CN111261967A - Recovery method of waste lithium battery and battery-grade nickel-cobalt-manganese mixed crystal prepared by recovery - Google Patents
Recovery method of waste lithium battery and battery-grade nickel-cobalt-manganese mixed crystal prepared by recovery Download PDFInfo
- Publication number
- CN111261967A CN111261967A CN202010074781.4A CN202010074781A CN111261967A CN 111261967 A CN111261967 A CN 111261967A CN 202010074781 A CN202010074781 A CN 202010074781A CN 111261967 A CN111261967 A CN 111261967A
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- China
- Prior art keywords
- cobalt
- nickel
- manganese
- solution
- battery
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000011084 recovery Methods 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- 239000013078 crystal Substances 0.000 title claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000243 solution Substances 0.000 claims abstract description 69
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000002893 slag Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000007599 discharging Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 235000021110 pickles Nutrition 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 29
- 238000002386 leaching Methods 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 11
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 235000002639 sodium chloride Nutrition 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 35
- 239000010941 cobalt Substances 0.000 abstract description 35
- 229910052759 nickel Inorganic materials 0.000 abstract description 35
- 150000002739 metals Chemical class 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 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 abstract description 5
- 239000011572 manganese Substances 0.000 description 31
- 229910052748 manganese Inorganic materials 0.000 description 30
- 239000000047 product Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical group [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- -1 manganese metals Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000010926 waste battery Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 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 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a recovery method of waste lithium batteries and a battery-grade nickel-cobalt-manganese mixed crystal prepared by recovery, wherein the recovery method of the waste lithium batteries comprises the following steps: (1) discharging waste lithium batteries, and obtaining anode powder through disassembly and sorting; (2) adding water to prepare slurry, and adding inorganic acid and a reducing agent to obtain pickle liquor; (3) adding a copper removing agent to remove copper; adding an oxidant and an alkali reagent to obtain a liquid after iron and aluminum removal; (4) adding a precipitator, and carrying out solid-liquid separation to obtain nickel-cobalt-manganese slag and a lithium-containing solution; (5) mixing the nickel-cobalt-manganese slag washed by pure water with the pure water, adding acid, and carrying out solid-liquid separation to obtain a nickel-cobalt-manganese mixed solution; (6) concentrating, stirring and cooling the concentrated solution, and performing centrifugal separation after crystallization to obtain the battery-grade nickel-cobalt-manganese mixed crystal. The method has the advantages of simple process, low production cost, safety and stability, high recovery rate of valuable metals of nickel, cobalt and manganese, excellent quality of the prepared ternary precursor and extremely high production yield.
Description
Technical Field
The invention relates to the technical field of waste lithium battery recovery, in particular to a waste lithium battery recovery method and a battery-grade nickel-cobalt-manganese mixed crystal prepared by recovery.
Background
By 2020, the yield of pure electric vehicles and plug-in hybrid electric vehicles in China exceeds 500 thousands of vehicles. The power battery industry chain is an important ring of the new energy automobile industry, driven by the requirements of the downstream whole automobile manufacturing market, and enters a rapid development stage. According to the relevant system data, in 2018, the loading amount of the power battery in China is 56.9GWH, and the equivalent weight is increased by 56.3%, wherein the proportion of the ternary material battery is 58.1%, and the proportion of the lithium iron battery is 39.0%.
While the lithium battery is produced and used in large scale, the recycling treatment after the lithium battery is decommissioned becomes a problem which cannot be ignored. According to statistics, the waste power battery reaches 12.08GWH in 2018, and the accumulated scrappage reaches 17.25 ten thousand tons. Wherein, the recovery market created by valuable metals such as cobalt, nickel, manganese, lithium and the like reaches 53.23 million yuan. The method can predict that the recovery of the waste lithium battery becomes a huge industrial chain in the future. The lithium battery has a relatively complex structure and components, and mainly comprises anode powder, aluminum foil, cathode graphite, copper foil, electrolyte, binder, steel shell and the like. If the materials are not recycled, the materials not only greatly waste the scarce resources such as cobalt, nickel and the like in China, but also cause environmental pollution. Therefore, the recycling of waste lithium batteries becomes a very important link for the strategic sustainable development of new energy in China.
The first link of the recovery of the waste lithium batteries is to discharge, disassemble, crush, sort and the like. The separated aluminum foil and copper foil are directly sold, and the anode powder needs to be recovered by a chemical method. The traditional method for comprehensively recovering the lithium battery comprises the steps of pretreating the lithium battery to sort out positive electrode powder, then leaching the positive electrode powder by using acid and a reducing agent, extracting lithium from a leaching solution by using a soluble fluoride, and further preparing battery-grade lithium carbonate, wherein cobalt, nickel and manganese in the solution after lithium extraction are prepared into high-purity sulfate in an extraction mode. Although the traditional method better realizes the comprehensive recovery of lithium, nickel, cobalt and manganese metals, the cost for extracting lithium from fluoride and preparing battery-grade lithium carbonate is higher, and the lithium recovery rate is low. And fluorine ions are introduced into the system, so that the subsequent wastewater treatment is very difficult. In addition, the nickel, cobalt and manganese metals are recovered by an extraction method, the occupied area of a workshop is large, the equipment investment is large, and the recovery cost is high.
In order to reduce the recovery cost, reduce the pressure of wastewater treatment and simultaneously realize the separation of lithium and nickel, cobalt and manganese, patent CN107017443 proposes a concept of "preferentially extracting lithium", in which carbon monoxide or hydrogen is introduced into pretreated anode powder at a high temperature of 450-700 ℃ for reduction roasting, the roasted product and water are made into slurry, carbon dioxide is introduced into the slurry for leaching to obtain a lithium bicarbonate solution, and the lithium bicarbonate solution is further prepared into battery-grade lithium carbonate. And selectively leaching metals such as copper, cobalt, nickel and the like from the nickel-cobalt-manganese metal slag subjected to water leaching by adopting an ammonia oxidation leaching process, and further separating and recovering the cobalt, the nickel, the manganese and the copper from the ammonia leaching solution in an extraction mode to prepare sulfate with lower added value. Compared with the traditional method, the method of 'preferentially extracting lithium' in the process makes a certain progress, but the high-temperature reduction roasting energy consumption is high, the requirements on equipment and personnel safety are very high, and the industrialization is difficult to a certain extent. In addition, the nickel, cobalt and manganese valuable metals are recovered by ammonia leaching and extraction processes, the consumption of saponification liquid alkali is large, the cost is high, and the cost for treating ammonia-containing wastewater in the wastewater is high.
In conclusion, the existing waste lithium battery recovery process has the problems of low recovery rate of valuable metals, long process flow, high recovery and treatment cost, low product added value and the like, and the waste water has complex components, high treatment difficulty and is easy to form secondary pollution.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the technical defects of the background technology and provides a method for recovering waste lithium batteries and a battery-grade nickel-cobalt-manganese mixed crystal prepared by recovery. The method has the advantages of simple process, low production cost, safety and stability, easy realization of industrial production, high recovery rate of valuable metals of nickel, cobalt and manganese, excellent quality of the prepared ternary precursor and extremely high production benefit.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for recovering waste lithium batteries comprises the following steps:
(1) pretreatment: putting the waste lithium battery into an electrolyte solution for discharging, and then performing disassembling and sorting processes on the discharged waste lithium battery to obtain positive electrode powder;
(2) reduction and acid leaching: adding water into the anode powder in the step (1) to prepare slurry, adding inorganic acid and a reducing agent with the theoretical amount of 1.0-2.0 times of that of the slurry to perform acid leaching reaction, and performing pressure filtration after stirring and leaching to obtain acid leaching solution;
(3) removing impurities: adding a copper removing agent with the theoretical amount of 1.1-2 times into the pickle liquor in the step (2) to remove copper; then adding an oxidant and an alkali reagent into the copper-removed solution, adjusting the pH value of the system to 4-5.5, and stirring and filter-pressing to obtain iron and aluminum-removed solution;
(4) hydrolysis and precipitation: adding a precipitator into the liquid obtained in the step (3) after iron and aluminum removal for hydrolysis precipitation reaction, and performing solid-liquid separation after the reaction is finished to obtain nickel-cobalt-manganese slag and a lithium-containing solution; washing the nickel-cobalt-manganese slag with pure water for later use, wherein the lithium-containing solution is used for preparing lithium carbonate;
(5) acidifying and dissolving: mixing the nickel-cobalt-manganese slag washed by pure water in the step (4) with pure water for size mixing, adding acid for acidification and dissolution reaction, and then carrying out solid-liquid separation to obtain a nickel-cobalt-manganese mixed solution;
(6) concentration and crystallization: and (4) pumping the nickel-cobalt-manganese mixed solution obtained in the step (5) into an evaporator for concentration, discharging the concentrated solution into a crystallization kettle for stirring and cooling, and performing centrifugal separation after crystallization to obtain the battery-grade nickel-cobalt-manganese mixed crystal.
Preferably, in the step (1), the concentration of the electrolyte solution is 1-5 mol/L.
Preferably, in the step (1), the electrolyte solution is any one or more of sodium chloride, sodium sulfate, manganese sulfate and ferrous sulfate.
Preferably, in the step (1), the discharging time is 12-24 hours.
Preferably, in the step (1), the positive electrode powder is any one or more of lithium cobaltate, lithium manganate and lithium nickel cobalt manganese oxide.
More preferably, in the step (1), the positive electrode powder is nickel cobalt lithium manganate series.
Preferably, in the step (2), the liquid-solid ratio of the slurry is 2: 1-10: 1 by mass ratio.
Preferably, in the step (2), the inorganic acid is any one or more of sulfuric acid, nitric acid and hydrochloric acid.
Preferably, in the step (2), the pH value of the system is adjusted to be 0.5-3.0 after the inorganic acid is added.
Preferably, in the step (2), the reducing agent is any one or more of hydrogen peroxide, sodium sulfite and sodium thiosulfate.
In the above technical scheme, in the step (2), the theoretical amount is calculated according to a stoichiometric ratio of a main component, such as nickel cobalt lithium manganate, in the positive electrode powder to the reducing agent.
Preferably, in the step (2), the temperature of the acid leaching reaction is 50-100 ℃ and the time is 1-5 h.
Preferably, in the step (3), the copper removing agent is any one or more of iron powder, nickel powder, manganese powder, cobalt powder and sodium sulfide; the copper removing agent is used for removing copper ions in a system.
In the above technical solution, in the step (3), the theoretical amount is calculated according to a stoichiometric ratio of copper ions to a copper remover in the system.
Preferably, in the step (3), the oxidant is any one or more of hydrogen peroxide, sodium chlorate and sodium hypochlorite.
Preferably, in the step (3), the alkali reagent is any one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium hydroxide and ammonia water.
Preferably, in the step (3), when the pH value of the system is adjusted, the reaction temperature is controlled to be 60-95 ℃.
Preferably, in the step (4), the precipitant is any one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia water.
Preferably, in the step (4), the mass fraction of the precipitant is 5% to 30%.
Preferably, in the step (4), the temperature of the hydrolysis precipitation reaction is 50-100 ℃.
Preferably, in the step (4), the pH value of the hydrolysis precipitation reaction is 6.0-9.0.
Preferably, in the step (4), the hydrolysis precipitation reaction is stopped when the concentration of nickel ions, cobalt ions and manganese ions in the system is less than 200 ppm.
Preferably, in the step (5), the liquid-solid ratio during size mixing is 1: 1-3: 1 according to the mass ratio.
Preferably, in the step (5), the acid is added by adding sulfuric acid.
Preferably, in the step (5), the pH of the system is adjusted to 3.5-5.0 after the acid is added.
Preferably, in the step (6), the total metal concentration of the mixed solution in the evaporator is 200-300 g/L.
Preferably, in the step (6), the crystallization time is 10-24 h.
Preferably, in the step (6), the crystallization temperature is 20-50 ℃.
Preferably, in the step (6), the stirring speed during crystallization is 50-100 r/min.
Preferably, in the step (6), the battery grade nickel-cobalt-manganese mixed crystal contains Al, Cu, Fe, Ca and Mg of less than 5ppm and Na of less than 200 ppm.
The battery grade nickel-cobalt-manganese mixed crystal is prepared by recycling the waste lithium battery by the recycling method.
The application of the battery-grade nickel-cobalt-manganese mixed crystal in preparing the ternary precursor is provided.
The application of the battery-grade nickel-cobalt-manganese mixed crystal in preparing the ternary precursor comprises the following steps:
and (3) synthesis reaction: dissolving the battery-grade nickel-cobalt-manganese mixed crystal by using pure water, adding nickel-cobalt-manganese soluble salt into the solution, adding alkali liquor and a complexing agent to perform coprecipitation reaction to obtain spherical nickel-cobalt-manganese hydroxide, and filtering, washing, drying and sieving to remove iron to obtain a ternary precursor.
Preferably, the molar ratio of nickel, cobalt and manganese in the system after the nickel, cobalt and manganese soluble salt is added is 5: 2: 3 or 6: 2 or 8: 1.
Preferably, the nickel-cobalt-manganese soluble salt is nickel-cobalt-manganese sulfate.
Preferably, the alkali liquor is sodium hydroxide.
More preferably, the concentration of the sodium hydroxide is 4-10 mol/L.
Preferably, the complexing agent is ammonia.
More preferably, the concentration of the ammonia water is 3-10 mol/L.
Preferably, the temperature of the coprecipitation reaction is 60-70 ℃, and the reaction time is 1-5 h.
Preferably, the pH value during the coprecipitation reaction is 10.5 to 11.50.
Preferably, the ternary precursor is any one of 5: 2: 3 type, 6: 2 type and 8: 1 type.
The basic principle of the invention is as follows:
the method comprises the steps of firstly carrying out pretreatment processes such as discharging, crushing, sorting and the like on the waste lithium batteries so as to sort out high-quality anode powder. Then, under an acid system, a reducing agent is added to leach the cobalt, the nickel, the manganese and the lithium into the aqueous solution together. And then adding a copper removing agent and an alkali agent to remove copper ions and impurity ions such as iron, aluminum and the like in the pickle liquor. Adding an alkali reagent into the obtained impurity-removed liquid, and adjusting the pH value of the system to ensure that cobalt, nickel and manganese are selectively hydrolyzed to form precipitates, thereby achieving the separation of calcium, magnesium and lithium from cobalt, nickel and manganese. The separated lithium-containing solution can be used for preparing lithium carbonate by purifying and removing impurities, and the formed cobalt, nickel and manganese precipitation slag is pulped and washed by pure water and dissolved by acid to prepare the nickel-cobalt-manganese solution with low impurity content. The solution is evaporated and crystallized to obtain the battery-grade nickel-cobalt-manganese salt (the purity is more than 99.9%). After dissolving the nickel-cobalt-manganese salt, reacting the nickel-cobalt-manganese salt with ammonia water and a sodium hydroxide solution to prepare the ternary precursor material.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method comprises the steps of taking waste lithium batteries as recovery objects, and obtaining anode powder through discharging, crushing and sorting; adding inorganic acid and a reducing agent into the positive electrode powder to leach the positive electrode powder, so that valuable metals of lithium, nickel, cobalt and manganese enter water as soluble salts; adding a copper removing agent to remove copper in the leaching solution, adding an oxidant and an alkali agent to remove iron and aluminum in the leaching solution, and performing filter pressing to obtain a solution after impurity removal; the pH value of the system is adjusted by adding a precipitator, so that cobalt, nickel and manganese are preferentially hydrolyzed and precipitated, the aim of removing calcium and magnesium can be fulfilled without the traditional extraction process, and the separation and recovery of lithium, nickel, cobalt and manganese are realized; the lithium-containing solution is used for further preparing battery-grade lithium carbonate; washing, acid-dissolving and crystallizing the nickel-cobalt-manganese slag to obtain a battery-grade nickel-cobalt-manganese sulfate salt; dissolving the obtained nickel-cobalt-manganese sulfate salt in pure water, and adding a proper proportion of sulfate to prepare a ternary precursor with a required model;
(2) the method has the advantages of simple process, low production cost, safety and stability, easy realization of industrial production, high recovery rate of valuable metals of nickel, cobalt and manganese, excellent quality of the prepared ternary precursor and extremely high production benefit.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a scanning electron microscope image of a ternary precursor prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a ternary precursor prepared in example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of the ternary precursor prepared in example 3 of the present invention.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It is to be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. In addition, it should be understood that the invention is not limited to the above-described embodiments, but is capable of various modifications and changes within the scope of the invention.
The calculation formula of the nickel recovery rate in the embodiments 1 to 3 is as follows: (nickel content in product/nickel content in raw material) x 100%;
the calculation formula of the cobalt recovery rate in the embodiments 1 to 3 is as follows: (cobalt content in product/cobalt content in raw material) x 100%;
the calculation formula of the manganese recovery rate in the embodiments 1 to 3 is as follows: (manganese content in product/manganese content in raw material) x 100%.
Example 1
The nickel-cobalt-manganese series waste lithium battery is placed into 2mol/L sodium chloride solution for discharging for 15 hours, and the discharged waste battery is crushed and sorted to obtain 100kg of anode powder (Ni: 34.89%, Co: 12.26%, Mn: 10.57%). Preparing slurry from the anode powder and water according to the liquid-solid ratio of 2: 1, adding sulfuric acid to adjust the pH value of a system to be 0.5, then adding 83.02kg of sodium sulfite according to 1.2 times of the required theoretical amount, controlling the reaction temperature to be 80 ℃, stirring and leaching for 1 hour, and then carrying out filter pressing to obtain 300L of acid leaching solution and 20kg of acid leaching residue. Adding 12kg of sodium sulfide into the solution according to 1.1 times of the theoretical amount calculated by a chemical reaction equation to remove copper, stirring the solution to react for 0.5h, and then performing filter pressing. And adding 10L of sodium chlorate and sodium hydroxide solution of 0.4kg into the copper-removed solution, adjusting the pH value of the system to be 4.0, controlling the reaction temperature to be 60 ℃, and performing filter pressing to obtain the impurity-removed solution.
Adding 5 percent of hydroxide by mass into the solution after impurity removalCarrying out hydrolysis precipitation reaction on sodium solution, wherein the flow rate of the precipitant solution is 5m3And h, controlling the pH value of the system to be 7.0 in the process when the reaction temperature is 70 ℃, stopping the reaction until the concentrations of nickel, cobalt and manganese in the solution are less than 200ppm, and performing solid-liquid separation to obtain nickel-cobalt-manganese slag and a lithium sulfate solution. The lithium sulfate solution is used for extracting lithium, and the nickel-cobalt-manganese slag is pulped and washed for 3 times by pure water according to the liquid-solid ratio of 1: 1. Mixing the washed nickel-cobalt-manganese slag and pure water according to the liquid-solid ratio of 1: 1, adding sulfuric acid until the pH value of the system is 3.5 after uniformly stirring, carrying out dissolution reaction, carrying out solid-liquid separation to obtain a nickel-cobalt-manganese mixed solution and dissolved slag, and returning the dissolved slag to the next step for continuous dissolution.
And (3) pumping the nickel-cobalt-manganese mixed solution into an evaporator for concentration, and stopping evaporation when the total metal concentration in the mixed solution reaches 200 g/L. And discharging the concentrated solution into a crystallization kettle, controlling the rotating speed at 60r/min, stirring, cooling and crystallizing at the crystallization temperature of 25 ℃, and performing centrifugal separation after 12 hours to obtain 244kg of nickel-cobalt-manganese mixed crystals.
Dissolving cobalt, nickel and manganese mixed crystals by using pure water, adding nickel sulfate, cobalt sulfate and manganese sulfate into the solution according to the designed molar ratio of nickel, cobalt and manganese of 5: 2: 3, adding 8mol/L ammonia water and 5mol/L sodium hydroxide solution to control the pH value of the system to be 10.50, controlling the synthesis reaction temperature to be 65 ℃, stirring for reaction for 2 hours, filtering, washing, drying, sieving and removing iron to obtain the 5: 2: 3 type ternary precursor material.
Example 2
Putting the nickel-cobalt-manganese series waste lithium battery into a 3mol/L manganese sulfate solution for discharging for 20 hours, and crushing and sorting the discharged waste battery to obtain 300kg of anode powder (35.96% of Ni, 11.46% of Co and 12.06% of Mn). Preparing slurry from the anode powder and water according to the liquid-solid ratio of 5: 1, adding hydrochloric acid to adjust the pH value of a system to be 1.5, then adding 91.69kg of sodium thiosulfate according to 1.5 times of the theoretical amount required by the calculation of a chemical reaction equation, controlling the reaction temperature to be 90 ℃, stirring and leaching for 3 hours, and then carrying out filter pressing to obtain 2100L of acid leaching solution and 30kg of acid leaching residue. 71.66kg of the mixture of reduced iron powder and cobalt powder is added according to 1.3 times of the theoretical amount calculated by the chemical reaction equation for copper removal, and the mixture is stirred for reaction for 1 hour and then is subjected to pressure filtration. Adding 3kg of hydrogen peroxide and 15L of a mixed solution of sodium carbonate and sodium bicarbonate into the copper-removed solution, adjusting the pH value of the system to 4.5, controlling the reaction temperature to be 80 ℃, and performing filter pressing to obtain a liquid after impurity removal.
Adding 15% lithium hydroxide solution into the solution after impurity removal for hydrolysis precipitation reaction, wherein the adding flow of the precipitator solution is 2m3And h, controlling the pH value of the system to be 8.0 in the process when the reaction temperature is 80 ℃, stopping the reaction until the concentrations of nickel, cobalt and manganese in the solution are less than 200ppm, and performing solid-liquid separation to obtain nickel-cobalt-manganese slag and a lithium chloride solution. Pulping and washing the nickel-cobalt-manganese slag for 2 times by pure water according to the liquid-solid ratio of 2: 1, then mixing the pulp with the pure water according to the liquid-solid ratio of 3: 1, adding sulfuric acid until the pH value of the system is 4.0 after uniformly stirring, carrying out dissolution reaction, carrying out solid-liquid separation to obtain a nickel-cobalt-manganese mixed solution and dissolved slag, and returning the dissolved slag to the next step for continuous dissolution.
And (3) pumping the nickel-cobalt-manganese mixed solution into an evaporator for concentration, and stopping evaporation when the total metal concentration in the mixed solution reaches 250 g/L. Discharging the concentrated solution into a crystallization kettle, controlling the rotating speed at 80r/min, stirring, cooling and crystallizing at the crystallization temperature of 30 ℃, and performing centrifugal separation after 20 hours. 751kg of nickel-cobalt-manganese mixed crystal is obtained.
Dissolving nickel, cobalt and manganese mixed crystals by using pure water, adding nickel sulfate, cobalt sulfate and manganese sulfate into the solution according to the designed molar ratio of nickel, cobalt and manganese of 6: 2, then adding 10mol/L ammonia water and 7mol/L sodium hydroxide solution to control the pH value of the system to be 11.20, controlling the synthesis reaction temperature to be 65 ℃, stirring for reaction for 4 hours, filtering, washing, drying, sieving and removing iron to obtain the 6: 2 type ternary precursor material.
Example 3
The nickel-cobalt-manganese series waste lithium battery is put into 3mol/L sodium chloride solution for discharging for 24 hours, and the discharged waste battery is crushed and sorted to obtain 400kg of anode powder (Ni: 47.93%, Co: 6.25%, Mn: 5.71%). Preparing slurry from the anode powder and water according to the liquid-solid ratio of 10: 1, adding nitric acid to adjust the pH value of a system to be 3.0, then adding 220kg and 30% hydrogen peroxide according to 2 times of the theoretical amount required by calculation of a chemical reaction equation, controlling the reaction temperature to be 80 ℃, stirring and leaching for 5 hours, and then carrying out filter pressing to obtain 5000L of acid leaching solution and 40kg of acid leaching residue. 26.25kg of the mixture of the reduced nickel powder and the manganese powder is added according to 2 times of the theoretical amount required by the calculation of a chemical reaction equation to remove copper, and the mixture is stirred to react for 2 hours and then is subjected to filter pressing. And adding 18L of mixed solution of 6.5kg of sodium hypochlorite, ammonium carbonate and ammonium bicarbonate into the copper-removed solution, adjusting the pH value of the system to 5.5, controlling the reaction temperature to be 95 ℃, and performing filter pressing to obtain the impurity-removed solution.
Adding 25% ammonia water solution into the solution after impurity removal for hydrolysis precipitation reaction, wherein the adding flow of the precipitator solution is 1m3And h, controlling the reaction temperature to be 95 ℃, controlling the pH value of the system to be 9.0 in the process, stopping the reaction until the concentrations of nickel, cobalt and manganese in the solution are less than 200ppm, and performing solid-liquid separation to obtain nickel-cobalt-manganese slag and a lithium nitrate solution. Pulping and washing the nickel-cobalt-manganese slag for 1 time by pure water according to the liquid-solid ratio of 3: 1, then mixing the pulp with the pure water according to the liquid-solid ratio of 2: 1, adding a sulfuric acid system with the pH value of 5.0 after uniformly stirring for dissolution reaction, performing solid-liquid separation to obtain a nickel-cobalt-manganese mixed solution and dissolved slag, and returning the dissolved slag to the next step for continuous dissolution.
And (3) pumping the nickel-cobalt-manganese mixed solution into an evaporator for concentration, and stopping evaporation when the total metal concentration in the mixed solution reaches 300 g/L. Discharging the concentrated solution into a crystallization kettle, controlling the rotating speed at 100r/min, stirring, cooling and crystallizing at the crystallization temperature of 50 ℃, and performing centrifugal separation after 24 hours. 1042kg of nickel-cobalt-manganese mixed crystal is obtained.
Dissolving the nickel-cobalt-manganese mixed crystal by pure water, wherein the mol ratio of nickel, cobalt and manganese is 8: 1. Adding nickel sulfate, cobalt sulfate and manganese sulfate into the solution, adding 9mol/L ammonia water and 5mol/L sodium hydroxide solution to control the pH value of the system to be 11.50, controlling the synthesis reaction temperature to be 65 ℃, stirring for reaction for 5 hours, filtering, washing, drying, sieving and removing iron to obtain the 8: 1 type ternary precursor material.
Effects of the embodiment
The process flow diagrams of examples 1-3 are shown in FIG. 1.
The technical indexes of the nickel-cobalt-manganese mixed crystal product prepared in example 1 are shown in table 1, wherein the recovery rate of nickel is 98.12%, the recovery rate of cobalt is 99.91%, and the recovery rate of manganese is 99.95%.
The technical indexes of the nickel-cobalt-manganese mixed crystal product prepared in example 2 are shown in table 1, wherein the nickel recovery rate is 98.43%, the cobalt recovery rate is 98.30%, and the manganese recovery rate is 97.56%.
The technical indexes of the nickel-cobalt-manganese mixed crystal product prepared in example 3 are shown in table 1, wherein the recovery rate of nickel is 98.48%, the recovery rate of cobalt is 98.36%, and the recovery rate of manganese is 98.54%.
The specification of the 5: 2: 3 ternary precursor product prepared in example 1 is shown in Table 2, and the SEM image is shown in FIG. 2.
The technical specifications of the 6: 2 ternary precursor product prepared in example 2 are shown in Table 2, and the SEM image is shown in FIG. 3.
The technical specifications of the 8: 1 ternary precursor product prepared in example 3 are shown in Table 2, and the SEM image is shown in FIG. 4.
TABLE 1 technical indices of Ni-Co-Mn mixed crystal products obtained in examples 1 to 3
TABLE 2 technical indices of the ternary precursor products prepared in examples 1-3
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (10)
1. A method for recovering waste lithium batteries is characterized by comprising the following steps:
(1) pretreatment: putting the waste lithium battery into an electrolyte solution for discharging, and then performing disassembling and sorting processes on the discharged waste lithium battery to obtain positive electrode powder;
(2) reduction and acid leaching: adding water into the anode powder in the step (1) to prepare slurry, adding inorganic acid and a reducing agent with the theoretical amount of 1.0-2.0 times of that of the slurry to perform acid leaching reaction, and performing pressure filtration after stirring and leaching to obtain acid leaching solution;
(3) removing impurities: adding a copper removing agent with the theoretical amount of 1.1-2 times into the pickle liquor in the step (2) to remove copper; then adding an oxidant and an alkali reagent into the copper-removed solution, adjusting the pH value of the system to 4-5.5, and stirring and filter-pressing to obtain iron and aluminum-removed solution;
(4) hydrolysis and precipitation: adding a precipitator into the liquid obtained in the step (3) after iron and aluminum removal for hydrolysis precipitation reaction, and performing solid-liquid separation after the reaction is finished to obtain nickel-cobalt-manganese slag and a lithium-containing solution; washing the nickel-cobalt-manganese slag with pure water for later use, wherein the lithium-containing solution is used for preparing lithium carbonate;
(5) acidifying and dissolving: mixing the nickel-cobalt-manganese slag washed by pure water in the step (4) with pure water for size mixing, adding acid for acidification and dissolution reaction, and then carrying out solid-liquid separation to obtain a nickel-cobalt-manganese mixed solution;
(6) concentration and crystallization: and (4) pumping the nickel-cobalt-manganese mixed solution obtained in the step (5) into an evaporator for concentration, discharging the concentrated solution into a crystallization kettle for stirring and cooling, and performing centrifugal separation after crystallization to obtain the battery-grade nickel-cobalt-manganese mixed crystal.
2. The method for recycling waste lithium batteries according to claim 1, wherein in the step (1), the concentration of the electrolyte solution is 1-5 mol/L; the electrolyte solution is any one or more of sodium chloride, sodium sulfate, manganese sulfate and ferrous sulfate; the discharge time is 12-24 hours; the anode powder is any one or more of lithium cobaltate system, lithium manganate system and nickel cobalt lithium manganate system.
3. The method for recycling waste lithium batteries according to claim 1, wherein in the step (2), the liquid-solid ratio of the slurry is 2: 1-10: 1 by mass ratio; the inorganic acid is any one or more of sulfuric acid, nitric acid and hydrochloric acid; adding the inorganic acid and then adjusting the pH value of the system to be 0.5-3.0; the reducing agent is any one or more of hydrogen peroxide, sodium sulfite and sodium thiosulfate; the temperature of the acid leaching reaction is 50-100 ℃, and the time is 1-5 h.
4. The method for recycling waste lithium batteries according to claim 1, wherein in the step (3), the copper removing agent is any one or more of iron powder, nickel powder, manganese powder, cobalt powder and sodium sulfide; the oxidant is any one or more of hydrogen peroxide, sodium chlorate and sodium hypochlorite; the alkali reagent is any one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium hydroxide and ammonia water; and when the pH value of the system is adjusted, controlling the reaction temperature to be 60-95 ℃.
5. The method for recycling waste lithium batteries according to claim 1, wherein in the step (4), the precipitant is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia water; the mass fraction of the precipitant is 5-30%; the temperature of the hydrolysis precipitation reaction is 50-100 ℃; the pH value of the hydrolysis precipitation reaction is 6.0-9.0; and stopping the reaction when the concentrations of nickel ions, cobalt ions and manganese ions in the system are less than 200ppm during the hydrolysis precipitation reaction.
6. The method for recycling waste lithium batteries according to claim 1, wherein in the step (5), the liquid-solid ratio during slurry mixing is 1: 1-3: 1 according to the mass ratio; and adjusting the pH value of the system to 3.5-5.0 after adding the acid.
7. The method for recycling waste lithium batteries according to claim 1, wherein in the step (6), the total metal concentration of the mixed solution in the evaporator is 200-300 g/L; the crystallization time is 10-24 h; the crystallization temperature is 20-50 ℃; the stirring speed during crystallization is 50-100 r/min.
8. A battery grade nickel-cobalt-manganese mixed crystal is characterized by being prepared by recovery through the recovery method of the waste lithium battery as claimed in any one of claims 1 to 7.
9. Use of the battery grade nickel cobalt manganese mixed crystal according to claim 8 for preparing a ternary precursor.
10. The use of the battery grade nickel cobalt manganese mixed crystal of claim 9 for preparing a ternary precursor, comprising the steps of:
and (3) synthesis reaction: dissolving the battery-grade nickel-cobalt-manganese mixed crystal by using pure water, adding nickel-cobalt-manganese soluble salt into the solution, adding alkali liquor and a complexing agent to perform coprecipitation reaction to obtain spherical nickel-cobalt-manganese hydroxide, and filtering, washing, drying and sieving to remove iron to obtain a ternary precursor.
Priority Applications (1)
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