CN110371943B - Selective recovery process of nickel cobalt lithium manganate and lithium iron phosphate mixed waste - Google Patents
Selective recovery process of nickel cobalt lithium manganate and lithium iron phosphate mixed waste Download PDFInfo
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- CN110371943B CN110371943B CN201910572470.8A CN201910572470A CN110371943B CN 110371943 B CN110371943 B CN 110371943B CN 201910572470 A CN201910572470 A CN 201910572470A CN 110371943 B CN110371943 B CN 110371943B
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- lithium
- iron phosphate
- nickel
- cobalt
- manganese
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 57
- 239000010812 mixed waste Substances 0.000 title claims abstract description 28
- 238000011084 recovery Methods 0.000 title claims abstract description 20
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- 238000002386 leaching Methods 0.000 claims abstract description 33
- 239000000706 filtrate Substances 0.000 claims abstract description 32
- 239000010941 cobalt Substances 0.000 claims abstract description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- 239000011572 manganese Substances 0.000 claims abstract description 18
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 13
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 11
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 11
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 7
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 6
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 3
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 28
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 23
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 230000001131 transforming effect Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 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 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 239000002699 waste material Substances 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 7
- TYIQHQFQWOZFMP-UHFFFAOYSA-E lithium cobalt(2+) iron(2+) manganese(2+) nickel(2+) triphosphate Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Ni+2].[Co+2].[Mn+2].[Li+].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] TYIQHQFQWOZFMP-UHFFFAOYSA-E 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910052742 iron Inorganic materials 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- DDXROPFGVVLFNZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) tricarbonate Chemical compound [Mn+2].[Co+2].C([O-])([O-])=O.[Ni+2].C([O-])([O-])=O.C([O-])([O-])=O DDXROPFGVVLFNZ-UHFFFAOYSA-H 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a selective recovery process of a mixed waste of nickel cobalt lithium manganate and lithium iron phosphate, which comprises the following steps: drying, crushing and sieving the mixed waste of the nickel cobalt lithium manganate and the lithium iron phosphate to obtain mixed powder; adding the mixed powder into an acid solution, adding a converting agent, carrying out acid leaching treatment, and filtering to obtain a ferro-phosphorus graphite residue and a nickel-cobalt-manganese-lithium iron phosphate filtrate respectively; adding a precipitator and a conversion agent into the nickel-cobalt-manganese-containing lithium iron phosphate filtrate, adjusting the pH value, and filtering to respectively obtain iron phosphate slag and nickel-cobalt-manganese-lithium-containing filtrate; adjusting the pH value of the filtrate containing nickel, cobalt, manganese and lithium, filtering to respectively obtain nickel, cobalt, manganese slag and a filtrate containing lithium, washing the nickel, cobalt and manganese slag with water, and drying to obtain nickel, cobalt, manganese carbonate or hydroxide; and adding sodium phosphate into the lithium-containing filtrate, extracting lithium, and filtering to obtain a lithium-precipitated solution and lithium phosphate respectively. The invention can selectively recycle the lithium iron phosphate waste containing nickel, cobalt and manganese, the leaching rate of lithium can reach 99 percent, and the leaching rate of nickel and manganese exceeds 95 percent.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery material recovery, and particularly relates to a selective recovery process of a mixed waste of nickel cobalt lithium manganate and lithium iron phosphate.
Background
Lithium iron phosphate (LiFePO4) has a stable structure, a long cycle life, environmental friendliness, abundant raw materials and low price, and is widely used as an anode active material of a lithium ion battery. With the lapse of time, an electric vehicle using a lithium iron phosphate battery is about to enter a large-scale scrapping stage, and it is expected that over 9000 tons of lithium iron phosphate batteries will enter the scrapping stage by 2021 years. Many of the waste lithium iron phosphate batteries are doped and modified by adding valuable metals such as nickel, cobalt, manganese and the like, and if the valuable metals are not treated, serious pollution is caused to the environment.
There are several methods reported for LiFePO4 waste treatment: (1) in patent CN106340692B (a method for cleanly recovering lithium in a cathode material), a lithium iron phosphate waste, a weak base, and water are mixed and reacted under carbon dioxide and heating conditions, and then solid-liquid separation is performed, after a lithium extraction solution is obtained, evaporation, solid-liquid separation, and drying are performed to obtain a lithium carbonate product, but the recovery rate of lithium in the waste is not high. (2) The invention patent CN 109193059a (a method for regenerating a lithium iron phosphate waste material) analyzes components of a lithium iron phosphate waste material, and then performs separation, component adjustment, preparation of a ferrous phosphate precursor, preparation of a lithium phosphate precursor, preparation of a mixed slurry, preparation of uncoated lithium iron phosphate, coating and sintering, to directly regenerate the material to obtain a lithium iron phosphate positive electrode material, but since the raw material contains aluminum and impurity removal processing is not performed, the regenerated lithium iron phosphate positive electrode material may contain some impurities, thereby affecting the performance of the material. (3) The invention patent CN108483418A (a lithium iron phosphate waste treatment process) adopts discharging, crushing and separating, alkali dissolving to remove aluminum, sulfuric acid leaching, phosphoric acid to precipitate iron to obtain battery-grade iron phosphate, and collects filtrate, adjusts pH value, adds urea to carry out heating reaction, filters, adds water to filter residue to prepare slurry, and introduces carbon dioxide to react until the pH value is 9, so as to obtain battery-grade lithium carbonate. The method realizes the recovery of phosphorus, iron and lithium, and the obtained product has high purity, but the process is complex, the steps are complicated, and the higher leaching rate is difficult to achieve. Most of the treated lithium iron phosphate waste materials in the current reports are pure lithium iron phosphate waste materials which are not doped, and few reports exist for treating mixed waste materials containing nickel, cobalt and manganese impurities.
Therefore, the development of a selective recovery process of the nickel cobalt lithium manganate and lithium iron phosphate mixed waste material with simple process and high recovery product purity is urgently needed.
Disclosure of Invention
The invention aims to provide a selective recovery process of a mixed waste of nickel cobalt lithium manganate and lithium iron phosphate, which has the advantages of simple process, recovered product purity, low pollution, low cost and higher economic benefit.
In order to achieve the purpose, the invention adopts the technical scheme that:
a selective recovery process of a mixed waste of nickel cobalt lithium manganate and lithium iron phosphate comprises the following steps:
(1) drying, crushing and sieving the mixed waste of the lithium nickel cobalt manganese oxide and the lithium iron phosphate to obtain mixed powder of the lithium nickel cobalt manganese oxide and the lithium iron phosphate;
(2) pouring mixed powder of the nickel cobalt lithium manganate and the lithium iron phosphate into an acid solution, adding a converting agent, carrying out acid leaching treatment, and filtering to respectively obtain ferrophosphorus graphite slag and a lithium iron phosphate filtrate containing nickel cobalt manganese;
(3) adding a precipitator and a conversion agent into the nickel-cobalt-manganese-containing lithium iron phosphate filtrate, adding an alkaline material to adjust the pH to 3-5, and filtering to respectively obtain iron phosphate slag and nickel-cobalt-manganese-lithium-containing filtrate;
(4) adjusting the pH value of the filtrate containing nickel, cobalt, manganese and lithium to 9-12, filtering to respectively obtain nickel, cobalt and manganese washing slag and a lithium-containing filtrate, and then washing and drying the nickel, cobalt and manganese washing slag to obtain nickel, cobalt and manganese carbonate or hydroxide;
(5) and adding sodium phosphate into the lithium-containing filtrate, extracting lithium, and filtering to obtain a lithium-precipitated solution and lithium phosphate respectively.
Preferably, in the step (1), the drying is to dry the mixed waste of lithium nickel cobalt manganese oxide and lithium iron phosphate until the water content is less than or equal to 1.0 wt%.
Preferably, in the step (2), the acid solution is selected from one or both of sulfuric acid and hydrochloric acid.
Preferably, in step (2), H of the acid solution+The dosage of the lithium is 1.2 to 6.2 times of the molar weight of lithium in the raw materials, and H of the used acid+The concentration is 0.5-4mol/L, and the mass ratio of the acid solution to the mixed powder is3-10:1。
Preferably, in the step (2), the acid leaching treatment is carried out at 30-90 ℃ for 1-5 hours.
Preferably, in the step (2), the converting agent is one or more selected from hydrogen peroxide, sodium chlorate, sodium hypochlorite, potassium chlorate, sodium perchlorate and hypochlorous acid.
Preferably, in the step (2), the conversion agent is added in a molar amount of 0.1 to 1.5 times the molar amount of lithium in the raw material.
Preferably, in the step (2), the conversion agent is added in a dropwise manner, and the dropwise addition time is 0-45 min.
Preferably, in the step (3), the precipitant is one or more of ferrous sulfate, ferrous chloride, ferric chloride and ferric sulfate.
Preferably, in the step (3), the amount of the precipitant is 1.0-3.0 times of the molar weight of the phosphorus in the solution; the dosage of the transforming agent is 1.0 to 5.0 times of the molar weight of the added precipitator; the temperature of adding the precipitant is 60-80 ℃.
Preferably, in the step (3), the alkaline material is one or more of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
Preferably, in the step (5), the amount of the sodium phosphate is 1.0 to 5.0 times of the molar amount of the lithium in the solution.
Preferably, in the step (5), the lithium extraction is carried out at 70-95 ℃ for 1-5 h.
The beneficial technical effects of the invention are as follows:
(1) the process can selectively recover the lithium iron phosphate waste containing nickel, cobalt and manganese, the leaching rate of lithium can reach more than 99 percent, the leaching rate of nickel and manganese exceeds 95 percent, the leaching rate of cobalt exceeds 92 percent, the leaching rate of phosphorus is less than 2 percent, the leaching rate of iron is less than 0.5 percent, and the selective recovery of valuable metals can be achieved.
(2) The method has the advantages of simple process flow, simple and convenient operation, little pollution, lower requirement on equipment, higher product value and good economic benefit.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail by examples below. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention.
Example 1
A process for selectively recovering mixed waste of lithium nickel cobalt manganese oxide and lithium iron phosphate comprises the following steps:
(1) drying the mixed waste of the lithium nickel cobalt manganese oxide and the lithium iron phosphate until the water content is less than or equal to 1.0 wt%, crushing, and sieving to obtain mixed powder of the lithium nickel cobalt manganese oxide and the lithium iron phosphate;
(2) 62.74g (0.628mol, 1.25 times of the molar weight of lithium in the raw material) of concentrated sulfuric acid is weighed and poured into 593.6mL of water under stirring to prepare a 1mol/L sulfuric acid solution;
(3) weighing 120.0g of mixed powder of nickel cobalt lithium manganate and lithium iron phosphate, pouring the mixed powder into the sulfuric acid prepared in the step (2), placing a beaker filled with the materials into a water bath kettle at 85 ℃, and starting stirring, wherein the liquid-solid ratio of acid to the materials in the reaction is 6.277: 1;
(4) 57.12g (1.0 time of the molar weight of lithium in the raw material) of 30% hydrogen peroxide solution is weighed, the hydrogen peroxide is slowly dripped into the reaction system in the step (3) by a dropper, the dripping is finished within 30min, the reaction time is calculated from the beginning of the dripping of the hydrogen peroxide, and the reaction is carried out for 4h, so as to obtain the material;
(5) filtering the material obtained after the reaction in the step (4), wherein the filtrate is a leachate containing nickel, cobalt, manganese and lithium, contains part of phosphorus and iron impurities, and has a volume of 572.0mL, and the filter residue is mixed leaching residue of acid-leaching insoluble substances and iron phosphate in the raw materials, and has a mass of 99.6 g;
(6) measuring contents of nickel, cobalt, manganese, lithium, phosphorus and iron in the leaching solution, washing the leaching residue with water for 5 times, oven drying, accurately weighing 1.00g of oven dried leaching residue, and adding aqua regia (HCl: HNO)31: 3), metering the volume to 250mL, filtering, measuring the contents of phosphorus, iron, nickel, cobalt, manganese and lithium in the slag solution, and calculating the leaching rate;
(7) 2.276g (2.0 times of the molar weight of phosphorus in the solution) of ferrous sulfate heptahydrate solid is added into the leachate at the temperature of 80 ℃ under stirring, 0.872g of sodium chlorate (1 time of the molar weight of the added ferrous sulfate) is added, the pH value is adjusted to 4.0 by using a sodium hydroxide solution, phosphorus and iron impurities are removed by filtering, the pH value of the filtrate is adjusted to 12 by continuously adding a sodium hydroxide solution, the filtrate is filtered, the filter residue is nickel-cobalt-manganese hydroxide, the filtrate is washed by water and dried to obtain 19.70g, 81.93g of sodium phosphate (1.0 time of the molar weight of lithium in the solution) is added into the filtrate at the temperature of 90 ℃, the lithium phosphate product is obtained by filtering after 4 hours of reaction, and the dried lithium phosphate product has the mass of.
The calculation results of the components in example 1 are shown in the following table 1:
TABLE 1 calculation results of the ingredients in example 1
Example 2
A process for selectively recovering mixed waste of lithium nickel cobalt manganese oxide and lithium iron phosphate comprises the following steps:
(1) drying the mixed waste of the lithium nickel cobalt manganese oxide and the lithium iron phosphate until the water content is less than or equal to 1.0 wt%, crushing, and sieving to obtain mixed powder of the lithium nickel cobalt manganese oxide and the lithium iron phosphate;
(2) 136.27g (1.387mol, 3 times of the molar weight of lithium in the raw material) of concentrated hydrochloric acid is weighed and poured into 577.03mL of water to prepare 2mol/L hydrochloric acid solution;
(3) weighing 100g of mixed powder of nickel cobalt lithium manganate and lithium iron phosphate, pouring the mixed powder into prepared hydrochloric acid, placing a beaker filled with the materials into a 75 ℃ water bath kettle, and starting stirring, wherein the liquid-solid ratio of acid to the materials in the reaction is 6.935: 1;
(4) weighing 41.92g (0.8 time of the molar weight of lithium in the raw material) of 30% hydrogen peroxide solution, slowly dripping the hydrogen peroxide into the reaction system in the step (3) by using a dropper, finishing dripping within 30min, calculating the reaction time from the beginning of dripping the hydrogen peroxide, and reacting for 3h to obtain a material;
(5) filtering the material obtained by the reaction in the step (4), wherein the filtrate is a leaching solution containing nickel, cobalt, manganese, lithium and part of phosphorus and iron, the volume of the leaching solution is 550.0mL, and the filter residue is mixed leaching residue of acid-leaching insoluble substances and iron phosphate in the raw materials, and the mass of the mixed leaching residue is 82.2 g;
(6) measuring the contents of nickel, cobalt, manganese, lithium, phosphorus and iron in a leaching solution, washing leaching residues for 5 times, drying, accurately weighing 1.00g, dissolving the residues with aqua regia (HCl: HNO3 ═ 3:1), fixing the volume to 250mL, filtering, measuring the contents of phosphorus, iron, nickel, cobalt, manganese and lithium in the residue solution, and calculating the leaching rate;
(7) adding 5.70g (5 times of the molar weight of phosphorus in the solution) of ferrous sulfate heptahydrate solid into the leachate at 75 ℃ under stirring, adding 1.75g (0.8 time of the molar weight of ferrous ions) of sodium chlorate solid, adjusting the pH to 4.0 by using a sodium hydroxide solution, filtering to remove phosphorus and iron impurities, adding a sodium hydroxide solution into the filtrate to adjust the pH to 12, filtering, wherein filter residues are nickel-cobalt-manganese hydroxides, washing with water, the mass of residues is 14.46g, adding 75.14g of sodium phosphate (1.0 time of the molar weight of lithium in the solution) into the filtrate at 95 ℃, reacting for 3 hours, filtering to obtain a sodium phosphate product, and drying to obtain 17.70g of the sodium phosphate product.
The calculation results of the components in example 2 are shown in the following table 2:
TABLE 2 calculation results of the ingredients of example 2
Example 3
A process for selectively recovering mixed waste of lithium nickel cobalt manganese oxide and lithium iron phosphate comprises the following steps:
(1) drying the mixed waste of the lithium nickel cobalt manganese oxide and the lithium iron phosphate until the water content is less than or equal to 1.0 wt%, crushing, and sieving to obtain mixed powder of the lithium nickel cobalt manganese oxide and the lithium iron phosphate;
(2) 31.4g (0.314mol, 1.15 times of the molar weight of lithium in the raw material) of concentrated sulfuric acid is weighed and poured into 296.7mL of water to prepare 1mol/L sulfuric acid solution;
(3) 60g of mixed powder of nickel cobalt lithium manganate and lithium iron phosphate is weighed and poured into prepared sulfuric acid, a beaker filled with the materials is placed in a water bath kettle at 90 ℃, stirring is started, and the liquid-solid ratio of acid to the materials in the reaction is 5.23: 1;
(4) weighing 18.42g (0.6 times of the molar weight of lithium in the raw material) of 30% hydrogen peroxide solution, slowly dripping the hydrogen peroxide into the reaction system in the step (3) by using a dropper, finishing dripping within 30min, calculating the reaction time from the beginning of dripping the hydrogen peroxide, and reacting for 5 h;
(5) filtering the materials obtained by the reaction in the step (4), wherein the filtrate is a leachate containing nickel, cobalt, manganese, lithium and a small amount of phosphorus and iron, the volume of the leachate is 285.0mL, and the filter residue is a mixed leaching residue of insoluble substances in the raw materials and the iron phosphate, and the mass of the mixed leaching residue is 51.7 g;
(6) measuring contents of nickel, cobalt, manganese, lithium, phosphorus and iron in the leaching solution, washing the leaching residue with water for 5 times, oven drying, weighing 1.00g, and adding aqua regia (HCl: HNO)31: 3), dissolving slag, fixing the volume to 250mL, filtering, measuring the contents of phosphorus, iron, nickel, cobalt, manganese and lithium in the slag solution, and calculating the leaching rate;
(7) adding 0.736g (1.5 times of the molar weight of phosphorus in the solution) of ferrous sulfate heptahydrate solid into the leachate at 60 ℃ under stirring, adding 20mL of 30% hydrogen peroxide, adjusting the pH to 4.5 by using a sodium hydroxide solution, filtering to remove phosphorus and iron impurities, adding a sodium carbonate solution into the filtrate to adjust the pH to 9-10 after filtering, wherein filter residues are nickel-cobalt-manganese carbonate products, washing the filter residues with water for multiple times, measuring the content of nickel, cobalt and manganese in the filtrate, calculating the precipitation rate, adding 44.56g of sodium phosphate (1 time of the molar weight of lithium in the solution) into the filtrate at 85 ℃, reacting for 5 hours, filtering to obtain a sodium phosphate product, and drying to obtain 10.60 g.
The calculation results of the components in example 3 are shown in the following table 3:
TABLE 3 calculation results for the ingredients of example 3
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A selective recovery process of a mixed waste of nickel cobalt lithium manganate and lithium iron phosphate is characterized by comprising the following steps:
(1) drying, crushing and sieving the mixed waste of the lithium nickel cobalt manganese oxide and the lithium iron phosphate to obtain mixed powder of the lithium nickel cobalt manganese oxide and the lithium iron phosphate;
(2) adding the mixed powder of the nickel cobalt lithium manganate and the lithium iron phosphate into an acid solution, adding a converting agent, carrying out acid leaching treatment, and filtering to respectively obtain a ferrophosphorus graphite residue and a lithium iron phosphate filtrate containing nickel cobalt manganese;
(3) adding a precipitator and a conversion agent into the nickel-cobalt-manganese-containing lithium iron phosphate filtrate, adding an alkaline material to adjust the pH value to 3-5, and filtering to respectively obtain iron phosphate slag and nickel-cobalt-manganese-lithium-containing filtrate;
(4) adjusting the pH value of the filtrate containing nickel, cobalt, manganese and lithium to 9-12, filtering to respectively obtain nickel, cobalt, manganese slag and a filtrate containing lithium, and then washing and drying the nickel, cobalt, manganese slag to obtain nickel, cobalt, manganese carbonate or hydroxide;
(5) adding sodium phosphate into the lithium-containing filtrate, extracting lithium, and filtering to respectively obtain a lithium-precipitated solution and lithium phosphate; in the step (3), the transforming agent is one or more selected from hydrogen peroxide, sodium chlorate, sodium hypochlorite, potassium chlorate, sodium perchlorate and hypochlorous acid; the precipitator is one or more of ferrous sulfate, ferrous chloride, ferric chloride and ferric sulfate.
2. The selective recycling process of lithium nickel cobalt manganese oxide and lithium iron phosphate mixed waste material according to claim 1, characterized in that in the step (1), the drying is to dry the lithium nickel cobalt manganese oxide and lithium iron phosphate mixed waste material until the water content is less than or equal to 1.0 wt%.
3. The selective recovery process of lithium nickel cobalt manganese oxide and lithium iron phosphate mixed waste material according to claim 1, characterized in that, in the step (2), the acid solution is selected from one or two of sulfuric acid and hydrochloric acid.
4. The selective recovery process of lithium nickel cobalt manganese oxide and lithium iron phosphate mixed waste material according to claim 1 or 3, characterized in that in the step (2), H in the acid solution+The amount of the acid is 1.2 to 6.2 times of the molar amount of lithium in the raw material, and H of the acid is used+The concentration is 0.5-4mol/L, and the mass ratio of the acid solution to the mixed powder is 3-10: 1.
5. The selective recovery process of lithium nickel cobalt manganese oxide and lithium iron phosphate mixed waste material according to claim 1 or 3, characterized in that, in the step (2), the acid leaching treatment is carried out at 30-90 ℃ for 1-5 hours.
6. The selective recovery process of lithium nickel cobalt manganese oxide and lithium iron phosphate mixed waste material according to claim 1, characterized in that, in the step (2), the amount of the conversion agent is 0.1-1.5 times of the molar amount of lithium in the raw material.
7. The selective recovery process of lithium nickel cobalt manganese oxide and lithium iron phosphate mixed waste material according to claim 1, characterized in that, in the step (3), the amount of the precipitant is 1.0-3.0 times of the molar weight of phosphorus in the solution; the dosage of the transforming agent is 1.0 to 5.0 times of the molar weight of the added precipitator; the temperature of adding the precipitant is 60-80 ℃.
8. The selective recovery process of lithium nickel cobalt manganese oxide and lithium iron phosphate mixed waste material according to claim 1, characterized in that, in the step (5), the amount of the sodium phosphate is 1.0-5.0 times of the molar amount of lithium in the lithium-containing filtrate.
9. The selective recovery process of lithium nickel cobalt manganese oxide and lithium iron phosphate mixed waste material according to claim 1, characterized in that, in the step (5), the lithium extraction is carried out at 70-95 ℃ for 1-5 h.
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| CN112342383B (en) * | 2020-09-17 | 2022-08-12 | 湖北金泉新材料有限公司 | Separation and recovery method of nickel, cobalt, manganese and lithium in ternary waste |
| CN113809424B (en) * | 2021-08-25 | 2023-05-05 | 广东邦普循环科技有限公司 | Recovery method of nickel cobalt lithium manganate and lithium iron phosphate mixed waste |
| CN114597399B (en) * | 2022-02-15 | 2024-10-18 | 广东邦普循环科技有限公司 | Preparation method and application of sodium vanadium phosphate material |
| CN115321502A (en) * | 2022-08-01 | 2022-11-11 | 广西埃索凯循环科技有限公司 | Comprehensive recovery process for waste lithium iron phosphate battery and nickel-cobalt-manganese ternary battery |
| CN115367725B (en) * | 2022-08-29 | 2024-05-10 | 广东邦普循环科技有限公司 | Doped lithium iron phosphate and preparation method and application thereof |
| CN116375022B (en) * | 2023-04-06 | 2025-02-07 | 骆驼集团资源循环襄阳有限公司 | A method for recovering graphite powder from waste lithium batteries |
| CN116581413B (en) * | 2023-05-22 | 2023-10-13 | 甘肃睿思科新材料有限公司 | Method for jointly recovering lithium, cobalt, iron and phosphorus from waste lithium iron phosphate and waste lithium cobaltate |
| CN116902999A (en) * | 2023-05-31 | 2023-10-20 | 广东盛祥新材料科技有限公司 | Ternary powder/lithium iron powder/lithium carbonate processing method and waste battery recycling method |
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