 3
The recovery method of the waste lithium battery cathode material of comparative example 3 is exactly the same as that of example 1, except that: in step S5, no No. 260 extractant was added to the extractant C, and the other materials and amounts were the same as in example 1.
Performance detection
Measurement of copper content in copper sulfate solution: the copper content in the copper sulfate solution was measured by the iodometric method, 80mL of 10% potassium iodide solution was added to the copper sulfate solution, and immediately titrated to a pale yellow color with 0.05mol/L sodium thiosulfate standard solution. Then 8mL of 1% starch solution is added, titration is continued until the solution is light blue, 40mL of 10% potassium thiocyanate is added, the solution turns deep blue after shaking, titration is continued until the blue just disappears by using 0.05mol/L sodium thiosulfate standard solution, the solution is in a white suspension state, the volume of the finally consumed sodium thiosulfate standard solution is recorded, and the copper content in the copper sulfate solution is calculated.
ω(Cu)＝[(c·v)Na 2 S 2 O 3 ×64]÷mCuSO 4 ×100
Wherein, (c.v) Na 2 S 2 O 3 : consuming the product of the volume of the sodium thiosulfate standard solution and the concentration of the sodium thiosulfate standard solution; mCuSO 4 : sulfuric acidVolume of copper solution, mL.
Determination of lithium content in lithium carbonate: adding 4.4L of water into lithium carbonate, adding 20mL of methyl red-bromocresol green indicator, and using the concentration of 12 mol.L -1 The method comprises the steps of (1) titrating the hydrochloric acid standard titration solution until the test solution is changed from green to red, boiling for 2min to remove carbon dioxide, cooling, continuing titrating until the solution is changed into wine red, recording the volume of the hydrochloric acid standard titration solution consumed by the titration test solution, then performing a blank experiment, recording the volume of the hydrochloric acid standard titration solution consumed by the titration blank solution, and finally calculating the lithium content in lithium carbonate according to the following formula.
ω(Li)＝[c(V 1 -V 0 )×6.94g/mol]÷1000m×100％
Wherein, c: actual concentration of hydrochloric acid standard titration solution, mol.L -1 ；V 1 : the titration test solution consumes the volume of the hydrochloric acid standard titration solution, mL; v (V) 0 : the titration blank solution consumes the volume of the hydrochloric acid standard titration solution, mL; m: mass of lithium sulfate, g.
Determination of the cobalt content of the cobalt sulfate solution: 200mL of EDTA solution with the concentration of 0.05mol/L is added into the cobalt sulfate solution, then ammonia water is used for adjusting the pH value to just turn red in Congo red test paper, 80mL of buffer solvent with the pH value of 5.7 is added, water is used for diluting to 800mL, a small amount of xylenol orange indicator is added, the titration of zinc chloride standard solution is used until just turn red in the solution, and finally the cobalt content in the cobalt sulfate is calculated according to the following formula.
k＝m 0 /V
Wherein, k: titration coefficient of zinc chloride standard solution to cobalt in unit volume, g/mL; m is m 0 : mass of metallic cobalt, g; v: the volume of zinc chloride standard solution was consumed, mL.
Determination of the Nickel content in the Nickel sulfate solution: adding water to a nickel sulfate solution until the volume of the solution is 7L, adding a 1L ammonia water ammonium chloride solution and ammonium violate mixed indicator, shaking uniformly, titrating the solution to be blue-purple by using 0.02mol/L EDTA standard solution, recording the volume of the consumed EDTA standard titration solution, and then performing blank experiments to record the volume of the consumed EDTA standard titration solution of the titration blank solution. And finally, calculating the nickel content in the nickel sulfate by the following formula.
ω(Ni)＝[c(V 1 -V 0 )×2.5×58.89g/mol]÷m×100％
Wherein, c: actual concentration of EDTA standard titration solution, mol.L -1 ；V 1 : the titration test solution consumes the volume of EDTA standard titration solution, mL; v (V) 0 : the titration blank solution consumes the volume of EDTA standard titration solution, mL; m: volume of nickel sulfate solution, mL.
TABLE 3 recovery method of different waste lithium Battery cathode materials recovery results of the materials performance test
The detection results in Table 3 show that the recovery rates of copper, lithium, cobalt and nickel obtained by the recovery method of the waste lithium battery positive electrode material are all above 90%, and the recovery rates of copper, lithium, cobalt and nickel can be respectively as high as 99.4%, 99.2%, 98.8% and 99.0%.
The recovery rates of copper, lithium, cobalt and nickel in example 1 are respectively 90%, 91.5%, 91.3% and 92.1, which are lower than those in examples 2-22, indicating that adding hydrogen peroxide to the leachate in S1 can improve the separation leaching of the leachate to copper, lithium, cobalt and nickel in the waste lithium battery positive electrode material, and is beneficial to the recovery of copper, lithium, cobalt and nickel in the positive electrode material.
The recovery rates of copper, lithium, cobalt and nickel of example 3 were 95.8%, 95.2%, 94.5% and 94%, respectively, higher than the recovery rates of copper, lithium, cobalt and nickel of example 2, indicating a significant effect when the extraction aid was added to the extractant. The recovery rates of copper, lithium, cobalt and nickel were all lower in examples 4-8 than in example 3, indicating that the addition of ethyl salicylate, cyclohexane, dispersant, 2-hydroxy-5-tert-octylacetophenone oxime and polyethylene glycol to the dispersant all improved the recovery rates of copper, lithium, nickel and cobalt. The recovery rates of copper, lithium, cobalt and nickel in example 10 were 97.8%, 96.9%, 96.1% and 96.9%, respectively, higher than those in example 9 and examples 11 to 12, indicating that the recovery rates of copper, lithium, cobalt and nickel in example 14 were 98.8%, 98.5%, 97.6% and 98.1%, respectively, higher than those in example 13 and examples 15 to 17, respectively, indicating that the effect was optimal when the weight ratio of octyl adipate to polyethylene glycol was 1:2, and the recovery rates of copper, lithium, cobalt and nickel in example 16 were 97.2%, 96.4%, 95.7% and 97%, respectively, lower than those in examples 13 to 15 and example 17, indicating that the effect was poor when the weight ratio of octyl adipate to polyethylene glycol was 2:1, i.e., the amount of octyl adipate to polyethylene glycol was large. The recovery rates of copper, lithium, cobalt and nickel in example 18 were 99.4%, 99.2%, 98.8% and 99.0%, respectively, higher than that in example 19, indicating that the effect is best when the weight ratio of hydrogen peroxide to leachate was 1:9.
In comparative example 1, after the 260# extractant in step S2 was replaced with 8-hydroxyquinoline, the recovery rate of copper was reduced by 40%, indicating that the 260# extractant has a superior extraction effect when extracting copper. When the No. 260 extractant is not added in the steps S4 and S5 in the comparative examples 2-3, the recovery rates of cobalt and nickel are respectively reduced by 32% and 37.5%, which shows that the No. 260 extractant is mixed with the P507 extractant and the P204 extractant to extract cobalt and nickel, respectively, and the recovery rate is high.
Therefore, the sulfuric acid is added in the leaching solution selected by the application, the extracting agent selected by extracting copper, lithium, cobalt and nickel and the extracting auxiliary agent added in the extracting agent obviously improve the recovery rate of copper, lithium, cobalt and nickel.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (3)
1. The method for recycling the anode material of the waste lithium battery is characterized by comprising the following operation steps:
s1, disassembling and crushing a waste lithium battery anode material, adding the crushed material into the leaching solution for soaking, adding 40-50mL of the leaching solution into 1g of waste, reacting, filtering, and collecting filtrate A;
s2, adding 65% of dilute sulfuric acid into the filtrate A, regulating the pH value of the filtrate A to be 2-3, adding an extractant A into the filtrate A, oscillating, standing, layering, and separating to obtain an upper layer liquid A and a lower layer liquid A; adding dilute sulfuric acid with the mass fraction of 65% which is equal to that of the filtrate A into the upper layer liquid A, uniformly mixing, standing, layering, and collecting the lower layer liquid B to obtain a copper sulfate solution;
s3, adding calcium carbonate into the lower layer liquid A, adjusting the pH value of the lower layer liquid A to 3-5, stirring and filtering, and collecting filtrate B; adding fluoride into the filtrate B, stirring and filtering, and collecting filtrate C and filter residue C; filter-pressing the filter residue C, adding the filter residue C into a calcium carbonate solution, adjusting the temperature to 85-95 ℃ and the pH value to 10-13, filtering, and collecting the filter residue D to obtain lithium carbonate;
s4, adding an extractant B into the filtrate C, oscillating uniformly at 60-80 ℃, standing, layering, and collecting an upper layer liquid C and a lower layer liquid C; adding dilute sulfuric acid with the mass fraction of 65% which is equal to that of the filtrate C into the upper layer liquid C, uniformly mixing, standing, layering, and collecting the lower layer liquid D to obtain a cobalt sulfate solution;
s5, adding an extractant C into the lower layer liquid C, oscillating for 1-2min, standing, layering, and collecting an upper layer liquid D; adding dilute sulfuric acid with the mass fraction of 65% which is equal to that of the lower layer liquid C into the upper layer liquid D, uniformly mixing, standing, layering, and collecting the lower layer liquid E to obtain a nickel sulfate solution;
extraction auxiliary agents are added into the extractant A, the extractant B and the extractant C; the weight ratio of the extraction auxiliary agent to the extractant A, the extractant B and the extractant C is 1 (19-21), and the extraction auxiliary agent is prepared from the following raw materials in parts by weight: 40-48 parts of 5-nonylsalicylaldoxime, 35-45 parts of 2-hydroxy-5-tert-octylacetophenone oxime, 12-20 parts of ethyl salicylate, 17-25 parts of diluent and 4-6 parts of dispersing agent;
the extractant A is a 260# extractant, the extractant B is a mixture of a P507 extractant and a 260# extractant with the volume ratio of (1-2), and the extractant C is a mixture of a P204 extractant and a 260# extractant with the volume ratio of (1-2);
the dispersing agent is a mixed solution of octyl adipate and polyethylene glycol, and the weight ratio of the octyl adipate to the polyethylene glycol is 1: (1-3); the preparation method of the extraction auxiliary agent comprises the following steps: uniformly mixing 5-nonylsalicylaldoxime and 2-hydroxy-5-tert-octylacetophenone oxime, adding a diluent, uniformly stirring, adding ethyl salicylate and a dispersing agent, and uniformly stirring to obtain an extraction auxiliary; the leaching solution is a mixed solution of 65% of dilute sulfuric acid and 28% of hydrogen peroxide in a volume ratio of 1 (8-10).
2. The method for recycling the anode material of the waste lithium battery according to claim 1, which is characterized in that: the diluent is selected from any one of cyclohexane, n-dodecane and anhydrous kerosene.
3. The material recovered by the method for recovering a positive electrode material of a waste lithium battery according to any one of claims 1 to 2.
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| JP2014162982A (en) * | 2013-02-27 | 2014-09-08 | Jx Nippon Mining & Metals Corp | Method of separating and recovering metal from metal mixed solution |
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| WO2021047352A1 (en) * | 2019-09-14 | 2021-03-18 | 湖南金源新材料股份有限公司 | Manganese-lithium separation and pre-extraction liquid preparation processes in comprehensive recovery of ternary battery waste, and method for comprehensive recovery of cobalt-nickel-manganese-lithium elements from ternary battery waste |
| CN111270073A (en) * | 2020-02-03 | 2020-06-12 | 广东省稀有金属研究所 | Method for recovering valuable metals from leachate of waste lithium ion battery electrode material |
| CN112646974A (en) * | 2020-11-12 | 2021-04-13 | 四川顺应动力电池材料有限公司 | Method for recovering valuable metals from waste ternary lithium battery positive electrode material |
| CN113444885A (en) * | 2021-06-07 | 2021-09-28 | 浙江工业大学 | Method for preferentially extracting metal lithium from waste ternary lithium ion battery and simultaneously obtaining battery-grade metal salt |
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