CN117317428A - Full-process recovery process of waste power battery - Google Patents
Full-process recovery process of waste power battery Download PDFInfo
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- CN117317428A CN117317428A CN202311383968.2A CN202311383968A CN117317428A CN 117317428 A CN117317428 A CN 117317428A CN 202311383968 A CN202311383968 A CN 202311383968A CN 117317428 A CN117317428 A CN 117317428A
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- lithium
- leaching
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- waste power
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000002699 waste material Substances 0.000 title claims abstract description 27
- 238000011084 recovery Methods 0.000 title claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000002386 leaching Methods 0.000 claims abstract description 67
- 239000000843 powder Substances 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 239000010413 mother solution Substances 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 62
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 26
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- 238000004804 winding Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- 230000001180 sulfating effect Effects 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 20
- 239000010941 cobalt Substances 0.000 abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000605 extraction Methods 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052748 manganese Inorganic materials 0.000 abstract description 8
- 239000011572 manganese Substances 0.000 abstract description 8
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 32
- 238000001914 filtration Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 125000005594 diketone group Chemical group 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010926 waste battery Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006115 defluorination reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 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 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000012826 global research Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of resource recovery, and discloses a full-process recovery process of a waste power battery. After the positive electrode powder is subjected to preferential lithium extraction, a nickel-cobalt-manganese mixed salt solution is obtained through simple leaching, copper removal, aluminum removal and fluorine removal processes, and can be used for directly synthesizing a precursor, and the yield of nickel, cobalt and manganese is high. Lithium in the mother solution is effectively recovered, and the lithium yield is effectively improved.
Description
Technical Field
The invention belongs to the technical field of resource recovery, and particularly relates to recovery of waste power batteries.
Background
With the increasing exhaustion of energy sources, lithium ion power batteries are becoming a hot spot for global research as one of the main power sources of new energy automobiles, but at the same time, environmental problems are also worrying. With the improvement of environmental protection consciousness, the harmfulness and recyclability of the waste batteries are gradually recognized, and the recycling of the waste batteries is widely concerned.
The recovery of the waste lithium ion power battery comprises the processes of battery disassembly, battery powder extraction and the like, wherein the battery disassembly is to crush and sort the waste battery by a mechanical physical method so as to realize the separation of each component in the battery and obtain the battery powder containing positive and negative electrode materials; the battery powder realizes the recovery of nickel, cobalt, manganese and lithium in the anode material through wet metallurgy processes such as leaching, purifying, extracting and the like.
At present, the battery is generally disassembled by directly crushing and sorting the battery to recycle each component, the obtained battery powder containing the anode and cathode materials enters a wet extraction process, each component is mutually entrained due to the roughness of the disassembly process, a large amount of impurity components are introduced into the battery powder, the metal yield is reduced, and meanwhile, the wet impurity removal process is also increased.
The recovery of nickel cobalt manganese lithium is realized by the battery powder containing the anode and cathode powder through a wet extraction process. The method mainly comprises two process routes of preferentially extracting lithium and extracting lithium from raffinate for lithium recovery. The method is characterized in that lithium is preferentially extracted, the lithium is firstly extracted by adopting a roasting-water leaching process to realize separation from nickel, cobalt and manganese, and the lithium carbonate is obtained by adopting sodium carbonate to precipitate lithium after water leaching liquid is purified. Extracting lithium from raffinate, namely extracting nickel, cobalt and manganese from the raffinate by adopting a leaching-purifying-extracting separation process. The preferential extraction of lithium and the extraction of lithium from raffinate can produce low-lithium high-sodium solution (mother solution after lithium carbonate precipitation and raffinate, wherein the lithium concentration is 2-3 g/L, and the sodium concentration is 60-80 g/L). The low-lithium high-sodium solution cannot directly adopt a carbonate lithium precipitation process, and generally adopts an MVR concentration post-precipitation lithium carbonate process or a process for preparing lithium phosphate by adopting trisodium phosphate direct precipitation. The adoption of MVR concentration low-lithium high-sodium solution for recycling lithium carbonate has the advantages of large investment, high cost, great loss (the lithium recycling rate in the low-lithium solution is only about 60 percent) due to the co-crystallization of lithium and sodium sulfate in the evaporation process, and low cost. The economic value of the lithium phosphate is relatively low, the lithium carbonate is further prepared, calcium salt, ferric salt, magnesium salt and the like are needed to be converted into a lithium-containing solution, phosphorus-containing waste residues are produced, a large amount of auxiliary materials are consumed, and meanwhile, the phosphorus-containing waste residues are byproduct, so that the disposal cost is increased.
For recovery of nickel, cobalt and manganese, due to different lithium recovery processes and different product types, battery powder is directly leached or water leaching residues after lithium extraction are leached, and then nickel sulfate, cobalt sulfate and manganese sulfate are obtained through complicated purification and extraction processes. The purification and extraction process generates a large amount of slag phase, consumes a large amount of auxiliary materials and generates a large amount of wastewater, so that the loss of nickel, cobalt and manganese reduces the metal yield, increases the production cost and reduces the economic benefit of battery recovery.
Disclosure of Invention
The invention aims to provide a full-process recovery process of waste power batteries, which has high economic benefit and simple treatment process.
In order to achieve the above object, the present invention provides the following specific technical solutions.
The invention provides a full-process recovery process of waste power batteries, which comprises the following steps:
finely disassembling the waste power battery to obtain a positive plate and a negative plate;
separating a current collector from positive electrode powder in the positive electrode plate;
sulfating and roasting the anode powder to obtain a sintered material;
leaching the sintered material with water to obtain leaching slag and lithium-containing solution;
leaching leached slag, and using the obtained leached slag for producing a precursor after copper removal, aluminum removal and fluorine removal;
removing fluorine, heavy metal ions and calcium from the lithium-containing solution, and precipitating lithium to obtain battery-grade lithium carbonate;
mixing a mother solution obtained by producing a precursor and a lithium precipitation mother solution, and extracting lithium to obtain a lithium-rich solution;
and depositing lithium in the lithium-rich solution to obtain the battery-grade lithium carbonate.
In a further preferred scheme, the fine disassembly process is as follows: and removing the shell of the battery, taking out the winding core, and reversing the winding core to obtain the positive plate, the negative plate and the diaphragm.
In a further preferred scheme, the current collector and the positive electrode powder in the positive electrode plate are separated by solvent soaking; the solvent is NMP (N-methylpyrrolidone) or DMF (dimethylformamide).
In a further preferred scheme, the auxiliary materials for sulfating roasting are at least one of ammonium sulfate, ammonium bisulfate, sulfuric acid, potassium bisulfate and sodium bisulfate.
In a further preferred scheme, the amount of auxiliary materials used in the sulfating roasting process is 1-2 times of the theoretical amount.
In a further preferred embodiment, the temperature of the sulfatizing roasting is 500-800 ℃.
In a further preferable scheme, the liquid-solid ratio of the water leached sintered material is 1-4 m 3 /t。
In a further preferred embodiment, the leaching residue is leached by a reducing acid leaching system, and the reducing agent is H 2 O 2 、Na 2 S 2 O 5 、Na 2 S 2 O 3 、Na 2 SO 3 One or two or more of them.
In a further preferred scheme, the auxiliary materials for copper removal are sodium thiosulfate and/or iron powder, and the copper removal temperature is more than or equal to 85 ℃.
In a further preferred embodiment, the process for removing aluminum comprises: at 85-95deg.C, adjusting pH of the aluminum material to be removed to 3.5-4.5 with one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide to remove aluminum.
In a further preferable scheme, resin is adopted for removing fluorine, the resin is Hp3500, and the pH value of the system during fluorine removal is 3-4.
In a further preferred scheme, the auxiliary materials for removing the heavy metal ions are at least one of liquid alkali, sodium carbonate and sodium bicarbonate, and the pH value of the system is 9-10 when the heavy metal ions are removed.
In a further preferred embodiment, the calcium is removed using a resin, hp4040.
In a further preferred scheme, the auxiliary materials for precipitating lithium are sodium carbonate, sodium bicarbonate and CO 2 At least one of them.
The invention has the following obvious beneficial effects:
according to the invention, the waste power batteries are finely disassembled, so that the anode material and the cathode material are effectively separated, the purity of the anode powder is relatively high, and the simplification of the subsequent process flow is facilitated.
The cathode powder can be prepared into the battery grade lithium carbonate through a short process of extracting lithium, removing fluorine, removing heavy metal ions, removing calcium and precipitating lithium by resin. After the positive electrode powder is subjected to preferential lithium extraction, a nickel-cobalt-manganese mixed salt solution is obtained through simple leaching, copper removal, aluminum removal and fluorine removal processes, and can be used for directly synthesizing a precursor, and the yield of nickel, cobalt and manganese is high.
Lithium in the mother solution is effectively recovered, and the lithium yield is effectively improved.
The valuable metal in the invention is effectively recovered, the yield is high, and the economic benefit is remarkable.
Drawings
Fig. 1 is a flow chart of a full-flow recovery process of the waste power battery provided by the invention.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The following examples are made mainly according to the flow chart shown in fig. 1.
Example 1
And removing the outer shell of the waste ternary lithium ion battery, taking out the winding core, and reversing the winding core to obtain the positive plate, the negative plate and the diaphragm. And soaking the positive plate with NMP to obtain aluminum foil and positive plate powder.
The content of a part of the element in the positive electrode powder was measured, and the results are shown in table 1.
TABLE 1 content of partial elements (wt%) in cathode powder
Roasting the positive electrode powder: 1000kg of sulfuric acid is added into 1000kg of positive electrode powder, and roasting is carried out for 2 hours at 650 ℃ to obtain a roasting material.
Water leaching roasting material: 2.4m is added into 1150kg of roasting material 3 And (3) leaching water at normal temperature for 2h by stirring to obtain leaching liquid I and leaching slag I.
The concentrations of the partial elements in the leaching solution I and the leaching residue I were analyzed, and the results are shown in tables 2 and 3.
TABLE 2 concentration of part of elements in leachate I
TABLE 3 content of part I element of leaching residue (wt%)
The leaching solution I is a lithium-containing solution. And respectively treating leaching liquid I and leaching slag I.
Treating leaching residue I:
600kg of leaching residue I is added to 2.5m 3 Adding 900kg sulfuric acid into water, reacting at 90deg.C for 2 hr, and adding H 2 O 2 2000kg, reacting for 2h to obtain leaching solution II.
The concentration of a part of the elements in the leachate II was analyzed and the results are shown in Table 4.
TABLE 4 concentration of partial elements in leachate II
Controlling the temperature of the leaching solution II at 90 ℃, adding 100kg of sodium thiosulfate, stirring and reacting for 2 hours, and filtering to obtain copper-removing slag and copper-removing liquid.
The solution after copper removal is further subjected to aluminum removal, and sodium carbonate is used for adjusting the pH value to be=4.0 at 90 ℃ to obtain aluminum removal slag and solution after aluminum removal.
And (3) passing the aluminum-removed liquid through Hp3500 fluorine-removing resin at a flow rate of 1BV to obtain the fluorine-removed liquid.
The concentration of a part of the element in the solution after the fluorine removal was measured, and the results are shown in Table 5.
TABLE 5 concentration of partial elements in the solution after defluorination
As is clear from the results of the measurements shown in Table 5, the recovery rates of nickel, cobalt and manganese in the defluorinated liquid were 99.3%, 99.3% and 99%, respectively.
The defluorinated liquid can be directly used for producing a precursor by a coprecipitation method.
Treating leaching liquid I:
and F, removing fluorine from the leaching solution I through Hp3500 resin at a flow rate of 1BV to obtain a fluorine-removed solution.
Adding sodium carbonate into the defluorinated liquid, regulating the pH value of the system to 10, and removing heavy metal ions to obtain a defluorinated liquid;
and (3) removing calcium from the solution after removing the weight through Hp4040 resin, wherein the flow rate is 1BV, and the solution after removing the calcium is obtained.
Adding sodium carbonate into the solution after calcium removal to precipitate lithium, thus obtaining lithium carbonate and lithium precipitation mother solution.
The purity of lithium carbonate was analyzed and the results are shown in table 6.
TABLE 6 impurity content (wt%) of lithium carbonate
It can be seen that the lithium carbonate obtained is battery grade lithium carbonate. The recovery rate of lithium was 94.5%.
The mother solution obtained by filtering after the precursor is produced can be further mixed with the lithium precipitation mother solution, and the lithium is extracted by adopting a diketone extractant to obtain a lithium-rich solution.
And returning the lithium-rich solution to the lithium precipitation process.
Example 2
And removing the outer shell of the waste ternary lithium ion battery, taking out the winding core, and reversing the winding core to obtain the positive plate, the negative plate and the diaphragm. And soaking the positive plate with NMP to obtain aluminum foil and positive plate powder.
The content of a part of the element in the positive electrode powder was measured, and the results are shown in table 7.
TABLE 7 content of partial elements (wt%) in cathode powder
Roasting the positive electrode powder: 1500kg of ammonium bisulfate is added into 1000kg of positive electrode powder, and the mixture is roasted for 3 hours at 500 ℃ to obtain a roasted material.
Water leaching roasting material: 1.2m is added into 1150kg of roasting material 3 And (3) leaching water under stirring at normal temperature for 4 hours to obtain leaching liquid I and leaching slag I.
The concentrations of the partial elements in the leaching solution I and the leaching residue I were analyzed, and the results are shown in tables 8 and 9.
TABLE 8 concentration of partial elements in leachate I
TABLE 9 content of partial elements in leached residue I (wt%)
The leaching solution I is a lithium-containing solution. And respectively treating leaching liquid I and leaching slag I.
Treating leaching residue I:
500kg of leaching residue is added into 2m 3 Adding 800kg sulfuric acid into water, reacting at 90deg.C for 2h, adding Na 2 S 2 O 5 2000kg, reacting for 2h to obtain leaching solution II.
The concentration of a part of the elements in the leachate II was analyzed and the results are shown in Table 10.
TABLE 10 concentration of partial elements in leachate II
Controlling the temperature of the leaching solution II at 90 ℃, adding 150kg of sodium thiosulfate, stirring and reacting for 2 hours, and filtering to obtain copper-removing slag and copper-removing liquid.
Further removing aluminum from the solution after copper removal, removing aluminum by sodium bicarbonate, wherein the aluminum removal temperature is 85 ℃, and the pH value is 3.5, so as to obtain aluminum removal slag and the solution after aluminum removal.
And (3) passing the aluminum-removed liquid through Hp3500 fluorine-removing resin at a flow rate of 1BV to obtain the fluorine-removed liquid.
The concentration of a part of the element in the solution after the fluorine removal was measured, and the results are shown in Table 11.
TABLE 11 concentration of partial elements in the defluorinated liquor
As is clear from the results of the measurements shown in Table 11, the recovery rates of nickel, cobalt and manganese in the defluorinated liquid were 99.2%, 99% and 99%, respectively.
The defluorinated liquid can be directly used for producing a precursor by a coprecipitation method.
Treating leaching liquid I:
and F, removing fluorine from the leaching solution I through Hp3500 resin at a flow rate of 1BV to obtain a fluorine-removed solution.
Adding sodium carbonate into the defluorinated liquid, regulating the pH value of the system to 10, and removing heavy metal ions to obtain a defluorinated liquid;
and (3) removing calcium from the solution after removing the weight through Hp4040 resin, wherein the flow rate is 1BV, and the solution after removing the calcium is obtained.
Adding sodium carbonate into the solution after calcium removal to precipitate lithium, thus obtaining lithium carbonate and lithium precipitation mother solution.
The purity of lithium carbonate was analyzed and the results are shown in table 12.
TABLE 12 impurity content (wt%) of lithium carbonate
It can be seen that the lithium carbonate obtained is battery grade lithium carbonate. The recovery rate of lithium was 93.1%.
The mother solution obtained by filtering after the precursor is produced can be further mixed with the lithium precipitation mother solution, and the lithium is extracted by adopting a diketone extractant to obtain a lithium-rich solution.
And returning the lithium-rich solution to the lithium precipitation process.
Example 3
And removing the outer shell of the waste ternary lithium ion battery, taking out the winding core, and reversing the winding core to obtain the positive plate, the negative plate and the diaphragm. And soaking the positive plate in DMF to obtain aluminum foil and positive plate powder.
The content of a part of the element in the positive electrode powder was measured, and the results are shown in table 13.
TABLE 13 content of partial elements (wt%) in cathode powder
Roasting the positive electrode powder: 2000kg of ammonium sulfate was added to 1000kg of the positive electrode powder, and the mixture was calcined at 800℃for 2 hours to obtain a calcined material.
Water leaching roasting material: adding 4m into 1150kg of roasting material 3 And (3) leaching water at normal temperature for 2h by stirring to obtain leaching liquid I and leaching slag I.
The concentrations of the partial elements in the leaching solution I and the leaching residue I were analyzed, and the results are shown in Table 14 and Table 15.
TABLE 14 concentration of part of elements in leachate I
TABLE 15 leaching residue I content (wt.%)
The leaching solution I is a lithium-containing solution. And respectively treating leaching liquid I and leaching slag I.
Treating leaching residue I:
400kg of leaching residue is added to 2.5m 3 Adding 700kg sulfuric acid into water, reacting at 90deg.C for 2H, and adding H 2 O 2 2000kg, reacting for 2h to obtain leaching solution II.
The concentrations of some elements in the leachate II were analyzed and the results are shown in Table 16.
TABLE 16 concentration of partial elements in leachate II
Controlling the temperature of the leaching solution II at 90 ℃, adding 100kg of iron powder, stirring and reacting for 2 hours, and filtering to obtain copper slag removal and copper removal liquid.
Further removing aluminum from the solution after copper removal, removing aluminum by sodium hydroxide, wherein the aluminum removal temperature is 95 ℃, and the pH value is 4.5, so as to obtain aluminum removal slag and the solution after aluminum removal.
And (3) passing the aluminum-removed liquid through Hp3500 fluorine-removing resin at a flow rate of 1BV to obtain the fluorine-removed liquid.
The concentration of a part of the element in the solution after the fluorine removal was measured, and the results are shown in Table 17.
TABLE 17 concentration of partial elements in the solution after defluorination
As is clear from the results of the measurements shown in Table 17, the recovery rates of nickel, cobalt and manganese in the defluorinated liquid were 99.1%, 99% and 99.1%, respectively.
The defluorinated liquid can be directly used for producing a precursor by a coprecipitation method.
Treating leaching liquid I:
and F, removing fluorine from the leaching solution I through Hp3500 resin at a flow rate of 1BV to obtain a fluorine-removed solution.
Adding sodium carbonate into the defluorinated liquid, regulating the pH value of the system to 10, and removing heavy metal ions to obtain a defluorinated liquid;
and (3) removing calcium from the solution after removing the weight through Hp4040 resin, wherein the flow rate is 1BV, and the solution after removing the calcium is obtained.
Adding sodium carbonate into the solution after calcium removal to precipitate lithium, thus obtaining lithium carbonate and lithium precipitation mother solution.
The purity of lithium carbonate was analyzed and the results are shown in table 18.
TABLE 18 impurity content (wt%) of lithium carbonate
It can be seen that the lithium carbonate obtained is battery grade lithium carbonate. The recovery rate of lithium was 93.48%.
The mother solution obtained by filtering after the precursor is produced can be further mixed with the lithium precipitation mother solution, and the lithium is extracted by adopting a diketone extractant to obtain a lithium-rich solution.
And returning the lithium-rich solution to the lithium precipitation process.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The full-process recovery process of the waste power battery is characterized by comprising the following steps of:
finely disassembling the waste power battery to obtain a positive plate and a negative plate;
separating the current collector from the positive electrode plate;
sulfating and roasting the positive electrode powder to obtain a sintered material;
leaching the sintering material with water to obtain leaching slag and lithium-containing solution;
leaching the leaching slag, and using the obtained leaching solution for producing a precursor after copper removal, aluminum removal and fluorine removal;
removing fluorine, heavy metal ions and calcium from the lithium-containing solution, and precipitating lithium to obtain battery-grade lithium carbonate;
mixing a mother solution obtained by producing a precursor and a lithium precipitation mother solution, and extracting lithium to obtain a lithium-rich solution;
and depositing lithium in the lithium-rich solution to obtain the battery grade lithium carbonate.
2. The full-process recycling process of waste power batteries according to claim 1, wherein the fine disassembly process is as follows: and removing the shell of the battery, taking out the winding core, and reversing the winding core to obtain the positive plate, the negative plate and the diaphragm.
3. The full-process recycling process of the waste power battery according to claim 1 or 2, wherein the current collector and the positive electrode waste in the positive electrode sheet are separated by solvent soaking;
preferably, the solvent is NMP or DMF.
4. The full-process recovery process of the waste power battery according to any one of claims 1 to 3, wherein the auxiliary materials for sulfating roasting are at least one of ammonium sulfate, ammonium bisulfate, sulfuric acid, potassium bisulfate and sodium bisulfate;
preferably, the temperature of the sulfatizing roasting is 500-800 ℃.
5. The full-process recovery process of the waste power battery according to any one of claims 1 to 4, wherein the liquid-solid ratio of the sintered material leached with water is 1 to 4m 3 /t。
6. The full-process recovery process for waste power batteries according to any one of claims 1 to 5, wherein the leaching system for leaching the leaching residue is a reducing acid leaching system, and the reducing agent is H 2 O 2 、Na 2 S 2 O 5 、Na 2 S 2 O 3 、Na 2 SO 3 One or two or more of them.
7. The full-process recycling process of the waste power battery according to claim 6, wherein the auxiliary materials for copper removal are sodium thiosulfate and/or iron powder;
preferably, the temperature of the copper removal is more than or equal to 85 ℃.
8. The full-process recycling process of waste power batteries according to claim 6, wherein said process for removing aluminum comprises: at 85-95deg.C, adjusting pH of the aluminum material to 3.5-4.5 with one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide.
9. The full-process recycling process of the waste power battery according to claim 1, wherein resin is adopted for removing fluorine, and the resin is Hp3500;
preferably, the pH value of the system is 3-4 during fluorine removal.
10. The full-process recycling process of waste power batteries according to claim 1, wherein the resin is used for removing calcium, and the resin is Hp4040.
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