CN112593075A - 低冰镍盐化焙烧-水浸同步提取镍、铜、钴及制备镍钴锰酸锂正极材料的方法 - Google Patents
低冰镍盐化焙烧-水浸同步提取镍、铜、钴及制备镍钴锰酸锂正极材料的方法 Download PDFInfo
- Publication number
- CN112593075A CN112593075A CN202011373617.XA CN202011373617A CN112593075A CN 112593075 A CN112593075 A CN 112593075A CN 202011373617 A CN202011373617 A CN 202011373617A CN 112593075 A CN112593075 A CN 112593075A
- Authority
- CN
- China
- Prior art keywords
- nickel
- cobalt
- copper
- low
- roasting
- 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.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 279
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 135
- 238000000034 method Methods 0.000 title claims abstract description 78
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 73
- 239000010949 copper Substances 0.000 title claims abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000010941 cobalt Substances 0.000 title claims abstract description 63
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 59
- 238000002386 leaching Methods 0.000 title claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001868 water Inorganic materials 0.000 title claims abstract description 41
- 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 title claims abstract description 24
- 239000010406 cathode material Substances 0.000 title claims abstract description 17
- 238000009938 salting Methods 0.000 title abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 16
- 235000011152 sodium sulphate Nutrition 0.000 claims description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 15
- 235000010755 mineral Nutrition 0.000 claims description 15
- 239000011707 mineral Substances 0.000 claims description 15
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 4
- 239000007772 electrode material Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 4
- 238000007664 blowing Methods 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229940079101 sodium sulfide Drugs 0.000 description 11
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000019635 sulfation Effects 0.000 description 4
- 238000005670 sulfation reaction Methods 0.000 description 4
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000009853 pyrometallurgy Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 102100024452 DNA-directed RNA polymerase III subunit RPC1 Human genes 0.000 description 1
- 101000689002 Homo sapiens DNA-directed RNA polymerase III subunit RPC1 Proteins 0.000 description 1
- 229910021311 NaFeO2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- CDUFCUKTJFSWPL-UHFFFAOYSA-L manganese(II) sulfate tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O CDUFCUKTJFSWPL-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
- C22B15/0017—Sulfating or sulfiding roasting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0082—Leaching or slurrying with water
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- 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
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- 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
-
- 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
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明公开了一种低冰镍盐化焙烧‑水浸同步提取镍、铜、钴及制备镍钴锰酸锂正极材料的方法,通过低冰镍盐化焙烧‑水浸同步提取镍、铜以及钴,实现绿色短流程化学工艺,同时,通过硫化钠除去浸出液中的铜元素,以含有镍钴元素的浸出液为原料制备镍钴锰酸锂正极材料。本发明是直接以低冰镍的除铜浸出液为原料制备单晶电极正极材料,避免了镍、铜及钴在转炉吹炼过程中的损失,实现了资源最大化利用,而且该材料与纯物质制备的电极材料性能相当。本发明方法流程简单,能有效减少有价金属的损失,综合最大化利用资源,无污染;而且制备的正极材料的电化学性能比纯化学物质的更好。
Description
技术领域
本发明涉及一种低冰镍盐化焙烧-水浸同步提取镍、铜、钴的方法,属于绿色短流程化学工艺技术。加入除铜剂以富含镍的浸出液为镍源,通过沉淀法和简单的热处理制备镍钴锰酸锂正极材料。
背景技术
低冰镍(低镍锍)是传统火法冶炼工艺中造锍熔炼的中间产物,因造锍熔炼获得的低镍锍在成分上不足以满足精炼工序的处理要求,需要将其进一步吹炼成高镍锍,得到的高镍锍进行铜镍分离,然后将得到的二次镍精矿熔铸成阳极板,最后电解得镍产品;另外,高镍锍也可经过两段硫酸浸出,除钴后进行电沉积得到电镍。但无论是哪种处理工艺,都无法回避需要将低冰镍吹炼成高镍锍的问题。虽然火法冶金的历史较长,研究较多,工艺相对成熟,但火法工艺冗长复杂,能耗较大,污染严重,且金属损失较大,尤其在吹炼过程中,钴以及贵金属会伴随铁一起氧化造渣,造成资源的浪费。
低冰镍与原矿相比,具有目标金属富集,含有脉石相少等优点,以低冰镍作为研究对象的起点,不仅可以简化工艺流程,而且也避免了吹炼过程中镍、钴等的损失。
中国专利CN 107475511 A公开了一种由低冰镍钙化焙烧-酸浸高效提取镍、铜、钴的方法,是将低冰镍与氧化钙混合焙烧,得到焙砂采用酸浸提取镍、铜及钴,该方法的优点是镍、铜及钴都有较高的回收率,但也存在明显的缺点,如焙烧温度较高,需要1100℃高温,焙烧后需要利用酸浸,并且酸浸过程中引入了铁离子,需要进一步进行除铁。
锂离子电池因具有能量密度高、循环寿命长、自放电小以及无记忆效应等优点而成为主要的新能源,被广泛应用于通讯、电子设备和电动车等领域。目前,锂离子正极电池已经商业化的有:锰酸锂、钴酸锂、磷酸铁锂和镍钴锰酸锂三元材料。三元正极材料中,当镍含量高于0.5时,可以提供很高的理论容量,但是混排严重,结构稳定性差,使其循环寿命和倍率性能较差。而组分为LiNi1/3Co1/3Mn1/3O2时,在高比容量、宽电压范围、低毒性、安全性好的前提下表现出较好的稳定性,因此LiNi1/3Co1/3Mn1/3O2正极材料成为未来动力电池、大型电池、储能电池的主流材料之一,但按照现有制备工艺制备LiNi1/3Co1/3Mn1/3O2正极材料成本高,制备工艺较复杂,存在较难处理的污染,所制备的LiNi1/3Co1/3Mn1/3O2正极材料品质也有待进一步提高,这成为亟待解决的技术问题。
发明内容
为了解决现有技术问题,本发明的目的在于克服已有技术存在的不足,提供一种低冰镍盐化焙烧-水浸同步提取镍、铜、钴及制备镍钴锰酸锂正极材料的方法,通过低冰镍硫酸盐化焙烧-水浸同步提取镍、铜以及钴,再用除去铜后,以此浸出液为镍源,通过沉淀法和热处理制备镍钴锰酸锂。本发明方法流程简单,能有效减少有价金属的损失,综合最大化利用资源,无污染;而且制备的正极材料的电化学性能比纯化学物质的更好。
为达到上述发明创造目的,本发明采用如下技术方案:
一种通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法,包括步骤如下:
a.采用低冰镍矿物为原料,将低冰镍矿物破碎、研磨后通过筛孔尺寸标准不高于200目的筛子,得到低冰镍矿粉,将低冰镍矿粉与可溶性盐按质量比为1:(0-0.15)的比例均匀混合,得到粉末原料,备用;可溶性盐采用硫酸盐或者氯化盐;将低冰镍与硫酸钠按比例均匀混合,为了能让其充分发生反应,实验前应将矿物破碎、研磨,过筛,进行充分的原料预处理;
b.将粉末原料转移至坩埚内,坩埚不加盖,将坩埚放入管式炉中进行焙烧处理,设置升温速率,并在达到不低于500℃的目标焙烧温度后进行保温20-180min;并在焙烧过程中采用氢氧化钠溶液吸收尾气;
c.焙烧完成后,将坩埚内连同焙烧产物进行随炉冷却,当冷至室温时,从管式炉中取出焙烧产物,将其磨成粉末状的产物粉体;
d.将上述产物粉体置于锥形瓶中,并加入100-150mL去离子水,将锥形瓶放在恒温磁力搅拌器上进行加热搅拌1-2h,利用水对产物粉体进行水浸溶解处理;
e.在水浸溶解处理过程完成后,趁热对产物粉体水浸溶解处理液进行过滤,并对锥形瓶和滤渣进行3-5次洗涤;
f.将所得到的滤液转移至容量瓶中保存,得到的滤液即为含有镍、铜以及钴的浸出液,实现从低冰镍矿物原料中同步提取镍、铜以及钴。
优选地,在所述步骤a中,所述可溶性盐采用硫酸钠、硫酸铵、氯化钾、氯化钙、氯化钠、氯化铵中的至少一种。
优选地,在所述步骤a中,按照质量比为1:(0.02-0.15)的比例将低冰镍矿粉与可溶性盐进行混合。
优选地,在所述步骤b中,所述被烧温度为500-700℃,升温速度不低于2℃/min。
优选地,在所述步骤d中,加热温度设置不低于90℃。
一种制备镍钴锰酸锂正极材料的方法,利用通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法制备的浸出液,通过沉淀法和热处理制备镍钴锰酸锂正极材料,包括步骤如下:
(1)对浸出液进行ICP成分测试,确定镍、铜以及钴的含量,按照不低于浸出液中铜的摩尔量称量硫化钠,将硫化钠配置成硫化钠水溶液并逐滴加入浸出液中,以除去浸出液中的铜,得到不含铜的浸出液,作为镍源,备用;优选加入适量的1mol/L的硫化钠溶液除去铜;
(2)按照在不含铜的浸出液中的镍的摩尔量,向不含铜的浸出液中加入含钴化合物和含锰化合物,得到含有镍、钴、锰离子的混合液,使混合液中镍、钴、锰离子的物质的量相同;或者使加入含钴化合物和含锰化合物中的钴和锰的物质的量皆与镍物质的量相同;
(3)将混合液置于恒温水浴中加热,连续搅拌,并将草酸溶液缓慢的滴加入混合液中,反应至少4h后,再置于室温下静置陈化至少12h,然后将产物混合液经过离心和水洗的处理步骤至少6次,收集固体物质,得到粉色前驱体(Ni1/3Co1/3Mn1/3)C2O4·H2O;
(4)将前驱体置于不低于60℃的鼓风干燥箱中,干燥至少12h,得到干燥物质;
(5)将干燥物质与锂盐在研钵中研磨至少30min,达到均匀混合,再将混合物置于管式炉中煅烧,得到镍钴锰酸锂正极材料。优选
优选地,在所述步骤(3)中,所述草酸的浓度为1mol/L,草酸与过渡金属的摩尔比为 1.05:1,且不用控制整个过程的pH值。
优选地,在所述步骤(3)中,恒温水浴温度不低于40℃。
优选地,在所述步骤(5)中,所述锂盐采用硝酸锂、氢氧化锂、乙酸盐中的至少一种。进一步优选锂盐采用氢氧化锂,Li:TM=1.05:1。
优选地,在所述步骤(5)中,所述煅烧温度为800-900℃,保温时间不少于15h。
本发明与现有技术相比较,具有如下显而易见的突出实质性特点和显著优点:
1.本发明方法通过低冰镍硫酸盐化焙烧-水浸同步提取镍、铜以及钴,所得滤液即含镍、铜及钴的浸出液,可用作提取镍、铜及钴;使用硫化钠除去浸出液中的铜,以此浸出液为镍源,通过沉淀法和热处理制备镍钴锰酸锂正极材料;本发明的原理是硫酸钠可以与低冰镍焙烧过程中生成的硫酸镍、硫酸铜等形成低熔点硫酸复盐,强化焙烧效果,极大提高有价金属镍、铜及钴的回收率;
2.本发明方法简化工艺流程,节约时间成本和劳动成本,避免镍、铜及钴在转炉吹炼过程中的损失,实现资源最大化利用;同时以除铜后的浸出液为镍源制备镍钴锰酸锂电极材料,其电化学性能与纯物质相当;
3.本发明方法简单易行,成本低,适合推广使用。
附图说明
图1为本发明通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法的流程图。
图2是本发明实施例一当硫酸钠与低冰镍的质量比为0.1:1,保温时间120min,镍、铜及钴浸出率随温度变化规律曲线。
图3是本发明实施例二当温度为600℃,保温时间120min,镍、铜及钴浸出率随硫酸钠添加量变化规律曲线。
图4是本发明实施例三当硫酸钠与低冰镍的质量比为0.1:1,温度600℃,镍、铜及钴浸出率随保温时间变化规律曲线。
图5是本发明浸出液除铜并制备镍钴锰酸锂正极材料的流程图。
图6是本发明实施例四方法制备的LNCM-I和对比例方法制备的LNCM-II的XRD图谱。
图7是本发明实施例五制备的锂离子电池正极材料LNCM-I和LNCM-II在2.8~4.3V, 1C(C=160mAh/g)下的循环性能图。
具体实施方式
以下结合具体的实施例子对上述方案做进一步说明,本发明的优选实施例详述如下:
实施例一:
在本实施例中,参见图1,一种通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法,其特征在于,包括步骤如下:
(1)称取1.0g低冰镍粉末与0.1g硫酸钠粉末,均匀混合;
(2)将混合后的样品均匀平铺在坩埚底部,并将坩埚置于管式炉中,设置2℃/min升温速率升温,并在达到目标温度后保温120min,焙烧过程中收集尾气;目标温度分别为500℃、550℃、600℃、650℃、700℃;
(3)焙烧完成后随炉冷却,冷至室温时从炉中取出样品,用玛瑙研钵将其磨成粉末;
(4)将上述粉末置于锥形瓶中,加入150mL去离子水,并将锥形瓶放在恒温磁力搅拌器上加热搅拌1h,加热温度设置为90℃;
(5)溶解过程完成后,趁热过滤,对锥形瓶和滤渣进行3-5次洗涤,所得滤液即是含镍、铜及钴的溶液,将滤液转移至容量瓶中,通过ICP测量Ni、Cu及Co的浓度,并将滤渣放入烘箱烘干。
本实施例通过浸出率变化曲线观察不同焙烧温度下镍、铜及钴的浸出率,如图2所示,可知600℃是最佳焙烧温度。
实施例二:
本实施例与实施例一基本相同,特别之处在于:
在本实施例中,参见图1,一种通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法,其特征在于,包括步骤如下:
(1)称取1.0g低冰镍粉末,按低冰镍与硫酸钠设定的质量比例混合加入硫酸钠粉末,磨匀;低冰镍与硫酸钠质量比分别为1:0、1:0.02、1:0.05、1:0.10、1:0.15;
(2)将混合后的样品均匀平铺在坩埚底部,并将坩埚置于管式炉中,设置2℃/min升温速率升温,并在达到600℃后保温120min,焙烧过程中收集尾气;
(3)焙烧完成后随炉冷却,冷至室温时从炉中取出样品,用玛瑙研钵将其磨成粉末;
(4)将上述粉末置于锥形瓶中,加入150mL去离子水,并将锥形瓶放在恒温磁力搅拌器上加热搅拌1h,加热温度设置为90℃;
(5)溶解过程完成后,趁热过滤,对锥形瓶和滤渣进行3-5次洗涤,所得滤液即是含镍、铜及钴的溶液,将滤液转移至容量瓶中,通过ICP测量Ni、Cu及Co的浓度,并将滤渣放入烘箱烘干。
本实施例通过浸出率变化曲线观察不同硫酸钠添加量下镍、铜及钴的浸出率,如图3所示,可知10%是最佳添加量。
实施例三:
本实施例与前述实施例基本相同,特别之处在于:
在本实施例中,参见图1,一种通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法,其特征在于,包括步骤如下:
(1)称取1.0g低冰镍粉末与0.1g硫酸钠粉末,均匀混合;
(2)将混合后的样品均匀平铺在坩埚底部,并将坩埚置于管式炉中,设置2℃/min升温速率升温,并在达到600℃后分别保温,焙烧过程中收集尾气;保温时间分别为20min、40min、60min、120min、180min;
(3)焙烧完成后随炉冷却,冷至室温时从炉中取出样品,用玛瑙研钵将其磨成粉末;
(4)将上述粉末置于锥形瓶中,加入150mL去离子水,并将锥形瓶放在恒温磁力搅拌器上加热搅拌1h,加热温度设置为90℃;
(5)溶解过程完成后,趁热过滤,对锥形瓶和滤渣进行3-5次洗涤,所得滤液即是含镍、铜及钴的溶液,将滤液转移至容量瓶中,通过ICP测量Ni、Cu及Co的浓度,并将滤渣放入烘箱烘干。
本实施例通过浸出率变化曲线观察不同保温时间下镍、铜及钴的浸出率,如图4所示,可知最佳保温时间是120min。通过对低冰镍进行硫酸盐化焙烧-水浸可以实现对有价金属镍、铜及钴的同步提取,在最佳条件下:添加10%硫酸钠600℃焙烧保温120min,所得滤液即含镍、铜及钴的浸出液,可用作提取镍、铜及钴。使用硫化钠除去浸出液中的铜,以此浸出液为镍源,通过沉淀法和热处理制备镍钴锰酸锂正极材料,镍、铜及钴的浸出率都可达90%以上。
实施例四:
在本实施例中,参见图5,一种制备镍钴锰酸锂正极材料的方法,利用通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法制备的浸出液,通过沉淀法和热处理制备镍钴锰酸锂正极材料,包括步骤如下:
(1)对实施例一利用1g低冰镍制备的浸出液定容为500ml并进行ICP成分测试,如表 1所述,确定镍、铜以及钴的含量,其中铜含量为2.76mmol;称取相同摩尔量的九水硫化钠 0.663g,配置成1mol/L硫化钠溶液逐滴加入以除去铜元素,得到不含铜的浸出液,作为镍源,备用;
(2)以除铜的浸出液为镍源,镍为3.16mmol,加入相同摩尔量的七水硫酸钴0.89g和四水硫酸锰0.79g,不断搅拌,记为溶液A;
(3)称取1.255g的草酸,配置1mol/L的溶液;溶液A置于40℃的水浴中加热搅拌,缓慢的滴加草酸溶液,反应4h后,再置于室温下静置老化12h,经过离心、水洗6次,得到粉色前驱体(Ni1/3Co1/3Mn1/3)C2O4·H2O;
(4)将上述粉色沉淀置于60℃鼓风干燥箱中,干燥12h,得到干燥物质;
(5)采用Li:TM=1.05:1的锂盐,将干燥后的沉淀与锂盐在研钵中研磨30min,达到均匀混合,再置于管式炉中煅烧;煅烧温度850℃,保温15h,升温速率3℃/min,得到镍钴锰酸锂正极材料LNCM-I。
表1. 1g低冰镍的原始浸出液和除铜浸出液的ICP成分测试结果(mg/L)
本实施例使用硫化钠除去浸出液中的铜,以此浸出液为镍源,通过沉淀法和热处理制备镍钴锰酸锂正极材料。
对比例:
在本实施例中,参见图5,一种制备镍钴锰酸锂正极材料的方法,包括步骤如下:
(1)以硫酸镍、硫酸锰和硫酸钴为原料;
(2)将硫酸镍、硫酸锰和硫酸钴加入水中混合均匀,不断搅拌,记为溶液B;
(3)称取1.255g的草酸,配置1mol/L的溶液;溶液B置于40℃的水浴中加热搅拌,缓慢的滴加草酸溶液,反应4h后,再置于室温下静置老化12h,经过离心、水洗6次,得到粉色前驱体(Ni1/3Co1/3Mn1/3)C2O4·H2O;
(4)将上述粉色沉淀置于60℃鼓风干燥箱中,干燥12h,得到干燥物质;
(5)采用Li:TM=1.05:1的锂盐,将干燥后的沉淀与锂盐在研钵中研磨30min,达到均匀混合,再置于管式炉中煅烧;煅烧温度850℃,保温15h,升温速率3℃/min,得到镍钴锰酸锂正极材料LNCM-II。
实验测试分析:
将实施例四制备的镍钴锰酸锂正极材料LNCM-I和对比例制备的镍钴锰酸锂正极材料 LNCM-II作为电极材料,制备纽扣电池,具体步骤如下:
(1)将电极材料、乙炔黑和粘结剂按照8:1:1的质量比混合,在室温下搅拌6小时,形成均匀的浆料,粘结剂为PVDF和NMP配置成20mg/L规格的溶液;
(2)用湿膜制备器将该浆料涂敷在干净的铝箔上面,置于80℃的真空干燥箱中干燥12h;
(3)干燥后的极片取出切成直径为12mm的极片,并称量每个极片的质量,分别装进密封袋,根据纯铝箔的质量和浆料的质量比计算每个极片的活性物质的质量;
(4)在充满氩气的手套箱中进行锂离子纽扣电池的组装,按照正极壳-正极片-电解液-隔膜 -电解液-锂负极-镍网-负极壳的顺序组装,经过封口机封口后从手套箱取出,静置12h待用。
通过图6的XRD图可知,LNCM-I和LNCM-II均为α-NaFeO2层状结构,且 I(003)/I(104)>1.2,阳离子混排很低;(006)与(102和(108)与(110)两对峰有明显的劈裂,表明有很好的层状结构。
对上述锂离子电池正极材料进行恒流充放电测试,从图7的结果来看,在2.8~4.3V, 1C(C=160mAh/g)的条件下,循环100圈,LNCM-I和LNCM-II的电化学性能相近,放电容量均从143mAh/g到110.6mAh/g,容量保持率77.3%。
本上述实施例通过低冰镍硫酸盐化焙烧-水浸同步提取镍、铜以及钴,实现绿色短流程化学工艺,同时,通过硫化钠除去浸出液中的铜元素,以含有镍钴元素的浸出液为原料制备镍钴锰酸锂正极材料。上述实施例通过低冰镍硫酸盐化焙烧-水浸同步提取镍、铜以及钴的方法,具体步骤如下:将低冰镍与硫酸钠按一定质量比为1:(0-0.15)的比例均匀混合,为了能让其充分发生反应,实验前应将矿物破碎、研磨后通过200目的筛子;将混合好的粉末样品转移至刚玉坩埚内,坩埚不加盖,并将坩埚放入管式炉中,设置一定的升温速率,并在达到目标温度后保温20-120min,焙烧过程中采用氢氧化钠溶液吸收尾气;焙烧完成后随炉冷却,冷至室温时从炉中取出样品,将其磨成粉末状;将上述粉末置于锥形瓶中,加入100-150mL 去离子水,并将锥形瓶放在恒温磁力搅拌器上加热搅拌1-2h,溶解过程完成后,趁热过滤,对锥形瓶和滤渣进行3-5次洗涤。以低冰镍浸出液为原料制备镍钴锰酸锂正极材料的具体步骤如下:所得到的滤液即是富含镍、铜以及钴的水溶液,通过ICP成分测试,确定其中铜含量,再加入适量的硫化钠出去铜元素。最后以含有镍钴的水溶液为镍源,加入相同摩尔量的钴和锰,以为沉淀剂制备单晶镍钴锰酸锂(LiNi1/3Co1/3Mn1/3)。上述实施例是直接以低冰镍的除铜浸出液为原料制备单晶电极正极材料,避免了镍、铜及钴在转炉吹炼过程中的损失,实现了资源最大化利用,而且该材料与纯物质制备的电极材料性能相当。
上面对本发明实施例结合附图进行了说明,但本发明不限于上述实施例,还可以根据本发明的发明创造的目的做出多种变化,凡依据本发明技术方案的精神实质和原理下做的改变、修饰、替代、组合或简化,均应为等效的置换方式,只要符合本发明的发明目的,只要不背离本发明的技术原理和发明构思,都属于本发明的保护范围。
Claims (10)
1.一种通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法,其特征在于,包括步骤如下:
a.采用低冰镍矿物为原料,将低冰镍矿物破碎、研磨后通过筛孔尺寸标准不高于200目的筛子,得到低冰镍矿粉,将低冰镍矿粉与可溶性盐按质量比为1:(0-0.15)的比例均匀混合,得到粉末原料,备用;可溶性盐采用硫酸盐或者氯化盐;
b.将粉末原料转移至坩埚内,坩埚不加盖,将坩埚放入管式炉中进行焙烧处理,设置升温速率,并在达到不低于500℃的目标焙烧温度后进行保温20-180min;并在焙烧过程中采用氢氧化钠溶液吸收尾气;
c.焙烧完成后,将坩埚内连同焙烧产物进行随炉冷却,当冷至室温时,从管式炉中取出焙烧产物,将其磨成粉末状的产物粉体;
d.将上述产物粉体置于锥形瓶中,并加入100-150mL去离子水,将锥形瓶放在恒温磁力搅拌器上进行加热搅拌1-2h,利用水对产物粉体进行水浸溶解处理;
e.在水浸溶解处理过程完成后,趁热对产物粉体水浸溶解处理液进行过滤,并对锥形瓶和滤渣进行3-5次洗涤;
f.将所得到的滤液转移至容量瓶中保存,得到的滤液即为含有镍、铜以及钴的浸出液,实现从低冰镍矿物原料中同步提取镍、铜以及钴。
2.根据权利要求1所述通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法,其特征在于:在所述步骤a中,所述可溶性盐采用硫酸钠、硫酸铵、氯化钾、氯化钙、氯化钠、氯化铵中的至少一种。
3.根据权利要求1所述通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法,其特征在于:在所述步骤a中,按照质量比为1:(0.02-0.15)的比例将低冰镍矿粉与可溶性盐进行混合。
4.根据权利要求1所述通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法,其特征在于:在所述步骤b中,所述被烧温度为500-700℃,升温速度不低于2℃/min。
5.根据权利要求1所述通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法,其特征在于:在所述步骤d中,加热温度设置不低于90℃。
6.一种制备镍钴锰酸锂正极材料的方法,其特征在于,利用通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴的方法制备的浸出液,通过沉淀法和热处理制备镍钴锰酸锂正极材料,包括步骤如下:
(1)对浸出液进行ICP成分测试,确定镍、铜以及钴的含量,按照不低于浸出液中铜的摩尔量称量硫化钠,将硫化钠配置成硫化钠水溶液并逐滴加入浸出液中,以除去浸出液中的铜,得到不含铜的浸出液,作为镍源,备用;
(2)按照在不含铜的浸出液中的镍的摩尔量,向不含铜的浸出液中加入含钴化合物和含锰化合物,得到含有镍、钴、锰离子的混合液,使混合液中镍、钴、锰离子的物质的量相同;或者使加入含钴化合物和含锰化合物中的钴和锰的物质的量皆与镍物质的量相同;
(3)将混合液置于恒温水浴中加热,连续搅拌,并将草酸溶液缓慢的滴加入混合液中,反应至少4h后,再置于室温下静置陈化至少12h,然后将产物混合液经过离心和水洗的处理步骤至少6次,收集固体物质,得到粉色前驱体(Ni1/3Co1/3Mn1/3)C2O4·H2O;
(4)将前驱体置于不低于60℃的鼓风干燥箱中,干燥至少12h,得到干燥物质;
(5)将干燥物质与锂盐在研钵中研磨至少30min,达到均匀混合,再将混合物置于管式炉中煅烧,得到镍钴锰酸锂正极材料。
7.根据权利要求6所述制备镍钴锰酸锂正极材料的方法,其特征在于:在所述步骤(3)中,所述草酸的浓度为1mol/L,草酸与过渡金属的摩尔比为1.05:1,且不用控制整个过程的pH值。
8.根据权利要求6所述制备镍钴锰酸锂正极材料的方法,其特征在于:在所述步骤(3)中,恒温水浴温度不低于40℃。
9.根据权利要求6所述制备镍钴锰酸锂正极材料的方法,其特征在于:在所述步骤(5)中,所述锂盐采用硝酸锂、氢氧化锂、乙酸盐中的至少一种。
10.根据权利要求6所述制备镍钴锰酸锂正极材料的方法,其特征在于:在所述步骤(5)中,所述煅烧温度为800-900℃,保温时间不少于15h。
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