CN109599602A - The method that the waste and old positive electrode of a kind of pair of lithium battery carries out resource utilization - Google Patents
The method that the waste and old positive electrode of a kind of pair of lithium battery carries out resource utilization Download PDFInfo
- Publication number
- CN109599602A CN109599602A CN201811452925.4A CN201811452925A CN109599602A CN 109599602 A CN109599602 A CN 109599602A CN 201811452925 A CN201811452925 A CN 201811452925A CN 109599602 A CN109599602 A CN 109599602A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- waste
- solid
- liquid
- old positive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 88
- 239000002699 waste material Substances 0.000 title claims abstract description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000007788 liquid Substances 0.000 claims abstract description 64
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 58
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 29
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- 238000011084 recovery Methods 0.000 claims abstract description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 52
- 239000000843 powder Substances 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 31
- 239000012071 phase Substances 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000007790 solid phase Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 22
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims 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 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 3
- 230000002000 scavenging effect Effects 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- BTYPWVDULNVBHU-UHFFFAOYSA-N disodium;dinitrate Chemical compound [Na+].[Na+].[O-][N+]([O-])=O.[O-][N+]([O-])=O BTYPWVDULNVBHU-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 33
- 239000012535 impurity Substances 0.000 abstract description 26
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 abstract description 20
- 238000000746 purification Methods 0.000 abstract description 20
- 239000007787 solid Substances 0.000 abstract description 20
- 239000010406 cathode material Substances 0.000 abstract description 19
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 27
- 239000004411 aluminium Substances 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 238000010574 gas phase reaction Methods 0.000 description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 13
- 238000003746 solid phase reaction Methods 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 description 10
- 238000004064 recycling Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 9
- 235000014413 iron hydroxide Nutrition 0.000 description 9
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000033116 oxidation-reduction process Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- BYOBIQOEWYNTMM-UHFFFAOYSA-N manganese;nitric acid Chemical compound [Mn].O[N+]([O-])=O BYOBIQOEWYNTMM-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000006479 redox reaction Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- BLOJZEAYCINVPY-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Ni+2].[Co+2].[Mn+2].[Li+] Chemical compound S(=O)(=O)([O-])[O-].[Ni+2].[Co+2].[Mn+2].[Li+] BLOJZEAYCINVPY-UHFFFAOYSA-L 0.000 description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 210000002966 serum Anatomy 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZYKTVIDNXTWTNS-UHFFFAOYSA-L [Co].[Mn].[Ni](O)O Chemical compound [Co].[Mn].[Ni](O)O ZYKTVIDNXTWTNS-UHFFFAOYSA-L 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
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- SFJBWZNTPHYOEH-UHFFFAOYSA-N cobalt Chemical compound [Co].[Co].[Co] SFJBWZNTPHYOEH-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen Sodium hydroxide Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses the methods that the waste and old positive electrode of a kind of pair of lithium battery carries out resource utilization.Method includes the following steps: (1) prepares liquid-solid mixed component system；(2) gaseous component is prepared；(3) three-phase single step reaction；(4) it is separated by solid-liquid separation；(5) leachate impurity and purification；(6) nickel cobalt manganese presoma is prepared；(7) lithium resource recycles；(8) new tertiary cathode material is prepared；(9) sodium nitrate recycles；(10) recovery ammonia.The unique three-phase single step reaction system that the present invention constructs can realize that the waste and old positive electrode of any component can obtain higher cobalt nickel manganese lithium single step reaction leaching efficiency.
Description
Technical field
The invention belongs to lithium battery material technical fields, and in particular to the waste and old positive electrode of a kind of pair of lithium battery carries out resource
Change the method utilized.
Background technique
Lithium ion battery is widely used in electric tool, electric car and mobile phone, notebook as energy storaging product
The fields such as computer, in people's production and life play an important role.In recent years, the high demand of energy storaging product causes
Lithium ion battery yield rises year by year.Lithium ion battery is in use after repeated charge, and electrode material is by anti-
Multiple dilation can be partially separated with collector leads to poor contact, meanwhile, the crystal form of positive electrode also can be in charge and discharge repeatedly
It changes in electric process, can make part lithium ion that cannot freely be embedded in abjection inside crystal structure and cause capacity attenuation
Seriously fail.In general, the cycle life of lithium ion battery is usually several hundred time to 1000 times or so (3-5), due to lithium from
Sub- battery is limited, this means that the yield of waste and old lithium ion battery is also increasing year by year, applying waste lithium ionic at that time
The recycling of battery will become a great problem.Battery belongs to serious pollution class solid waste, is a kind of important environmental contaminants, institute
It is recycled with place's lithium to old and useless battery very urgent.
Lithium ion battery be closely combined by positive plate, negative electrode tab and diaphragm by stacked or takeup type together with,
After being packed into shell, it is prepared after injection organic electrolyte such as tightly encapsulates at the series of processes.Due to current industrialized production
In four big mainstream positive pole material of lithium cobalt acid, LiMn2O4, in LiFePO 4 and nickel-cobalt lithium manganate material, nickle cobalt lithium manganate ternary
Material has high specific discharge capacity, high discharge voltage plateau, and the advantages such as high-energy density are known as most promising in recent years
Positive electrode.
Due in waste and old lithium ion battery lithium and the precious metals resource such as cobalt, nickel, manganese be concentrated mainly on positive electrode,
Therefore, lithium manganese cobalt nickel is recycled from waste and old tertiary cathode material, is the core stage of waste and old lithium ion battery recycling.Ternary is just
Mainly by lithium manganese cobalt nickel oxygen active material (quality accounting is about 87%-90%), acetylene black conductor, (quality accounting is about for pole material
For 5%-6%), organic adhesive (quality accounting is about 3%-4%), the aluminium carried secretly in shattering process, iron tramp (quality accounting
About 1%-3%) composition, while battery undergoes complicated charge and discharge process and high/low temperature conversion in use, so that useless
The existing forms of object phase are extremely complex in old positive electrode, and the existing forms of cobalt nickel manganese lithium have very very much not compared with new positive electrode
Together, while there is also complicated organic substance, inorganic matter is mutually wrapped with organic matter in physical aspect between above several substances
It wraps up in and inlays, Components of Acid-Base coexists with oxidation-reduction quality component on chemical form, causes its regeneration process difficult, it is difficult to
The lithium manganese cobalt nickel product for obtaining satisfied high-quality is regenerated by existing method.
There is partial monopoly to report the recycling of positive electrode at present, according to the difference of its mechanism, substantially
On can be divided into three classes:
(1) pyrogenic process+wet process process；Such technology uses positive electrode solid phase roasting technique, holds in roasting process
It is also easy to produce fluoride exhaust emission environment, high-temperature roasting energy consumption is high, additional reducing agent is at high cost, and in roasting process and ternary
Oxidation state species and the insufficient contact of reducing agent in positive electrode, the problems such as reduction efficiency is low.
(2) Whote-wet method process；Such technology has that reducing agent is at high cost, easy residual, and the reduction being added
The cost that agent often will form new impurity, increase purification of leaching liquor removal of impurities.
(3) acid solution+vapour phase reduction agent extract technology is used；Reducing agent employed in such technology is H2、CO、
SO2、NH3、H2S、CH4Equal gases only have reproducibility, and H2、CO、CH4, the use costs such as hydrazine hydrate are high, more difficult in production
It obtains, NH3、H2S is hypertoxicity substance, be easy to cause serious pollution；And the gas phase reaction component of this method is only capable of providing reduction
Property atmosphere, the oxidizing substance in induced positive electrode material, but do not have oxidizing substance needs to be oxidized removal for organic matter etc.
Substance for almost without effect, with the progress of reaction, it is difficult to make in the positive electrode of non-reacted parts by organic matter packet
The component wrapped up in continues to leach, and leads to that the leaching rate of nickel cobalt manganese lithium is not high, reaction residues amount is big, residual organic matter is in purification of leaching liquor
The problems such as being polluted in cobalt nickel manganese product in removal process, influencing its purity and recycle.
Since there are the main problems such as energy consumption height, secondary pollution to be difficult to promote and apply for traditional roasting+acid leaching process, and mesh
Preceding reported wet processing, generally without being directed to the waste and old positive electrode complicated components of leaching process, Leach reaction is complicated, soda acid
The redox reaction of substance neutralization reaction and redox, substance intersects progress, deploys and reacts to Leach reaction component and controls
Make demanding problem and propose effective workaround, cause to be difficult there are leaching process control, leaching efficiency it is unsatisfactory,
The lithium manganese cobalt nickel product quality that the more purification and impurity removals of leachate impurity are difficult, obtain is difficult to meet cell positive material ingredient requirement etc.
Problem.
Summary of the invention
For above-mentioned deficiency in the prior art, the present invention provides the waste and old positive electrode of a kind of pair of lithium battery and carries out recycling
The method utilized can effectively solve prior art low efficiency, and clean difficult problem.
To achieve the above object, the technical solution adopted by the present invention to solve the technical problems is:
The method that the waste and old positive electrode of a kind of pair of lithium battery carries out resource utilization, comprising the following steps:
(1) waste and old positive electrode is crushed as powder, and is mixed with metal powder, form solid-phase mixture；It then will be double
Oxygen water is mixed with condensed water, forms liquid phase mixture；Solid-phase mixture and liquid phase mixture are mixed again；
The weight ratio of waste and old positive electrode powder and metal powder is 1:0.05~1；The volume ratio of hydrogen peroxide and condensed water
For 1:50~1000；The solid-liquid ratio of solid-phase mixture and liquid phase mixture is 1:1~10；Metal powder is in manganese, cobalt or nickel
It is one or more；
(2) by nitric oxide, nitrogen dioxide and oxygen mix, gas phase mixture is formed；Nitric oxide, nitrogen dioxide and oxygen
The volume ratio of gas is 1:0.05~10:0.5~100；
(3) step (1) products therefrom is mixed with gas phase mixture, and adjusting system pH is that 0.5~3.0, ORP is
250~550mv；The ratio of the volume ratio of step (1) products therefrom and gas phase mixture is 0.05~50；
(4) step (3) products therefrom is separated by solid-liquid separation, collects liquid phase, adjusting its pH value is 5.0~7.0, keeps 2
It is separated by solid-liquid separation after~5h, collection is purified liquid；
(5) pH value for adjusting scavenging solution is 10.0~12.0, and is allowed to warm to 40~80 DEG C, after keeping 2~3h, is carried out
It is separated by solid-liquid separation, collects solid phase respectively and separating liquid is spare, then solid phase is washed 3~5 times；
(6) sodium carbonate liquor is added into separating liquid obtained in step (5), reaction is generated to without precipitating, is collected and clear
Wash sediment；
(7) then solid phase obtained by step (5) is mixed with step (6) gained sediment, in 750~1200 DEG C of calcinings 8~
10h；Solid phase and the weight ratio of sediment are 1:0.3~0.5.
Further, the weight ratio of waste and old positive electrode powder and metal powder is 1:0.1 in step (1)；Hydrogen peroxide with
The volume ratio of condensed water is 1:44；The solid-liquid ratio of solid-phase mixture and liquid phase mixture is 1:2.3.
Further, the partial size of waste and old positive electrode powder and metal powder is 80~120 mesh.
Further, the volume ratio of nitric oxide, nitrogen dioxide and oxygen is 1:0.5:1 in step (2).
Further, the ratio of the volume ratio of step (1) products therefrom and gas phase mixture is 10 in step (3).
Further, the ingredient that pH value is reconciled in step (5) is ammonium hydroxide and sodium hydroxide.
It further, further include recycling, separating to filtered fluid by evaporation and concentration, Crystallization Separation in step (6)
To sodium nitrate sodium and secondary separating liquid, and will be in the condensing hot air furnace that generated in removal process to step (6) and step (7).
Further, sodium hydroxide is added into secondary separating liquid, adjust its pH value be 8~10, respectively obtain ammonia and
Sodium nitrate solution, and by Ammonia recovery to step (5), sodium nitrate solution is recycled in step (6).
Further, it is washed with steam condensate (SC) in step (5) and step (6), and by the condensed water after washing
It is recycled in step (1).
Further, solid phase and the weight ratio of sediment are 1:0.4 in step (7).
Reaction principle and parameter setting principle of the invention is as follows:
1, unique component constructed by unique liquid and solid phase reaction component and step (2) constructed by step (1) is adjustable
Gas phase reaction component and the unique three-phase single step reaction system of step (3), be one and complete solve control reaction and leach
Each component is mutually wrapped up and being inlayed in physical aspect in the process, and different pH values requires and oxidationreduction atmosphere on chemical form
It is required that technical solution.
In reaction initial phase, the nitrogen dioxide in gas phase reaction component is in sour gas, with liquid and solid phase reaction component
It is converted into a certain amount of nitric acid and nitrous acid after water haptoreaction, the acid needed for waste and old positive electrode neutral and alkali substance leaches is provided
Degree；Meanwhile nitric oxide and nitrogen dioxide have reproducibility, provide going back needed for oxidizing substance leaches in waste and old positive electrode
Originality atmosphere；Oxygen is oxidizing substance, provides the oxidation atmosphere needed for reducing substances leach in waste and old positive electrode；And
Hydrogen peroxide in liquid and solid phase reaction component provides the oxidation atmosphere of auxiliary, and zeroth order manganese/cobalt/nickel by powder provides the reproducibility of auxiliary
Atmosphere；In waste and old positive electrode reacting between lithium manganese cobalt nickel oxysome and nitric oxide, nitrogen dioxide, oxygen be one extremely fast
Highly selective reaction, lithium manganese cobalt nickel is converted into lithium nitrate, cobalt nitrate, nickel nitrate, manganese nitrate solution from solid phase reaction, and liquid is solid
Cobalt nickel manganese powder end in phase is reacted with the reaction rate of acidic materials far below this, as long as controlling the reaction time, this stage cobalt
Nickel manganese powder end is not involved in substantially with acidic materials reacts；With the progress of above-mentioned reaction, positive electrode powder is constantly reacted molten
Liquid is solved, gradually contracting core, the hydrogen peroxide meeting in solid-liquid phase reaction component at this time and leaching are anti-containing lithium manganese cobalt nickel oxysome powder particle
A small amount of ferrous ion of middle generation is answered to be built into the unique Fenton system with extremely strong oxidisability, zeroth order manganese/cobalt/nickel powder again
It is last that (mainly acetylene black is conductive with the new carbon containing organic substance constantly generated after waste and old positive electrode particle reaction contracting core
Agent) be built into it is unique itself have extremely strong oxidisability light electrolysis system, under Strong oxdiative-light electrolysis double action, anode
Organic adhesive in material loses bonding activity, so that the package for dissociating waste and old positive electrode particle inlays volume morphing, so that
The progress of above-mentioned reaction mechanism mechanism of reaction continuous and effective, until waste and old positive electrode particle will be completely dissociated, react, lithium manganese cobalt nickel almost may be used
All to be leached into solution.
Still further aspect, in above-mentioned reaction process, lithium manganese cobalt nickel oxysome and nitric oxide, titanium dioxide in waste and old positive electrode
The reaction of nitrogen, oxygen is an extremely fast highly selective reaction, and the iron aluminium in waste and old positive electrode and acidic materials react
Rate is far below the reaction, as long as controlling the reaction time, the iron aluminium base in waste and old positive electrode is originally not involved in reaction, therefore,
Iron aluminium impurity content is extremely low in leachate, is conducive to subsequent purification removal of impurities.In above-mentioned reaction process, contain in waste and old positive electrode
Acetylene black conductor only have denier and ferrous ion that Fenton reaction occurs, organic adhesive only lose it is Nian Jie active,
Be not involved in reaction, therefore as the dissociation and reaction of lithium manganese cobalt nickel oxysome particle in positive electrode are leached, remaining acetylene black and
Bonding agent becomes the main component of residue after reaction.
2, it is one complex reaction involved in step (3), satisfied positive electrode should be reached in reaction process
Leaching rate, realizes the efficient utilization of various substances again, therefore, it is necessary to which find out has directive significance in actual application
Key parameter.
For acid-base neutralization reaction, pH is its key parameter, and pH is excessively high, then basic component leaches insufficient, pH mistake
Low, then acidic materials are superfluous, and the additive amount of neutralizer is big in subsequent dedoping step, and reagent cost increases, for this purpose, this method uses
PH value is control parameter, is 0.5~3.0 by reaction process pH control；In addition, anti-for the redox convenient for regulation reaction system
Atmosphere is answered, uses the ORP (oxidation-reduction potential) of solution for control parameter, if ORP is excessively high, the oxidisability of leachate is higher,
It is difficult to realize the leaching of the cobalt, manganese of oxidation state, if ORP is too low, the oxidisability in system is insufficient, it is difficult to realize ferrous ion
The removal of oxidation and organic matter, therefore it is to be ensured that the cobalt nickel manganese lithium in positive electrode solid particle is completely converted into corresponding nothing
Machine sulfate then needs to control the ORP of reaction system in the range of 250~550mv.
3, in three-phase single step reaction leaching process described in step (3), the size of solid granulates is to leaching rate in ore pulp
Having a significant impact, partial size is smaller, and granule surface area is bigger, and gas-liquid-solid three-phase contact is more abundant, and leaching rate is faster, therefore, step
Suddenly it is used to prepare the powder ternary material of ore pulp described in (1), cobalt/nickel/manganese powder end granularity is not less than 80 mesh.
4, nitric oxide, nitrogen dioxide and oxygen mixed gas can pass through three kinds in gaseous component described in step (2)
Gas is directly mixed to get, and can also make part nitric oxide turn later by the way that the exhaust gas containing nitric oxide of gained containing burning is inverted
Nitrogen dioxide is turned to obtain.The two access approaches fire the difference is that used combustion adjuvant is generally air when burning
Containing containing having neither part nor lot in the inert nitrogen gas of burning, and nitrogen is not involved in Leach reaction in nitric oxide production exhaust gas after burning, for
Leaching process is without influence；Therefore, the mixed gas that two kinds of approach obtain is suitable for this Leaching Systems, however, being obtained using which kind of
Mode, the volume ratio of nitric oxide, nitrogen dioxide and oxygen in mixed gas be preferably kept in 1:0.05~10:0.5~
In the range of 100.
5, waste and old positive electrode powder, manganese or cobalt or nickel by powder and dioxygen in the middle gained liquid and solid phase reaction component of step (1)
Ratio between water is related to the component of waste and old positive electrode, and the component of waste and old positive electrode is different, the component of mixed serum
It is not identical.According to adjustment mixed serum component to reach in step (3) pH can be in the actual production process, 0.5~3.0,
ORP is the requirement of 250~550mv, to realize that the positive electrode of different component can achieve the leaching of satisfied cobalt nickel manganese lithium
Efficiency.
6, in step (2) in gas phase reaction component between nitric oxide, nitrogen dioxide and oxygen proportionate relationship and it is waste and old just
The component of pole material is related, and the component of waste and old positive electrode is different, and the component of nitrogenous gas leaching agent is not also identical.In practical life
It to reach pH in step (3) can be 0.5~3.0, ORP 250 according to adjustment nitrogenous gas leaching agent component during production
The requirement of~550mv, to realize that the positive electrode of different component can achieve the leaching efficiency of satisfied cobalt nickel manganese lithium.
7, to reach the requirement that pH is 0.5~3.0, ORP is 250~550mv in step (3), it can be by individually adjusting
Both the component of gas phase reaction component is realized in the component of liquid-solid phase or step (2) in step (1), can also adjust simultaneously
Component realize.
The invention has the benefit that
(1) the unique three-phase single step reaction system of this method building can realize that the waste and old positive electrode of any component can
Obtain higher cobalt nickel manganese lithium single step reaction leaching efficiency.
For complicated components in waste and old positive electrode, inorganic matter and organic matter are mutually wrapped up and are inlayed, acid-base neutralization reaction
The problem of difficult regulation coexists with redox reaction, existing method is difficult to the problem of obtaining satisfied leaching effect, passes through group
The adjustable oxidationreduction characteristic that has both is divided to mix gas phase reaction component and have both redox-characteristic liquid and solid phase reaction component
This unique gas-liquid-solid complementary system, it is anti-to construct a unique acid-base neutralization reaction-redox reaction-light electrolysis
Should intersect the one step multiple reaction system of three-phase of progress, to realize that the positive electrode of different component in leaching process needs not
The purpose that same oxidation-reduction reaction atmosphere, inorganic component and organic component package mosaics can dissociate, so that this method pair
Higher cobalt nickel manganese lithium single step reaction leaching efficiency can be obtained in the positive electrode of any component.
(2) the unique gas-liquid-solid complementary interaction components system of this method building does not introduce new impurity substances, so that
Leachate impurity is few, is compared with other methods, and impurity and purification are easy, and obtained solution quality is high, is conducive to subsequent lithium manganese cobalt nickel
The high efficiente callback of resource.
Unique gas phase reaction component constructed by this method are as follows: nitric oxide, nitrogen dioxide, oxygen, liquid-solid phase component
Are as follows: in addition to this waste and old positive electrode, hydrogen peroxide and zeroth order manganese/cobalt/nickel and clean steam condensate (SC) do not need any
Other additional substances；And the nitric oxide of gas phase, nitrogen dioxide, oxygen and liquid-solid phase waste and old positive electrode, hydrogen peroxide and zero
Valence manganese/cobalt/nickel and clean steam condensate (SC) pass through the unique three-phase single step reaction system of this method building, all substances
It is finally converted into manganese nitrate, the cobalt nitrate, nickel nitrate, lithium nitrate of subsequent step needs, is generated without other impurities substance.
In addition, it is selective reaction, i.e. sulphur in gaseous component that the uniqueness of this reaction system, which is also embodied in Leach reaction,
Base and nitrogen-based gas and oxygen, and can in waste and old positive electrode preferentially with the lithium manganese cobalt nickel component reaction in waste and old positive electrode
The iron aluminium impurity that can contain seldom reacts, or even is not involved in reaction；Therefore, the leachate impurity content that this method obtains is few, makes
Subsequent purification and impurity removal is obtained to be easier.
(3) purifying and impurity-removing method of leaching solution that this method uses does not introduce new impurity, and purification and impurity removal is high-efficient, obtains
Scavenging solution quality is good.
Compared with the impurity-removing methods such as the extraction and back extraction or ferric hydroxide precipitate method being widely used, this method is based on preamble
The lower lithium manganese cobalt nickel sulfate leachate system of the iron content aluminium impurity that processing step obtains, using need to only adjust solution temperature and
The synchronous removal ferrisodium impurity of the in situ Precipitation of pH value, then the pH precipitation method are adjusted except aluminium, to obtain impure extremely low quality
High lithium manganese cobalt nickel sulfate liquor, is conducive to the high efficiente callback of subsequent lithium manganese cobalt nickel resource.
(4) this method is advantageously implemented manganese cobalt nickel efficient resource using the synchronous recycling manganese cobalt nickel resource of a step coprecipitation
Change.
Advantage of this method based on the extremely low high-quality lithium manganese cobalt nickel sulfate liquor of the impurity that preamble technique obtains, passes through
The ammonium hydroxide and sodium hydroxide centainly matched is added, it can realization obtains the manganese cobalt nickel that high-quality meets tertiary cathode material requirement
The purpose of hydroxide co-precipitate presoma, is advantageously implemented manganese cobalt nickel high efficient resourcing.
(5) this method recycles lithium resource using carbonate precipitation method, is advantageously implemented the high efficient resourcing of lithium.
This method high-quality lithium sulfate solution extremely low based on the impurity that preamble process advantage obtains, it is only necessary to pass through addition
The sodium carbonate centainly matched, it can realize and obtain the purpose for the lithium carbonate that high-quality meets tertiary cathode material requirement, favorably
In the high efficient resourcing for realizing lithium.
(6) the costly new positive material of high-quality is made in the low waste and old tertiary cathode material of this method use value
Material, is truly realized the regeneration of waste and old tertiary cathode material.
Advantage of this method based on preamble series of processes advantage overlapped in series, it is only necessary to which obtained high-quality is met into ternary
The carbon for meeting tertiary cathode material requirement of manganese cobalt nickel hydroxide co-precipitate presoma and high-quality that positive electrode requires
Sour lithium is calcined, both the new tertiary cathode material of available high-quality according to certain stoichiometric ratio combination, thus
Really realize the regeneration of waste and old tertiary cathode material.
(7) this method level of clean production height, energy-saving and environmental protection.
It based on unique process system constructed by this method, is compared with other methods, the entire process procedure of this method is not
Generate technique waste water；This method can realize waste and old positive electrode all of not generating waste residue；This method sulfenyl gas effciency
Up to 99.9%, realize exhaust gas near-zero release.
This method all recycles the steam condensate (SC) of generation, realizes waste heat all of to ammonia progress system
Interior recycling all recycles nitric acid waste liquor of sodium.
(8) this method is easier to realize automation, intelligentized scale industrial production.
For the one step Leach reaction system of unique three-phase of this method building, and reacting is acid-base neutralization reaction and oxidation
Reduction reaction intersects the unique reaction system of progress, and this method is according to the spy of acid-base neutralization reaction and redox reaction
Point, it is innovative using pH and ORP as the key index in reaction process, and on this basis, pass through and adjust mixed serum
Achieve the purpose that save reagent cost with the component in gas component with the proportion and leaching condition of being optimal, and pH and
Two parameters of ORP are easy to on-line checking and realize automation control, so that this method is easier to realize automation, intelligentized rule
Modelling industrial production.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
A specific embodiment of the invention is described below, in order to facilitate understanding by those skilled in the art this hair
It is bright, it should be apparent that the present invention is not limited to the ranges of specific embodiment, for those skilled in the art,
As long as various change is in the spirit and scope of the present invention that the attached claims limit and determine, these variations are aobvious and easy
See, all are using the innovation and creation of present inventive concept in the column of protection.
Embodiment 1
The method that the waste and old positive electrode of a kind of pair of lithium battery carries out resource utilization, comprising the following steps:
(1) allotment of liquid-solid reaction component: it will be crushed and cross the waste and old positive electrode powder 10kg and zeroth order cobalt of 80 meshes
Powder 1kg mixing, obtains solid component 11kg；By gained solid phase components and 25L steam condensate (SC) mixed pulp, and stir evenly
Afterwards, the hydrogen peroxide that 450ml concentration is 30% is added, obtains satisfactory liquid-solid reaction component.
(2) allotment of gas phase reaction component: being 1:0.5:1's according to volume by pure nitric oxide, nitrogen dioxide and oxygen
Ratio mixing, obtains the gas phase reaction component of satisfactory nitric oxide, nitrogen dioxide and oxygen mixed gas；
(3) three-phase single step reaction: by gas phase reaction component obtained by liquid and solid phase reaction component obtained by step (1) and step (2)
It is sent into one step leaching reactor of three-phase simultaneously according to a certain percentage, comes into full contact with airwater mist cooling, and, make in reaction process
The pH of solution stablizes in the range of 1.5~2.0 and ORP (oxidation reduction potential value) stablizes in 400~500mv, reacts 5h
Afterwards, will react sufficient slurries discharge reactor, the slurries after react, after tested cobalt, nickel, manganese, lithium leaching rate distinguish
It is 99.34%, 99.25%, 99.64% and 99.57%；
(4) solid-liquor separation: slurries obtained by step (3) are separated by solid-liquid separation, respectively obtain containing cobalt nitrate, nickel nitrate,
Manganese nitrate, lithium nitrate are main component and the extremely low iron of concentration, aluminium, the leachate that fluoride is impurity and contain conductive agent
With the leached mud of adhesive, a small amount of aluminium skimmings, this part leached mud can be directly as raw material of industry recycling treatment；
(5) leachate impurity and purification: being added sodium hydroxide solution for leachate obtained by step (4), pH be adjusted to 6.2,
The iron in solution, aluminium ion is set to be converted into iron hydroxide and aluminum hydroxide precipitation；Then it will contain iron hydroxide and aluminium hydroxide
Slurries be separated by solid-liquid separation, obtain the purification slag containing iron hydroxide and aluminium hydroxide and containing cobalt nitrate, nickel nitrate, nitric acid
Manganese, lithium nitrate be main component and iron, aluminium, fluorine content be below the purification qualifying liquid of 0.5mg/L；
(6) nickel cobalt manganese precursor preparation: the ammonium hydroxide being added in the purification qualifying liquid obtained by step (5) makees complexing agent, hydrogen
Sodium hydroxide solution makees precipitating reagent, is stirred, precipitation reaction, is maintained at the pH value of solution in 10.0~12.0 ranges, temperature
It is 70 DEG C, reaction time 2.5h；Then it is separated by solid-liquid separation, contains manganous hydroxide, cobalt hydroxide, nickel hydroxide to what is obtained
Solid powder mixture, washed using the steam condensate (SC) of subsequent handling, to respectively obtain satisfactory Gao Pin
The nickel cobalt manganese presoma of matter and separating liquid containing sodium nitrate, ammonium nitrate, lithium hydroxide, the washing water that this step generates return to
Step (1) uses；
(7) lithium resource recycles: obtained by the step (6) containing sodium nitrate, ammonium nitrate, lithium hydroxide separating liquid in carbonic acid is added
Sodium solution makes lithium hydroxide be converted into lithium carbonate precipitating, is then separated by solid-liquid separation, used to obtained lithium carbonate solid powder
The steam condensate (SC) of subsequent handling is washed, thus respectively obtain satisfactory high-quality lithium carbonate and containing sodium nitrate,
The separating liquid of ammonium nitrate.The washing water that this step generates is used back to step (1)；
(8) preparation of new tertiary cathode material: by high-quality nickel cobalt manganese hydroxide precursor powder obtained by step (6) and
High-quality lithium carbonate powder obtained by step (6) is mixed according to the ratio that mass ratio is 1:0.4 and calcines 8h at 950 DEG C,
Obtain the new tertiary cathode material of high-quality；
(9) sodium nitrate recycles: the sodium nitrate separating liquid obtained by step (7) containing a small amount of ammonium nitrate is evaporated concentration,
Crystallization is cooled down to concentrate, magma is separated by solid-liquid separation, obtains industrial grade sodium nitrate and separating liquid；This step is steamed
The condensed water generated during hair is sent to step (7) respectively, (8) make slurry；
(10) recovery ammonia: being added sodium hydroxide in the separating liquid obtained by step (9), adjusting pH is 10.0, turns ammonium nitrate
Turn to ammonia and sodium nitrate, ammonia is washed with water be recovered as ammonium hydroxide after return step (6) as complexing agent recycle；Sodium nitrate is molten
Liquid return step (9).
Embodiment 2
The method that the waste and old positive electrode of a kind of pair of lithium battery carries out resource utilization, comprising the following steps:
(1) allotment of liquid-solid reaction component: waste and old positive electrode powder 10kg, the zeroth order cobalt sieved with 100 mesh sieve after will be broken
The mixing of the ratio of 0.2kg and manganese 0.8kg, obtains 11kg solid mixed component；Obtained solid mixed component and 50L steam are condensed
Water mixing system will be stirring evenly and then adding into the hydrogen peroxide that 550ml concentration is 28%, obtain satisfactory solid phase reaction component；
(2) allotment of gas phase reaction component: will lead to containing the exhaust gas that nitric oxide concentration is 10%, oxygen concentration is 10%
Enter in catalytic reactor, make part conversion of nitric oxide gas nitrogen dioxide, obtaining nitric oxide concentration is that 8%, nitrogen dioxide is dense
The mixed gas that degree is 2%, oxygen concentration is 9%；
(3) three-phase single step reaction: liquid and solid phase reaction component obtained by step (1) and gas phase reaction group obtained by step (2) are sent
Enter one step leaching reactor of three-phase, come into full contact with airwater mist cooling, while adjusting in gaseous component nitric oxide to dioxy
Change the transformation efficiency of nitrogen, adjusts the ratio of nitric oxide, nitrogen dioxide and oxygen in gas phase, make the pH stable of solution 1.0
In the range of~2.0, and in the range of 350~500mv of ORP (oxidation reduction potential value) holding, after reacting 10h, reaction is filled
Point slurries be discharged reactor, the slurries after react, measure cobalt, nickel, manganese, lithium leaching rate point than be 99.33%,
99.41%, 99.65% and 99.72%.
(4) solid-liquor separation: slurries obtained by step (3) are separated by solid-liquid separation, are obtained containing cobalt nitrate, nickel nitrate, nitric acid
Manganese, lithium nitrate are main component and the extremely low iron of concentration, aluminium, the leachate that fluoride is impurity and contain conductive agent and viscous
The leached mud of mixture, a small amount of aluminium skimmings, leached mud is directly as raw material of industry recycling treatment；
(5) leachate impurity and purification: sodium carbonate liquor is added in leachate obtained by step (4), pH is adjusted to 5.5, is made
Iron, aluminium ion in solution are converted into iron hydroxide and aluminum hydroxide precipitation；It finally will be containing iron hydroxide and aluminium hydroxide
Slurries are separated by solid-liquid separation, and are obtained the purification slag containing iron hydroxide and aluminium hydroxide and are contained cobalt nitrate, nickel nitrate, nitric acid
Manganese, lithium nitrate are main component of iron, the content of aluminium, fluorine is below the purification qualifying liquid of 0.5mg/L；
(6) nickel cobalt manganese precursor preparation: ammonium hydroxide is added in the purification qualifying liquid obtained by step (5) and makees complexing agent, hydroxide
Sodium solution makees precipitating reagent, is stirred, precipitation reaction, is maintained at the pH value of solution in 11.0~12.0 ranges, temperature 65
DEG C, reaction time 3.0h；Then it is separated by solid-liquid separation, to obtaining consolidating containing manganous hydroxide, cobalt hydroxide, nickel hydroxide
Body mixture of powders is washed using the steam condensate (SC) of subsequent handling, to respectively obtain satisfactory high-quality
Nickel cobalt manganese presoma and separating liquid containing sodium nitrate, ammonium nitrate, lithium hydroxide, the washing water that this step generates return to step
(1) it uses；
(7) lithium resource recycles: obtained by the step (6) containing sodium nitrate, ammonium nitrate, lithium hydroxide separating liquid in be added it is certain
The sodium carbonate liquor of amount makes lithium hydroxide be converted into lithium carbonate precipitating, is then separated by solid-liquid separation, to obtained lithium carbonate solid
Powder is washed using the steam condensate (SC) of subsequent handling, to respectively obtain satisfactory high-quality lithium carbonate and contain
The separating liquid of sodium nitrate, ammonium nitrate.The washing water that this step generates is used back to step (1)；
(8) preparation of new tertiary cathode material: by high-quality nickel cobalt manganese hydroxide precursor powder obtained by step (6) and
High-quality lithium carbonate powder obtained by step (6) is mixed according to the ratio that mass ratio is 1:0.4 and is calcined at 950 DEG C
10h obtains the new tertiary cathode material of high-quality；
(9) sodium nitrate recycles: the sodium nitrate separating liquid obtained by step (7) containing a small amount of ammonium nitrate is evaporated concentration,
Crystallization is cooled down to concentrate, magma is separated by solid-liquid separation, obtains industrial grade sodium nitrate and separating liquid；This step is steamed
The condensed water generated during hair is sent to step (7) respectively, (8) make slurry；
(10) recovery ammonia: being added sodium hydroxide in the separating liquid obtained by step (9), adjusting pH is 9.5, converts ammonium nitrate
For ammonia and sodium nitrate, ammonia is washed with water be recovered as ammonium hydroxide after return step (6) recycled as complexing agent；Sodium nitrate solution
Return step (9).
Embodiment 3
The method that the waste and old positive electrode of a kind of pair of lithium battery carries out resource utilization, comprising the following steps:
(1) waste and old positive electrode powder 20kg, the zeroth order manganese of 120 meshes the allotment of liquid-solid reaction component: are crossed after will be broken
The mixing of the ratio of 0.5kg, zero-valent nickel 0.5kg and zeroth order cobalt 0.5kg, obtains 21.5kg solid mixed component；Obtained solid is mixed
Be combined the system of point being mixed with 50L steam condensate (SC) will, be stirring evenly and then adding into the hydrogen peroxide that 600ml concentration is 28%, met
It is required that solid phase reaction component；
(2) allotment of gas phase reaction component: add containing the exhaust gas that nitric oxide concentration is 1%, oxygen concentration is 10%
Enter nitrogen dioxide gas, obtaining nitric oxide, nitrogen dioxide and oxygen concentration is 1:0.5:10 mixed gas；
(3) three-phase single step reaction: liquid and solid phase reaction component obtained by step (1) and gas phase reaction group obtained by step (2) are sent
Enter one step leaching reactor of three-phase, come into full contact with airwater mist cooling, in leaching process the pH stable of solution 1.0~
In the range of 2.5, and in the range of 450~550mv of ORP (oxidation reduction potential value) holding, after reacting 10h, it will react abundant
Slurries be discharged reactor, the slurries after react, measure cobalt, nickel, manganese, lithium leaching rate point than be 99.36%,
99.27%, 99.59% and 99.64%.
(4) solid-liquor separation: slurries obtained by step (3) are separated by solid-liquid separation, are obtained containing cobalt nitrate, nickel nitrate, nitric acid
Manganese, lithium nitrate are main component and the extremely low iron of concentration, aluminium, the leachate that fluoride is impurity and contain conductive agent and viscous
The leached mud of mixture, a small amount of aluminium skimmings, leached mud is directly as raw material of industry recycling treatment；
(5) leachate impurity and purification: sodium carbonate liquor is added in leachate obtained by step (4), pH is adjusted to 6.0, is made
Iron, aluminium ion in solution are converted into iron hydroxide and aluminum hydroxide precipitation；It finally will be containing iron hydroxide and aluminium hydroxide
Slurries are separated by solid-liquid separation, and are obtained the purification slag containing iron hydroxide and aluminium hydroxide and are contained cobalt nitrate, nickel nitrate, nitric acid
Manganese, lithium nitrate are main component of iron, the content of aluminium, fluorine is below the purification qualifying liquid of 0.5mg/L；
(6) nickel cobalt manganese precursor preparation: ammonium hydroxide is added in the purification qualifying liquid obtained by step (5) and makees complexing agent, hydroxide
Sodium solution makees precipitating reagent, is stirred, precipitation reaction, is maintained at the pH value of solution in 11.0~12.0 ranges, temperature 75
DEG C, reaction time 2.5h；Then it is separated by solid-liquid separation, to obtaining consolidating containing manganous hydroxide, cobalt hydroxide, nickel hydroxide
Body mixture of powders is washed using the steam condensate (SC) of subsequent handling, to respectively obtain satisfactory high-quality
Nickel cobalt manganese presoma and separating liquid containing sodium nitrate, ammonium nitrate, lithium hydroxide, the washing water that this step generates return to step
(1) it uses；
(7) lithium resource recycles: obtained by the step (6) containing sodium nitrate, ammonium nitrate, lithium hydroxide separating liquid in be added it is certain
The sodium carbonate liquor of amount makes lithium hydroxide be converted into lithium carbonate precipitating, is then separated by solid-liquid separation, to obtained lithium carbonate solid
Powder is washed using the steam condensate (SC) of subsequent handling, to respectively obtain satisfactory high-quality lithium carbonate and contain
The separating liquid of sodium nitrate, ammonium nitrate.The washing water that this step generates is used back to step (1)；
(8) preparation of new tertiary cathode material: by high-quality nickel cobalt manganese hydroxide precursor powder obtained by step (6) and
High-quality lithium carbonate powder obtained by step (6) is mixed according to the ratio that mass ratio is 1:0.4 and is calcined at 1000 DEG C
8h obtains the new tertiary cathode material of high-quality；
(9) sodium nitrate recycles: the sodium nitrate separating liquid obtained by step (7) containing a small amount of ammonium nitrate is evaporated concentration,
Crystallization is cooled down to concentrate, magma is separated by solid-liquid separation, obtains industrial grade sodium nitrate and separating liquid；This step is steamed
The condensed water generated during hair is sent to step (7) respectively, (8) make slurry；
(10) recovery ammonia: being added sodium hydroxide in the separating liquid obtained by step (9), adjusting pH is 11.0, turns ammonium nitrate
Turn to ammonia and sodium nitrate, ammonia is washed with water be recovered as ammonium hydroxide after return step (6) as complexing agent recycle；Sodium nitrate is molten
Liquid return step (9).
Performance detection is carried out to the tertiary cathode material that Examples 1 to 3 is prepared, the result is shown in tables 1.
1 tertiary cathode material performance of table
From the data in table 1, it can be seen that the tertiary cathode material that Examples 1 to 3 is prepared, which obtains performance, meets professional standard rule
It is fixed, show that using the method for carrying out resource utilization to the waste and old positive electrode of lithium battery referred in the present invention be practical
, the quality for the new tertiary cathode material being prepared can also be guaranteed.
Claims (10)
1. the method that the waste and old positive electrode of a kind of pair of lithium battery carries out resource utilization, which comprises the following steps:
(1) waste and old positive electrode is crushed as powder, and is mixed with metal powder, form solid-phase mixture；Then by hydrogen peroxide
It is mixed with condensed water, forms liquid phase mixture；Solid-phase mixture and liquid phase mixture are mixed again；
The weight ratio of the waste and old positive electrode powder and metal powder is 1:0.05~1；The body of the hydrogen peroxide and condensed water
Product is than being 1:50~1000；The solid-liquid ratio of the solid-phase mixture and liquid phase mixture is 1:1~10；The metal powder is
One of manganese, cobalt or nickel are a variety of；
(2) by nitric oxide, nitrogen dioxide and oxygen mix, gas phase mixture is formed；The nitric oxide, nitrogen dioxide and oxygen
The volume ratio of gas is 1:0.05~10:0.5~100；
(3) step (1) products therefrom is mixed with gas phase mixture, and adjust system pH be 0.5~3.0, ORP be 250~
550mv；Wherein, the volume ratio 0.05~50 of step (1) products therefrom and gas phase mixture；
(4) step (3) products therefrom is separated by solid-liquid separation, collects liquid phase, adjusting its pH value is 5.0~7.0, keeps 2~5h
After be separated by solid-liquid separation, collection be purified liquid；
(5) pH value for adjusting scavenging solution is 10.0~12.0, and is allowed to warm to 40~80 DEG C, after keeping 2~3h, carries out solid-liquid
Separation collects solid phase respectively and separating liquid is spare, then washs 3~5 times to solid phase；
(6) sodium carbonate liquor is added into separating liquid obtained in step (5), reaction is heavy to without precipitating generation, collecting and cleaning
Starch；
(7) then solid phase obtained by step (5) is mixed with step (6) gained sediment, is in 750~1200 DEG C of 8~10h of calcining
It can；The solid phase and the weight ratio of sediment are 1:0.3~0.5.
2. the method according to claim 1 for carrying out resource utilization to the waste and old positive electrode of lithium battery, which is characterized in that
The weight ratio of waste and old positive electrode powder and metal powder described in step (1) is 1:0.1；The body of the hydrogen peroxide and condensed water
Product is than being 1:44；The solid-liquid ratio of the solid-phase mixture and liquid phase mixture is 1:2.3.
3. the method according to claim 1 or 2 for carrying out resource utilization to the waste and old positive electrode of lithium battery, feature exist
In the partial size of the waste and old positive electrode powder and metal powder is 80~120 mesh.
4. the method according to claim 1 for carrying out resource utilization to the waste and old positive electrode of lithium battery, which is characterized in that
The volume ratio of nitric oxide, nitrogen dioxide and oxygen described in step (2) is 1:0.5:1.
5. the method according to claim 1 for carrying out resource utilization to the waste and old positive electrode of lithium battery, which is characterized in that
The ratio of the volume ratio of step (1) products therefrom and gas phase mixture described in step (3) is 10.
6. the method according to claim 1 for carrying out resource utilization to the waste and old positive electrode of lithium battery, which is characterized in that
The ingredient that pH value is reconciled in step (5) is ammonium hydroxide and sodium hydroxide.
7. the method according to claim 6 for carrying out resource utilization to the waste and old positive electrode of lithium battery, which is characterized in that
It further include being recycled to filtered fluid, isolated sodium nitrate sodium and secondary by evaporation and concentration, Crystallization Separation in step (6)
Separating liquid, and will be in the condensing hot air furnace that generated in removal process to step (6) and step (7).
8. the method according to claim 7 for carrying out resource utilization to the waste and old positive electrode of lithium battery, which is characterized in that
Sodium hydroxide is added into the secondary separating liquid, adjusting its pH value is 8~10, ammonia and sodium nitrate solution are respectively obtained, and
By in Ammonia recovery to step (5), sodium nitrate solution is recycled in step (6).
9. the method according to claim 1 for carrying out resource utilization to the waste and old positive electrode of lithium battery, which is characterized in that
It is washed with steam condensate (SC) in step (5) and step (6), and will be in the condensing hot air furnace after washing to step (1).
10. the method according to claim 1 for carrying out resource utilization to the waste and old positive electrode of lithium battery, feature exist
In solid phase described in step (7) and the weight ratio of sediment are 1:0.4.
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