CN109193057A - A method of positive electrode material precursor is prepared using waste and old ternary lithium battery - Google Patents
A method of positive electrode material precursor is prepared using waste and old ternary lithium battery Download PDFInfo
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- CN109193057A CN109193057A CN201811045199.4A CN201811045199A CN109193057A CN 109193057 A CN109193057 A CN 109193057A CN 201811045199 A CN201811045199 A CN 201811045199A CN 109193057 A CN109193057 A CN 109193057A
- Authority
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- China
- Prior art keywords
- waste
- lithium battery
- positive electrode
- ammonium
- electrode material
- Prior art date
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 99
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002699 waste material Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000002243 precursor Substances 0.000 title claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 154
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 69
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 41
- 239000010941 cobalt Substances 0.000 claims abstract description 41
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 239000004411 aluminium Substances 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 23
- 239000000908 ammonium hydroxide Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- 239000003638 chemical reducing agent Substances 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- FOJJCOHOLNJIHE-UHFFFAOYSA-N aluminum;azane Chemical compound N.[Al+3] FOJJCOHOLNJIHE-UHFFFAOYSA-N 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- 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 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000011112 process operation Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 2
- 238000002386 leaching Methods 0.000 abstract description 65
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 239000010406 cathode material Substances 0.000 abstract description 11
- 150000002739 metals Chemical class 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 17
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 15
- 238000000975 co-precipitation Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- 239000005030 aluminium foil Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 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 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- RVWQPNFMNZMPLI-UHFFFAOYSA-N [Li+].N.[Co+2].[Ni+2] Chemical compound [Li+].N.[Co+2].[Ni+2] RVWQPNFMNZMPLI-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- IWTZGPIJFJBSBX-UHFFFAOYSA-G aluminum;cobalt(2+);nickel(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2].[Ni+2] IWTZGPIJFJBSBX-UHFFFAOYSA-G 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- BOMINLBVYNPVIK-UHFFFAOYSA-N azane;manganese(2+) Chemical compound N.[Mn+2] BOMINLBVYNPVIK-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 2
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910011669 LiNi0.7Co0.2Mn0.1O2 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910018058 Ni-Co-Al Inorganic materials 0.000 description 1
- 229910017238 Ni0.8Co0.15Al0.05(OH)2 Inorganic materials 0.000 description 1
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 1
- 229910018144 Ni—Co—Al Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 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
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal 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
Abstract
The present invention provides a kind of methods using waste and old ternary lithium battery preparation positive electrode material precursor, use first segment leaching to go out for pressure ammonia leaching, recycle while realizing lithium, nickel, cobalt；It is normal pressure acidleach that second segment, which leaches, realizes the recycling of doping metals (manganese or aluminium).The present invention realizes the low cost of waste and old tertiary cathode material, short route recycling and reusing, wherein the synthesis leaching rate of the valuable metals such as pressure ammonia leaching process nickel, cobalt, lithium reaches 92%, two sections of leachings realize that the valuable metals comprehensive recoveries such as waste and old tertiary cathode material nickel, cobalt, lithium, manganese, aluminium reach 95% or more, ammonia and leaching acid realize closed cycle, the ternary anode material precursor of regeneration preparation can satisfy different series tertiary cathode material preparation demand, have good prospects for commercial application.
Description
Technical field
The present invention relates to waste and old ternary lithium battery recovery technology field more particularly to a kind of waste and old ternary lithium battery systems of utilization
The method of standby positive electrode material precursor.
Background technique
With the fast development of electric car and energy storage field, lithium battery demand and yield are increased sharply, and old and useless battery quantity is anxious
Play is soaring.There is research, it is expected that about 500,000 tons, by 2023, will scrap up to 32.2Gwh to the year two thousand twenty dynamic lithium battery learies
It measures and is up to 101Gwh, about 1,160,000 tons.Ternary lithium ion battery is because of function admirable, it has also become the mainstream of current lithium ion battery
Technology, its market share reaches 44.71% within 2017, it is contemplated that the following main composition that will become old and useless battery.Ternary lithium-ion electric
Usually contain cobalt 5%~20%, nickel 5%~10%, lithium 5%~7%, organic solvent 15%, plastics 7% in pond.Therefore, quantity is huge
Big waste and old ternary lithium battery material contains the valuable elements such as lithium abundant, nickel, cobalt, and potential resources is huge, recycles economic valence
Value is high, and system carries out recycling and the regeneration techniques of waste and old ternary lithium battery material, it will help the pollution of prevention and treatment old and useless battery is alleviated
Nickel cobalt lithium shortage of resources pressure promotes the benign development of China's lithium battery industry.
Currently, waste lithium ion cell anode material recovery method mainly has: pyrogenic process, wet process, Bioleaching method.At pyrogenic process
Science and engineering skill is simpler, but energy consumption is high, generates large quantity of exhaust gas.It studies and what application was most is wet-treating, mainly pass through inorganic acid
Or organic acid leaches metal, is used as leaching agent using inorganic acid (HCl, H2SO4, HNO3 etc.) etc., leaching efficiency is high, treating capacity
Greatly, but toxic and harmful gas (Cl2, SO2, NO2) can be generated etc., remaining acid waste liquid is difficult to handle, and can bring secondary pollution；
Leaching agent is used as using organic acid (citric acid, oxalic acid, ascorbic acid, grape acid etc.), the cost is relatively high, but organic acid is to three
The high treating effect of first based lithium-ion power battery, the pH of acid waste liquid is low, is easy to subsequent processing recycling.But subsequent nickel cobalt manganese
Separation process is complex, increases cost recovery.Bioleaching method is high-efficient, at low cost, environmentally friendly, but the more difficult culture of bacterium,
Leaching cycle is long and leaching rate is lower, and which has limited its processes of industrialization.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, it is prepared the purpose of the present invention is to provide a kind of using waste and old ternary lithium battery
The method of positive electrode material precursor, it is intended to solve the problems, such as that positive electrode recovery efficiency is low in existing waste and old ternary lithium battery.
Technical scheme is as follows:
A method of positive electrode material precursor is prepared using waste and old ternary lithium battery, wherein comprising steps of
The anode split out from waste and old ternary lithium battery is put into aqueous slkali, removing obtains waste and old ternary lithium battery anode material
Material；
The waste and old ternary anode material of lithium battery is dried, calcination processing, will treated waste and old ternary lithium battery just
Pole material is ground, and powder is obtained；
The mixed liquor of the powder, ammonium salt and ammonium hydroxide and reducing agent are added to high pressure to answer in kettle, carried out under a predetermined
Leach reaction;
Reaction product is separated, obtains being mixed with lithium, nickel, the ammonium complex solution of cobalt and the filter containing manganese metal or aluminium
Slag；
The filter residue containing manganese metal or aluminium is mixed with reducing agent and acid solution, is obtained by filtration containing manganese salt or aluminium salt
Solution, then ammonium hydroxide is added into the manganese salt or aluminum salt solution and obtains the complex solution of manganese or aluminium ammonium；
By it is described be mixed with lithium, nickel, the ammonium complex solution of cobalt, the complex solution of the manganese or aluminium ammonium and aqueous slkali be added to it is heavy
In the reaction kettle of shallow lake, it is passed through protective gas and carries out ammonia still process operation, obtain positive electrode material precursor.
The method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein the aqueous slkali is hydrogen
Any one of sodium oxide molybdena, potassium hydroxide, calcium hydroxide are formed by solution.
The method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein the partial size of the powder
For 200 ~ 500 mesh.
The method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein the ammonium salt includes sulphur
One of sour ammonium, ammonium chloride, ammonium nitrate are a variety of.
The method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein the ammonium salt and ammonium hydroxide
Mixed liquor total ammonia density be 5~12mol/L.
The described method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein the reducing agent includes
One of hydrazine hydrate, azanol, sodium sulfite, hydrogen peroxide are a variety of.
The method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein the Leach reaction item
Part are as follows: 40-150 DEG C of temperature, pressure 0.6Mpa-1.5 Mpa.
The method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein the Leach reaction condition
Are as follows: liquid-solid ratio 3:1-20:1.
The method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein the dosage of the reducing agent
It is 2-5 times of cobalt mole in ternary anode material of lithium battery.
The method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein filter residue dissolution is used to go back
Former agent includes one of hydrazine hydrate, azanol, sodium sulfite, hydrogen peroxide or a variety of.
The method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein filter residue dissolution is used to go back
Former agent dosage is 1-3 times of manganese and aluminium mole in filter residue.
The method using waste and old ternary lithium battery preparation positive electrode material precursor, wherein the acid solution includes sulphur
One of acid, hydrochloric acid, nitric acid are a variety of.
The utility model has the advantages that the present invention recycles waste and old tertiary cathode material using two sections of leachings, first segment pressure ammonia leaching method will give up
The valuable metals such as lithium, cobalt, nickel in the tertiary cathode material of old lithium pond are with Ni (NH3)6 3+、Co(NH3)6 2+、Li+Form dissolves into
Enter ammonia leaching solution, is recycled while realization to lithium, nickel, cobalt；It is normal pressure acidleach that second segment, which leaches, realizes doping metals (manganese or aluminium)
Recycling；The Leaching Systems of normal pressure acidleach are selected and the consistent acid ion of pressure leaching, by the pH value and ammonia that control solution
Concentration realizes that the segmentation of main lithium metal nickel cobalt and doping metals is leached, to regulate and control matching for nickel in synthesis process, cobalt and doping salt
Than realizing the demand of different series ternary material precursor production.The present invention realize waste and old tertiary cathode material it is low at
Originally, short route recycling and reusing, wherein the synthesis leaching rate of the valuable metals such as pressure ammonia leaching process nickel, cobalt, lithium reaches 92%, two
Section, which leaches, realizes that the valuable metals comprehensive recoveries such as waste and old tertiary cathode material nickel, cobalt, lithium, manganese, aluminium reach 95% or more, regeneration
The ternary anode material precursor of preparation can satisfy different series tertiary cathode material preparation demand, and there is good industry to answer
Use prospect.
Detailed description of the invention
Fig. 1 is that the method provided by the present invention for preparing positive electrode material precursor using waste and old ternary lithium battery is preferably implemented
The flow chart of example.
Fig. 2 is the method and process process provided by the present invention that positive electrode material precursor is prepared using waste and old ternary lithium battery
Figure.
Fig. 3, the hydroxide nickel cobalt manganese presoma SEM figure prepared for the embodiment of the present invention 1.
Fig. 4 is hydroxide nickel cobalt manganese presoma XRD diagram prepared by the embodiment of the present invention 1.
Fig. 5 is nickel cobalt aluminum hydroxide presoma SEM figure prepared by the embodiment of the present invention 2.
Fig. 6 is nickel cobalt aluminum hydroxide presoma Elemental redistribution EDS map prepared by the embodiment of the present invention 2.
Fig. 7 is hydroxide nickel cobalt manganese presoma SEM figure prepared by the embodiment of the present invention 3.
Fig. 8 is hydroxide nickel cobalt manganese particle size distribution figure prepared by the embodiment of the present invention 3.
Specific embodiment
The present invention provides a kind of methods using waste and old ternary lithium battery preparation positive electrode material precursor, to make the present invention
Purpose, technical solution and effect it is clearer, clear, below in conjunction with attached drawing and specific embodiment to of the invention further detailed
It describes in detail bright.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is the side provided by the present invention for preparing positive electrode material precursor using waste and old ternary lithium battery
The flow chart of method preferred embodiment, as shown, itself comprising steps of
S1, the anode split out from waste and old ternary lithium battery is put into aqueous slkali, removing is obtaining waste and old ternary lithium battery just
Pole material；
It further include that waste and old ternary lithium battery is put in sodium chloride solution by step before the step S1 specifically in conjunction with Fig. 2
Middle deep discharge, because electricity remaining in old and useless battery can impact the dismantling of battery, there are security risks.After discharging
Waste and old ternary lithium battery disassembled, crushing and screening obtains positive pole aluminium foil (tertiary cathode piece), negative copper foil, shell, diaphragm,
Tab etc..
The step S1, obtained positive pole aluminium foil is put into alkaline solution, and the aqueous slkali is including but not limited to hydrogen
Sodium oxide molybdena, potassium hydroxide, calcium hydroxide are formed by solution.The concentration of the alkaline solution is 1-3mol/L(such as 1 mol/L),
For the positive pole aluminium foil after aqueous slkali soaking, removing obtains waste and old ternary anode material of lithium battery (tertiary cathode material).
S2, the waste and old ternary anode material of lithium battery is dried, calcination processing, it will treated waste and old ternary lithium
Cell positive material is ground, and powder is obtained；
Specifically, obtained waste and old ternary anode material of lithium battery is put in drying box and is dried, drying temperature 60-
90 DEG C (such as 80 DEG C), drying time 8-12 hour (such as 12 hours), remove remaining alkali on waste and old ternary anode material of lithium battery
Solution.Waste and old ternary anode material of lithium battery after drying is put into batch-type furnace calcine and isolates Kynoar
(PVDF).
S3, it the mixed liquor of the powder, ammonium salt and ammonium hydroxide and reducing agent is added to high pressure answers in kettle, in predetermined pressure
Lower carry out Leach reaction;
Specifically, the powder ground in step S2 is sieved, obtains the powder between 200-500 mesh (such as 300 mesh)
Material, separates waste and old powder with big partial size impurity, improves powder lot dispersing degree, guarantees leaching efficiency.The powder is added to height
It presses in reaction kettle, adds the mixed liquor of ammonium salt and ammonium hydroxide into autoclave by set mixing channel, then anti-to high pressure
It answers kettle that reducing agent is added and carries out Leach reaction.The ammonium salt include but is not limited to one of ammonium sulfate, ammonium chloride, ammonium nitrate or
It is a variety of；The reducing agent includes but is not limited to one of hydrazine hydrate, azanol, sodium sulfite, hydrogen peroxide or a variety of.
The Leach reaction leaching condition are as follows: solid-to-liquid ratio is 3:1-20:1, that is, powder: mixed liquor=3:1-20:1, temperature 40-
150 DEG C, mixing speed be 300-900 r/min, the dosage of pressure 0.6Mpa-1.5 Mpa, the reducing agent is ternary lithium electricity
Total ammonia density of the mixed liquor of 2-5 times of cobalt mole in the positive electrode of pond, ammonium salt and ammonium hydroxide is 5-12mol/L, it is preferred that total
Ammonia density is 8mol/L, n (NH3) : n(NH4+) = 2:1。
S4, reaction product is separated, obtain being mixed with lithium, nickel, the ammonium complex solution of cobalt and containing manganese metal or
The filter residue of aluminium；
Specifically, obtained reaction product is filtered under diminished pressure, obtains ammonia leaching solution and leached mud, contains in the ammonia leaching solution
Lithium metal, nickel, cobalt contain manganese metal or aluminium in the leached mud.Obtained ammonia leaching solution is cleaned with ammonium hydroxide, then to institute
It states ammonia leaching solution progress purified treatment and removes the other impurities element that waste and old tertiary cathode material is brought into.Wherein, the purification method
Including but not limited to chemical precipitation method, chemical displacement method, physical absorption, extraction.Purified ammonia leaching solution as needed to its at
It is stand-by after dividing to be regulated and controled.
S5, the filter residue containing manganese metal or aluminium and reducing agent and acid solution are mixed, is obtained by filtration containing manganese
Salt or aluminum salt solution, then ammonium hydroxide is added into the manganese salt or aluminum salt solution and obtains the complex solution of manganese or aluminium ammonium；
Specifically, the filter residue containing manganese metal or aluminium is added in a reaction kettle, reducing agent and acid is added, after reaction
Obtain the solution of manganese salt or aluminium salt.Addition ammonium hydroxide obtains manganese or aluminium ammonium after carrying out purified treatment to the solution of the manganese salt or aluminium salt
Complex solution.The reducing agent includes but is not limited to one of hydrazine hydrate, azanol, sodium sulfite, hydrogen peroxide or a variety of.Institute
Stating acid includes but is not limited to one of sulfuric acid, hydrochloric acid, nitric acid or a variety of.Wherein, filter residue dissolution reducing agent dosage used is
1-3 times of manganese and aluminium mole in filter residue.
S6, by the complex solution and aqueous slkali for being mixed with lithium, nickel, the ammonium complex solution of cobalt, the manganese or aluminium ammonium
It is added in precipitation reaction kettle, is passed through protective gas and carries out ammonia still process operation, obtain positive electrode material precursor.
Specifically, the complex solution for being mixed with lithium, nickel, the ammonium complex solution of cobalt and manganese or aluminium ammonium after ingredient being regulated and controled
It is mixed under stirring conditions according to a certain percentage, is added drop-wise in coprecipitation reaction kettle and is stirred with certain flow velocity after mixing
It mixes, is passed through protective gas identical with ammonia steaming operation temperature, by the pH value of pH meter detection reaction system, pass through the side that alkali is added dropwise
Formula controls the pH value of reaction system in a certain range, the NH under mechanical stirring and the collective effect of airflow stirring3Slowly volatilization,
Reaction system slowly releases nickel, cobalt, manganese ion or nickel, cobalt, aluminium ion, and coprecipitation reaction occurs for the ion released,
Liquid after carrying out isolated positive electrode material precursor after reaction and being co-precipitated.
Further, the recovery ammonia to be volatilized in operation is steamed to ammonia to be back in mixing channel, reused.To acquired
Co-precipitation after carbonic acid is added in liquid, so that the lithium ion after co-precipitation in liquid is formed lithium carbonate with carbonate ining conjunction with and precipitate, separate
Liquid after lithium carbonate and sinker is obtained, to realize the recycling to lithium metal.
Further, liquid after the sinker is also back in mixing channel, is reused to reduce cost recovery.
Positive electrode material precursor is prepared using waste and old ternary lithium battery below by specific embodiment is a kind of to the present invention
Method is explained:
Embodiment 1
By waste and old NCM721(LiNi0.7Co0.2Mn0.1O2) ternary lithium battery is placed in 2 mol/L sodium chloride solutions, when placement
Between 36 h, by hand disassemble battery, isolate positive pole aluminium foil, negative copper foil, shell, diaphragm, tab etc..Positive pole aluminium foil is put in 1
In mol/L sodium hydroxide solution, positive electrode is then separated, and is washed and stripped down with 1 mol/L sodium hydroxide solution
Positive electrode.It is then placed in 80 DEG C of drying box, dry 12 h.And 600 DEG C of 6 h of calcining in batch-type furnace are put it into,
It is cooled to room temperature in furnace, is drawn off being put into mortar and grind, and is filtered with 200 mesh sieve, is obtaining waste and old ternary lithium battery just
Pole material powder.Then it weighs 53g positive electrode powder to be put into autoclave, it is 8 mol/L, n that total ammonium concentration, which is added,
(NH3) : n(NH4+The ammonium sulfate and ammonium hydroxide mixed solution 800mL of)=2:1；Then 80% hydrazine hydrate is added as reducing agent,
Dosage is 2 times of cobalt mole in raw material.Above-mentioned material stirring is uniform, kettle cover is covered, adjusting mixing speed is 600r/min,
90 DEG C of extraction temperature, control autoclave pressure is 0.6 MPa, leaches 3 hours, obtains ammonia leaching solution and ammonia leaching residue.Through depressurizing
Filter obtains the ammonia leaching residue of ammonia leaching solution and enrichment manganese rich in Ni, Co, Li with 4mol/L ammonia scrubbing ammonia leaching residue, using flame original
Sub- absorption spectrometry measures the content of nickel, cobalt, lithium, manganese in ammonia leaching solution and leached mud respectively.Based on the analysis results, pressure ammonia leaching mistake
Journey nickel, cobalt, lithium, manganese leaching rate be respectively 98.3%, 92.1%, 95.8%, 1.2%.According to the content of nickel in ammonia leaching solution and cobalt, press
Nickel, cobalt, ammonia molar ratio 0.7:0.2:7.2 ratio, add nickel salt, cobalt salt and ammonium hydroxide, be sufficiently mixed, formed stablize it is equal
One ammonium nickel cobalt lithium complex solution.Above-mentioned ammonia leaching residue is leached using 40g/L sulfuric acid solution, is passed through hydrogen peroxide as reducing agent,
Reducing agent dosage 0.6mol/L, extraction time 2 hours, obtains manganese sulfate leachate, the leaching rate of manganese reaches by 60 DEG C of extraction temperature
98.6%.After the purified removal of impurities of leachate, the ammonium hydroxide that concentration is 14mol/L is added into solution under stirring conditions, ammonium hydroxide is pressed
According to the molar ratio NH of ammonia and manganese ion3:Mn2+The ratio of=8:1 is added, and the ammonium manganese complex solution of stable uniform is formed.
By two kinds of ammoniums-metal complex solution of above-mentioned acquisition, according to Ni0.7Co0.2 Mn0.1(OH)2Stoichiometric ratio be
The ratio of Ni:Co:Mn=0.7:0.2:0.1 mixes, and obtains mixed solution after mixing with 600 revs/min of mixing speed；Then
It is added drop-wise in coprecipitation reaction kettle and is stirred with the flow velocity of 100mL/min, mixing speed is 600 revs/min, with the stream of 10L/min
Speed is passed through 80 DEG C of argon stream ammonia still process, by pH meter detection architecture pH value, (NH in chemical titration detection architecture3·H2O+NH4 +) concentration, controlling the reaction temperature in reaction kettle is 80 DEG C, starts to be slowly added to when system pH drops to 11.0 ± 0.05 dense
Degree is the NaOH solution of 5mol/L, and is 12.0 ± 0.05 by adjusting flow control system pH；Reaction process strict control
(NH3·H2O+NH4+) concentration, pH value, temperature.After reaction starts, mechanical stirring and air-flow stirring action make NH3Slowly volatilization,
PH is reduced, and coprecipitation reaction occurs for slow release Ni-Co-Mn ion, is stopped after solution system material size reaches 10 ± 0.5 μm
It only reacts, obtains crystallinity height, the high hydroxide nickel cobalt manganese presoma of even particle size distribution, tap density, the ammonia steamed is received
Collection, which returns, to be leached.Fig. 3 is its SEM figure, as can be seen that presoma pattern is spherical or spherical, size distribution collection from SEM figure
In；Fig. 4 is its XRD diagram, as can be seen that material crystalline degree is very high from XRD spectrum.
Embodiment 2
Waste and old NCA ternary lithium battery is placed in 2 mol/L sodium chloride solutions, 36 h of standing time, disassembles battery by hand, point
Separate out positive pole aluminium foil, negative copper foil, shell, diaphragm, tab etc..Positive pole aluminium foil is put in 1 mol/L sodium hydroxide solution, so
After separate positive electrode, and wash the positive electrode stripped down with 2 mol/L sodium hydroxide solutions.It is then placed in 90 DEG C
Drying box in, dry 12 h.And 600 DEG C of 6 h of calcining in batch-type furnace are put it into, it is cooled to room temperature in furnace, is drawn off
It is put into mortar and grinds, and filtered with 300 mesh sieve, obtain waste and old ternary anode material of lithium battery powder.Then 53g is weighed just
Pole material powder is put into autoclave, and it is 7.5 mol/L, n (NH that total ammonium concentration, which is added,3) : n(NH4+The sulphur of)=2:1
Sour ammonium and ammonium hydroxide mixed solution 800mL；Then sodium sulfite is added as reducing agent, dosage is 5 times of cobalt mole in raw material.
Above-mentioned material stirring is uniform, kettle cover is covered, adjusting mixing speed is 900r/min, 60 DEG C of extraction temperature, controls autoclave pressure
Power is 0.8 MPa, leaches 3 hours, obtains ammonia leaching solution and ammonia leaching residue.Through being filtered under diminished pressure, with 4mol/L ammonia scrubbing ammonia leaching residue,
It obtains the ammonia leaching solution rich in Ni, Co, Li and is enriched with the ammonia leaching residue of aluminium, ammonia leaching solution is measured using flame atomic absorption spectrometry respectively
With the content of nickel, cobalt, lithium, aluminium in leached mud.Based on the analysis results, the leaching rate difference of pressure ammonia leaching process nickel, cobalt, lithium, aluminium
Reach 96.7%, 91.3%, 95.2%, 11.3%.According to the content of nickel in ammonia leaching solution and cobalt, by the molar ratio 0.800 of nickel, cobalt, ammonia:
The ratio of 0.150:7.00, adds nickel salt and cobalt salt, is sufficiently mixed, and the ammonium nickel cobalt lithium complex solution of stable uniform is formed.
Above-mentioned ammonia leaching residue is leached using 260g/L sulfuric acid solution, and extraction temperature is 180 DEG C, liquid-solid ratio 5:1, and extraction time is 3 hours,
Aluminum sulfate leachate is obtained, aluminium leaching rate reaches 92.7%, after purified removal of impurities, is added under stirring conditions into solution dense
Degree is the ammonium hydroxide of 14mol/L, and ammonium hydroxide is according to ammonia and aluminum ions molar ratio NH3:Mn2+The ratio of=7:1 is added, and is formed and is stablized
One ammonium manganese complex solution.
By two kinds of ammoniums-metal complex solution of above-mentioned acquisition, according to Ni0.8Co0.15Al 0.05(OH)2Stoichiometric ratio be
The ratio of Ni:Co:Al=0.80:0.15:0.05 mixes, and obtains mixed solution after mixing with 500 revs/min of mixing speed；So
It is added drop-wise in coprecipitation reaction kettle and is stirred with the flow velocity of 60mL/min afterwards, mixing speed is 500 revs/min, with the stream of 5L/min
Speed is passed through 100 DEG C of air draught ammonia still process, by pH meter detection architecture pH value, (NH in chemical titration detection architecture3·H2O+NH4 +) concentration, controlling the reaction temperature in reaction kettle is 100 DEG C, starts to be slowly added to when system pH drops to 12.0 ± 0.05 dense
Degree is the NaOH solution of 5mol/L, and is 12.0 ± 0.05 by adjusting flow control system pH；Reaction process strict control
(NH3·H2O+NH4+) concentration, pH value, temperature.After reaction starts, mechanical stirring and air-flow stirring action wave NH3 slowly
Hair, pH are reduced, and coprecipitation reaction occurs for slow release Ni-Co-Al ion, reach 10 ± 0.5 μm to solution system material size
Stop reaction afterwards, obtains crystallinity height, the high nickel cobalt aluminum hydroxide presoma of even particle size distribution, tap density.Fig. 5 is it
SEM figure, as can be seen that presoma pattern is spherical or spherical, size distribution concentration from SEM figure；Fig. 6 is its Elemental redistribution
EDS map, from can be seen that in map, Elemental redistribution in obtained material is uniform.
Embodiment 3
By waste and old NCM622(LiNi0.6Co0.2Mn0.2O2) ternary lithium battery is placed in 2 mol/L sodium chloride solutions, when placement
Between 36 h, by hand disassemble battery, isolate positive pole aluminium foil, negative copper foil, shell, diaphragm, tab etc..Positive pole aluminium foil is put in 1
In mol/L sodium hydroxide solution, positive electrode is then separated, and is washed and stripped down with 1 mol/L sodium hydroxide solution
Positive electrode.It is then placed in 80 DEG C of drying box, dry 12 h.And 700 DEG C of 2 h of calcining in batch-type furnace are put it into,
It is cooled to room temperature in furnace, is drawn off being put into mortar and grind, and is filtered with 500 mesh sieve, is obtaining waste and old ternary lithium battery just
Pole material powder.Then it weighs 100g positive electrode powder to be put into autoclave, it is 12 mol/L, n that total ammonium concentration, which is added,
(NH3) : n(NH4+The ammonium chloride and ammonium hydroxide mixed solution 1000mL of)=1.5:1；Then hydroxylamine hydrochloride is added as reduction
Agent, dosage are 3 times of cobalt mole in raw material.Above-mentioned material stirring is uniform, kettle cover is covered, adjusting mixing speed is 500r/
Min, 150 DEG C of extraction temperature, control autoclave pressure is 1.5 MPa, leaches 3 hours, obtains ammonia leaching solution and ammonia leaching residue.Through subtracting
Press filtration obtains the ammonia leaching residue of ammonia leaching solution and enrichment manganese rich in Ni, Co, Li, using fire with 4mol/L ammonia scrubbing ammonia leaching residue
Flame atomic absorption spectrography (AAS) measures the content of nickel, cobalt, lithium, manganese in ammonia leaching solution and leached mud respectively.Based on the analysis results, pressurize ammonia
Dipped journey nickel, cobalt, lithium, manganese leaching rate be respectively 99.0%, 96.1%, 97.9%, 1.1%.According to containing for nickel in ammonia leaching solution and cobalt
Amount, in nickel, cobalt, ammonia molar ratio 0.8:0.1:10 ratio, add nickel salt, cobalt salt and ammonium hydroxide, be sufficiently mixed, formed steady
Fixed uniform ammonium nickel cobalt lithium complex solution.Above-mentioned ammonia leaching residue is leached using 3mol/L hydrochloric acid solution, is passed through hydrogen peroxide as also
Former agent, reducing agent dosage 0.6mol/L, extraction time 2 hours, obtain manganese chloride leachate, the leaching of manganese by 60 DEG C of extraction temperature
Rate reaches 97.8%.After the purified removal of impurities of leachate, the ammonium hydroxide that concentration is 14mol/L is added into solution under stirring conditions,
Ammonium hydroxide according to ammonia and manganese ion molar ratio NH3:Mn2+The ratio of=9:1 is added, and the ammonium manganese complex solution of stable uniform is formed.
By two kinds of ammoniums-metal complex solution of above-mentioned acquisition, according to Ni0.8Co0.1 Mn0.1(OH)2Stoichiometric ratio be
The ratio of Ni:Co:Mn=0.8:0.1:0.1 mixes, and obtains mixed solution after mixing with 400 revs/min of mixing speed；Then
It is added drop-wise in coprecipitation reaction kettle and is stirred with the flow velocity of 50mL/min, mixing speed is 400 revs/min, with the flow velocity of 40L/min
It is passed through 50 DEG C of stream of nitrogen gas ammonia still process, by pH meter detection architecture pH value, (NH in chemical titration detection architecture3·H2O+NH4+)
Concentration, controlling the reaction temperature in reaction kettle is 50 DEG C, starts to be slowly added to concentration when system pH drops to 11.5 ± 0.05
It for the NaOH solution of 10mol/L, and is 11.5 ± 0.05 by adjusting flow control system pH；Reaction process strict control
(NH3·H2O+NH4+) concentration, pH value, temperature.After reaction starts, mechanical stirring and air-flow stirring action make NH3Slowly volatilization,
PH is reduced, and coprecipitation reaction occurs for slow release Ni-Co-Mn ion, is stopped after solution system material size reaches 15 ± 0.5 μm
It only reacts, obtains crystallinity height, the high hydroxide nickel cobalt manganese presoma of even particle size distribution, tap density.Fig. 7 is its SEM figure,
As can be seen that presoma pattern is spherical or spherical from SEM figure；Fig. 8 is its particle size distribution figure, diagram data explanation, material
Particle size distribution is uniformly and in normal distribution.
In conclusion the present invention use pressure ammonia leaching method, can by waste lithium cell tertiary cathode material lithium, cobalt,
The valuable metals such as nickel are with Ni (NH3)6 3+、Co(NH3)6 2+、Li+Form dissolution enters ammonia leaching solution, pressure leaching process and preparation forerunner
The co-precipitation process of body uses consistent solution system, and total ammonia density that two systems are controlled by ammonia distillation process is different, from
And it realizes and leaches, the closed cycle of the cycle operation of co-precipitation and ammonia.Meanwhile the present invention is using two sections of leaching recycling waste and old three
First positive electrode, it is pressure leaching that first segment, which leaches, mainly realizes and recycles while lithium, nickel, cobalt；It is normal pressure acid that second segment, which leaches,
The high efficiente callback of doping metals (manganese or aluminium) is mainly realized in leaching；The Leaching Systems of normal pressure acidleach are selected and pressure leaching is consistent
Acid ion realizes that the segmentation of main lithium metal nickel cobalt and doping metals is leached by the pH value and ammonia density of control solution, from
And regulate and control nickel in synthesis process, cobalt and the proportion for adulterating salt, realize the demand of different series ternary material precursor production.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of method using waste and old ternary lithium battery preparation positive electrode material precursor, which is characterized in that comprising steps of
The anode split out from waste and old ternary lithium battery is put into aqueous slkali, removing obtains waste and old ternary lithium battery anode material
Material；
The waste and old ternary anode material of lithium battery is dried, calcination processing, will treated waste and old ternary lithium battery just
Pole material is ground, and powder is obtained；
The mixed liquor of the powder, ammonium salt and ammonium hydroxide and reducing agent are added to high pressure to answer in kettle, carried out under a predetermined
Leach reaction;
Reaction product is separated, obtains being mixed with lithium, nickel, the ammonium complex solution of cobalt and the filter containing manganese metal or aluminium
Slag；
The filter residue containing manganese metal or aluminium is mixed with reducing agent and acid solution, is obtained by filtration containing manganese salt or aluminium salt
Solution, then ammonium hydroxide is added into the manganese salt or aluminum salt solution and obtains the complex solution of manganese or aluminium ammonium；
By it is described be mixed with lithium, nickel, the ammonium complex solution of cobalt, the complex solution of the manganese or aluminium ammonium and aqueous slkali be added to it is heavy
In the reaction kettle of shallow lake, it is passed through protective gas and carries out ammonia still process operation, obtain positive electrode material precursor.
2. the method according to claim 1 using waste and old ternary lithium battery preparation positive electrode material precursor, feature exist
In the aqueous slkali is that any one of sodium hydroxide, potassium hydroxide, calcium hydroxide are formed by solution.
3. the method according to claim 1 using waste and old ternary lithium battery preparation positive electrode material precursor, feature exist
In the partial size of the powder is 200-500 mesh.
4. the method according to claim 1 using waste and old ternary lithium battery preparation positive electrode material precursor, feature exist
In the ammonium salt includes one of ammonium sulfate, ammonium chloride, ammonium nitrate or a variety of.
5. the method according to claim 1 using waste and old ternary lithium battery preparation positive electrode material precursor, feature exist
In total ammonia density of the mixed liquor of the ammonium salt and ammonium hydroxide is 5-12mol/L.
6. utilizing the method for waste and old ternary lithium battery preparation positive electrode material precursor, feature according to claim 1 or 5
It is, the reducing agent includes one of hydrazine hydrate, azanol, sodium sulfite, hydrogen peroxide or a variety of.
7. the method according to claim 1 using waste and old ternary lithium battery preparation positive electrode material precursor, feature exist
In the Leach reaction condition are as follows: 40-150 DEG C of temperature, pressure 0.6Mpa-1.5 Mpa.
8. according to claim 1 or 7 methods using waste and old ternary lithium battery preparation positive electrode material precursor, feature exist
In the Leach reaction condition are as follows: liquid-solid ratio 3:1-20:1.
9. utilizing the method for waste and old ternary lithium battery preparation positive electrode material precursor according to claim 1, which is characterized in that
The dosage of the reducing agent is 2-5 times of cobalt mole in ternary anode material of lithium battery.
10. according to claim 1 using the method for waste and old ternary lithium battery preparation positive electrode material precursor, feature exists
In in the ammonia still process operating process, temperature is 50-100 DEG C, pH value 11.0-12.5.
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| CN111129488A (en) * | 2019-11-18 | 2020-05-08 | 中南大学 | Preparation method of lithium ion battery nickel-cobalt binary oxide positive electrode material precursor |
| CN111304438A (en) * | 2020-03-30 | 2020-06-19 | 中国恩菲工程技术有限公司 | Multistage leaching system and control method thereof |
| CN111477985A (en) * | 2020-04-15 | 2020-07-31 | 中南大学 | Method for recycling waste lithium ion batteries |
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