CN114906863A - Comprehensive recovery method of waste lithium manganate cathode material - Google Patents
Comprehensive recovery method of waste lithium manganate cathode material Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000011084 recovery Methods 0.000 title claims abstract description 42
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- 239000010406 cathode material Substances 0.000 title claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 68
- 238000002425 crystallisation Methods 0.000 claims abstract description 63
- 230000008025 crystallization Effects 0.000 claims abstract description 63
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 60
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 60
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 60
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 51
- 239000012535 impurity Substances 0.000 claims abstract description 35
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 34
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 31
- 239000011572 manganese Substances 0.000 claims abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 26
- 239000012452 mother liquor Substances 0.000 claims abstract description 26
- 238000002386 leaching Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000010413 mother solution Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 239000007774 positive electrode material Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000012629 purifying agent Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 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
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009388 chemical precipitation Methods 0.000 abstract description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 abstract description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 abstract description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 12
- 238000001953 recrystallisation Methods 0.000 description 10
- 238000003825 pressing Methods 0.000 description 9
- 239000010405 anode material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- -1 iron and the like Chemical class 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
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 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 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a comprehensive recovery method of a waste lithium manganate battery cathode material, which takes the waste lithium manganate cathode material as a raw material and comprises the steps of sequentially leaching anode black powder, chemically removing impurities from a leaching solution, crystallizing and separating an impurity-removed solution, recrystallizing crude manganese sulfate to prepare battery-grade manganese sulfate, crystallizing and separating a mother solution to prepare battery-grade lithium carbonate and the like. According to the invention, separation and recovery of lithium and manganese can be realized without adopting chemical precipitation separation and extraction processes, manganese is preferentially separated out in a crystallization mode through a high-temperature pressurization crystallization separation method from the leaching solution containing manganese and lithium, and battery-grade manganese sulfate is prepared, lithium still remains in the mother liquor in the form of lithium sulfate, and the crystallized mother liquor is further precipitated and recovered to prepare battery-grade lithium carbonate. The process method has the advantages of high recovery rate of valuable metal lithium manganese, simple process, short flow, low production cost, environmental protection, high added value of products and the like.
Description
Technical Field
The invention relates to the technical field of waste cathode material recovery, in particular to a comprehensive recovery method of a waste lithium manganate cathode material.
Background
In recent years, the electric automobile industry in China is rapidly developed, and the sales volume of electric automobiles is increasing day by day. However, the average service life of the power battery in the electric automobile is about 10 years, and the electric automobile which enters the market at an early stage has already entered the battery retirement stage at present. 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, ternary lithium batteries, lithium titanate batteries, lithium manganate batteries and the like according to different anode materials, and lithium manganate batteries are increasingly emphasized by virtue of the advantages of good rate performance, easiness in preparation, low cost and the like. At present, the price of metal raw materials such as lithium, manganese and the like for preparing a ternary cathode material or a lithium manganate cathode material is high and the demand is large. Therefore, the method for extracting metals such as lithium, manganese and the like from the waste lithium batteries can solve the problem of raw material supply and create great benefit for the society.
The key link of the recovery of the lithium manganate anode material is to separate and purify lithium and manganese in the lithium manganate anode material, and then further prepare related lithium salt and manganese salt. According to the Chinese patent with the application number of 201710380170.0, the lithium manganate positive electrode material obtained by disassembly is added with organic acid for reduction leaching, lithium is extracted from the leaching solution through a phosphoric acid extractant, and the back extraction solution is added with carbonate to prepare lithium carbonate. The method adopts organic acid leaching, so that the leaching rate of valuable metals is low, and the difficulty and the cost of later-stage wastewater treatment are higher; meanwhile, the lithium is extracted from the manganese-containing lithium leaching solution by the extractant, so that the selectivity is poor, the extraction efficiency is low, and the production cost is high. The Chinese patent with the application number of 201811093693.8 utilizes a nanofiltration membrane technology to separate lithium ions from other cations different from the lithium ions in the acidified leachate to obtain a lithium-containing solution and a solution containing other cations, and then adopts a reverse osmosis technology to concentrate and enrich the lithium-containing solution and the solution containing other cations respectively; the process has the advantages of low lithium separation efficiency, large water consumption and low lithium enrichment concentration, so the recovery process is long and the cost is high. The Chinese patent with the application number of 202110677455.7 puts the pretreated lithium manganate anode material into inorganic acid, and after high-pressure reaction, alpha-MnO is obtained 2 Or beta-MnO 2 Or gamma-MnO 2 Thereby preparing MnO with larger specific surface area and porous structure 2 The product can be further used for battery anode materials andand (3) super capacitor electrode material. Although the method can well realize the recycling of the lithium manganate cathode material, impurity ions are difficult to control in the treatment process, and the obtained material is not stable enough in performance and is not suitable for wide popularization and application.
In conclusion, the existing waste lithium manganate positive electrode material recovery process has the problems of low recovery rate of valuable metals, long process flow, low production efficiency, high recovery treatment cost, low added value of products and the like.
Disclosure of Invention
The invention aims to provide a comprehensive recovery method of waste lithium manganate cathode materials, which can recover battery-grade manganese sulfate and battery-grade lithium carbonate and has high recovery rate.
In view of this, the application provides a comprehensive recovery method of waste lithium manganate cathode material, comprising the following steps:
A) mixing the waste lithium manganate positive electrode material with water to obtain slurry, and carrying out reduction leaching on the slurry to obtain leachate;
B) adding an impurity removing agent into the leachate for removing impurities, and then adding an oxidant to obtain an impurity-removed solution;
C) carrying out high-temperature crystallization on the impurity-removed solution, and carrying out centrifugal separation to obtain a crude manganese sulfate crystal and a lithium-containing crystallization mother solution;
D) dissolving the crude manganese sulfate crystals, then carrying out high-temperature crystallization again, and carrying out centrifugal separation to obtain refined manganese sulfate crystals and crystallization mother liquor;
E) drying the refined manganese sulfate crystal to obtain battery-grade manganese sulfate, adding a purifying agent into the lithium-containing crystal mother liquor, and reacting to obtain a lithium-containing purified liquid;
F) and precipitating lithium from the lithium-containing purified solution to obtain a lithium carbonate wet material and a lithium precipitation mother solution, and washing and drying the lithium carbonate wet material to obtain the battery-grade lithium carbonate.
Preferably, in the step a), the reagents for reduction leaching are sulfuric acid and a reducing agent, the sulfuric acid is 98% concentrated sulfuric acid, the pH of the system is adjusted to 0.5-3.0, and the reducing agent is one or more selected from hydrogen peroxide, sodium sulfite and sodium thiosulfate.
Preferably, in the step A), the liquid-solid ratio of the water to the waste lithium manganate positive electrode material is 2: 1-5: 1.
Preferably, in step B), the impurity removing agent is one or more selected from sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium hydroxide and ammonia water, and the oxidant is one or more selected from hydrogen peroxide, sodium chlorate and sodium hypochlorite.
Preferably, in step C), the high-temperature crystallization process specifically comprises:
and (3) pouring the impurity-removed solution into a crystallization reaction kettle for high-temperature crystallization, and when the manganese concentration reaches 80-120 g/L, performing centrifugal separation on the obtained crystallization slurry to obtain rough manganese sulfate crystals and lithium-containing crystallization mother liquor.
Preferably, in the step C), the temperature of the high-temperature crystallization is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and the time is 1-3 h.
Preferably, the high-temperature crystallization in step D) is specifically:
and adding the crude manganese sulfate crystals into pure water for dissolving, pumping into a crystallization reaction kettle again for high-temperature crystallization, and performing centrifugal separation when the manganese concentration reaches 80-120 g/L to obtain refined manganese sulfate crystals and crystallization mother liquor.
Preferably, in the step D), the temperature of the high-temperature crystallization is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and the time is 1-3 h.
Preferably, in the step E), the purifying agent is selected from one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia water, the concentration of the purifying agent is 5-30%, the pH value of the reaction is 10.0-12.0, and the reaction time is 0.5-1 h.
Preferably, the lithium precipitating reagent is a sodium carbonate solution with the concentration of 200-300 g/L, the reaction temperature of lithium precipitation is 50-100 ℃, and the time is 1-5 h.
The comprehensive recovery method of the waste lithium manganate positive electrode material is characterized in that the waste lithium manganate positive electrode material is used as a recovery object, and comprehensive recovery of lithium and manganese can be realized through steps of reduction leaching of positive electrode black powder, chemical impurity removal of leachate, crystallization separation of impurity removal liquid, recrystallization preparation of battery-grade manganese sulfate by crude manganese sulfate, preparation of battery-grade lithium carbonate by crystallization separation mother liquor and the like; the recovery method does not need the traditional extraction process and the chemical precipitation separation process, and the separation and recovery of lithium and manganese are realized by utilizing the difference of the solubility of manganese sulfate and lithium sulfate along with the change of temperature; the method has the advantages of simple and stable process, high production efficiency, low production cost, zero discharge of wastewater and the like, is easy to realize industrial production, has high recovery rate of valuable metals manganese and lithium, and has excellent quality of the prepared manganese sulfate and lithium carbonate and extremely high production benefit.
Drawings
Fig. 1 is a schematic flow chart of a comprehensive recovery method of waste lithium manganate positive electrode materials provided by the invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the technical problems of the recovery processing of the waste lithium manganate positive electrode material in the prior art, the application provides a comprehensive recovery method of the waste lithium manganate positive electrode material, which comprises the steps of carrying out reduction leaching on the waste lithium manganate positive electrode material, adding a precipitant into a leachate to remove impurities such as copper, iron and aluminum, carrying out crystallization separation on manganese and lithium by the impurity-removing solution under the high-temperature condition, carrying out recrystallization on crude manganese sulfate to prepare battery-grade manganese sulfate, and carrying out crystallization separation on a mother liquor to prepare battery-grade lithium carbonate, wherein the flow is shown in fig. 1; through a series of operations, high-quality manganese sulfate and lithium carbonate can be prepared. Specifically, the embodiment of the invention discloses a comprehensive recovery method of a waste lithium manganate positive electrode material, which comprises the following steps:
A) mixing the waste lithium manganate positive electrode material with water to obtain slurry, and carrying out reduction leaching on the slurry to obtain leachate;
B) adding an impurity removing agent into the leachate for removing impurities, and then adding an oxidant to obtain an impurity-removed solution;
C) carrying out high-temperature crystallization on the impurity-removed solution, and carrying out centrifugal separation to obtain a crude manganese sulfate crystal and a lithium-containing crystallization mother solution;
D) dissolving the crude manganese sulfate crystals, then performing high-temperature crystallization again, and performing centrifugal separation to obtain refined manganese sulfate crystals and crystallization mother liquor;
E) drying the refined manganese sulfate crystal to obtain battery-grade manganese sulfate, adding a purifying agent into the lithium-containing crystal mother liquor, and reacting to obtain a lithium-containing purified liquid;
F) and precipitating lithium from the lithium-containing purified solution to obtain a lithium carbonate wet material and a lithium precipitation mother solution, and washing and drying the lithium carbonate wet material to obtain the battery-grade lithium carbonate.
In the comprehensive recovery method of the waste lithium manganate positive electrode material, firstly, reduction leaching is carried out, namely, the waste lithium manganate positive electrode material is mixed with water to obtain slurry, and then the slurry is subjected to reduction leaching to obtain leachate; in the process, manganese in the waste lithium manganate positive electrode material is reduced and leached under the action of a reducing agent. The reagent for reduction leaching is sulfuric acid and a reducing agent, the sulfuric acid is 98% concentrated sulfuric acid, the pH of the system is adjusted to 0.5-3.0, and the reducing agent is selected from one or more of hydrogen peroxide, sodium sulfite and sodium thiosulfate; in a specific embodiment, the reducing agent is selected from sodium sulfite or sodium thiosulfate, and the pH of the system is adjusted to 0.5-2.0. The liquid-solid ratio of the water to the waste lithium manganate positive electrode material is 2: 1-5: 1, and more specifically, the liquid-solid ratio of the water to the waste lithium manganate positive electrode material is 3: 1-4: 1. The temperature of the reduction leaching is 50-100 ℃, and the time is 1-5 h; more specifically, the temperature of the reduction leaching is 60-80 ℃, and the time is 2-4 hours.
Chemical impurity removal is carried out, an impurity removing agent is added into the leachate for impurity removal so as to remove impurities such as copper, iron, aluminum and the like in the leachate, an oxidant is added, and the leachate after impurity removal is obtained after stirring and filter pressing; in the process, the impurity removing agent is selected from one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium hydroxide and ammonia water, and the oxidant completely oxidizes impurity ions such as iron and the like, and is specifically selected from one or more of hydrogen peroxide, sodium chlorate and sodium hypochlorite.
According to the invention, carrying out high-temperature crystallization of manganese sulfate on the obtained solution after impurity removal in a crystallization reaction kettle, preferably, when the manganese concentration reaches 80-120 g/L, putting the crystallization slurry into a centrifuge for centrifugal separation to obtain rough manganese sulfate crystals and lithium-containing crystallization mother liquor; wherein the crude manganese sulfate crystal is used for preparing battery-grade manganese sulfate, and the lithium-containing crystallization mother liquor is used for preparing lithium carbonate; in the process, the solution after impurity removal contains manganese, and the manganese is separated in a crystallization mode in the high-temperature crystallization process. And adding the rough manganese sulfate crystals into pure water for dissolving, stirring and dissolving, then pumping into a crystallization reaction kettle again for high-temperature crystallization of manganese sulfate, when the manganese concentration reaches 80-120 g/L, putting the crystallized slurry into a centrifuge for centrifugal separation to obtain refined manganese sulfate crystals and recrystallization mother liquor, drying the refined manganese sulfate crystals to obtain a battery-grade manganese sulfate product, and returning the recrystallization mother liquor to the first step for size mixing. In the process, the temperature of the high-temperature crystallization is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and the time is 1-3 h; more specifically, the temperature of the high-temperature crystallization is 120-180 ℃, the reaction pressure is 0.2-0.4 MPa, and the time is 1.5-2.5 h.
The application then adds a purifying agent into the lithium-containing crystallization mother liquor, and obtains a lithium-containing purified liquor after reaction. In the process, the purifying agent is selected from one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia water, the concentration of the purifying agent is 5-30%, the pH value of the reaction is 10.0-12.0, and the reaction time is 0.5-1 h; more specifically, the concentration of the purifying agent is 10-20%, and the reaction time is 0.6-0.8 h. The above process is used to purify the residual manganese and impurity elements.
This application will at last contain lithium purification back liquid and deposit lithium, obtain the wet material of lithium carbonate and deposit lithium mother liquor, will the wet material of lithium carbonate washes, dries, obtains battery level lithium carbonate. In the process, the lithium precipitating reagent is a sodium carbonate solution with the concentration of 200-300 g/L, the reaction temperature of lithium precipitation is 50-100 ℃, and the time is 1-5 hours, specifically, the lithium precipitating reagent is a sodium carbonate solution with the concentration of 220-270 g/L, the reaction temperature of lithium precipitation is 60-80 ℃, and the time is 2-4 hours; the washing temperature is 50-100 ℃, the washing times are 1-3 times, and the solid-to-solid ratio of the washing liquid is 1: 1-3: 1; the drying temperature is 100-200 ℃, and the drying time is 5-10 h.
In this application, waste lithium manganate positive electrode material is at least one of anodal powder, the anodal positive leftover bits of anodal mill output of battery disassembly factory output.
For further understanding of the present invention, the comprehensive recycling method of waste lithium manganate cathode material provided by the present invention is described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
100kg of waste lithium manganate anode material (Li: 3.2%; Mn: 60%) purchased from a battery dismantling plant is mixed with water and recrystallization mother liquor according to the liquid-solid ratio of 2:1 to prepare slurry, 98% of sulfuric acid is added to adjust the pH value of a system to be 0.5, 76.1kg of sodium sulfite is added according to 1.1 times of the required theoretical amount, the reaction temperature is controlled to be 85 ℃, and the mixture is stirred and leached for 2 hours and then is subjected to pressure filtration to obtain 400L of leachate and 15kg of acid leaching residue; adding 5kg of sodium carbonate into the leaching solution for impurity removal, adjusting the pH of the system to 5.0, then adding 1.1kg of hydrogen peroxide, stirring for reaction for 1 hour, and then carrying out filter pressing; carrying out filter pressing to obtain a liquid after impurity removal;
feeding the solution after impurity removal into a high-temperature crystallization kettle, keeping the temperature at 120 ℃ for 1.5h, performing centrifugal separation, and feeding the obtained rough manganese sulfate crystal into a new solution after impurity removal for concentration; and after the steps are repeated for many times, when the manganese concentration reaches 120g/L, performing high-temperature crystallization on the concentrated solution again, mixing the rough manganese sulfate crystals with 280L of water to dissolve, re-pouring the solution into a high-temperature crystallization kettle to perform high-temperature recrystallization after the solution is completely dissolved, keeping the temperature at 120 ℃ for 1.5h, performing centrifugal separation, and drying the refined manganese sulfate crystals to obtain 180.7kg of battery-grade manganese sulfate product No. 1. The recovery rate of manganese is 98 percent, and the main content of manganese sulfate is 99.3 percent.
Example 2
The embodiment is further optimized on the basis of the embodiment 1, and specifically includes:
adding 6kg of 30% sodium hydroxide solution into the obtained lithium-containing crystal mother liquor, adjusting the pH value of the system to 11.0, keeping the temperature at 50 ℃, stirring for 1h, and performing filter pressing to obtain purified liquid containing lithium; pumping the purified liquid into a reaction kettle, adding 93.2L of 260g/L sodium carbonate solution which is 1.1 times of the required theoretical amount, keeping the temperature at 80 ℃, stirring for reaction for 1 hour, and then carrying out centrifugal separation to obtain 18.42kg of lithium carbonate wet material; washing twice at the temperature of 90 ℃ according to the liquid-solid ratio of 1:1, and drying the centrifugally separated material in a 120 ℃ oven for 5 hours to finally obtain 16.13kg of battery-grade lithium carbonate. The recovery rate of lithium reaches 95.2 percent, and the main content of lithium carbonate is 99.6 percent.
Example 3
300kg of waste lithium manganate positive electrode leftover materials (Li: 3.5%; Mn: 61%) produced in a positive electrode factory, water and recrystallization mother liquor are prepared into slurry according to the liquid-solid ratio of 3:1, 98% sulfuric acid is added to the slurry to adjust the pH value of a system to be 1.5, 132kg of hydrogen peroxide is added according to 1.8 times of the required theoretical amount, the reaction temperature is controlled to be 50 ℃, the mixture is stirred and leached for 5 hours, and then the mixture is subjected to pressure filtration to obtain 1200L of leachate and 10kg of acid leaching residue; adding 13.8kg of sodium hydroxide into the leachate for impurity removal, adjusting the pH of the system to 4.5, adding 1.6kg of sodium chlorate, stirring for reaction for 1 hour, performing pressure filtration, and performing pressure filtration to obtain an impurity-removed solution;
feeding the solution after impurity removal into a high-temperature crystallization kettle, keeping the temperature for 3h at the crystallization temperature of 160 ℃, performing centrifugal separation, and feeding the obtained crude manganese sulfate crystals into a new solution after impurity removal again for concentration; repeating the steps for many times, performing high-temperature crystallization on the concentrated solution again when the manganese concentration reaches 100g/L, mixing the crude manganese sulfate crystal with 1830L of water for dissolving, re-pouring into a high-temperature crystallization kettle for high-temperature recrystallization after complete dissolution, keeping the temperature at 160 ℃, performing centrifugal separation after 2.5h, and drying the refined manganese sulfate crystal to obtain 557.84kg of cell-grade manganese sulfate product No. 2. The recovery rate of manganese is 98.3%, and the main content of manganese sulfate is 99.1%.
Example 4
The embodiment is further optimized on the basis of the embodiment 3, and specifically includes:
adding 10kg of 10% lithium hydroxide solution into the obtained lithium-containing crystal mother liquor, adjusting the pH value of the system to 10, keeping the temperature at 30 ℃, stirring for 0.5h, and performing filter pressing to obtain purified liquid containing lithium; pumping the purified solution into a reaction kettle, adding 382.8L of 270g/L sodium carbonate solution which is 1.3 times of the required theoretical amount, keeping the temperature at 95 ℃, stirring for 5 hours, and then carrying out centrifugal separation to obtain 61.66kg of wet lithium carbonate; adding pure water according to the liquid-solid ratio of 3:1, washing for three times at the temperature of 90 ℃, and drying the centrifugally separated material in a 200 ℃ oven for 8 hours to finally obtain 53.39kg of battery-grade lithium carbonate. The recovery rate of lithium reaches 96.3 percent, and the main content of lithium carbonate is 99.6 percent.
Example 5
500kg of waste lithium manganate anode material (Li: 3.0%; Mn: 58.8%) purchased from a battery dismantling plant is made into slurry with water and recrystallization mother liquor according to the liquid-solid ratio of 5:1, 98% sulfuric acid is added to adjust the pH value of the system to 2.0, then 60.45kg of sodium thiosulfate is added according to 1.5 times of the required theoretical amount, the reaction temperature is controlled to 60 ℃, and after stirring and leaching are carried out for 3h, filter pressing is carried out to obtain 3200L of leachate and 70kg of acid leaching residue; adding 10kg of ammonia water into the leachate for impurity removal, adjusting the pH of the system to 5.0, adding 2.5kg of sodium hypochlorite, stirring for reaction for 0.5h, carrying out filter pressing, and carrying out filter pressing to obtain an impurity-removed solution.
Feeding the solution after impurity removal into a high-temperature crystallization kettle, keeping the temperature for 2h at the crystallization temperature of 180 ℃, performing centrifugal separation, and feeding the obtained crude manganese sulfate crystals into a new solution after impurity removal again for concentration; and after the steps are repeated for many times, when the manganese concentration reaches 110g/L, performing high-temperature crystallization on the concentrated solution again, mixing the rough manganese sulfate crystal with 9126.3L water for pulp dissolution, putting the solution into a high-temperature crystallization kettle again for high-temperature recrystallization after the solution is completely dissolved, keeping the temperature at 180 ℃, performing centrifugal separation after 2 hours, and drying the refined manganese sulfate crystal to obtain 887.24kg of battery-grade manganese sulfate product 1 #. The recovery rate of manganese is 98.2 percent, and the main content of manganese sulfate is 99.2 percent.
Example 6
The embodiment is further optimized on the basis of the embodiment 5, and specifically includes:
adding 65kg of 20% potassium hydroxide solution into the obtained lithium-containing crystal mother liquor, adjusting the pH value of the system to 12, stirring for 1h at normal temperature, and performing filter pressing to obtain purified liquid containing lithium; pumping the purified solution into a reaction kettle, adding 608.4L of 280g/L sodium carbonate solution which is 1.5 times of the required theoretical amount, keeping the temperature at 100 ℃, stirring for 3 hours, and then carrying out centrifugal separation to obtain 88.1kg of lithium carbonate wet material; washing once at the temperature of 95 ℃ according to the liquid-solid ratio of 2:1, and drying the centrifugally separated material in a 160 ℃ oven for 6 hours to finally obtain 75.3kg of battery-grade lithium carbonate. The recovery rate of lithium reaches 94.7 percent, and the main content of lithium carbonate is 99.7 percent.
The technical indexes of the manganese sulfate prepared in the above examples 1, 3 and 5 are shown in Table 1, and the technical indexes of the lithium carbonate product prepared in the examples 2, 4 and 6 are shown in Table 2:
TABLE 1 technical indices of manganese sulfate for battery grade prepared in examples 1, 3 and 5
Table 2 technical indices of battery grade lithium carbonate prepared in examples 2, 4 and 6
As can be seen from table 1, the content of manganese sulfate recovered by the method provided in the example is high, and the content of impurities is extremely low, and as can be seen from table 2, the content of lithium carbonate recovered by the method provided in the example is high, and the content of impurities is extremely low, so that the recovery method provided by the present application can obtain battery-grade manganese sulfate and lithium carbonate.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A comprehensive recovery method of waste lithium manganate cathode materials comprises the following steps:
A) mixing the waste lithium manganate positive electrode material with water to obtain slurry, and carrying out reduction leaching on the slurry to obtain leachate;
B) adding an impurity removing agent into the leachate for removing impurities, and then adding an oxidant to obtain an impurity-removed solution;
C) carrying out high-temperature crystallization on the impurity-removed solution, and carrying out centrifugal separation to obtain a crude manganese sulfate crystal and a lithium-containing crystallization mother solution;
D) dissolving the crude manganese sulfate crystals, then performing high-temperature crystallization again, and performing centrifugal separation to obtain refined manganese sulfate crystals and crystallization mother liquor;
E) drying the refined manganese sulfate crystal to obtain battery-grade manganese sulfate, adding a purifying agent into the lithium-containing crystal mother liquor, and reacting to obtain a lithium-containing purified liquid;
F) and precipitating lithium from the lithium-containing purified solution to obtain a lithium carbonate wet material and a lithium precipitation mother solution, and washing and drying the lithium carbonate wet material to obtain the battery-grade lithium carbonate.
2. The comprehensive recovery method according to claim 1, wherein in the step A), the reagents for reducing and leaching are sulfuric acid and a reducing agent, the sulfuric acid is 98% concentrated sulfuric acid, the pH of the system is adjusted to 0.5-3.0, and the reducing agent is one or more selected from hydrogen peroxide, sodium sulfite and sodium thiosulfate.
3. The comprehensive recovery method according to claim 1, wherein in the step A), the liquid-solid ratio of the water to the waste lithium manganate positive electrode material is 2: 1-5: 1.
4. The integrated recovery method according to claim 1, wherein in step B), the impurity removing agent is selected from one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium hydroxide and ammonia water, and the oxidant is selected from one or more of hydrogen peroxide, sodium chlorate and sodium hypochlorite.
5. The integrated recovery method according to claim 1, wherein in step C), the high temperature crystallization process is specifically:
and (3) pouring the impurity-removed solution into a crystallization reaction kettle for high-temperature crystallization, and when the manganese concentration reaches 80-120 g/L, performing centrifugal separation on the obtained crystallization slurry to obtain rough manganese sulfate crystals and lithium-containing crystallization mother liquor.
6. The comprehensive recovery method of claim 1 or 5, wherein in the step C), the temperature of the high-temperature crystallization is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and the time is 1-3 h.
7. The integrated recovery process according to claim 1, characterized in that the high temperature crystallization in step D) is in particular:
and adding the crude manganese sulfate crystals into pure water for dissolving, pumping into a crystallization reaction kettle again for high-temperature crystallization, and performing centrifugal separation when the manganese concentration reaches 80-120 g/L to obtain refined manganese sulfate crystals and crystallization mother liquor.
8. The comprehensive recovery method of claim 1 or 7, wherein in the step D), the temperature of the high-temperature crystallization is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and the time is 1-3 h.
9. The integrated recycling method according to claim 1, wherein in step E), the purifying agent is selected from one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia water, the concentration of the purifying agent is 5-30%, the pH value of the reaction is 10.0-12.0, and the reaction time is 0.5-1 h.
10. The comprehensive recovery method of claim 1, wherein the lithium precipitating reagent is a sodium carbonate solution with a concentration of 200-300 g/L, and the reaction temperature of lithium precipitation is 50-100 ℃ and the time is 1-5 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116119690A (en) * | 2022-12-16 | 2023-05-16 | 安徽格派锂电循环科技有限公司 | Method for selectively recycling lithium from waste lithium battery |
| CN116837216A (en) * | 2023-09-01 | 2023-10-03 | 北京怀柔北珂新能源科技有限公司 | Impurity removal method for recycling positive electrode powder of lithium ion battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342390A (en) * | 2013-07-18 | 2013-10-09 | 广西南宁晟瑞冶化技术有限公司 | Method for high-purity manganese sulfate monohydrate |
| CN103606719A (en) * | 2013-12-02 | 2014-02-26 | 河南师范大学 | Method for preparing lithium manganate cathode material by taking waste lithium ion batteries as raw material |
| CN104078719A (en) * | 2014-06-20 | 2014-10-01 | 奇瑞汽车股份有限公司 | Method for preparing nickel lithium manganate by using waste lithium manganate battery |
| CN107699692A (en) * | 2017-09-18 | 2018-02-16 | 北京理工大学 | A kind of recovery and the method for regenerating waste used anode material for lithium-ion batteries |
| CN109234524A (en) * | 2018-09-19 | 2019-01-18 | 中国科学院青海盐湖研究所 | A kind of method and system of the comprehensively recovering valuable metal from waste and old ternary lithium battery |
| CN110013822A (en) * | 2018-01-07 | 2019-07-16 | 中南大学 | A kind of method of waste and old lithium ion battery recycling co-production lithium adsorbent |
| CN110451569A (en) * | 2019-09-10 | 2019-11-15 | 贵州大龙汇成新材料有限公司 | A kind of manganese sulfate solution purification and impurity removal preparation method |
| CN112158894A (en) * | 2020-09-24 | 2021-01-01 | 广东邦普循环科技有限公司 | Method for recovering anode material of waste lithium battery |
-
2022
- 2022-05-31 CN CN202210606493.8A patent/CN114906863B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342390A (en) * | 2013-07-18 | 2013-10-09 | 广西南宁晟瑞冶化技术有限公司 | Method for high-purity manganese sulfate monohydrate |
| CN103606719A (en) * | 2013-12-02 | 2014-02-26 | 河南师范大学 | Method for preparing lithium manganate cathode material by taking waste lithium ion batteries as raw material |
| CN104078719A (en) * | 2014-06-20 | 2014-10-01 | 奇瑞汽车股份有限公司 | Method for preparing nickel lithium manganate by using waste lithium manganate battery |
| CN107699692A (en) * | 2017-09-18 | 2018-02-16 | 北京理工大学 | A kind of recovery and the method for regenerating waste used anode material for lithium-ion batteries |
| CN110013822A (en) * | 2018-01-07 | 2019-07-16 | 中南大学 | A kind of method of waste and old lithium ion battery recycling co-production lithium adsorbent |
| CN109234524A (en) * | 2018-09-19 | 2019-01-18 | 中国科学院青海盐湖研究所 | A kind of method and system of the comprehensively recovering valuable metal from waste and old ternary lithium battery |
| CN110451569A (en) * | 2019-09-10 | 2019-11-15 | 贵州大龙汇成新材料有限公司 | A kind of manganese sulfate solution purification and impurity removal preparation method |
| CN112158894A (en) * | 2020-09-24 | 2021-01-01 | 广东邦普循环科技有限公司 | Method for recovering anode material of waste lithium battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116119690A (en) * | 2022-12-16 | 2023-05-16 | 安徽格派锂电循环科技有限公司 | Method for selectively recycling lithium from waste lithium battery |
| CN116837216A (en) * | 2023-09-01 | 2023-10-03 | 北京怀柔北珂新能源科技有限公司 | Impurity removal method for recycling positive electrode powder of lithium ion battery |
| CN116837216B (en) * | 2023-09-01 | 2023-11-21 | 北京怀柔北珂新能源科技有限公司 | Impurity removal method for recycling positive electrode powder of lithium ion battery |
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