CN117210685A - Method for recycling valuable metals in retired lithium ion battery by using recyclable chelating agent - Google Patents
Method for recycling valuable metals in retired lithium ion battery by using recyclable chelating agent Download PDFInfo
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- CN117210685A CN117210685A CN202311133288.5A CN202311133288A CN117210685A CN 117210685 A CN117210685 A CN 117210685A CN 202311133288 A CN202311133288 A CN 202311133288A CN 117210685 A CN117210685 A CN 117210685A
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- lithium
- leaching
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- cyanide
- stirring
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- 239000002738 chelating agent Substances 0.000 title claims abstract description 16
- 150000002739 metals Chemical class 0.000 title claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 83
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 56
- 239000002253 acid Substances 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000002378 acidificating effect Effects 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 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 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- -1 metal complex cyanide Chemical class 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- VJQKUDKYRCLZST-UHFFFAOYSA-N [K+].[K+].[K+].[K+].[K+].[K+].[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N VJQKUDKYRCLZST-UHFFFAOYSA-N 0.000 claims description 2
- MPMRXKGCZMTPMO-UHFFFAOYSA-N [Mn](=O)(=O)([O-])C#N.[Mn](=O)(=O)([O-])C#N.[Mn](=O)(=O)([O-])C#N.[Mn](=O)(=O)([O-])C#N.[Mn](=O)(=O)([O-])C#N.[Mn](=O)(=O)([O-])C#N.[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] Chemical compound [Mn](=O)(=O)([O-])C#N.[Mn](=O)(=O)([O-])C#N.[Mn](=O)(=O)([O-])C#N.[Mn](=O)(=O)([O-])C#N.[Mn](=O)(=O)([O-])C#N.[Mn](=O)(=O)([O-])C#N.[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] MPMRXKGCZMTPMO-UHFFFAOYSA-N 0.000 claims description 2
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 claims description 2
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 claims 1
- 239000010941 cobalt Substances 0.000 abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 abstract description 17
- 238000011084 recovery Methods 0.000 abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011572 manganese Substances 0.000 abstract description 6
- 239000002893 slag Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000009920 chelation Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 22
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- 239000002699 waste material Substances 0.000 description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 6
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 6
- 238000009854 hydrometallurgy Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UTYXJYFJPBYDKY-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide;trihydrate Chemical compound O.O.O.[K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UTYXJYFJPBYDKY-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BYMZQQLCZDLNKW-UHFFFAOYSA-N nickel(2+);tetracyanide Chemical compound [Ni+2].N#[C-].N#[C-].N#[C-].N#[C-] BYMZQQLCZDLNKW-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 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 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical group [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- PANJMBIFGCKWBY-UHFFFAOYSA-N iron tricyanide Chemical compound N#C[Fe](C#N)C#N PANJMBIFGCKWBY-UHFFFAOYSA-N 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical group O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of retired battery material recovery, in particular to a method for recovering valuable metals in retired lithium ion batteries by using a recyclable chelating agent. The invention adopts low-cost metal coordination cyanide as chelating agent, selectively leaches lithium under acidic condition through chelation, and the obtained acidic leaching slag is subjected to dechelation reaction with alkaline solution to obtain iron/nickel/cobalt/manganese (hydrogen) oxide precipitate, and simultaneously new metal coordination cyanide is generated, and the selective leaching of lithium in the next cycle is performed after pH is regulated. The method can recover lithium and transition metal from the anode of the retired lithium ion battery step by step, efficiently and selectively, the recovery rate is over 95.5 percent, and meanwhile, the clean and green recycling of the chelating agent is realized. The method has the advantages of simple operation, low acid/alkali consumption, high recovery rate and selectivity of lithium and transition metal, cleanness, environmental protection and high universality, can generate good social, environmental and economic benefits, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of retired battery material recovery, in particular to a method for recovering valuable metals in retired lithium ion batteries by using a recyclable chelating agent.
Background
The lithium ion battery has the advantages of high energy/power density, no memory effect, long cycle life and the like, and is widely applied to various small and medium-sized electronic equipment and large-scale energy storage fields. Along with the continuous development of social economy, the use amount of the lithium ion battery is continuously increased, and the yield of the retired lithium ion battery is gradually increased. The waste lithium batteries contain a large amount of metal elements (cobalt, nickel, lithium, aluminum, copper and the like), and the effective recovery of the waste lithium batteries has important significance for the development of lithium ion batteries; meanwhile, if harmful substances such as organic solvents and lithium salts in the battery are discarded at will without any treatment, serious injury and pollution are caused to human beings and the environment. Therefore, the recycling of the waste lithium batteries brings economic and environmental benefits, has important significance for sustainable development of human and ecological environments, and has become one of the important problems of the current scientific research.
The waste battery anode is used as a component with highest recycling value, and the whole method is mainly divided into a fire method and a hydrometallurgical process. The pyrometallurgy has the defects of high energy consumption, heavy pollution and the like, and has the advantages of low energy consumption, high efficiency, high flow controllability, small pollution in the sustainable chemical process in comparison with hydrometallurgy. Acid leaching is the simplest and most common method in hydrometallurgy, and metal ions are leached with inorganic acids (such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) or organic acids (citric acid, malic acid, lactic acid, glycine, etc.), and then precipitated out for recovery by pH adjustment or salt addition. In the related art, a sulfuric acid solution is used for dissolving metal ions in ternary anode powder, then a large amount of alkali is added, the acidity of the leaching solution is adjusted to be alkaline, transition metal ions are precipitated, lithium-rich liquid is obtained, sodium hydroxide is added, sodium sulfate is crystallized and separated out, and lithium hydroxide is recrystallized. The related art also discloses a mixed solvent composed of polyethylene glycol-citric acid, which can selectively leach cobalt and lithium ions of lithium cobaltate, and has relatively low leaching rate on aluminum and copper. These hydrometallurgical processes often suffer from long process flows, poor selectivity, low solvent recycle availability, and low versatility.
Therefore, in view of the existing hydrometallurgy, development of a green recyclable process that can be applied to all positive electrode powder recovery in the market and can efficiently and selectively extract valuable metals is needed.
Disclosure of Invention
The present invention aims to solve the technical problems in the prior art described above. Therefore, the invention provides a method for recycling valuable metals in retired lithium ion batteries by using a recyclable chelating agent. The method can recover lithium and transition metal from the anode material of the retired lithium ion battery step by step, efficiently and selectively, and realize green recycling of the leaching solvent.
In a first aspect of the invention, there is provided a method for recovering valuable metals in retired lithium ion batteries using a recyclable chelating agent, comprising the steps of:
s1, under an acidic condition, using metal coordination cyanide to stir and leach out a retired lithium ion battery anode material, and filtering to obtain a lithium-containing leaching solution and acid leaching residues;
s2, washing and drying the acid leaching residue obtained in the step S1, adding an alkaline solution, stirring, filtering to obtain filtrate and alkaline leaching residue, washing and drying the alkaline leaching residue to obtain transition metal oxide and transition metal hydroxide, wherein the filtrate is a regenerated metal coordination cyanide solution;
s3, re-throwing the metal coordination cyanide solution regenerated in the step S2 into the step S1, adjusting the pH value to the acidic condition in the step S1, and recycling the steps S1 to S3 to realize the recycling of the metal coordination cyanide.
The invention adopts low-cost metal coordination cyanide as chelating agent, lithium is selectively leached out by chelation under acidic condition, the obtained acidic leaching slag is subjected to decrepitation reaction with alkaline solution to obtain iron/nickel/cobalt/manganese (hydrogen) oxide precipitate, new metal coordination cyanide is generated at the same time, and after pH is regulated, the regenerated metal coordination cyanide can enter the next cycle for selective leaching of lithium.
In general, the method can be used for recycling lithium and transition metal from the anode material of the retired lithium ion battery step by step, efficiently and selectively, the recycling rate is more than 95.5%, and meanwhile, the recycling of the chelating agent is realized, so that the method has the advantages of cleanness and greenness.
The recovery method of valuable metals disclosed by the invention has universality to the current lithium ion battery, and particularly, the lithium ion battery suitable for the invention can be selected from lithium cobalt oxide (LiCoO) 2 ) Lithium iron phosphate (LiFePO) 4 ) Lithium nickel cobalt manganate (NCM 811, NCM622, NCM523, NCM 111) and lithium manganate (LiMn) 2 O 4 ) At least one of them.
In some embodiments of the invention, in step S1, the acidic condition is obtained by adding 0.6 to 2.0mol/L of an acid solution; the concentration of the acid solution includes, but is not limited to: 0.6 to 1.2mol/L and 0.6 to 1.0mol/L.
In some embodiments of the invention, the acid solution is a mineral acid solution, including at least one of sulfuric acid solution, hydrochloric acid solution.
In some embodiments of the invention, the mass to volume ratio of the positive electrode material to the acid solution is 1g: 30-60 mL.
In some embodiments of the invention, in step S1, the metal coordination cyanide is selected from at least one of potassium hexacyanoferrate, sodium hexacyanoferrate, potassium hexacyanoferrate, sodium hexacyanocobaltate, potassium hexacyanomanganate, sodium hexacyanomanganate, potassium hexacyanodinitrate, sodium hexacyanodinitrate, potassium tetracyanonickelate, sodium tetracyanonickelate, or a hydrate thereof.
In some embodiments of the present invention, in step S1, the mass ratio of the positive electrode material to the metal-coordinated cyanide is 1:2-8.
In some embodiments of the present invention, in step S1, the volume ratio of the amount of the metal complex cyanide species to the acid solution is 0.1 to 1.2mol/L, including but not limited to: 0.1 to 1.0mol/L, 0.1 to 0.8mol/L, 0.1 to 0.6mol/L, 0.1 to 0.4mol/L, 0.1 to 0.3mol/L and 0.1 to 0.25mol/L.
In some embodiments of the present invention, in step S1, the temperature of the agitation leaching is 20 to 90 ℃, including but not limited to: 20-80 ℃, 20-60 ℃, 20-50 ℃, 20-40 ℃ and 20-30 ℃; and/or the agitation leaching time is 1 to 6 hours, including but not limited to: 1 to 5 hours, 1 to 4 hours, 1 to 3 hours, 1 to 2.5 hours, 1.5 to 3 hours, 1.5 to 2.5 hours; and/or the agitation speed of the agitation leaching is 200-1000 rpm, including but not limited to: 200-800 rpm, 200-600 rpm, 300-600 rpm, 400-600 rpm, 450-600 rpm.
In some embodiments of the present invention, in step S2, the number of times of washing the acid leaching residue is 2 to 4.
In some embodiments of the present invention, in step S2, the drying temperature of the acid leaching residue is 60 to 90 ℃; and/or the drying time is 8-24 h.
In some embodiments of the present invention, in step S2, the alkaline substance in the alkaline solution is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
In some embodiments of the invention, in step S2, the concentration of the alkaline solution is 1 to 2mol/L, including but not limited to 1 to 1.8mol/L, 1 to 1.6mol/L, 1 to 1.4mol/L.
In some embodiments of the present invention, in step S2, the solid-to-liquid ratio of the acid leaching residue to the alkaline solution is 1 g/5 to 10mL.
In some embodiments of the invention, in step S2, the temperature of the stirring is 90-100 ℃; and/or the stirring time is 1-48 hours, including but not limited to: 1 to 36 hours, 1 to 24 hours, 12 to 24 hours, 4 to 12 hours and 4 to 24 hours; and/or the stirring speed is 400-1000 rpm, including but not limited to: 400-800 rpm, 400-600 rpm, 500-600 rpm.
In some embodiments of the present invention, in step S2, the number of times of washing the alkaline leaching residue is 3 to 5.
In some embodiments of the present invention, in step S2, the drying temperature of the alkaline leaching residue is 60 to 100 ℃; the drying time is 8-48 h.
In some embodiments of the present invention, in the step S2, the transition metal hydroxide includes nickel and/or cobalt and/or manganese and/or iron hydroxide, and the transition metal oxide includes nickel and/or cobalt and/or manganese and/or iron oxide.
In some embodiments of the invention, in step S3, the number of cycles is 1 to 20.
In some embodiments of the present invention, the method for recovering valuable metals in retired lithium ion batteries by using the recyclable chelating agent further includes step S4, collecting the lithium-containing leaching solution obtained in step S1, adding an iron source, precipitating, filtering, adding carbonate into the filtrate, heating, and obtaining the precipitate which is lithium carbonate.
In some embodiments of the invention, in step S4, the iron source comprises at least one of a ferrous salt and a ferric salt; further, the iron source is selected from at least one of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, or a hydrate thereof.
In some embodiments of the invention, in step S4, the iron source may be reacted with a metal coordination cyanide to produce a precipitate (prussian blue precipitate), the molar equivalent of the iron source being 1 to 1.5 times the theoretical required equivalent.
In some embodiments of the invention, in step S4, the time of the precipitation is 2 to 6 hours.
In some embodiments of the present invention, in step S4, the carbonate may be selected from sodium carbonate, potassium carbonate, and the like, preferably sodium carbonate, and the sodium carbonate is preferably present in the form of a saturated sodium carbonate solution.
In some embodiments of the invention, in step S4, the heating is performed at a temperature of 60 to 100 ℃ for a time of 0.5 to 12 hours.
The method for recycling valuable metals from the retired lithium ion battery according to the embodiment of the invention has at least the following beneficial effects:
(1) According to the technical scheme provided by the invention, lithium and transition metal can be recovered from the positive electrode of the retired lithium ion battery step by step with high selectivity, the products are lithium carbonate and transition metal (hydrogen) oxide respectively, and the recovery rate can reach more than 95.5%;
(2) According to the technical scheme provided by the invention, the green clean recycling of the cyanide chelating agent can be realized based on the chelating-dechelating strategy of metal coordination cyanide on transition metal;
(3) The technical scheme provided by the invention can be suitable for the anode of retired lithium ion batteries of almost all kinds on the market, and has good universality;
(4) The invention provides a process with high efficiency, high selectivity, low acid/alkali consumption, cyclic utilization of solvent and high universality, and has great economic and environmental benefits and wide application prospects.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Fig. 2 is a graph showing the result of selective leaching of lithium by reacting a waste lithium cobaltate anode with a potassium ferrocyanide solution in example 1 of the present invention, wherein graphs A, B and C correspond to the effect of potassium ferrocyanide concentration, sulfuric acid concentration and leaching time on cobalt and lithium leaching, respectively.
Fig. 3 is a graph showing the results of recovery of cobalt and potassium ferrocyanide from acid leaching residues using a potassium hydroxide solution according to the present invention, wherein graphs A, B and C correspond to the effect of potassium hydroxide concentration, leaching temperature and leaching time on cobalt and iron leaching, respectively.
FIG. 4 is a graph showing the results of the cyclic selective leaching of lithium (A) under acidic conditions and the cyclic selective recovery of cobalt (B) under alkaline conditions of the waste lithium cobaltate, the cyclic selective leaching of lithium (C) under acidic conditions and the cyclic selective recovery of iron (D) under alkaline conditions of the waste lithium iron phosphate, and the cyclic selective leaching of lithium (E) under acidic conditions and the cyclic selective recovery of nickel/cobalt/manganese (F) under alkaline conditions of the waste ternary positive electrode (NCM 111).
Fig. 5 is an XRD pattern of the lithium carbonate powder obtained in the present invention.
FIG. 6 is a graph of the ultraviolet-visible spectra of the original potassium ferrocyanide solution and the regenerated potassium ferrocyanide solution of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
The invention discloses a process and a method which can be suitable for recycling valuable metals from positive poles of retired lithium ion batteries step by step, efficiently and selectively. As shown in figure 1, the invention adopts low-cost metal coordination cyanide as a chelating agent, lithium is selectively leached by chelation under an acidic condition, the obtained acidic leaching slag is subjected to decrepitation reaction with alkaline solution to obtain iron/nickel/cobalt/manganese (hydrogen) oxide precipitate, new metal coordination cyanide is generated at the same time, the new metal coordination cyanide is used as the chelating agent after the pH value is readjusted, and the selective leaching of lithium in the next cycle is carried out.
Example 1
(1) Discharging and disassembling the retired lithium cobalt oxide battery to obtain powder of waste lithium cobalt oxide;
(2) 5mL of a 0.8mol/L sulfuric acid solution was prepared, and 1mmol (0.4224 g) of potassium ferrocyanide trihydrate (K) 4 [Fe(CN) 6 ]·3H 2 O, also called as potassium hexacyanoferrate), and obtaining a solution after dissolution, weighing 0.097g of waste lithium cobaltate powder, adding the solution into the solution, leaching for 2 hours at the temperature of 25 ℃ and the stirring speed of 500rpm, and filtering to obtain a leaching filtrate containing lithium and acid leaching residues, wherein the leaching rate of lithium is 96.82% and cobalt is not leached through ICP-MS analysis. The specific results are shown in FIG. 2. On this basis, the influence of the concentration of potassium ferrocyanide, the concentration of sulfuric acid and the leaching time on the leaching rate of lithium and cobalt is examined by changing a single factor, and the result is shown in figure 2.
(3) The acid leaching residue is repeatedly washed with water for 3 times and dried at 80 ℃ for 12 hours, then the acid leaching residue is added into 5mL of 1mol/L potassium hydroxide solution, after stirring reaction is carried out at 90 ℃ for 12 hours, the stirring rotation speed is 500rpm, potassium ferrocyanide solution and black powder are obtained by filtering, the black powder is cobalt hydroxide and cobaltosic oxide, the acid leaching residue is washed with water for 3 times and dried at 80 ℃ for 6 hours, and the recovery rate of the potassium ferrocyanide and the cobalt can reach 100+/-0.1 percent through ICP-MS analysis. The specific results are shown in FIG. 3. On this basis, the influence of alkali concentration, leaching temperature and leaching time on the leaching rate of iron and cobalt is examined by changing a single factor, and the result is shown in figure 3.
(4) Adding 0.3mL of concentrated sulfuric acid into the obtained potassium ferrocyanide solution to obtain an acidic potassium ferrocyanide solution, adding 0.097g of waste lithium cobaltate again, carrying out a second leaching reaction under the stirring of 400rpm, filtering after 3 hours of leaching reaction, obtaining acidic leaching residue and lithium-containing leaching solution again, and calculating the leaching rate of lithium to be 95.94% through ICP-MS analysis.
(5) Adding ferric sulfate with the same molar weight as ferrous cyanide in the solution into the lithium-containing filtrate in the step (2), stirring and precipitating for 3 hours, and filtering to obtain the lithium-rich purified liquid. Adding sodium carbonate into the lithium-rich purifying liquid to saturate the lithium-rich purifying liquid, stirring and heating to 90 ℃, stirring and precipitating for 2 hours, and obtaining precipitated white crystals which are lithium carbonate.
Example 2
(1) Discharging and disassembling the retired ternary battery (NCM 111 type) to obtain powder of the waste ternary positive electrode;
(2) Preparing 5mL of 1mol/L sulfuric acid solution, adding 1.2mmol (0.6336 g) of potassium ferrocyanide trihydrate, dissolving to obtain a solution, weighing 0.1g of waste ternary positive electrode powder, adding the solution, leaching for 2.5h at room temperature and stirring speed of 450rpm, filtering to obtain a leaching filtrate containing lithium and acid leaching residues, and analyzing by ICP-MS, wherein the leaching rate of lithium is 100+/-0.1%, and cobalt is not leached.
(3) The acid leaching residue is repeatedly washed with water for 3 times, dried for 12 hours at 80 ℃, added into 5mL of 1.2mol/L potassium hydroxide solution, stirred for reaction for 16 hours at 95 ℃, and then stirred at 600rpm, and filtered to obtain potassium ferrocyanide solution and black powder, wherein the black powder is ternary transition metal (hydrogen) oxide, and the recovery rate of the potassium ferrocyanide and the transition metal can reach 100+/-0.1 percent through ICP-MS analysis.
(4) Adding 0.4mL of concentrated sulfuric acid into the obtained potassium ferrocyanide solution to change the potassium ferrocyanide solution into an acidic potassium ferrocyanide solution, adding 0.1g of waste ternary anode again, carrying out a second leaching reaction under the stirring of 500rpm, filtering after 2h of leaching reaction, obtaining acidic leaching residue and lithium-containing leaching solution again, and calculating the leaching rate of lithium to be 97.76% through ICP-MS analysis.
(5) Adding ferric sulfate with the same molar weight as ferrous cyanide into the solution in the lithium-containing filtrate in the step (2), stirring and precipitating for 4 hours, and filtering to obtain the lithium-rich purified solution. Adding sodium carbonate into the lithium-rich purifying liquid to saturate the lithium-rich purifying liquid, stirring and heating to 80 ℃, stirring and precipitating for 12 hours, and obtaining precipitated white crystals which are lithium carbonate.
Example 3
(1) Discharging and disassembling the retired lithium iron phosphate battery to obtain waste lithium iron phosphate anode powder;
(2) Preparing 5mL of 0.6mol/L sulfuric acid solution, adding 0.8mmol (0.3379 g) of potassium ferrocyanide trihydrate, dissolving to obtain a solution, weighing 0.1577g of waste lithium iron phosphate anode powder, adding the solution, leaching for 1.5h at room temperature under the stirring speed of 600rpm, filtering to obtain a leaching filtrate containing lithium and acid leaching slag, and analyzing by ICP-MS, wherein the leaching rate of lithium is 100+/-0.1%, and cobalt is not leached.
(3) The acid leaching slag is repeatedly washed 3 times and dried for 24 hours at 80 ℃, then the acid leaching slag is added into 5mL of 1mol/L potassium hydroxide solution, after stirring reaction is carried out for 24 hours at 90 ℃, the stirring rotation speed is 500rpm, potassium ferrocyanide solution and tan powder are obtained by filtering, the tan powder is iron (hydrogen) oxide, and the recovery rate of the potassium ferrocyanide and the iron can reach 100+/-0.1 percent through ICP-MS analysis.
(4) Adding 0.45mL of concentrated sulfuric acid into the obtained potassium ferrocyanide solution to obtain an acidic potassium ferrocyanide solution, adding 0.1577g of waste lithium iron phosphate anode again, carrying out a second leaching reaction under the stirring of 600rpm, filtering after 2h of leaching reaction, obtaining acidic leaching residue and lithium-containing leaching solution again, and calculating the leaching rate of lithium to be 97.76% through ICP-MS analysis.
(5) Adding ferric chloride with the same molar quantity as ferric cyanide in the solution into the lithium-containing filtrate in the step (2), stirring and precipitating for 6 hours, and filtering to obtain the lithium-rich purified liquid. Adding sodium carbonate into the lithium-rich purifying liquid to saturate the lithium-rich purifying liquid, stirring and heating to 90 ℃, stirring and precipitating for 6 hours, and obtaining precipitated white crystals which are lithium carbonate.
In addition, FIG. 4 shows waste lithium cobalt oxide (LiCoO) 2 ) Lithium iron phosphate (LiFePO) 4 ) And NCM111, and from the results, it can be seen that the chelating agent-based acid chelating-alkaline dechelating process can efficiently and highly selectively recover lithium and transition metals of the three waste positive electrode powders step by step.
Fig. 5 is an XRD pattern of the lithium carbonate powder obtained in the example of the present invention, and the result shows that the obtained lithium carbonate has good purity.
FIG. 6 is an ultraviolet-visible spectrum of regenerated potassium ferrocyanide solution and original solution, where the initial potassium ferrocyanide solution has a consistent position of absorption peak in alkaline leaching solution, indicating that the resulting alkaline leaching process results in a regenerated potassium ferrocyanide solution.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A method for recovering valuable metals in retired lithium ion batteries by using a recyclable chelating agent, which is characterized by comprising the following steps:
s1, under an acidic condition, using metal coordination cyanide to stir and leach out a retired lithium ion battery anode material, and filtering to obtain a lithium-containing leaching solution and acid leaching residues;
s2, washing and drying the acid leaching residue obtained in the step S1, adding an alkaline solution, stirring, filtering to obtain filtrate and alkaline leaching residue, washing and drying the alkaline leaching residue to obtain transition metal oxide and/or transition metal hydroxide, wherein the filtrate is a regenerated metal coordination cyanide solution;
s3, re-throwing the metal coordination cyanide solution regenerated in the step S2 into the step S1, adjusting the pH value to the acidic condition in the step S1, and recycling the steps S1 to S3 to realize the recycling of the metal coordination cyanide.
2. The method of claim 1, wherein in step S1, the metal coordination cyanide is selected from at least one of potassium hexacyanoferrate, sodium hexacyanoferrate, potassium hexacyanocobaltate, sodium hexacyanocobaltate, potassium hexacyanomanganate, sodium hexacyanomanganate, potassium hexacyanodinitrate, sodium hexacyanodinitrate, potassium tetracyanonelate, sodium tetracyanonelate, or a hydrate thereof.
3. The method according to claim 1, wherein in step S1, the acidic condition is obtained by adding 0.6 to 2.0mol/L of an acid solution; and/or the volume ratio of the amount of the metal complex cyanide species to the acid solution is 0.1 to 1.2mol/L.
4. The method according to claim 1, wherein in step S1, a mass ratio of the positive electrode material to the metal-coordinated cyanide is 1:2-8.
5. The method according to claim 1, wherein in step S1, the temperature of the agitation leaching is 20 to 90 ℃; and/or the stirring leaching time is 1-6 h; and/or the stirring speed of the stirring leaching is 200-1000 rpm.
6. The method according to claim 1, wherein in step S2, the concentration of the alkaline solution is 1 to 2mol/L; and/or the solid-to-liquid ratio of the acid leaching residue to the alkaline solution is 1 g/5-10 mL.
7. The method according to claim 1, wherein in step S2, the temperature of the stirring is 90 to 100 ℃; and/or stirring for 1-48 h; and/or the stirring speed is 400-1000 rpm.
8. The method according to claim 1, wherein in step S3, the number of cycles is 1 to 20.
9. The method of claim 1, further comprising the step of collecting the lithium-containing leachate obtained in the step S1, adding an iron source, precipitating, filtering, adding carbonate into the filtrate, heating, and obtaining a precipitate which is lithium carbonate.
10. The method according to claim 9, wherein in step S4, the molar equivalent of the iron source is 1 to 1.5 times the theoretical required equivalent; and/or, the heating temperature is 60-100 ℃; and/or the heating time is 0.5-12 h.
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