CN116216797A - Method for preparing lithium ion battery anode material by recycling waste lithium battery dismantling black powder and anode powder - Google Patents
Method for preparing lithium ion battery anode material by recycling waste lithium battery dismantling black powder and anode powder Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- 239000000843 powder Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001914 filtration Methods 0.000 claims abstract description 37
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 31
- 239000010941 cobalt Substances 0.000 claims abstract description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 21
- 239000011575 calcium Substances 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- 230000001681 protective effect Effects 0.000 claims abstract description 21
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical class [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 66
- 239000000706 filtrate Substances 0.000 claims description 50
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 32
- 238000000227 grinding Methods 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 19
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 18
- 239000007774 positive electrode material Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 230000001276 controlling effect Effects 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical group [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 8
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 7
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- -1 fluorine ions Chemical class 0.000 claims description 6
- 239000012982 microporous membrane Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000007363 regulatory process Effects 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 abstract description 11
- 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 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 4
- 229940044175 cobalt sulfate Drugs 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229940053662 nickel sulfate Drugs 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000012066 reaction slurry Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 3
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- FIERVQVZJPYIIV-UHFFFAOYSA-N [Mn].[Co].[Ni].[Fe].[Cu] Chemical compound [Mn].[Co].[Ni].[Fe].[Cu] FIERVQVZJPYIIV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing lithium ion battery anode material by reclaiming waste lithium power dismantling black powder and anode powder, which belongs to the field of comprehensive reclaiming of lithium ion batteries, wherein raw materials to be reclaimed are placed into a container, acid leaching is carried out on the raw materials, filtering is carried out on the raw materials after reaction, iron and aluminum removal and calcium and magnesium removal are carried out on filter residues, the processed raw materials are sequentially subjected to ultrafiltration, defluorination and ratio adjustment, after the raw materials are subjected to the processing, the raw materials are put into mixed alkali liquid of sodium hydroxide and ammonium hydroxide, protective gas is introduced, meanwhile, mixed sulfuric acid solution of nickel, cobalt and manganese, mixed alkali liquid of sodium hydroxide and ammonium hydroxide are added, EDTA is added, the pH value is controlled to carry out a primary sedimentation process, after the primary sedimentation reaction is finished, a primary sedimentation reaction solution is sent into a reaction container, protective gas is introduced and stirred, saturated ammonium bicarbonate solution is then added, filter residues are obtained after the reaction is finished, and finally the filter residues are washed, dried, calcined and finely ground and washed.
Description
Technical Field
The invention relates to the field of comprehensive recovery of lithium ion batteries, in particular to a method for preparing a lithium ion battery positive electrode material by recovering waste lithium electricity dismantling black powder and positive electrode powder.
Background
The waste lithium battery dismantling black powder is a product in the lithium ion battery dismantling process, and is black solid powder which is mainly a mixture of a positive electrode (such as nickel cobalt lithium manganate), a negative electrode (such as graphite) and a small amount of aluminum powder and copper powder of a lithium battery. The waste lithium battery positive electrode powder is solid powder formed by crushing waste positive electrode materials and unqualified products of a lithium battery positive electrode material factory, waste materials, leftover materials, pole pieces and the like generated by a battery factory, and is mainly a mixture of nickel cobalt lithium manganate and a small amount of aluminum powder. The lithium ion battery anode material is nickel cobalt lithium manganate, which is formed by calcining nickel cobalt manganese mixed hydroxide (commonly called ternary precursor) and lithium salt, and the waste lithium battery dismantling black powder and the lithium battery waste anode powder contain a large amount of heavy metals, wherein the heavy metals have adverse effects on the environment; meanwhile, the waste lithium battery dismantling black powder and the lithium battery waste positive electrode powder contain metals such as nickel, cobalt manganese, lithium and the like, so that the waste lithium battery dismantling black powder and the lithium battery waste positive electrode powder have great recovery values; cobalt, nickel, manganese and lithium in the waste lithium battery dismantling black powder and the lithium battery waste positive electrode powder are important strategic metals, a large number of inlets are needed, and recovery treatment is an important source supplement, so that the waste lithium battery dismantling black powder and the lithium battery waste positive electrode powder are needed to be recovered.
The ternary precursor is coprecipitation generated under certain conditions by controlling sulfate of nickel, cobalt and manganese and alkali, and is a mixed hydroxide; the lithium salt is typically lithium carbonate or lithium hydroxide, and is mainly derived from ore extraction and recovery of crude lithium-containing products and waste materials. At present, the positive electrode material of the lithium ion battery is prepared by mixing and calcining a ternary precursor and lithium salt according to a certain proportion after the two processes.
In the patent 2022110511099, the recovered ternary positive electrode of the waste lithium ion battery is used as a raw material, the raw material is subjected to chemical oxidation treatment and chemical vulcanization treatment, and a proper amount of functional additive is added to the vulcanized ternary composite oxide to prepare the positive electrode of the alkaline secondary battery, and the alkaline secondary battery is assembled. The patent has great limitation on raw materials, is not applicable to raw materials containing carbon powder, copper, aluminum and the like, and the prepared positive electrode of the alkaline secondary battery has great limitation on application and is not applicable to most lithium ion batteries. The application range of the lithium battery cathode powder is high to raw materials, and the application range of the lithium battery cathode powder comprises waste lithium battery dismantling black powder and lithium battery waste cathode powder.
In the patent 2021113864929, namely a method for recovering cobalt, nickel and manganese from waste lithium batteries, the waste lithium batteries are discharged and disassembled to obtain a positive electrode material, then the positive electrode material is mixed with ferric sulfate according to a certain proportion for roasting, and then the roasted product is leached by deionized water, and a nickel-cobalt-manganese-lithium mixed solution is obtained after filtering. The patent adds a large amount of ferric sulfate salt, so that a large amount of slag containing iron can be generated after leaching, and the treatment difficulty is high. Finally, a mixed solution is prepared, which has high impurity content and needs further treatment for several metals. The slag generated by adding materials is less, and the prepared product is a ternary positive electrode material and can be directly used for a ternary lithium battery.
In the patent 2012100048069, namely a method for recovering valuable metals from waste lithium ion batteries, the valuable metals are nickel, cobalt, manganese, copper and iron. The method takes waste lithium ion batteries as raw materials, and valuable metals such as nickel cobalt manganese copper iron and the like are recovered through steps of drying, sieving, magnetic separation, leaching, impurity removal, crystallization and the like. The end product of this patent is a mixture of one or more sulphates, and the recovery of lithium from the raw material is insufficient. The nickel cobalt manganese lithium of the raw materials is recycled and circularly treated, and the prepared product is a ternary positive electrode material and can be directly used for a ternary lithium battery.
In the patent application 2021104607475, namely a method for recycling waste lithium ion batteries, the waste lithium ion batteries are discharged, disassembled and separated to obtain anode-cathode mixed powder. Roasting the anode and cathode mixed powder to obtain a roasting product, adding water into the roasting product to prepare slurry, adding sulfuric acid to perform leaching reaction, and separating to obtain leaching liquid and leaching slag; removing impurities from the leaching solution to obtain an impurity-removed solution; adding sulfuric acid and ammonium sulfate into the impurity-removing solution to react, evaporating and crystallizing, and separating to obtain nickel cobalt manganese ammonium sulfate mixed salt and mixed solution; the nickel-cobalt-manganese ammonium sulfate mixed salt is subjected to thermal decomposition to obtain nickel-cobalt-manganese sulfate mixed salt; and (3) refining the mixed solution to remove impurities, adding ammonium bicarbonate and ammonia water to perform precipitation reaction, and separating to obtain lithium carbonate and lithium precipitation mother liquor. The patent only recovers nickel cobalt manganese and lithium separately from the feedstock into a crude product. The nickel-cobalt-manganese-lithium composite material is comprehensively recycled, impurity elements are not added in the process of adding materials, and the prepared product is a ternary positive electrode material and can be directly used for a ternary lithium battery.
From the above, in the conventional method for obtaining the positive electrode material of the lithium ion battery, the procedures and processes are relatively long, and the process loss and pollution risk are high. Particularly, the scrappage of the lithium ion battery is larger and larger at present, and basically, the positive electrode material required by the lithium ion battery can be obtained through the complex process. The patent is to disassemble the waste lithium battery into black powder and directly restore the waste lithium battery positive electrode powder to produce the lithium ion battery positive electrode material.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a method for preparing a lithium ion battery anode material by recycling waste lithium battery dismantling black powder and anode powder, which comprises the following steps:
s1: firstly filling a reaction container with a prepared acid solution, putting raw materials to be recovered into the reaction container, then raising the temperature of the reaction container to T1, then carrying out reaction for T1, putting a reducing agent into the reaction container for reaction after the reaction is finished for T2, and adjusting the ph value of the solution to be a after the reaction is finished.
S2: filtering the raw materials after the reaction, and then carrying out process treatment of removing iron, aluminum, calcium and magnesium on filter residues.
S3: and sequentially carrying out ultrafiltration, defluorination and ratio-regulating process treatment on the treated raw materials.
S4: and (3) putting the treated raw materials into mixed alkali liquor of sodium hydroxide and ammonium hydroxide, introducing protective gas, stirring, adding mixed solution of nickel, cobalt and manganese and sulfuric acid, mixed alkali liquor of sodium hydroxide and ammonium hydroxide and EDTA, controlling the pH value to 11-12, and controlling the temperature at 25-45 ℃ in the reaction process.
S5: after the reaction is finished, the reaction solution is sent into a reaction container, protective gas is introduced and the reaction solution is stirred, then the reaction container is heated to T2, the stirring time is T3, then saturated ammonium bicarbonate solution is added and protective gas is continuously introduced, and the stirring is carried out in the process, wherein the stirring time is T4.
S6: and (3) obtaining filter residues after the reaction is finished, and finally washing, drying, calcining and finely grinding the filter residues.
Further, the acid solution in the S1 is a dilute sulfuric acid solution with the concentration of 2-3 mol/L, and the mass ratio of the dilute sulfuric acid solution to the raw materials is 0.15-0.35: 1, wherein T1 is 75-95 ℃, T1 is 120-140 minutes, T2 is 60-120 minutes, a is 1.0-1.5, and the reducing agent is ferrous sulfide.
Further, the iron and aluminum removing process in the step S2 comprises the following steps:
s31: adding the leached filtrate into a reactor, heating the reaction vessel to 75 ℃, and adding hydrogen peroxide with the addition amount of 10-20 kg per cubic volume.
S32: adding hydrogen peroxide, reacting for 30-60 min, adding nickel carbonate to regulate pH value to 2.0-2.5, and adding Mn powder.
S33: the mass ratio of the addition amount of the manganese powder to the copper content in the solution is 1:1.1 to 1.8, continuing to react for 60 to 90 minutes after the manganese powder is added, and filtering after the reaction is finished to obtain filtrate and filter residues.
Further, the calcium and magnesium removal process in the step S2 comprises the following steps:
s41: adding the filtrate after removing iron and aluminum into a calcium and magnesium removal reactor, and heating to 90 ℃.
S42: the content of calcium and magnesium in the solution can be analyzed and detected by an atomic absorber, lithium fluoride with the theoretical dosage of 10-15 times is added according to the amount of calcium and magnesium, the lithium fluoride is in a slurried colloid state, the reaction is carried out for 240-360 minutes, and calcium and magnesium slag and filtrate are obtained after the reaction is finished.
Further, the ultrafiltration process in S3 includes the following steps:
s51: and filtering the filtrate subjected to calcium, magnesium and iron and aluminum removal treatment by using a microporous membrane filter twice, wherein the filtering pore diameter of the microporous membrane filter for the first time is 0.5 mu m.
S52: the filtrate after the treatment of removing calcium, magnesium and iron and aluminum contains superfine and suspended particles, wherein the superfine and suspended particles comprise silicate, calcium fluoride and magnesium fluoride, and the filter pore diameter of the second microporous membrane filter is selected to be 0.1 mu m, so that the superfine and suspended particles in the solution are filtered cleanly.
Further, the defluorination process in S3 is as follows: treating the ultrafiltered solution with a fluorine-removing special resin, and controlling the concentration range of fluorine ions in the solution to be as follows: 0.3-1 mg/L.
Further, the scaling process in S3 includes the following steps:
s71: the precipitation front adjusting ratio is to adjust the content of nickel, cobalt and manganese in the solution by using sulfate of nickel, cobalt and manganese according to each specification and model of the ternary positive electrode material, and the total molar concentration of nickel, cobalt and manganese is 1.5-2.4 mol/L.
S72: adding complexing agent EDTA with the addition amount of 0.1-0.2 g/L. The calcination front adjusting ratio is to adjust the ratio of nickel, cobalt and manganese to lithium, and the ratio of lithium is adjusted to be 1.05-1.2 of theoretical quantity according to the content of nickel, cobalt and manganese.
Further, the concentration of sodium hydroxide in S4 is: 25% -27%, the concentration of ammonia water is: 5-7 mol/L, and the volume ratio of sodium hydroxide to ammonia water is (4-6): 1, the introducing rate of the protective gas is 3-5 m 3 And/h, the addition amount of EDTA is 100-200 g/m 3 . The total flow rate of each liquid is 1/10-1/20 of the volume of the reactor.
Further, in the step S5, the T2 is 75-90 ℃, and the input rate of the introduced shielding gas is 3-5 m 3 And/h, wherein t3 is 30-60 minutes, the addition amount of the saturated ammonium bicarbonate solution is 1.1-1.4 times of the theoretical value of lithium ion precipitation, and the addition flow rate is as follows:the idle volume/(2-3) of the reactor is kept unchanged after the addition of the ammonium bicarbonate is completed, and the flow rate of the protective gas is kept unchanged, wherein t4 is 60-90 minutes. Filtering after the reaction is finished to obtain filtrate and filter residues, wherein the filter residues are a mixture of nickel cobalt manganese coprecipitation hydroxide and lithium carbonate.
Further, the washing and drying in the step S6 needs to control the water content in the reactant to be 1-2%.
In the step S6, the dried mixture is reacted for 120-240 minutes at 600-700 ℃ in a calcining furnace after being mixed, and then reacted for 120-240 minutes at 800-1000 ℃.
The calcined material in the step S6 is subjected to wet fine grinding, and the mass liquid-solid ratio of the fine grinding is (3-5): 1, fine grinding with granularity of 100% and 400 meshes, filtering the slurry after fine grinding, and then mixing the slurry with the slurry according to the mass liquid-solid ratio of (3-5): 1, washing once, filtering and drying to obtain the ternary anode material.
Compared with the prior art, the invention has the beneficial effects that: (1) Ferrous sulfide is used as a reducing agent, the ferrous sulfide is fully utilized to react with sulfuric acid to generate a reducing substance, and meanwhile, the reducing effect is achieved, and the effect of controlling acidity can be achieved; (2) The method adopts pulpified colloidal lithium fluoride as a calcium-magnesium remover, so that on one hand, calcium ions and magnesium ions can be removed, and on the other hand, free fluoride ions in the solution can be reduced; (3) The impurities such as copper, iron, cadmium, aluminum and the like can be removed at one time by adopting the impurity remover of nickel carbonate and manganese powder; (4) The mixed precipitation of nickel, cobalt, manganese and lithium is realized by adopting a two-stage precipitation reaction, the process flow is shortened, and the working procedures are reduced; (4) The precipitation process is controlled by adopting an oxygen-isolation atmosphere, and under the condition of adding a complexing agent, the complexing and dispersing effects of ammonia ions are fully utilized to achieve a synergistic effect, so that the oxidation of cobalt and manganese in the precipitation process is effectively inhibited, and the co-precipitation is affected.
Drawings
Fig. 1 is a schematic diagram of the overall structure of the present invention.
FIG. 2 is a table showing the analysis results of the ternary positive electrode material according to example 1 of the present invention.
FIG. 3 is a table showing the analysis results of the ternary positive electrode material according to example 2 of the present invention.
FIG. 4 is a table showing the analysis results of ternary positive electrode materials in example 3 of the present invention.
FIG. 5 is a table showing the analysis results of the ternary positive electrode material according to example 4 of the present invention.
Description of the embodiments
The technical scheme of the invention is further described in the following by combining with the specific embodiments.
Example 1
The method is used for preparing the NCM523 type lithium ion battery anode material by recovering the lithium battery dismantling black powder.
350kg of concentrated sulfuric acid is added into the reactor to prepare 2.3mol/L dilute sulfuric acid solution. Then 1000kg of lithium power dismantling black powder is put into the reactor, the temperature is raised to 85 ℃, and the reaction is carried out for 180 minutes. After the reaction was completed, 40kg of ferrous sulfide was added thereto, and the reaction was continued for 90 minutes at a final pH of 1.3. And filtering after the reaction is finished to obtain filtrate and filter residue.
2000L of the filtrate is taken and added into a reactor, 40kg of hydrogen peroxide is added after the temperature is raised to 75 ℃, and the reaction is carried out for 45 minutes. Firstly, nickel carbonate is added to adjust the PH value to 2.2, then 15.2kg of manganese powder (5.12 g/L of copper is detected in filtrate) is added, and the reaction is continued for 75 minutes. Filtering to obtain filtrate and residue.
2000L of the filtrate was taken and added into a reactor, the temperature was raised to 90 ℃, 23.7kg of lithium fluoride (0.63 g/L of filtrate for detection of calcium and 0.27g/L of magnesium) was added, and after 300 minutes of reaction, filtration was carried out to obtain a filter residue and a filtrate. After ultrafiltration for 2 times, the filtrate is defluorinated by defluorination special resin, and the fluorine content in the solution is 0.67mg/L.
Taking a solution after fluorine removal, adding cobalt sulfate, nickel sulfate and manganese sulfate to adjust the total concentration to 2mol/L, wherein the contents of nickel, cobalt and manganese in the solution are respectively as follows: 58.71g/L, 23.49g/L, 32.82g/L. EDTA was added simultaneously in an amount of 0.2g/L.
Preparing mixed alkali liquor of sodium hydroxide and ammonium hydroxide, wherein the concentration of the alkali liquor is 27%, the concentration of ammonia water is 7mol/L, and the adding volume ratio of alkali to ammonia is 5:1. according to 5m in a primary reactor 3 Nitrogen is introduced at a flow rate of/h. After stirring is started, the temperature is controlled at 27 ℃, and meanwhile, mixed sulfuric acid solution of nickel, cobalt and manganese, mixed alkali solution of sodium hydroxide and ammonium hydroxide and EDTA with good mixing ratio are added. Controlling the PH value to 11.2, and controlling the addition amount of EDTA to be 200g/m 3 . The total flow of each liquid addition was 134L/hr and the effective reactor volume was 2000L. After the reactor is full, the feed is maintained and the reaction slurry overflows into the secondary reactor. In the secondary sedimentation reactor, 5m is controlled 3 The protective gas nitrogen is introduced at a flow rate of/h. Heating to 80 ℃, stirring for 45 minutes, adding saturated ammonium bicarbonate solution with the addition amount being 1.4 times of the theoretical value of lithium ion precipitation, adding the solution at the flow rate of 800L/h, and the effective volume of the reactor being 2000L. After the addition of ammonium bicarbonate was completed, the flow rate of the protective gas was kept constant and the reaction was continued with stirring for another 60 minutes. Filtering after the reaction is finished to obtain filtrate and filter residue, wherein the filter residue is a mixture of nickel cobalt manganese coprecipitation hydroxide and lithium carbonate.
The secondary sedimentation filter residue is dried after being washed by pure water, and the water content is 1.07 percent. Adjusting the ratio of lithium to be 1.1 of theoretical amount according to the content of nickel, cobalt and manganese, then reacting for 240 minutes in a calcining furnace at 670 ℃, and reacting for 240 minutes at 900 ℃. The calcined material is subjected to wet fine grinding, and the mass liquid-solid ratio of the fine grinding is 3:1, the fine grinding granularity is 100% and passes through 400 meshes. Filtering the finely ground slurry, and then mixing the slurry with the slurry according to a mass liquid-solid ratio of 3:1, washing once, filtering and drying to obtain the ternary anode material.
Example 2
In the case, the lithium battery dismantling black powder is recycled to prepare the NCM622 type lithium ion battery anode material.
350kg of concentrated sulfuric acid is added into the reactor to prepare 2.0mol/L dilute sulfuric acid solution. Then 1000kg of lithium power dismantling black powder is put into the reactor, the temperature is raised to 85 ℃, and the reaction is carried out for 120 minutes. After the reaction was completed, 50kg of ferrous sulfide was added, and the reaction was continued for 120 minutes at an end point pH of 1.2. And filtering after the reaction is finished to obtain filtrate and filter residue.
2000L of the filtrate is taken and added into a reactor, 35kg of hydrogen peroxide is added after the temperature is raised to 75 ℃, and the reaction is carried out for 60 minutes. Nickel carbonate was added to adjust the pH to 2.5, then 13.5kg of manganese powder (3.85 g/L copper content of the filtrate was measured) was added, and the reaction was continued for 90 minutes. Filtering to obtain filtrate and residue.
2000L of the filtrate is taken and added into a reactor, the temperature is raised to 90 ℃, 16.5kg of lithium fluoride (0.44 g/L of filtrate detection calcium and 0.13g/L of magnesium) is added, and the mixture is filtered after 360 minutes of reaction, thus obtaining filter residues and filtrate. After ultrafiltration for 2 times, the filtrate is defluorinated by defluorination special resin, and the fluorine content in the solution is 0.38mg/L.
Taking a solution after fluorine removal, adding cobalt sulfate, nickel sulfate and manganese sulfate to adjust the total concentration to 1.5mol/L, wherein the contents of nickel, cobalt and manganese in the solution are respectively as follows: 53.07g/L, 17.55g/L and 16.61g/L. EDTA was added simultaneously in an amount of 0.15g/L.
Preparing mixed alkali liquor of sodium hydroxide and ammonium hydroxide, wherein the concentration of the alkali liquor is 25%, the concentration of ammonia water is 7mol/L, and the adding volume ratio of alkali to ammonia is 6:1. according to 5m in a primary reactor 3 Nitrogen is introduced at a flow rate of/h. After stirring is started, the temperature is controlled at 27 ℃, and meanwhile, mixed sulfuric acid solution of nickel, cobalt and manganese, mixed alkali solution of sodium hydroxide and ammonium hydroxide and EDTA with good mixing ratio are added. Controlling the pH value to 11.7, and controlling the addition amount of EDTA to 170g/m 3 . The total flow rate of each liquid addition was 117L/hr and the effective reactor volume was 2000L. After the reactor is full, the feed is maintained and the reaction slurry overflows into the secondary reactor. In the secondary sedimentation reactor, 3m is controlled 3 The protective gas nitrogen is introduced at a flow rate of/h. Heating to 80 ℃, stirring for 45 minutes, adding saturated ammonium bicarbonate solution with the addition amount being 1.3 times of the theoretical value of lithium ion precipitation, adding the solution at the flow rate of 800L/h, and the effective volume of the reactor being 2000L. After the addition of ammonium bicarbonate was completed, the flow rate of the protective gas was kept constant and the reaction was continued with stirring for another 60 minutes. Filtering after the reaction is finished to obtain filtrate and filter residue, wherein the filter residue is a mixture of nickel cobalt manganese coprecipitation hydroxide and lithium carbonate.
The secondary sedimentation filter residue is dried after being washed by pure water, and the water content is 1.83 percent. The ratio of lithium is regulated to be 1.1 of theoretical amount according to the content of nickel, cobalt and manganese, and then the mixture is reacted for 240 minutes in a calcining furnace at 630 ℃ and then reacted for 240 minutes at 1000 ℃. The calcined material is subjected to wet fine grinding, and the mass liquid-solid ratio of the fine grinding is 3:1, the fine grinding granularity is 100% and passes through 400 meshes. Filtering the finely ground slurry, and then mixing the slurry with the slurry according to a mass liquid-solid ratio of 3:1, washing once, filtering and drying to obtain the ternary anode material.
Example 3
The method for preparing the NCM111 type lithium ion battery anode material by recycling the waste anode powder of the lithium battery is provided.
300kg of concentrated sulfuric acid was added to the reactor to prepare a dilute sulfuric acid solution of 3.0 mol/L. Then 1000kg of lithium power dismantling black powder is put into the reactor, the temperature is raised to 85 ℃, and the reaction is carried out for 120 minutes. After the reaction was completed, 40kg of ferrous sulfide was added, and the reaction was continued for 120 minutes at an end point pH of 1.5. And filtering after the reaction is finished to obtain filtrate and filter residue.
2000L of the filtrate is taken and added into a reactor, 35kg of hydrogen peroxide is added after the temperature is raised to 75 ℃, and the reaction is carried out for 60 minutes. Nickel carbonate was added to adjust the pH to 2.5, then 15.3kg of manganese powder (4.33 g/L copper content of the filtrate was measured) was added, and the reaction was continued for 90 minutes. Filtering to obtain filtrate and residue.
2000L of the filtrate is taken and added into a reactor, the temperature is raised to 90 ℃, 22.8kg of lithium fluoride (0.39 g/L of filtrate detection calcium and 0.41g/L of magnesium) is added, and the mixture is filtered after 360 minutes of reaction, thus obtaining filter residues and filtrate. After ultrafiltration for 2 times, the filtrate is defluorinated by defluorination special resin, and the fluorine content in the solution is 0.55mg/L.
Taking a solution after fluorine removal, adding cobalt sulfate, nickel sulfate and manganese sulfate to adjust the total concentration to 2.4mol/L, wherein the contents of nickel, cobalt and manganese in the solution are respectively as follows: 47.09g/L, 46.91g/L, 44.10g/L. EDTA was added simultaneously in an amount of 0.2g/L.
Preparing mixed alkali liquor of sodium hydroxide and ammonium hydroxide, wherein the concentration of the alkali liquor is 25%, the concentration of ammonia water is 7mol/L, and the adding volume ratio of alkali to ammonia is 5:1. according to 5m in a primary reactor 3 Nitrogen is introduced at a flow rate of/h. After stirring is started, the temperature is controlled at 27 ℃, and meanwhile, mixed sulfuric acid solution of nickel, cobalt and manganese, mixed alkali solution of sodium hydroxide and ammonium hydroxide and EDTA with good mixing ratio are added. Controlling the pH value to 10.8, and controlling the addition amount of EDTA to 190g/m 3 . The total flow of each liquid addition was 120L/hr and the effective reactor volume was 2000L. After the reactor is full, the feed is maintained and the reaction slurry overflows into the secondary reactor. In the secondary sedimentation reactor, the flow rate of 5m3/h is controlled to be introduced with protective gas nitrogen. Heating to 80 ℃, stirring for 45 minutes, adding saturated ammonium bicarbonate solution with the addition amount being 1.3 times of the theoretical value of lithium ion precipitation, adding the solution at the flow rate of 800L/h, and the effective volume of the reactor being 2000L. After the addition of ammonium bicarbonate was completed, the flow rate of the protective gas was kept constant and the reaction was continued with stirring for another 60 minutes. Filtering after the reaction is finishedFiltrate and filter residue can be obtained, and the filter residue is a mixture of nickel cobalt manganese coprecipitation hydroxide and lithium carbonate.
The secondary sedimentation filter residue is dried after being washed by pure water, and the water content is 1.42 percent. The ratio of lithium is regulated to be 1.2 of theoretical amount according to the content of nickel, cobalt and manganese, and then the mixture is reacted for 240 minutes in a calcining furnace at 700 ℃ and then for 240 minutes at 900 ℃. The calcined material is subjected to wet fine grinding, and the mass liquid-solid ratio of the fine grinding is 3:1, the fine grinding granularity is 100% and passes through 400 meshes. Filtering the finely ground slurry, and then mixing the slurry with the slurry according to a mass liquid-solid ratio of 3:1, washing once, filtering and drying to obtain the ternary anode material.
Example 4
The method for preparing NCM811 lithium ion battery anode material by recycling waste anode powder of lithium battery is provided.
300kg of concentrated sulfuric acid was added to the reactor to prepare a dilute sulfuric acid solution of 3.0 mol/L. Then 1000kg of lithium power dismantling black powder is put into the reactor, the temperature is raised to 85 ℃, and the reaction is carried out for 120 minutes. After the reaction was completed, 35kg of ferrous sulfide was added thereto, and the reaction was continued for 120 minutes at a final pH of 1.4. And filtering after the reaction is finished to obtain filtrate and filter residue.
2000L of the filtrate is taken and added into a reactor, 35kg of hydrogen peroxide is added after the temperature is raised to 75 ℃, and the reaction is carried out for 60 minutes. Nickel carbonate was added to adjust the pH to 2.5, then 5.5kg of manganese powder (1.73 g/L copper content of the filtrate was measured) was added, and the reaction was continued for 90 minutes. Filtering to obtain filtrate and residue.
2000L of the filtrate is taken and added into a reactor, the temperature is raised to 90 ℃, 24kg of lithium fluoride (0.20 g/L of filtrate for detecting calcium and 0.61g/L of magnesium) is added, and the mixture is filtered after 360 minutes of reaction, thus obtaining filter residues and filtrate. After ultrafiltration for 2 times, the filtrate is defluorinated by defluorination special resin, and the fluorine content in the solution is 0.40mg/L.
Taking a solution after fluorine removal, adding cobalt sulfate, nickel sulfate and manganese sulfate to adjust the total concentration to 2.2mol/L, wherein the contents of nickel, cobalt and manganese in the solution are respectively as follows: 103.33g/L, 12.83g/L and 12.14g/L. EDTA was added simultaneously in an amount of 0.2g/L.
Preparing mixed alkali liquor of sodium hydroxide and ammonium hydroxide, wherein the concentration of the alkali liquor is 25%, the concentration of ammonia water is 7mol/L, and the adding volume ratio of alkali to ammonia is 5:1. according to 5m in a primary reactor 3 Nitrogen is introduced at a flow rate of/h. After stirring is started, the temperature is controlled at 27 ℃, and meanwhile, mixed sulfuric acid solution of nickel, cobalt and manganese, mixed alkali solution of sodium hydroxide and ammonium hydroxide and EDTA with good mixing ratio are added. The pH was controlled to 11.5 and the EDTA addition was 200g/m3. The total flow of each liquid addition was 120L/hr and the effective reactor volume was 2000L. After the reactor is full, the feed is maintained and the reaction slurry overflows into the secondary reactor. In the secondary sedimentation reactor, the flow rate of 5m3/h is controlled to be introduced with protective gas nitrogen. Heating to 80 ℃, stirring for 45 minutes, adding saturated ammonium bicarbonate solution with the addition amount being 1.3 times of the theoretical value of lithium ion precipitation, adding the solution at the flow rate of 800L/h, and the effective volume of the reactor being 2000L. After the addition of ammonium bicarbonate was completed, the flow rate of the protective gas was kept constant and the reaction was continued with stirring for another 60 minutes. Filtering after the reaction is finished to obtain filtrate and filter residue, wherein the filter residue is a mixture of nickel cobalt manganese coprecipitation hydroxide and lithium carbonate.
The secondary sedimentation filter residue is dried after being washed by pure water, and the water content is 0.93 percent. The ratio of lithium is regulated to be 1.2 of theoretical amount according to the content of nickel, cobalt and manganese, and then the mixture is reacted for 240 minutes in a calcining furnace at 650 ℃, and then reacted for 240 minutes at 900 ℃. The calcined material is subjected to wet fine grinding, and the mass liquid-solid ratio of the fine grinding is 3:1, the fine grinding granularity is 100% and passes through 400 meshes. Filtering the finely ground slurry, and then mixing the slurry with the slurry according to a mass liquid-solid ratio of 3:1, washing once, filtering and drying to obtain the ternary anode material.
Claims (10)
1. A method for preparing a lithium ion battery anode material by recycling waste lithium electricity dismantling black powder and anode powder is characterized by comprising the following steps: the method comprises the following steps:
s1: firstly filling a reaction container with a prepared acid solution, putting raw materials to be recovered into the reaction container, then raising the temperature of the reaction container to T1, then carrying out reaction for T1, putting a reducing agent into the reaction container for reaction for T2 after the reaction is finished, and adjusting the ph value of the solution to be a after the reaction is finished;
s2: filtering raw materials after the reaction, and then carrying out process treatment of removing iron, aluminum, calcium and magnesium on filter residues;
s3: sequentially carrying out ultrafiltration, defluorination and ratio-regulating process treatment on the treated raw materials;
s4: adding the treated raw materials into mixed alkali liquor of sodium hydroxide and ammonium hydroxide, introducing protective gas, stirring and adding mixed solution of nickel, cobalt and manganese and sulfuric acid, mixed alkali liquor of sodium hydroxide and ammonium hydroxide and EDTA, controlling the pH value to 11-12, and controlling the temperature at 25-45 ℃ in the reaction process;
s5: after the reaction is finished, sending a reaction solution into a reaction container, introducing protective gas and stirring the reaction solution, heating the reaction container to T2, stirring for T3, adding saturated ammonium bicarbonate solution and continuously introducing the protective gas, and stirring for T4 in the process;
s6: and (3) obtaining filter residues after the reaction is finished, and finally washing, drying, calcining and finely grinding the filter residues.
2. The method for preparing the lithium ion battery anode material by recycling the waste lithium battery dismantling black powder and the anode powder according to claim 1, which is characterized in that: the acid solution in the S1 is a dilute sulfuric acid solution with the concentration of 2-3 mol/L, and the mass ratio of the dilute sulfuric acid solution to the raw materials is 0.15-0.35: 1, wherein T1 is 75-95 ℃, T1 is 120-140 minutes, T2 is 60-120 minutes, a is 1.0-1.5, and the reducing agent is ferrous sulfide.
3. The method for preparing the lithium ion battery anode material by recycling the waste lithium battery dismantling black powder and the anode powder according to claim 2, which is characterized in that: the iron and aluminum removing process in the step S2 comprises the following steps of:
s31: leaching filtrate, adding the filtrate into a reactor, heating the reaction vessel to 75 ℃, and adding hydrogen peroxide with the addition amount of 10-20 kg per cubic volume;
s32: adding hydrogen peroxide, reacting for 30-60 minutes, adding nickel carbonate, adjusting the pH value to 2.0-2.5, and then adding manganese powder;
s33: the mass ratio of the addition amount of the manganese powder to the copper content in the solution is 1:1.1 to 1.8, continuing to react for 60 to 90 minutes after the manganese powder is added, and filtering after the reaction is finished to obtain filtrate and filter residues.
4. The method for preparing the lithium ion battery anode material by recycling the waste lithium battery dismantling black powder and the anode powder according to claim 3, which is characterized in that: the calcium and magnesium removal process in the step S2 comprises the following steps:
s41: adding filtrate after iron and aluminum removal into a calcium and magnesium removal reactor, and heating to 90 ℃;
s42: the content of calcium and magnesium in the solution can be analyzed and detected by an atomic absorber, lithium fluoride with the theoretical dosage of 10-15 times is added according to the amount of calcium and magnesium, the lithium fluoride is in a slurried colloid state, the reaction is carried out for 240-360 minutes, and calcium and magnesium slag and filtrate are obtained after the reaction is finished.
5. The method for preparing the lithium ion battery anode material by recycling the waste lithium battery dismantling black powder and the anode powder according to claim 1, which is characterized in that: the ultrafiltration process in the step S3 comprises the following steps:
s51: filtering the filtrate subjected to calcium, magnesium and iron and aluminum removal treatment by using a microporous membrane filter twice, wherein the filtering pore diameter of the microporous membrane filter for the first time is 0.5 mu m;
s52: the filtrate after the treatment of removing calcium, magnesium and iron and aluminum contains superfine and suspended particles, wherein the superfine and suspended particles comprise silicate, calcium fluoride and magnesium fluoride, and the filter pore diameter of the second microporous membrane filter is selected to be 0.1 mu m, so that the superfine and suspended particles in the solution are filtered cleanly.
6. The method for preparing the lithium ion battery anode material by recycling the waste lithium battery dismantling black powder and the anode powder according to claim 5, which is characterized in that: the defluorination process in the step S3 is as follows: treating the ultrafiltered solution with a fluorine-removing special resin, and controlling the concentration range of fluorine ions in the solution to be as follows: 0.3-1 mg/L.
7. The method for preparing the lithium ion battery anode material by recycling the waste lithium battery dismantling black powder and the anode powder according to claim 6, which is characterized in that: the ratio regulating process in the step S3 comprises the following steps:
s71: the precipitation front adjustment ratio is to adjust the content of nickel, cobalt and manganese in the solution by using sulfate of nickel, cobalt and manganese according to each specification and model of the ternary positive electrode material, and the total molar concentration of nickel, cobalt and manganese is 1.5-2.4 mol/L;
s72: adding complexing agent EDTA with the addition amount of 0.1-0.2 g/L; the calcination front adjusting ratio is to adjust the ratio of nickel, cobalt and manganese to lithium, and the ratio of lithium is adjusted to be 1.05-1.2 of theoretical quantity according to the content of nickel, cobalt and manganese.
8. The method for preparing the lithium ion battery anode material by recycling the waste lithium battery dismantling black powder and the anode powder according to claim 7, which is characterized in that: the concentration of sodium hydroxide in the S4 is as follows: 25% -27%, the concentration of ammonia water is: 5-7 mol/L, and the volume ratio of sodium hydroxide to ammonia water is (4-6): 1, the introducing rate of the protective gas is 3-5 m 3 And/h, the addition amount of EDTA is 100-200 g/m 3 . The total flow rate of each liquid is 1/10-1/20 of the volume of the reactor.
9. The method for preparing the lithium ion battery anode material by recycling the waste lithium battery dismantling black powder and the anode powder according to claim 8, which is characterized in that: in the S5, the T2 is 75-90 ℃, and the input rate of the introduced protective gas is 3-5 m 3 And/h, wherein t3 is 30-60 minutes, the addition amount of the saturated ammonium bicarbonate solution is 1.1-1.4 times of the theoretical value of lithium ion precipitation, and the addition flow rate is as follows: the idle volume/(2-3) of the reactor is kept unchanged after the addition of the ammonium bicarbonate is completed, and the flow rate of the protective gas is kept unchanged, wherein t4 is 60-90 minutes. Filtering after the reaction is finished to obtain filtrate and filter residues, wherein the filter residues are a mixture of nickel cobalt manganese coprecipitation hydroxide and lithium carbonate.
10. The method for preparing the lithium ion battery anode material by recycling the waste lithium battery dismantling black powder and the anode powder according to claim 9, which is characterized in that: the washing and drying in the step S6 is required to control the water content in the reactant to be within 1-2 percent;
in the step S6, the dried mixture is subjected to mixing ratio and then reacts for 120-240 minutes at 600-700 ℃ in a calcining furnace, and then reacts for 120-240 minutes at 800-1000 ℃;
the calcined material in the step S6 is subjected to wet fine grinding, and the mass liquid-solid ratio of the fine grinding is (3-5): 1, fine grinding with granularity of 100% and 400 meshes, filtering the slurry after fine grinding, and then mixing the slurry with the slurry according to the mass liquid-solid ratio of (3-5): 1, washing once, filtering and drying to obtain the ternary anode material.
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