CN111206148B - Method for recycling and preparing ternary cathode material by using waste ternary lithium battery - Google Patents
Method for recycling and preparing ternary cathode material by using waste ternary lithium battery Download PDFInfo
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- CN111206148B CN111206148B CN202010182830.6A CN202010182830A CN111206148B CN 111206148 B CN111206148 B CN 111206148B CN 202010182830 A CN202010182830 A CN 202010182830A CN 111206148 B CN111206148 B CN 111206148B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 81
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 239000010406 cathode material Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- 238000002386 leaching Methods 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000012535 impurity Substances 0.000 claims abstract description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 39
- 239000010941 cobalt Substances 0.000 claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011572 manganese Substances 0.000 claims abstract description 37
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000605 extraction Methods 0.000 claims abstract description 29
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 25
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 25
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 25
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 25
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 25
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 25
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 25
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 24
- 229940053662 nickel sulfate Drugs 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000002791 soaking Methods 0.000 claims abstract description 20
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 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 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 239000003350 kerosene Substances 0.000 claims description 23
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000007127 saponification reaction Methods 0.000 claims description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 4
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 229940073644 nickel Drugs 0.000 abstract description 38
- 238000011084 recovery Methods 0.000 abstract description 26
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- -1 aluminum ions Chemical class 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000004615 ingredient Substances 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
- 150000002739 metals Chemical class 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
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- 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
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
-
- 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
- C22B23/02—Obtaining nickel or cobalt by dry 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
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
-
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- 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
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- 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
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- 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
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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
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Abstract
The invention provides a method for recycling and preparing a ternary cathode material by utilizing a waste ternary lithium battery, which comprises the following steps of: 1) mixing the pretreated waste nickel cobalt lithium manganate positive electrode powder with sulfate, and roasting to obtain a roasted product; 2) soaking the roasted product in water to obtain a water soaking solution and water soaking slag; the water leaching solution contains lithium salt; 3) reacting the water leaching residue with an acid solution and hydrogen peroxide to obtain a nickel-cobalt-manganese leaching solution; 4) removing impurities from the nickel-cobalt-manganese leaching solution, and then extracting cobalt, manganese and nickel to obtain organic phase, saponifying and back extracting to obtain cobalt sulfate, manganese sulfate and nickel sulfate solution; 5) and coprecipitating the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution with a sodium hydroxide solution and ammonia water, mixing the obtained precursor with lithium carbonate, sintering, and screening iron to obtain the ternary cathode material. According to the method provided by the invention, lithium is extracted firstly, so that the influence of lithium on the subsequent nickel-cobalt-manganese extraction is reduced, the impurity content in the ternary cathode material is reduced, and the recovery rate of nickel-cobalt-manganese is greatly improved; and the recovery rate of lithium can be improved.
Description
Technical Field
The invention belongs to the technical field of waste lithium battery recovery, and particularly relates to a method for preparing a ternary cathode material by recovering waste ternary lithium batteries.
Background
In recent 10 years, the electric automobile industry in China has been rapidly developed. Meanwhile, electric vehicles that enter the market at the earliest have now entered the battery decommissioning stage, and the number of decommissioned batteries has also increased dramatically in the next few years. According to the market research and prediction, the scrappage of the lithium battery for the automobile reaches 32GWh in 2020, and the scrappage of the battery is converted into the quality of about 50 ten thousand tons; by 2030 years, the scrappage of the lithium battery for the vehicle can reach 300GWH, and the scrappage of the lithium battery is about 300 ten thousand tons. Lithium batteries are mainly classified into lithium iron phosphate batteries and ternary lithium batteries according to different anode materials, and the ternary lithium batteries become the mainstream of new energy automobile batteries due to the advantages of high energy density, long service life and the like.
The ternary lithium battery contains metal elements such as cobalt and nickel, and if the ternary lithium battery is not recycled, not only is the resource greatly wasted, but also the ecological environment is polluted, so that the sustainable development of the new energy automobile industry is limited. At present, the price of the metal raw materials such as nickel, cobalt, lithium and the like for preparing the ternary cathode material is high and the demand is large. Therefore, metals such as nickel, cobalt, lithium and the like are extracted from the ternary waste lithium battery, so that the problem of raw material supply can be solved, and huge benefits can be created for the society.
The method for recovering the ternary cathode material from the waste lithium battery in China generally adopts a full-wet method: the method comprises the steps of disassembling and crushing waste lithium batteries, sorting out positive electrode powder with low impurity content, reducing and leaching manganese, nickel, cobalt and lithium in the positive electrode powder, recovering nickel, cobalt and manganese through processes such as extraction and the like, and recovering lithium by adding a precipitator into a leaching solution or extracting a nickel, cobalt and manganese raffinate.
The all-wet recovery method has the following problems: (1) after manganese, nickel, cobalt and lithium in the anode material are reduced and leached together, the lithium element in the solution influences the recovery of nickel and cobalt, so that the impurity content of the final precursor product is high, and the electrochemical performance of the ternary anode material is influenced. (2) After the leaching solution is subjected to extraction separation, a small part of lithium is carried away by mixed phase or is extracted, and the content of lithium in the leaching solution is low, so that the subsequent recovery cost is high and the recovery rate is low.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for recycling and preparing a ternary cathode material from a waste ternary lithium battery, wherein the method has a high nickel-cobalt-manganese recovery rate.
The invention provides a method for recycling and preparing a ternary cathode material by utilizing a waste ternary lithium battery, which comprises the following steps of:
1) mixing the pretreated waste nickel cobalt lithium manganate positive electrode powder with sulfate, and roasting to obtain a roasted product;
2) soaking the roasted product in water to obtain a water soaking solution and water soaking slag;
3) reacting the water leaching residue with an acid solution and hydrogen peroxide to obtain a nickel-cobalt-manganese leaching solution;
4) removing impurities from the nickel-cobalt-manganese leaching solution, and then extracting cobalt, manganese and nickel to obtain organic phase, saponifying and back extracting to obtain pure cobalt sulfate, manganese sulfate and nickel sulfate solution;
5) and coprecipitating the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution with a sodium hydroxide solution and ammonia water, mixing the obtained precursor with lithium carbonate, sintering, and screening iron to obtain the ternary cathode material.
Preferably, the sulfate salt in step 1) is selected from one or more of ammonium sulfate, potassium bisulfate and sodium bisulfate;
the roasting temperature is 350-750 ℃, and the roasting time is 0.5-2.5 h.
Preferably, the water immersion in the step 2) is carried out at the temperature of 30-90 ℃ for 0.5-4 h, and the liquid-solid ratio is 1-5: 1.
Preferably, the acid solution in the step 3) is selected from a sulfuric acid solution, and the concentration of the sulfuric acid solution is 150-250 g/L; the concentration of hydrogen peroxide is 5-15 g/L;
the reaction temperature of the water leaching residues, the acid solution and the hydrogen peroxide is 30-90 ℃, and the reaction time is 2-6 hours.
Preferably, the organic extraction of cobalt, manganese and nickel after removing impurities from the nickel-cobalt-manganese leaching solution in the step 4) specifically comprises:
performing impurity extraction on impurity-removed liquid obtained after copper and aluminum removal procedures are performed on the nickel-cobalt-manganese leaching solution to obtain impurity-extracted liquid; and extracting cobalt, manganese and nickel in the impurity extraction liquid.
Preferably, the extractant used for impurity extraction is P204-sulfonated kerosene; the extractant used for extracting cobalt and manganese is P507-sulfonated kerosene, and the extractant used for extracting nickel is P204-sulfonated kerosene.
Preferably, the amount ratio of nickel sulfate to cobalt sulfate to nickel-cobalt-manganese substances in the manganese sulfate solution in the step 5) is 5:2:3, 6:2:2 or 8:1: 1;
the concentration of the sodium hydroxide solution is 3.5-10 mol/L; the concentration of the ammonia water is 2-10 mol/L;
the sintering temperature is 500-1200 ℃.
Preferably, the water extract obtained in the step 2) is concentrated by evaporation to enrich lithium, liquid alkali is added, and CO is introduced2And then adding a sodium carbonate solution to precipitate lithium after adjusting the pH value to remove impurities, washing and drying to obtain the battery-grade lithium carbonate.
Preferably, the concentration of the enriched lithium is 15-25 g/L, and the pH value is adjusted to 10-13;
the temperature of the lithium deposition is 60-100 ℃, and the time is 2-5 h;
the concentration of the sodium carbonate solution is 200-300 g/L.
Preferably, the waste lithium nickel cobalt manganese oxide positive electrode powder pretreated in the step 1) is prepared according to the following steps:
and (2) placing the waste lithium battery in 1-3 mol/L NaCl solution for discharging, coarsely crushing and finely crushing, pyrolyzing at 200-600 ℃, and sorting to obtain the pretreated waste nickel cobalt lithium manganate positive electrode powder.
The invention provides a method for recycling and preparing a ternary cathode material by utilizing a waste ternary lithium battery, which comprises the following steps of: 1) mixing the pretreated waste nickel cobalt lithium manganate positive electrode powder with sulfate, and roasting to obtain a roasted product; 2) soaking the roasted product in water to obtain a water soaking solution and water soaking slag; the water leaching solution contains lithium salt; 3) reacting the water leaching residue with an acid solution and hydrogen peroxide to obtain a nickel-cobalt-manganese leaching solution; 4) removing impurities from the nickel-cobalt-manganese leaching solution, and then extracting cobalt, manganese and nickel to obtain organic phase, saponifying and back extracting to obtain pure cobalt sulfate, manganese sulfate and nickel sulfate solution; 5) and coprecipitating the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution with a sodium hydroxide solution and ammonia water, mixing the obtained precursor with lithium carbonate, sintering, and screening iron to obtain the ternary cathode material. Roasting the pretreated ternary positive electrode waste powder, and preferentially recovering lithium salt through water immersion; then, obtaining a sulfate solution of nickel, cobalt and manganese through acid leaching, impurity removal and extraction, and directly preparing the ternary cathode material as a raw material; but also can improve the recovery rate of lithium and reduce the recovery cost. The experimental results show that: the highest recovery rates of nickel, cobalt and manganese are 97%, 98% and 98% respectively, and the purity can reach 99.8%; the recovery rate of lithium is up to 97%, and the purity is up to 99.61%.
Drawings
FIG. 1 is a schematic view of a process for recycling and preparing a ternary cathode material from a waste ternary lithium battery according to the present invention;
FIG. 2 is a scanning electron microscope image of the ternary cathode material obtained in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the ternary cathode material obtained in example 3 of the present invention.
Detailed Description
The invention provides a method for recycling and preparing a ternary cathode material by utilizing a waste ternary lithium battery, which comprises the following steps of:
1) mixing the pretreated waste nickel cobalt lithium manganate positive electrode powder with sulfate, and roasting to obtain a roasted product;
2) soaking the roasted product in water to obtain a water soaking solution and water soaking slag; the water leaching solution contains lithium salt;
3) reacting the water leaching residue with an acid solution and hydrogen peroxide to obtain a nickel-cobalt-manganese leaching solution;
4) removing impurities from the nickel-cobalt-manganese leaching solution, and then extracting cobalt, manganese and nickel to obtain organic phase, saponifying and back extracting to obtain pure cobalt sulfate, manganese sulfate and nickel sulfate solution;
5) and coprecipitating the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution with a sodium hydroxide solution and ammonia water, mixing the obtained precursor with lithium carbonate, sintering, and screening iron to obtain the ternary cathode material.
The method comprises the steps of roasting the pretreated ternary anode waste powder, and preferentially recovering lithium salt through water immersion. Then, obtaining a sulfate solution of nickel, cobalt and manganese through acid leaching, impurity removal and extraction, and directly preparing the ternary cathode material as a raw material; but also can improve the recovery rate of lithium and reduce the recovery cost.
The method mixes the waste nickel cobalt lithium manganate anode powder and sulfate which are pretreated, and roasting to obtain a roasted product. In the invention, the pretreated waste nickel cobalt lithium manganate positive electrode powder is prepared according to the following steps:
and (2) placing the waste lithium battery in 1-3 mol/L NaCl solution for discharging, coarsely crushing and finely crushing, pyrolyzing at 200-600 ℃, and sorting to obtain the pretreated waste nickel cobalt lithium manganate positive electrode powder.
In a specific embodiment of the invention, the concentration of the NaCl solution is 1.5mol/L or 2 mol/L. The pyrolysis temperature is specifically 300 ℃ or 400 ℃. Pyrolysis is carried out under oxygen-free conditions or under nitrogen conditions.
The sulfate is preferably selected from one or more of ammonium sulfate, potassium bisulfate and sodium bisulfate; the addition amount of the sulfate is preferably 0.5-2 times of the theoretical amount. The theoretical amount is the theoretical molar amount of the sulfate required by calculation from a chemical reaction equation.
The roasting temperature is 350-750 ℃, and the roasting time is 0.5-2.5 h. In a specific embodiment, the roasting temperature is 500 ℃ or 600 ℃; the time is 2 h.
After a roasted product is obtained, the roasted product is soaked in water to obtain a water soaking solution and water soaking slag; the water immersion liquid contains lithium salt. According to the invention, the lithium salt is recovered into the water leaching solution after the roasted product is soaked in water, so that the loss of lithium in the subsequent process in the full-wet recovery process is avoided, the recovery rate of lithium is improved, and the recovery cost is reduced. The roasting process adopts sulfate mixed roasting, and has the advantages of low cost, simple equipment requirement, safe production environment and the like. The water immersion temperature is preferably 30-90 ℃, the time is 0.5-4 h, and the liquid-solid ratio is 1-5: 1. In a specific embodiment, the water immersion temperature is 65 ℃ or 60 ℃, the time is 3 hours, and the liquid-solid ratio is 5:1 or 4: 1.
In the present invention, the aqueous leach solution is preferably enriched in lithium by evaporative concentration, added with caustic and CO-fed2And then adding a sodium carbonate solution to precipitate lithium after adjusting the pH value to remove impurities, washing and drying to obtain the battery-grade lithium carbonate. According to the invention, after lithium is preferentially extracted, the influence of lithium on the extraction of nickel, cobalt and manganese is reduced in the subsequent process of recovering nickel, cobalt and manganese, the recovery rate of nickel, cobalt and manganese is greatly improved, the purity can reach more than 99.8%, and the production yield is effectively improved.
In the invention, the concentration of the enriched lithium is preferably 15-25 g/L; adjusting the pH value to 10-13; the temperature of the lithium deposition is 60-100 ℃, and the time is 2-5 h; the concentration of the sodium carbonate solution is 200-300 g/L.
In a specific embodiment, the liquid alkali is selected from a sodium hydroxide solution with the mass concentration of 30-35%; in a specific embodiment, the liquid alkali is a sodium hydroxide solution with the mass concentration of 30%; the concentration of lithium enrichment is 17g/L or 19 g/L; the pH value is adjusted to 12. Adding liquid caustic soda to lead to CO2Adjusting the pH value to precipitate impurity ions, and filtering and separating to obtain purified lithium liquid; adding a sodium carbonate solution into the purified lithium solution to precipitate lithium; the addition amount of the sodium carbonate solution is 0.7-1.6 times of the theoretical amount. In the specific embodiment, the addition amount of the sodium carbonate solution is 1.3 times or 1.1 times of the theoretical amount; the concentration of the sodium carbonate solution is 270g/L or 280 g/L. The temperature for depositing lithium is 95 ℃,the time is 2 h.
After the water leaching residue is obtained, the water leaching residue is reacted with an acid solution and hydrogen peroxide to obtain a nickel-cobalt-manganese leaching solution. In the invention, the acid solution is preferably selected from sulfuric acid solution, and the concentration of the sulfuric acid solution is 150-250 g/L; the concentration of hydrogen peroxide is 5-15 g/L; the reaction temperature of the water leaching residues, the acid solution and the hydrogen peroxide is 30-90 ℃, and the reaction time is 2-6 hours. In a specific embodiment, the acid solution is a sulfuric acid solution of 205g/L or a sulfuric acid solution of 210 g/L; the concentration of the hydrogen peroxide is 7g/L or 10 g/L. Carrying out acid leaching on the water leaching residue at a liquid-solid ratio of 1-7: 1; in a specific example, the water leaching slag is subjected to the reaction of acid solution and hydrogen peroxide at a liquid-solid ratio of 5:1 or 6: 1. The reaction temperature of the water leaching residues, the acid solution and the hydrogen peroxide is specifically 50 ℃ or 60 ℃, and the reaction time is 4 hours or 5 hours. After the reaction, the metal or the metal oxide is converted into metal sulfate, and the metal sulfate solution is obtained after filter pressing.
And removing impurities from the nickel-cobalt-manganese leaching solution, and then extracting cobalt, manganese and nickel to obtain organic phase, saponifying and back-extracting to obtain pure cobalt sulfate, manganese sulfate and nickel sulfate solution.
In the invention, the organic extraction of cobalt, manganese and nickel after removing impurities from the nickel-cobalt-manganese leaching solution preferably comprises the following steps:
performing impurity extraction on impurity-removed liquid obtained after copper and aluminum removal procedures are performed on the nickel-cobalt-manganese leaching solution to obtain impurity-extracted liquid; and extracting cobalt, manganese and nickel in the impurity extraction liquid.
The invention preferably removes copper by controlling the pH value of the nickel-cobalt-manganese leaching solution; and controlling the pH value of the nickel-cobalt-manganese leaching solution to be 1.5-2.5 for copper removal. Adding hydrogen peroxide into the feed liquid after copper removal, reacting for 25-35 min at 70-100 ℃, and then adding a sodium hydroxide solution or a sodium carbonate solution to precipitate iron and aluminum ions so as to remove iron and aluminum.
The impurity-removed liquid obtained after copper, iron and aluminum are removed is subjected to impurity extraction, and impurities such as calcium, magnesium, zinc and the like are extracted and removed to obtain impurity-extracted liquid. The extractant used for impurity extraction is P204-sulfonated kerosene, more specifically P204(25 vol%) -sulfonated kerosene (75 vol%) or P204(20 vol%) -sulfonated kerosene (80 vol%), and impurities such as calcium, magnesium, copper, zinc and the like in the impurity-removed liquid and part of manganese are extracted into a P204 organic phase. According to the invention, cobalt and manganese in the impurity extraction liquid are preferably extracted by adopting P507-sulfonated kerosene and enter an organic phase, and in the specific embodiment, cobalt and manganese in the impurity extraction liquid are extracted by adopting P507(25 vol%) -sulfonated kerosene (75 vol%) or P507(20 vol%) -sulfonated kerosene (80 vol%); the nickel is left in the water phase, and the P204-sulfonated kerosene is preferably adopted to extract the nickel from the mixed cobalt manganese raffinate; in the specific embodiment, P204(25 vol%) -sulfonated kerosene (75 vol%) or P204(20 vol%) -sulfonated kerosene (80 vol%) is used.
Saponifying the organic phase obtained by extraction by using 5-10 mol/L sodium hydroxide solution; the saponification rate of the organic liquid is 45-70%. Preferably, 1-2.5 mol/L sulfuric acid solution is adopted for back extraction; in the specific embodiment, the stripping adopts 1.5mol/L sulfuric acid solution or 1mol/L sulfuric acid solution.
The nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution are coprecipitated with a sodium hydroxide solution and ammonia water, the obtained precursor is mixed with lithium carbonate and then sintered, and iron is sieved, so that the ternary cathode material is obtained. The nickel sulfate, cobalt sulfate and manganese sulfate obtained by extraction can be directly used for precursor production and preparation of the ternary cathode material by adjusting the proportion of nickel sulfate, cobalt sulfate and manganese sulfate according to the component requirement of the ternary cathode material, so that the process of ingredient dissolution is omitted, the production flow is simplified, and the product quality and the production efficiency are improved.
In the invention, the mass ratio of nickel, cobalt and manganese in the nickel sulfate, cobalt sulfate and manganese sulfate solution is 5:2:3, 6:2:2 or 8:1: 1; the concentration of the sodium hydroxide solution is 3.5-10 mol/L; the concentration of the ammonia water is 2-10 mol/L. In the specific embodiment, the concentration of the sodium hydroxide solution adopted by the coprecipitation is 5mol/L or 7 mol/L; the concentration of the ammonia water is 8mol/L or 10 mol/L. Filtering, washing and drying the coprecipitated product to obtain a precursor, mixing the precursor with lithium carbonate and then sintering; the addition amount of the lithium carbonate is 0.7-1.6 times of the theoretical amount; the sintering temperature is 500-1200 ℃; in specific embodiments, the sintering temperature is 830 ℃ or 930 ℃. And screening iron after sintering to obtain the ternary cathode material.
For further illustration of the present invention, the following will describe in detail a method for recycling and preparing a ternary cathode material by using a waste ternary lithium battery according to the present invention with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Fig. 1 is a schematic flow chart of the process for recovering and preparing a ternary cathode material from a waste ternary lithium battery, and the following embodiment refers to fig. 1:
example 1
(1) The waste lithium battery is placed in 1.5mol/L NaCl solution for discharge treatment, the discharged waste lithium battery is cleaned, dried, coarsely crushed and finely crushed, and is placed in a rotary kiln for pyrolysis at the temperature of 300 ℃ under the protection of nitrogen, and then 100kg of waste ternary cathode powder (Li:11.76, Ni:25.63, Co:8.91 and Mn:13.38 wt%) is obtained through sorting.
(2) And mixing the waste ternary cathode powder obtained by pretreatment with ammonium sulfate of which the theoretical amount is 1.2 times that of the waste ternary cathode powder, and then sending the mixture into a high-temperature furnace to roast for 2 hours at the temperature of 500 ℃.
(3) Adding pure water into the roasted waste anode powder at a liquid-solid ratio of 5:1 for leaching, wherein the water leaching time is 3 hours and the water leaching temperature is 65 ℃. And (3) carrying out filter pressing on the slurry after water leaching to obtain a lithium-containing leaching solution, and recovering lithium by removing impurities, concentrating and adding sodium carbonate.
(4) Adding 205g/L sulfuric acid and 7g/L hydrogen peroxide into leached residues after water leaching according to the liquid-solid ratio of 5:1 for acid leaching, wherein the terminal pH value is about 2, stirring for 5 hours at 50 ℃, converting metal or metal oxide into metal sulfate, and performing filter pressing to obtain a metal sulfate solution.
(5) Controlling the pH value of the filtrate after acid leaching to be 1.5, and removing impurity copper. Adding hydrogen peroxide with the theoretical amount of 1.2 times into the copper-removed feed liquid, stirring and reacting for 0.5h at the temperature of 90-95 ℃, adding a metered sodium hydroxide solution, adjusting the pH value to 4.5, and precipitating and separating iron and aluminum ions in the feed liquid.
(6) And (3) extracting impurities in the solution after impurity removal by using a P204 (20%) -sulfonated kerosene (80%) system, so that impurities such as calcium, magnesium, copper, zinc and the like in the solution and part of manganese are extracted into a P204 organic phase. And then performing cobalt-manganese extraction in the raffinate by using a P507 (20%) -sulfonated kerosene (80%) system, wherein cobalt and manganese enter an organic phase, nickel is remained in an aqueous phase, and nickel is extracted in the raffinate by using a P204 (20%) -sulfonated kerosene (80%) system. And (3) saponifying the organic phase by using 5mol/L sodium hydroxide solution, carrying out back extraction on 1mol/L sulfuric acid with the saponification rate of the organic liquid being 50% to obtain pure cobalt sulfate, manganese sulfate and nickel sulfate solutions, wherein the cobalt sulfate, the manganese sulfate and the nickel sulfate are respectively 22.95kg, 36.02kg and 65.53kg in quality through detection and analysis.
(7) Adjusting the proportion of nickel, cobalt and manganese in the nickel sulfate, cobalt sulfate and manganese sulfate solution to 5:2:3, and adding 5mol/L sodium hydroxide solution and 8mol/L ammonia water for coprecipitation reaction. And after the reaction is finished, filtering, washing and drying to obtain a precursor. And mixing the precursor with metered lithium carbonate, sintering at 930 ℃, and sieving to remove iron to obtain the ternary cathode material.
FIG. 2 is a scanning electron microscope image of the ternary cathode material obtained in example 1 of the present invention.
In this example 1, the recovery rates of nickel, cobalt, and manganese are 97%, 98%, and 98%, respectively, and the purity can reach 99.8%, so that the ternary cathode material with excellent quality is finally prepared.
Example 2
The embodiment is further optimized on the basis of embodiment 1, and specifically includes:
s1 concentration of lithium in the water extract obtained in example 1 to 17g/L by evaporation concentration, then adding liquid alkali, namely 30% sodium hydroxide solution by mass concentration, adjusting pH value to 12, and introducing CO2The impurity ions are precipitated and separated by filtration.
S2 sodium carbonate solution with the theoretical amount of 1.1 times of that of the purified lithium solution obtained by filtering is added into the purified lithium solution with the concentration of 270g/L, the solution reacts for 2 hours at the temperature of 95 ℃, and then the battery-grade lithium carbonate is prepared by washing and drying.
In example 2, the recovery rate of lithium was 96% and the purity was 99.53%.
Example 3
The embodiment provides a method for recycling and preparing a precursor from a waste ternary lithium battery, which comprises the following steps:
(1) the waste lithium batteries are placed in 2mol/L NaCl solution for discharging treatment, the discharged waste lithium batteries are washed, dried, coarsely crushed and finely crushed, and are placed in a rotary kiln for pyrolysis at 400 ℃ under the anaerobic condition, and then 100kg of waste ternary cathode powder (Li:11.67, Ni:28.87, Co:9.82 and Mn:9.62 wt%) is obtained through sorting.
(2) And mixing the waste ternary cathode powder obtained by pretreatment with sodium bisulfate with the theoretical amount of 1.5 times, then sending the mixture into a high temperature furnace, and roasting the mixture for 2 hours at the temperature of 600 ℃.
(3) Adding pure water into the roasted anode powder at a liquid-solid ratio of 4:1 for leaching, wherein the water leaching time is 3 hours and the water leaching temperature is 60 ℃. And (3) carrying out filter pressing on the slurry after water leaching to obtain a lithium-containing leaching solution, and recovering lithium by removing impurities, concentrating and adding sodium carbonate.
(4) Adding 210g/L sulfuric acid and 10g/L hydrogen peroxide into leached residues after water leaching according to the liquid-solid ratio of 6:1 for acid leaching, wherein the terminal pH value is about 1.5, stirring for 4 hours at 60 ℃, converting metal or metal oxide into metal sulfate, and performing filter pressing to obtain a metal sulfate solution.
(5) Controlling the pH value of the filtrate after acid leaching to be 2.5, and removing impurity copper. Adding hydrogen peroxide with the theoretical amount of 1.3 times into the copper-removed feed liquid, stirring and reacting for 0.5h at the temperature of 90-95 ℃, adding a metered sodium carbonate solution, adjusting the pH value to 4, and precipitating and separating iron ions and aluminum ions in the feed liquid.
(6) And (3) extracting impurities in the solution after impurity removal by using a P204 (25%) -sulfonated kerosene (75%) system, so that impurities such as calcium, magnesium, copper, zinc and the like and part of manganese in the solution are extracted into a P204 organic phase. And then performing cobalt-manganese extraction in the raffinate by using a P507 (25%) -sulfonated kerosene (75%) system, wherein cobalt and manganese enter an organic phase, nickel is remained in an aqueous phase, and nickel is extracted in the raffinate by using a P204 (25%) -sulfonated kerosene (75%) system. And (3) saponifying the organic phase by using 10mol/L sodium hydroxide solution, carrying out back extraction on sulfuric acid with the organic liquid saponification rate of 55% and the concentration of 1.5mol/L to obtain pure cobalt sulfate, manganese sulfate and nickel sulfate solutions, wherein the quality of the cobalt sulfate, the quality of the manganese sulfate and the quality of the nickel sulfate are respectively 25.04kg, 25.64kg and 73.05kg through detection and analysis.
(7) Adding 7mol/L sodium hydroxide solution and 10mol/L ammonia water into the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution according to the proportion of nickel, cobalt and manganese of 6:2:2 for coprecipitation reaction. After the reaction is finished, a precursor product is obtained by filtering, washing, drying, sieving and removing iron. And mixing the precursor with metered lithium carbonate, sintering at 830 ℃, and sieving to remove iron to obtain the ternary cathode material.
FIG. 3 is a scanning electron microscope image of the ternary cathode material obtained in example 3 of the present invention.
In this embodiment 3, the recovery rates of nickel, cobalt, and manganese are 96%, 97%, and 97%, respectively, and the purity can reach 99.8%, so that the ternary cathode material with excellent quality is finally prepared.
Example 4
The embodiment is further optimized on the basis of the embodiment 3, and specifically includes:
s1 concentration of lithium in the water extract obtained in the third example to 19g/L by evaporation concentration, then adding liquid alkali, namely 30% sodium hydroxide solution by mass concentration, adjusting the pH value to 12, and introducing CO2The impurity ions are precipitated and separated by filtration.
S2 sodium carbonate solution with the theoretical amount of 1.3 times that of the purified lithium solution obtained by filtering is added into the purified lithium solution with the concentration of 280g/L, the solution reacts for 2 hours at the temperature of 95 ℃, and then the battery-grade lithium carbonate is prepared by washing and drying.
In example 4, the recovery rate of lithium was 97%, and the purity was 99.61%.
The technical indexes of the ternary cathode materials prepared in the above examples 1 and 3 are shown in table 1, and the technical index of the lithium carbonate product is shown in table 2:
table 1 technical indices of ternary cathode materials prepared in examples 1 and 3
Table 2 technical indices of lithium carbonate prepared in example 2 and example 4
The embodiment can show that the invention provides a method for preparing a ternary cathode material by recycling waste ternary lithium batteries, which comprises the following steps: 1) mixing the pretreated waste nickel cobalt lithium manganate positive electrode powder with sulfate, and roasting to obtain a roasted product; 2) soaking the roasted product in water to obtain a water soaking solution and water soaking slag; the water leaching solution contains lithium salt; 3) reacting the water leaching residue with an acid solution and hydrogen peroxide to obtain a nickel-cobalt-manganese leaching solution; 4) removing impurities from the nickel-cobalt-manganese leaching solution, and then extracting cobalt, manganese and nickel to obtain organic phase, saponifying and back extracting to obtain pure cobalt sulfate, manganese sulfate and nickel sulfate solution; 5) and coprecipitating the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution with a sodium hydroxide solution and ammonia water, mixing the obtained precursor with lithium carbonate, sintering, and screening iron to obtain the ternary cathode material. Roasting the pretreated ternary positive electrode waste powder, and preferentially recovering lithium salt through water immersion; then, obtaining a sulfate solution of nickel, cobalt and manganese through acid leaching, impurity removal and extraction, and directly preparing the ternary cathode material as a raw material; but also can improve the recovery rate of lithium and reduce the recovery cost. The experimental results show that: the highest recovery rates of nickel, cobalt and manganese are 97%, 98% and 98% respectively, and the purity can reach 99.8%; the recovery rate of lithium is up to 97%, and the purity is up to 99.61%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A method for recycling and preparing a ternary cathode material by utilizing a waste ternary lithium battery comprises the following steps:
1) mixing the pretreated waste nickel cobalt lithium manganate positive electrode powder with sulfate, and roasting to obtain a roasted product; the sulfate in the step 1) is selected from one or more of ammonium sulfate, potassium bisulfate and sodium bisulfate; the roasting temperature is 350-750 ℃, and the roasting time is 0.5-2.5 h;
the waste nickel cobalt lithium manganate positive electrode powder pretreated in the step 1) is prepared according to the following steps:
placing the waste lithium battery in 1-3 mol/L NaCl solution for discharging, coarsely crushing and finely crushing, pyrolyzing at 200-600 ℃, and sorting to obtain pretreated waste nickel cobalt lithium manganate positive electrode powder;
2) soaking the roasted product in water to obtain a water soaking solution and water soaking slag; the water leaching solution contains lithium salt; the water leaching in the step 2) is carried out at the temperature of 30-90 ℃ for 0.5-4 h, and the liquid-solid ratio is 1-5: 1;
enriching lithium in the water extract obtained in the step 2) by evaporation and concentration, adding liquid alkali and introducing CO2Removing impurities by adjusting the pH value, adding a sodium carbonate solution to precipitate lithium, washing and drying to obtain battery-grade lithium carbonate; the concentration of the enriched lithium is 15-25 g/L, and the pH value is adjusted to 10-13; the temperature of the lithium deposition is 60-100 ℃, and the time is 2-5 h; the concentration of the sodium carbonate solution is 200-300 g/L;
3) reacting the water leaching residue with an acid solution and hydrogen peroxide to obtain a nickel-cobalt-manganese leaching solution; the acid solution in the step 3) is selected from a sulfuric acid solution, and the concentration of the sulfuric acid solution is 150-250 g/L; the concentration of hydrogen peroxide is 5-15 g/L; the reaction temperature of the water leaching residues, the acid solution and the hydrogen peroxide is 30-90 ℃, and the reaction time is 2-6 hours;
4) performing impurity extraction on impurity-removed liquid obtained after copper and aluminum removal procedures are performed on the nickel-cobalt-manganese leaching solution to obtain impurity-extracted liquid; performing organic extraction on cobalt, manganese and nickel in the impurity-extracted liquid to obtain organic phase, and performing saponification and back extraction to obtain pure cobalt sulfate, manganese sulfate and nickel sulfate solution; the extracting agent adopted for impurity extraction is P2O 4-sulfonated kerosene; extracting agent adopted for extracting cobalt and manganese is 25 vol% P5O7-75 vol% sulfonated kerosene or 20 vol% P5O7-80 vol% sulfonated kerosene, and extracting agent adopted for extracting nickel is 25 vol% P2O4-75 vol% sulfonated kerosene or 20 vol% P2O4-80 vol% sulfonated kerosene;
5) coprecipitating the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution with a sodium hydroxide solution and ammonia water, mixing the obtained precursor with lithium carbonate, sintering, and screening iron to obtain a ternary cathode material;
the mass ratio of nickel sulfate, cobalt sulfate and nickel, cobalt and manganese in the manganese sulfate solution in the step 5) is 5:2:3, 6:2:2 or 8:1: 1;
the concentration of the sodium hydroxide solution is 3.5-10 mol/L; the concentration of the ammonia water is 2-10 mol/L;
the sintering temperature is 500-1200 ℃.
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| CN111893319A (en) * | 2020-08-13 | 2020-11-06 | 衢州华友资源再生科技有限公司 | Method for extracting lithium from waste battery powder |
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